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(12) United States Patent (10) Patent No.: US 9,328,300 B2 Ferrara (45) Date of Patent: May 3, 2016

(54) METHOD, APPARATUS AND CHEMICAL (56) References Cited PRODUCTS FORTREATING PETROLEUM EQUIPMENT U.S. PATENT DOCUMENTS 3,677,819 A T. 1972 Thiel (71) Applicant: Marcello Ferrara, Syracuse (IT) 4,762,958 A * 8/1988 Martens et al...... 585,613 4,810,397 A 3, 1989 Dvoracek (72) Inventor: Marcello Ferrara, Syracuse (IT) 5,076,856. A 12/1991 Schweiger 5,266, 186 A * 1 1/1993 Kaplan ...... 208.48 AA (*) Notice: Subject to any disclaimer, the term of this 3. A g Stick et al. patent is extended or adjusted under 35 5,611,869 A 3, 1997 Hart U.S.C. 154(b) by 228 days. 5,935,276 A 8, 1999 DeRosa et al. 5,972,206 A 10/1999 Lenglet (21) Appl. No.: 13/836,857 6,138,691 A 10/2000 Voloshin et al. (Continued) (22) Filed: Mar 15, 2013 FOREIGN PATENT DOCUMENTS (65) Prior Publication Data DE 442O579 A1 12, 1995 US 2013/027O157 A1 Oct. 17, 2013 FR 2815 639 4/2002 (Continued) Related U.S. ApplicationO O Data OTHER PUBLICATIONS (60) Provisional application No. 61/624,629, filed on Apr. Search Report for Application No. ITRM20120162 dated Dec. 18, 16, 2012. 2012. (Continued) (30) Foreign Application Priority Data Primary Examiner — Brian McCaig Apr. 16, 2012 (IT) ...... ITRM2O12O162 (74) Attorney, Agent, or Firm — Smith, Gambrell & Russell LLP. (51) Int. Cl. CIOG 75/04 (2006.01) (57) ABSTRACT F24D L7/00 (2006.01) The present invention provides a method, an apparatus and F24D L7/02 (2006.01) chemical products for treating petroleum equipment wherein (52) U.S. Cl. a fluid is flowing, preferably of the hydrocarbon type, and CPC ...... CI0G 75/04 (2013.01); F24D 17/002I wherein treating is performed by establishing a closed or (2013.01); F24D 17/0031 (201301). F24D semi-closed flow circulation loop, during the normal produc 1702 (2013,01): YIOT 29/49 (201501) tion operations of the equipment. The treatment can refer to (58) Field of Classification Search the cleaning of equipment, to yield improvement as compared CPC ...... C10G 9/16; C10G 75/00; C10G 75/02: to normal run conditions and/or to a reduction of coke forma C1 OG 75/04 tion and/or to coke removal on catalysts. See application file for complete search history. 71 Claims, 15 Drawing Sheets

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(56) References Cited KR 20010092.131 10, 2001 WO 96.20255 A1 T 1996 U.S. PATENT DOCUMENTS WO 03.103863 A1 12/2003 WO 2008/070299 A1 6, 2008 6,273,102 B1 8/2001 Kawakami et al. WO 2011/126880 A2 10/2011 6,485,578 B1 1 1/2002 Parket al. 6,858,090 B2 2, 2005 Hebert 7.682,460 B2 3/2010 Ferrara OTHER PUBLICATIONS 7.998.281 B2 8/2011 McCoy et al. ck 388853. A. 1858 yishl al...... 208.48 AA Written Opinion of the International Searching Authority (Form 2011/0247967 A1 10, 2011 Sundaram et al. IT237) dated Dec. 18, 2012 for Application NO. ITRM20120162 including partial English language translation of Opinion. FOREIGN PATENT DOCUMENTS GB 2361 282 A 10, 2011 * cited by examiner U.S. Patent May 3, 2016 Sheet 1 of 15 US 9,328,300 B2

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US 9,328,300 B2 1. 2 METHOD, APPARATUS AND CHEMICAL present invention the term "heavy compounds’ means chemi PRODUCTS FORTREATING PETROLEUM cal compounds, alone or mixtures thereof, having a boiling EQUIPMENT point >100° C. Such heavy compounds generally show up as a deposit inside said equipment, with related equipment mal CROSS REFERENCE TO RELATED functioning, and generally result from degradation of fluids APPLICATIONS which are part of the process. Sometimes degradation can even lead to coke and coke-like deposits. In some processes, This application claims benefit of U.S. Provisional Appli especially the petrochemical ones, such heavy compounds cation No. 61/624,629 filed Apr. 16, 2012 as well as Italian show up as polymeric compounds. It is therefore necessary to Application No. ITRM20120162 filed on Apr. 16, 2012. 10 remove said heavy compounds from the equipment to recover These priority applications are incorporated herein by refer its normal performance. CCC. Petroleum plants suffer from fouling of equipment. As BACKGROUND OF THE INVENTION used in the present invention the terms “petroleum plant’ or “plant” refer to any industrial plant wherein there is processed The present invention is inclusive of a method, an appara 15 a crude oil or any crude oil derivative, direct or indirect, that tus and chemical products for cleaning petroleum equipment, is derived from the processing of one or more derivative(s) of preferably of the hydrocarbon processing type, wherein the crude oil. It is to be considered, even crude oil just as cleaning is performed by establishing a closed or semi-closed extracted gives rise to fouling problems within the industrial flow circulation loop, during the normal production opera plantarising from heavy compounds precipitation inside pro tions of said equipment. duction equipment. For example, oil-gas separators, stabili The present invention is further inclusive of a method, an Zation/distillation columns, heat exchangers, and filters are apparatus and chemical products for increasing distillation Subject to Such fouling. Once the crude oil is processed in yields of a petroleum plant. refining plants, these refining plants also experience heavy The present invention is also inclusive of a monitoring compound fouling. Fouling generally increases by increasing system to Verify the cleaning status during execution of the 25 process temperature and/or by having a heavier plant feed claimed method. and/or a feed made up of residues of the preceding plants. The present invention is still further inclusive of a method, Among the equipment which experiences fouling, there can an apparatus and chemical products for cleaning, degassing be mentioned, as explanatory but not limiting examples: dis and decontamination of petroleum equipment, before main tillation columns (including their internals), furnaces, reac tenance. 30 tors (including their catalysts), filters, pumps, lines and heat The present invention realizes the cleaning of the equip exchangers. All of the hydrocarbon processing industry is ment during the normal run of the plant it is a part of without experiencing this problem from oil fields to refining and the need of excluding it from the production cycle and/or petrochemical plants, as well as fine chemicals production. without the need of stopping production and/or the flow of the Among the refining plants subject to fouling there can be fluid which is normally flowing in said equipment. This is an 35 mentioned, e.g.: Topping (CDU), Vacuum (VDU), Visbreak improvement over the current state of the art. ing (VBU), Fluid Catalytic Cracking (FCC). Resid Catalytic By cleaning petroleum equipment with a closed or semi Cracking, Hydrotreating, Hydrofining, Unionfining, Reform closed flow circulation loop, the present invention realizes, ing, Coking, Hydrocracking. Thermal Cracking, Deasphalt among others (e.g., when compared to common mechanical ing, Alkylation, Isomerization, Demetallization, Dewaxing, cleaning systems), the following improvements: i) elimina 40 Flexicoking, Flexicracking, GO-Fining, Isocracking, tion of equipment decommissioning and/or opening and/or LC-Fining, Magnaforming, Lube and wax processing, Lube out of service; ii) cleaning time reduction; iii) recovery and Isocracking, Lube oil dewaxing, Platforming, Resid Oil reuse of fouling product; iv) achieving simultaneous cleaning Supercritical Extraction (ROSE), Residfining, Residue ther of multiple equipment pieces; V) reduction of production loss mal cracking, Selective Yield Delayed Coking (SYDEC), arising from equipment being out of service. 45 Solvahl Solvent Deasphalting, Unicracking, Continuous The present invention also realizes a new design/engineer Catalytic Reforming (CCR), Aromatics extractive distilla ing method to dimension petroleum equipment, wherein said tion, Asphalt oxidation, Gasification, Desulfurization, dimensioning can be done without taking into account per Hydrodesulfurization, Olefins recovery, Spent oil lube re formance reduction due to fouling. refining; and generally all of the plants which are part of a Other techniques are available in the state of the art which 50 petroleum refinery and/or related sites. realize equipment cleaning on a closed flow circulation loop In the petrochemical plants, fouling from heavy com (none of these operate with a semi-closed flow circulation pounds show up, besides from the heavy compounds them loop), but such techniques imply, the equipment and/or the selves, also as polymeric compounds which plug equipment. plant they are part of, to be excluded from the production Such a phenomenon is particularly strong in the plants which cycle or even the entire plant to be out of production. The 55 produce raw materials for the polymer/rubber industry or present invention improves the state of the art by realizing the which directly produce polymer/rubber. Among the petro cleaning of the equipment and/or of the plant they are part of chemical plants Subject to fouling there can be mentioned, without stopping the production cycle, during normal plant e.g.: Ethylene, Butadiene, Phenol, Cumene, Alpha Olefins, U. BTX aromatics, Alkylbenzene, Caprolactam, Dimethyl The present invention also provides a yield increase and/or 60 terephthalate, Polyethylene, Polypropilene, Polystyrene, coke formation reduction or coke removal on catalysts in a PVC, Styrene, Vinyl Chloride Monomer, Xylene Isomeriza petroleum plant. tion, Styrene-Butadiene Rubber (SBR), Nitrilic-Butadiene Rubber (NBR), Acrylonitrile, Acrylonitrile-Styrene-Butadi STATE OF THE ART ene (ABS), Toluendiisocyanate (TDI), Normal Paraffin, ISO 65 SIV; and generally all of the petrochemical plants. Generally speaking, fouling of process equipment arises In all of the above exemplary cases, fouling reduces plant from deposition of heavy compounds. For the purposes of the performance and makes it necessary for equipment shut US 9,328,300 B2 3 4 down, placement out of service, decommissioning, cleaning In the state of the art many chemical products are available and Subsequent commissioning and then getting it back on which are used to prevent fouling of petroleum equipment. stream. In any case, fouling associated costs imply: i) energy Said chemical products are introduced in Small amount (e.g., costs, as it is more difficult to Supply or exchange heat when maximum 100 ppm) in the feed during the normal run of the the equipment is fouled, with related increase in fuel con plant, with the plant in the production mode and with the Sumption; ii) production loss costs, as fouling limits through produced products completely exiting the plant (without any put and/or plant yields or can lead to an anticipated shutdown; closed or semi-closed circulation loop which introduces said iii) maintenance costs. Such as a specialized company chemical products inside the petroleum plant). Said chemical mechanically cleaning the equipment; iv) environmental products are normally injected on a continuous basis, 365 costs, as waste is generated, and needs to be disposed of (with 10 days a year. Furthermore their dosage rate is normally con related waste disposal costs); environmental burdens, stant and does not depend in any case on injection time. In no together with waste disposal, generation of emissions of air case are said chemical products injected during a closed or borne pollutants, included those related to increased fuel con semi-closed circulation phase, wherein a distillate is reintro sumption. The above costs are almost inevitable with current duced in the petroleum plant in order to clean one or more technologies. Embodiments of the present invention are 15 pieces of equipment and/or to increase distillation yield and/ Suited for avoiding or at least lessening to some extent all or or to reduce coke formation on catalysts and/or to remove some of the above noted problems. coke from catalysts. Finally said chemical products fail to The state of the art of equipment cleaning implies a tailor clean fouled equipment, and thus are used instead to prevent made cleaning for each piece of equipment. Heat exchangers equipment from fouling. As a matter of fact, notwithstanding are generally cleaned by bundle extraction and washing with the injection of said chemical products, the equipment treated high pressure water jetting (with pressures even >600 bar), with said chemical products do foul anyway; as proof of that, generally in a different place with respect to the place where the treated equipment is mechanically cleaned both during the equipment is located. Distillation columns are cleaned by normal plant run or during plant shutdown. Generally speak manual cleaning (e.g., Scratching) and/or washing with high ing, plant shutdown is mostly dictated by the need of pressure water jetting. Filters and pumps are cleaned by 25 mechanical cleaning of fouled equipment. U.S. Pat. No. decommissioning and manual cleaning. In a furnace, coke is 5,076,856 describes a system to clean heat exchangers removed, e.g., by means offlowing an air/steam mixture or by wherein a solvent flows for about 15 minutes, followed by a inserting and running a pig in the coils. In a catalyst, coke is flushing with compressed air; the system operates as an open removed after dumping the catalyst from the reactor and by ex circuit. U.S. Pat. No. 5,425,814 describes an embodiment situ controlled coke combustion. To perform Such an opera 30 featuring a closed loop decontamination method, which uses tion the catalyst is sent to a specific regeneration plant of a chemical products to be dissolved in water; the water and the specialized company. chemical products are circulated in the equipment while The above operations, besides having the mentioned draw being excluded from the production cycle. U.S. Pat. No. backs, can also cause damage to the equipment to be cleaned. 6.273,102 describes a method for downloading a catalyst, For heat exchanger bundles to be extracted, e.g., their lifting 35 which uses chemical products for safely softening/wetting/ by means of crane and slings or an extractor is required: this downloading a catalyst from a reactor during plant shutdown; causes bundle bending and in turn damage to tubes and bor i.e., when the reactor is excluded from the production cycle ing; furthermore, removal and re-assembling of floating and the plant is shutdown. heads might lead to potential leaking when the gasket is not The state of the art is also inclusive of the following refer perfectly placed. Air/steam decoking of furnaces, besides 40 ences WO2008/070299; U.S. Pat. No. 7,682,460; US2009/ prolonged downtime, might lead to carburation of coils which 0266742: WO2011/126880; WO96/20255; U.S. Pat. No. might cause tuberupture. Finally, in a petroleum plant, clean 6,485,578. ing of equipment is performed for each single piece of equip The state of the art of equipment cleaning includes there ment, with different timing, and is a labor intensive job. fore the exclusion from the production cycle of the equipment Upon performing cleaning of equipment on a closed or 45 to be cleaned and eventually the plant shutdown or the shut semi-closed system, during plant run, there is avoided open down of individual pieces of equipment. This is a serious ing of said equipment and/or there is avoided potential dam technical problem because cleaning implies reduced/stopped ages arising from current techniques, and/or there is provided production of the plant and/or of said equipment. Moreover, a reduction in waste generation, and/or airborne emissions, in the state of the art the circulation of a plant is performed on and/or there is provided for the cleaning of more pieces of 50 a closed loop basis only, generally during shutdown opera equipment simultaneously, and, hence, an improvement over tions before maintenance and in no case during plant run. In the current state of the art can be achieved. Whenever said no case is a semi-closed circulation performed. closed or semi-closed system cleaning is performed without Under the present invention, the term “semi-closed loop stopping production and/or the flow of the fluid which passes circulation' defines a process wherein a hydrocarbon fluid through said equipment and/or the plant wherein said equip 55 produced in a petroleum plant, which is therefore a portion of ment is part of an additional improvement over the current the normal production, is: i) partially exiting the petroleum state of the art can be achieved. plant (as per normal production process) and, ii) partially The present invention realizes an improvement over the withdrawn from one or more plant locations and introduced in current state of the art by achieving the cleaning of the equip one or more plant locations, preferably upstream of the equip ment and/or of the petroleum plant by means of a closed or 60 ment to be cleaned; and in a preferred embodiment said semi-closed circulation loop inside the equipment and/or the hydrocarbon fluid will be thereafter distilled and, re-with petroleum plant to be cleaned and by introducing a first and/or drawn and re-introduced, thereby continuing the cycle. second hydrocarbon fluid in said closed or semi-closed cir During a plant run the equipment is indeed actively culation loop, during the normal run of the equipment and/or included in the production cycle and the process fluid fully of the petroleum plant, without stopping the plant and/or 65 passes through it as per design conditions. A plant run implies without removing the fluid which passes through said equip the introduction at a plants inlet of a feed, specific for that ment and/or said petroleum plant. plant, and the Submission of the various equipment at process US 9,328,300 B2 5 6 conditions, in particular temperature and pressure (e.g., a distillation yield increase and/or the reduction of coke forma normal operation state or normal run). Such as to produce tion on catalysts and/or the removal of coke on catalysts are specific products at the plants outlet. As used in the present realized. invention “normal operation state' or “normal run, and the like, defines, relative to embodiments of the invention, a 5 SUMMARY OF THE INVENTION condition of the plant wherein distillate(s) meet one or more pre-established criteria or specifications as to render said In one preferential embodiment, the present invention distillate(s) suited for plant output. For example, in a Crude relates to a method, an apparatus, one or more chemical Distillation Unit (CDU or Topping), crude oil is introduced at product(s) and a monitoring system to clean, in a closed or a plant inlet and at the outlet are produced LPG, gasoline, 10 semi-closed loop, during plant run, one or more pieces of naphtha, kerosene, gas oil, atmospheric residue; feed rate petroleum equipment which have been fouled up by heavy normally depends upon production needs of the CDU and/or organic compounds, as defined by the present invention. of the refinery. The throughput of the products at a plant outlet In another preferential embodiment, the present invention (“distillation yield”, “plant yield' or “conversion yield) relates to a method, an apparatus and chemical product(s) to depends upon many factors, but it is the same for the same 15 clean during the plant run of a petroleum plant. feed at the same operating conditions. Plant shutdown or feed In still another preferential embodiment, the present inven reduction are a penalty for the plant owner. tion relates to a method, an apparatus and chemical product(s) In the state of the art, during the cleaning of one or more to increase distillation yield of a petroleum plant. pieces of equipment, normal run conditions are missing in In a further preferential embodiment, the present invention that, in order to perform the cleaning, said equipment is 20 relates to a method, an apparatus and chemical product(s) to excluded from the production cycle and the process fluid does simultaneously realize the cleaning and the increase of dis not pass through it, as opposite to design conditions, and/or tillation yield of a petroleum plant. the plant itself is shutdown or its throughput is reduced in In still a further preferential embodiment, the present order to allow said exclusion (obviously, by missing one or invention relates to a method for monitoring closed or semi more pieces of the plant designed for an on-line State or for 25 closed cleaning operations and/or distillation yield increase normal plant usage, the same cannot run at the same through under the present invention. put). In the state of the art, the main technical problem which In another preferential embodiment, the present invention hampers the cleaning of the equipment during a plant run is relates to a method, an apparatus and chemical product(s) to attributable to the stoppage of plant production and/or the reduce coke formation on catalysts. stoppage of the normal flow which passes through said equip- 30 In still another preferential embodiment, the present inven ment in order to clean it. tion relates to a method, an apparatus and chemical product(s) In the state of the art it was not thinkable to achieve the to remove coke on catalysts. equipment cleaning during plant run because all of the exist In still a further preferential embodiment, the present ing techniques implied the stoppage of the normal flow which invention relates to a method, an apparatus and chemical passes through said equipment. In the state of the art it was not 35 product(s) to simultaneously realize the cleaning and the thinkable to realize an internal circulation of distillates, by increase of distillation yield of a petroleum plant and/or the means of a closed or semi-closed loop, because in all of the reduction of coke formation on catalysts. existing petroleum plants the distillates are completely In another preferential embodiment, the present invention removed from said plant, or from the equipment wherein they relates to a method, an apparatus and chemical product(s) to pass through, once they are produced. In the state of the art it 40 clean and to achieve gas-free conditions and/or to achieve was finally not thinkable to circulate a distillate upstream of safe entry conditions of equipment in a petroleum plant. the equipment to be cleaned by “self-producing said distil An embodiment features a method for treating a petroleum late by means of a variation offeed rate, because the feed rate plant or equipment of the petroleum plant during a running of is exclusively defined by production needs (market demand) the petroleum plant that comprising maintaining, during a and it is in no way bound to plant cleaning needs (besides the 45 treatment period, the petroleum plant under a production throughput limitations related to fouling, which impose a operating condition, typical of the plant itself, while provid throughput reduction and is one of the technical limits which ing fresh feed to the petroleum plant. Also, while maintaining are addressed by the present invention). No person skilled in the petroleum plant under the production operating condition, the art would therefore think to clean equipment during the there is carried out one or both of a) and b): with a) being plant run because, with the current techniques, this would 50 introducing in the petroleum plant, during the treatment imply: i) production loss of said plant; ii) the modification of period, a hydrocarbon-based treatment fluid; b) being varying all the state of the art on plant design/engineering and/or on an established feed rate, present at initiation of the treatment plant production processes. of the petroleum plant or equipment of the petroleum plant, Unexpectedly, by applying an operating method under the which established feed rate ranges from a maximum opera present invention, not used in the state of the art, together with 55 tion rate for the petroleum plant, which is inclusive of a design an apparatus in accordance with the present invention, in rate for the petroleum plant, to a minimum operation rate order to create a closed or semi-closed loop during plant run, which is set at a level for satisfying a minimum production and by introducing a first and/or second hydrocarbon fluid, operating state in the petroleum plant. Said introduction of a the cleaning of equipment during plant run can be realized, hydrocarbon-based treatment fluid and/or said variation to without stopping the plant and/or without excluding said 60 the treatment feed rate is inclusive of the providing of an equipment and/or without stopping the flow which normally additional source or sources for distallation with respect to passes through the same. the amount provided by the established rate. There is also the Still unexpectedly, by applying an operating method under distillation of said additional source or sources for distillation the present invention, not used in the state of the art, together for the purpose of plant treatment. with an apparatus in accordance with the present invention, in 65 An embodiment includes the additional source or sources order to create a closed or semi-closed loop during plant run, of distillate as being that which is generated by the variation and by introducing a first and/or second hydrocarbon fluid, a to the treatment feed rate to he fed into the plant (e.g., into the US 9,328,300 B2 7 8 current fresh feed of the plant) as the introduction source “a)” Summed together to a desired treatment feed rate and wherein or as a Supplement to an alternate introduction source “a) a controller is configured as to monitor and adjust the fresh (e.g., an introduction being a re-introduction of distillate to feed rate to the plant based on a (e.g., sensed) current input another point in the plant from the distillate sources output level of the drawn off distillate being received in said one or Such as by use of a closed or semi-closed loop associated with 5 more fresh feed passageways, a current fresh feed to the plant, the plant) to the plant (e.g., as Supplement to an external and a set desired treatment feed rate in the plant. Source or another plant source). An embodiment further includes having the drawn off dis An embodiment includes, for varying the established rate, tillate introduced into a fresh feed passageway of the plant an adjustment of the established rate to a treatment feed rate and wherein introduction of the hydrocarbon-based fluid either by an increase in the established feed rate when the 10 includes introduction (or re-introduction) of a first and/or established feed rate falls below the treatment feed rate or a second hydrocarbon-based fluid, and varying the established reduction in the established feed rate when the established feed rate is carried out by an introduction of the first and/or feed rate falls above the treatment feed rate. second hydrocarbon treatment fluids, with the introduction of An embodiment includes, for setting the established feed the first and/or second hydrocarbon treatment fluids including rate, an adjustment of the established feed rate in association 15 both the drawn off distillate plus an external source of said with an introduction of the hydrocarbon-based treatment fluid first and/or second hydrocarbons placed into combination at least partly derived from an external source and wherein with the drawn off distillate so as to establish desired treat said first externally derived hydrocarbon-based treatment ment feed rate. fluid is introduced into a closed or semi-closed loop at least An embodiment further includes introducing into a closed partly formed by said plant. or semi-closed loop of the petroleum plant, during the treat An embodiment of the invention further comprises adding ment period, the hydrocarbon-based fluid, with the hydrocar equipment to an existing plant to form the closed or semi bon-based fluid being derived from either an external source closed loop and wherein a majority of the closed or semi of the hydrocarbon-based fluid, an internal plant source of the closed loop is represented by equipment previously existing hydrocarbon-based fluid or both. in the plant for normal run usage. 25 An embodiment further includes having the introduction of An embodiment includes having the hydrocarbon-based the hydrocarbon-based fluid comprised of the introduction of fluid being one that is a fluid that cleans a heavy deposit in the a first and/or second hydrocarbon based fluid, with the first plant by removal of the heavy deposit from a source location hydrocarbon based fluid being introduced in a ratio com in the plant and passing the removed heavy deposit with the prised between 0% and 100% with respect to a current fresh cleaning hydrocarbon-based fluid to an outlet of the plant. 30 feed in the plant; and, if a second hydrocarbon-based fluid is An embodiment includes, for varying the established feed introduced introducing it in a ratio comprised between 0.01% rate, an increase adjustment in the plant fresh feed rate from and 50% with respect to a current fresh feed in the plant (with said established feed rate to a level above the established feed a provision in this embodiment being that, when the addi rate as to generate an additional quantity of distillates relative tional portion of distillates is 0%, the amount of the first to a quantity generated at the established feed rate, and draw 35 hydrocarbon based fluid is higher than 0%). ing off at least some of an overall quantity of distillate gen An embodiment includes passing one or more distillates erated from the increased plant feed rate and introducing the and/or products of the plant from a non-treatment, normal, drawn off distillate into a treatment region of said plant. An plant operation mode passage route to a treatment mode pas embodiment further comprises passing the drawn off distil sage route by feeding at least a portion of the one or more late through a closed or semi-closed loop forming at least a 40 distillates and/or products into a closed or semi-closed circu portion of said plant and extending through the treatment lation loop (at least partially passing inside the plant and that region; with, for example, the closed or semi-closed loop of passes the one or more distillates and/or products of the plant) the plant being configured such that drawn off distillate is to a different location in the plant than when directed in the re-introduced into a distillation device of the plant which is a non-treatment mode. For example, the different location in source of the initially drawn off distillate and drawing off a 45 the plant can be a location positioned upstream of plant equip recirculation output of distillate from the distillation device ment to be treated (as in an input location in a passage or following receipt of the re-introduced drawn off distillate and communication line that extends between an equipment piece passing the recirculation output of distillate to the treatment being treated that is immediately downstream from another region. piece of equipment on the same passage line not being An embodiment further comprises introducing the drawn 50 treated). off distillate to one or more fresh feed rate passageways of the An embodiment features circulating in the closed or semi plant and a lowering of a current fresh feed rate to the plant closed loop one or both of a first hydrocarbon-based fluid and Such that upon introduction into a loop of the plant there is a second hydrocarbon-based fluid inside the equipment to be provided a source or a supplement for the introduction of the treated as part of the introduction of hydrocarbon-based fluids hydrocarbon based treatment fluid to the treatment feed rate 55 in the plant, such that a portion of the products distilling and such that the lowered fresh feed rate plus the additional during said circulation are re-introduced in said closed or drawn off distillate passing though one or more common semi-closed loop, whereas another portion of the distillates passages in the plant Sum to conform with plus or minus 60% makes up the petroleum plant production and/or the normal of the established rate, alternatively one that has the sum to distillate flow stream. conformat plus or minus 30% of the established rate, or, even 60 There is also an embodiment featuring an adjustment in further alternatively, one that is essentially at the established plant configuration to include the closed or semi-closed loop rate. (with one embodiment including the addition of a distillation An embodiment further comprises introducing an increas generation device that is added into the loop for treatment ing amount of the drawn off distillate to one or more fresh purposes and in one embodiment is not part of the non feed passageways of the plant and a coordinated lowering of 65 treatment or normal run portion of the plant). a current fresh feed rate to the plant such that the lowered An embodiment includes a method wherein there is circu fresh feed rate plus the additional drawn off distillate is lated in the closed or semi-closed loop one or both of the first US 9,328,300 B2 9 10 hydrocarbon-based fluid and a second hydrocarbon-based routing to another petroleum plant; and (vi) any combination fluid inside the equipment to be treated, for a time of at least or subcombination of (i) to (v). 20 minutes, at a temperature comprised between 100° C. and An embodiment includes a method wherein the introduc 900° C. and at a pressure comprised between 1 bar and 400 tion of the hydrocarbon based fluid includes the introduction bar of one or both of a first hydrocarbon-based fluid and a second An embodiment includes a method wherein a monitoring hydrocarbon fluid that is or are capable of solubilizing the criteria associated with a running of said plant is monitored, deposits in said equipment to be cleaned essentially under and wherein the introduction of the hydrocarbon based fluid near critical or Supercritical conditions at the operating con includes the circulation withina closed or semi-closed loop of ditions of the plant. the first hydrocarbon-based fluid or the first and second 10 An embodiment includes a method wherein the first hydro hydrocarbon based fluids, and which circulation is carried out carbon-based fluid contains one or more chemical products in repeated fashion until the monitoring criteria is deemed and said first hydrocarbon-based fluid and said chemical satisfactory. products are mixed in a proportion designed in order to be An embodiment includes a method wherein the plant oper utilized in a solution form, and wherein said first hydrocar ating running conditions during treatment are such that there 15 bon-based fluid forms the solvent of said chemical products. is continued distillation of fresh feed source material. An embodiment includes a method wherein, in the ratio An embodiment includes a method wherein the petroleum solvent/chemical products varies in the range: solvent 70%- plant runs at increased feed or at the design feed rate (or 99.99%, chemical products 0.01%-30%. higher), so as to produce a major amount of distillates, there An embodiment includes a method wherein the solvent after progressively reducing the fresh feed rate, such that the coincides with the first hydrocarbon fluid and is “self-pro increased amount of produced distillates, with respect to the duced' and circulated inside the petroleum plant. amount of distillates produced with the pre-existing fresh An embodiment includes a method wherein the treatment feed rate, be circulated in parts of the plant to be treated. is carried out according to one of i) once-through continuous An embodiment includes a method wherein setting the injection of the first hydrocarbon fluid introduced in any part feed rate includes, a reduction in the established feed rate of 25 of the plant; ii) injection of the first hydrocarbon fluid intro the plant to a value comprised between 40% and below 100% duced from outside of the plant and further introduced in any with respect to the design feed rate, followed by the introduc part of the plant, upstream a distillation column, which is tion of the hydrocarbon-based fluid which comprises an intro thereafter distilled and introduced in any part of the plant; iii) duction of first and/or the second hydrocarbon-based fluid(s) self-production of the first hydrocarbon fluid produced by in an amount as to compensate up to the difference among the 30 distillation at a certain feed rate, followed by the variation of rate at which the plant is running and its design feed rate, and fresh feed rate, the withdrawal of said hydrocarbon fluid from so as to manage up to the maximum allowable plant distillate any part of the plant and the introduction of said distillate in flow rate or in any case the distillate flow rate applicable prior any part of the plant; iv) introduction of the first hydrocarbon to the introduction of the first and/or the second hydrocarbon fluid according to one or more of the above points i), ii) and based fluid(s), such as to run the plant at the flow rate resulting 35 iii), and V) the introduction according to (iv) together with a from the sum: flow rate of reduced fresh feed--flow rate of second hydrocarbon fluid which is introduced simultaneously the first and/or the second hydrocarbon-based fluid(s), and or subsequently said first hydrocarbon fluid. wherein said flow rate is equal to or higher to the one prior to An embodiment includes a method wherein the introduc the reduction in feed rate. tion of the hydrocarbon based fluid comprises the introduc An embodiment includes a method wherein the introduc 40 tion of a first hydrocarbon fluid or the first and a second tion of the hydrocarbon based fluid comprises introduction in hydrocarbon fluid, and which first and/or second hydrocar the plant of a first and a second hydrocarbon-based fluid from bon fluid is or are selected from a group consisting of distil separate sources, and which second hydrocarbon-based fluid lation products from crude oil originating from the petroleum joins and passes together with the first hydrocarbon-based plant and/or being anyway present in the petroleum plant, by fluid to a common treatment introduction point of the petro 45 being finished products, blending components of finished leum plant. products, intermediate products or feed to the petroleum plant An embodiment includes a method wherein the treatment and are selected from the group consisting of gasoline, die is carried out in a plant with a furnace and wherein the treat sel, gas oil, Virgin naphtha, kerosene, reformed gasoline, ment increases a value setting for a furnace inlet temperature pyrolysis gasoline, pyrolysis gas oil, light cycle oil from of the furnace existing at the point of initiation of the treat 50 FCCU, decant oil from FCCU, methyl-tert-butyl-ether ment (e.g., a final state before a treatment effect is applicable). (MTBE), benzene, toluene, xylenes, cumene, methanol, An embodiment includes a method wherein the treatment cyclohexane, cyclohexanone, ethylbenzene, linear alkylben increases the plant distillation yield in a manner beyond the Zene (LAB), dimethylterephthalate, phtalic anhydride, sty quantity derivable from an equal overall feed amount to the rene, tert-amyl-methyl-ether (TAME), ethanol, dimethylfor plant distillation Source(s) at a point of treatment initiation. 55 mamide (DMF), dioctylphthalate, isopropyl alcohol, butyl An embodiment includes a method wherein the treatment alcohol, allyl alcohol, butylglycol, methylglycol, ethyl-tert reduces plant catalysts agglomeration and/or reduces coke buthyl-ether (ETBE), ethanolamines, acetone, octyl alcohol, formation on plant catalysts and/or reduces heavy com methyl-ethyl-ketone (MEK), methyl-isobutyl-ketone pounds deposits, including coke, on plant catalysts and/or (MIBK), crude oil, fuel oil, quench oil from Ethylene Unit, reduces differential pressure in a plant reactor containing a 60 aromatic gasoline from Reforming Unit, benzene/toluene? catalyst. xylenes (BTX) as produced by an Aromatic Extraction Unit An embodiment includes a method wherein the hydrocar (inclusive. of the Sulfolane. Furfural, Glycols or Formylmor bon-based fluid used for the treatment is recovered or reused pholine type), the gasoline and/or the gas oil produced in an in a way selected from the group consisting of i) routing as a Ethylene Unit (pyrolysis gasoline/gas oil). blend component of a fuel/heavy oil; ii) routing to a crude 65 An embodiment includes a method wherein the first and/or tank; iii) routing to slop; iv) routing inside the petroleum plant the second hydrocarbon fluid is or are used in combination containing the equipment which has (have) been treated; v) with one or more compounds, as a standalone or mixture US 9,328,300 B2 11 12 thereof, selected from the group consisting of polymetacry predominantly hydrocarbon character, as e.g. the hydrocar lates, polyisobutylene Succinimmides, polyisobutylene Suc bon groups, including aliphatic, (e.g. alkyl or alkenyl), alicy cinates; laurylacrylate/hydroxyethylmetacrylate copolymer; clic (e.g. cycloalkyl or cycloalkenyl), aromatic, aliphatic alkylarylsulfonates, alcanolamine-alkylarylsulfonates and and/or alicyclic-substituted aromatic, condensated aromatic; alkylarylsulfonic acids; substituted amines, where the sub 5 aliphatic groups are preferably Saturated, as e.g.: methyl, stituent is an hydrocarbon containing at least 8 carbonatoms; ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, octa acylated compounds containing nitrogen and having a Sub decyl cyclohexyl, phenyl, said groups may also contain non stituent with at least 10 aliphatic carbonatoms, such substitu hydrocarbon sustituents provided they do not alter the pre ent being obtained by reaction of an acylant carboxylic acid dominantly hydrocarbon character of the group, e.g. the with at least an aminic compound containing at least a group 10 groups selected from: keto, hydroxy, nitro, alkoxy, acyl, Sul NH-, said acylant agent being joined to said aminic com phonic, Sulphoxid, Sulphur, amino, said groups may also or pound by way of a imido, amido, amidine or acyloxyammo alternatively contain atoms other than carbon in a chain or nium bridge; nitrogen containing condensated compounds of ring otherwise composed of carbon atoms, e.g. hetheroatoms a phenol, an aldehyde oranaminic compound, having at least selected from the group of nitrogen, oxygen and Sulfur. An a group —NH-; esters of a Substituted carboxylic acid; 15 embodiment of the method features the introduction of the hydrocarbyl substituted phenols: alcoxylated derivatives of hydrocarbon based treatment fluid by way of the introduction an alcohol, a phenol or an amine; phthalates; organic phos in the petroleum plant of a first hydrocarbon-based fluid in a phates; oleic acids esters; diethylhydroxylamine:glycols and/ ratio comprised between 0.1% and 100% with respect to or their derivatives, said glycols and/or their derivatives being current plant fresh feed and a second hydrocarbon-based fluid not in a polymeric form, in the sense that they are molecules in a ratio comprised between 0.01% and 50% with respect to of single compounds, also in an adduct form, and not mol a curret plant fresh feed; and wherein the second hydrocarbon ecules constituted by a chain where a single monomer is fluid is selected from the group consisting of methanol, etha repeated, e.g.: tetraethyleneglycol; mono- and di-ethers, nol, propanol, isopropanol, butanol, isobutanol, methylglycol mono- and di-esters, ether-esters and thioethers of single monomethylether, butylglycol monobutylether, toluene, ali glycols; glycol of general formula CH2OH (CH)nOHn 25 phatic amines C8<--> ethoxylated with at least 6 moles eth CH2OH where n=0-10; glycol ethers of general formula ylene oxide, arylsulfonates, benzene, diphenyl, phenan R1-O-CH2-CH2-O-R2 where R1 is an hydrocarbyl sub threne, nonylphenol. 1-methyl-2-pyrrolidinone, diethyl stituent C1-C20 and R2 is Hatom or anhydrocarbyl substitu ether, dimethylformamide (DMF), tetrahydrofuran (THF), ent C1-C20; glycol esters of general formula R1-O-O- ethylenediamine, diethylamine, triethylamine, trimethy CH2-CH2-O-O-R2 where R1 is an hydrocarbyl 30 lamine, propylamine, 1-(3-aminopropyl)-2-pyrrolidone, substituent C1-C20 and R2 is H atom or an hydrocarbyl 1-(3-aminopropyl)imidazole, N-hydroxyethyl-imidazolidi substituent C1-C20; thioglycols of general formula none, N-aminoethyl-imidazolidinone, 2-(2-aminoethy HO—R1-S R2-OH where R1 is an hydrocarbyl substituent lamino)ethanol, isopropylamine, cumene, 1, 3, 5 trimethyl C1-C10 and R2 is H atom or an hydrocarbyl substituent benzene, 1, 2, 4 trimethylbenzene, maleic anhydride, C1-C10: glycol ethers-esters of general formula R1-O 35 p-toluidine, o-toluidine, dipropylamine, diphenyl ether, hex CH2-CH2-O-O-R2 where R1 and R2 are an hydrocarbyl amethylbenzene, propylbenzene, cyclohexylamine, 1-iso substituent C1-C20; ethers of general formula R1-O R2 propyl-4-methyl-benzene, 1,2,3,5 tetramethylbenzene, hex where R1 or R2 is an hydrocarbyl substituent C1-C20; sub anol, morpholine, o-Xylene, m-Xylene, p-Xylene, butylamine, stituted benzenes of general formula where n=1-6 and R can methylamine, mesitylene, examine. Succinic anhydride, be indifferently H atom, —OH group, —COOH group, 40 decahydronaphthalene, ethylbenzene, 1, 2 dimethylnaphtha —CHO group, —NH2 group, —HSO3 group, the same or lene, 1, 6 dimethylnaphthalene, p-cymene, ethyl ether, iso different hydrocarbyl substituent C1-C30, ketons of general propyl ether, etoxybenzene, phenyl ether, acetophenone, formula R1-CO R2 where R1 or R2 is an hydrocarbyl sub monoethanolamine (MEA), diethanolamine (DEA), trietha stituent C1-C20; anhydrides of general formula R1-CO— nolamine (TEA), diethyleneglycol, triethyleneglycol, tetra O—CO—R2, included those where R1 and R2 are bound 45 ethyleneglycol, hexyl glycol, dodecylbenzene, lauryl alco together to form cyclic anhydrides, where R1 or R2 is an hol, myristyl alcohol, thiodiglycol, dioctylphthalate, hydrocarbyl substituent C1-C20; amides of general formula disooctylphthalate, didecylphthalate, diisodecylphthalate, where R, R1,R2 are indifferently H atom or an hydrocarbyl dibutylphthalate, dinonylphthalate, methylethylketone substituent C1-C20; heterocyclic compounds, preferably of (MEK), methylisobutylketone (MIBK), methyl-tert-butyl the hydrogenated type, containing from 0 to 3 hydrocarbyl 50 ether (MTBE), cyclohexane, cyclohexanone, methyl- or substituent C1-C20; heterocyclic compounds selected from ethyl-esters offatty acids achieved by esterification of vegetal the group consisting of furans, pyrrols, imidazoles, triazoles, and/or animal oils (biodiesel); dimethylamine, ethylamine, oxazoles, thiazoles, oxadiazoles, pyranes, pyridine, ethyl formate, methyl acetate, dimethylformamide (DMF), pyridazine, pyrimidine, pyrazine, pyperazine, piperidine, tri propanol, propylamine, isopropylamine, trimethylamine, tet azines, oxadiazines, morpholine, indane, indenes, benzo 55 rahydrofuran (THF), ethyl vinyl ether, ethyl acetate, propyl furanes, benzothiophenes, indoles, indazole, indoxazine, formate, butanol, methyl propanol, diethyl ether, methyl pro benzoxazole, anthranile, benzopyrane, coumarines, quino pyl ether, isopropyl methyl ether, diethylsulfide, butylamine, lines, benzopyrones, cinnoline, quinazoline, naphthyridine, isobutylamine, diethylamine, diethylhydroxylamine, cyclo pyrido-pyridine, benzoxazines, carbazole, Xanthene, acry pentanol, 2-methyltetrahydrofuran, tetrahydropyran, penta dine, purine, benzopyrroles, benzothiazoles, cyclic amides, 60 nal, isobutyl formate, propyl acetate, pentanoic acid, butyl benzoquinolines, benzocarbazoles, indoline, benzotriazoles; methyl ether, tert-butyl methyl ether, ethylpropyl ether, meth including all the possible compounds configurations, includ ylpyridines, methylcyclopentane, cyclohexanol, hexanal, ing the iso-form: e.g. the term “dithiols” is meant to include pentyl formate, isobutyl acetate, 2-ethoxyethyl acetate, 1.2 dithiol and 1.3 dithiol, “quinolines” is mean to include methyl pentyl ether, dipropyl ether, diisopropyl ether, hex quinoline and isoquinoline; the term “hydrocarbyl Substitu 65 anol, methyl pentanols, triethylamine, dipropylamine, diiso ent” refers to a group having a carbon atom directly attached propylamine, benzaldehyde, toluene, cresols, benzyl alcohol, to the rest of the molecule and having a hydrocarbon or methylanilines, dimethylpyridines, furfural, pyridine, meth US 9,328,300 B2 13 14 ylcyclohexane, heptanol, acetophenone, ethylbenzene, Zofuran, dibenzylamine, diethylene glycol dibenzyl ether, Xylenes, ethylphenols, Xylenols, anilines, dimethylaniline, diethylene glycol monolaurate, diethylene glycol (2-hydrox ethylaniline, octanenitrile, ethyl propanoate, methyl ypropyl) ether, diethylenetriamine, di-O-naphthylamine, di butanoate, methyl isobutanoate, propyl propanoate, ethyl B-naphthylamine, dioctylamine, diphenylamine, diphenyl 2-methyl propanoate, methyl pentanoate, heptanoic acid, methane, 4,4'-diamino diphenyl, 4,4'-dimethylamino octanoic acid, 2-ethylhexanoic acid, propyl 3-methylbu diphenyl, 4-hydroxy diphenyl, diphenylmethanol, diphenyl tanoate, octanoles, 4-methyl-3-heptanol, 5-methyl-3-hep ethylamine, di-(CL-phenylethyl)amine, di-iso-propanolamine, tanol, 2-ethyl-1-hexanol, dibutyl ether, di-tert-butyl ether, di-2-tolylamine, eicosanol, 1.1.2 triphenylethane, ethylene dibutylamine, diisobutylamine, quinoline, isoquinoline, glycol 1.2 diphenyl, ethyl-di-benzylamine, ethylene glycol 10 monobenzyl ether, ethylene glycol monophenyl ether, N.N- indane, cumene, propylbenzene, 1,2,3-trimethylbenzene, diphenylformamide, phenylformamide, tolylformamide, 1,2,4-trimethylbenzene, mesitylene, o-toluidine, N,N-dim 2-benzoylfurane, 2.5 diphenylfurane, glycerine and related ethyl-o-toluidine, nonanoic acid, nonanols, naphthalene, esters, heptadecylamine, heptadecanol, cetyl alcohol, hexa butylbenzene, isobutylbenzene, cymenes, p-diethylbenzene, decanamine, cethylic alcohol, hydroxyethyl-2-tolylamine, 1,2,4,5-tetramethylbenzene, decahydronaphthalene, triethanolamine, cyclohexanone, imidazole, methylimida decanoic acid, decanol. 1-methylnaphthalene, carbazole, 15 Zole, phenylimidazole, 5-amino-indane, 5-hexyl-indane, diphenyl, hexamethylbenzene, dodecanols, diphenyl 1-phenyl-1,3,3-trimethyl-indane, 2.3 diphenyl-indene, indo methane, tridecanols, tetradecanols, hexadecanols, heptade le, 2.3 dimethyl-indole, tryptamine, 2-phenyl-indole, isocou canols, terphenyls, octadecanols, eicosanols; fatty amines marin, diethyl-isophthalate, isoquinoline, benzyl laurate, and their mixtures, p-toluidine, toluene, dipropylamine, phenyl laurate, lauryl alcohol, lauryl amine, lauryl Sulphate, disobutyl acetate, propyl acetate, propyl-ethyl-ether, triethy diethyl-benzyl-malonate, melamine, diphenylmethane, lamine, ethylbenzene, propylbenzene, butylbenzene, triphenylmethane, 4-benzyl-morpholine, 4-phenyl-morpho cumene, para-Xylene, hexamethylbenzene, triethanolamine, line, 4-(4-tolyl)-morpholine, myristic alcohol, 9,10-dihydro diphenylmethane, MTBE, dioctylphthalate, diisodecylphtha naphthacene, acethyl-naphthalene, benzyl-naphthalene, late, diisoctylphthalate, nonylether, methyloleate, dio butyl-naphthalene, dihydro-naphthalene, dihydroxy-naph ctylether; the compounds named in plural refer to all possible 25 thalene, methyl-naphthalene, phenyl-naphthalene, naphthol, isomers of said compound: e.g. the term "xylenes' indicated naphthlamine, methyl-naphthylamine, naphthylphenyl o-Xylene, m-Xylene, p-Xylene; said compounds can also be amine, C.-naphthyl-2-tolyl-ketone, nonacosanol, octade used under Supercritical conditions. canol, octyl-phenyl-ether, pentadecylamine, pentadecanol, An embodiment features the second hydrocarbon fluid as 3-hydroxyacetophenone, tyramine, 4-hydroxyphenylaceto 30 nitrile, o-phenylenediamine, N-phenyl-phenylenediamine, comprising one or more compound(s) working as Swelling 4-methyl-phenylenediamine, diphenylether, bis-(2-phenyl agent selected from those forming hydrogen bonds and those ethyl)amine, phosphine derivatives as phenyl, triphenyl and not forming hydrogen bonds, wherein the Swelling agents not oxide, triphenylphosphite, dibutyl phthalate, dibenzyl phtha forming hydrogen bonds are selected from the group consist late, diethyl phthalate, dioctyl phthalate, diisoctyl phthalate, ing of benzene, toluene, cyclohexane, naphthalene, diphe didecyl phthalate, diphenyl phthalate, phthalic anhydride, nyl, Xylene, tetraline, methylcyclohexane; and wherein the 35 N-benzoylpiperidine, 1,3-diphenoxypropane, N-(2-tolyl) Swelling agents forming hydrogen bonds are selected from propionamide, 1-methyl-3-phenyl-pyrazoline, pyridine the group consisting of pyridine, methanol, ethanol, ethyl derivatives as 3-acetamido, 3-benzyl, 4-hydroxy, 2-phenyl, enediamine, propanol. 1,4-dioxane, acetone, formamide, phenylsuccinic anhydride, Succinimide, N-benzylsuccinim aniline, tetrahydrofuran, N,N-dimethylaniline, diethylether, ide, N-phenylsuccinimide, o-terphenyl, m-terphenyl, 1,14 dimethylsulphoXyde, acetophenone, dimethylformamide, 40 tetradecanediol, tetradecanol, tetraethyleneglycol, tetraethyl ethyl acetate, methyl acetate, methylethylketone, 1-methyl enepentamine, 2,5-diaminotoluene, 3,5-dihydroxytoluene, 2-pyrrolidone, quinoline. 4-phenyltoluene, p-toluenesulfonic acid and related methyl An embodiment features the introduction of the hydrocar and propyl esters, o-toluic acid and related anhydride, N-ben bon based treatment fluid as including the introduction in the Zyl-toluidine (o-, m-e p-), tribenzylamine, tributylamine, tri petroleum plant of a first hydrocarbon-based fluid in a ratio 45 ethanolamine, tryethyleneglycol and related monobutylether, comprised between 0.1% and 100% with respect to current triheptylamine, trioctylamine, triphenylamine, tritane, tri plant fresh feed and a second hydrocarbon-based fluid in a tanol, 2-pyrrolidone, Xanthene, Xanthone, Xylidine. ratio comprised between 0.01% and 50% with respect to a An embodiment of the method of the invention further current plant fresh feed; and wherein the second hydrocarbon comprises monitoring treatment level and wherein the moni fluid comprises one or more compound(s) having a boiling 50 toring is performed with one or more analysis method temperature >150° C. selected from the group selected of: selected from the group consisting of Viscosity (e.g. ASTM anthraquinone, eicosanol, benzalacetophenone, benzan D 445); density (e.g. ASTM D1298); atmospheric or vacuum thracene, hydroquinone, dodecylbenzene, hexaethylbenzene, distillation (e.g. ASTM D86, D1160); carbon residue (e.g. hexamethylbenzene, nonylbenzene, 1,2,3-triaminobenzene, ASTM D4530, D 189); sediments by hot filtration (e.g. IP 1,2,3-trihydroxybenzene, 1,3,5-triphenylbenzene, diphenyl 375, 390); sediments by extraction (e.g. ASTM D473); sedi methanol, p-benzidine, benzil, 2-benzoylbenzofurane, ben 55 menti by filtration (e.g. ASTM 4807); ash (e.g. ASTM D482, Zoic anhydride, 2-benzoyl-methyl benzoate, benzyl ben EN6245); asphaltene (e.g. IP143), color (e.g. ASTM D1500), Zoate, 4-tolyl benzoate, benzophenone, 4,4'-bis water and sediments (e.g. ASTM D2709, D1796); or an (dimethylamino) benzophenone, 2,2'- analysis method of the physical type, selected from the group dihydroxybenzophenone, 2,2'-dimethylbenzophenone, 4,4'- consisting of i) evalutation of the fouling factor, defined as dimethylbenzophenone, methylbenzophenone, 2-amino 60 the ratio among the heat transfer coefficient of clean equip benzyl alcohol, 3-hydroxybenzyl alcohol, a-1-naphthylben ment and the heat transfer coefficient of the equipment at the Zyl alcohol, benzyl-ethyl-phenyl-amine, benzylaniline, ben time when the value is recorded; ii) evalutation of pressure in Zyl ether, phenylacetophenone, 2-acetamide diphenyl, various points of the plant; iii) evalutation of temperature in 2-amino diphenyl, 4,4'-bis(dimethylamino) diphenyl, biphe various points of the plant. nol, butyl-bis(2-hydroxyethyl)amine, butylphenylamine, 65 An embodiment of the invention includes a method and butylphenylketone, carbazole, diphenylcarbonate, cetyl alco means for carrying out the additional following steps to hol, cetylamine, benzylcinnamate, coumarin, lindane, diben achieve gas freef safe entry conditions: US 9,328,300 B2 15 16 a) Suspension of feed introduction; mula RCH ( OCHCH ), OSOM wherein R is an b) optional circulation in a closed or semi-closed loop of the hydrocarbyl substituent Cs-Co. n=1-5 and M is the ion first and/or second hydrocarbon fluid inside the equipment Sodium, ammonium, triethanolammonium, ethoxylated alco to be treated, for a time of at least 20 minutes, at a tempera hols of general formula R—(—O CHCH ), OH ture comprised between 100° C. and 900° C. and at a wherein R is an hydrocarbyl substituent Cs-Co. n=1-30; pressure comprised between 1 bar and 400 bar; ethoxylated alkyl phenols of general formula RCH c) cooling of the equipment/plant; (OCH2CH2—), OH wherein R is an hydrocarbyl substitu d) emptying of the equipment/plant from all of the hydrocar ent Cs-Co., n-1-40; mono- and di-fatty acids glyceric esters bons; wherein acid contains an hydrocarbyl Substituent Co-Co.; e) introduction of water inside the equipment/plant; 10 f) implementing a closed circulation loop encompassing the mono- and di-polyoxyethylene esters of oils and fatty acids of equipment/plant; general formula RCO ( OCH ), OH and RCO (— g) introduction in the closed circulation loop of one or more OCH ), OOCR wherein the oil is of the “tall oil” or chemical washing/cleaning products and their mixtures; “rosin oil type, n=1-40 and the acid contains and hydrocar h) setting up the temperature and the pressure inside the 15 byl substituent Co-Cao; ethoxylated “castor oils” (castor oil closed circulation loop at values comprised between 60° C. is a triglyceride abundant in ricinoleic esters) containing a and 350° C. and between 1 bar and 50 bar; number of polyethoxylated ethylene oxide groups variable i) circulation of the water solution of the chemical product(s) between 5 and 200; mono- and di-ethanolamides of fatty inside the closed circulation loop under conditions oftem acids of general formula RCONHCHOOCR and RCON perature and pressure comprised between 60° C. and 350° (CHOH)CHOOCR wherein R is anhydrocarbyl substitu C. and between 1 and 50 bar, for a time comprised between ent Co-Ca.; Surfactants of poly(Oxyethylene-co-oxypropy 20 minutes and 60 days; lene), also known as block polymer, having molecular weight j) cooling (including the eventual introduction of fresh water of 50-10000; mono-, di- and poly-aliphatic amines derived in the loop) and emptying of the loop from the water from fatty acids, such as RNHCHCHCH-NH wherein Ris Solution; 25 an hydrocarbyl Substituent Co-Cao, N-alkyltrimethylendi k) optional routing of the water solution to the oily water amines of general formula treatment plant; 1) optional repeating of the steps from e) to k). An embodiment of the invention features a method and R Suitable means for carrying the method that is represented by 30 replacing the steps from e) to k) by the steps: m) introduction inside of the apparatus/plant of steam at a ses pressure comprised between 1.5 bar and 100 bar; n) introduction in said steam of one or more washing/cleaning chemical product(s) including their mixtures; 35 wherein R is an hydrocarbyl Substituent Co-Co., 2-alkyl-2- o) introduction inside of the equipment/plant of the mixture imidazolines of general formula steam/chemical product(s) according to present invention, for a time of at least 20 minutes, p) optional circulation of condensed steam, containing a R chemical product according to present invention; 40 q) emptying of condenses from the equipment/plant; 1. r) optional routing of condenses to the oily water treatment N1 YNC, HNH plant; An embodiment of the invention features a method wherein the chemical product used for washing/clearing 45 under any of the above described compatible method tech wherein R is an hydrocarbyl Substituent Co-Cao, amine niques is selected from the group consisting of non-ionic oxides of general formula RNO(CH), and RNO(CHOH), Surfactants, anionic Surfactants, terpenes derivatives, emulsi wherein R is an hydrocarbyl substituent C-C ethoxylated fiers, hydrogen Sulphide scavengers, mercury scavengers and alkylamines of general formula their mixtures in any proportion, including their aqueous 50 Solutions. (CHO).H An embodiment of the invention further features, relative RN1 2 to, for example, any of the above described compatible tech niques, anionic and non-ionic Surfactants that are selected from the group consisting of alkyl-, aryl-, or alkylaryl-ben 55 Zensulphonates of general formula RCHSOM wherein R wherein m+n=2-40; 2-alkyl-1-(2-hydroxyethyl)-2-imidazo is an hydrocarbyl substituent Cs-Co and M is the ion H, Na, lines of general formula Ca, ammonium, triethanolammonium, isopropylammonium; dialkylsulfosuccinates of general formula ROCCHCH R (SONa)COR wherein R is an hydrocarbyl substituent 60 C-C alkylsulfates of general formula ROSOM wherein R is anhydrocarbyl Substituent Cs-Co and M is the ion Sodium, als ammonium, triethanolammonium; ethoxylated and Sul phated alcohols of general formula R—(—OCH2CH2)— OSOM wherein R is an hydrocarbyl substituent Cs-Co. 65 n=1-5 and M is the ion sodium, ammonium, triethanolammo wherein Risan hydrocarbyl Substituent Co-Cao; alkoxylated nium; ethoxylated and Sulphated alkyphenols of general for ethylendiamines of general formula US 9,328,300 B2 17 18 said product(s) exiting the plant in the closed or semi-closed circulation loop and/or in one or more selected point(s) of the H--OCH2CH2-), (OCH),v cho-CHCHO-H NCH2CHN plant, said pump(s) being already part of said petroleum or A V chemical plant, or installed on purpose, or in mobile and/or H--OCH2CH2-) (OCH), (CH6O),-(CH2CH2O)-H 5 temporary execution; an inlet system of a hydrocarbon fluid or mixtures of hydro wherein X and y=4-100; carbon fluids, to allow the introduction of said hydrocarbon terpenic products derivatives are selected from the group fluid(s) in the closed or semi-closed loop: consisting of limonene, pinene, canfor, menthol, eucalipthol, one or more lines and/or connection systems to close the 10 closed or semi-closed loop comprising the withdrawal eugenhol, geraniol, thymol; emulsifiers are selected from the point(s) and/or introduction point(s) of the distillate(s), the group consisting of Tween 60, Tween 80, nonyl phenol poly pump(s) and the equipment, having Sufficient characteristics ethylene glicol ether, oleates, Sorbitan oleates, glycerol to circulate said distillate(s) and/or said product exiting the monostearate, nonyl phenol ethoxylates, iso-propyl palmi plant inside the closed or semi-closed loop and/or in one or tate, polyglycerol esters of fatty acids, tridecyl alcohol 15 more selected point(s) in the plant, said lines and/or connec ethoxylates, fatty alcohol ethoxylates, linear alkyl benzene tions being already part of said petroleum or chemical plant, Sulphonic acid, dioctyl phthalate, sodium tripolyphosphate, or installed on purpose, or in mobile and/or temporary execu citric acid, soybean oleic acid, trisodium phosphate, sodium tion; dodecyl sulfate, didecyl dimethyl ammonium chloride, oleic a discharge system of the fluids, to allow their removal from acid diethanolamine, dodecyl dimethyl benzil ammonium the closed or semi-closed loop; gauges and/or controllers of chloride, Sodium acetate, oleamide, polyethylen glycol, lano temperature, pressure, flow rate; and lin, ethoxylated (E20) sorbitan monooleate, sorbitan valves and/or sectioning and/or non-return systems. monooleate, sulfosuccinammates: H.S Scavengers are In an embodiment the withdrawal means is configured to selected from the group consisting of diethanolamine, mono withdraw one or more hydrocarbon fluid(s) having the fol ethanolamine, methyl-diethanolamine, diisopropylamine, 25 lowing intervals of boiling points: a) up to 75° C.; b) from 75° formaldehyde, maleimides, amidines, polyamidines, gly C. to 175° C.; c) from 175° C. to 350° C.; d) above 350° C.: oxal, Sodium nitrite, reaction products of polyamide-formal and wherein introduction means introduce it (them) in any dehyde, triazines, carboxamides, alkylcarboxyl-azo com one or more point(s) of the plant. pounds, cumine-peroxide compounds, bisoxazolidines, An embodiment of a petroleum plant apparatus that is glycidyl ethers, potassium formate; mercury Scavenger are 30 suited (but not limited to) enabling the performance of one or selected from the group consisting of thiourea, caustic soda, more of the above described, compatible method embodi sodium carbonate, trimercapto-s-triazine trisodium salt. ments, features a distillate source wherein a distillate from An embodiment includes a petroleum plant apparatus to said distillate source is withdrawn from a point within a perform a method according to any one or more of the com closed or semi-closed loop forming at least a portion of said patible method embodiments described above, comprising: i) 35 plant, and an entry point whereinthere is introduced upstream withdrawal means from one or more point(s) in the petroleum of equipment to be treated the drawn off distillate and then plant of one or more hydrocarbon fluid(s); ii) introduction redistilled to be thereafter re-withdrawn from the same point means of said one or more hydrocarbon fluid(s) as above and re-introduced in the same equipment to be treated for a withdrawn into one or more point(s) of the petroleum plant; time necessary to treat said equipment. iii) distillation means of said one or more hydrocarbon 40 An embodiment of a petroleum plant apparatus that is fluid(s) as above introduced into one or more point(s) of the suited (but not limited to) enabling the performance of one or petroleum plant; iv) re-withdrawal and re-introduction means more of the above described, compatible method embodi of said one or more hydrocarbon fluid(s) as above distilled to ments, features withdrawal means that are located in one or re-withdraw said distilled fluid(s) and re-introduce it (them) more point(s) of the plant that is(are) selected from the group into one or more point(s) of the petroleum plant, wherein said 45 consisting of: re-withdrawal and re-introduction means can be the same Suction/discharge of the produced gasoline pump; withdrawal and introduction means as above; v) connection Suction/discharge of the overhead reflux pump; means in order to form a closed or semi-closed loop, encom Suction/discharge of one or more bottom/middle/top passing the equipment to be treated, wherein said one or more pumparound pump(s): hydrocarbon fluid(s) will be continuously distilled, with 50 Suction/discharge of the produced kerosene pump; drawn and introduced; vi) a discharge system of the hydro Suction/discharge of the produced gas oil pump; carbon fluid(s), to allow their removal from the closed or Suction/discharge of any distilled hydrocarbon pump; semi-closed loop; vii) control means, to control or regulate hydrocarbon line exiting any petroleum apparatus; temperature and/or pressure and/or flowrate; viii) optional Suction/discharge of the crude oil booster pump at desalter filtration means. 55 outlet; An apparatus embodiment inclusive of set ups for the wherein introduction means are located in one or more above described apparatus embodiment and compatible point(s) of the plant selected from the group consisting of method technique features: Suction/discharge of the plant feed pump; one or more withdrawal point(s) of a distillate or mixtures of Suction/discharge of the crude oil booster pump at desalter distillates; 60 outlet; one or more introduction point(s) of a distillate or mixtures of Suction/discharge of a column bottom pump; distillates, as previously withdrawn; Suction/discharge of the heavy gas oil pump; one or more introduction point(s) of a first and/or second inlet of the preheat train; hydrocarbon fluid; inlet of the equipment to be treated: one or more pump(s) connected to said withdrawal point(s) of 65 distillation residue line, upstream/downstream of any heat distillate(s) and/or of the product(s) exiting the plant, having exchanger, sufficient characteristics to introduce said distillate(s) and/or column bottom; US 9,328,300 B2 19 20 in a pump external of the plant, being part of another plant amount of distillates, thereafter progressively reducing the or installated on purpose, in temporary or permanent fresh feed rate, such that the increased amount of produced execution; distillates, with respect to the amount of distillates produced wherein distillation means are located in one or more point(s) with the pre-existing fresh feed rate, be circulated in parts of of the petroleum plant selected from the group consisting of 5 the plant to be treated. atmospheric distillation column; An embodiment of the invention further comprises a vacuum distillation column; method, such as for any of the compatible methods described extractive distillation column; above, wherein adjusting the feed rate includes an initial and wherein the withdrawal point(s) and the introduction reduction in the established feed rate of the plant to a value point(s) of said one or more hydrocarbon fluid(s) are con 10 comprised between 40% and below 100% with respect to the nected to form a closed or semi-closed loop. design feed rate, followed by the introduction of the hydro An embodiment of the invention includes a method of carbon-based fluid which comprises an introduction of first designing a plant that is Suited (but not limited to) providing and/or the second hydrocarbon-based fluid(s) in an amount as the performance of one or more of the above described, com to compensate up to the difference among the rate at which patible treatment method embodiments, and features a plant 15 the plant is running and its design feed rate, and so as to design wherein plant equipment that is subject to treatment is manage up to the maximum allowable plant distillate flow designed under not conservative conditions, wherein there is rate or in any case the distillate flow rate applicable prior to avoided inputting into the equipment a greater than 20% the introduction of the first and/or the second hydrocarbon fouling factor (e.g., having a fouling factor level of 0 to less based fluid(s), such as to run the plant at the flow rate resulting than 20%) as well as the avoidance of the presentment of any from the sum: flow rate of reduced fresh feed--flow rate of fouling back up equipment in the plant design in the relevant the first and/or the second hydrocarbon-based fluid(s), and area (e.g., in the closed or semi-closed loop). wherein said flow rate is equal to or higher to the one prior to An embodiment of the invention includes a method of the reduction in feed rate. manufacturing of a plant comprising rendering into a physical Additional aspects and embodiments will be evident by plant based on a plant design wherein the equipment Subject 25 reading the following invention detailed description. to treatment is designed under not conservative conditions, wherein there is avoided inputting into the equipment a BRIEF DESCRIPTION OF THE DRAWINGS greater than 20% fouling factor (e.g., having a fouling factor level of 0 to less than 20%) as well as the avoidance of the FIG. 1 is an exemplary Schematic diagram of a conven presentment of any fouling back up equipment in the plant 30 tional Crude Distillation Unit. design Such as in the relevant treatment area described above. FIGS. 2 through 7 are schematic diagrams of different An embodiment of the invention includes having the applications of the present invention in a Crude Distillation treated equipment feature a surface from 0.1% to 100% lower Unit. with respect to a non-treated equipment. FIG. 8 is a schematic diagram for carrying out the present An embodiment of the invention features a method for 35 invention in an Ethylene Unit. treating a petroleum plant or equipment of the petroleum FIG. 9 is a schematic diagram for carrying out the present plant during a running of the petroleum plant, comprising: invention in an FCC Unit. maintaining, during a treatment period, the petroleum plant FIG. 10 is a schematic diagram for carrying out the present under a production operating condition, typical of the plant invention in a CCR Unit. itself, while providing fresh feed to the petroleum plant; while 40 FIG. 11 is a schematic diagram for carrying out the present maintaining the petroleum plant under the production oper invention simultaneously in a CDU, VDU and VBU. ating condition, introducing in the petroleum plant, during the FIG. 12 is a schematic diagram for carrying out the present treatment period, a hydrocarbon-based treatment fluid; and invention, wherein a portion of the petroleum plant is cleaned adjusting of the fresh feed by increasing the plant fresh feed and does not contribute to production, while the other portion rate from an established feed rate to a level above the estab 45 of the plant is running and makes up the production. lished feed rate as to generate an additional quantity of dis FIGS. 13A to 13C are schematic diagrams of portions of an tillates relative to a quantity generated at the established feed apparatus under the present invention with reference to FIG. rate, and drawing off at least some of an overall quantity of 12. distillate generated from the increased plant feed rate and FIG. 14 is a schematic diagram for carrying out the present introducing the drawn off distillate into a treatment region of 50 invention in a crude stabilizer plant, following the extraction said plant for enabling the cleaning of heavy deposits from of crude oil in an oil field. one or more pieces of equipment in the treatment region. FIG. 15 is a schematic diagram for carrying out the present An embodiment of the invention further comprises passing invention wherein the first and/or second hydrocarbon drawn off distillate, such as the drawn off or withdrawn dis fluid(s) are specifically distilled before re-introduction and tillate described herein, through a closed or semi-closed loop 55 circulation. forming at least a portion of said plant and extending through the treatment region, and wherein said closed or semi-closed DETAILED DESCRIPTION OF THE INVENTION loop of said plant is configured such that drawn off distillate is re-introduced into a distillation device of the plant which is By realizing a closed or semi-closed circulation loop of one a source of the initially drawn off distillate and drawing off a 60 or more chemical product(s) admixed with one or more recirculation output of distillate from said distillation device hydrocarbon fluids introduced and/or self-produced in the following receipt of the re-introduced drawn off distillate and petroleum plant under the present invention, at temperature passing the recirculation output of distillate to a treatment and pressure conditions under the present invention, under the region(s). method of the present invention, the solubilization or the An embodiment of the invention further comprises a 65 modification of a not pumpable product (which is fouling the method wherein the petroleum plant runs at increased feed or equipment and is originating from a heavy compound) into a at the design feed rate (or higher), so as to produce a major pumpable product is realized. Said heavy compound is there US 9,328,300 B2 21 22 fore removed from said equipment by simply pumping out the 9. optionally opening the closed or semi-closed loop, such solution which contains it in a soluble or modified form. In that the fluids of steps from 2 to 7 can be removed from the Such a way the equipment is cleaned without the need of petroleum plant by utilizing the normal production cycle. decommissioning or without the need of stopping its produc For embodiments of the present invention, non limiting tion process, thereby realizing improvements over the state of 5 examples of a treatment feed rate represented by a combina the art which are addressed by way of the present invention. tion of a current fresh feed (utilized in a plant running in a In the description that follows, numerous specific details normal mode) as well as added introduced hydrocarbon based are set forth by way of example for the purposes of explana treatment fluid can be seen by examples (a) (b), described tion and in the furtherance of teaching one skilled in the art to below (or a combination of the same): practice the invention. It will, however, be understood that the 10 a) current fresh feed plus introduced first and/or second invention is not limited to the specific embodiments disclosed hydrocarbon based fluid(s), such as from an external and discussed herein and that the invention can be practiced Source inclusive of a source tank in line with the plant, an without such specific details and/or substitutes therefore. The upstream different plant feed, a downstram different present invention is limited only by the appended claims and plant feed; a mobile source, etc.; and/or may include various other embodiments which are not par 15 b) a treatment rate component as in one resulting from an ticularly described herein which remain within the scope and increase in feed rate from an established feed rate exist the spirit of the present invention. ing at initiation of the treatment method to a new “raised Under the present invention the term “self-produced to-rate level (e.g., one greater than a design feed rate), defines a hydrocarbon fluid which is introduced and/or dis together with a self-production of distillates which are tilled in the petroleum plant, hence withdrawn from any plant withdrawn (e.g., drawn off), introduced and circulated, location and re-introduced in any plant location, preferably followed, for example, by a reduction in the current upstream of the withdrawal point; Subsequent to said re “raised to feed rate to a desired treatment feed rate introduction, said hydrocarbon fluid will, in embodiments of (inclusive of any current fresh feed rate plus the added the invention, be distilled and hence withdrawn and re-intro introduced distillate(s), with or without input from (a) duced as above specified, thereby creating an introduction/ 25 above) which treatment feed rate can be, for example, distillation/withdrawal/re-introduction cycle wherein a lower than the “raised-to-rate” as well as above, at, or “fresh hydrocarbon fluid will not be introduced, but the same below the design feed rate. circulating hydrocarbon fluid will be used, as generated dur Chemical products or mixtures of chemical products mak ing the circulation. ing up the hydrocarbon fluids under the present invention can A cleaning (or treating) method of petroleum equipment, 30 be used as Such at any proportion, or can be dissolved at any being part of any production plant, under an embodiment of proportion in an appropriate hydrocarbon solvent, so as to be the present invention comprises the following steps: used as a solution. 1. keeping the petroleum plant under production operating As used in the present invention the terms “chemical prod conditions, typical of the plant itself, with the fresh feed uct” or “chemical products' can refer to either a single chemi inserted and production of products typical of the plant 35 cal product or to a mixture of chemical products under the itself present invention and/or their solutions in any proportion 2. introducing in said petroleum plant a first hydrocarbon with an appropriate solvent and/or a hydrocarbon fluid under based fluid in a ratio comprised between 0.1% and 100% the present invention. with respect to a current fresh feed; The recovery or reuse of Washing fluids containing the 3. optionally introducing in said planta second hydrocarbon 40 chemical product(s) under the present invention and the solu based fluid in a ratio comprised between 0.01% and 50% bilized/modified heavy compound, which was originally with respect to a current fresh feed; present in the equipment to be cleaned, can be done in differ 4. optionally implementing a closed or semi-closed circula ent ways, such as: i) blending with fuel oil/heavy oil; ii) tion loop inside said plant, wherein one or more distillates blending with crude; iii) blending with slop oil; iv) reprocess and/or products exiting the plant can be withdrawn, 45 ing in the same petroleum plant containing the equipment thereby including the possibility of implementing a tailor which has been cleaned; v) reprocessing in anotherpetroleum made withdrawal system from any point of the petroleum plant. An additional advantage of the reuse/reprocessing of plant, and introducing the same inside the apparatus(es) to washing fluids is, besides all the environmental aspects, the be cleaned (treated); ability to reuse the chemical product under the present inven 5. optionally circulating in a closed or semi-closed loop the 50 tion in order to avoid additional equipment fouling arising first and/or the second hydrocarbon-based fluid(s) inside during the normal run of the petroleum plant (when the the apparatus(es) to be cleaned (treated). Such that a portion present invention is not applied on a continuous basis). of the products distilling during said circulation are re In one preferred embodiment the present invention pro introduced in said closed or semi-closed loop, whereas vides a method, an apparatus, one or more chemical another portion of the distillates make up the petroleum 55 product(s) and a monitoring system for the cleaning of, e.g.: plant production and/or the normal flow streams; heat exchangers; process furnaces; reactors and/or their cata 6. optionally circulating in a closed or semi-closed loop the lysts; distillation tower internals, including trays and/or dis first and/or the second hydrocarbon-based fluid(s) inside tributors and/or downcomers) and/or packings; lines; filters; the apparatus(es) to be cleaned (treated), for a time of at vessels (including their internals); process pumps. least 20 minutes, at a temperature comprised between 100° 60 In still another preferred embodiment the present invention C. and 900° C. and at a pressure comprised between 1 bar provides a method, an apparatus, one or more chemical prod and 400 bar; uct(s) and a monitoring system to increase the furnace inlet 7. monitoring the cleaning (treatment) operations according temperature of petroleum plants. As a matter of fact, plant to the method of the present invention; furnaces are generally preceded by heat exchangers which are 8. optionally repeating the steps from 2 to 7 (preferably with 65 used to recover process heat and to raise as much as possible the conditions of step 1 still met during the one or more the furnace inlet temperature (FIT). When said exchangers repeats); (preheat exchangers) are fouled a reduction in FIT will occur, US 9,328,300 B2 23 24 with related energy/economic/environmental losses. The of service to perform Subsequent maintenance operations, is cleaning of heat exchangers under the present invention “flushing performed, typically with gas oil (sometimes with allows for an increase in the FIT without the need of opening water). In Such a case, during the flushing, in the plant there is the heat exchangers and without the need of stopping the introduced a “flushing oil', e.g., gas oil, which, by coming petroleum plant. from a storage tank (not from the inside of the plant), enters In another preferred embodiment the present invention the feed line, flows through the equipment and leaves the provides a method, an apparatus, one or more chemical prod plant from the residue line. In Such flushing operation, the gas ucts and a monitoring system to increase the furnace run oil enters and leaves the plant in the same quantity and no length of petroleum plants. As a matter of fact, plant furnaces circulation is generally performed; flushing is therefore a are generally shutdown and decoking operations are per 10 once-through operation, which generally lasts 1-4 hours. Far formed, following fouling build-up inside the coils which more important, during Such flushing no products distillation increase the tube metal temperature (TMT) until the design occurs, as said operation is performed at a temperature lower limit is reached. Such fouling appears in the form of coke than the initial boiling point of the flushing oil (e.g., light gas inside the coils. By cleaning the equipment during the run, the oil). As a matter of fact, flushing is performed during shut coke precursors, which arise from deposition of fouling mate 15 down procedures in the phase of furnace temperature rial and which thereafter will degrade to coke, will be decrease; after the flushing is completed, the furnace is shut removed from the coils thereby avoiding coke build-up. The off and the petroleum plant is cooled down to allow subse cleaning of one or more heat exchangers upstream of the quent maintenance operations. The flushing is an operation furnace, under the present invention, also contributes to a which is performed according to the following steps: a) stop lower firing of the furnace and to operations under a lower ping feed introduction; b) stopping plant production and duty; this in turn will give an additional contribution toward a reducing furnace outlet temperature; c) introducing gas oil furnace run length increase. and passing it through the equipment; d) a simultaneous In still another preferred embodiment the present invention download of the gas oil which has been introduced into the provides a method, an apparatus, one or more chemical prod plant (once-through operation); e) sending the dirty gas oil to ucts and a monitoring system to clean internals of a petroleum 25 a storage tank, f) shutting off the furnace and cooling down plant. As used in the present invention the term “internals' the plant; g) opening the equipment for maintenance. refers to everything which is present inside the equipment of During flushing normally no circulation is performed a petroleum plant and/or of its production process. As an inside the plant. In some cases, e.g., in the CDU, flushing is illustrative and non-limitative example, the internals are performed with water. Flushing operations have the only made up of catalysts, trays, distributors, packings, demisters, 30 purpose of removing the soluble hydrocarbons which are filters, heat exchangers surfaces, lines/piping Surfaces, sepa inside the plant when it is shut down and has no effect on the rators, corrugated plates/packings, columns surfaces, Vessels removal of the heavy compounds (which generate fouling) Surfaces, equipment surfaces, downcomers, feed inlet from the equipment. Flushing only eases up emptying the devices, etc. plant before maintenance operations and mainly avoids, some In still another preferred embodiment the present invention 35 hydrocarbons being left in the plant. When not removed, said provides a method, an apparatus, one or more chemical prod hydrocarbons will solidify once the plant is cooled down ucts and a monitoring system to increase distillation yield. As (when shutting down the plant at ambient temperature), a matter of fact, the introduction of a first and/or a second thereby making more difficult and longer both opening opera hydrocarbon fluid causes an increase in distillation of light tions (e.g., exchangers’ bundles extraction would become products (of greater value) in spite of the heavier ones (of 40 almost prohibitive) and starting-up operations (in the lines a lower value). Without being bound to any theory, yield solid would be left, which is difficult to remove during start increase can be attributable, to, for example, the following up operations). The final proof of flushing inefficacy on effects or their combination(s): a) better separation of the equipment cleaning is, at the end of flushing operations, species contained in the feed, following a reduced entrain equipment is opened and mechanically cleaned. ment of lighter products in the heavier ones; b) better sepa 45 The normal run of a petroleum plant is typically performed ration of the species contained in the feed, following a better at a feed rate equal to or very near the design one. When cleaning status of a distillation column (improved distillation market conditions are unfavorable, the feed rate is reduced efficiency); c) intrinsic effect of the first and/or second hydro with respect to the design one; generally in Such conditions carbon fluid. Moreover, in the cracking processes (both ther the feed rate is reduced to 80-90% of the design one. The mal and catalytic) the action of the first and/or the second 50 “technical minimum’ feed rate is generally 50-60% of the hydrocarbon fluid is that of improving the cracking in the design one. The technical minimum feed rate is the lower feed same operating conditions, in spite of heavy compounds/coke rate wherein the plant is running under regular conditions, by formation. In such a connection the present invention also maintaining production conditions. For a feed rate lower than provides a method, an apparatus, one or more chemical prod the technical minimum the plant gets blocked (e.g., all the ucts and a monitoring system to increase distillation yield in 55 logic controlling operations and safety systems are calculated thermal/catalytic cracking processes and to reduce heavy for that) and the production is not possible. A plant runs at the compounds/coke formation on catalysts. technical minimum only under exceptional conditions, The normal production layout of a petroleum plant implies because running at the technical minimum is typically a net the introduction of a feed and the outlet of one or more economic loss for the plant owner. It is worthy of mention, distillation products, which are totally sent to storage and/or 60 that all the fixed costs are the same, and yet production is external delivery means and/or other petroleum plants for lowered by 40-50%. Subsequent processing, thereby making up the feed, or a In an embodiment of the present invention the petroleum portion of the feed, of downstream plants. In no case are there plant is already at the technical minimum, or is brought at the introduced in a petroleum plant, during its run, any fluids technical minimum, or the feed rate is reduced, or the plant is which are different from the ones which normally make up its 65 already running at a reduced rate, with respect to the design typical feed. Only and exclusively during the shutdown pro feed rate, with the precise scope to perform a cleaning opera cedures of a petroleum plant, before setting the equipment out tion. As a matter of fact, when running under technical mini US 9,328,300 B2 25 26 mum conditions or at a reduced feed rate, more space will be established fresh feed rate is 60% of DR; if the treatment fresh available inside the plant to introduce a major quantity of the feed rate (or raised to rate for additional distillate production) first and/or second hydrocarbon fluid(s) under the present is 80% of DR there will be self-produced 20% of DR of first invention, thereby raising the cleaning (or treatment) perfor and/or second hydrocarbon, which can be withdrawn, intro mance. Differently stated, a major quantity and/or a major 5 duced and circulated under the present invention. With this concentration of cleaning fluids will be inside the petroleum drawn off and reintroduced additional hydrocarbon(s) there plant, while the plant is continuing production. can be progressively lowered the current fresh feed rate to In an embodiment of the present invention the petroleum offset the newly introduced drawn off hydrocarbon(s) (e.g., plant feed rate is reduced (or brought) to a value comprised between 40% and 100% with respect to the design feed rate. 10 dropping down from raised to rate of 80% of DR down to the Preferably, the feed rate is reduced to the technical minimum. original 60% of DR fresh feed rate with the supplementing The first and/or second hydrocarbon fluid(s) is then intro drawn off hydrocarbons bringing it to 80% of DR). There is duced preferably at a quantity to compensate the difference still room to introduce 20% DR first and/or second hydrocar among the current feed rate and (up to), for example, the bon feed to make it 100% of DR, which can be introduced in design one, and Such as to manage a distillate throughput up 15 the plant from an external source into any point or points of to the maximum (normally the design one) or, in any case, to the plant. In this case, there would be at least an increase in the manage a distillate throughput as the one before the feed rate desired plant feed rate of 60% DR up to 80% of DR (or reduction and the insertion of the first and/or second hydro equivalent throughput) coupled with the 20% of current feed carbon fluid(s) under the present invention. For example, for rate (or equivalent throughput) for the first and/or second an embodiment of the present invention wherein the plant 20 hydrocarbons. A more typical scenario however, is one where feed rate is reduced (or brought) to a value between 40% and the plant has an established rate close to or at the DR and there 100% with respect to the design feed rate, the first and/or is a reduction in the established rate below the DR rate to the second hydrocarbon(s) can be introduced in a compensation extent of intended first and/or second hydrocarbons. For quantity of 0.1% to 60% (as well, for example, as any of the instance, a 90% of DR treatment plant feed rate following a 0.1% intermediates between 0.1% to 60%) of the design feed 25 10% reduction in the established feed rate (that was set at the rate in order to place the plants treatment feed rate (with DR under normal operation state). In this case, an introduc hydrocarbon(s) added) at the design rate (or higher). Alter tion of 1% to 30% at the first and/or second hydrocarbons nate embodiments of the invention feature compensation provide for the sum amount being put closer toward the DR quantities of the first and/or second hydrocarbon(s) that result (plus 1% to 9%) at the DR (plus 10%) or higher than the DR in the plants treatment feed rate being +/-60% of the design 30 (11% to 30%). feed rate, or +/-30% of the design feed rate, or +/-20% of the An additional embodiment of the invention also features an design feed rate or at the design feed rate. In this embodiment embodiment wherein the plant is running at a rate which is the petroleum plant is therefore run at a rate resulting from the higher than the design rate. As a matter of fact, given for Sum: (e.g., reduced fresh feed rate--first and/or second hydro granted the existing plants are designed under conservative carbon fluid(s) rate). The equivalent distillates throughput as 35 conditions to take into account the fouling-related limita resulting from fresh feed distillation at the conditions pre tions, upon eliminating/reducing said limitations, the present existing the application of the present invention will be sent to invention will make available to the production the portion of the downstream plants or to storage; the equivalent distillates the plant which have been over-dimensioned for the purpose. throughput as resulting from the distillation of the first and/or For example, if a preheat train has been designed with a 30% second hydrocarbon fluid(s), which have been introduced 40 Surface increase to take into consideration fouling and said according to the present invention, will be circulated in the fouling is eliminated by the present invention, said preheat petroleum plant parts which are intended to be cleaned train can be passed through by 30% more feed, by maintain (treated). ing the same performances. In case the rest of the plant has In embodiments of the invention, the distillates drawn off been dimensioned with a 30% more of surface, it will be easy under the distillate self production technique described above 45 to increase the feed rate of the plant by 30% over the design can be introduced into the plant system at one or more treat rate. In case the rest of the plant has design constraints, the ment location(s) having no impact on the fresh feed rate revamping of said rest of the plant can easily overcome Such entering the plant or can be input so as to have an impact on constraints and allow for an increase offeed rate by 30% over the plants fresh feed rate as by the above described supple the design rate. The revamping will be therefore limited to mentation of the fresh feed rate. 50 only a portion of the plant and this will have a tremendous As used in the present invention, the term "equivalent impact on capital expenditure reduction, e.g., for revamping a throughput defines the distillates throughput corresponding plant in order to increase its capacity. to the one achieved during plant run before the application of Under an embodiment of the present invention, the method the present invention, or the throughput of the products result for cleaning (treating) a petroleum plant during its run com ing from the distillation of the first and/or the second hydro- 55 prises the following steps: carbon fluid(s), which have been introduced and/or self-pro 1. keeping the petroleum plant under production operating duced under the present invention. conditions, typical of the plant itself, with the fresh feed An additional embodiment of the invention also features an inserted and production of products typical of the plant embodiment wherein the plant, prior to implementation of the itself present treatment, is running at an established fresh feed rate 60 2. Varying the fresh feed rate, including the possibility to (e.g., under a normal operation state that is well below the reach the technical minimum; design rate (DR) value (e.g., 60% of DR)) and wherein the set 3. optionally introducing in said petroleum planta first hydro desired treatment fresh feed rate for the treatment process carbon-based fluid in a ratio comprised between 0.1% and (“treatment fresh feed rate) is a value higher than the estab 100% with respect to the current fresh feed; lished fresh feed rate (“established feed rate” or “established 65 4. optionally introducing in said planta second hydrocarbon rate') but lower than the DR value to accommodate first based fluid in a ratio comprised between 0.01% and 50% and/or second hydrocarbon(s) introduction. Suppose the with respect to the current fresh feed; US 9,328,300 B2 27 28 5. implementing a closed or semi-closed circulation loop columns, the internals will be essentially free of any heavy inside said plant, wherein one or more distillates and/or compounds. The petroleum plant will continue its run under products exiting the plant can be withdrawn, thereby cleaner conditions, without the need of opening equipment to including the possibility of implementing a tailor made clean it. Only in case of plant shutdown for maintenance, withdrawal system from any point of the petroleum plant, under the method of the present invention, there will be added and an introduction inside or upstream the equipment to be Some steps in order to achieve gas-free and/or safe entry cleaned (treated); conditions. 6. keeping operating run conditions typical of the petroleum Under an embodiment of the present invention, when there plant, such as to allow distillation of products; is the need of opening equipment to perform maintenance or 7. circulating the distillate products, optionally containing the 10 inspection jobs, with related entry of operating personnel, in first and/or the second hydrocarbon fluid(s), in a closed or semi-closed loop comprising the equipment to be cleaned order to achieve gas-free and/or safe entry conditions it will (treated). Such that a portion of the products distilling dur be appropriate to add the optional following steps: ing said circulation are re-introduced in said closed or 13. stopping the introduction offeed; semi-closed loop, whereas the other portion of the distil 15 14. optionally circulating in a closed or semi-closed loop of lates make up the petroleum plant production and/or the the first and/or second hydrocarbon fluid(s) inside the normal flow streams; equipment to be cleaned (treated), for a time of at least 20 8. circulating the distillate products, optionally containing the minutes, at a temperature comprised between 100° C. and first and/or the second hydrocarbon fluid(s), in a closed or 900° C. and at a pressure comprised between 1 bar and 400 semi-closed loop encompassing the equipment to be bar: cleaned (treated), for a time of at least 20 minutes, at a 15. cooling of the equipment/plant; temperature comprised between 100° C. and 900° C. and at 16. optionally emptying the equipment/plant from all of the a pressure comprised between 1 bar and 400 bar; hydrocarbons; 9. monitoring the cleaning (treatment) operations according 17. introducing water inside the equipment/plant; to the method of the present invention; 25 18. implementing a closed circulation loop encompassing the 10. optionally re-introducing the first and/or the second equipment/plant; hydrocarbon fluid; 19. introducing in the closed circulation loop a chemical 11. optionally repeating the steps from 2 to 10; product under the present invention (one or more chemical 12. optionally opening the closed or semi-closed loop. Such washing/cleaning products and their mixtures); that the fluids of steps from 2 to 11 can be removed from the 30 20. Setting up the temperature and the pressure inside the petroleum plant by utilizing the normal production cycle. closed circulation loop at values comprised between ambi The above operations can be modified, e.g., when the con ent temperature and 350° C. and between 1 bar and 50 bar; centration of heavy products in the distillates exiting the 21. circulating the water Solution of the chemical product(s) petroleum plant is too high for their Subsequent processing in inside the closed circulation loop under conditions oftem downstream plants. In such a case, a step will be added, 35 perature and pressure comprised between ambient tem wherein all the produced distillates will exit the petroleum perature and 350° C. and between 1 and 50 bar, for a time plant, as per normal production cycle, and the step of intro of at least 20 minutes; ducing of the hydrocarbon fluid(s) will be repeated, as well as 22. cooling, if required, (including the eventual introduction its (their) circulation in the petroleum plant. of fresh water in the loop) and emptying of the loop from Alternatively, the fresh feed rate of the petroleum plant 40 the water solution; (with respect to the rate wherein the plant was running before 23. optionally routing of the water solution to the oily water the application of the present invention) can be increased to treatment plant; any value up to the design feed rate (or below or higher as in 24. optionally repeating of the steps from 17) to 23). the aforementioned +/-5%, or +/-30% of the design rate). In Under the present invention, as an alternative to the above an embodiment of the invention, the fresh feed rate will be 45 described steps, the achievement of gas-free and/or safe entry thereafter progressively reduced, while the increased amount conditions can also be realized as follows: of produced distillates, with respect to the one produced when 13'. stopping the introduction of feed; being at the rate wherein the plant was running before the 14'. optionally circulating in a closed or semi-closed loop of application of the present invention, will be circulated inside the first and/or second hydrocarbon fluid inside the equip the portions of the petroleum plant which the owner wishes to 50 ment to be cleaned (treated), for a time of at least 20 clean (treat). This is, for example, the case wherein the plant minutes, at a temperature comprised between 100° C. and is running at a reduced rate or at the technical minimum for 900° C. and at a pressure comprised between 1 bar and 400 any reason (e.g., market conditions, limitations of other bar: plants, etc.); in this case the feed rate will be increased to 15'. cooling of the equipment/plant; produce distillates under the present invention and then 55 16'. optionally emptying of the equipment/plant from all of brought back at the rate wherein the plant was running before the hydrocarbons; the application of the present invention (or in any case, at a 17. introducing inside of the equipment/plant steam at a lower rate from the “raised-to-rate”). In this case a contin pressure comprised between 1.5 bar and 100 bar; gency will be used to improve the performance of the petro 18. introducing in the steam of point 17" of a chemical prod leum plant. This is a particularly useful application of the 60 uct under the present invention (one or more chemical present invention in that, it is well known in the industry, that washing/cleaning products and their mixtures); petroleum plants do foul more easily when running at a low 19. introducing inside of the equipment/plant of the mixture rate. steam/chemical product(s) according to present invention, The cleaning procedure under the present invention will be for a time of at least 20 minutes; terminated when the monitoring system under present inven 65 20', optionally circulating condensed steam, containing a tion, as previously defined, gives appropriate indications. At chemical product(s) according to present invention; that point, e.g., the heat exchangers, the pums, the lines, the 21'. emptying of condensates from the equipment/plant; US 9,328,300 B2 29 30 22'. optionally routing of condensates to the oily water treat cleaned (treated); iii) by self-producing a hydrocarbon fluid ment plant; produced by distillation at a certain feed rate, followed by the 23'. cooling, if needed, (including the eventual introduction of variation of the fresh feed rate of the petroleum plant, the fresh water in the loop) and emptying of the equipment. withdrawal of said hydrocarbon fluid from any one or more For purposes of the present invention any steam of any points of the petroleum plant and the introduction of said characteristics (temperature and pressure) can be utilized, distillate in any one or more points of the petroleum plant, preferably with a pressure >3 bar. Obviously, before any preferably upstream of the equipment to be cleaned (treated): personnel entry, the equipment will be appropriately cooled iv) by injection of a first hydrocarbon fluid as per the preced (e.g., with water or nitrogen) and aerated. The examples 1, 2 ing points i), ii), iii) into which a second hydrocarbon fluid is and 10 are supplied to better clarify the application of the 10 introduced simultaneously or Subsequently relative to said present invention. first hydrocarbon fluid. In the normal operating conditions of a petroleum plant The hydrocarbon fluid (e.g., the first and/or second hydro circulation of distilled product is not performed, nor is there carbon fluid) introduced under the present invention com introduced any chemical product, as defined under the present prises chemical product(s) or mixtures thereof able to solu invention, under the method of the present invention, to per 15 bilize deposits inside the equipment to be cleaned. Preferably form the effective cleaning (treatment) of equipment during a it is able to solubilize and/or stabilize asphaltenes. Most pref plant run. erably, it is under near critical or Supercritical conditions at In all of the illustrative examples hereinafter reported, the the operating conditions of the petroleum plant under the introduction of the chemical product under the present inven present invention. tion can occur in any point or points of the closed or semi The present invention allows the cleaning of the equipment closed loop implemented as described hereinbefore. It is also without any penalty in terms of production loss and therefore evident, any combination of the illustrative examples herein at economic conditions much more favourable with reference after reported falls among the scopes of the present invention. to the current state of the art. Any of the examples reported in the present description is to For the scopes of the present invention, the chemical prod be interpreted only as an illustrative example and it is not 25 uct(s) utilized, as such or mixtures thereof, under the method intended to limit the present invention in anyway. of the present invention, are selected from the following In one additional preferred embodiment, the present inven group: polymetacrylates, polyisobutylene Succinimmides, tion introduces one or more hydrocarbon fluid(s) which speed polyisobutylene Succinates; laurylacrylate/hydroxyethyl up and/or make more efficient the dissolution of heavy depos metacrylate copolymer; alkylarylsulfonates, alcanolamine its which are present in the petroleum plant. Such hydrocar 30 alkylarylsulfonates and alkylarylsulfonic acids; substituted bon fluid(s) can be, for example, introduced as a second fluid, amines, where the Substituent is anhydrocarbon containing at introducing it in the fluid which is distilled and hence re least 8 carbon atoms; acylated compounds containing nitro introduced in the plant, or directly in the feed of the plant. The gen and having a Substituent with at least 10 aliphatic carbon introduction of said second fluid can occur in any point or atoms, such substituent being obtained by reaction of an points of the petroleum plant, preferably upstream of the 35 acylant carboxylic acid with at least an aminic compound equipment to be cleaned, simultaneously or Subsequently to containing at least a group-NH-, said acylant agent being the introduction of the first hydrocarbon fluid. The introduc joined to said aminic compound by way of an imido, amido, tion of said second hydrocarbon fluid can occur either in the amidine or acyloxyammonium bridge; nitrogen containing case where the first hydrocarbon fluid is to be distilled and condensated compounds of a phenol, an aldehyde or an circulated in the petroleum plant, or in the case where the first 40 aminic compound, having at least a group —NH-; esters of hydrocarbon fluid is to be passed once-through in the petro a substituted carboxylic acid; hydrocarbyl substituted phe leum plant. nols; alcoxylated derivatives of an alcohol, a phenol or an When introduced as a second hydrocarbon fluid, said amine; phthalates; organic phosphates; oleic acids esters; hydrocarbon fluid will be introduced at a dosage comprised diethylhydroxylamine. between 0.01% and 100% with respect to the quantity of the 45 For the scopes of the present invention, the chemical prod first hydrocarbon fluid, for a time of for example, at least 1 uct(s) utilized, as such or mixtures thereof, under the method hour. The time of introduction and/or circulation of said sec of the present invention, are also selected from the following ond hydrocarbon fluid can vary with respect to the dosage, by group: glycols and/or their derivatives, said glycols and/or being lower for a greater quantity introduced in said first their derivatives being not in a polymeric form, in the sense hydrocarbon fluid. Alternatively, said second hydrocarbon 50 that they are molecules of single compounds, also in an fluid can be introduced continuously during the petroleum adduct form, and not molecules constituted by a chain where plant run, as a first hydrocarbon fluid, by introducing it a single monomer is repeated; for the scopes of the present upstream of the equipment to be cleaned (treated). When invention there can be considered as glycol examples: tetra introduced as a first hydrocarbon fluid, said hydrocarbon fluid ethyleneglycol, mono- and di-ethers, mono- and di-esters, will be introduced at a dosage comprised between 0.01% and 55 ether-esters and thioethers of single glycols; glycol of general 50% with respect to the quantity of the current fresh feed of formula CH-OH-(CH), OH, CH-OH where n=0-10; gly the petroleum plant, for a time of at least 1 hour. The time of col ethers of general formula R—O—CH2—CH2—O—R introduction and/or circulation of said hydrocarbon fluid can where R is an hydrocarbyl Substituent C-Co and R is H vary with respect to the dosage, by being lower for a greater atom or an hydrocarbyl Substituent C-Co., glycol esters of quantity introduced. 60 general formula R—O—O—CH2—CH2—O-O-R- The present invention can be therefore realized; e.g., in the where R is an hydrocarbyl substituent C-C and R is H following ways: i) by continuous injection once-through of a atom or an hydrocarbyl Substituent C-Co.; thioglycols of hydrocarbon fluid introduced in any part of the petroleum general formula HO R S R OH where R is an plant, preferably upstream of the equipment to be cleaned hydrocarbyl Substituent C-Co and R is Hatom or anhydro (treated); ii) by injection of a hydrocarbon fluid introduced 65 carbyl Substituent C-Co., glycol ethers-esters of general for externally of the petroleum plant and injected in any part or mula R—O—CH2—CH2—O—O—R where R and R2 are parts of said plant, preferably upstream of the equipment to be an hydrocarbyl Substituent C-Co. US 9,328,300 B2 31 32 For the scopes of the present invention the chemical prod groups selected from: keto, hydroxy, nitro, alkoxy, acyl, Sul uct(s) utilized, as such or mixtures thereof, under the method phonic, Sulphoxid, Sulphur, amino. Said groups may also or of the present invention, are also additionally selected from alternatively contain atoms other than carbon, Such atoms the following group: ethers of general formula R—O—R being in a hydrocarbon chain or ring otherwise composed of where R or R is hydrocarbyl substituent C-C; substituted 5 carbonatoms. Hetheroatoms of this type are selected from the benzenes of general formula group of nitrogen, oxygen and Sulfur. Among the abovementioned compounds are to be pre ferred the ones selected from the group consisting of metha nol, ethanol, propanol, isopropanol, butanol, isobutanol, 10 methylglycol monomethylether, butylglycol monobu tylether, toluene, aliphatic amines Cethoxylated with at least 6 moles ethylene oxide, arylsulfonates, benzene, diphenyl, Rn phenanthrene, nonylphenol. 1-methyl-2-pyrrolidinone, diethyl ether, dimethylformamide (DMF), tetrahydrofuran where n=1-6 and R can be indifferently Hatom, —OH group, 15 (THF), ethylenediamine, diethylamine, triethylamine, trim —COOH group, —CHO group, —NH group, —HSO ethylamine, propylamine, 1-(3-aminopropyl)-2-pyrrolidone, group, the same or different hydrocarbyl Substituent C-Co.; 1-(3-aminopropyl) imidazole, N-hydroxyethyl-imidazolidi ketons of general formula R—CO—R where R or R is none, N-aminoethyl-imidazolidinone, 2-(2-aminoethy hydrocarbyl Substituent C-Co., anhydrides of general for lamino)ethanol, isopropylamine, cumene, 1, 3, 5 trimethyl mula R CO-O CO. R.; included those where R and benzene, 1, 2, 4 trimethylbenzene, maleic anhydride, Rare bound together to form cyclic anhydrides, where R or p-toluidine, o-toluidine, dipropylamine, diphenyl ether, hex R is a hydrocarbyl substituent C-Co. amides of general amethylbenzene, propylbenzene, cyclohexylamine, 1-iso formula propyl-4-methyl-benzene, 1,2,3,5 tetramethylbenzene, hex anol, morpholine, o-Xylene, m-Xylene, p-Xylene, butylamine, 25 methylamine, mesitylene, examine. Succinic anhydride, decahydronaphthalene, ethylbenzene, 1, 2 dimethylnaphtha lene, 1, 6 dimethylnaphthalene, p-cymene, ethyl ether, iso propyl ether, etoxybenzene, phenyl ether, acetophenone, monoethanolamine (MEA), diethanolamine (DEA), trietha 30 nolamine (TEA), diethyleneglycol, triethyleneglycol, tetra ethyleneglycol, hexyl glycol, dodecylbenzene, lauryl alco where R. R. R. are indifferently H atom or hydrocarbyl hol, myristyl alcohol, thiodiglycol, dioctylphthalate, Substituent C-Co.; heterocyclic compounds, preferably of disooctylphthalate, didecylphthalate, diisodecylphthalate, the hydrogenated type, containing from 0 to 3 hydrocarbyl dibutylphthalate, dinonylphthalate, methylethylketone Substituent C-Co. 35 (MEK), methylisobutylketone (MIBK), methyl-tert-butyl For the scopes of the present invention the chemical prod ether (MTBE), cyclohexane, cyclohexanone, methyl- or uct(s) utilized, as such or mixtures thereof, under the method ethyl-esters offatty acids achieved by esterification of vegetal of the present invention, are also heterocyclic compounds and/or animal oils (biodiesel). selected from the group consisting of furans, pyrrols, imida It should also be noted that under embodiments of the Zoles, triazoles, oxazoles, thiazoles, oxadiazoles, pyranes, 40 present invention, and when compatible, there can be utilized pyridine, pyridazine, pyrimidine, pyrazine, pyperazine, pip one or more options from one group together with one or eridine, triazines, oxadiazines, morpholine, indane, indenes, more options from an alternate group (or groups). benzofuranes, benzothiophenes, indoles, indazole, indoX In still another preferred embodiment of the present inven azine, benzoxazole, anthranile, benzopyrane, coumarines, tion the chemical compounds hereinabove defined preferably quinolines, benzopyrones, cinnoline, quinazoline, naphthyri 45 reach near critical or Supercritical conditions at the petroleum dine, pyrido-pyridine, benzoxazines, carbazole, Xanthene, plant's operating conditions. As a matter of fact, it is known acrydine, purine, benzopyrroles, benzothiazoles, cyclic that, supercritical fluids are capable to solubilize coke. How amides, benzoquinolines, benzocarbazoles, indoline, benzo ever, their use has never been proposed for the cleaning of triazoles. equipment during the run of petroleum plant(s), wherein said In the description of the above group, the plural is to be 50 petroleum plant(s) are producing products, as well as it has intended as including all the possible compounds configura never been proposed an apparatus Suitable for the scope, tions, including the iso-form: e.g., the term “dithiols' is wherein the equipment cleaning is performed by circulation meant to include 1.2 dithiol and 1.3 dithiol, “quinolines” is of chemical product(s) dissolved in a hydrocarbon fluid “self mean to include quinoline and isoquinoline. As used in the produced by the petroleum plant and introduced in a closed present invention, the term “hydrocarbyl substituent” refers 55 or semi-closed loop inside said petroleum plant and/or to a group having a carbonatom directly attached to the rest of wherein there is added a second hydrocarbon fluid under the the molecule and having a hydrocarbon or predominantly present invention. The present invention should be therefore hydrocarbon character. Among these mention is made of the considered as an improvement of the State of the art. hydrocarbon groups, including aliphatic, (e.g., alkyl or alk A list of chemical compounds which can be in Supercritical enyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, 60 conditions under present invention can be found in the Hand aliphatic- and/or alicyclic-substituted aromatic, condensated book of Chemistry and Physics 74th Edition CRC Press— aromatic; aliphatic groups that are preferably saturated. page 6-54 through page 6-65 (which pages are incorporated Examples of the above include the following groups: methyl, herein by reference). Among these compounds are to be pre ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, octa ferred under the present invention those selected from the decyl cyclohexyl, phenyl. Said groups may also contain non 65 following group: dimethylamine, ethylamine, ethyl formate, hydrocarbon substituents provided they do not alter the pre methyl acetate, dimethylformamide (DMF), propanol, pro dominantly hydrocarbon character of the group, e.g., the pylamine, isopropylamine, trimethylamine, tetrahydrofuran US 9,328,300 B2 33 (THF), ethyl vinyl ether, ethyl acetate, propyl formate, TABLE 1-continued butanol, methyl propanol, diethyl ether, methyl propyl ether, isopropyl methyl ether, diethyl sulfide, butylamine, isobuty Critical Critical lamine, diethylamine, diethylhydroxylamine, cyclopentanol, Compound temperature (C.) pressure (bar) 2-methyltetrahydrofuran, tetrahydropyran, pentanal, isobutyl Diisooctylphatalate 577.8 11.8 Nonylether 462.8 13 formate, propyl acetate, pentanoic acid, butyl methyl ether, Methyloleate 490.8 12.8 tert-butyl methyl ether, ethyl propyl ether, methylpyridines, Dioctylether 433.8 14.4 cyclohexanone, cyclohexane, methylcyclopentane, cyclo hexanol, hexanal, pentyl formate, isobutyl acetate, 2-ethoxy ethyl acetate, methylpentyl ether, dipropyl ether, diisopropyl 10 Among the compounds of the present invention nitrogen ether, hexanol, methyl pentanols, triethylamine, dipropy compounds in general, preferably the amines, still preferably lamine, diisopropylamine, benzaldehyde, toluene, cresols, cyclic amines, contribute to modify coke morphology. benzyl alcohol, methylanilines, dimethylpyridines, furfural, Another useful compound in Such connection is, e.g., toluene pyridine, methylcyclohexane, heptanol, acetophenone, ethyl which makes a fibrous, needle coke. As an additional 15 example, tetrabutylammonium hydroxide is a very good benzene, Xylenes, ethylphenols, Xylenols, anilines, dimethy laniline, ethylaniline, octanenitrile, ethyl propanoate, methyl Swelling agent and can be included in formulation as it con butanoate, methyl isobutanoate, propyl propanoate, ethyl tributes to change the morphology of formed coke, which will 2-methyl propanoate, methyl pentanoate, eptanoic acid, be more easily removable. octanoic acid, 2-ethylhexanoic acid, propyl 3-methylbu The Swelling agents are well known in coal solubilization/ tanoate, octanoles, 4-methyl-3-heptanol, 5-methyl-3-hep extraction techniques, but have not been utilized in the petro tanol, 2-ethyl-1-hexanol, dibutyl ether, di-tert-butyl ether, leum/petrolchemical industry during the run of a plant. In dibutylamine, diisobutylamine, quinoline, isoquinoline, their known applications, Swelling agents penetrate coal and indan, cumene, propylbenzene, 1,2,3-trimethylbenzene, 1.2, provoke its Swelling. Factors influencing the amount of 4-trimethylbenzene, mesitylene, o-toluidine, N,N-dimethyl Swelled coal in a solvent are: a) solvent-coal interaction 25 degree; b) cross-link density. The Swelling ratio is the ratio o-toluidine, nonanoic acid, nonanols, naphthalene, butylben between the volume of swelled coal, in equilibrium with the Zene, isobutylbenzene, cymenes, p-diethylbenzene, 1,2,4,5- Solvent, in respect to the Volume of original coal. In general, tetramethylbenzene, decahydronaphthalene, decanoic acid, the solvents utilized for Such purposes have good character decanol, 1-methylnaphthalene, carbazole, diphenyl, hexam istics of coal solubilization. By using Swelling agents, decok ethylbenzene, dodecanols, diphenylmethane, tridecanols, tet 30 ing of equipment, e.g., of process heaters, will be easied up radecanols, hexadecanols, heptadecanols, terphenyls, octa due to change in morphology of formed coke (from “needle decanols, eicosanols. The compounds named in plural refer to like” to “fluffy” or “cloud-like'). all the possible isomers of said compound: e.g., the term Solvents used as Swelling agents are classified in two “Xylenes' indicates o-Xylene, m-Xylene and p-Xylene. classes: forming hydrogen bonds and non forming hydrogen A particular note is deserved to fatty amines and mixtures 35 bonds. In general, the first are reported to be 25-50% more thereof: as it is well known, critical pressure decreases with effective as the latter; the effectiveness of the latter can be the increasing of the aliphatic chain, the fatty amines and increased following a first coal extraction with a solvent mixtures thereof will likely have a low critical pressure (Pc) forming hydrogen bonds with coal. Swelling effectiveness, and could effectively be used also in such connection. The and hence coal penetration, is attributed to replacement of same applies to commercial products containing fatty amines 40 carbon-carbon hydrogenbonding with solvent-carbon hydro and mixtures thereof. gen bonding: the same principle is used, among the others, in Of particular interest are those compounds having a critical the present invention. pressure (Pc)<5 MPa, preferably those with a Pc <3.5 MPa. A Among non forming hydrogen bonds Swelling agents are list of compounds, useful under the present invention, with to be preferred those selected from the group consisting of their relative critical constants is exemplary reported in Table 45 benzene, toluene, cyclohexane, naphthalene, diphenyl, 1: Xylene, tetraline, methylcyclohexane. Among forming hydrogen bonds Swelling agents are to be preferred those TABLE 1. selected from the group consisting of pyridine, methanol, Critical Critical ethanol, ethylenediamine, propanol, 1,4-dioxane, acetone, Compound temperature (C.) pressure (bar) 50 formamide, aniline, tetrahydrofuran, N,N-dimethylaniline, diethylether, acetophenone, dimethylformamide, ethyl p-Toluidine 394 23 Ethylbutyrate 293 30 acetate, methyl acetate, methylethylketone, 1-methyl-2-pyr Dipropylamine 277 31 rolidone, quinoline. Sobutyl acetate 288 31 In situations where circulation of chemical product(s) is Propyl acetate 276.2 32.9 55 performed at atmospheric pressure and at a temperature Propyl-ethyl-ether 227.4 32.1 Triethylamine 262 30 >150° C., under the present invention, there is preferred the Ethylbenzene 344 38 compounds having boiling temperature (Teb) preferably Propylbenzene 365.2 32.3 >150° C., most preferably the ones with Teb >250° C. An Butylbenzene 387.2 30.4 exemplary list of Such compounds can be found in the Hand Cumene 357.9 32.3 para-xylene 342.8 36.1 60 book of Chemistry and Physics 74th Edition—CRC Hexamethylbenzene 494 23.5 Press—, pages 3-12 through 3-523, the noted pages of which Triethanolamine S14.3 24.2 are incorporated herein by reference. Diphenyl methane 497 28.6 Among those compounds are to be preferred those selected Diphenyl S16 38.5 MTBE 224 34.3 from the group consisting of anthraquinone, eicosanol, ben Dioctylphtalate S32.8 11.8 65 Zalacetophenone, benzanthracene, hydroquinone, dodecyl Diisodecylphtalate 613.8 10 benzene, hexaethylbenzene, hexamethylbenzene, nonylben Zene, 1,2,3-triaminobenzene, 1,2,3-trihydroxybenzene, 1.3, US 9,328,300 B2 35 36 5-triphenylbenzene, diphenylmethanol, p-benzidine, benzil, leum plant, by being finished products, blending components 2-benzoylbenzofurane, benzoic anhydride, 2-benzoyl-me of finished products, intermediate products or feed to petro thylbenzoate, benzyl benzoate, 4-tolylbenzoate, benzophe leum plants, and are preferably selected from the group con none, 4,4'-bis(dimethylamino) benzophenone, 2,2'-dihy sisting of gasoline, diesel, gas oil, Virgin naphtha, kerosene, droxybenzophenone, 2,2'-dimethylbenzophenone, 4,4'- reformed gasoline, pyrolysis gasoline, pyrolysis gas oil, light dimethylbenzophonone, methylbenzophenone, 2-amino cycle oil from FCCU, decant oil from FCCU, methyl-tert benzyl alcohol, 3-hydroxybenzyl alcohol, C.-1-naphthylben butyl-ether (MTBE), benzene, toluene, xylenes, cumene, Zyl alcohol, benzyl-ethyl-phenyl-amine, benzylaniline, ben methanol, cyclohexane, cyclohexanone, ethylbenzene, linear Zyl ether, phenylacetophenone, 2-acetamide diphenyl, alkylbenzene (LAB), dimethylterephthalate, phtalic anhy 2-amino diphenyl, 4,4'-bis(dimethylamino) diphenyl, biphe 10 dride, styrene, tert-amyl-methyl-ether (TAME), ethanol, nol, butyl bis(2-hydroxyethyl)amine, butylphenylamine, dimethylformamide (DMF), dioctylphthalate, isopropyl butylphenylketone, carbazole, diphenylcarbonate, cetyl alco alcohol, butyl alcohol, allyl alcohol, butylglycol, methylgly hol, cetylamine, benzylcinnamate, coumarin, lindane, diben col, ethyl-tert-buthyl-ether (ETBE), ethanolamines, acetone, Zofuran, dibenzylamine, diethylene glycol dibenzyl ether, octyl alcohol, methyl-ethyl-ketone (MEK), methyl-isobutyl diethylene glycol monolaurate, diethylene glycol (2-hydrox 15 ketone (MIBK). Said solvents can originate from any petro ypropyl)ether, diethylenetriamine, di-O-naphthylamine, di leum plant as above defined. B-naphthylamine, dioctylamine, diphenylamine, diphenyl Generally, the solvents under the present invention can be methane, 4,4'-diamino diphenyl, 4,4'-dimethylamino chosen among the ones produced by petroleum plants or diphenyl, 4-hydroxy diphenyl, diphenylmethanol, diphenyl anyway being present in a petroleum plant by being finished ethylamine, di-(C-phenylethyl)amine, di-iso-propanolamine, products, blending components of finished products, inter di-2-tolylamine, eicosanol, 1.1.2 triphenylethane, ethylene mediate products or feedstocks of petroleum plants. In some glycol 1.2 diphenyl, ethyl-di-benzylamine, ethylene glycol cases, the same crude oil, the fuel oil or the quench oil from an monobenzyl ether, ethylene glycol monophenyl ether, N.N- Ethylene plant can be used as solvents of the chemical prod diphenylformamide, phenylformamide, tolylformamide, uct(s) or mixtures thereof, under the present invention. The 2-benzoylfurane, 2.5 diphenylfurane, glycerine and related 25 solvents as above defined can also be used as the first hydro esters, heptadecylamine heptadecanol, cerylic alcohol, hexa carbon fluid under the present invention. decanamine, cetyl alcohol, hydroxyethyl-2-tolylamine, tri A particular solvent under the present invention is the ethanolamine, cyclohexanone, imidazole, methylimidazole, MTBE present in an oil refinery or produced in a petrochemi phenylimidazole, 5-amino-indane, 5-hexy-indane, 1-phenyl cal plant. MTBE is utilized in an oil refinery exclusively as a 1,3,3-trimethyl-indane, 2.3 diphenyl-indene, indole, 2.3 dim 30 blending component in lead-free gasoline formulation, in ethyl-indole, tryptamine, 2-phenyl-indole, isocoumarin, order in boost octane number of formulated gasoline; its diethyl-isophthalate, isoquinoline, benzyl laurate, phenyl presence in an oil refinery is exclusively due to this purpose. laurate, lauryl alcohol, lauryl amine, lauryl Sulphate, diethyl Utilization of MTBE under the present invention differs from benzyl-malonate, melamine, diphenylmethane, triphenyl the state of the art and has to be considered an innovative step. methane, 4-benzyl-morpholine, 4-phenyl-morpholine, 4-(4- 35 Under the present invention MTBE can be pumped and cir tolyl)-morpholine, myristic alcohol, 9,10-dihydro culated in a closed or semi-closed loop in any petroleum naphthacene, acethyl-naphthalene, benzyl-, naphthalene, plant, alone or admixed with chemical compound(s) under butyl-naphthalene, dihydro-naphthalene, dihydroxy-naph the present invention, for the purpose of cleaning (treating) thalene, methyl-naphthalene, phenyl-naphthalene, naphthol, equipment. naphthalene, methylnaphthlamine, naphthylphenylamine, 40 The same arguments defined for MTBE may also apply to C.-naphthyl-2-tolyl-ketone, nonacosanol, octadecanol, octyl Virgin naphtha, aromatic gasoline arising from a Reforming phenyl-ether, pentadecylamine, pentadecanol, 3-hydroxyac plant (reformed gasoline) and/or to benzene/toluene/Xylene etophenone, tyramine, 4-hydroxyphenylacetonitrile, o-phe (BTX) products as Such and/or as a mixture produced in an nylenediamine, N-phenyl-phenylenediamine, 4-methyl Aromatic Extraction plant (e.g., of the Sulfolane. Furfural, phenylenediamine, diphenylether, bis-(2-phenylethyl)amine, 45 Glycols or Formylmorpholine type) and/or to the gasoline phosphine derivatives as phenyl, triphenyl and oxyde, triph and/or the gas oil produced in an Ethylene Unit (pyrolysis enylphosphite, dibutyl phthalate, dibenzyl phthalate, diethyl gasoline/pyrolysis gas oil). phthalate, dioctyl phthalate, diisoctyl phthalate, didecyl Without being bound to any specific ratio among the com phthalate, diphenyl phthalate, phthalic anhydride, N-ben ponents, the chemical product(s) dosage under the present Zoylpiperidine, 1,3-diphenoxypropane, N-(2-tolyl)propiona 50 invention can preferably be in the range: solvent 0%-400%, mide, 1-methyl-3-phenyl-pyrazoline, pyridine derivatives as chemical products) 100%-0%; most preferably in the range: 3-acetamido, 3-benzyl, 4-hydroxy, 2-phenyl, phenylsuccinic solvent 50%-99%, chemical product(s) 50%-1%; still most anhydride. Succinimide, N-benzylsuccinimide, N-phenyl preferably in the range: solvent 70%-95%, chemical Succinimide, o-terphenyl, m-terphenyl, 1.14 tetradecanediol. product(s) 5%-30%. In some embodiments of the invention, tetradecanol, tetraethyleneglycol, tetraethylenepentamine, 55 the use of the solvent alone in a closed or semi-closed loop 2,5-diaminotoluene, 3,5-dihydroxytoluene, 4-phenyltoluene, allows for the equipment cleaning (treating) under the present p-toluenesulfonic acid and related methyl and propyl esters, invention. As already stated, in embodiments of the invention o-toluic acid and related anhydride, N-benzyl-toluidine (o- the solvent can coincide with the first (and, optionally the m-e p-), tribenzylamine, tributylamine, triethanolamine, tri second as well) hydrocarbon fluid and hence be “self-pro ethyleneglyco, and related monobutylether, triheptylamine, 60 duced' and circulated inside the petroleum plant. trioctylamine, triphenylamine, tritane, tritanol, 2-pyrroli It is important to underline, that the chemical compounds done, Xanthene, Xanthone, Xylidine, used in the present invention are utilized in a different con The compounds under the present invention can be utilized nection with respect to the state of the art, in that: a) they are alone or in a mixture with appropriate solvents. Typical Sol utilized during the normal run of the petroleum plant with the vents in the applications of the present invention can also be 65 Scope of equipment cleaning and/or yield increase and/or the distillation products from crude oil originating from any reduction of coke formation and/or coke removal on cata petroleum plant and/or being anyway present in any petro lysts; b) they are utilized in a closed or semi-closed loop US 9,328,300 B2 37 38 during the petroleum plant run; c) they are utilized following catalyst is used, the coke formation on said catalyst is reduced the implementation of a novel apparatus, Such that their cir with respect to the one occurring before the introduction of culation during plant run is enabled; d) they can be “self the first and/or second hydrocarbon fluid(s) under the present produced by means of distillation inside said petroleum invention. The above contributes both to increase distillation plant and Subsequent circulation. yield and/or in the performance of the catalytic plant and the During the equipment cleaning steps the cleaning status operating costs, in that there will be, e.g., a lower catalyst can be monitored by performing some chemical analysis, as replacement requirement to achieve the same process perfor defined by the methods published by the American Society mance. A reduced coke formation in the catalyst during plant for Testing Materials (ASTM) for petroleum products (col run implies, among others, a better performance of the cata lected e.g., in the Book of ASTM Standards for Petroleum 10 lytic plant, reduced energy consumption, reduced downtime, Products) or by the Institute of Petroleum of London (IP), or reduced cost in buying new catalyst, reduced maintenance by European Norms EN, selected from the group consisting costs. The present invention also reduces the catalyst agglom of viscosity (e.g., ASTM D 445); density (e.g., ASTM eration, in that a lower amount of heavy compounds will D1298); atmospheric or vacuum distillation (e.g., ASTM cover the catalyst, thereby facilitating the downloading of D86, D1160); carbon residue (e.g., ASTM D4530, D 189); 15 spent catalyst. The present invention also addresses differen sediments by hot filtration (e.g., IP 375, 390); sediments by tial pressure build up in a reactor containing a catalyst, in that extraction (e.g., ASTM D473); sediments by filtration (e.g., by avoiding heavy deposits/coke from forming a lower reac ASTM 4807); ash content (e.g., ASTM D482, EN6245): tor delta P will show up during plant run, and/or will reduce asphaltene content (e.g., IP143), colour (e.g., ASTM D1500), the delta P in the reactor once this delta P creates any concern water and sediments by centrifuge (e.g., ASTM D2709, to the plant owner (i.e., the coke will be removed from the D1796). catalyst). One or more monitoring systems of the physical type can In the state of the art, such an improvement is impossible to also be utilized for the purpose of monitoring under the achieve, in that the existing cleaning systems can operate on present invention, selected from the group consisting of i) a closed loop circulation, but the petroleum plant is stopped evaluation of the fouling factor, defined as the ratio among the 25 and no production of any kind occurs and, as a result, the heat transfer coefficient of clean apparatus and the heat trans catalyst cannot work under Such conditions (or the reactor is fer coefficient of the apparatus at the time when the value is even by-passed during cleaning operations). recorded; ii) evaluation of pressure in various points of the The present invention provides therefore the simultaneous petroleum plant; iii) evaluation of temperature in various cleaning of the petroleum plant and the distillation yield points of the petroleum plant and the combination and all 30 increase. This is a Surprising result over the state of the art, in Sub-combinations of same. that equipment fouling implies a production loss following As a matter of fact, as long as the equipment is cleaned, the both the decay of operating/plant conditions during the run heavy compounds are solubilized in the cleaning fluid and and the downtime during cleaning operations. hence circulating fluid becomes heavier: this is evidenced In Such connection the present invention can be used not for e.g., by an increase in Viscosity and/or density and/or carbon 35 the ultimate purpose of cleaning equipment from time to time, residue and/or ashes; likewise, equipments fouling factor but on a continuous basis for the purpose to increase distilla and/or pressure loss will decrease, while heat transfer rate tion yield of a petroleum plant and run it under continuous and/or temperature at equipment outlet, or FIT will increase. clean conditions. In Such connection, the present invention For example, cleaning operations can be maintained until a can be used during all of the plant run, all year round, 365 days decrease in fouling factor and/or pressure drop, within 40 in a year. +/-10%, is recorded; or any variation in viscosity and/or The present invention allows, among others, the elimina density and/or carbon residue and/or ashes, within +/-5%, is tion or avoidance of the shutdown of a plant in order to clean recorded. it and/or to reduce the maintenance shutdown downtime, with Such chemical analysis and physical systems are routinely related additional improvement over the state of the art. This utilized within the general state of the art for evaluating com 45 is an additional Surprising result over the state of the art, as the mercial specifications of petroleum products or during nor state of the art implies the equipment shutdown to proceed to mal plant operation (in the production phase). In embodi the cleaning, with related downtime. ments of the present invention one or more physical In one further preferred embodiment, the present invention monitoring systems can be used alone or in combination with provides a method to design petroleum plants, wherein the one or more of the chemical monitoring systems (as well as all 50 equipment Subject to fouling can be designed under not con the potential sub-combinations thereof). servative conditions. As a matter of fact, all the current As already described, another Surprising benefit of design/engineering practices is to over-dimension the equip embodiments of the present invention is that, while the equip ment which is Subject to fouling. This is because fouling ment cleaning is performed, the distillation yield increases limits the performance of said equipment and the designers with respect to the one that a skilled person would expect 55 consider on a conservative basis a certain amount of fouling from the sum of (a+b) with: a) distillates produced at a certain which can be tolerated by the equipment, for sake of having feed rate--b) hydrocarbons introduced from outside of the the equipment running the most of the operating time and not petroleum plant and/or self-produced by feed rate variation, having it on hold for the purpose of cleaning, thereby impair which are subsequently distilled and re-introduced in the ing, or even stopping, petroleum plant production. For petroleum plant. 60 example, heat exchangers are designed by taking into account In the state of the art, such an improvement is impossible to a “fouling factor” which relates the duty under clean condi achieve, in that the existing cleaning systems can operate on tions versus the duty under dirty conditions. This is a standard a closed loop circulation, but the petroleum plant is stopped procedure in the current state of the art. It is quite common to and no production of any kind occurs (and obviously, by see in a petroleum plant, e.g., the heat exchangers are dimen definition, no distillation yield can occur). 65 sioned 20-50% more than the heat they are supposed to Stillan additional surprising benefit of embodiments of the exchange (sometimes their surface can even reach up to 100% present invention is that, in the petroleum plants wherein a of the theoretical one, just to take into account foulant Ser US 9,328,300 B2 39 40 vices) or to see spare exchangers in place, which run while the Apparatus embodiments of the present invention to be other exchanger is Submitted to cleaning and vice versa. All implemented in a petroleum plant under the present invention the above has a dramatic impact on capital expenditure when comprise: i) withdrawal means for withdrawal from one or designing and during the engineering, procurement and con more point(s) in the petroleum plant of one or more hydro struction of a new petroleum plant, as well as on the operating carbon fluid(s) preferably having one of the following boiling costs of an existing petroleum plant. By reducing/eliminating ranges: a) up to 75° C.; b) from 75° C. to 175°C.; c) from 175° the possibility of fouling to impact plant performance, the C. to 350° C.; d) higher than 350° C.; ii) introduction means present invention provides a new method for designing/engi for introduction of said one or more fluid(s) as above with neering (inclusive of manufacturing) petroleum plants and drawn into one or more point(s) of the petroleum plant, pref related equipment, wherein said equipment is dimensioned 10 erably upstream the equipment to be cleaned (treated); iii) distillation means for distillation of said one or more fluid(s) by taking into account a reduced, or even Zero, fouling. For as above introduced into one or more point(s) of the petro example, heat exchangers usable under embodiments of the leum plant; iv) re-withdrawal and re-introduction means of present invention feature heat exchangers having less than a said one or more fluid(s) as above distilled to re-withdraw said 50% fouling factor based dimension increase, and, more pref 15 distilled fluid(s) and re-introduce it (them) into one or more erably a 0% to less than 20% fouling factor dimension point(s) of the petroleum plant, wherein said re-withdrawal increase. The same can also apply to any other equipment and re-introduction means can be the same withdrawal and which is treated under the present invention. For example, introduction means as above; v) connection means in order to following the increase in distillation yield, the feed line form a closed or semi-closed loop, encompassing the equip dimension can be reduced as well as any other piping and/or ment to be treated, wherein said one or more fluid(s) will be equipment; for example distillation columns can be smaller continuously distilled, withdrawn and introduced; vi) a dis as the feed entering them will be lower as compared to the charge system of the fluid(s), to allow their removal from the not-treated case. All the above will have an impact on equip closed or semi-closed loop; vii) control means, which are ment dimensions, with particular reference to Surface. configured to control or regulate temperature and/or pressure The present invention also includes manufacturing petro 25 and/or flowrate, wherein said control means can also incor leum plants having said heat exchangers with the noted low porate or be itself incorporated by a control unit for control ered or avoided fouling factor dimensions as well as the ling/regulating the process variables Such as those described manufacturing of systems that not only utilize the aforemen herein (e.g., as to also including temperature and/or pressure tioned low or no-fouling compensation requirement in the and/or flowrate and/or flow direction) of the petroleum plant equipment but avoid the need for backup similar type or 30 at one or more point(s) of said petroleum plant; viii) optional redundant equipment provided to compensate for the fouling filtration means. By introducing said one or more hydrocar factor noted above. bon fluid(s) in a fluid upstream of a distillation column, said An additional embodiment of the invention also features an one or more hydrocarbon fluid(s) can be re-withdrawn and embodiment wherein the plant is running at a rate which is re-introduced, thereby forming a closed or semi-closed loop higher than the design rate. As a matter of fact, given for 35 wherein they will be continuously distilled, withdrawn and granted the existing plants are designed under conservative introduced. The distillation means wherein said one or more conditions to take into account the fouling-related limita hydrocarbon fluid(s) can be re-withdrawn can be of any kind tions, upon eliminating/reducing said limitations, the present and can be part of the petroleum plant or installed (e.g., added invention will make available to the production the portion of to a preexisting and complete plant design Suited for normal the plant which have been over-dimensioned for the purpose. 40 operation) as to complete or establish a closed or semi-closed For example, if a preheat train has been designed with a 30% flow circulation loop. Surface increase to take into consideration fouling and said The apparatus under the present invention will include, fouling is eliminated by the present invention, said preheat among the others: train can be passed through by 30% more feed, by maintain A. withdrawal means for withdrawal of one or more hydro ing the same performances. In case the rest of the plant has 45 carbon fluid(s) from any one or more point(s) of the been dimensioned with a 30% more of surface, it will be easy petroleum plant, preferably selected from the group con to increase the feed rate of the plant by 30% over the design sisting of: rate. In case the rest of the plant has design constraints, the a) Suction/discharge of the produced gasoline pump; revamping of said rest of the plant can easily overcome Such b) suction/discharge of the overhead reflux pump; constraints and allow for an increase offeed rate by 30% over 50 c) Suction/discharge of one or more bottom/middle/top the design rate. The revamping will be therefore limited to pumparound pump(s): only a portion of the plant and this will have a tremendous d) Suction/discharge of the produced kerosene pump; impact on capital expenditure reduction, e.g., for revamping a e) Suction/discharge of the produced gas oil pump; plant in order to increase its capacity. f) Suction/discharge of any distilled hydrocarbon pump; As already described, to perform the present invention, an 55 g) hydrocarbon line exiting any petroleum apparatus; apparatus can be installed, so as to realize a closed or semi h) Suction/discharge of the crude oil booster pump at a closed circulation loop. As a petroleum plant has no possi desalter outlet; bilities, during the run, of circulating the distillates exiting a i) and a combination or sub-combinations for the items listed distillation column with the purpose of performing cleaning above; of equipment, the present invention also includes among its 60 B. introduction means for introduction of, for example, the preferred embodiments the realization of appropriate with withdrawn fluid, into one or more plant points and which drawal, introduction and circulation systems of any hot/cold is hence located in one or more point(s) of the petroleum distillates, in any of one or more points of the petroleum plant. plant, and which is preferably selected from the group The modifications to be implemented in the petroleum plant consisting of: to realize appropriate withdrawal, introduction and circula 65 i) Suction/discharge of the plant feed pump; tion systems of distillates, are part of said apparatus and are ii) Suction/discharge of the crude oil booster pump at a therefore included in the scopes of the present invention. desalter outlet; US 9,328,300 B2 41 42 iii) Suction/discharge of the column bottom pump; Under the present invention, equipment gas-free and safe iv) suction/discharge of the heavy gas oil pump; entry conditions can be quickly achieved by following the V) inlet of the preheat train; cleaning during plant run, under the present invention, with a vi) inlet of the equipment to be treated; circulation step of an aqueous Solution of a chemical product vii) distillation residue line, upstream/downstream of any 5 soluble or dispersible in water, or with the introduction of said heat exchanger, chemical product(s) into the steam used for the steam-out. In viii) column bottom; Some cases, said chemical product(s) can also be introduced iX) in a pump external of the plant, being part of another plant in the nitrogen. or installated on purpose, in temporary or permanent execution; 10 In one preferred embodiment, the present invention pro X) and a combination or Sub-combinations for the items listed vides a sole method to both clean the equipment and to make above; it gas-free and safe for entry, thereby reducing downtime and C. distillation means for distillation of a fluid in said plant improving environmental performance and operational and which is located in one or more point(s) of the safety. In this way the present invention achieves the simul petroleum plant, and which preferably selected from the 15 taneous benefit of quick and safe equipment cleaning and group consisting of: quick and effective achievement of gas-freef safe entry con I) atmospheric distillation column; ditions, thereby contributing to dramatically reduce down II) vacuum distillation column; time (e.g., by eliminating the mechanical cleaning time) and III) extractive distillation column; hence production loss and to improve safety. IV) any combination or sub-combination of the above listed items; The chemical products used for achieving gas-freef safe wherein the internals of said distillation columns can be of entry conditions under the present invention are selected from any kind (trays, packing, etc.) and wherein said distillation the group consisting of non-ionic Surfactants, anionic Surfac columns are designed according to any known design/engi tants, terpenes derivatives, emulsifiers, hydrogen Sulphide neering practices and are equipped with reboiler(s) and any 25 Scavengers, mercury scavengers and their mixtures in any other device for implementing/controlling distillation of said proportion, including their aqueous solutions. one or more fluid(s). Among the anionic and non-ionic Surfactants are to be The above apparatus also include the implementation of a preferred the ones selected from the group consisting of closed or semi-closed loop between the withdrawal point(s) alkyl-, aryl-, or alkylaryl-benzensulphonates of general for and the introduction point(s) of said one or more fluid(s). In 30 mula RCHSOM wherein R is a hydrocarbyl substituent an alternate embodiment of the invention a plurality of closed Cs-Co and M is the ion H. Na, Ca, ammonium, triethanola or semi-closed loops are provided for a plant with indepen mmonium, isopropylammonium; dialkylsulfoSuccinates of dent or mutual withdrawn and/or introduction points. general formula ROCCHCH(SONa)COR wherein R is a After the application of the present invention the heat hydrocarbyl substituent C.-Co.; alkylsulfates of general for exchangers, pumps, lines, distillation columns, furnaces, fil 35 ters, vessels and any other equipment will be essentially free mula ROSOM wherein R is a hydrocarbyl substituent from heavy compounds and the petroleum plant will continue Cs-Co and M is the ion Sodium, ammonium, triethanolam its run under cleaner conditions, without the need of opening monium; ethoxylated and Sulphated alcohols of general for the equipment. In case the opening of equipment is dictated mula R—(—OCHCH ), OSOM wherein R is a hydro by maintenance or inspection works, there can be added the 40 carbyl Substituent Cs-Co. n=1-5 and M is the ion Sodium, steps which have been previously described to achieve gas ammonium, triethanolammonium; ethoxylated and Sul free or safe entry conditions. phated alkyphenols of general formula RCH (— When the cleaning in the hydrocarbon phase is over, only in OCHCH ), OSOM wherein R is a hydrocarbyl sub the cases wherein it is required that the cleaned equipment be stituent Cs-Co., n-1-5 and M is the ion sodium, ammonium, opened in order to perform inspection/maintenance works 45 triethanolammonium; ethoxylated alcohols of general for (e.g., during a maintenance shutdown), it is necessary to carry mula R—(—O CHCH ), OH wherein R is a hydro out further activity to guarantee the absence in the equipment carbyl substituent Cs-Co. n=1-30; ethoxylated alkyl phenols of hydrocarbons or compounds which might cause fires or of general formula RCH (—OCH2CH2—), OH explosions, as well as toxic compounds for personnel. When wherein R is an hydrocarbyl substituent Cs-Co. n=1-40; inside the equipment there is no explosivity or light hydro 50 mono- and di-fatty acids glyceric esters whereinacid contains carbons, this is declared gas-free or degassed; when there a hydrocarbyl Substituent Co-Cao; mono- and di-polyoxyeth arent toxic compounds for entry personnel (e.g., H2S, mer ylene esters of oils and fatty acids of general formula RCO - captains, benzene, mercury) the equipment, besides being (—OCH ), OH and RCO ( OCH ), OOCR gas-free, is also decontaminated and safe for entry. wherein the oil is of the “tall oil” or “rosin oil type, n=1-40 In the state of the art in order to achieve equipment gas 55 freef safe entry, generally steam is passed through it for a time and the acid contains a hydrocarbyl Substituent Co-Co.; comprised between 1 and 5 days (steam-out). In some cases, ethoxylated “castor oils” (castor oil is a triglyceride abundant instead of Steam is used nitrogen. Such procedure has many in ricinoleic esters) containing a number of polyethoxylated drawbacks, in that: i) it is time consuming; ii) generates ethylene oxide groups variable between 5 and 200; mono- and airborne hydrocarbon emissions; iii) and/or does not com 60 di-ethanolamides of fatty acids of general formula pletely remove all of the toxic compounds inside the equip RCONHCHOOCR and RCON(CHOH)CHOOCR mentand; among other issues, this operation limits petroleum wherein R is a hydrocarbyl Substituent Co-Cao: surfactants plant productivity, in that it is a bottle neck and a controlling of poly(Oxyethylene-co-oxypropylene), also known as block step for shutdown operations. Upon being able to reduce polymer, having a molecular weight of 50-10000; mono-, di downtime and to improve efficiency in achieving gas-freef 65 and poly-aliphatic amines derived from fatty acids, such as safe entry conditions in the equipment, an improvement over RNHCHCHCH-NH wherein R is a hydrocarbyl substitu the state of the art can be achieved. ent Co-Cao: N-alkyltrimethylendiamines of general formula US 9,328,300 B2 43 44 ethanolamine, methyl-diethanolamine, diisopropylamine, R formaldehyde, maleimides, amidines, polyamidines, gly oxal, sodium nitrite, reaction products of polyamide-formal dehyde, triazines, carboxamides, alkylcarboxyl-azo com ses pounds, cumine-peroxide compounds, bisoxazolidines, glycidyl ethers, potassium formate. Among the mercury Scavengers are to be preferred those wherein R is a hydrocarbyl Substituent Co-Co., 2-alkyl-2- selected from the group consisting of thiourea, caustic soda, imidazolines of general formula Sodium carbonate, trimercapto-s-triazine trisodium salt. 10 By referring to the attached drawings, in FIG. 1 is reported an exemplary Schematic diagram of a conventional Crude R Distillation Unit. In the FIGS. 2-11 are reported some illus trative examples of the present invention. For sake of illustra N als NC, HNH tive simplicity, the present invention is exemplary illustrated 15 into more details in the application of a CDU (Crude Distil lation Unit). It is understood, such illustrative exemplification do not limit in any way the present invention, which is appli wherein R is a hydrocarbyl Substituent Co-Cao, amine oxides cable to any petroleum plant. The CDU has been chosen in of general formula RNO(CH) and RNO(CHOH) that it contains feed preheat, distillation and distillated prod wherein R is a hydrocarbyl substituent C-C ethoxylated ucts recovery systems, which are similar to the ones of other alkylamines of general formula petroleum plants. FIG. 1 is an exemplary Schematic diagram of a conven tional Crude Distillation Unit, normally located inside a petroleum refinery. During the normal production cycle, the RN 25 plant feed coming from a tank (28) is pumped to the plant battery limits and then to the feedline (29), hence by means of pump (1) is sent to heat exchangers (2), (4), (5), (6) to get a preheat and then in a desalter (7) to reduce the salts content. At wherein m+n=2-40; 2-alkyl-1-(2-hydroxyethyl)-2-imidazo the desalter's outlet, the pump (8) sends the crude to the heat lines of general formula 30 exchangers (9), (10), (11), (12) and then the feed is sent to the furnace (13) and, by means of line (31), to the distillation column (14). The distillation column residue, by means of R line (32), pump (22) and line (33), is sent to the exchangers (11) and (12) to preheat the feed and then, by means of line N als NC, H, OH 35 (21), is sent to another petroleum plant and/or to storage (24). The products at the distillation column outlet enter in some strippers (15), wherein by injection of steam they are further purified. The distillates gathering at Strippers bottoms are wherein R is a hydrocarbyl Substituent Co-Co.; alkoxylated pumped out of the plant by means of pumps (16), (17), (18), ethylendiamines of general formula 40 (19). Before being sent to other petroleum plants and/or to storage tanks (25), (26), (27), (23) the distillates give their sensible heat to the cold crude entering the plant in the heat H--OCH2CH2-) (OCH),w cho-CHCHO-H exchangers (4), (5), (6), (10), (9). To control the thermal NCH2CHN profile of the distillation column (14) are installed pumpa A V 45 round systems, which withdraw the distillates at a certain H--OCH2CH2-) (OCH), (CH6O),-(CH2CH2O)-H height by means of pumps (35), (36), (37), let them cool down in the exchangers (38), (39). (40) and re-introduce them into wherein X and y=4-100; the column by means of lines (204), (203), (202). The pumpa Among the terpenic products derivatives are to be preferred round also exchange heat with the crude preheat train (for those selected from the group consisting of limonene, 50 sake of illustrative simplicity Such thermal integration is not pinene, canfor, menthol, eucalipthol, eugenhol, geraniol, thy reported in this and the other figures). The produced gasoline mol. from the overhead, by means of pump (42) and line (111), is Among the emulsifiers are to be preferred those selected on one part sent to storage and/or to other plants (41), by from the group consisting of Tween 60, Tween 80, nonyl means of line (112), and on the other part is refluxed in the phenol polyethylene glicol ether, oleates, Sorbitan oleates, 55 column by means of line (113). The partitioning of the two glycerol monostearate, nonyl phenol ethoxylates, iso-propyl streams is made, e.g., by regulating the pneumatic valves palmitate, polyglycerol esters of fatty acids, tridecyl alcohol placed in the lines (112) and (113); for sake of illustrative ethoxylates, fatty alcohol ethoxylates, linear alkyl benzene simplicity all of the control/regulation systems typical of the Sulphonic acid, dioctyl phthalate, sodium tripolyphosphate, petroleum plant are not reported in this and the other figures). citric acid, soybean oleic acid, trisodium phosphate, sodium 60 The general layout of the petroleum plants schematically dodecyl sulfate, didecyl dimethyl ammonium chloride, oleic consists of a feed inlet, a preheat System (e.g., by means of acid diethanolamine, dodecyl dimethyl benzil ammonium heat exchangers), a heating system (e.g., a furnace to reach chloride, Sodium acetate, oleamide, polyethylen glycol, lano the process temperature) and a distillation system. The distil lin, ethoxylated (E20) sorbitan monooleate, sorbitan lation column is provided with pumparounds/reflux to regu monooleate, SulfoSuccinammates. 65 late its thermal profile and set the distillation intervals of the Among the HS Scavengers are to be preferred those products exiting the plant. In the state of the art, systems for selected from the group consisting of diethanolamine, mono internal circulation of distillates do not exist, which are used US 9,328,300 B2 45 46 during plant run to withdraw a distillate from any point of the example: i) it has a different purpose (i.e., a treatment under plant and introduce said distillate in any other point of the the present invention vs. controlling the temperature profile of plant (e.g., at a location not associated with the distillation the column); and/or ii) the fluid which passes through it column and/or one associated with a distillation column) with contains first and/or a second hydrocarbon fluid(s) under the the scope of equipment cleaning and/or increase distillation 5 present invention; and/or iii) the composition of the fluid yield and/or reduce coke formation and/or coke removal on which passes through it is different than the one which passes catalysts. through a pumparound line; and/or iv) the ratio among the The only petroleum plant which is equipped with an inter components of the fluid which passes through it is different nal circulation system to the feed during the run is the Coking. than the one which passes through a pumparound line; and/or The circulation of a distillate (generally heavy gas oil) into the 10 v) the temperature of the fluid which passes through it is feed is however dictated by the fact, that this is the only different than the one which passes through a pumparound petroleum plant wherein the feed enters directly the distilla line. Furthermore, in a pumparound the withdrawal point is tion column; said circulation makes up therefore the bottom always only one and only from the distillation column, while pumparound. As a matter of fact, Such circulation is utilized to in the line (158) the withdrawal point(s) can be one or more regulate the final boiling point of the heavy gas oil and not for 15 and from any point(s) of the plant. Additionally, a pumpa the scopes of the present invention. Moreover, a high recycle round system is always made up by more than one pumpa ratio (duantity of heavy gas oil/quantity of feed) has a detri round, preferably three (top, medium, bottom), while the line mental effect on the distillation yield, in that it increases the (158), in the illustrated embodiment, is only one. In the cases pressure in the coke drums. The state of the art trend for this of lines (158)/(159) will also apply the same considerations particular petroleum plant is therefore the one of reducing the on the control of column (14) bottom level and/or any other recycle ratio and in the market are already operative Coking operative constrain, well known and manageable in the art. plants which do not recycle distillates on the feed (Zero Whenever the monitoring system would detect in the plant an recycle ratio). insufficient amount of the first and/or the second hydrocarbon In the FIGS. 2, 3, 4, 5, 6 and 7 are reported some illustrative fluid, said fluid(s) can be re-introduced in the plant. The examples of the present invention for the CDU. Similar 25 gasoline circulated by means of line (105) can indifferently be examples of the present invention can be applied to any petro sent in any Suitable point of the plant, e.g., in the Suction or the leum plant. discharge of plant pumps, by taking into account the normal The plant cleaning can occur in one single phase or in process and/or operative considerations (e.g., pump cavita Subsequent phases. tion). FIG. 2 shows configurations of the present invention inclu 30 Embodiments of the present invention therefore comprise sive of an arrangement, Such as to make up an apparatus under all of the design/engineering part of plant modification(s) to the present invention, wherein, on the discharge of gasoline be implemented, such as to make up an apparatus under the pump (42), line (105) is inserted to facilitate the circulation of present invention suitable, to realize features of the present gasoline to one or more desired points of the plant. The first invention. For example, lines (105), (106), (107), (108), and/or second hydrocarbon fluid is, e.g., taken from tank 35 (109), (110), (117), (118), (119), (114), (115), when featured (320) and sent to the suction offeed pump (1) by means of line in an embodiment (e.g., one or more as in all or some com (321). From the line (105) there is branched, for example: i) a bination of said lines) are calculated by considering the line (117) to send the gasoline downstream of the desalter (7): design operating conditions relative to the plant, equipped ii) a line (106) to send the gasoline to the suction offeed pump with suitable equipment as shut-off valves and/or, flow con (1) by means of line (107) or to the discharge offeed pump (1) 40 trolling valves (e.g., a pneumatic valve) in order to control the by means of line (108); iii) a line (110) to send the gasoline to distillate(s) flow which is circulated, as well as all of the other the Suction or to the discharge of bottom pump (22); iv) a line control means (e.g., temperature, pressure) and devices well (109) to send the gasoline in the suction or in the discharge of known in the state of the art and in particular in the design/ heavy gas oil pump (19). In the case gasoline sent to the engineering of petroleum plants. The method of the present bottom pump (22), a portion or all of the residue thereby 45 invention can also be applied by utilizing additional configu modified, instead of being sent to storage or another plant rations/modifications of the plant. (24), can be deviated from the line (21) by means of a line FIG. 3 illustrate additional configurations of the present (119) and hence be sent, e.g., to a tank for out of specification invention inclusive of an arrangement, such as to make up an products (116) by means of line (114) and/or for being circu apparatus under the present invention, wherein in the dis lated with the feed by means of line (115); in such latter case, 50 charge of pumparound pumps (35) and/or (36) and/or (37) are the flowrate will be regulated so as to control the bottom level inserted the lines (120) and/or (121) and/or (122) for circula in the distillation column (14) according to methods well tion of distillates in one or more of any points of the plant; said known in the state of the art. In the case the gasoline is sent to lines by means of the line (123) can thereafter branch to any the heavy gas oil pump (19), a portion or all of the heavy gas one or more additional points of the plant. The lines (120) oil thereby modified, instead of being sent to storage or 55 and/or (121) and/or (122) can be derived upstream and/or another plant (23) can be deviated from the line (20) by means downstream of the heat exchangers (38) and/or (39) and/or of a line (118) and hence be sent to a tank (116) (e.g., an out (40) of the pumparound system. From the line (123) can of specification products tank or a slop tank) by means of line branch, as previously described in FIG. 2, e.g., one or more (114) and/or being circulated in the feed by means of line (including any sub-combination) of the lines (297), (106), (115) or any other dedicated line, not represented in the fig 60 (107), (108), (110), (109). As per the lines (119), (114), (115), ure, save the considerations on the level of distillation column (118), (158), (159) they will apply the same considerations as (14) and/or any other operative constrain, well known and illustrated in FIG.2. Whenever the monitoring system detects manageable in the art. An additional circulation possibility is in the plant an insufficient amount of the first and/or the for example the introduction directly in the column (14), by second hydrocarbon fluid, said fluid(s) can be re-introduced means of a line (158) or directly in the line a furnace outlet 65 in the plant. The distillate circulated by means of line (123) (31) by means of line (159). The line (158) under the present can indifferently be sent in any suitable point(s) of the plant, invention differentiates from a pumparound line in that, for e.g., in the Suction and/or the discharge of plant pumps, by US 9,328,300 B2 47 48 taking into account the normal process and/or operative con late flowrate which is circulated, as well as with other control siderations (e.g., pump cavitation). means (e.g., temperature, pressure) and devices well known FIG. 4 illustrates a further configuration of the present in the state of the art and in particular in the design/engineer invention, inclusive of an arrangement, Such as to make up an ing of petroleum plants; the pumps (128), (129), (130), if apparatus under the present invention, wherein in the dis Some or all are utilized, should be dimensioned by taking into charge of distillate pumps (16) and/or (17) and/or (18) are account the circulating distillate flowrate and the process inserted the lines (124) and/or (125) and/or (126) for the conditions in the withdrawal/introduction point(s). All of the circulation of distillates in any one or more points of the plant; design/engineering should also take into account when appli said lines by means of the line (127) can thereafter branch in cable to the apparatus utilized under the present invention all any one or more points of the plant. For example, the lines 10 other aspects well known in the State of the art, like, e.g., (124) and/or (125) and/or (126) can be derived upstream thermal balancing, safety, operating management, etc. and/or downstream of the heat exchangers (4) and/or (5) For the scopes of the present invention also existing circu and/or (6) of the plant. From the line (127) can branch, as lation lines, which have been designed in the plant for differ previously described in FIG. 2, e.g., one or more (or any ent purposes, can be used. sub-combination of the lines (297), (106), (107), (108), (110), 15 FIG. 6 illustrates additional configurations, including an (109). As per the lines (119), (114), (115), (118), (158), (159) arrangement of the present invention, such as to make up an they will apply the same considerations as illustrated in FIG. apparatus under the present invention, wherein the circulation 2. Whenever the monitoring system would detect in the plant of distillates is realized by using lines of the petroleum plant, an insufficient amount of the first and/or the second hydro which are normally utilized for other purposes. For example, carbon fluid, said fluid(s) can be re-introduced in the plant. in the start-up phase only, the lines (143), (144), (145), (146) The distillate circulated by means of line (127) can indiffer allow the circulation of distillates until the normal operating ently be sent in any Suitable point or points of the plant, e.g., conditions (or a normal operating state) of the plant are in the Suction or the discharge of plant pumps, by taking into reached and the distillates meet the specifications, so they can account the normal process and/or operative considerations be pumped out from the plant. As a matter of fact, until the (e.g., pump cavitation). 25 normal operating conditions are reached the distillation prod Still further applicative examples can be developed by ucts are out of specification and cannot be pumped out to being encompassed into the scopes of the present invention; storage and/or another plant. Therefore it may exist in the for example, the discharge of heavy gas oil pump (19) could plant a line (147) which collects all of the out of specification also be branched and sent in any point or points of the plant. distillates during the start-up phase (wherein the process tem FIG. 5 illustrates a further example of configurations of the 30 perature is increased slowly in the furnace, from ambient present invention including an arrangement, such as to make temperature to process temperature, and the distillation col up an apparatus under the present invention, wherein the umns thermal profile is not the one of normal operating pumps (128) and/or (129) and/or (130) are installed on pur conditions), introducing them in the feed line (29) directly or pose to withdraw distillates and send them to any one or more by means of the residue circulation line (148), which is also points of the plant. In such a case the lines (131) and/or (132) 35 utilized in the start-up phase to circulate the out of specifica and/or (133) are, e.g., installed on distillates withdrawal tion residue. The residue circulation line can also be utilized means, as in the Suction of pumps (16) and/or (17) and/or to keep the plant warm when the plant is not producing (e.g., (18), and hence, in one embodiment, the line (134) is con there is a contingency in another plant, or a contingency in nected to the suction of pump (128); the line (135) at pump market conditions), but the owner wants to have it “ready to (128) discharge is branched as previously described. The 40 go'. lines (136) and/or (137) and/or (138) are, e.g., installed on a The lines (143), (144), (145), (146), (147), (148), wherever pumparound withdrawal, in the suction of pumps (37) and/or existing, are currently used for Scopes which are different (36) and/or (35), and hence the line (139) is connected to the from the ones of the present invention; moreover, they do not suction of pump (129); the line (140) at the pump (129) circulate a first and/or second hydrocarbon fluid under the discharge is branched as previously described. The line (141) 45 present invention and their operation is not dictated by the is installed on the gasoline withdrawal, in the Suction of pump method under the present invention. For the scopes of the (42); the line (142) at pump (130) discharge is branched as present invention, one or more (or any sub-combination) of previously described. the lines (143), (144), (145), (146), (147), (148) are used to In the case wherein one or more pump(s) are installed on circulate a first and/or second hydrocarbon fluid under the purpose to withdraw one or more distillate(s) and to introduce 50 present invention, according to the method of the present it (them) in any point or points of the plant (e.g., at a location invention. not associated with the distillation column and/or one asso As evident to those skilled in the art, under the present ciated with a distillation column), the same pump(s) can be invention, different closed or semi-closed loops can be arranged, e.g., to withdraw one or more distalles (e.g., by defined, which circulate one or more distillates to satisfy the arranging more suctions, with each one preferably equipped 55 requirements of different petroleum plants, without departing with at least one shut-off valve) and send them to any point(s) from the scopes of the present invention. All the possible of the plant (e.g., by arranging more discharges, with each one layouts of closed or semi-closed loops, which circulate one or preferably equipped with at least one shut-off valve). more distillates whereas the plant is under production condi The Scopes of the present invention also comprise the tions are therefore encompassed by the scopes of the present design/engineering of plant modifications to be implemented, 60 invention. Such to make up an apparatus under the present invention, to For example, the heating system of the closed or semi realize the present invention. For example, all or some Sub closed loops can be part of another petroleum plant and be combination of the respective lines (105), (106), (107), (108), effectively connected with the equipment to be cleaned, such (109), (110), (297), (112), (113), (114), (115), if utilized, to realize a closed or semi-closed loop with this. should be calculated by taking into account the operating 65 In another illustrative example, the pumps installed on conditions, should preferably be equipped with flow control purpose can be e.g., cart- or skid-mounted. Such that the same valves, e.g., a pneumatic valve, in order to control the distil pump can be used in different locations of the plant or in other US 9,328,300 B2 49 50 plants. In still a further illustrative example, one or more FIG. 9 illustrates still further configurations of the present pump(s) installed on purpose can have one or more Suction(s) invention in the case of an FCCU. In the case of an FCC plant, and/or discharge(s) in order to Suck from one or more points in an embodiment of the present invention, e.g., to clean the of the plant or another plant and/or discharge the circulating slurry loop (230, 231, 232, 233,234, 235, 236, 239, 240) a fluids in different point(s) of the same or other plants. 5 line (308) is installed on the discharge line (307) of the pump FIG. 7 illustrates additional configurations of the present (222) in order to send the distillate in the suction/discharge of invention, inclusive of an arrangement, Such as to make up an the bottom pump (232). As previously described, other dis apparatus under the present invention, wherein the first and/or tillate lines (309) and/or (310) might also be used thereby second hydrocarbon fluid is introduced from a tank and/or sending all the distillates to a collector (311) and hence in the another plant (150) and pumped in the plant by means of line 10 pump (232). In the same way, an external pump can be (151), from there it is branched to one or more (or any sub installed (not reported in the figure). From the collector (311) combination) of the lines (117), (106), (107), (108), (109), there can also branch a line (312) to send the distillated and/or (110) as previously described (inclusive here, above and the first and/or second hydrocarbon fluid(s) in the feed line below, of block off or redirect valving or passage and/or the (313) and hence to the reactor (211). Said line (312) can also lack of one of more lines in the closed or semi-closed loop at 15 be useful in other embodiments of the present invention, e.g., the design stage). Also, per the lines (119), (114), (115), to increase distillation yield and/or to reduce coke formation (118), (158), (159) they will apply the same considerations as on catalyst. The same or a different first and/or second hydro illustrated in FIG. 2. carbon fluid(s) (e.g., from any of the above noted possible FIG. 8 illustrates additional configurations of realization of Sources, such as a Source tank like (320)) under the present the present invention in the case of an Ethylene plant. In a 20 invention can come, e.g., (alternatively or in Supplemental typical Ethylene plant, e.g., one preferably with a current fashion to the distilled circulation input) from a tank (320) liquid feed, during the normal production cycle, the bottom and hence by means of a line (321) introduced in any of the product of the fractionation column (52) is sent, by means of lines (308), (309), (310), (311), (312), or in the suction of line (98), filter (99) and pump (53) into hydrocyclones (55) pump (232). As previously described, the first and/or second and from there to heat exchangers (57), (58), (59), (60), (61). 25 hydrocarbon fluid(s) can be re-introduced in the loop when In Such a way the column bottom product is cooled and ever its (their) concentration in the closed or semi-closed re-introduced in the column (52) by means of line (100), loop is insufficient relative to the scopes of the present inven thereby making up the so-named “quench' or 'quench oil'. A tion. portion of the quench oil is sent, by means of line (104), to FIG. 10 illustrates additional configurations of the present additional cooling in the exchanger (74) and hence to storage 30 invention in the case of a CCR (Continuous Catalytic (103). The overhead of the fractionator (52) enters the quench Reforming) plant. In a CCR plant the present invention can be column (70) wherein the process gas is cooled down and applied to clean, e.g., the feed/effluent exchanger(s) (182) by separated from the gasoline (pyrolysis gasoline), which is installing in the discharge line (204) of pump (197) a line further separated in a separator (67), wherein by means of a (203) to send the distillate in the line (202) in the discharge of pump (68) and a line (101) is on one part refluxed in the top of 35 feed pump (or in the Suction, not reported in the figure). The fractionator (52) and on the other part, by means of line (149), first and/or second hydrocarbon fluid(s) can, e.g., (alterna sent to a stripper (64), to be sent to storage (102) by means of tively or in supplemental fashion to the distilled circulation pump (65) and line (155). The plant also includes, among the input) come from a tank (320) and, by means of a line (321), others, the “middle oil loop, comprising the exchangers (50), be introduced in the line (203) or in the line (202). As previ (94), (91), (93), (66), (72); the cooling system of the quench 40 ously described, other distillates lines can also be used (which tower (70), comprising the exchangers from (72) to (88); the are not reported in the figure). In the same way, it can be condensate stripper (95) and the recycle gas separator (97). installed on purpose an external pump (not reported in the During the normal run of the Ethylene plant, for example, the figure). It is worth to note, the same arrangement described exchangers (57), (58), (59), (60), (61) are fouled by the heavy hereinabove, can also simultaneously realize additional compounds which are presents in the column bottom product 45 embodiments of the present invention, e.g., while achieving and are therefore opened, extracted and mechanically the cleaning of the equipment (in this case the feed-preheat cleaned. Additional fouling is also experienced, for example, heat exchanger(s)) simultaneously achieving the reduction of in the quench tower exchangers from (72) to (88) and in the coke formation on catalyst and/or coke removal on catalyst. separator (67). This can be done by proper selection of the first and/or the For the scopes of the present invention the equipment 50 second hydrocarbon fluid(s) under the present invention. cleaning (treatment) during the run of the Ethylene plant can FIG.11 illustrates an exemplary schematic of an additional be performed, e.g., by inserting a line (156)—which is not embodiment of the present invention, wherein the hydrocar included/provided in the original design—to send the gaso bon fluid(s) under the present invention is (are) sent in a line from pump (65) to the preheat train (47), (48), (49), (50). cascade mode to other plants, in order to provide the simul Another line (157) can also be inserted, e.g., to send the 55 taneous cleaning (treatment) of a plant and one or more plants gasoline on pump (53) for cleaning the items (55), (56), (57), which are downstream from said plant. In the case of FIG. 11 (58), (59), (60), (61). In this case will also apply the consid are simultaneously cleaned (treated) the plants CDU. Vacuum erations already made about the modification/design/engi (VDU), Visbreaker (VBU) during their run. In such a case, neering/management/operations of plants, concerning the e.g., the present invention can be applied starting with the installation of pumps, dedicated lines, etc. The first and/or 60 CDU by injecting in the feed line (160) a first and/or second second hydrocarbon fluid(s) under the present invention can hydrocarbon fluid(s) (161); this will be withdrawn from any be introduced, e.g., in the line (156) and/or in the line (157), one or more points of the plant (as previously described) as e.g., by coming from a tank (320) and by means of lines (321) distillate (175) (and/or from a source tank) and partially cir and/or (3211). culated (162) inside the CDU and/or it will leave the plant to The above applies for any quench oil loop or any loop in a 65 make up a product (206) and partially (164) introduced in the petroleum plant, for example the quench of a Visbreaker or residue line (163), where it will make up part of the VDU feed the slurry oil loop of an FCCU. (165). Whenever needed, the first and/or second hydrocarbon US 9,328,300 B2 51 52 fluid(s) (161) can be re-introduced in the VDU feed (165). In separately or altogether the single lines of the cold train the VDU, the first and/or second hydrocarbon fluid(s) will be (upstream the desalter) and/or the hot train (downstream the withdrawn from any one or more points of the plant (as desalter), or to withdraw/introduce a hydrocarbon fluid in any previously described) as distillate (167) and partially circu point or points of the plant. The same approach can be used to lated (169) inside the VDU and/or it will leave the plant to realize the other applications of the present invention. make up a product (207) and partially (168) introduced in the In the subsequent example 3, which refers to FIG. 12, are residueline (166), where it will make up part of the VBU feed utilized the pumps which already exist in the plant, in order to (170). Whenever needed, the first and/or second hydrocarbon reduce implementation costs (e.g., there can be used a spare fluid(s) (161) can be re-introduced in the VBU feed (170). In pump, which is normally on stand-by) and the tie-ins to create the VBU, the first and/or second hydrocarbon fluid(s) can be 10 withdrawn from any point of the plant (as previously the circulation loop can be realized when the pump is not described) as distillate (176) and partially circulated (172) running, for example by inserting a valved tee in the Suction/ inside the VBU and/or it can be sent out from the plant to discharge spool. Alternate embodiments feature the use of an make up a product (208) and, at the same time, partially (173) appropriate Suitable external pump. In Such a case, another introduced in the residue line (171), where it will make up a 15 valved tee can be inserted in the inlet/outlet spools of the loop fluid (174) which can be used or reprocessed as previously or of the equipment to be cleaned. Such to realize a closed described. loop. FIG. 12 illustrates additional configurations of the present FIGS. 13 A to 13C illustrate some modification examples, invention, inclusive of an arrangement wherein a portion of arranged to represent apparatus embodiments under the the plant is cleaned and does not contribute to the production, present invention, to be realized with reference to FIG. 12. whereas the other portion runs and contributes to the produc For example, at exchanger (416) outlet, the spool (554) can be tion. For example, a preheat train in a CDU, divided in two removed (by removing it between the flanges at the exchanger production lines, is cleaned by operating in two steps, (416) outlet and the valve (520)) and hence insert in said spool wherein firstly a line of heat exchangers is cleaned, while the the line (524) and the valve (531) and connect the line (524) other is left with the feed inserted, and vice versa. Under an 25 with line (546); or there can be performed a hot tapping and embodiment of the present invention, in Such an application weld the line (524) equipped with a valve (534) to both lines are realized some plant modifications. Such as to make up an (554) and (546). The connections of pump (500) can be modi apparatus under the present invention, with the scope of fied by inserting on the discharge a non-return check valve implementing a closed loop comprising the equipment to be (NRV) (557) and a valve (555), downstream of which are cleaned; the dashed lines represent the modifications to be 30 connected the lines (523) and (540), as well as the line (548), implemented, while the solid lines represent the normal plant which is also equipped with a NRV (561) and a valve (547). A configuration. In Such a connection, e.g., at the exchanger NRV (560) can also be inserted in the line (549), together with (416) outlet, there is installed, on purpose, a line (524) to valve (550), in the suction of pump (500). A PCV (558) can circulate: e.g., i) a first and/or second hydrocarbon fluid(s) also be inserted in the suction of pump (500) to set the pres under the present invention coming from a tank (320) and 35 sure during circulation. The by-pass line (552) will allow, by introduced by means of a line (321) in the suction of pump means of valve (551), pump safe operation in case of low (500), and/or e.g., ii) a fluid withdrawn by realizing a line flowrate, as, e.g., there could occur during the step of intro (526) in the discharge line (525) of the pump (419) of the ducing a first and/or second hydrocarbon fluid(s). Addition middle pumparound, and/or e.g., iii) a fluid withdrawn by ally in the suction of pump (500) there can also be inserted a realizing a line (537) in the line (443) of the kerosene to 40 valve (559) in order to introduce the second hydrocarbon fluid storage or to other plant (444). Always for the same purpose, by means of line (321). All of the above illustrative exemplary at the exchanger (408) outlet is installed a proper line (433) in modifications are not included in the state of the art and are order to circulate a first and/or second hydrocarbon fluid(s) examples of suitable configurations to make up an apparatus under the present invention, coming from tank (320) by under embodiments of the present invention. The same prin means of a line (321), in the suction of pump (402) and/or a 45 ciple can be followed for the other schematically/exemplary fluid withdrawn by realizing a line (435) in the discharge line illustrative modifications, such as to make up an apparatus (525) of the medium pumparound pump (419). Obviously, under the scopes of the present invention. any hydrocarbon Suitable under the present invention can be The present invention therefore also comprises all of the withdrawn from any point of the plant and introduced in any modifications. Such to makeup an apparatus under the present other point or points of the plant. From the line (526) the 50 invention, to be implemented in the petroleum plant in order withdrawn fluid can be branched in any point or points of the to realize it. For example, in case the light gas oil pump has a plant, e.g., by means of, for example, lines (527) and (536) in discharge pressure of 15 bar and said light gas oil is to be the suction line (521) of booster pump (500) by realizing a introduced in the discharge of the crude feed pump, having a line (549), or in its discharge line (522), by realizing a line pressure of 40 bar, the present invention comprises the (548); or by means of lines (435) and (441) in the suction line 55 replacement (or Supplementing) of the original pump with (431) of feed pump (402) by realizing a line (456), or in its one having Suitable characteristics (alone or in combination) discharge line (432), by realizing a line (454). The pumps and/or the installation of a new pump with Suitable charac (402) and (500) are equipped under the present invention with teristics and/or the installation of a temporary pump, e.g., a a by-pass valve (458) and (552) in order to set the flowrate cart/skid mounted one, having Suitable characteristics. The during the various steps and eventually with a PCV (pressure 60 same applies for the circulation line. control valve) in order to set the inlet pressure. In the dis The present invention also comprises the design/engineer charge line (522) of the pump (500) is realized a line (523) and ing/procurement/construction/modification, e.g.: i) of the a line (540) in order to close the circulation loop at exchanger existing drains/connections in order to create a circulation (410) and (509) inlet. In the discharge line (432) of the pump loop; ii) of the flowrate/pressure/temperature control/regula (402) is realized a line (430) and a line (447) in order to close 65 tion equipment to be included in the loop; iii) of line/safety the loop at exchanger (404) and (503) inlet. The modifications valve dimensioning; iv) of any portion of the plant to be are completed with the realization of lines in order to circulate included in the circulation loop. The dimensioning calcula US 9,328,300 B2 53 54 tions of the components for the realization of the present neously control the feed rate (inclusive of its variation) under invention will be performed according to the methods known the present invention. As an illustrative example, in the dis in the state of the art. charge line (707), preferably from the control valve which is FIG. 14 illustrates additional configurations of the present controlling/regulating the flow of the first and/or second invention to a plant of Crude Oil Stabilization for the crude hydrocarbon fluid(s) (not shown in the figure) a signal is extracted from one or more oil wells. The crude coming from withdrawn by means of line (719) (which can consist of a the wells (600) is sent to a separator (601), wherein a gas cable, a wi-fi signal, a radio signal, or any other Suitable phase (607) and a water phase (608) are separated; by means means), and is connected to a controller (720) which, in turn, of line (611) the crude after preheating (602) is sent to a by means of line (721) (which can consist of a cable, a wi-fi Stabilizer column (603) wherein, due to heating by means of 10 signal, a radio signal, or any other Suitable means) will deliv a reboiler (606), in the overheadline (617) is distilled a light ery said signal to the control valve (not shown in the figure) of phase which, after condensation (604) goes to an accumulator feedpump (1) in order to regulate the feed rate. In this way the (613), wherein a gas phase (614) and condensated gasoline self-production of the first and/or second hydrocarbon (619) are separated. The pump (605) by means of lines (612) fluid(s) can be automated and/or controlled/regulated from and (615) sends said condensed gasoline as a reflux in the 15 the control room of the petroleum plant. The embodiment of Stabilizer column (603); the stabilized crude leaves from the the present invention will also include all of the logic and the column bottom and is sent to storage by means of line (609). devices (including, for example, Software and/or hardware) In order to perform a cleaning during plant run, under the which are used to implement said control/regulation of feed method of the present invention, there is, e.g., built a line rate and/or the introduction of the first and/or second hydro (616) in the discharge line (612) and said line (616) is con carbon fluid(s). The same can be applied to line (703) for the nected to separator (601) inlet, in the line (600) of inlet of controller (713). FIG. 15 also illustrates further additional crude from wells, in a way that a part of the condensate configurations of the present invention, inclusive of an gasoline is circulated at the plants inlet. A first and/or second embodiment wherein control means are added in order to hydrocarbon fluid under the present invention can also (either regulate the introduction of the first and/or second hydrocar alternatively or as a Supplemental) for example beintroduced 25 bon fluid(s) and simultaneously control the feed rate (inclu in the line (616) by means of line (321), by coming from a sive of its variation) under the present invention, Subject to a tank (320). monitoring of the process under the present invention. As an FIG. 15 illustrates additional configurations of the present illustrative example, the process data of an equipment are invention, inclusive of an embodiment wherein the first and/ collected, elaborated and returned in form of a signal which or second hydrocarbon fluid(s) are distilled on purpose, by 30 can control the introduction of the first and/or second hydro means of a specific column, before re-introduction and circu carbon fluid(s) and/or of the feed rate. This is, e.g., the case lation. For example, in an embodiment of the invention, the wherein the run data of heat exchanger (12) are collected and first and/or second hydrocarbon fluid(s) have boiling point(s) elaborated in order to calculate the current fouling factor (or such that they are gathered in the suction of the pump (16) delta P or any other control parameter) of said exchanger. The and/or (42). Said first and/or second hydrocarbon fluid(s) are 35 system can be designed, e.g., in order to alert plant personnel shown to be specifically distilled by modifying the discharge to perform the treatment under the present invention. Said line (152) of pump (16). The original discharge line (152) (see treatment will be automated, e.g., by regulating the flowrate FIGS. 1 and 6 for example) is interrupted at a convenient of the first and/or second hydrocarbon fluid(s) and/or the feed point, thereby creating a new discharge line (701), which will rate, and by continuing the introduction of the first and/or enter the column (700). With an arrangement wherein the first 40 second hydrocarbon fluid(s) until the control parameter sig and/or second hydrocarbon fluid(s) go to the overhead line nal (fouling factor, delta P. etc.) returns to a pre-definite value. (709) of column (700), after eventual condensation by means As an illustrative example, this can be realized by having the of a cooler (708) and separation/collection in a separator/ controllers (720) and (722) interacting by means of a line drum (710), said first and/or second hydrocarbon fluid(s) can (725) (which can consist of a cable, a wi-fi signal, a radio be re-introduced in any point (or points) of the plant by means 45 signal, or any other Suitable communication means). The of pump (711) and line (703), while the bottom of column same applies to any other equipment treated under the present (700) by means of line (702) will connect to the original line invention. For example the delta P of reactor containing a (152). The same applies for pump (42), wherein the discharge catalyst can be controlled in the same way. The embodiment line (111) is modified to enter the column (705) by means of of the present invention will also include all of the logic and a new discharge line (704). With an arrangement wherein the 50 the devices (including, for example, Software and/or hard first and/or second hydrocarbon fluid(s) go to the overhead ware) which are used to implement said control/regulation of line (715) of column (705), said first and/or second hydrocar feed rate and/or the introduction of the first and/or second bon fluid(s) can be re-introduced in any point (or points) of hydrocarbon fluid(s), as well as all of the logic and the devices the plant by means of line (707), as previously described, (including software and/or hardware) which are used to moni while the bottom of column (705), by means of line (706), 55 tor and calculate the control parameter(s). will connect to the original line (111). The above applies to The characteristics and the achievable results of the present any other withdrawal point of the first and/or second hydro invention can be better illustrated by further illustrative carbon fluid(s). The columns (700)/(705), or any other col examples. All the examples hereinafter and hereinabove umn introduced under the present invention, will be designed reported are to be interpreted as illustrative and in no case can according to design/engineering practices and, if applicable 60 be interpreted as a limitation of the present invention. relative to the arrangement utilized, will be equipped with reboiler(s) and any other device for implementing/controlling Example N.1 distillation of said first and/or second hydrocarbon fluid(s). FIG. 15 also illustrates additional configurations of the A crude atmospheric distillation plant (CDU) has a design present invention, inclusive of an embodiment wherein con 65 throughput of 500 tons per hour (T/h) and a technical mini trol means are added in order to regulate the introduction of mum throughput of 250 T/h. Based on design throughput the first and/or second hydrocarbon fluid(s) and simulta there have also been designed downstream plants, which US 9,328,300 B2 55 56 receive the products resulting from distillation as well as feed rate increase and Subsequent feed rate reduction(s) in distillation residue. The distillation yield of the typical pro order to self-produce a hydrocarbon fluid(s) in the plant, cessed crude is: 20% gasoline, 20% kerosene, 30% gas oil, which is subsequently distilled and circulated. 30% atmospheric residue. At the design throughput this cor In the above examples 1 and 2 together with the first intro responds to 100 T/h gasoline, 100 T/h kerosene, 150 T/h gas duced hydrocarbon fluid (gas oil, in this case), it can be also oil, 150 T/h atmospheric residue. When the fresh feed rate is introduced a second hydrocarbon fluid under the present 250T/h, a yield of 50 T/h gasoline, 50 T/h kerosene, 75 T/h invention; this latter will also be distilled and circulated like gas oil, 75 T/h atmospheric residue will be achieved. The the first one. plant is however designed to manage a production up to 150 Obviously, the above operations will be performed by tak T/h gas oil and a feed of 500 T/h, therefore it is possible to 10 ing into account both the balancing (mass, thermal, etc.) of introduce in the plant, in one or more points (e.g., in the feed), the plant under cleaning (treatment) and the balancing of up to 75 TWh gas oil (e.g., coming from storage). In this latter downstream plants, if present, according to common petro case therefore, the feed will be now made up of 250 T/h of leum plants management techniques, as well as to design fresh feed and of 75 T/h of gas oil (total 325 T/h) and the limits of the equipment wherein the first and/or second hydro production will be 50 T/h gasoline, 50 T/h kerosene, 150 T/h 15 carbon fluid(s) pass(es) through. Generally, it is preferable to gas oil, 75 T/h atmospheric residue. From the produced 150 run at a defined feed rate (e.g., the technical minimum), T/h gas oil, 75 T/h will exit the plant in order to satisfy introduce the first and/or second hydrocarbon fluid(s) and production needs, while 75 T/h will be re-introduced in the then distill and circulate them. A progressive introduction plant and circulated; the cycle will continue until the moni step by step of the first and/or second hydrocarbon fluid(s) toring under the present invention will indicate, the cleaning will allow anyway to face eventual operative problems. operation to be terminated. The monitoring will also define when and if it will be necessary to pump out of the plant all of Example N.3 the produced distillates (i.e., all of the 150T/h gas oil will exit the plant) and repeat the introduction of a hydrocarbon With reference to FIG. 12, during the normal run, two feed fluid(s) in the plant, its Subsequent distillation and circulation. 25 pumps (401) and (403) are running, while the pump (402) is Obviously, the same effect can be achieved by running the idle and in stand-by as a spare of (401) and (403. The same plant at 500T/handby progressively reducing the feed rate to applies to the booster pump (500), a spare of (501) and (502), 250T/h (or to any value lower than 500T/h, depending on the which during the normal run will have the valves (516) and volume of hydrocarbon fluid which is meant to be circulated): (517) closed. Moreover, all of the cold train exchangers (from in Such a case the 75 TWh gas oil (or any value resulting from 30 404 to 408 and from 503 to 507), the desalters (409 and 508) the reduction in feed rate) will be “self-produced' and hence and all of the hot train exchangers (from 410 to 416 and from progressively circulated as soon as they will be “self-pro 509 to 515), are inserted in the production cycle (valves 427, duced. It is important to note, in both of the above cases the 428, 518, 520, 437, 438, 529, 530 opened). Hereinafter are circulating 75T/h of gas oil (or any value resulting either from exemplary described the operations, under the present inven the introduction of a hydrocarbon fluid and/or the reduction in 35 tion, to clean one hot preheat line, while the other preheat line feed rate) will be “self-produced, and therefore (besides the is inserted in the production cycle and allows for the run of the "bleedings” of the loop) the introduction and/or the “self plant. In order to realize the present invention, e.g., to clean production' will be theoretically performed only one time one hot preheat line, firstly the valves (518), (520) are closed and not continuously (i.e., the introduction of a hydrocarbon to isolate the equipment to be cleaned; the valves (516) and fluid and/or the reduction in feed rate will be accomplished 40 (517) still remain closed in order to isolate the booster pump only once). The continuous introduction of gas oil into the (500), which will be used as a circulation pump. A first and/or plant can reduce cleaning time, but impacts the economics of second hydrocarbon fluid(s), under the present invention, is the system. thereafter introduced in the line (521) by means of line (321), by coming from a tank (320); alternatively (or in addition Example N.2 45 thereto), the first and/or second hydrocarbon fluid(s) can be introduced by opening the valve (519), by withdrawing the The crude atmospheric distillation plant (CDU) of example gas oil for middle pumparound directly from the column 1 runs at a fresh feed flowrate of 400 T/h, therefore the (418) (by means of lines 527 and 536, by having the valve 519 production will be 80T/h gasoline, 80T/h kerosene, 120 T/h opened), or at exchanger (412) outlet (by means of lines 533 gas oil, 120 T/h atmospheric residue. The fresh feed rate is 50 and 536, by having the valve 519 closed and the valve 534 then increased to 500T/h, and the “exceeding 30 T/h gas oil opened). Thereafter are opened the valve (528) in the line will be re-introduced and circulated in the plant. The fresh (523) and the valve (520) at exchanger (416) outlet, and the feed rate is then decreased back to 400 T/h and the gas oil pump (500) is started up (in case the circulating fluid(s) is “exceeding the one of normal production will be re-intro introduced in the suction by means of line 549, with valve 550 duced and circulated in the plant. The plant can thereafter 55 open and valve 547 closed) to allow the outflow of fluids into continue to run under these conditions (fresh feed 400 T/h, the column (418), wherein they will be distilled, and the circulating self-produced gas oil 30 T/h) or by reducing, e.g., filling of the loop to be cleaned. If the first hydrocarbon fluid the fresh feed to 300 T/h, by having 60T/h of “exceeding gas is introduced by means of line (536), and then by means of oil re-introduced and circulated in the plant. The fresh feed line (546) it will be introduced in the suction/discharge of can then be reduced to 250T/h, thereby distilling 150 T/h gas 60 pump (500), the second hydrocarbon fluid will be subse oil. From the distilled 150T/h gas oil, e.g., 75T/h will exit the quently introduced by means of line (321) in the line (521). plant to satisfy production needs, while 75 T/h will be re The first hydrocarbon fluid can also be introduced by means introduced in the plant and circulation will continue until the of line (537) which enters the line (546), after having opened monitoring system under the present invention will indicate the valve (538), with the valve (553) closed. Thereafter, the the termination of cleaning operations. The monitoring will 65 valves (519)/(538) and (520) are closed and the valve (531) is also define when and if it will be necessary to pump out of the opened in order to establish a closed loop and perform the plantall of the produced distillates and repeat the operation of circulation under the present invention. The circulation dura US 9,328,300 B2 57 58 tion will be determined by performing the monitoring under Example N.6 the present invention. Upon terminating the circulation, the above operations can be repeated by opening the valve (520) A Delayed Coking pilot plant has been modified under the and by introducing a first and/or second hydrocarbon fluid present invention, by inserting the facilities to circulate in the under the present invention by means of line (321) and/or by feed a portion of the produced gasoline. A normal run by opening the valves (519)/(538) as previously described. Upon using the conventional process Scheme, without activating the terminating the cleaning operations, the cleaned equipment modifications under the present invention, has been per will be re-inserted in the production cycle by opening the formed in order to measure the distillation yield and take it as valves (518) and (520), by closing the valves (528) and (531) a reference. A Subsequent run with the same feed, under the and by stopping the pump (500). Simultaneously with the 10 same operating conditions, has been thereafter performed by cleaning of one line of the hot preheat, the corresponding line introducing in the feed 0.5% of coking naphtha and by circu in the cold preheat can also be cleaned, by utilizing the same lating in the feed the same amount (0.5% with respect to the method as previously described. The cold and the hot preheat feed) of the produced naphtha. On the “self-produced naph trains can also the cleaned at the same time, by using the lines (545) and (532) and by opening the valve (544) and by having 15 tha, a hydrocarbon fluid under the present invention has been the valve (535) closed. In such a way the hydrocarbon fluid at introduced at a concentration of 0.1%, said fluid having the exchanger (416) outlet will enter the pump (402) by means of follow composition: 30% Xylene, 20% Toluene, 30% Eth lines (441) and (434) and will be circulated on a closed loop omeen S22, 20% Butylglycol. Distillation yield have been throughout the entire cold train and hot train. During the cold measured, by achieving the results Summarized in Table 2: and/or hot train cleaning, the desalter(s) (409)/(508) can be inserted in the cleaning loop (valves 442/451 closed and TABLE 2 valves 459/460/471 or 461/462/473 opened), or being by Reference Run under the passed (valves 442/451 opened) after having isolated it l present invention (them) from the circulation loop (valves 459/460/471 or 461/ Fraction wt % wt % 25 462/473 closed); during the normal run the valves 471/473 HS O.78 O.92 are closed; the lines 470/472 are built on purpose, under the H2 O.O2 O.O2 present invention, to realize the cleaning of desalter(s) during GAS (C-C) 6.27 8.35 plant run. Upon termination of one preheat train line cleaning, PI-75 C. 1.48 1.72 this will be re-inserted in the production cycle; the other train 75-175o C. 7.06 7.87 30 175-350° C. 22.26 22.74 (cold and/or hot) will be then be excluded from the production 350-370° C. 4.2O 4.13 cycle in order to perform its cleaning (if required), thereafter 370- C. 23.28 23.64 it will be re-inserted in the production cycle and the CDU will COKE 34.6S 30.61 continue its run with both of the trains under clean conditions, thereby running under improved operative conditions. 35 Example N.7 Example N.4 The coke content of an exhausted catalyst sample, taken A foulant deposit of 100 g, taken during mechanical clean during the downloading of a catalytic bed of a Virgin Naphtha ing of a Visbreaker bottom column exchanger, is placed in a Hydrodesulphurization plant, has been analyzed. 100 grams laboratory reactor equipped with a reflux condenser, together 40 with 100 grams of gasoline and 20 grams of a hydrocarbon of said exhausted catalyst were placed in a laboratory reactor fluid composed of:50% MTBE,30%Xylene, 10% Ethomeen equipped with a reflux condenser, together with 100 grams of S 22 (aliphatic amine C ethoxyilated with 10 moles of Virgin naphtha and 20 grams of a hydrocarbon fluid composed ethylene oxyde), 5% Dimethylformamide, 5% Dioctylphta of 30%Xylene, 30% Toluene, 30% Butylglycol, 10% Cyclo late. The temperature is thereafter increased up to 450° C. 45 hexane. The temperature was thereafter increased up to 450° while the produced distillate is condensed, re-introduced in C. while the produced distillate was condensated, re-intro the reactor and then re-distilled and re-introduced, so as to duced in the reactor and then re-distilled and re-introduced, so create a circulation of said distillate between the reactor and as to create a circulation of said distillate between the reactor the condenser, Such conditions have been maintained for 24 and the condenser; Such conditions have been maintained for hours. Upon opening the reactor, 100% of the foulant deposit 50 24 hours. Upon opening the reactor, 50% of the coke which had been solubilized in the hydrocarbon fluid. was originally present in the catalyst had been solubilized in the hydrocarbon fluid. Example N.5 Example N.8 A foulant deposit of 100 g, taken during mechanical clean 55 ing of the quench oil loop of an Ethylene plant, is placed in a In a Virgin Naphtha Hydrodesulphurization pilot plant, a laboratory reactor equipped with a reflux condenser, together reference blank run was performed in order to evaluate coke with 100 grams of pyrolysis gasoline and 20 grams of a formation on catalyst. The same plant was modified accord hydrocarbon fluid composed of 30% Xylene, 20% Toluene, ing to the present invention, by implementing a circulation in 20% Butylglycol, 30% Methylglycol. The temperature is 60 the feed of 1% desulphurated virgin naphtha and the intro thereafter increased up to 350° C. while the produced distil duction in the feed of 300 ppm of a hydrocarbon fluid com late is condensed, re-introduced in the reactor and then re posed of 30% Xylene, 30% Toluene, 30% Butylglycol, 10% distilled and re-introduced. Such to create a circulation of said Cyclohexane. The pilot plant was thereafter run under the distillate between the reactor and the condenser; such condi same operative conditions (same feed, same temperatures and tions have been maintained for 24 hours. Upon opening the 65 pressures, same run duration, same catalyst) in order to evalu reactor, 100% of the foulant deposit had been solubilized in ate the coke in the catalyst. A reduction of 50% in coke the hydrocarbon fluid. formation has been achieved with respect to the blank run. US 9,328,300 B2 59 60 Example N.9 apparatus and/or chemical products for: a) equipment clean ing in a petroleum plant during the run of said plant; and/or b) In a Visbreaker pilot plant, a reference blank run (at 90% of distillation yield increase of a petroleum plant; and/or c) coke design throughput) was performed in order to evaluate foul formation reduction in catalysts of a petroleum plant; and/or ing formation in the preheat train exchangers and distillation d) coke removal in catalysts of a petroleum plant. In the above yield. Said pilot plant was thereafter shutdown and cleaned by description, the word “clean' (and its derivated nouns, verbs) circulating for two days at 150° C. a gas oil which contained can therefore be interpreted as “distillation yield increase' 0.5% vol of a hydrocarbon fluid composed of 50% MTBE, and/or 'coke formation reduction in catalysts”, “coke 30% Xylene, 10% Ethomeen S22.5% Dimethylformamide, removal in catalysts’ as appropriate. By considering the 5% Dioctylphthalate. The pilot plant was thereafter re-started 10 above and the fact, the embodiments of the present invention in order to evaluate the fouling factor of the above exchangers can be exploited on a single basis or cumulatively; in the after said cleaning. A reduction of 60% of fouling factor has above description and/or in the appended claims we refer to been achieved with respect to the fouling factor before shut the word “treat' (and its derivated nouns, verbs) to include all down and cleaning by circulation. The same pilot plant has of the above embodiments a)/b)/c)/d). been degassed by Steaming it out for 3 days, then mechani 15 In the above specification, all data obtained during lab tests cally cleaned and hence modified by installing an apparatus and experiments have been included for completeness. under the present invention. A second run has been then Efforts to exclude any value outside acceptable error limits performed in the same operating conditions, with the same have not been made. It is believed that, during course of these feed and for the same time as per the blank run. At this point, tests and experiments, possible errors in preparing samples instead of stopping the plant and proceeding to the closed and in making measurements may have been made which loop cleaning as previously performed, the apparatus under may account for any occasional data that is not supportive of the present invention was put in service, by continuing the this art. plant run and by executing a circulation in the feed of 1% vol While the illustrative embodiments of the invention have of the gas oil withdrawn from the stripper and by introducing been described with particularity, it will be understood that in said gas oil 0.5% vol (referred to the feed) of the same 25 various other modifications will be apparent to and can be hydrocarbon fluid used in the previous cleaning. The cleaning readily made by those skilled in the art without departing during the run lasted 2 days, after that the plant run in the same from the spirit and scope of the invention. Accordingly, it is operating conditions as the blank run. An average preheat not intended that the scope of the claims appended hereto be train fouling factor reduction of about 30% has been achieved limited to the examples and descriptions set forth hereinabove with respect to the cleaning performed by stopping the pro 30 but rather that the claims are construed as encompassing all duction and circulating on a closed loop. Moreover a distil the features of patentable novelty which reside in the present lation yield increase of an average 3% could be noted with invention, including all features which would be treated as respect to the yield achieved in the same operating conditions, equivalents thereof by those skilled in the art to which the without activating the apparatus under the present invention. invention pertains. 35 The invention claimed is: Example N.10 1. A method for treating a petroleum plant or equipment of the petroleum plant during a running of the petroleum plant, In the Visbreaker pilot plant of Example N.9 at the end of comprising: the second run a final cleaning has been performed by execut maintaining, during a treatment period, the petroleum plant ing a circulation in the feed of 1% vol of the gas oil withdrawn 40 under a production operating condition, typical of the from the stripper and by introducing in said gas oil 0.5% vol plant itself, which includes providing fresh feed to the (referred to the feed) of the same hydrocarbon fluid used in petroleum plant; the Example N.9. The cleaning during the run lasted 2 days, while maintaining the petroleum plant under the produc after that the feed was discontinued, the plant drained and tion operating condition, there is carried out one or both steaming out operations started. This time, however, a chemi 45 of a) and b); cal under the present invention has been introduced into the a) introducing in the petroleum plant, during the treatment steam, said chemical being composed of: 50% water, 20% period, a hydrocarbon-based treatment fluid; Teewn 80, 10% iso-propyl alcohol, 5% diisopropylamine, b) varying an established feed rate, present at initiation of 15% iso-propyl palmitate. By injecting said chemical into the the treatment of the petroleum plant or equipment of the steam, the degassing of the plant has been achieved in 1 day. 50 petroleum plant, which established feed rate ranges By considering the impact on yield, the present invention from a maximum operation rate for the petroleum plant, can be used continuously, by evaluating the right balance which is inclusive of a design rate for the petroleum among the reduction in throughput and the yield increase. In plant, to a minimum operation rate which is set at a level such connection the time of introduction of the first and/or the for satisfying a minimum production operating state in second hydrocarbon fluid can be up to the whole calendar 55 the petroleum plant; year. wherein said introduction of a hydrocarbon-based treat Without departing from the scope of the present invention, ment fluid and/or said variation to the established feed all of the formulations of chemical compounds described in rate generates an additional source or sources for distil the present invention can also include amounts, as Suitable for lation with respect to the amount provided by the estab the scope, of compounds already known in the state of the art, 60 lished rate present at initiation of treatment; and which can be useful for the scope. Therefore the introduction distilling said additional source or sources for distillation in of e.g., dispersant, asphaltene Stabilizers, detergents, in the conjunction with the distillation of a plant process stream as formulation of the compounds hereby claimed cannot preju to form a combination distillate, and diverting a portion of dice the novelty of the present invention, as characterized by said combination distillate from a flow stream of said com its claims. 65 bination distillate as to form both a flowing continuation By considering the detailed description of the invention it stream of the combination distillate and a diverted stream of is evident, the present invention provides a method and/or the combination distillate, and re-introducing the diverted US 9,328,300 B2 61 62 stream containing combination distillate to the or another rate to the plant includes a coordinated lowering of a current plant process stream such that the combination distillate fresh feed rate to the plant such that the lowered fresh feed rate passes within a plant treatment Zone for the purpose of plant plus the additional drawn off distillate is summed together to treatment. a desired treatment feed rate and wherein a controller is 2. The method of claim 1 wherein b) is carried out for configured as to monitor and adjust the fresh feed rate to the purposes of plant treatment, and the additional source or plant, based on an input level of the drawn off distillate being sources of distillate generated by the variation to the estab received in said one or more fresh feed passageways, a current lished feed rate is fed into the current fresh feed of the plantas fresh feed to the plant, and a set desired treatment feed rate in the introduction source "a) or as a Supplement to an alternate the plant. introduction source "a) to the plant. 10 12. The method of claim 5 wherein the drawn off distillate 3. The method of claim 1 wherein b) is carried out for is introduced into a fresh feed passageway of the plant and purposes of plant treatment, and varying the established feed wherein there is an introduction of hydrocarbon-based fluid rate includes an adjustment of the established feed rate in that includes introduction of a first and/or second hydrocar association with an introduction of the hydrocarbon-based bon-based fluid, and varying the established feed rate com treatment fluid at least partly derived from an external source 15 prises an introduction of the first and/or second hydrocarbon and wherein said first externally derived hydrocarbon-based treatment fluids, with the introduction of first and/or second treatment fluid is introduced into a closed or semi-closed loop hydrocarbon treatment fluids including both the drawn off at least partly formed by said plant. distillate plus an external source of said first and/or second 4. The method of claim 3 wherein said hydrocarbon-based hydrocarbons placed into combination with the drawn off fluid is a fluid that cleans a heavy deposit in said plant by distillate so as to establish a desired treatment feed rate. removal from a source location in the plant and passing the 13. The method of claim 1 further comprising introducing removed heavy deposit with the cleaning hydrocarbon-based into a closed or semi-closed loop of the petroleum plant, fluid to an outlet of said plant. during the treatment period, the hydrocarbon-based fluid, 5. The method of claim 1 wherein b) is carried out, and the with the hydrocarbon-based fluid being derived from either varying of the established feed rate includes varying the fresh 25 an external source of the hydrocarbon-based fluid, an internal feed rate to the plant by an increase adjustment in the plant plant source of the hydrocarbon-based fluid or both. fresh feed rate from said established feed rate to a level above 14. The method of claim 13 wherein the introduction of the the established feed rate as to generate an additional quantity hydrocarbon-based fluid comprises the introduction of a of distillates relative to a quantity generated at the established hydrocarbon based fluid A and/or a hydrocarbon based fluid feed rate, and the diverting of at least a portion of a flow of said 30 B, with hydrocarbon based fluid Abeing introduced in a ratio combination distillate includes the drawing off at least some comprised between 0% and 100% with respect to a current of an overall quantity of distillate generated from the fresh feed in the plant. increased plant feed rate and the re-introducing of the 15. The method of claim 14 further comprising introducing diverted portion for the purpose of plant treatment includes in said plant hydrocarbon-based fluid B in a ratio comprised introducing the drawn off distillate into a treatment region of 35 between 0.01% and 50% with respect to a current fresh feed said plant. in the plant. 6. The method of claim 5 further comprising passing the 16. The method of claim 1 wherein the diverting of at least diverted flow of said combination distillate, which includes a portion of the flow of said combination distillate comprises said drawn off distillate, through a closed or semi-closed loop passing at least a portion of the combination distillate from a forming at least a portion of said plant and extending through 40 non-treatment, normal, plant operation mode passage route to the treatment region. a treatment mode passage route by feeding combination dis 7. The method of claim 6 wherein said closed or semi tillate into a closed or semi-closed circulation loop at least closed loop of said plant is configured such that drawn off partially passing inside the plant and which closed or semi distillate is re-introduced into a distillation device of the plant closed circulation loop passes the combination distillate which is a source of the initially drawn off distillate and 45 received therein to a different location in the plant than when drawing off a recirculation output of distillate from said dis directed in the non-treatment mode. tillation device following receipt of the re-introduced drawn 17. The method of claim 16 wherein said different location off distillate and passing the recirculation output of distillate in the plant is at a location positioned upstream of plant to the treatment region. equipment to be treated. 8. The method of claim 6 further comprising adjusting a 50 18. The method of claim 16 wherein there is circulated in plant configuration to include the closed or semi-closed loop. the closed or semi-closed loop one or both of a first hydro 9. The method of claim 5 further comprising introducing carbon-based fluid and a second hydrocarbon-based fluid the drawn off distillate to one or more fresh feed rate passage inside the equipment to be treated as part of the introduction ways of the plant such that, upon introduction to the fresh feed ofhydrocarbon-based fluids in the plant, such that a portion of rate passageways of the plant, the introduced drawn off dis 55 the products distilling during said circulation are re-intro tillate provides a source for said introduction of said hydro duced in said closed or semi-closed loop, whereas another carbon-based treatment fluid or a Supplement thereto, and portion of the distillates makes up the petroleum plant pro varying the fresh feed rate includes a lowering of a current duction and/or the normal distillate flow stream. fresh feed rate to the plant such that the lowered fresh feed rate 19. The method of claim 16 wherein there is circulated in plus the additional drawn off distillate passing through one or 60 the closed or semi-closed loop one or both of a first hydro more common passages in the plant Sum to conform with plus carbon-based fluid and a second hydrocarbon-based fluid or minus 60% of the established rate. inside the equipment to be treated, for a time of at least 20 10. The method of claim 9 wherein the sum to conform is minutes, at a temperature comprised between 100° C. and plus or minus 30% of the established rate. 900° C. and at a pressure comprised between 1 bar and 400 11. The method of claim 5 further comprising introducing 65 bar. an increasing amount of the drawn off distillate to one or more 20. The method of claim 1 wherein a treatment Zone clean fresh feed passageways of the plant and varying the fresh feed ing status monitoring criteria associated with a running of US 9,328,300 B2 63 64 said plant is monitored, and wherein the introduction of the solution form, and wherein said first hydrocarbon-based fluid hydrocarbon based fluid includes the circulation within a forms the solvent of said chemical products. closed or semi-closed loop of a first hydrocarbon-based fluid 30. The method of claim 29 wherein in the ratio solvent/ or a first and a second hydrocarbon based fluids, and which chemical products varies in the range: solvent 70%-99.99%, circulation is carried out in repeated fashion until the treat 5 chemical products 0.01%-30%. ment Zone cleaning status monitoring criteria is deemed sat 31. The method of claim 29 wherein the solvent coincides isfactory. with the first hydrocarbon fluid and is internally generated in 21. The method of claim 1 wherein the plant operating said plant and circulated inside the petroleum plant. running conditions during treatment are such that there is 32. The method of claim 1 wherein the treatment is carried continued distillation of fresh feed source material. 10 out according to one of i) injection of a first hydrocarbon fluid introduced from outside of the plant and further intro 22. The method of claim 1 wherein varying the established duced in any part of the plant, upstream a distillation column, feed rate includes, a reduction in the established feed rate by which is thereafter distilled and introduced in any part of the varying the fresh feed rate of the plant to a value comprised plant; ii) internal plant generation of a first hydrocarbon fluid between 40% and below 100% with respect to the design feed 15 produced by distillation at a certain feed rate, followed by the rate, followed by the introduction of the hydrocarbon-based variation of fresh feed rate, the withdrawal of said hydrocar fluid which comprises an introduction of first and/or the sec bon fluid from any part of the plant and the introduction of ond hydrocarbon-based fluid(s) in an amount as to compen said internal plant produced distillate in any part of the plant; sate up to the difference among the rate at which the plant is iii) introduction of the first hydrocarbon fluid according to running and its design feed rate, and so as to manage up to the one or more of the above points i) and ii) and iv) the intro maximum allowable plant distillate flow rate or in any case duction according to iii) together with a second hydrocarbon the distillate flow rate applicable prior to the introduction of fluid which is introduced simultaneously with or subse the first and/or the second hydrocarbon-based fluid(s), such as quently to said first hydrocarbon fluid. to run the plant at the flow rate resulting from the sum: flow 33. The method according to claim 1 wherein the introduc rate of reduced fresh feed--flow rate of the first and/or the 25 tion of the hydrocarbon based fluid comprises the introduc second hydrocarbon-based fluid(s), and wherein said flow tion of a first hydrocarbon fluid or the first and a second rate is equal to or higher to the one prior to the reduction in hydrocarbon fluid, and which first and/or second hydrocar fresh feed rate. bon fluid is or are selected from a group consisting of distil 23. The method of claim 1 wherein the introduction of the lation products from crude oil originating from the petroleum hydrocarbon based fluid comprises introduction in the plant 30 plant and/or being anyway present in the petroleum plant, by of a first and a second hydrocarbon-based fluid from separate being finished products, blending components of finished sources, and which second hydrocarbon-based fluidjoins and products, intermediate products or feed to the petroleum plant passes together with the first hydrocarbon-based fluid to a and are selected from the group consisting of gasoline, die common treatment introduction point of the petroleum plant. sel, gas oil, Virgin naphtha, kerosene, reformed gasoline, 24. The method of claim 1 wherein the treatment is carried 35 pyrolysis gasoline, pyrolysis gas oil, light cycle oil from out in a plant with a furnace and wherein the treatment FCCU, decant oil from FCCU, methyl-tert-butyl-ether increases a value setting for a furnace inlet temperature of the (MTBE), benzene, toluene, xylenes, cumene, methanol, furnace, and/or for reducing or avoiding the increase of a cyclohexane, cyclohexanone, ethylbenzene, linear alkylben value setting for the tube metal temperature of the furnace, Zene (LAB), dimethylterephthalate, phtalic anhydride, sty existing at the point of initiation of the treatment. 40 rene, tert-amyl-methyl-ether (TAME), ethanol, dimethylfor 25. The method of claim 1 wherein the treatment increases mamide (DMF), dioctylphthalate, isopropyl alcohol, butyl the plant distillation yield in a manner beyond the quantity alcohol, allyl alcohol, butylglycol, methylglycol, ethyl-tert derivable from an equal overall feed amount to the plant butyl-ether (ETBE), ethanolamines, acetone, octyl alcohol, distillation source(s) at a point of treatment initiation. methyl-ethyl-ketone (MEK), methyl-isobutyl-ketone 26. The method of claim 1 wherein the treatment reduces 45 (MIBK), crude oil, fuel oil, quench oil from Ethylene Unit, plant catalysts agglomeration and/or reduces coke formation aromatic gasoline from Reforming Unit, benzene/toluene? on plant catalysts and/or reduces heavy compounds deposits, xylenes (BTX) as produced by an Aromatic Extraction Unit including coke, on plant catalysts and/or reduces differential (inclusive of the Sulfolane, Furfural, Glycols or Formylmor pressure in a plant reactor containing a catalyst. pholine type), the gasoline and/or the gas oil produced in an 27. The method of claim 1 wherein the hydrocarbon-based 50 Ethylene Unit (pyrolysis gasoline/gas oil). fluid used for the treatment is recovered or reused in a way 34. The method according to claim 33 wherein the first selected from the group consisting of i) routing as a blend and/or the second hydrocarbon fluid is or are used in combi component of a fuel/heavy oil; ii) routing to a crude tank; iii) nation with one or more compounds, as a standalone or mix routing to slop; iv) routing inside the petroleum plant con ture thereof, selected from the group consisting of poly taining the equipment which has (have) been treated; v) rout 55 methacrylates, polyisobutylene Succinimmides, ing to another petroleum plant; and (vi) any combination or polyisobutylene Succinates; laurylacrylate/hydroxyethyl subcombination of (i) to (V). methacrylate copolymer; alkylarylsulfonates, alkanolamine 28. The method of claim 1 wherein the hydrocarbon based alkylarylsulfonates and alkylarylsulfonic acids; substituted fluid includes the introduction of one or both of a first hydro amines, where the Substituent is anhydrocarbon containing at carbon-based fluid and a second hydrocarbon fluid that is or 60 least 8 carbon atoms; acylated compounds containing nitro are capable of Solubilizing the deposits in said equipment to gen and having a Substituent with at least 10 aliphatic carbon be treated essentially under near critical or Supercritical con atoms, such substituent being obtained by reaction of an ditions at the operating conditions of the plant. acylant carboxylic acid with at least an aminic compound 29. The method of claim 28 wherein the first hydrocarbon containing at least a group-NH-, said acylant agent being based fluid contains one or more chemical products and said 65 joined to said aminic compound by way of a imido, amido, first hydrocarbon-based fluid and said chemical products are amidine or acyloxyammonium bridge; nitrogen containing mixed in a proportion designed in order to be utilized in a condensated compounds of a phenol, an aldehyde or an US 9,328,300 B2 65 66 aminic compound, having at least a group —NH-; esters of quinoline and isoquinoline; the term “hydrocarbyl Substitu a substituted carboxylic acid; hydrocarbyl substituted phe ent” refers to a group having a carbon atom directly attached nols; alkoxylated derivatives of an alcohol, a phenol or an to the rest of the molecule and having a hydrocarbon or amine; phthalates; organic phosphates; oleic acids esters; predominantly hydrocarbon character, as e.g. the hydrocar diethylhydroxylamine; glycols and/or their derivatives, said 5 bon groups, including aliphatic, (e.g. alkyl or alkenyl), alicy glycols and/or their derivatives being not in a polymeric form, clic (e.g. cycloalkyl or cycloalkenyl), aromatic, aliphatic in the sense that they are molecules of single compounds, also and/or alicyclic-substituted aromatic, condensated aromatic; in an adduct form, and not molecules constituted by a chain aliphatic groups are preferably Saturated, as e.g.: methyl, where a single monomer is repeated, e.g.: tetraethylenegly ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, octa col; mono- and di-ethers, mono- and di-esters, ether-esters 10 decyl cyclohexyl, phenyl, said groups may also contain non and thioethers of single glycols; glycol of general formula hydrocarbon substituents provided they do not alter the pre CH-OH (CH), OH, CHOH where n=0-10; glycol ethers dominantly hydrocarbon character of the group, e.g. the of general formula R—O—CH2—CH2—O—R where R groups selected from: keto, hydroxy, nitro, alkoxy, acyl, Sul is an hydrocarbyl substituent C-C and R is H atom or an phonic, Sulphoxid, Sulphur, amino, said groups may also or hydrocarbyl Substituent C-Co., glycol esters of general for 15 alternatively contain atoms other than carbon in a chain or mula R-O-O CH-CH -O-O-R, where R is an ring otherwise composed of carbon atoms, e.g. heteroatoms hydrocarbyl Substituent C-C and R is Hatom or anhydro selected from the group of nitrogen, oxygen and Sulfur. carbyl Substituent C-Co.; thioglycols of general formula 35. The method of claim 1 wherein the introduction of the HO—R—S—R OH where R is anhydrocarbyl substitu hydrocarbon based treatment fluid includes the introduction ent C-C and R is H atom or an hydrocarbyl Substituent in the petroleum plant of a first hydrocarbon-based fluid in a C-Co., glycol ethers-esters of general formula R—O— ratio comprised between 0.1% and 100% with respect to CH, CH, O O—R where RandR are anhydrocarbyl current plant fresh feed and a second hydrocarbon-based fluid Substituent C-C ethers of general formula R—O—R in a ratio comprised between 0.01% and 50% with respect to where R or R is an hydrocarbyl Substituent C-Co.; Substi a current plant fresh feed; and tuted benzenes of general formula 25 wherein the second hydrocarbon fluid is selected from the group consisting of methanol, ethanol, propanol, iso propanol, butanol, isobutanol, methylglycol monometh ylether, butylglycol monobutylether, toluene, aliphatic amines Cs' ethoxylated with at least 6 moles ethylene 30 oxide, arylsulfonates, benzene, diphenyl, phenanthrene, Rn nonylphenol, 1-methyl-2-pyrrolidinone, diethyl ether, dimethylformamide (DMF), tetrahydrofuran (THF), ethylenediamine, diethylamine, triethylamine, trim where n=1-6 and R can be indifferently Hatom, —OH group, ethylamine, propylamine, 1-(3-aminopropyl)-2-pyrroli —COOH group, —CHO group, —NH group, —HSO 35 done, 1-(3-aminopropyl) imidazole, N-hydroxyethyl group, the same or different hydrocarbyl substituent C-Co. imidazolidinone, N-aminoethyl-imidazolidinone, 2-(2- ketones of general formula R—CO—R where R or R is an aminoethylamino)ethanol, isopropylamine, cumene, 1, hydrocarbyl Substituent C-Co., anhydrides of general for 3, 5 trimethylbenzene, 1, 2, 4 trimethylbenzene, maleic mula R—CO O—CO R, included those where R and anhydride, p-toluidine, o-toluidine, dipropylamine, Rare bound together to form cyclic anhydrides, where R or 40 diphenyl ether, hexamethylbenzene, propylbenzene, R is an hydrocarbyl substituent C-Co., amides of general cyclohexylamine, 1-isopropyl-4-methyl-benzene, 1, 2, formula 3, 5 tetramethylbenzene, hexanol, morpholine, o-Xy lene, m-Xylene, p-Xylene, butylamine, methylamine, mesitylene, examine. Succinic anhydride, decahy 45 dronaphthalene, ethylbenzene, 1, 2 dimethylnaphtha lene, 1, 6 dimethylnaphthalene, p-cymene, ethyl ether, isopropyl ether, etoxybenzene, phenyl ether, acetophe none, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethyleneglycol, tri 50 ethyleneglycol, tetraethyleneglycol, hexyl glycol, dode where R. R. R. are indifferently H atom or an hydrocarbyl cylbenzene, lauryl alcohol, myristyl alcohol, thiodigly Substituent C-Co.; heterocyclic compounds, preferably of col, dioctylphthalate, disooctylphthalate, the hydrogenated type, containing from 0 to 3 hydrocarbyl didecylphthalate, diisodecylphthalate, dibutylphthalate, Substituent C-Co. heterocyclic compounds selected from dinonylphthalate, methylethylketone (MEK), methyl the group consisting of furans, pyrrols, imidazoles, triazoles, 55 isobutylketone (MIBK), methyl-tert-butyl-ether oxazoles, thiazoles, oxadiazoles, pyranes, pyridine, (MTBE), cyclohexane, cyclohexanone, methyl- or pyridazine, pyrimidine, pyrazine, piperazine, piperidine, tri ethyl-esters of fatty acids achieved by esterification of azines, oxadiazines, morpholine, indane, indenes, benzo Vegetal and/or animal oils (biodiesel); dimethylamine, furanes, benzothiophenes, indoles, indazole, indoxazine, ethylamine, ethyl formate, methyl acetate, dimethylfor benzoxazole, anthranile, benzopyran, coumarins, quinolines, 60 mamide (DMF), propanol, propylamine, isopropy benzopyrones, cinnoline, quinazoline, naphthyridine, lamine, trimethylamine, tetrahydrofuran (THF), ethyl pyrido-pyridine, benzoxazines, carbazole, Xanthene, acri vinyl ether, ethyl acetate, propyl formate, butanol, dine, purine, benzopyrroles, benzothiazoles, cyclic amides, methyl propanol, diethyl ether, methylpropyl ether, iso benzoquinolines, benzocarbazoles, indoline, benzotriazoles; propyl methyl ether, diethyl sulfide, butylamine, isobu including all the possible compounds configurations, includ 65 tylamine, diethylamine, diethylhydroxylamine, cyclo ing the iso-form: e.g. the term “dithiols” is meant to include pentanol, 2-methyltetrahydrofuran, tetrahydropyran, 1.2 dithiol and 1.3 dithiol, “quinolines” is mean to include pentanal, isobutyl formate, propyl acetate, pentanoic US 9,328,300 B2 67 68 acid, butyl methyl ether, tert-butyl methyl ether, ethyl Zoic anhydride, 2-benzoyl-methyl benzoate, benzyl ben propyl ether, methylpyridines, methylcyclopentane, Zoate, 4-tolyl benzoate, benzophenone, 4,4'-bis cyclohexanol, hexanal, pentyl formate, isobutyl acetate, (dimethylamino) benzophenone, 2,2'- 2-ethoxyethyl acetate, methyl pentyl ether, dipropyl dihydroxybenzophenone, 2,2'-dimethylbenzophenone, 4,4'- ether, diisopropyl ether, hexanol, methyl pentanols, tri dimethylbenzophenone, methylbenzophenone, 2-amino ethylamine, dipropylamine, diisopropylamine, benzal benzyl alcohol, 3-hydroxybenzyl alcohol, C.-1-naphthylben dehyde, toluene, cresols, benzyl alcohol, methyla Zyl alcohol, benzyl-ethyl-phenyl-amine, benzylaniline, ben nilines, dimethylpyridines, furfural, pyridine, Zyl ether, phenylacetophenone, 2-acetamide diphenyl, methylcyclohexane, heptanol, acetophenone, ethylben 2-amino diphenyl, 4,4'-bis(dimethylamino) diphenyl, biphe Zene, Xylenes, ethylphenols, Xylenols, anilines, dim 10 nol, butyl-bis(2-hydroxyethyl)amine, butylphenylamine, ethylaniline, ethylaniline, octanenitrile, ethyl pro butylphenylketone, carbazole, diphenylcarbonate, cetyl alco panoate, methylbutanoate, methyl isobutanoate, propyl hol, cetylamine, benzylcinnamate, coumarin, lindane, diben propanoate, ethyl 2-methyl propanoate, methyl pen Zofuran, dibenzylamine, diethylene glycol dibenzyl ether, tanoate, heptanoic acid, octanoic acid, 2-ethylhexanoic diethylene glycol monolaurate, diethylene glycol (2-hydrox acid, propyl 3-methylbutanoate, octanoles, 4-methyl-3- 15 ypropyl) ether, diethylenetriamine, di-O-naphthylamine, di heptanol, 5-methyl-3-heptanol, 2-ehtyl-1-hexanol, B-naphthylamine, dioctylamine, diphenylamine, diphenyl dibutyl ether, di-tert-butyl ether, dibutylamine, diisobu methane, 4,4'-diamino diphenyl, 4,4'-dimethylamino tylamine, quinoline, isoquinoline, indane, cumene, pro diphenyl, 4-hydroxy diphenyl, diphenylmethanol, diphenyl pylbenzene, 1,2,3-trimethylbenzene, 1, 2, 4, -trimethyl ethylamine, di-(C-phenylethyl) amine, di-iso-propanola benzene, mesitylene, o-toluidine, N,N-dimethyl-o- mine, di-2-tolylamine, eicosanol. 1.1.2 triphenylethane, eth toluidine, nonanoic acid, nonanols, naphthalene, ylene glycol 1.2 diphenyl, ethyl-di-benzylamine, ethylene butylbenzene, isobutylbenzene, cymenes, p-diethylben glycol monobenzyl ether, ethylene glycol monophenyl ether, Zene, 1,2,4,5-tetramethylbenzene, decahydronaphtha N,N-diphenylformamide, phenylformamide, tolylforma lene, decanoic acid, decanol. 1-methylnaphthalene, car mide, 2-benzoylfurane, 2.5 diphenylfurane, and related bazole, diphenyl, hexamethylbenzene, dodecanols, 25 esters, heptadecylamine, heptadecanol, cetyl alcohol, hexa diphenylmethane, tridecanols, tetradecanols, hexade decanamine, cethylic alcohol, hydroxyethyl-2-tolylamine, canols, heptadecanols, terphenyls, octadecanols, triethanolamine, cyclohexanone, imidazole, methylimida eicosanols; fatty amines and their mixtures, p-toluidine, Zole, phenylimidazole, 5-amino-indane, 5-hexyl-indane, toluene, dipropylamine, diisobutyl acetate, propyl 1-phenyl-1,3,3-trimethyl-indane, 2.3 diphenyl-indene, acetate, propyl-ethyl-ether, triethylamine, ethylben 30 indole, 2.3 dimethyl-indole, tryptamine, 2-phenyl-indo le. Zene, propylbenzene, butylbenzene, cumene, para-Xy isocoumarin, diethyl-isophthalate, isoquinoline, benzyl lau lene, hexamethylbenzene, triethanolamine, diphenyl rate, phenyl laurate, lauryl alcohol, lauryl amine, lauryl sul methane, MTBE, dioctylphthalate, diisodecylphthalate, phate, diethyl-benzyl-malonate, melamine, diphenyl diisoctylphthalate, nonylether, methyloleate, dio methane, triphenylmethane, 4 benzyl-morpholine, 4-phenyl ctylether; the compounds named in plural refer to all 35 morpholine, 4-(4 tolyl)-morpholine, myristic alcohol, 9,10 possible isomers of said compound: e.g. the term dihydro-naphthacene, acetyl-naphthalene, benzyl “Xylenes' indicated o-Xylene, m-Xylene, p-Xylene; said naphthalene, butyl-naphthalene, dihydro-naphthalene, compounds can also be used under Supercritical condi dihydroxy-naphthalene, methyl-naphthalene, phenyl-naph tions. thalene, naphthol, naphthylamine, methylnaphthylamine, 36. The method according to claim 35 wherein the second 40 naphthylphenalamine, C.-naphthyl-2-tolyl-Ketone, nona hydrocarbon fluid comprises one or more compound(s) work cosanol, octadecanol, octyl-phenyl-ether, pentadecylamine, ing as Swelling agent selected from those forming hydrogen pentadecanol, 3-hydroxyacetophenone, tyramine, 4-hydrox bonds and those not forming hydrogen bonds, wherein the yphenylacetonitrile, o-phenylenediamine, N-phenyl-phe Swelling agents not forming hydrogen bonds are selected nylenediamine, 4-methyl-phenylenediamine, diphenylether, from the group consisting of benzene, toluene, cyclohexane, 45 bis-(2-phenylethyl)amine, phosphine derivatives as phenyl, naphthalene, diphenyl, Xylene, tetralin, methylcyclohexane: triphenyl and oxide, triphenylphosphite, dibutyl phthalate, and wherein the Swelling agents forming hydrogen bonds are dibenzyl phthalate, diethyl phthalate, dioctyl phthalate, selected from the group consisting of pyridine, methanol, diisoctyl phthalate, didecyl phthalate, diphenyl phthalate, ethanol, ethylenediamine, propanol, 1,4-dioxane, acetone, phthalic anhydride, N-benzoylpiperidine, 1,3-diphenoxypro formamide, aniline, tetrahydrofuran, N,N-dimethylaniline, 50 pane, N-(2-tolyl)propionamide, 1-methyl-3-phenyl-pyrazo diethylether, dimethylsulphoxide, acetophenone, dimethyl line, pyridine derivatives as 3-acetamido, 3-benzyl, 4-hy formamide, ethyl acetate, methylacetate, methylethylketone, droxy, 2-phenyl, phenylsuccinic anhydride. Succinimide, 1-methyl-2-pyrrolidone, quinoline. N-benzylsuccinimide, N-phenylsuccinimide, o-terphenyl, 37. The method of claim 1 wherein the introduction of the m-terphenyl, 1.14 tetradecanediol, tetradecanol, tetraethyl hydrocarbon based treatment fluid includes the introduction 55 eneglycol, tetraethylenepentamine, 2,5-diaminotoluene, 3.5- in the petroleum plant of a first hydrocarbon-based fluid in a dihydroxytoluene, 4-phenyltoluene, p-toluenesulfonic acid ratio comprised between 0.1% and 100% with respect to and related methyl and propyl esters, o-toluic acid and related current plant fresh feed and a second hydrocarbon-based fluid anhydride, N-benzyl-toluidine (o-, m- ep-), tribenzylamine, in a ratio comprised between 0.01% and 50% with respect to tributylamine, triethanolamine, triethyleneglycol and related a current plant fresh feed; and wherein the second hydrocar 60 monobutylether, trihepylamine, trioctylamine, tripheny bon fluid comprises one or more compound(s) having a boil lamine, tritane, tritanol, 2-pyrrolidone, Xanthene, Xanthone, ing temperature >150° C. selected from the group selected of: xylidine. anthraquinone, eicosanol, benzalacetophenone, benzan 38. Method according to claim 1 further comprising moni thracene, hydroquinone, dodecylbenzene, hexaethylbenzene, toring treatment level and wherein the monitoring is per hexamethylbenzene, nonylbenzene, 1,2,3-triaminobenzene, 65 formed with one or more analysis method selected from the 1,2,3-trihydroxybenzene, 1,3,5-triphenylbenzene, diphenyl group consisting of Viscosity (e.g. ASTM D 445); density methanol, p-benzidine, benzil, 2-benzoylbenzofurane, ben (e.g. ASTM D1298); atmospheric or vacuum distillation (e.g. US 9,328,300 B2 69 70 ASTM D86, D1160); carbon residue (e.g. ASTM D4530, D ent Cs-Co and M is the ion H. Na, Ca, ammonium, trietha 189); sediments by hot filtration (e.g. IP375, 390); sediments nolammonium, isopropylammonium; dialkylsulfoSuccinates by extraction (e.g. ASTM D473); sediments by filtration (e.g. of general formula ROCCHCH(SONa)COR wherein Ris ASTM 4807); ash (e.g. ASTM D482, EN6245); asphaltene an hydrocarbyl Substituent C-Co.; alkylsulfates of general (e.g. IP143), color (e.g. ASTM D1500), water and sediments formula ROSOM wherein R is an hydrocarbyl substituent (e.g. ASTM D2709, D1796); or an analysis method of the Cs-Co and M is the ion Sodium, ammonium, triethanolam physical type, selected from the group consisting of i) evalu monium; ethoxylated and Sulphated alcohols of general for ation of the fouling factor, defined as the ratio among the heat mula R—(—OCHCH2-)-OSOM wherein R is an hydro transfer coefficient of clean equipment and the heat transfer carbyl Substituent Cs-Co. n=1-5 and M is the ion Sodium, coefficient of the equipment at the time when the value is 10 recorded; ii) evaluation of pressure in various points of the ammonium, triethanolammonium; ethoxylated and Sul plant; iii) evaluation of temperature in various points of the phated alkylphenols of general formula RCH (— plant. OCHCH ), OSOM wherein R is an hydrocarbyl sub 39. Method according to claim 1 further comprising the stituent Cs-Co., n-1-5 and M is the ion Sodium, ammonium, following steps to achieve gas free/safe entry conditions: 15 triethanolammonium; ethoxylated alcohols of general for a) Suspension of feed introduction; mula R—(—O CHCH ), OH wherein R is an hydro b) optional circulation in a closed or semi-closed loop of carbyl substituent Cs-Co. n=1-30; ethoxylated alkyl phenols the first and/or second hydrocarbon fluid inside the of general formula RCH (—OCHCH ), OH equipment to be treated, for a time of at least 20 minutes, wherein R is an hydrocarbyl substituent Cs-Co. n=1-40; at a temperature comprised between 100° C. and 900°C. mono- and di-fatty acids glyceric esters whereinacid contains and at a pressure comprised between 1 bar and 400 bar; an hydrocarbyl substituent Co-Ca.; mono- and di-polyoxy c) cooling of the equipment/plant; ethylene esters of oils and fatty acids of general formula d) emptying of the equipment/plant from all of the hydro RCO—(—OCH ), OH and RCO-(—OCH ), carbons; OOCR wherein the oil is of the “tall oil” or “rosin oil” type, e) introduction of water inside the equipment/plant; 25 n=1-40 and the acid contains and hydrocarbyl substituent f) implementing a closed circulation loop encompassing Co-Cao; ethoxylated "castor oils” (castor oil is a triglyceride the equipment/plant; abundant in ricinoleic esters) containing a number of poly g) introduction in the closed circulation loop of one or more ethoxylated ethylene oxide groups variable between 5 and chemical washing/cleaning products and their mixtures; 200; mono- and di-ethanolamides of fatty acids of general h) setting up the temperature and the pressure inside the 30 closed circulation loop at values comprised between 60° formula RCONHCHOOCR and RCON(CHOH) C. and 350° C. and between 1 bar and 50 bar; CHOOCR wherein R is an hydrocarbyl substituent Co i) circulation of the water solution of the chemical Co., Surfactants of poly(oxyethylene-co-oxypropylene), also product(s) inside the closed circulation loop under con known as block polymer, having molecular weight of ditions of temperature and pressure comprised between 35 50-10000; mono-, di- and poly-aliphatic amines derived from 60° C. and 350° C. and between 1 and 50 bar, for a time fatty acids, such as RNHCHCHCH-NH wherein R is an comprised between 20 minutes and 60 days; hydrocarbyl substituent Co-Cao: N-alkyltrimethylendi j) cooling (including the eventual introduction of fresh amines of general formula water in the loop) and emptying of the loop from the water solution; 40 R k) optional routing of the water solution to the oily water treatment plant; 1) optional repeating of the steps from e) to k). ses 40. Method according to claim39 wherein the steps from e) to k) are replaced by the steps: 45 m) introduction inside of the apparatus/plant of steam at a pressure comprised between 1.5 bar and 100 bar; wherein R is an hydrocarbyl substituent C10-C40; 2-alkyl-2- n) introduction in said steam of one or more washing/ imidazolines of general formula cleaning chemical product(s) including their mixtures; o) introduction inside of the equipment/plant of the mix 50 R ture steam/chemical product(s) according to present invention, for a time of at least 20 minutes, 1. p) optional circulation of condensed steam, containing a N1 YNCHNH chemical product; q) emptying of condenses from the equipment/plant; 55 r) optional routing of condenses to the oily water treatment wherein R is an hydrocarbyl substituent C10-C40; amine plant. oxides of general formula RNO(CH3)2 and RNO 41. The method according to claim 40 wherein the chemi (C2H4OH)2 wherein R is an hydrocarbyl substituent cal product used for washing/cleaning is selected from the C1-C20; ethoxylated alkylamines of general formula group consisting of non-ionic Surfactants, anionic Surfac 60 tants, terpenes derivatives, emulsifiers, hydrogen Sulphide Scavengers, mercury scavengers and their mixtures in any (CHO).H proportion, including their aqueous solutions. A 42. Method according to claim 41 wherein the anionic and RN non-ionic Surfactants are selected from the group consisting 65 of alkyl-, aryl-, or alkylaryl-benzensulphonates of general formula RCHSOM wherein R is an hydrocarbyl substitu US 9,328,300 B2 71 72 wherein m+n=2-40; 2-alkyl-1-(2-hydroxyethyl)-2-imidazo phated alkylphenols of general formula RCH (— lines of general formula OCHCH ), OSOM wherein R is an hydrocarbyl sub stituent Cs-Co., n-1-5 and M is the ion Sodium, ammonium, triethanolammonium; ethoxylated alcohols of general for R mula R-(-O CHCH ), OH wherein R is an hydro carbyl substituent Cs-Co. n=1-30; ethoxylated alkyl phenols N 1. NC, H, OH of general formula RCH (—OCH2CH2—), OH wherein R is an hydrocarbyl substituent Cs-Co. n=1-40; mono- and di-fatty acids glyceric esters whereinacid contains 10 wherein R is an hydrocarbyl substitutent C10-C40: alkoxy an hydrocarbyl Substituent Co-Co., mono- and di-polyoxy lated ethylendiamines of general formula ethylene esters of oils and fatty acids of general formula RCO—(—OCH ), OH and RCO-(—OCH ), OOCR wherein the oil is of the “tall oil” or “rosin oil” type, 15 n=1-40 and the acid contains and hydrocarbyl substituent H--OCH2CH2-) (OCH),w cho-CHCHO-H Co-Cao; ethoxylated “castor oils” (castor oil is a triglyceride NCH2CHN M V abundant in ricinoleic esters) containing a number of poly H--OCH2CH2-), (OCH), (C.H.O),-(CH2CH2O)-H ethoxylated ethylene oxide groups variable between 5 and 200; mono- and di-ethanolamides of fatty acids of general wherein X and y=4-100: formula RCONHCHOOCR and RCON(CHOH) terpenic products derivatives are selected from the group CHOOCR wherein R is an hydrocarbyl substituent Co consisting of limonene, pinene, canfor, menthol, Cao, Surfactants of poly(oxyethylene-co-oxypropylene), also eucalipthol, eugenol, geraniol, thymol; emulsifiers are known as block polymer, having molecular weight of selected from the group consisting of Tween 60, Tween 50-10000; mono-, di- and poly-aliphatic amines derived from 80, nonyl phenol polyethylene glycol ether, oleates, Sor 25 fatty acids, such as RNHCHCHCH-NH wherein R is an bitan oleates, glycerol monostearate, nonyl phenol hydrocarbyl substituent Co-C: N-alkyltrimethylendi ethoxylates, iso-propyl palmitate, polyglycerol esters of amines of general formula fatty acids, tridecyl alcohol ethoxylates, fatty alcohol ethoxylates, linear alkylbenzene Sulphonic acid, dioctyl 30 R phthalate, sodium tripolyphosphate, citric acid, soybean oleic acid, trisodium phosphate, sodium dodecyl sulfate, didecyl dimethyl ammonium chloride, oleic acid dietha es nolamine, dodecyl dimethylbenzil ammonium chloride, Sodium acetate, oleamide, polyethylene glycols, lanolin, 35 ethoxylated (E20) sorbitan monooleate, sorbitan wherein R is an hydrocarbyl substituent C10-C40; 2-alkyl-2- monooleate, Sulfo Succinamates; H S Scavengers are imidazolines of general formula Selected from the group consisting of diethanolamine, monoethanolamine, methyl-diethanolamine, diisopro pylamine, formaldehyde, maleimides, amidines, polya 40 R midines, glyoxal, Sodium nitrite, reaction products of polyamide-formaldehyde, triazines, carboxamides, alkylcarboxyl-azo compounds, compounds, bisoxazo 1s, H. NH lidines, glycidyl ethers, potassium formate; mercury Scavenger are selected from the group consisting of: 45 thiourea, caustic Soda, Sodium carbonate, trimercapto wherein R is an hydrocarbyl substituent C10-C40; amine S-triazine trisodium salt. oxides of general formula RNO(CH3)2 and RNO 43. The method according to claim 39 wherein the chemi (C2H4OH)2 wherein R is an hydrocarbyl substituent cal product used for washing/cleaning is selected from the C1-C20; ethoxylated alkylamines of general formula group consisting of non-ionic Surfactants, anionic Surfac 50 tants, terpenes derivatives, emulsifiers, hydrogen Sulphide Scavengers, mercury scavengers and their mixtures in any proportion, including their aqueous solutions. 44. Method according to claim 43 wherein the anionic and non-ionic Surfactants are selected from the group consisting 55 of alkyl-, aryl-, or alkylaryl-benzensulphonates of general wherein m+n=2-40; 2-alkyl-1-(2-hydroxyethyl)-2-imidazo formula RCHSOM wherein R is an hydrocarbyl substitu lines of general formula ent Cs-Co and M is the ion H. Na, Ca, ammonium, trietha nolammonium, isopropylammonium; dialkylsulfoSuccinates of general formula ROCCHCH(SONa)COR wherein Ris 60 R an hydrocarbyl substituent C-Co.; alkylsulfates of general formula ROSOM wherein R is an hydrocarbyl substituent es. HOH Cs-Co and M is the ion sodium, ammonium, triethanolam monium; ethoxylated and Sulphated alcohols of general for mula R—(—OCH2CH2-), OSOM wherein R is an hydro 65 carbyl Substituent Cs-Co. n=1-5 and M is the ion Sodium, wherein R is an hydrocarbyl substituent C10-C40; alkoxy ammonium, triethanolammonium; ethoxylated and Sul lated ethylendiamines of general formula US 9,328,300 B2 73 74 same point and re-introduced in the same equipment to be H-(OCH2CH2. (OCH), (CHO)-(CH2CHO)-H treated for a time necessary to treat said equipment. NCHCHN 48. The apparatus of claim 47 wherein withdrawal means H-OCHCH-(OCH)1 (CHO),-(CH2CH2O)-H are located in one or more point(s) of the plant that is (are) 5 selected from the group consisting of: wherein X and y=4-100; Suction/discharge of a produced gasoline pump; terpenic products derivatives are selected from the group Suction/discharge of an overhead reflux pump; consisting of limonene, pinene, canfor, menthol, eucalipthol, Suction/discharge of one or more bottom/middle/top eugenhol, geraniol, thymol; emulsifiers are selected from the pumparound pump(s): group consisting of Tween 60, Tween 80, nonyl phenol poly 10 Suction/discharge of a produced kerosene pump; ethylene glycol ether, oleates, Sorbitan oleates, glycerol Suction/discharge of a produced gas oil pump; monostearate, nonyl phenol ethoxylates, iso-propyl palmi Suction/discharge of any distilled hydrocarbon pump; tate, polyglycerol esters of fatty acids, tridecyl alcohol hydrocarbon line exiting any petroleum apparatus; ethoxylates, fatty alcohol ethoxylates, linear alkyl benzene 15 Suction/discharge of a crude oil booster pump at desalter Sulphonic acid, dioctyl phthalate, sodium tripolyphosphate, outlet; citric acid, soybean oleic acid, trisodium phosphate, sodium any combination or Sub-combinations for the items listed dodecyl sulfate, didecyl dimethyl ammonium chloride, oleic above; acid diethanolamine, dodecyl dimethyl benzil ammonium wherein introduction means are located in one or more chloride, sodium acetate, oleamide, polyethylene glycols, point(s) of the plant selected from the group consisting of lanolin, ethoxylated (E20) sorbitan monooleate, sorbitan Suction/discharge of a plant feed pump; monooleate, SulfoSuccinammates; H S Scavengers are Suction/discharge of a crude oil booster pump at desalter selected from the group consisting of diethanolamine, mono outlet; ethanolamine, methyl-diethanolamine, diisopropylamine, Suction/discharge of a column bottom pump; formaldehyde, maleimides, amidines, polyamidines, gly 25 Suction/discharge of a heavy gas oil pump; oxal, Sodium nitrite, reaction products of polyamide-formal inlet of an preheat train; dehyde, triazines, carboxamides, alkylcarboxyl-azo com inlet of an equipment to be treated; pounds, cumene-peroxide compounds, bisoxazolidines, distillation residue line, upstream/downstream of any heat glycidyl ethers, potassium formate; mercury Scavenger are exchanger, selected from the group consisting of thiourea, caustic soda, 30 Sodium carbonate, trimercapto-s-triazine trisodium salt. column bottom; 45. A petroleum plant apparatus to perform the method in a pump external of the plant, being part of another plant according to claim 1 comprising: i) withdrawal means from or installed on purpose, in temporary or permanent one or more point(s) in the petroleum plant of one or more execution; hydrocarbon fluid(s); ii) introduction means of said one or 35 any combination or Sub-combinations for the items listed more hydrocarbon fluid(s) as above withdrawn into one or above; more point(s) of the petroleum plant; iii) distillation means of wherein distillation means are located in one or more said one or more hydrocarbon fluid(s) as above introduced point(s) of the petroleum plant selected from the group into one or more point(s) of the petroleum plant; iv) re consisting of: withdrawal and re-introduction means of said one or more 40 atmospheric distillation column; hydrocarbon fluid(s) as above distilled to re-withdraw said vacuum distillation column; distilled fluid(s) and re-introduce it (them) into one or more extractive distillation column; point(s) of the petroleum plant, wherein said re-withdrawal any combination or Sub-combinations for the items and re-introduction means can be the same withdrawal and listed above; introduction means as above; v) connection means in order to 45 and wherein the withdrawal point(s) and the introduction form a closed or semi-closed loop, encompassing the equip point(s) of said one or more hydrocarbon fluid(s) are con ment to be treated, wherein said one or more hydrocarbon nected to form a closed or semi-closed loop. fluid(s) will be continuously distilled, withdrawn and intro 49. A method of designing a plant for carrying out the duced; vi) a discharge system of the hydrocarbon fluid(s), to method of claim 1 wherein the equipment subject to treatment allow their removal from the closed or semi-closed loop; vii) 50 is designed Such that there is avoided inputting into the equip control means, to control or regulate temperature and/or pres ment an equal to or greater than 20% fouling factor as well as sure and/or flowrate; viii) optional filtration means. presentment of fouling backup equipment in the plant design. 46. The apparatus of claim 45 wherein said withdrawal 50. A method of manufacturing of a plant for carrying out means has the one or more withdrawal points positioned as to the method of claim 1 comprising rendering into a physical withdraw one or more hydrocarbon fluid(s) having the fol 55 plant based on a plant design wherein the equipment Subject lowing intervals of boiling points: a) up to 75° C.; b) from 75° to treatment is designed Such that there is avoided inputting C. to 175° C.; c) from 175° C. to 350° C.; d) above 350° C.: into the equipment an equal to or greater than 20% fouling and wherein introduction means introduce the one or more factor as well as presentment of fouling backup equipment in withdrawn hydrocarbon fluid(s) in any one or more point(s) the plant design. of the plant. 60 51. The method of claim 50 wherein the treated equipment 47. A petroleum plant apparatus to perform the method has a surface from 0.1% to 100% lower with respect to a according to claim 1 comprising a distillate source wherein a non-treated equipment. distillate from said distillate source is withdrawn from a point 52. The method of claim 1 wherein the hydrocarbon-based within a closed or semi-closed loop forming at least a portion treatment fluid is utilized and is limited to an internal-to-plant of said plant, and an entry point wherein there is introduced 65 originated distillation product that is circulated and recircu upstream of equipment to be treated the drawn off distillate lated within the plant to a treatment Zone upstream or down and then redistilled to be thereafter re-withdrawn from the stream from the distillation source location of the plant. US 9,328,300 B2 75 76 53. The method of claim 1, further comprising plant, to a minimum operation rate which is set at a level varying the fresh feed rate to the plantinassociation witha) for satisfying a minimum production operating state in and/or b). the petroleum plant; 54. The method of claim 1 wherein, following distilling wherein said introduction of a hydrocarbon-based treat said additional source or sources for distillation for the pur ment fluid and/or said variation to the established feed pose of plant treatment, distillate source or sources used for rate generates an additional source or sources for distil plant treatment are circulated and recirculated continuously lation with respect to the amount provided by the estab and without interruption within the plant until output from the lished rate present at initiation of treatment; and plant with output plant product. distilling said additional Source or sources for distillation 55. The method of claim 1 wherein said introduction of a 10 for the purpose of plant treatment, and hydrocarbon-based treatment fluid includes that which is wherein the petroleum plant runs, relative to a pre-existing sourced from a distillation device of the plant; and distilling fresh feed rate, at an increased fresh feed rate that is said additional source or sources for distillation for the pur below a design fresh feed rate of the plant, or at the pose of plant treatment is carried out within the distillation 15 design fresh feed rate, or higher than the design fresh device. feed rate, so as to produce an increased amount of dis 56. The method of claim 1 wherein the additional source or tillates, and, thereafter, varying the fresh feed rate to the sources of distillate is associated with a variation to the fresh plant by progressively reducing the fresh feed rate. Such feed rate being fed into the plant, and wherein there is a that the increased amount of produced distillates, with re-introduction of distillate to another point in the plant respect to the amount of distillates produced with the through a closed or semi-closed loop associated with the pre-existing fresh feed rate, is circulated in parts of the plant, and wherein the plant runs continuously and without plant to be treated. interruption both during and between production of the addi 64. A method for treating a petroleum plant or equipment tional Source or sources and the reintroduction of distillate. of the petroleum plant during a running of the petroleum 57. The method of claim 1 wherein the process stream 25 plant, comprising: involved in the formation of the combination distillate com maintaining, during a treatment period, the petroleum plant prises fresh feed of the plant. under a production operating condition, typical of the 58. The method of claim 1 wherein, in the step of passing plant itself, while providing fresh feed to the petroleum the diverted stream containing combination distillate to the plant; process stream, the diverted stream containing combination 30 while maintaining the petroleum plant under the produc distillate is fed through a closed or semi-closed loop, at least tion operating condition, introducing, during the treat partly formed by said plant, to the process stream of the plant. ment period, a hydrocarbon-based treatment fluid into a 59. The method of claim 1 wherein the relative concentra closed or semi-closed loop forming at least part of the tion of the distillates forming the combination distillate is the 35 petroleum plant with the hydrocarbon-based fluid being same in each of the continuation stream and the diverted derived from either an external source of the hydrocar stream after diversion. bon-based fluid, an internal plant source of the hydro 60. The method of claim 1 wherein the diverted stream is carbon-based fluid or both; and placed in contact with equipment of the plant positioned in the varying a fresh feed rate to the petroleum plant in conjunc plant treatment Zone and upstream of a distillation unit that 40 tion with the introduction of the hydrocarbon-based forms the combination distillate. treatment fluid. 61. The method of claim 1 wherein the combination distill 65. The method of claim 64 wherein varying a fresh feed late is formed by a first distillation unit and the combination rate to the petroleum plant in conjunction with the introduc distillate stream formed by the first distillation unit is directed tion of the hydrocarbon-based treatment fluid includes an to a separation unit as to recover Some or all of the hydrocar 45 initial reduction in an established feed rate of the plant to a bon-based treatment fluid for the purpose of plant treatment. value comprised between 40% and below 100% with respect 62. The method of claim 1 wherein the diverted stream is to the design feed rate, followed by the introduction of the subjected to a second distillation and then hydrocarbon-based hydrocarbon-based fluid which comprises an introduction of treatment fluid is separated out from the second distilled first and/or the second hydrocarbon-based fluid(s) in an diverted stream for the purpose of plant treatment. 50 amount as to compensate up to the difference among the rate 63. A method for treating a petroleum plant or equipment at which the plantis running and its design feed rate, and so as of the petroleum plant during a running of the petroleum to manage up to the maximum allowable plant distillate flow plant, comprising: rate or in any case the distillate flow rate applicable prior to maintaining, during a treatment period, the petroleum plant the introduction of the first and/or the second hydrocarbon under a production operating condition, typical of the 55 based fluid(s), such as to run the plant at the flow rate resulting plant itself, which includes providing fresh feed to the from the sum: flow rate of reduced fresh feed--flow rate of petroleum plant; the first and/or the second hydrocarbon-based fluid(s), and while maintaining the petroleum plant under the produc wherein said flow rate is equal to or higher to the one prior to tion operating condition, there is carried out one or both the reduction in feed rate. ofa) and b); 60 66. The method of claim 64 wherein the internal plant a) introducing in the petroleum plant, during the treatment source of the hydrocarbon-based fluid is a distillation column period, a hydrocarbon-based treatment fluid; and distillate from the column is sent to a treatment region of b) varying an established feed rate, present at initiation of the plant upstream or downstream from said distillation col the treatment of the petroleum plant or equipment of the l petroleum plant, which established feed rate ranges 65 67. A method for treating a petroleum plant or equipment from a maximum operation rate for the petroleum plant, of the petroleum plant during a running of the petroleum which is inclusive of a design rate for the petroleum plant, comprising: US 9,328,300 B2 77 78 maintaining, during a treatment period, the petroleum plant acteristics to circulate said distillate(s) and/or said prod under a production operating condition, typical of the uct exiting the plant inside the closed or semi-closed plant itself, while providing fresh feed to the petroleum loop and/or in one or more selected point(s) in the plant, plant; said lines and/or connections being already part of said while maintaining the petroleum plant under the produc- 5 petroleum plant, or installed on purpose, or in mobile tion operating condition, introducing in the petroleum and/or temporary execution; plant, during the treatment period, a hydrocarbon-based a discharge system of the fluids, to allow their removal treatment fluid; and from the closed or semi-closed loop: adjusting of the fresh feed by increasing the plant fresh feed gauges and/or controllers of temperature, pressure, flow rate from an established feed rate to a level above the 10 established feed rate as to generate an additional quan rate; and tity of distillates relative to a quantity generated at the Valves and/or sectioning and/or non-return systems. established feed rate, and drawing offat least some of an 69. The method of claim 67 further comprising passing overall quantity of distillate generated from the said drawn off distillate through a closed or semi-closed loop increased plant feed rate and introducing the drawn off 15 forming at least a portion of said plant and extending through distillate into a treatment region of said plant for the the treatment region, and wherein said closed or semi-closed purpose of cleaning deposits from one or more pieces of loop of said plant is configured such that drawn off distillate equipment in the treatment region. is re-introduced into a distillation device of the plant which is 68. A petroleum plant apparatus to perform the method a source of the initially drawn off distillate and drawing off a according to claim 67, comprising: 2O recirculation output of distillate from said distillation device one or more withdrawal point(s) of a distillate or mixtures following receipt of the re-introduced drawn off distillate and of distillates: passing the recirculation output of distillate to the treatment one or more introduction point(s) of a distillate or mixtures region. of distillates, as previously withdrawn; 70. The method of claim 67 wherein the petroleum plant one or more introduction point(s) of a first and/or second 25 runs, relative to a pre-existing fresh feed rate, at an increased hydrocarbon fluid; fresh feed rate that is below a design fresh feed rate of the one or more pump(s) connected to said withdrawal point(s) plant, or at the design fresh feed rate, or higher than the design of distillate(s) and/or of the product(s) exiting the plant, fresh feed rate, so as to produce an increased amount of having sufficient characteristics to introduce said distil distillates, thereafter progressively reducing the fresh feed late(s) and/or said product(s) exiting the plant in the 30 rate. Such that the increased amount of produced distillates, closed or semi-closed circulation loop and/or in one or with respect to the amount of distillates produced with the more selected point(s) of the plant, said pump(s) being pre-existing fresh feed rate, is circulated in parts of the plant already part of said petroleum plant, or installed on to be treated. purpose, or in mobile and/or temporary execution: 71. The method of claim 67 wherein the treatment region is an inlet system of an hydrocarbon fluid or mixtures of 35 upstream or downstream from a distillation device from hydrocarbon fluids, to allow the introduction of said which distillate is sourced, and wherein introducing the hydrocarbon fluid(s) in the closed or semi-closed loop: drawn off distillate into a treatment region of said plant is one or more lines and/or connection systems to close the carried out in a continuously re-circulating manner and closed or semi-closed loop comprising the withdrawal removes heavy deposits from one or more pieces of equip point(s) and/or introduction point(s) of the distillate(s), 40 ment in the treatment region. the pump(s) and the equipment, having sufficient char