WO2012030492A2 - Traitement d'une charge d'hydrocarbures - Google Patents

Traitement d'une charge d'hydrocarbures Download PDF

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Publication number
WO2012030492A2
WO2012030492A2 PCT/US2011/047202 US2011047202W WO2012030492A2 WO 2012030492 A2 WO2012030492 A2 WO 2012030492A2 US 2011047202 W US2011047202 W US 2011047202W WO 2012030492 A2 WO2012030492 A2 WO 2012030492A2
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WIPO (PCT)
Prior art keywords
titanate
feed
catalyst
metal
acid number
Prior art date
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PCT/US2011/047202
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English (en)
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WO2012030492A3 (fr
Inventor
Shabbir Husain
Lin Li
Zhen Zhou
Alexander E. Kuperman
Zunqing He
Huping Luo
Original Assignee
Chevron U.S.A. Inc.
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
Priority claimed from US12/873,113 external-priority patent/US8389782B2/en
Priority claimed from US12/889,715 external-priority patent/US8815085B2/en
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to EP11822320.5A priority Critical patent/EP2611884A4/fr
Priority to BR112013004568-0A priority patent/BR112013004568B1/pt
Publication of WO2012030492A2 publication Critical patent/WO2012030492A2/fr
Publication of WO2012030492A3 publication Critical patent/WO2012030492A3/fr

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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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • 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
    • Y02P30/40—Ethylene production

Definitions

  • the disclosure relates to a process for treating a hydrocarbon feed, including removing oxygen from a biologically derived oil for a hydrocarbon products suitable for use as transportation fuel, or reducing the total acid number of a hydrocarbon feed.
  • a high acid crude oil can cause corrosion of equipment utilized in refining operations, resulting in higher operating expenses involved in maintaining equipment and refinery shutdowns due to equipment failure.
  • the corrosion is generally attributed to the high concentration of naphthenic acids and other acidic species in the crude oil.
  • Naphthenic acids are found in various crudes, such as, for example, crudes from California, Venezuela, North Sea, Western Africa, India, China and Russia.
  • Chemical reactions to reduce total acid number (TAN) of crude oil have been investigated.
  • Such TAN reduction technologies can be divided into the categories of hydrotreating, chemical neutralization, esterification, amidation and decarboxylation.
  • biodiesel Another type of hydrocarbon feedstock is biodiesel, which is biologically derived oils and fats.
  • Biodiesel has attracted increased attention due to its potential of providing a significant portion of transportation fuels.
  • Biologically derived oils and fats are complex mixtures of triglycerides and free fatty acids.
  • Transesterification i.e. reacting triglycerides with methanol to produce fatty acid methyl-ester (FAME)
  • FAMEs generally have a high cetane number and are considered to burn cleanly, but they still contain problematic levels of oxygen.
  • a major drawback of this type of biodiesel is that it generally has poor oxidative and thermal stability.
  • Hydrotreating is one route to remove oxygen from triglycerides, but it has the disadvantage that it consumes large amounts of hydrogen since during hydrotreating, oxygen is reacted with hydrogen and removed through the formation of water. The heat release from hydrotreating reactions is also a significant challenge for reactor design.
  • Decarboxylation is another route to remove oxygen from biofuels. Although the hydrocarbons produced through decarboxylation may contain less carbon than its fatty acid or ester counterpart and those from the hydrotreating route, decarboxylation does not consume hydrogen. Generally speaking, consuming the carbon contained in a biologically derived feedstock to remove oxygen is less costly than consuming hydrogen which must be produced through expensive processes.
  • hydrocarbon feedstock such as biologically derived oils to produce transportation fuels.
  • the improved method can also be used to treat other hydrocarbon feedstock, such as, for example, a high acid crude, to render it less corrosive to processing equipment.
  • the invention relates to a process for removing oxygen from a hydrocarbon feedstock such as biologically derived oil feed comprising fatty acids and/or fatty acid esters, by contacting the feed with a catalyst comprising a metal titanate having an MT1O 3 structure wherein M is a metal having a valence of 2+ in the absence of added hydrogen gas, resulting in a hydrocarbon product having a final oxygen content less than the initial oxygen content.
  • a hydrocarbon feedstock such as biologically derived oil feed comprising fatty acids and/or fatty acid esters
  • the invention in another embodiment, relates to a process for reducing the total acid number in a liquid hydrocarbon feed by, contacting the feed having an initial total acid number of at least 0.5 with a catalyst comprising a metal titanate having an MT1O 3 structure, wherein M is a metal having a valence of 2+ at a temperature of between 200° C. and 400° C, thereby resulting in a treated hydrocarbon product having a final total acid number at least 10% lower than the initial total acid number.
  • the invention relates to a process for refining a low acid crude oil and a high acid crude oil, comprising separately introducing a relatively low acid crude oil feed and a relatively high acid crude oil feed to an atmospheric distillation column, wherein the relatively high acid crude oil feed is contacted with a catalyst comprising a metal titanate having an MT1O 3 structure, wherein M is a metal having a valence of 2+ prior to introduction to the atmospheric distillation column.
  • Figure 1 is a block flow diagram illustrating an embodiment for a unit utilizing a catalyst comprising a metal titanate having an MT1O 3 structure, for the treatment of a high
  • TAN hydrocarbon feedstock or for the removal of oxygen from a biofuel.
  • Figure 2 is a process flow diagram illustrating an embodiment for a process to refine a crude oil feed, illustrating various locations at which a total acid number reduction unit can be utilized to treat various streams within the process scheme.
  • Figure 3 is a process flow diagram illustrating another embodiment for a process scheme in which a relatively low acid crude and a high acid crude are fed to an atmospheric distillation column, and a total acid number reduction unit is utilized to treat the high acid crude.
  • Figure 4 is a graph illustrating deoxygenation effects in a reaction employing an employing of a catalyst having an MT1O 3 structure.
  • Figure 5 is a graph comparing the deoxygenation effects (in terms of C0 2 release) in reactions with and without employing a catalyst having an MT1O 3 structure.
  • Hydrocarbon feed refers to a feed that includes hydrocarbons.
  • Hydrocarbon feed may include, but is not limited to, crude oil, synthetic crude, distillate products, straight run feed, atmospheric and vacuum bottoms, vacuum gas oil, biologically derived oils, or mixtures thereof.
  • Naphthenic acid refers to the carboxylic acid content of a sample of hydrocarbon feed including but not limited to alkyl substituted acyclics, fatty acids, aromatic acids, carbazoles and isoprenoid acids.
  • Examples in certain crude oils include complex acid structures with two, three or four carboxylic groups (tetrameric acids as well as structures containing heteroatoms, e.g., sulfur, oxygen, and nitrogen).
  • Total acid number refers to the amount of KOH in milligrams required to neutralize one gram sample of hydrocarbon feed. TAN is determined by ASTM Method D664.
  • bio refers to an association with a renewable resource of biological origin, such resources generally being exclusive of fossil fuels.
  • a “biologically-derived oil” or “biofuel” as defined herein refers to any triglyceride- containing oil that is at least partially derived from a biological source such as, but not limited to, biomass such as crops, vegetables, microalgae, and the like. Such oils may further comprise free fatty acids. Plant and animal oils and fats typically contain 0-30 wt% free fatty acids, which are formed during hydrolysis (e.g. enzymatic hydrolysis) of triglycerides. The amount of free fatty acids present in vegetable oils is typically 1-5 wt% and in animal fat, 10-25 wt%. The biological source is henceforth referred to as "biomass.”
  • Triglyceride refers to class of molecules having the following general formula:
  • R 1 , R 2 , and R 3 are molecular chains comprising carbon and hydrogen, and can be the same or different, and wherein one or more of the branches defined by R 1 , R 2 , and R 3 can have unsaturated regions.
  • Teriglyceride-based as defined herein, is used to describe biofuel precursor material comprising triglyceride species in the majority (by weight), but possibly also comprising other oxygenate species such as free fatty acids.
  • a “carboxylic acid” or “fatty acid,” as defined herein, is a class of organic acids having the general formula: R-COOH, where R is generally a saturated (alkyl)hydrocarbon chain or a mono- or polyunsaturated (alkenyl)hydrocarbon chain.
  • Transesterification refers to the reaction between a fatty acid or ester (e.g., a triglyceride) and an alcohol to yield an ester species.
  • a fatty acid or ester e.g., a triglyceride
  • Transportation fuels refer to hydrocarbon-based fuels suitable for consumption by vehicles including, but are not limited to, diesel, gasoline, jet fuel and the like.
  • Diesel fuel as defined herein, is a material suitable for use in diesel engines and conforming to the current version at least one of the following specifications: ASTM D 975— "Standard Specification for Diesel Fuel Oils”; European Grade CEN 90; Japanese Fuel Standards JIS K 2204; The United States National Conference on Weights and Measures (NCWM) 1997 guidelines for premium diesel fuel; and The United States Engine
  • Biodiesel refers to diesel fuel that is at least significantly derived from a biological source, and which is generally consistent with ASTM International Standard Test Method D-6751. Often, biodiesel is blended with conventional petroleum diesel. B20 is a blend of 20 percent biodiesel with 80 percent conventional diesel. B 100 denotes pure biodiesel.
  • Carbon number or “C n ,” where “n” is an integer, describes a hydrocarbon or hydrocarbon-containing molecule or fragment (e.g., an alkyl or alkenyl group) wherein “n” denotes the number of carbon atoms in the fragment or molecule.
  • hydrocarbons are substantially comprised of carbon and hydrogen
  • hydrocarbon-based materials can include molecules with heteroatoms, e.g., alcohols, carboxylic acids, and the like; the heteroatoms generally being atoms other than C or H, and typically atoms selected from the group consisting of O, N, S, P, and combinations thereof.
  • Deoxygenation refers to the removal of oxygen from organic molecules, such as fatty acid derivatives, alcohols, ketones, aldehydes or ethers.
  • Decarboxylation refers to the removal of carboxyl oxygen from acid molecules.
  • Decarbonylation refers to the removal of carbonyl oxygen from organic molecules with carbonyl functional groups other than acids.
  • a biologically derived oil feed is deoxygenated by contacting the oil feed with a metal titanate catalyst in the absence of added hydrogen gas.
  • the total acid number, also referred to as TAN, of a hydrocarbon feed is reduced by contacting the hydrocarbon feed with a metal titanate catalyst in a suitable reactor.
  • the hydrocarbon feedstock is a bio oil and/or fat, originating from renewable sources, such as fats and oils from plants and/or animals and/or fish and compounds derived from them.
  • the basic structural unit of a typical plant or vegetable or animal oil/fat useful as the feedstock is a triglyceride, which is a triester of glycerol with three fatty acid molecules, having the structure presented in the following formula I: CH 2 OCOR 1
  • R 1 , R 2 , and R 3 can be alkyl chains. Fatty acids found in natural triglycerides are almost solely fatty acids of even carbon number. Therefore R 1 , R 2 , and R 3 generally are C 5 -C 23 alkyl groups, typically C 11 -C 19 alkyl groups and often C 15 or C 17 alkyl groups. R 1 , R 2 , and R 3 may contain carbon-carbon double bonds. These alkyl chains can be saturated, unsaturated or polyunsaturated.
  • Suitable bio oils are plant and vegetable oils and fats, animal fats, fish oils, and mixtures thereof containing fatty acids and/or fatty acid esters.
  • suitable materials are wood-based and other plant-based and vegetable-based fats and oils such as rapeseed oil, colza oil, canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, algae oil, as well as fats contained in plants bred by means of gene manipulation, animal-based fats such as lard, bacon fat, tallow, train oil, and fats contained in milk, as well as recycled fats of the food industry and mixtures of the above.
  • the feedstock is a bio oil comprising pyrolysis oil.
  • the hydrocarbon feedstock is a bio oil comprising FAME.
  • Bio oils and fats suitable as feed may comprise C 12 -C 24 fatty acids, derivatives thereof such as anhydrides or esters of fatty acids as well as triglycerides of fatty acids or combinations thereof.
  • Fatty acids or fatty acid derivatives, such as esters may be produced via hydrolysis of bio oils or by their fractionalization or transesterification reactions of triglycerides.
  • the hydrocarbon feedstock is a traditional feed including but are not limited to, crude oil, synthetic crude oil, straight run feed, distillate products, atmospheric and vacuum bottoms, vacuum gas oil and biologically derived oils having an initial total acid number of at least 0.5.
  • the liquid hydrocarbon feed is a high acid crude, i.e. crude oil having a TAN of at least 0.5.
  • Catalysts suitable for use in the embodiments described herein include metal titanates, also referred to herein interchangeably as titanates, which can be expressed as MT1O 3 wherein M is a metal having a valence of 2+.
  • the metal M may also be capable of multiple valences.
  • the catalyst consists essentially of at least a metal titanate of the formula MT1O 3 .
  • the catalyst contains a mixture of a metal titanate with at least a metal oxide, with both basic and acid properties.
  • the catalyst consists essentially of at least a metal titanate with at least a basic oxide.
  • Examples of basic (metal) oxides include, but are not limited to calcium oxide, magnesium oxide, magnesium aluminum oxide, zinc oxide, lanthanum oxide, cerium oxide, barium oxide and mixtures thereof.
  • the molar ratio of metal titanate to metal oxide ranges from 1 : 10 to 10: 1. In a second embodiment, the molar ratio ranges from 1 :5 to 5 : 1. In a third embodiment, the ratio ranges from 1 :2 to 2: 1.
  • suitable metal titanates for use in the catalyst include, but are not limited to, magnesium titanate, copper titanate, nickel titanate, iron(II) titanium oxide, cobalt titanium oxide, manganese(II) titanium oxide, lead(II) titanate, calcium titanate, barium titanate, zinc titanate, and mixtures thereof.
  • the catalyst contains at least 80% by weight titanate. In another embodiment, the catalyst contains at least 1% by weight titanate based on the total weight of the catalyst; in another embodiment at least 5% wt. % titanate; in another embodiment at least 10% 5wt. % titanate, including any other desirable active components as well as optional support material.
  • the actual amount of titanate needed will vary depending on whether or not a support is used, and how the catalyst is dispersed on the support.
  • the catalyst has a BET surface area greater than 20 m 2 /g; in another embodiment the BET surface area is greater than 200 mVg; in yet another embodiment the BET surface area is greater than 400 m 2 /g.
  • the catalyst is a supported catalyst.
  • Suitable support materials include silica, alumina, silica-alumina, carbon, molecular sieves and mixtures thereof.
  • the catalyst is deposited on a carbon support having a BET surface area of between 500 m 2 /g and 1500 m 2 /g.
  • the catalyst is deposited on a support selected from silica, alumina, silica-alumina and mixtures thereof, and the support has a BET surface area of between 150 m 2 /g and 600 m 2 /g.
  • the support can be a monolithic support. Alternatively, the catalyst can be unsupported.
  • the treatment process includes contacting the hydrocarbon feed with a metal titanate catalyst within a suitable reactor.
  • a single catalyst bed or multiple catalyst beds may be used for the treatment.
  • the feed is passed over a catalyst, e.g., a monolithic catalyst, in a fixed bed reactor operating in continuous mode.
  • the feed contacts the catalyst in a slurry bed reactor in continuous mode. Either an upflow or downflow type reactor can be used.
  • the feed can also be contacted with the catalyst in a batch reactor.
  • the reaction is conducted in the absence of added hydrogen.
  • the pressure within the reactor is between 100 kPa and 1000 kPa (all pressures indicated herein are absolute); in another embodiment the pressure is between 30 psi (210 kPa) and 100 psi (690 kPa). The pressure can be below 100 kPa, although depending on the pressure in the surrounding equipment, it may be necessary to pump the stream exiting the reactor to a higher pressure.
  • the LHSV is between 0.1 and 10 h “1 ' in another embodiment, the LHSV is between 0.2 and 5.0 h “1 ; in another embodiment, the LHSV is between 0.4 and 2.0 h “1 .
  • LHSV refers to the volumetric liquid feed rate per total volume of catalyst and is expressed as the inverse of hours (h _1 ).
  • the treatment is carried out under inert condition, meaning with the addition of a light hydrocarbon gas, e.g., C1-C4 gas, or an inert gas such as nitrogen, helium, neon, and argon, etc., and with very little if any added hydrogen.
  • a light hydrocarbon gas e.g., C1-C4 gas
  • an inert gas such as nitrogen, helium, neon, and argon, etc.
  • very little hydrogen gas introduced to the reactor is such that the mole ratio of hydrogen to hydrocarbon feed is less than 0.1.
  • the treatment process can be utilized to treat various streams within a crude refining operation, e.g., for the pre-treatment of high acid crudes prior to further processing thus avoiding corrosion of equipment used in refining operations.
  • the treatment unit can be selectively located prior to critical pieces of equipment for the treatment of high acid crude prior to being introduced to the equipment, e.g., heaters, distillation columns, and the like.
  • the equipment for the high acid crude feeds can be isolated from the equipment for the low acid crude, and being placed in operation whenever there is a need to treat a high acid feedstock.
  • the deoxygenation treatment step may optionally be followed by various other steps, e.g., isomerisation, hydrofinishing, etc., depending on the biofuel being used as the hydrocarbon feedstock as well as the desired final product.
  • Treated Product In one embodiment, the process is for treating high acid crude oils before reaching FCC (fluid catalytic cracking) or hydroprocessing units located downstream. After treatment, the TAN can be reduced significantly, allowing high acid crude to be treated prior to downstream processing in refineries. The TAN can be reduced by various amounts.
  • the final TAN of the treated hydrocarbon product is at least 10% lower than the initial TAN of the liquid hydrocarbon feed; in a second embodiment, the final TAN is at least 50% lower than the initial TAN; in a third embodiment, the final TAN is at least 90% lower than the initial TAN.
  • the actual reduction will depend on the particular feed and the desired TAN of the treated hydrocarbon product.
  • the feed is a high acid crude having a TAN of at least 10
  • the treated crude has a TAN of less than 5.
  • the TAN reduction is at least 50% resulting in a treated crude with a TAN of 10 or less.
  • the treated product has a lower oxygen content than that of the feed.
  • the oxygen content of the treated product is at least 20% less than the initial oxygen content of the feed.
  • the final oxygen content is at least 50% less than the initial oxygen content of the feed.
  • a hydrocarbon feed 2 is fed to a fixed bed reactor 4 containing a bed of catalyst comprising a metal titanate having an MT1O 3 structure.
  • the process can alternatively be conducted in a slurry bed reactor (not shown).
  • Treated product stream 8 is removed from the reactor for further processing as desired.
  • gas stream 6 containing various components including, but not limited to, carbon dioxide and water vapor, is removed from the reactor and passes through condenser 10 utilizing incoming cooling water 12.
  • the gas stream 6 may further comprise methane, carbon monoxide, and light hydrocarbons.
  • Effluent cooling water 14 exits from the condenser.
  • Condensed and mixed stream 16 is sent to three-phase separator 18.
  • Gas stream 20 is removed from the separator and processed.
  • Water 22 is removed from the separator.
  • Light ends stream 24 is removed from the separator and can be combined with the treated product stream, e.g., low acid crude stream 8.
  • the metal titanate catalyst bed can optionally be subjected to the flow of a stripping gas stream 28, which can be, for example, refinery gas or associated gas, depending on the location and application of the total acid number reduction unit.
  • the stripping gas can also be an inert gas, e.g. nitrogen, for example, for the treatment of a biofuel as the feedstock.
  • a blower or compressor 30 can be used to feed optional low pressure stripping gas stream 28 to the reactor. This gas stream serves to strip carbon dioxide, water vapor and other light gases if any from the reactor 4.
  • the flow of gas is countercurrent to the flow of the hydrocarbon feed.
  • the flow of gas is between 50 and 200 scf/bbl (standard cubic feet of gas per barrel of hydrocarbon feed).
  • Crude oil feed 32 which can be a high acid crude or a blend of multiple crudes, is initially routed through heat exchanger 34, desalter 36 and second heat exchanger 38 prior to separation in flash drum 42.
  • Light fraction 44 is separated overhead, and heavy fraction 46 is passed to fired heater 48 prior to being introduced to atmospheric distillation column 50.
  • Various fractions 52, 54, 56, 58, 60 and 62 are removed from distillation column 50.
  • Vacuum column 68 is used to treat the atmospheric distillation residue 67, thus producing vacuum overhead stream 70, multiple cuts of vacuum gas oil stream 72 and vacuum residual stream 74.
  • the TAN reduction 40 unit can be located to treat any refinery stream, such as those locations indicated in Figure 2 by the letters A through G.
  • a TAN reduction unit at location A is used to treat stream 46 prior to entering heater 48, thus protecting the heater from corrosion.
  • a TAN reduction unit 40 at location B can be used to treat the stream exiting heater 48.
  • a TAN reduction unit can be located at location C in order to treat the atmospheric distillation residue from distillation column 50 prior to entering heater 66. Where isolation of the desalting and heating train cannot be accomplished, this reduces the overall quantity of crude that must be processed through the TAN reduction unit.
  • a TAN reduction unit can be located at location D in order to treat the atmospheric gas oil fraction 62.
  • a TAN reduction unit can be located at location E in order to treat the diesel fraction 60.
  • a TAN reduction unit can be located at location F in order to treat kerosene fraction 58.
  • a TAN reduction unit can be located at location G in order to treat vacuum gas oil fraction 72, which is a petroleum fraction where acids are known to concentrate. While each of these locations indicated by letters A through G represents separate possible embodiments, a TAN reduction unit can be located at multiple of these locations.
  • Figure 3 illustrates one embodiment in which a relatively low acid crude oil feed 82 and a relatively high acid crude oil feed 102 are separately fed to a refining operation.
  • Each feed is heated through a heat exchanger (84 and 104, respectively), passes a desalter (86 and 106), a second heat exchanger (88 and 108), a flash drum (90 and 110) and a heater (96 and 114) prior to each stream being introduced to atmospheric distillation column 120.
  • Relatively high acid crude 102 passes through a total acid number reduction unit 40 prior to being introduced to the distillation column 20.
  • Various fractions 122, 124, 126, 128, 130, 132 and 134 are taken off the distillation column.
  • Atmospheric distillation residue 134 is sent to heater 136 and vacuum column 138 from which fractions 140, 142 and 144 are taken off.
  • the equipment for the high acid crude feeds can be isolated from the equipment for the low acid crude. This configuration minimizes the size of the reaction column and quantity of catalyst required in the total acid number reduction unit 40.
  • TAN Total acid number
  • Example 1 The feed was prepared by mixing crude oil derived naphthenic acids
  • a CaO-CaTi03 (3: 1 mole ratio) catalyst mixture was prepared by a thermal spray method from inorganic precursors and calcined at 750° C. for 2 hours in air.
  • a 50 ml round bottom flask equipped with a glass coated magnetic stirrer was used. The flask was heated using a heating mantle, and a condenser (using dry ice) was used to minimize evaporative losses.
  • a nitrogen gas sweep ( ⁇ 50 ml/min) was used to carry any C0 2 and water vapor formed from the flask.
  • a number of catalyst / feed combinations listed in Table 1 were initially tested in a batch process using approximately 5 wt. % catalyst with respect to the high acid feed.
  • the catalysts and feed were heated to 150° C. and held for two hours, followed by heating to 200° C. and holding for two hours, followed by heating to 300° C. and holding for two hours.
  • Catalytic activity was measured at the end of the reaction with TAN measurements.
  • Albacora crude was used to test the response of the catalysts (ZnTi0 3 product number 634409, supplied by Sigma-Aldrich Corp.) on real crude feeds.
  • Albacora is a Brazilian high acid crude with a TAN of 1.88 mg KOH.
  • the experiments were run at ambient pressure and stripping gas (N 2 ) SGV of 25 cm/min with 1 mm diameter borosilicate glass beads used as a control to isolate the effects of temperature on TAN reduction.
  • N 2 ambient pressure and stripping gas
  • SGV 25 cm/min with 1 mm diameter borosilicate glass beads used as a control to isolate the effects of temperature on TAN reduction.
  • Table 4 the experimental data suggests that the titanate is very effective in reducing the TAN of Albacora crude versus the control case using borosilicate glass beads.
  • Example 3 A batch reactor was loaded with 16 g stearic acid having 3.55 mmol 0 2 /g (P&G Chemicals, Cincinnati, Ohio) and 4 g ZnTi0 3 (product number 634409, Sigma-Aldrich Corp., St. Louis, Missouri) catalyst. N 2 was used as a purge gas to remove C0 2 formed through decarboxylation reactions. C0 2 concentration was measured to monitor the progress of the reaction. Figure 4 shows the results. It can be seen that at 350° C. there was a marked C0 2 release. The rate of C0 2 release is equivalent to the deoxygenation rate when considered on a molar basis. The highest deoxygenation rate was 0.089 mmol 0 2 /min, indicating accelerated decarboxylation reaction.
  • Example 4 To examine catalyst activity for deoxygenation of triglycerides, 10 g canola salad oil having 3.39 mmol 0 2 /g (sold under the name "Superb" from Costco

Abstract

Les modes de réalisation ci-décrits concernent un procédé de traitement d'une charge d'hydrocarbures. Dans un mode de réalisation utilisant une huile dérivée biologiquement comme charge, la charge d'huile dérivée biologiquement est désoxygénée par mise en contact de la charge avec un catalyseur de titanate métallique ayant une structure MTiO3 où M est un métal ayant une valence de 2+. Dans un autre mode de réalisation utilisant une huile brute fortement acide comme charge, le catalyseur de titanate métallique est utilisé pour réduire l'indice d'acide total de la charge d'hydrocarbures par mise en contact de la charge avec le catalyseur de titanate métallique, et obtenir un produit hydrocarboné ayant un indice d'acide total final inférieur à l'indice d'acide total initial de la charge. Le procédé peut être intégré à des opérations de raffinage classiques afin de traiter les flux d'alimentation des raffineries, qu'ils proviennent d'une source de biocarburant, ou d'un brut fortement acide.
PCT/US2011/047202 2010-08-31 2011-08-10 Traitement d'une charge d'hydrocarbures WO2012030492A2 (fr)

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EP11822320.5A EP2611884A4 (fr) 2010-08-31 2011-08-10 Traitement d'une charge d'hydrocarbures
BR112013004568-0A BR112013004568B1 (pt) 2010-08-31 2011-08-10 processo para tratar uma alimentação de hidrocarboneto líquido e processo para refinar uma alimentação de óleo bruto de ácido baixo e de óleo bruto de ácido alto

Applications Claiming Priority (4)

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US12/873,113 US8389782B2 (en) 2010-08-31 2010-08-31 Biofuel production through catalytic deoxygenation
US12/873,113 2010-08-31
US12/889,715 2010-09-24
US12/889,715 US8815085B2 (en) 2010-09-24 2010-09-24 Process for reducing the total acid number of a hydrocarbon feed

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WO2024010770A1 (fr) * 2022-07-07 2024-01-11 Uop Llc Procédé de récupération de solvant d'extraction d'huile de pyrolyse

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BR112013004568A2 (pt) 2016-09-06
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WO2012030492A3 (fr) 2012-07-05
EP2611884A2 (fr) 2013-07-10

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