GB2355726A - Fuel oil compositions with improved cold flow properties - Google Patents

Fuel oil compositions with improved cold flow properties Download PDF

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Publication number
GB2355726A
GB2355726A GB9925643A GB9925643A GB2355726A GB 2355726 A GB2355726 A GB 2355726A GB 9925643 A GB9925643 A GB 9925643A GB 9925643 A GB9925643 A GB 9925643A GB 2355726 A GB2355726 A GB 2355726A
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weight
fraction
range
composition
present
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GB9925643A
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GB9925643D0 (en
Inventor
Heather Dunlop Cochrane
Veronica Cloke-Browne
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
Exxon Research and Engineering Co
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Application filed by ExxonMobil Research and Engineering Co, Exxon Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Priority to GB9925643A priority Critical patent/GB2355726A/en
Publication of GB9925643D0 publication Critical patent/GB9925643D0/en
Priority to DE60025511T priority patent/DE60025511D1/en
Priority to CA002388616A priority patent/CA2388616A1/en
Priority to EP00971389A priority patent/EP1230325B1/en
Priority to AT00971389T priority patent/ATE315623T1/en
Priority to PCT/EP2000/010185 priority patent/WO2001032810A1/en
Priority to JP2001535495A priority patent/JP2003514065A/en
Publication of GB2355726A publication Critical patent/GB2355726A/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

This invention relates to a fuel oil composition having improved cold-flow properties and comprising a cold flow additive and streams from various pipestills of a petroleum crude refinery process: <SL> <LI>a. a relatively heavy fraction from a catalytically cracked heavy gasoil in turn derived from an atmospheric or vacuum pipestill, said fraction having a boiling range of 170 to 380{C in an amount of 3 to 20% by weight and <LI>b. a gasoil product from an atmospheric pipestill, said product having a boiling range of 225 to 360{C in an amount of 30-50% by weight, </SL> whereby components (a) and/or (b) is at least partially replaced by at least one relatively light naphtha fraction (c) from the atmospheric or vacuum pipestills, fraction (c) having a boiling range of 130 to 235{C and being present in an amount of 3 to 20% by weight.

Description

2355726 FUEL OIL COMPOSITIONS WITH IMPROVED COLD FLOW PROPERTIES This
invention relates to ftiel oil compositions, especially middle distillate ftiel oil compositions, with improved flow properties.
It is important that ftiel oil compositions, especially middle distillate oil compositions such as automotive diesel oils, heating oils and gas oils (hereafter collectively referred to as "fuel oil" for convenience) retain their flow properties at relatively low temperatures. The main cause of such loss of flow properties is due to the formation of wax which tends to precipitate out and agglomerate thereby plugging burner and vehicle fuel filters and hence impairing flow. The temperature at which the wax starts to appear is termed the cloud point of the fuel. The cold filter plugging point (CFPP) is recognised as a measure of the operability of a fuel and the temperature at which a fuel will start to block vehicle filters. It is generally less than or equal to the cloud point of the fuel. This problem has been well recognized in the art and has hitherto been mitigated by the use of various flow improving additives also known as middle distillate flow improvers (MDFI) which reduce the CFPP of responsive fuels. One such example is Paraflow@ 240 (commercially sold by Infineum). The flow improvers can change the size or the shape of the crystals as they precipitate out of the oil at low temperatures thereby allowing them to pass through the vehicle filter easily and avoid blockage of the fuel filter of the vehicle. Either way, it is important that the flow properties of the ftiel oils are maintained.
Hitherto, crude oil was refined into motor gasoline, automotive diesel oils (hereafter "ADO") and gas oils used as heating oils (fuel oils) and their respective specifications were such that it was possible to easily treat ADO, gasoil and heating oils.
However, recent legislation to minimise the amount of sulphur and also constrain other properties, eg density, in ADOs has meant that some of the heavier components of ADOs, such as e.g. catalytically cracked heating oils, have been displaced into the gasoil and heating oil fractions. These changes in the composition of ADO, gasoils and heating oils may mean that the effectiveness of conventional cold flow improvers such as Paraflow@ 240 is lessened.
2 It is an object of the present invention to improve the flow properties of fuel oils (as herein defined) containing conventional flow improvers by incorporating therein a heavy-catalytically cracked naphtha.
Accordingly, the present invention is a ftiel oil composition having improved cold-flow properties, said composition comprising a cold flow additive and the following components from various pipestills of a petroleum crude refinery process:
a. a relatively heavy fraction from a catalytically cracked heavy gasoil in turn derived from an atmospheric or vacuum pipestill, said fraction having a boiling 10 range of 170 to 380'C in an amount of 3 to 20% by weight and b. a gasoil product from an atmospheric pipestill, said product having a boiling range of 225 to 360C in an amount of 30-50% by weight, characterized in that components (a) and/or (b) in said composition is at least partially replaced by at least one relatively light naphtha fraction (c) from the atmospheric or vacuum pipestills, said light fraction (c) having a boiling range of 130 to 235'C and being present in an amount of 3 to 20% by weight, all weights being based on the total weight of the fuel oil composition.
In the fuel compositions of the present invention, the various components referred to are all derivable from various process streams of a petroleum crude refinery process.
Such methods are well known in the art and are described in detail for instance by Keith Owen and Trevor Colley in "Automotive Fuels Reference Book", Second Edition, published by the Society of Automotive Engineers, Inc, Warrendale, PA, USA (1995), and specifically to Chapter 3 of this text-book at pages 29-49, Chapter 16 at pages 419 469 and 865-890, the latter pages forming Appendix 12 which is a'Glossary of Terms' used in this art. Thus, reference to component (a) means a heavy fraction produced by catalytic cracking of heavy gas oil from the atmospheric or vacuum pipestill. This fraction suitably has a boiling point in the range from 184 to 376C. This fraction is suitably present in the compositions of the present in an amount ranging from about 5-18 % by weight of the total fuel oil composition.
In the fuel oil composition of the present invention, the reference to component (b) means a gasoil product from an atmospheric pipestill which suitably has a boiling point in the range from about 244 to 330C. This product is suitably present in the 3 compositions of the present in an amount ranging from about 35-45% by weight of the total fuel oil composition.
The third essential component in the fuel oil compositions of the present invention is a light naphtha fraction (c) derived by the catalytic cracking of a heavy gasoil from an atmospheric or a vacuum pipestill. This naphtha fraction (c) suitably has a boiling point in the range from 136 to 23 1 C and preferably component (a) and/or (b) in the fuel composition in an amount from about 5-15% by weight of the total composition.
Fraction (c) suitably has an aromatics content in the range from about 60 - 75% by io weight.
The fuel oil compositions of the present invention may contain in addition other conventional distillate fractions from a petroleum crude refinery process under atmospheric or vacuum conditions. These include inter alia components (d) to (g) described below:
(d) a fraction from a vacuum pipestill which suitably has a boiling point in the range from about 200 to 400C, preferably from about 240-365C. This fraction (d) is suitably present in the compositions of the present in an amount ranging from about 3-7% by weight, preferably from about 4-6 % by weight of the total composition.
(e) a fraction from an atmospheric pipestill which suitably has a boiling point in the range from about 160-380C, preferably from about 183 to331C. This fraction (e) is suitably present in the compositions of the present in an amount ranging from about 5 to 15% by weight, preferably from about 9 to 10% by weight, typically about 9.5-10.0% by weight.
(f) a fraction from an atmospheric pipestill which suitably has a boiling point in the range from about 230 -350'C, preferably from about 231 to 344"C. This fraction (f) is suitably present in the compositions of the present in an amount ranging from about to 30% by weight, preferably from about 20-25% by weight.
(g) a fraction from an atmospheric pipestill which suitably has a boiling point in the range from about 210-420C, preferably from about 216 to 395C. This fraction is suitably present in the compositions of the present in an amount ranging from about 3 to 8% by weight, preferably from about 4-6 % by weight.
The fuel oil compositions of the present invention having an n-paraffin (C12+) 4 content of less than 20% by weight particularly benefit by blending with the light naphtha fraction (c). Such fuel oil compositions suitably have a cloud point of about -3 to -4'C.
The cold flow additive in fuel oil composition is suitably one of those generally available provided it is soluble in the fuel oil composition, although copolymers of ethylene and at least one other unsaturated monomer which may be an additional mono olefin or an unsaturated ester such as eg vinyl acetate, vinyl propionate, vinyl butyrate, ethyl acrylate and lauryl methacrylate or the like. The other unsaturated monomer can also be a mixture of an unsaturated mono-ester or diester and a straight chain or branched io chain a-monoolefin. Mixtures of copolymers, such as eg a copolymer of ethylene and vinyl acetate with an alkylated polystyrene or with an acylated polystyrene, can also be used. Where the flow additive is a coolymer, it suitably consists of I to 40, preferably I to 20 and more preferably 3 to 20 molar proportions of ethylene per molar proportion of the other unsaturated monomer, said additive copolymer being oil soluble and having a number average molecular weight in the range from about 1,000 to 50,000, preferably about 1,000 to about 5,000. The cold flow additive is preferably an ethylene-vinyl carboxylate copolymer which may be selected from one or more of Paraflow(&240, Paraflow(D 226, ParaflowO 222, Paraflow@) 275, ParaflowO 255, Paraflow(D 223, Paraflow@ 332, Paraflow& 209, Paraflow@ 206, Paraflow@ 480, Paraflow@ 482, ParaflowO 479 (all ex Infineum), KF 6100S, KF 6100, KF 6301, KF 6101 (ex BASF), and DF 4842 (ex Clariant).
The cold flow additive is suitably present in the oil composition in an amount from about 0.00 1 -2.0% by weight of the total ftiel oil composition.
The surprising feature of the present invention is that component (c), which is a relatively light fraction compared to the distribution of heavier components in fuel oils, is able to improve the effectiveness of conventional cold flow improvers in such ftiel oils. It has been found that by using an aliquot of component (c) in the fuel oil compositions, it is possible to depress the cloud point and the temperature of operability, the latter as determined by the cold-filter plugging point (hereafter "CFPP") to a significant extent.
The present invention is further illustrated with reference to the following Examples:
EXAMPLES:
The following data was generated by subjecting a variety of ftiel oils each of which contained 500 vol/vol ppm of an ethylene-vinyl acetate copolymer (Paraflow@ 240, ex Infineum) cold flow additive and a 1050 vol/vol ppm of a gasoil marker dye to a cold flow plugging point (CFPP) test. The test is described in detail in the text-book by Owen & Coley referred to above at pages 422-426 in Chapter 16.1.5. This is an IP 309 test and is also published as a European Standard by CEN, ENI 16:1981. Briefly, a 40 ml of a sample of the test oil is cooled by a bath maintained at about -34'C. Periodically (at each I'C drop in temperature starting from not less than 5'C above the cloud point thereof), the cooled oil is tested for its ability to flow through a fine screen in a given time period. This cold flow property is tested with a device consisting of a pipette the lower end of which is attached an inverted ftmnel positioned below the surface of the test oil.
Stretched across the mouth of the funnel is a 350 mesh screen having an area of about 0.45 in2. The periodic tests are each initiated by applying a vacuum to the upper end of the pipette whereby oil is drawn through the screen up into the pipette to a mark indicating 20 ml. The test is repeated with each I C drop in temperature until the oil fails to fill the pipette up to that 20 ml mark within 60 seconds. The temperature at which the last filtration commenced is recorded as the CFPP.
6 TABLE
Components Fuel Composition Fuel Composition 2 Fuel Composition 3 1 (Wt %) (Wt %) (Wt 0/0) Component (g) 4.9 4.9 4.9 Component (e) 9.9 9.9 9.9 Component (a) 16.2 8.4 5.0 Component (c) - 7.8 15.0 Component (b) 42.2 42.2 38.4 Component (f) 21.8 21.8 21.8 Component (d) 5.0 5.0 5.0 Total 100 100 100 Cloud point ("C) -3 -4 -4 CFPP (-C) -8 -10 -15 The above results show that partially replacing some of the conventional gas oil components in fuel oils with light naphtha fraction from the catalytic cracking of heavy gasoil clearly improves the CFPP of the fuel oils to a significant extent.
7

Claims (13)

  1. We Claim:
    I. A fuel oil composition having improved cold-flow properties, said composition comprising a cold flow additive and the following components from various pipestills of a petroleum crude refinery process:
    a. a relatively heavy fraction from a catalytically cracked heavy gasoil in turn derived from an atmospheric or a vacuum pipestill, said fraction having a boiling range of 170 to 380'C in an amount of 3 to 20% by weight and b. a gasoil product from an atmospheric pipestill, said product having a boiling range of 225 to 335'C in an amount of 30-50% by weight, io characterized in that components (a) and/or (b) in said composition is at least partially replaced by at least one relatively light naphtha fraction (c) from an atmospheric or a vacuum pipestill, said light fraction (c) having a boiling range of 130 to 235'C and being present in an amount of 3 to 20% by weight, all weights being based on the total weight of the fuel oil composition.
  2. 2. A composition according to Claim I wherein component (a) has a boiling point in the range from 184 to 376'C.
  3. 3. A composition according to Claim I or 2 wherein component (a) is present in the composition in an amount ranging from about 5-18 % by weight of the total fuel oil composition.
  4. 4. A composition according to any one of the preceding Claims wherein component (b) has a boiling point in the range from about 244 to 3300C.
  5. 5. A composition according to any one of the preceding Claims wherein component (b) is present in the composition in an amount ranging from about 35-45% by weight of the total fuel oil composition.
  6. 6. A composition according to any one of the preceding Claims wherein the light naphtha fraction (c) has a boiling point in the range from136 to 23 I'C.
    8
  7. 7. A composition according to any one of the preceding Claims wherein the light naphtha fraction (c) is present in the composition in an amount from about 5-15% by weight of the total composition.
  8. 8. A composition according to any one of the preceding Claims wherein the light naphtha fraction has an aromatics content in the range from about 60 - 75% by weight.
  9. 9. A composition according to any one of the preceding Claims wherein the fuel oil io composition contains in addition one or more distillate fractions selected from (d) a fraction from a vacuum pipestill has a boiling point in the range from about 200 to 400C and is present in an amount ranging from about 3-7% by weight; (e) a fraction from an atmospheric pipestill which has a boiling point in the range from about 160 to3 80'C and is present in an amount ranging from about 5 to 15 % by weight; (f) a fraction from an atmospheric pipestill which has a boiling point in the range from about 230 to 350'C and is present in an amount ranging from about 15 to 30% by weight; and (g) a fraction from an atmospheric pipestill which has a boiling point in the range from about 2 10 to 420'C and is present in an amount ranging from about 3 to 8% by weight, all weights being based on the total weight of the fuel oil composition.
  10. 10. A composition according to any one of the preceding Claims wherein the fuel oil composition contains in addition one or more distillate fractions selected from (d) a fraction from a vacuum pipestill has a boiling point in the range from about 240 to 365'C and is present in an amount ranging from about 3-7% by weight; (e) a fraction from an atmospheric pipestill which has a boiling point in the range from about 183 to33 PC and is present in an amount ranging from about 5 tol 5% by weight; (f) a fraction from an atmospheric pipestill which has a boiling point in the range from about 231 to 344"C and is present in an amount ranging from about 15 to 30% by weight; and 9 (g) a fraction from an atmospheric pipestill which has a boiling point in the range from about 216 to 395C and is present in an amount ranging from about 3 to 8% by weight, all weights being based on the total weight of the fuel oil composition.
  11. 11. A composition according to any one of the preceding Claims wherein the cold flow additive is present in said composition in an amount from 0. 00 1 to 2. 0% by weight of the total fuel oil composition.
    io
  12. 12. A composition according to any one of the preceding Claims wherein the coldflow additive is an ethylene vinyl acetate copolymer.
  13. 13. A method of improving the cold flow properties of a fuel oil composition comprising a cold flow additive and the following components from various pipestills of a petroleum crude refinery process:
    a. a relatively heavy fraction from a catalytically cracked heavy gasoil in turn derived from an atmospheric or vacuum pipestill, said fraction having a boiling range of 180 to 380C in an amount of 3 to 20% by weight and b. a gasoil product from an atmospheric pipestill, said product having a boiling range of 240 to 335'C in an amount of 30-50% by weight, said method comprising replacing at least partially components (a) and/or (b) in said composition by at least one relatively light naphtha fraction (c) from an atmospheric or a vacuum pipestill, said light fraction (c) having a boiling range of 130 to 235C and being present in an amount of 3 to 20% by weight, all weights being based on the total weight of the fuel oil composition.
GB9925643A 1999-10-29 1999-10-29 Fuel oil compositions with improved cold flow properties Withdrawn GB2355726A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
GB9925643A GB2355726A (en) 1999-10-29 1999-10-29 Fuel oil compositions with improved cold flow properties
DE60025511T DE60025511D1 (en) 1999-10-29 2000-10-17 FUEL OIL COMPOSITION WITH IMPROVED COLD FLOW CHARACTERISTICS
CA002388616A CA2388616A1 (en) 1999-10-29 2000-10-17 Fuel oil compositions with improved cold flow properties
EP00971389A EP1230325B1 (en) 1999-10-29 2000-10-17 Fuel oil compositions with improved cold flow properties
AT00971389T ATE315623T1 (en) 1999-10-29 2000-10-17 FUEL OIL COMPOSITION WITH IMPROVED COLD FLOW PROPERTIES
PCT/EP2000/010185 WO2001032810A1 (en) 1999-10-29 2000-10-17 Fuel oil compositions with improved cold flow properties
JP2001535495A JP2003514065A (en) 1999-10-29 2000-10-17 Fuel oil compositions with improved cold flow properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9925643A GB2355726A (en) 1999-10-29 1999-10-29 Fuel oil compositions with improved cold flow properties

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GB9925643D0 GB9925643D0 (en) 1999-12-29
GB2355726A true GB2355726A (en) 2001-05-02

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GB9925643A Withdrawn GB2355726A (en) 1999-10-29 1999-10-29 Fuel oil compositions with improved cold flow properties

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EP (1) EP1230325B1 (en)
JP (1) JP2003514065A (en)
AT (1) ATE315623T1 (en)
CA (1) CA2388616A1 (en)
DE (1) DE60025511D1 (en)
GB (1) GB2355726A (en)
WO (1) WO2001032810A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2496855C1 (en) * 2012-06-26 2013-10-27 Федеральное автономное учреждение "25 Государственный научно-исследовательский институт химмотологии Министерства обороны Российской Федерации" Fuel composition for displacement-type ships

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2297442C2 (en) 2005-07-18 2007-04-20 Общество с ограниченной ответственностью "Ойлтрейд" Heavy petroleum fuel
RU2297443C2 (en) 2005-07-18 2007-04-20 Общество с ограниченной ответственностью "Ойлтрейд" Light petroleum fuel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994000535A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Additives and fuel compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717858A (en) * 1952-02-14 1955-09-13 Exxon Research Engineering Co Heating oil blends
US2892769A (en) * 1953-09-02 1959-06-30 Tidewater Oil Company Automatic burner fuels and process of making them

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994000535A1 (en) * 1992-06-30 1994-01-06 Exxon Chemical Patents Inc. Additives and fuel compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2496855C1 (en) * 2012-06-26 2013-10-27 Федеральное автономное учреждение "25 Государственный научно-исследовательский институт химмотологии Министерства обороны Российской Федерации" Fuel composition for displacement-type ships

Also Published As

Publication number Publication date
EP1230325A1 (en) 2002-08-14
JP2003514065A (en) 2003-04-15
EP1230325B1 (en) 2006-01-11
ATE315623T1 (en) 2006-02-15
DE60025511D1 (en) 2006-04-06
WO2001032810A8 (en) 2002-05-23
GB9925643D0 (en) 1999-12-29
WO2001032810A1 (en) 2001-05-10
CA2388616A1 (en) 2001-05-10

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