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

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(12) United States Patent (10) Patent No.: US 9,328,300 B2 Ferrara (45) Date of Patent: May 3, 2016 USOO9328300B2 (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 - a g s2 US 9,328,300 B2 Page 2 (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 (Ee* (Esls* ()(Ele se 8 U.S. Patent May 3, 2016 Sheet 2 of 15 US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 3 of 15 US 9,328,300 B2 - a s as a r on + on ge x y as 7 s e. s s - H-1 2 g A. J s()), DT" U.S. Patent US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 5 Of 15 US 9,328,300 B2 gelnöt-, U.S. Patent May 3, 2016 Sheet 6 of 15 US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 7 Of 15 US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 8 of 15 US 9,328,300 B2 E. s:B E E 3 s sS.w 5. : x3 is 3 ; 3. in II ) U.S. Patent May 3, 2016 Sheet 9 Of 15 US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 10 of 15 US 9,328,300 B2 is (E) S.() U.S. Patent May 3, 2016 Sheet 11 of 15 US 9,328,300 B2 'S U.S. Patent May 3, 2016 Sheet 12 of 15 US 9,328,300 B2 U.S. Patent US 9,328,300 B2 U.S. Patent May 3, 2016 Sheet 14 of 15 US 9,328,300 B2 119 509 |19 109' 109 U.S. Patent May 3, 2016 Sheet 15 Of 15 US 9,328,300 B2 !€).· |-------{}){---+---+---+---+---+---+---+---------------------------------------------+ ·gp3Jn51-? 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.
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