US 20l00l46845Al (19) United States (12) Patent Application Publication (10) Pub. N0.2 US 2010/0146845 A1 Burgazli et al. (43) Pub. Date: Jun. 17, 2010
(54) ADDITIVE COMPOSITIONS FOR (30) Foreign Application Priority Data CORRECTING OVERTREATMENT OF CONDUCTIVITY ADDITIVES IN Sep. 12, 2006 (US) ...... 035589 PETROLEUM FUELS
P . . . . (75) Inventors: Cenk R. Burgazli, MiddletoWn, DE ubhcatlon Classl?catlon (US); Cyrus P. Henry, Avondale, (51) Int- Cl PA (Us) C10L 1/192 (2006.01) C10L 1/222 (2006.01) Correspondence Address: C10L 1/24 (2006.01) BURNS & LEVINSON, LLP C10L 1/26 (2006.01) 125 SUMMER STREET C10L 1/188 (2006.01) BOSTON, MA 02110 (US) C10L 1/19 (2006.01) (73) Assignee: INNOSPEC FUEL SPECIAL U.S...... 44/386; .. 44/417; 44/418; 44/422; 44/435 (21) Appl. No.: 12/441,028 (22) PCT Filed: Sep. 27, 2006 (57) ABSTRACT (86) PCT NO; PCT/Us06/37255 Disclosed herein are methods for correcting fuel oil compo sitions having excess conductivity. The oil compositions § 371 (0X1), comprise a Petroleum Based Component, a Conductivity (2), (4) Date; Oct. 1, 2009 additive and a Conductivity Correcting Additive.
Conductivity Responece Stadis (R) 425
E 1400 i i 5 g_ 1200 l g 1000 - El Fuel with 10 mg/l of ‘*3 800 ~ Conductivity Additive % e00 - i1 5 400 _ III Conductivity Additive + 2 200 _ 200 mg/l of Conductivity g 0 Correcting Additive LL “ Ill Conductivity. . Additive. . + ‘l, 400 mg/l of Conductivity '\o" Correcting. Additive. .
Conductivity Correcting Additive
T 9125 is a product produced by Baker Petrolite; it is believed to be mono fatty amide MCC 2200 - is a product produced by Lubrizol corp, it is believed to be an fatty acid R-69O is a product produced by Infenium; it is believed to be a dimmer trimer fatty acid di ester 011 9070 x - is a product produced by Innospec, it is believed to be a alkyl succinic diester T-9l27 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide T-9l37 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide Patent Application Publication Jun. 17, 2010 Sheet 1 0f 2 US 2010/0146845 A1
Conductivity Responece Stadis (R) 425
El Fuel with 10 mg/l of pS/mConductivityFuel Conductivity Additive ill Conductivity Additive + 200 mg/l of Conductivity Correcting Additive [Ii Conductivity Additive + 400 mg/l of Conductivity Correcting Additive
Conductivity Correcting Additive
T 9125 is a product produced by Baker Petrolite; it is believed to be mono fatty amide MCC 2200 ~ is a product produced by Lubrizol c0rp., it is believed to be an fatty acid R-69O is a product produced by Infenium; it is believed to be a dimmer trimer fatty acid di ester 011 9070 X - is a product produced by Innospec, it is believed to be a alkyl succinic diester T-9127 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide T-9l37 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide
FIG. 1 Patent Application Publication Jun. 17, 2010 Sheet 2 0f 2 US 2010/0146845 A1
Tolad 3514 Responce
I] Fuel with 10 mg/l of pSImConductivityFuel Conductivity Additive iii Conductivity Additive + 200 mg/l of Conductivity Correcting Additive I] Conductivity additive + 400 mg/ Conductivity Correcting Additive Conductivity Correcting Additive
T 9125 is a product produced by Baker Petrolite; it is believed to be mono fatty amide MCC 2200 - is a product produced by Lubrizol corp., it is believed to be an fatty acid R-690 is a product produced by Infenium; it is believed to be a dimmer trimer fatty acid di ester 011 9070 x - is a product produced by Innospee, it is believed to be a alkyl succinic diester T-9127 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide T-9137 - is a product produced by Baker Petrolite, it is believed to be fatty mix ester amide
FIG. 2 US 2010/0146845 A1 Jun. 17, 2010
ADDITIVE COMPOSITIONS FOR ganic solvents and cleaning ?uids) are inherently poor con CORRECTING OVERTREATMENT OF ductors. Static charge accumulates in these ?uids because CONDUCTIVITY ADDITIVES IN electric charge moves very sloWly through these liquids and PETROLEUM FUELS can take a considerable time to reach a surface Which is grounded. Until the charge is dissipated, a high surface-volt CROSS-REFERENCE TO RELATED age potential can be achieved Which can create an incendiary APPLICATIONS spark, resulting in an ignition or an explosion. [0001] This application claims priority of International [0010] The risk of static discharge ignition is further com Application No. PCT/US06/35589, ?led Sep. 12, 2006, pounded by the neWly enacted legislation designed to Which is incorporated herein in its entirety by reference. improve emissions characteristics from combustion of fossil fuels. FIELD OF THE INVENTION [0011] In order to meet emissions and fuel e?iciency goals, automotive original equipment manufacturers (OEM’s) are [0002] This invention relates generally to fuel oil compo investigating the use of NOx traps, particulate traps and direct sitions, and particularly relates to additives Which can be injection technologies. Such traps and catalyst systems tend utilized to correct excessive conductivity in hydrocarbon to be intolerant to sulfur. This coupled With the demonstrated fuels. The invention further relates to a method of using such adverse environmental consequences of burning sulfur rich compositions. fuels has resulted in a global effort to reduce the sulfur content of fuels (Reference World-Wide Fuel Charter, April 2000, BACKGROUND OF THE INVENTION Issued by ACEA, Alliance of Automobile Manufacturers, the [0003] A critical issue confronting the hydrocarbon fuel entire teaching of Which is incorporated herein by reference). industry is the introduction of Ultra LoW Sulfur (ULS) fuels. These loW sulfur and ultra-loW sulfur fuels are becoming The processes utiliZed to diminish sulfur content of fuels can increasingly necessary to ensure compliance With emissions also affect other fuel properties. A fuel property Which is requirements over the full useful life of the latest technologi directly impacted by such processes is fuel Electrostatics. cal generation of vehicles. Governments are also introducing [0004] Fuel electrostatics is the ability of a hydrocarbon to further legislation for the reduction in particulate matter and transport or dissipate charge accumulated in the material. fuel emissions. Fuel electrostatics directly affects the probability of an inci [0012] In the United States, the Environmental Protection dent (?re or explosion) due to Static Discharge Ignitions Agency (EPA) regulations require the sulfur content of on (SDI). The real risk associated With SDI is a paramount safety road fuel to meet Ultra LoW Sulfur speci?cation, speci?cally concern for the fuel industry. less than 15 ppm by mass of sulfur in the ?nished fuel. Similar [0005] The risks associated With SDI are Well documented. regulations are also in place globally. In the 1980’s and 1990’s the American Petroleum Institute [0013] The method most commonly utiliZed to reduce the (API) compiled reports of road tanker explosions in Europe sulfur content of fuels is described as hydro treating. Hydro folloWing the introduction of LoW Sulfur Diesel (LSD), treating is a process by Which hydrogen, under pressure, in the despite the use of grounding leads. These incidents Were presence of a catalyst, reacts With sulfur compounds in the speci?cally attributed to static charge induced ignition of fuel fuel to form hydrogen sul?de gas and a hydrocarbon. HoW vapor during fuel transfer operations. ever, hydro treating to reduce sulfur content results not only in [0006] Electrostatics: It is Widely knoWn that electrostatic the removal of sulfur from the fuel but also the removal of charges can be frictionally transferred betWeen tWo dissimi other polar compounds Which normally increase the conduc lar, nonconductive materials. When this occurs, the electro tivity characteristics of the fuel. static charge thus created appears at the surfaces of the con [0014] Generally, a non-hydro treated fuel has conductivity tacting materials. The magnitude of the generated charge is in the range of l 0 to about 30 pS/m2, Whereas, a hydro treated dependent upon the nature of and, more particularly, the fuel (below 15 ppm limit) is normally below 1 pS/m2. Con respective conductivity of each material. The potential for ductivity beloW <3 pS/m greatly increases the risk of cata electrostatic ignition and explosion is probably at its greatest strophic electrostatic ignition. (KattenWinkel, H. D., Electri during product handling, transfer, and transportation. cal Conductivity, Will a minimum level be required for all loW [0007] Electrostatic charging is knoWn to occur during sol S fuels in the future, 2nd CEN/TC l9 Symposium Automo vent or fuel pumping operations. In such operations, the ?oW tive Fuels, 2003. Walmsley, H. L. An assessment of electro of loW conductivity liquid through conduits With high surface static ignition risks and ?lling rules for loading road tankers area or through “?ne” ?lters combined With the disintegration With loW sulfur diesel, Institute of Petroleum, November of a liquid column and splashing during high speed tank 2000; the entire teachings of Which are incorporated herein by loading can result in static charging. Such static charging can reference). result in electrical discharge (spark) With catastrophic poten [0015] In order to correct the detrimental effects of hydro tial in highly ?ammable environments. treating, re?neries and fuel handlers are routinely utiliZing [0008] Countermeasures designed to prevent accumulation Static Dissipaters/Conductivity Improvers. These additives of electrostatic charges on a container being ?lled such as When used properly minimize the risk of electro static ignition container grounding (i.e., “ear‘thing”) and bonding are rou in hydrocarbon fuels and solvents. There is a great Wealth of tinely employed. HoWever, it has been recogniZed that knoWledge and experience regarding the use of Static Dissi grounding and bonding alone are insu?icient to prevent elec paters/ Conductivity Improver additives (ASTM D-4865 trostatic build-up in loW conductivity organic liquids. Standard Guide for Generation and Dissipation of Static [0009] Organic liquids such as distillate fuels (diesel, gaso Electricity in Petroleum Fuel Systems, and API Recom line, jet fuel, turbine fuels, home heating fuels, and kerosene) mended Practice 2003iProtection Against Ignition Arising and relatively contaminant free light hydrocarbon oils (or Out Of Static, Lightening, and Spray Currents; the entire US 2010/0146845 A1 Jun. 17, 2010
teachings of Which are incorporated herein by reference). The fuel in many cases canbe subjected to further processing such diversity of additives Which have been patented and utilized hydrogen-treatment or other processes to improve fuel prop in the fuel industry exempli?es the importance of risk asso erties. The material can be described as a gasoline or middle ciated With ignition due to static discharge. distillate fuel oil. [0016] As a consequence of the re?nery processes [0026] Gasoline is a loW boiling mixture of aliphatic, ole employed to reduce Diesel sulfur and aromatics content, the ?nic, and aromatic hydrocarbons, and optionally, alcohols or majority of Diesel fuels marketed today Will require treat other oxygenated components. Typically, the mixture boils in ment With additives to restore fuel electrical conductivity. the range from about room temperature up to about 225° C. [0027] Middle distillates can be utiliZed as a fuel for loco BRIEF SUMMARY OF THE INVENTION motion in motor vehicles, airplanes, ships and boats as burner [0017] The present invention is directed to compositions fuel in home heating and poWer generation and as fuel in and methods for correcting fuel oil compositions having multipurpose stationary diesel engines. excess conductivity. The oil compositions can comprise a [0028] Engine fuel oils and burner fuel oils generally have Petroleum Based Component, a Conductivity Additive and a ?ash points greater than 38° C. Middle distillate fuels are Conductivity Correcting Additive. higher boiling mixtures of aliphatic, ole?nic, and aromatic [0018] In another aspect, additional additives can be uti hydrocarbons and other polar and non-polar compounds hav liZed With the conductivity correcting additive added such as: ing a boiling point up to about 3500 C. Middle distillate fuels (a) loW temperature operability/cold ?oW additives, (b) cor generally include, but are not limited to, kerosene, jet fuels, rosion inhibitors, (c) cetane improvers, (d) detergents, (e) and various diesel fuels. Diesel fuels encompass Grades No. lubricity improvers, (f) dyes and markers, (g) anti-icing addi 1-Diesel, 2-Diesel, 4-Diesel Grades (light and heavy), Grade tives, (h) demulsi?ers/ anti haZe additives, (i) antioxidants, (j) 5 (light and heavy), and Grade 6 residual fuels. Middle dis metal deactivators, (k) biocides, and (1) thermal stabiliZers tillates speci?cations are described inASTM D-975, for auto The invention further describes a method of using such com motive applications (the entire teaching of Which is incorpo positions formulations. rated herein by reference), and ASTM D-396, for burner applications (the entire teaching of Which is incorporated BRIEF DESCRIPTION OF THE DRAWINGS herein by reference). [0029] Middle distillates fuels for aviation are designated [0019] FIG. 1 is a graphical representation of the effect of by such terms as JP-4, JP-5, JP-7, JP-8, Jet A, Jet A-1. JP-4 lubricity additives on Stadis® 425 conductivity response. and JP-5. The Jet fuels are de?ned by US. military speci? [0020] FIG. 2 is a graphical representation of the effect of cation MIL-T-5624-N, the entire teaching of Which is incor lubricity additives on T 3514 conductivity response. porated herein by reference and J P-8 is de?ned by US. Mili [0021] In describing the embodiments of the invention, tary Speci?cation MIL-T83133-D the entire teaching of speci?c terminology Will be resorted to for the sake of clarity. Which is incorporated herein by reference. Jet A, Jet A-1 and HoWever, it is not intended that the invention be limited to the Jet B are de?ned by ASTM speci?cation D-1655 and Def. speci?c term so selected, and it is to be understood that each Stan. 91 91 the entire teachings of Which are incorporated speci?c term includes all technical equivalents Which operate herein by reference. in a similar manner to accomplish a similar purpose. The [0030] These petroleum fuels as described can comprise technical equivalence of the additional terms Will be readily blends With Bio based fuels. The bio based components as recogniZed by a person Who is skilled in the art pertaining to part of the fuel blend are commonly knoWn as Bio Diesel. Bio this invention. Diesel as de?ned by ASTM speci?cation D-6751 (the entire teachings of Which are incorporated herein by reference) is a DETAILED DESCRIPTION OF THE INVENTION fatty acid mono alkyl esters of vegetable or animal oils. Com [0022] The present invention is directed to fuel oil compo mon oils used in Bio Diesel production are Rapeseed, Soya, sitions, comprising a Petroleum Based Component, a Con Palm TalloW, Sun?ower, and used cooking oil or animal fats. ductivity Additive, and a Conductivity Correcting Additive to [0031] The different fuels described (Engine fuels, Burner correct excess fuel Conductivity. Disclosed herein are suit fuels and Aviation Fuels) each have further to their speci?ca able Conductivity Correcting Additive compositions and tion requirements (ASTM D-975, ASTM D-396 and D-1655 methods directed toWard the utiliZation of these Conductivity respectively) alloWable sulfur content limitations. These limi Correcting Additive composition. tations are generally on the order of up to 15 ppm of sulfur for [0023] Petroleum Based Component: In the present On-Road fuels, up to 500 ppm of sulfur for Off-Road appli embodiment, a Petroleum Based Component is a hydrocar cations and up to 3000 ppm of sulfur for Aviation fuels. bon derived from re?ning petroleum or as a product of Fis [0032] Conductivity Additive: Static Dissipaters (SD), cher-Tropsch processes (Well knoWn to those skilled in the Conductivity Improver (CI), or Anti Stats (AS) are de?ned as art). The hydrocarbon may also be a solvent. The fuel prod any chemical species Which are either present or added to ucts are commonly referred to as Petroleum Distillate Fuels. fuels to increase the conductivity or the rate of charge dissi [0024] Petroleum Distillate Fuels encompass a range of pation in such fuels. distillate fuel types. These distillate fuels are used in a variety [0033] The diversity of additives Which have been patented of applications, including automotive diesel engines and in and utiliZed in the fuel industry exempli?es the importance of non on-road applications under both varying and relatively risk associated With ignition due to static discharge. constant speed and load conditions. [0034] The types of Static Dissipaters/ Conductivity [0025] Petroleum Distillate Fuel oils can comprise atmo Improver additives Which have been patented and can be spheric or vacuum distillates. The distillate fuel can contain utiliZed as part of this invention are described as having cracked gas oil or a blend of any proportion of straight run, components derived from the chemical families that include: thermally or catalytically cracked distillates. The distillate aliphatic amines-?uorinated polyole?ns (U .S. Pat. No. 3,652, US 2010/0146845 A1 Jun. 17, 2010
238), chromium salts and amine phosphates (US. Pat. No. results in loss of valuable fuel. The spilled fuel can contami 3,758,283), alpha-ole?n-sulfone copolymer classipolysul nate the environment and must be cleaned up. While both phone and quaternary ammonium salt (US. Pat. No. 3,811, these results have great ?nancial impact on the tank operator, 848), polysulphone and quaternary ammonium salt amine/ they are minor as compared to the safety risks associated With epichlorhydrin adduct dinonylnaphthylsulphonic acid (US. fuel spills. The fuel spilled as a result of tank over?oW can Pat. No. 3,917,466), copolymer of an alkyl vinyl monomer travel great distances from the spill location. The fuel air and a cationic vinyl monomer (US. Pat. No. 5,672,183), mixture associated With spills can be ignited by stray sparks alpha-ole?n-maleic anhydride copolymer class (US. Pat. or even hot automobile exhaust pipes. There are documented Nos. 3,677,725; 4,416,668), methyl vinyl ether-maleic anhy instances of such ?res, a particularly catastrophic example dride copolymers and amines (US. Pat. No. 3,578,421), occurred in a UK. tank farm in 2005 causing billions of alpha-ole?n-acrylonitrile (US. Pat. Nos. 4,333,741; 4,388, dollars in damage. 452), alpha-ole?n-acrylonitrile copolymers and polymeric [0042] The gauges utiliZed to measure volumes in bulk fuel polyamines (US. Pat. No. 4,259,087), and copolymer of an tanks can be affected by the conductivity of the fuel. Many of alkylvinyl monomer and a cationic vinyl monomer and these volume measuring instruments take into consideration polysulfone (US. Pat. No. 6,391,070), an ethoxylated quat the dielectric constant of the fuel When measuring fuel tank (US. Pat. No. 5,863,466), hydrocarbyl monoamine or hydro volumes. The effect of an over conductive fuel can impede the carbyl-substituted poly(alkylenieamine (US. Pat. No. 6,793, function of these devices resulting in erroneous volume read 695), acrylic-type ester-acrylonitrile copolymers and poly ings and possible over ?lling of fuel tanks. meric polyamines (US. Pat. Nos. 4,537,601, 4,491,651), [0043] For the reasons described, it Would be very bene? diamine succinamide reacted With an adduct of a ketone and cial to be able to correct problems associated With fuels hav S02 ([3-sutlone chemistry) (US. Pat. No. 4,252,542), the ing excessive levels of conductivity. entire teachings of Which are incorporated herein by refer [0044] The present invention describes the use of fuel addi ence. tives speci?cally matched to alleviate or correct excess con [0035] As a consequence of EPA ULS regulation and hydro ductivity in fuels. The conductivity control is achieved by the treating required to meet sulfur and aromatics content use of Conductivity Correcting Additives. The Conductivity requirements, the majority of ultra-loW sulfur Diesel fuels Correcting Additives can have a retarding affect on the con marketed today Will require treatment With an electrical con ductivity enhancement by fuel conductivity additives. ductivity additive to ensure safe operation. This Will greatly [0045] Generally, it is desirable to have additives Which do increase the use of static dissipater additives in the general not negatively impact the performance of other additives in fuel market. the fuel. The present invention utiliZes additive chemistries [0036] The use of Conductivity Additives can also become Which on their oWn perform to meet their intended purpose, mandated by current ballot actions in ASTM. The ballot pro but When combined in the desired manner alloW for the dimin poses to modify ASTM D-975 (on road Diesel speci?cation) ishment of excess conductivity in the fuel Without adversely to require conductivity additives to meet a minimum conduc affecting other fuel properties. tivity of 50 pS/m at time of use in all ground fuels. The neW [0046] The invention utiliZes the unexpected interaction speci?cation can also impose an upper limit on fuel conduc betWeen Conductivity Correcting Additives and Conductivity tivity. Additives to correct high levels of conductivity in fuels. [0037] Currently, aviation fuel speci?cation ASTM [0047] Suitable compositions that can serve as a Conduc D-1655 alloWs the use of conductivity additives in US. civil tivity Correcting Additive are components derived from aviation. Conductivity additives are mandated in US. mili chemical families that include: long chain fatty acid, deriva tary speci?cations, EU. military speci?cation (Def Stan. 91 tives of such fatty acids include, but not limited to, salts (both 91) and are also required in civil jet fuels in the rest of the mineral and organic), amides and esters; polymeric analogs World. These speci?cations not only require a minimum con of organic acids knoWn as dimer/trimer acids, derivatives of ductivity in the fuel but also have set a maximum conductivity such polymeric analogs include, but not limited to, salts (both level at Which the fuel is ?t for purpose. Conductivities out mineral and organic), amides and esters; and poly and alkyl side this limit Will make fuel non-conforming to speci?ca amines (Which are generally knoWn as “?lming amines”) and tions. their derivatives such as amides, salts, and oxyalkylates. [0038] It is commonly knoWn that the increased haZard [0048] Suitable Conductivity Correcting Additives consid presented by loW conductivity organic liquids can be dealt ered Within the scope of this invention are described by the With by the use of speci?c additives to increase the conduc general formula: tivity of the respective ?uid. [0039] HoWever, there are conditions in Which elevated levels of conductivity in the fuel can be detrimental to fuel handling and fuel storage equipment Which comes in contact With the fuel. [0040] Excess fuel conductivity has detrimental effects on certain aviation fuel gauges. These gauges are sensitive to fuel conductivity and malfunction With high conductivity fuel. The gauges can record erroneous fuel volume readings Which Wherein, can result in in-?ight loW fuel Warning requiring airplanes to [0049] R1 can be alkyl-linear, branched, saturated, unsat make emergency landings. urated, C140, aromatic, cyclic, polycyclic; [0041] Accurate measurement of fuel volume in terminal or [0050] R2 can be alkyl-linear, branched, saturated, unsat re?nery holding tanks is a critical economic, environmental urated, C140, aromatic, cyclic, polycyclic, H, or analogs and safety issue. Over ?ling of tanks beyond their capacity of R3iNH2 or R3iOH; US 2010/0146845 A1 Jun. 17, 2010
[0051] R3 can be alkyl-linear, branched, saturated, unsat [0061] The use of a Conductivity Correcting Additive as urated, C140, aromatic, cyclic, polycyclic, repeating disclosed in the present invention is unknoWn in the fuel/fuel units based on ethylene, propylene or butylene oxide, or additives industries. Furthermore, the concept of using tWo repeating units based on ethylene, propylene or butylene additives to diminish excess conductivity is also unappreci aZiridine; ated in the fuel and additives industries. [0052] R4 can be alkyl-linear, branched, saturated, unsat [0062] The discovery of this interaction is very important in urated, C140, aromatic, cyclic, polycyclic, H, R3iOH, the fuel industry, speci?cally as it alloWs the correction of alcohol, ester, or an acid; fuels Which may have conductivity beyond acceptable speci [0053] X can be 0, NH, NR1, S, or P; ?cation requirements or equipment tolerances. [0054] Y can be 1-6; and [0063] It is further considered as part of this invention, a [0055] Z can be organic functional groups (H, alco method of decreasing the conductivity of a hydrocarbon fuel hols, aldehydes, ketones, acids, esters, amides, or solvent by metering into the fuel, a suitable Conductivity amines, imides, ester amines, amido amines, imido Correcting Additive. Thus, the invention can be practiced by amines, imidaZolines, carbamates, ureas, imines, and adding to the fuel a mixture of Conductivity Correcting Addi enamines) present on the R1 hydrocarbon backbone. tive and conductivity additive, or by adding to the fuel in succession, the conductivity additive and the Conductivity [0056] Speci?c examples of products Which function as Correcting Additive. Conductivity Correcting Additive are: a condensate product of an alcohol amine and an organic acid, and alkoxylates of [0064] The conductivity and Conductivity Correcting dimeriZed trimeriZed fatty acids. Additive additives can be added in any order, and at any point in the fuel production and handling process. That is, for [0057] Reactions products of an alcohol amine and an example, the conductivity additive can be added at a re?nery organic acid yields a mixture of alcohol amides and ester and the Conductivity Correcting Additive subsequently amines. A common example is described by the reaction: added at a terminal or even at a fueling rack. Another example is the blending of tWo or more fuels Where one fuel contains 0 a conductivity additive and another contains a Conductivity Correcting Additive. A further example is the addition to a NH2 fuel a single or multi component formulation comprising a 1 3 OH HO/\/ conductivity additive and another single or multi component formulation comprising a Conductivity Correcting Additive. 1 [0065] The control of elevated conductivity in fuels Will 0 occur once the additives are present in the fuel, regardless of the method, formulation or order in Which they Were deliv MON“ ered to the fuel. 11 O [0066] The Conductivity Correcting Additive in the formu lation is speci?cally chosen to be present in the fuel oil com position in an amount effective to improve the desired fuel ANNA/OH properties. [0067] The Conductivity Correcting Additive can be added separately to the fuel in amounts from 1 to 10,000 mg/l of [0058] Depicted is a C18 fatty acid hoWever, other chain fuel. It can also be added as part of a conductivity/Conduc length fatty acids (CS-C22) are also applicable. The alcohol tivity Correcting Additive package, or as part of another multi amine depicted is ethanol amine, although other alcohol component package and can eventually be present in the fuel amines such as di ethanol amine and tri ethanol amine can be betWeen 1 to 1000 mg/l. utiliZed. The carbon spacer instead of ethylene can be propy [0068] It is additionally considered as part of the present lene or butylene. The ratio of amide to ester can vary depend invention the combination of the Conductivity Correcting ing of process conditions. Additive described herein With other additives typically used [0059] DimeriZed/TrimeriZed fatty acids are generally in fuel oils, these additives being present in such amounts so described as a mixture of products derived from reactions of as to provide their normal attendant functions. A non exclu unsaturated fatty acids. Chemistries involved in coupling of sive list of these additives are: (a) loW temperature operabil these acids are knoWn as 2+2, Ene, and Dials Alder reactions. ity/cold ?oW additives such as ethylene-unsaturated ester These complex mixtures can subsequently be reacted With copolymers, comb polymers containing hydrocarbyl groups ethylene glycol or ethylene oxide to produce the desired pendant from a polymer backbone, polar nitrogen com Conductivity Correcting Additive. pounds having a cyclic ring system, hydrocarbyl, hydrocar [0060] Currently, the only method available to diminish the bon polymers such as ethylene alpha-ole?n copolymers, level of fuel conductivity is dilution of a high conductivity polyoxyethylene esters, ethers and ester/ether mixtures such fuel With a loW conductivity fuel. Often this type of correction as behenic diesters of polyethylene glycol, (b) corrosion is physically impossible due to large volumes associated, and inhibitors, such as fatty amines, poly amines and amides there lack of free tank space available for dilution. This type of of knoWn as ?lming amines, and polymers of fatty acids dilution is also unavailable if the fuel is being transported via knoWn as dimmer trimer acids, (c) cetane improvers such as a pipeline. A Conductivity Correcting Additive can address 2-ethyl hexyl nitrite (2EHN) and di tert butyl peroxide both pipeline and tank constraint issues by directly being (DTBP), (d) detergents, (e) lubricity improvers, such as com injection either into the tanks or into a pipeline. The Conduc ponents derived from chemical families that include: long tivity Correcting Additive can be handled in the customary chain fatty acid, derivatives of such fatty acids to include salts fashion as other additives currently used in fuels. (both mineral and organic), amides and esters; dimers/trimers US 2010/0146845 A1 Jun. 17, 2010
of fatty acids; and poly and alkyl amines (Which are generally [0070] Corrosion Inhibitors are a group of additives Which known as “?lming amines”) and their derivatives such as are utiliZed to prevent or retard the detrimental interaction of amides, salts, and oxyalkylates, (f) dyes and markers, (g) fuel and materials present in the fuel With engine components. anti-icing additives such as ethylene glycol monomethyl The additives used to impart corrosion inhibition to fuels ether or diethylene glycol monomethyl ether (h) demulsi?ers/ generally also function as lubricity improvers. Examples of anti-haZe additives such as those produced from a phenol and Corrosion Inhibitors marketed by Innospec Inc. of NeWark, an aldehyde under acidic or basic polymerization condition Del. are DCI 6A, and DCI 4A. (industrially knoWn as resoles or novelacs) and their alkoxy [0071] Cetane Improvers are used to improve the combus lated (ethylene, propylene or butylene oxide) products, (i) tion properties of middle distillates. As discussed in Us. Pat. antioxidant compounds such as hindered phenols exempli?ed No. 5,482,518 (the entire teaching of Which is incorporated by 2,6-di-t-butyl-4-methyl phenol (BHT, butylated hydroxy herein by reference) fuel ignition in diesel engines is achieved toluene), 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol, through the heat generated by air compression, as a piston in 2-t-butyl-4-octyl phenol, 2-t-butyl-4-dodecyl phenol, 2,6-di the cylinder moves to reduce the cylinder volume during the t-butyl-4-heptyl phenol, 2,6-di-t-butyl-4-dodecyl phenol, compression stroke. In the engine, the air is ?rst compressed, 2-methyl-6-di-t-butyl-4-heptyl phenol, and 2-methyl-6-di-t then the fuel is injected into the cylinder; as the fuel contacts butyl-4-dodecy-1 phenol, ortho coupled phenols to include the heated air, it vaporiZes and ?nally begins to burn as the 2,2'-bis(6-t-butyl-4-heptyl phenol); 2,2'-bis(6-t-butyl-4-octyl self-ignition temperature is reached. Additional fuel is phenol), and 2,2'-bis(6-t-butyl-4-dodecyl phenol), Where injected during the compression stroke and the fuel burns BHT is suitable, as are 2,6- and 2,4-di-t-butylphenol and almost instantaneously, once the initial ?ame has been estab 2,4,5- and 2,4,6-triisopropylphenol for use in jet fuels, (j) lished. Thus, a period of time elapses betWeen the beginning metal deactivators such as (1) BenZotriaZoles and derivatives of fuel injection and the appearance of a ?ame in the cylinder. thereof, for example, 4- or 5-alkylbenZotriaZoles (e.g. tolu This period is commonly called “ignition delay” and must be triaZole) and derivatives thereof; 4,5,6,7-tetrahydrobenZot relatively short in order to avoid “diesel knock”. A major riaZole and 5,5'-methylenebisbenZotriaZole, Mannich bases contributing factor to diesel fuel performance and the avoid of benZotriaZole or tolutriaZole, e. g. 1-[bis(2-ethylhexyl)ami ance of “diesel knock” is the cetane number of the diesel fuel. nomethyl]tolutriaZole, 1 - [bis(2 -ethylhexyl)amin-omethyl] Diesel fuels of higher cetane number exhibit a shorter ignition benZotriaZole, and alkoxyalkylbenZotriaZoles such as delay than do diesel fuels of a loWer cetane number. There 1 -(nonyloxymethyl) -benZotriaZole, 1 -(1 -butoxyethyl)benZo fore, higher cetane number diesel fuels are desirable to avoid triaZole and 1-(1-cyclohexyloxybutyl)-tolutriaZole, (2) 1,2,4 diesel knock. Most diesel fuels possess cetane numbers in the triaZoles and derivatives thereof, for example, 3-alkyl(or range of about 40 to 55. A correlation betWeen ignition delay aryl)-1,2,4-triaZoles, and Mannich bases of 1,2,4-triaZoles, and cetane number has been reported in “HoW Do Diesel Fuel such as 1-[bis(2-ethylhexyl)aminomethyl-1,2,4-triaZole; Ignition Improvers Work” Clothier, et al., Chem. Soc. Rev, alkoxyalkyl-1,2,4-triaZoles such as 1-(1-butoxytheyl)-1,2,4 1993, pg. 101 -108. Cetane improvers have been used for triZole, and acylated 3-amino-1,2,4-triaZoles, (3) ImidaZole many years to improve the ignition quality of diesel fuels. derivatives, for example 4,4'-methylenebis(2-undecyl-5-me Example of a Cetane Improvers marketed by Innospec Inc. of thylimidaZole) and bis[(N-methyl)imidaZol-2-yl]carbinol NeWark Del. is CI-0801. octyl ether (4) Sulfur-containing heterocyclic compounds, for [0072] Detergents are additives Which can be added to example 2-mercaptobenZothiaZole, 2,5-dimercapto-1,3,4 hydrocarbon fuels to prevent or reduce deposit formation, or thiadiaZole and derivatives thereof, and 3,5-bis[di(2-ethyl to remove or modify formed deposits. It is commonly knoWn hexyl)aminomethyl]-1,3,4-thiadiaZolin-2-o-ne, and (5) that certain fuels have a propensity to form deposits Which Amino compounds and imino compounds, such as N,N' may cause fuel injectors to clog and affect fuel injector spray disalicylidene propylene diamine (DMD), salicylaminogua patterns. The alteration of fuel spray patterns may cause non nadine and salts thereof, (k) biocides, (1) thermal stabiliZers. uniform distribution and/or incomplete atomiZation of fuel [0069] LoW temperature operability/cold ?oW additives are resulting in poor fuel combustion. The accumulation of used in fuels to enable users and operators to handle the fuel deposits is characterized by overall poor drivability including at temperatures beloW Which the fuel Would normally cause hard starting, stalls, rough engine idle and stumbles during operational problems. Distillate fuels such as diesel fuels tend acceleration. Furthermore if deposit build up is alloWed to to exhibit reduced ?oW at loW temperatures due in part to proceed unchecked, irreparable harm may result Which may formation of Waxy solids in the fuel. The reduced How of the require replacement or non-routine maintenance. In extreme distillate fuel affects transport and use of the distillate fuels in cases, irregular combustion could cause hot spots on the re?nery operations and internal combustion engine. This is a pistons Which can resulted in total engine failure requiring a particular problem during the Winter months and especially in complete engine overhaul or replacement. Examples of northern regions Where the distillates are frequently exposed Detergents marketed by Innospec Inc. of NeWark, Del. are to temperatures at Which solid formation begins to occur in DDA 350, and OMA 580. the fuel, generally knoWn as the cloud point (ASTM D 2500) [0073] Lubricity improver’s increase the lubricity of the or Wax appearance point (ASTM D 3117). The formation of fuel, Which impacts the ability of the fuel to prevent Wear on Waxy solids in the fuel Will in time essentially prevent the contacting metal surfaces in the engine. A potential detrimen ability of the fuel to How, thus plugging transport lines such as tal result of poor lubricating ability of the fuel can be prema re?nery piping and engine fuel supply lines. Under loW tem ture failure of engine components (for example, fuel injection perature conditions during consumption of the distillate fuel, pumps). Examples of Lubricity Improvers marketed by Inno as in a diesel engine, Wax precipitation and gelation can cause spec Inc. of NeWark, Del. are OLI 9070.x, and OLI9101.x. the engine fuel ?lters to plug resulting in engine inoperability. [0074] Fuel lubricity is the ability of the fuel to prevent Example of LoW temperature operability/cold ?oW marketed Wear on contacting metal surfaces. Certain diesel engine by Innospec Inc. of NeWark, Del. is PPD 8500. designs rely on fuel as a lubricant for their internal moving US 2010/0146845 A1 Jun. 17, 2010
components. The problem of poor lubricity in these fuels is and engine system, 60 to 70° C. (140 to 175° F.), but the fuel likely to be exacerbated by future engine system develop is subjected to these higher temperatures for shorter periods ments aimed at further decreasing emissions. This Will result of time than in normal storage, and 3) In (or near) the in an increase in the fuel oil lubricity requirement relative to engineiWhere temperatures reach temperatures as high as requirements for present engines. For example, the use of 150° C. (302° F.) before injection or recycling, but for even high pressure unit injectors Will likely increase the need for shorter periods of time. Thermal stability additives protect the better fuel oil lubricity. Fuel lubricity requirements can be fuel uniformity/ stability against these types of exposures. achieved by the use of lubricity additives. Examples of Thermal Stabilizers marketed by Innospec Inc. [0075] Dyes and Markers are materials used by the EPA of NeWark, Del. are FOA 3 and FOA 6. (Environmental Protection Agency) and the IRS (Internal [0082] The invention fully discloses the use of Conductiv Revenue Service) to monitor and track fuels. Since 1994 the ity Correcting Additive additives to control over conductivity principle use for dyes in fuel is attributed to the federally of fuels, by selecting and properly matching a Conductivity mandated dying or marking of untaxed “off-road” middle Correcting Additive to a conductivity additive thereby utiliZ distillate fuels as de?ned in the Code of Federal Regulations, ing their interaction to minimiZe fuel conductivity in order to Title 26, Part 48.4082-1(26 CFR 48.4082-1). Dyes are also meet fuel or operational speci?cations. used in Aviation Gasoline; Red, Blue andYelloW dyes denote [0083] The invention is further described by the folloWing octane grade in Avgas. Markers are used to identify, trace or illustrative but non-limiting example. mark petroleum products Without imparting visible color to the treated product. One of the main applications for markers EXAMPLE in fuels is in Home Heating Oil. Examples of Dyes and Markers marketed by Innospec Inc. of NeWark, Del. are Oil [0084] Conductivity Test Method: Conductivity of the fuel Red B4 and Oil Color IAR. is measured by using procedures outlined in ASTM D-2624 [0076] Anti-Icing Additives are mainly used in the aviation Standard Test Methods for Electrical Conductivity of Avia industry and in cold climates. They Work by combining With tion and Distillate Fuels. The complete method is incorpo any free Water and loWering the freeZe point of the mixture rated herein by reference. that no ice crystals are formed. Examples of Anti-Icing addi tives marketed by Innospec Inc. of NeWark, Del. are Dri-Tech Conductivity Correcting Additive Test Method: and DEGME. [0085] General Additive Survey: The effect on conductivity [0077] Demulsi?ers/Anti HaZe additives are mainly added upon combining other fuel additives With conductivity addi to the fuel to combat cloudiness problems Which maybe tives Was evaluated. A series of additives available in the fuel caused by the distribution of Water in a Wet fuel by dispersant industry Were added to #2 ULS Diesel containing 1 mg/l of used in stability packages. Examples of Demulsi?ers/Anti market available conductivity additives. The additives Which HaZe additives marketed by Innospec Inc. of NeWark, Del. are exhibited the greatest conductivity control response Were DDH 10 and DDH 20. then reevaluated at higher doses of conductivity additive. [0078] Antioxidants are used to inhibit the degradation of [0086] Conductivity Correcting Additive Screen: The base fuels by interaction of the fuel With atmospheric oxygen. This line conductivity of the fuel containing 10 mg/l of conductiv process is knoWn as “Oxidative Instability”. The oxidation of ity additive Was measured. The additives selected from the the fuel results in the formation of alcohols, aldehydes, General Additive Survey Were then dosed into a high conduc ketones, carboxylic acids and further reaction products of tivity fuel (10 mg/l of conductivity additive) at amounts these functional groups, some of Which may yield polymers. equivalent to 200 mg/l, and 400 mg/l. The conductivity of the Antioxidants function mainly by interrupting free radical fuel containing conductivity additive and Conductivity Cor chain reactions thus inhibiting peroxide formation and fuel recting Additive Was then evaluated. degradation. Examples of Antioxidants additives marketed [0087] Static Dissipater I (Stadis® 425): The effect on con by Innospec Inc. of NeWark, Del. are AO 37 and AO 29. ductivity upon combining a Conductivity Correcting Addi [0079] Metal Deactivators are chelating agents that form tive With Stadis® 425 Was evaluated. The conductivity of the stable complexes With speci?c metals. Certain metals (Cop fuel With 10 mg/l of Stadis® 425 along With 200 and 400 mg/l per, Zinc) are very detrimental to fuel stability as they cata of Conductivity Correcting Additive is depicted in FIG. 1. lyZe oxidation processes resulting in fuel degradation (in [0088] Analyses of the conductivity control experiments crease in gums, polymers, color, and acidity). Examples of indicate that Conductivity Correcting Additive T 9125, T Metal Deactivator marketed by Innospec Inc. of NeWark, Del. 9127, T 9137, and R 690 exhibited the best conductivity is DMD. control properties With Stadis® 425 conductivity additive. [0080] Biocides are used to control microorganisms such as [0089] The data clearly exempli?es the need to correctly bacteria and fungi (yeasts, molds) Which can contaminate match Conductivity Correcting Additive and conductivity fuels. Biological problems are generally a function of fuel additive in order to obtain the greatest level of control over system cleanliness, speci?cally Water removal from tanks and high conductivity. loW point in the system. Example of Biocide marketed by [0090] Static Dissipater II (Tolad 3514): The affect on con Innospec Inc. of NeWark, Del. is 6500. ductivity upon combining a Conductivity Correcting Addi [0081] Thermal Stabilizers are additives Which help pre tive With Tolad 3514 Was evaluated. The conductivity of the vent the degradation of fuel upon exposure to elevated tem fuel With 10 mg/l of Tolad 3514 along With 200 and 400 mg/l peratures. Fuel during its use cycle is exposed to varying of Conductivity Correcting Additive is depicted in FIG. 2. thermal stresses. These stresses are: 1) In storageiWhere [0091] Analyses of the conductivity control experiments temperatures are loW to moderate, 0 to 49° C. (32 to 120° F.), indicate that Conductivity Correcting Additive T 9125, and R for long periods of time, 2) In vehicle fuel systemsiWhere 690 exhibited the best conductivity control properties With temperatures are higher depending on ambient temperature Tolad 3415 conductivity additive. US 2010/0146845 A1 Jun. 17, 2010
[0092] The data indicates that it is critical to properly select Z can be organic functional groups (H, alcohols, alde and combine additives to adequately address fuel excess con hydes, ketones, acids, esters, amides, amines, imides, ductivity. ester amines, amido amines, imido amines, imidaZo [0093] All of the compositions and methods disclosed and lines, carbamates, ureas, imines, and enamines) present claimed herein can be manufactured and executed Without on the R1 hydrocarbon backbone. undue experimentation in light of the present disclosure. 7) The fuel oil composition of claim 1, Wherein said Con While the compositions and methods of this invention have ductivity Correcting Additive is present in the fuel betWeen been described in terms of speci?c embodiments, it Will be about 10 to about 10,000 mg/l of fuel. apparent to those of skill in the art that variations may be 8) The fuel oil composition of claim 1, Wherein said Con applied to the compositions and/ or methods and in the steps or ductivity Correcting Additive is present in the fuel betWeen in the sequence of steps of the methods described herein about 50 to about 1000 mg/l of fuel. Without departing from the concept, spirit and scope of the 9) The fuel oil composition of claim 1, Wherein said Con invention. More speci?cally, it Will be apparent that certain ductivity Correcting Additive is present in the fuel betWeen compositions Which are chemically related can be substituted about 50 to about 300 mg/l of fuel. for the compositions described herein While the same or simi 10) The fuel oil composition of claim 1, Wherein said lar results Would be achieved. All such similar substitutes and Conductivity Additive comprises additives selected from the modi?cations apparent to those skilled in the art are deemed group consisting of: alpha-ole?n-sulfone copolymer such as to be Within the spirit, scope and concept of the invention as polysulphone and quaternary ammonium salt, polysulphone de?ned by the appended claims. and quaternary ammonium salt amine/epichlorhydrin adduct What is claimed is: dinonylnaphthylsulphonic acid, copolymer of an alkyl vinyl 1) A fuel oil composition comprising: monomer and a cationic vinyl monomer, alpha-ole?n-maleic a. a Petroleum Based Component, anhydride copolymer class, methyl vinyl ether-maleic anhy b. a Conductivity Additive, and dride copolymers and amines, alpha-ole?n-acrylonitrile, c. a Conductivity Correcting Additive. alpha-ole?n-acrylonitrile copolymers and polymeric 2) The fuel oil composition of claim 1, Wherein said Petro polyamines, and copolymer of an alkylvinyl monomer and a leum Based Component is a middle distillate fuel, a jet fuel, or cationic vinyl monomer and polysulfone, a ethoxylated quat, a Fischer-Tropsch fuel. hydrocarbyl monoamine or hydrocarbyl-substituted poly 3) The fuel oil composition of claim 1, Wherein said Petro alkylenieamine, acrylic-type ester-acrylonitrile copolymers leum Based Component comprises less then about 500 ppm and polymeric polyamines, and diamine succinamide reacted by mass of sulfur. With an adduct of a ketone and S02. 4) The fuel oil composition of claim 1, Wherein said Petro 11) The fuel oil composition of claim 1, Wherein said leum Based Component comprises less then about 15 ppm by Conductivity Additive is present in the fuel betWeen about mass of sulfur. 0.01 to about 100 mg/l of fuel. 5) The fuel oil composition of claim 1, Wherein said Con 12) The fuel oil composition of claim 1, Wherein said ductivity Correcting Additive comprises additives selected Conductivity Additive is present in the fuel betWeen about 0.1 from the group consisting of: organic acids, polymeric ana to about 15 mg/l of fuel. logs of organic acids and their ester or amides derivatives. 13) The fuel oil composition of claim 1, Wherein said 6) The fuel oil component of claim 5, Wherein said Con Conductivity Additive is present in the fuel betWeen about 0.3 ductivity Correcting Additive is represented by general for to about 5 mg/l of fuel. mula: 14) A method of controlling the conductivity of a hydro carbon fuel or solvent by metering into the fuel said Conduc tivity Correcting Additive of claim 5. 15) The method of claim 14, Wherein said Conductivity Correcting Additive and a Conductivity Additive are metered together. 16) The method of claim 14, Wherein said Conductivity Correcting Additive and a Conductivity Additive are metered separately. wherein; 17) The fuel composition of claim 1 further comprising R1 can be alkyl-linear, branched, saturated, unsaturated, additives selected from the group consisting of (a) loW tem C140; aromatic, cyclic, polycyclic; perature operability/ cold ?oW additives, (b) corrosion inhibi R2 can be alkyl-linear, branched, saturated, unsaturated, tors, (c) cetane improvers, (d) detergents, (e) lubricity C140; aromatic, cyclic, polycyclic, H, or analogs of improvers, (f) dyes and markers, (g) anti-icing additives, (h) R3iNH2 or R34OH; demulsi?ers/anti haZe additives, (i) antioxidants, (j) metal R3 can be alkyl-linear, branched, saturated, unsaturated, deactivators, (k) biocides, and (1) thermal stabiliZers. C140; aromatic, cyclic, polycyclic, repeating units based 18) A method of operating an internal combustion engine on ethylene, propylene or butylene oxide, or repeating such as a compression-ignition engine using as fuel for the units based on ethylene, propylene or butylene aZiridine; engine a fuel oil composition as recited in claim 1. R4 can be alkyl-linear, branched, saturated, unsaturated, 19) The method of claim 18, Wherein said fuel oil is a C140; aromatic, cyclic, polycyclic; H, R34OH; Alco middle distillate fuel containing less than 500 ppm by mass of hol; Ester; or anAcid; sulfur. X can be 0, NH, NR1, S, or P; Y can be 1-6; and