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WO2011066058A1 - Composition de carburant mélangé ayant des propriétés d'écoulement à froid améliorées - Google Patents

Composition de carburant mélangé ayant des propriétés d'écoulement à froid améliorées Download PDF

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Publication number
WO2011066058A1
WO2011066058A1 PCT/US2010/054757 US2010054757W WO2011066058A1 WO 2011066058 A1 WO2011066058 A1 WO 2011066058A1 US 2010054757 W US2010054757 W US 2010054757W WO 2011066058 A1 WO2011066058 A1 WO 2011066058A1
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WIPO (PCT)
Prior art keywords
renewable
fuel
diesel
based component
fuel composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2010/054757
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English (en)
Inventor
Xiaochun Xu
Yun BAO
Jianhua Yao
Dhananjay B. Ghonasgi
Edward L. Sughrue Ii
Lisa L. Myers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ConocoPhillips Co
Original Assignee
ConocoPhillips Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ConocoPhillips Co filed Critical ConocoPhillips Co
Priority to AU2010325135A priority Critical patent/AU2010325135A1/en
Priority to CA2775148A priority patent/CA2775148A1/fr
Priority to BR112012013032A priority patent/BR112012013032A2/pt
Priority to EP10833750.2A priority patent/EP2507348A4/fr
Publication of WO2011066058A1 publication Critical patent/WO2011066058A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
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    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/1037—Hydrocarbon fractions
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/304—Pour point, cloud point, cold flow properties
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    • C10G2400/04—Diesel oil
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates generally to fuel compositions. More specifically, the present invention relates to a blended fuel composition comprising petroleum based fuel and renewable fuel which exhibit improved cold flow properties. The present invention also relates to the method of making such compositions.
  • hydrocarbons for producing fuels and chemicals
  • natural carbon resources or renewable hydrocarbons
  • oils and fats are widely available, and remain a target alternative source for the production of hydrocarbons.
  • oils and fats have been successfully hydrotreated to produce hydrocarbons/fuel range hydrocarbons which is also called “Renewable fuel” such as renewable diesel fuels.
  • renewable diesel fuels are gaining greater market acceptance as a cutter stock to extend petroleum diesel market capacity.
  • the blends of renewable diesel fuels with petroleum diesel are being used as fuel for diesel engines, utilized for heating, power generation, and for locomotion with ships, boats, as well as motor vehicles.
  • renewable diesel may be prepared by reacting vegetable oils and/or animal fats with a hydrogenation and deoxygenation catalyst at the hydrogenation and deoxygenation conditions.
  • the main components in renewable diesel are n-C15 to n-C18 paraffins.
  • renewable diesel exhibits poor cold flow properties, e.g., cloud point, pour point and Cold Filter Plugging Point (CFPP).
  • CFPP Cold Filter Plugging Point
  • the cold flow properties of renewable diesel can be improved by using dewaxing technology, either cracking or isomerization, to lower the cold flow properties, thereby minimizing the impact of renewable diesel on the cold flow proerties of petroleum diesel.
  • dewaxing technology either cracking or isomerization
  • the cold flow properties of renewable diesel can also be improved by adding cold flow additives.
  • cold flow additives are expensive. With the implementation of renewable diesel, the use of cold flow additives is expected to increase. Therefore, using cold flow additive is economically unfavorable.
  • the present invention relates generally to fuel compositions. More specifically, the present invention relates to a blended fuel composition comprising petroleum based fuel and renewable based fuel which exhibit improved cold flow properties.
  • a composition comprising a petroleum based component and a renewable based component, wherein at least 20% of the compounds in the petroleum based component having boiling point range equal or greater than the boiling point of the renewable based component.
  • the amount of the renewable based component is in the range between 0.1 vol. % to 50 vol. %, based on the total volume of the fuel composition.
  • the renewable based component comprises hydrocarbons that are derived from natural, replenishable feed stock which can be utilized as source of energy.
  • the petroleum based component comprises hydrocarbons derived from petroleum refining process.
  • the petroleum based component can be a diesel base fuel having boiling points within the range of 150° C to 400° C.
  • a method for preparing a fuel composition comprising blending a petroleum based fuel and a renewable based fuel, wherein at least 20 % of the compounds in the petroleum based component having boiling point range equal or greater than the boiling point of the renewable based component.
  • the present invention relates generally to fuel compositions. More specifically, the present invention relates to a blended fuel composition comprising petroleum based fuel and renewable based fuel which exhibit improved cold flow properties. The present invention also relates to the method of making such compositions. [00018] According to one embodiment of the current invention, there is provided a fuel composition comprising petroleum based component and a renewable based component, wherein at least 20% of the compounds in said petroleum based component having boiling point range equal or greater than the boiling point of said renewable based component.
  • a process for preparing a fuel composition comprising blending a petroleum based fuel and a renewable based fuel, wherein at least 20%> of the compounds in the petroleum based component having boiling point range equal or greater than the boiling point of the renewable based component.
  • the petroleum based component is a hydrocarbon derived from petroleum refining process.
  • Petroleum based fuel refers to a fuel that includes a fractional distillate of petroleum.
  • the distillate fuel in many cases can be described as a gasoline or middle distillate fuel oil.
  • middle distillate fuels typically are divided into several types fuels including: jet or turbine fuels, automotive diesel fuels, railroad diesel fuels, and heating oils. These products are blended from a variety of refinery streams to meet the desired specifications.
  • Other examples of middle distillate fuel may include industrial gas oils, distillate marine fuels, kerosene fuels such as aviation fuels or heating kerosene, light and heavy cycle oils as obtained in a fluid catalytic cracking unit, a Fisher-Tropsch derived fuel, in particular a Fischer-Tropsch derived diesel fuel.
  • Petroleum derived gas oil may be obtained from refining and optionally hydroprocessing crude petroleum source. It may be a single gas oil stream obtained from such a refinery process or a blend of several gas oil fractions obtained in the refinery process via different processing routes. Examples of such gas oil fractions are straight run gas oil, atmospheric gas oil, vacuum gas oil, gas oil as obtained in a thermal cracking process, and gas oil as obtained from a hydrocracker unit.
  • the fuel composition to which the present invention is preferably to use is for an internal combustion engine, for example a diesel fuel composition which is used in an automotive diesel engine.
  • the petroleum based component may be any known diesel base fuel, and it may itself comprise a mixture of diesel fuel components. It may have a sulfur content of 0 to 20,000 ppmw (parts per million by weight). It may also have a sulfur content of 0 to 15 ppmw.
  • Typical diesel fuel components comprise liquid hydrocarbon middle distillate fuel oils, for instance petroleum jet or turbine fuels, automotive diesel fuels, railroad diesel fuels, heating oils and gas oil They will typically have boiling points within the usual diesel range of 150° C to 400° C, depending on grade and use.
  • a renewable based component is a hydrocarbon that is derived from natural, replenishable feed stock which can be utilized as source of energy.
  • Suitable examples of a renewable based component include, but not limited to, bio-diesel which is a product derived from the transesterification of a material of biological origin with an alcohol or from reacting a fatty acid with an alcohol; renewable diesel which is a product derived from hydrotreating a material of biological origin; alcohol; other oxygenate; vegetable oil or vegetable oil derivatives; a biomass pyrolysis bio-oils, or any combinations thereof.
  • the above mentioned material of biological origin can be selected from any triglyceride containing feedstock e.g. vegetable oils, vegetable fats, animal fats, fish oils, algae oil; any mixtures thereof.
  • alcohols used here include methanol, ethanol, and mixtures thereof, although virtually any Cl-10 alcohol can be used.
  • Bio-diesel is commonly produced by the reaction of a material of biological origin with alcohols in the presence of a suitable catalyst.
  • a material of biological origin is natural triglycerides derived from plant or animal sources.
  • the reaction of natural triglycerides with an alcohol to produce a fatty acid ester and glycerin is commonly referred to as transesterification.
  • bio-diesel can be produced by the reaction of a fatty acid with an alcohol to form the fatty acid ester.
  • the fatty acid segments of triglycerides are typically composed of C10-C24 fatty acids, where the fatty acid composition can be uniform or a mixture of various chain lengths.
  • the bio-diesel may be produced from single sourced components, or blends of multiple triglyceride containing feed stocks.
  • triglyceride is used generally to refer to any naturally occurring ester of a fatty acid and/or glycerol having the general formula CH 2 (OCORi)CH(OCOR2)CH2(OCOR 3 ), where R h R 2 , and R 3 are the same or different, and may vary in chain length.
  • Vegetable oils such as for example, canola and soybean oils contain triglycerides with three fatty acid chains.
  • Useful triglycerides in the present invention include, but are not limited to, triglycerides that may be converted to hydrocarbons when contacted under suitable reaction conditions.
  • triglycerides useful in the present invention include, but are not limited to, vegetable oils including soybean and corn oil, peanut oil, sunflower seed oil, coconut oil, babassu oil, grape seed oil, poppy seed oil, almond oil, hazelnut oil, walnut oil, olive oil, avocado oil, sesame oil, tall oil, cottonseed oil, palm oil, rice bran oil, canola oil, cocoa butter, shea butter, butyrospermum, wheat germ oil, illipse butter, meadowfoam, seed oil, rapeseed oil, borange seed oil, linseed oil, castor oil, vernoia oil, tung oil, jojoba oil, ongokea oil, Jatropha oil, algae oil, yellow grease (for example, as those derived from used cooking oils), and animal fats, such as tallow animal fat, beef fat, and milk fat, and the like and mixtures and combinations thereof.
  • vegetable oils including soybean and corn oil, peanut oil, sunflower seed oil, coconut oil, babassu oil, grape
  • a renewable based component may be a renewable diesel that is produced by hydrotreating triglyceride containing feedstock in the presence of a suitable catalyst.
  • Useful catalyst compositions for the hydrotreating process include any catalysts which may be effective in the conversion of triglycerides to hydrocarbons (e.g. renewable diesel) when contacted under suitable reaction conditions.
  • suitable catalysts include hydrotreating catalysts.
  • hydrotreating catalysts useful in one embodiment of the present invention include, but are not limited to, materials containing compounds selected from Group VI and Group VIII metals, and their oxides and sulfides.
  • suitable support materials for the hydrogenation catalysts include, but are not limited to, silica, silica-alumina, aluminum oxide (A1 2 0 3 ), silica-magnesia, silica-titania and acidic zeolites of natural or synthetic origin.
  • hydrotreating catalysts include but are not limited to alumina supported cobalt- molybdenum, nickel sulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum.
  • Other catalysts useful in the present invention are sorbent compositions. Sorbent compositions can be used in either the fixed-bed reactor or the fluidized bed reactor embodiments.
  • the reaction zone may comprise any suitable type of reactor.
  • Exemplary reactors include fixed bed reactors and fluidized bed reactors.
  • the reaction conditions at which the reaction zone is maintained generally include a temperature in the range of from about 260°C to about 430°C. In another embodiment, the temperature is in the range of from about 300°C to about 400°C.
  • the reaction conditions at which the reaction zone is maintained generally include a pressure less than about 2000 psig, and more particularly between about 100 psig to about 750 psig.
  • the pressure is maintained between about 100 psig to about 350 psig.
  • the pressure is maintained between about 400 psig to about 750 psig.
  • a cold flow property of fuel is a measure of the inherent handling and the use characteristics of a fuel at diminished temperature.
  • the cold flow property of a given fuel is generally considered as the lowest temperature at which the given fuel can be utilized without causing operational difficulties.
  • the cold flow properties of a given fuel is estimated by its cloud point (CP), pour point (PP) and its CFPP.
  • the CP of a fuel is the point at which first visible crystals are detected in the fuel.
  • the PP is a standardized term for the temperature at which oil, for example, mineral oil, diesel fuel or hydraulic oil, stops flowing upon cooling.
  • the Cold Filter Plugging Point (CFPP) of a fuel is the temperature at and below which wax in the fuel will cause severe restrictions to flow through a filter screen. CFPP is believed to correlate well with vehicle operability at lower temperatures.
  • the invention can be practiced at high renewable based fuel concentration, wherein the renewable based component is up to 100% by volume of the finished fuel blend.
  • the renewable based component is typically up to about 50% by volume of the finished fuel blend, more typically up to about 35%) by volume of the finished fuel blend, and alternatively up to about 20%> by volume of the finished fuel blend.
  • the invention is also applicable at renewable based component concentrations as low as about 15, 10, and 5%> by volume of the finished fuel blend, and even at very low renewable fuel concentrations as low as about 4, 3, 2, 1, and 0.5%) by volume of the finished fuel blend.
  • the main components in renewable diesel are n-C15 to n-C18 paraffins.
  • renewable diesel exhibits poor cold flow properties, e.g., CP, PP and CFPP.
  • CP cold flow properties
  • PP PP
  • CFPP CFPP
  • renewable diesel has little impact on the cold flow properties of petroleum diesel. This phenomenon has been successfully demonstrated on the blended fuel composition containing up to 20%> renewable based diesel. It is therefore discovered that the impact of renewable diesel on the cold flow properties of petroleum diesels depends on the boiling point range of the petroleum diesels. The higher the boiling point of petroleum diesel, the less the impact of renewable diesel on the cold flow properties.
  • petroleum diesel has high percentage (e.g., > 20 %) of compounds with boiling points higher than renewable diesel (e.g. 626 °F)
  • renewable diesel has little impact on the cold flow properties of petroleum diesel.
  • petroleum diesel has high percentage (e.g., > 50%) products with boiling temperatures lower than renewable diesel (e.g., 519°F)
  • blending renewable diesel has a big impact on the cold flow properties of petroleum diesel.
  • the present invention is able to provide a more optimized method for improving the cold flow performance of a diesel fuel composition comprising renewable based component. It has now been found that by controlling the selection of the boiling point of the petroleum based diesel, the impact of the renewable based diesel on the cold flow properties of petroleum based diesels may be minimized or eliminated.
  • Table 1 shows the CP, PP, CFPP and boiling point of tallow renewable diesel.
  • tallow renewable diesel ⁇ 99% of the compounds boil below 626.2 °F. This is because the main components of renewable diesel are n-C15 to n-C18 paraffins, which have boiling points between 519°F and 602 °F, respectively.
  • CP, PP and CFPP are 60 °F, 54 °F and 10 °C, respectively.
  • Table 2 shows the impact of renewable diesel on the cold flow properties of diesel 1.
  • CP, PP and CFPP all increased rapidly with renewable diesel concentration.
  • Boiling point of diesel 1 is shown in Table 3.
  • boiling point of diesel 1 is low.
  • 50%> of the compounds in diesel 1 is lighter than tallow renewable diesel and less than 5% is heavier than renewable diesel. Therefore, blending renewable diesel has a big impact on cold flow properties of petroleum diesel.
  • Table 4 shows the impact of renewable diesel on the cold flow properties of diesel 2.
  • CP, PP and CFPP all increased with renewable diesel concentration.
  • the impact of renewable diesel on the cold flow properties of diesel 2 is smaller than that of diesel 1.
  • Boiling point of diesel 2 is shown in Table 5.
  • the boiling point of diesel 2 is still low. For example, ⁇ 45% of the compounds in diesel 2 are lighter than tallow renewable diesel and ⁇ 10% is heavier than renewable diesel. Therefore, blending renewable diesel still has impact on cold flow properties of petroleum diesel.
  • the boiling point of diesel 2 is higher than that of diesel 1 , the impact of renewable diesel on the cold flow properties of diesel 2 is smaller than that of diesel 1.
  • Table 6 shows the impact of renewable diesel on the cold flow properties of diesel 3.
  • Renewable diesel has little impact on the cold flow properties of petroleum diesel up to 20 volume%>.
  • Boiling point of diesel 3 is shown in Table 7.
  • renewable diesel on the cold flow properties of petroleum diesels depends on the boiling point range of the petroleum diesels. The higher the boiling point of petroleum diesel, the less the impact of renewable diesel on the cold flow properties.
  • petroleum diesel has high percentage (e.g., > 20 %) of compounds with boiling points higher than renewable diesel (e.g. 626 °F), renewable diesel has little impact on the cold flow properties of petroleum diesel.
  • petroleum diesel has high percentage (e.g., > 50%>) products with boiling temperatures lower than renewable diesel (e.g., 519°F)
  • blending renewable diesel has a big impact on the cold flow properties of petroleum diesel.

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Abstract

L'invention porte sur une composition de carburant, qui comprend un composant à base de pétrole et un composant à base de carburant renouvelable, au moins 20 % des composés dans ledit composant à base de pétrole ayant une plage de point d'ébullition supérieure ou égale au point d'ébullition dudit composant à base de carburant renouvelable.
PCT/US2010/054757 2009-11-30 2010-10-29 Composition de carburant mélangé ayant des propriétés d'écoulement à froid améliorées Ceased WO2011066058A1 (fr)

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AU2010325135A AU2010325135A1 (en) 2009-11-30 2010-10-29 A blended fuel composition having improved cold flow properties
CA2775148A CA2775148A1 (fr) 2009-11-30 2010-10-29 Composition de carburant melange ayant des proprietes d'ecoulement a froid ameliorees
BR112012013032A BR112012013032A2 (pt) 2009-11-30 2010-10-29 composição de combustível misturada com propriedades de fluxo a frio melhoradas
EP10833750.2A EP2507348A4 (fr) 2009-11-30 2010-10-29 Composition de carburant mélangé ayant des propriétés d'écoulement à froid améliorées

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US26507609P 2009-11-30 2009-11-30
US61/265,076 2009-11-30
US12/915,502 US20110126449A1 (en) 2009-11-30 2010-10-29 Blended fuel composition having improved cold flow properties
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EP2507348A4 (fr) 2014-12-10
BR112012013032A2 (pt) 2016-11-22
AU2010325135A1 (en) 2012-05-10
EP2507348A1 (fr) 2012-10-10
US20110126449A1 (en) 2011-06-02

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