Classifications

• • 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/0463—The hydrotreatment being a hydrorefining
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
  • C10G47/16—Crystalline alumino-silicate carriers
  • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/049—The hydrotreatment being a hydrocracking
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • 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
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
• • 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
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the invention relates to an integrated process for treating whole crude oil to remove asphalt and other impurities therefrom.
• the integrated process comprises the steps of separating asphalt from the whole crude oil, followed by treating the deasphalted oil via hydrotreatment/hydrocracking with a catalyst, to remove materials such as sulfur and nitrogen.
• the recovered, asphalt containing fraction can be gasified, to produce hydrogen that is then used in the hydrocracking step.
• the vacuum gas oil in turn, is usually cracked via fluid catalytic cracking or hydrocracking, to produce more valuable light transportation fuel products, while the residuum can be processed further, to yield additional useful products.
• the methods involved in these processes can include, e.g., hydrotreating or fluid catalytic cracking of the residuum, coking, and solvent deasphalting. Any materials recovered from crude distillation at fuel boiling points have typically been used, directly, as fuels.
• solvent deasphalting is a physical, separation process, where feed components are recovered in their original states, i.e., they do not undergo chemical reactions.
• a paraffinic solvent containing 3-8 carbon molecules, is used to separate the components of the heavy crude oil fractions. It is a flexible process, which essentially separates atmospheric, and vacuum heavy residues, typically into two products: (i) asphalt and (ii) deasphalted or demetallized oil, referred to as "DAO" or "DMO,” respectively hereafter.
• DAO deasphalted or demetallized oil
• the DAO will be used in conversion practices, like fluid catalytic cracking, solvents with higher molecular weights (e.g., butane or pentane, or mixtures thereof), are used.
• the products of DAO solvation include those described supra, as well as lube hydrocracking feed, fuels, hydrocracker feed, fluid catalytic cracking feed, or fuel oil blends.
• the asphalt product may be used as a blending component for various grades of asphalt, as a fuel oil blending component, or as a feedstock for heavy oil conversion units (e.g., cokers.)
• Hydrocracking processes are used commercially in many refineries.
• a typical application of a hydrocracking process involves processing feedstreams which boil at 370°C to 520°C in conventional units, and those which boil at 520°C and above, in so-called “residue units.”
• hydrocracking is a process by which C-C bonds of large molecules in a feed stream, are broken, to form smaller molecules, which have higher volatility and economic value.
• hydrocracking processes typically improve the quality of hydrocarbon feedstock, by increasing the H/C ratio by hydrogenation of aromatic compounds, and by removing organo-sulfur, and organic nitrogen compounds.
• hydrocracking units usually include two principal zones: a reaction zone and a separation zone. There are also three standard configurations: single stage, series- flow ("once-through"), with and without recycling, and two stage processes, with recycling.
• reaction zone configuration depends upon various parameters, such as feedstock quality, the product specification and processing objectives, and catalyst selection.
• Single or multiple catalyst systems can be used depending upon, e.g., the feedstock processed and product specifications.
• Single stage hydrocracking units are generally the simplest configuration, designed to maximize middle distillate yield over a single or dual catalyst system.
• Dual catalyst systems are used in stacked-bed configurations or in two different reactors.
• Feedstock is typically refined over one or more amorphous-based hydrotreating catalysts, either in the first catalytic zone in a single reactor, or in the first reactor of a two- reactor system.
• the effluents of the first stage are then passed to the second catalyst system which consists of an amorphous-based catalyst or zeolite catalyst having hydrogenation and/or hydrocracking functions, either in the bottom of a single reactor or the second reactor of a two- reactor system.
• the feedstock is refined by passing it over a hydrotreating catalyst bed in the first reactor.
• the effluents, together with the second stage effluents, are passed to a fractionator column to separate the H 2 S, NH 3 , light gases (C 1 -C 4 ), naphtha and diesel products which boil at a temperature range of 36-370 °C.
• the unconverted bottoms, free of H 2 S, NH 3 , etc. are sent to the second stage for complete conversion.
• the hydrocarbons boiling above 370 °C are then recycled to the first stage reactor or the second stage reactor.
• Hydrocracking unit effluents are sent to a distillation column to fractionate the naphtha, jet fuel/kerosene, diesel, and unconverted products which boil in the nominal ranges of 36-180 °C, 180-240 °C, 240-370 °C and above 370 °C, respectively.
• the hydrocracked jet fuel/kerosene products i.e., smoke point >25 mm
• diesel products i.e., cetane number >52
• While hydrocracking unit effluents generally have low aromaticity, any aromatics that remain will lower the key indicative properties of smoke point and cetane numbers for these products.
• the current invention simplifies and improves the prior art process, by eliminating the need for distillation, and for treating the naptha and diesel fractions. Rather, the invention, as will be seen, simplifies whole crude oil processing by hydrocracking the whole stream, and eliminating the steps referred to supra.
• Figure 1 shows a schematic depiction of the process of the invention, suing a single reactor embodiment
• the "DAO" "13" is transferred to a hydrocracking / hydrotreating zone "14."
• the reactor contains one or more catalysts which remove heteroatoms, such as sulfur and nitrogen from the DAO.
• Such catalysts are well known to the art, and are not repeated herein. Exemplary of such are catalysts described in, e.g.. PCT/US 11/46272 filed August 2, 2011 and incorporated by reference herein.
• the cracking reaction takes place in the presence of hydrogen, which is supplied as explained infra.
• the hydrocracking process takes place at standard hydrocracking conditions, i.e., pressures ranging from about 100 to about 200 bars, temperatures ranging from about 350°C (to about 450°C, LHSVs of between 0.1 and 4.0 h -1 , and hydrogen oil ratios of from about 500 to about 2,500 SLt/Lt.
• pressures ranging from about 100 to about 200 bars
• temperatures ranging from about 350°C (to about 450°C, LHSVs of between 0.1 and 4.0 h -1
• hydrogen oil ratios of from about 500 to about 2,500 SLt/Lt.
• the asphalt fraction was gasified by oxygen and steam combining it into membrane wall reactor or gasification chamber, depicted at "14" in Figure 1.
• the mixture was heated to 1045°C, with a water to carbon ration of 0.6 (in terms of weight), and an oxygen:pitch ratio of 1.0.
• the foregoing disclosure sets forth the features of the invention, which is a simplified methodology for reducing impurities, such as sulfur and nitrogen, in a feedstock, such as crude oil, which does not involve distillation.
• a feedstock such as crude oil
• the crude oil is solvent deasphalted, resulting in DAO and asphalt.
• the DAO is then hydrocracked in the presence of a catalyst so as to desulfurize and denitrogenize it, and to convert any hydrocarbons which have a boiling point over 370°C into distillates.
• the asphalt fraction is gasified so as to produce hydrogen.
• the hydrogen is channeled back into the hydrocracking reactor and used in that process.
• the nature of the feedstock will, of course vary and may include ash in an amount ranging from about 2% to about 10% of the total feedstock.
• the feedstock may be liquid or solid. Liquid feedstocks having components with boiling points of from about 36°C to about 2000°C are preferred.
• the feedstock may be, e.g., bituminous, oil, sand, shale oil, coal, or a bio liquid, and preferably contains less than 20 ppmw of sulfur.
• the solvent comprises one or more C 3 - C 7 alkanes, which may be straight chained or branched.
• the solvent comprises one or, most preferably, a mixture of butanes. Solvation takes place at temperatures and pressures, which are below the critical values for both of these.
• the DAO is transmitted to a hydrocracking unit, where hydrocracking is carried out at conditions which may vary, but are preferably a pressure of from about 100 to about 200 bars, a temperature of from about 350°C to about 500°C, an LHSV of from about 0.1 to about 4.0 h -1 , and a hydrogen:oil ratio of from about 500 to about 2500 SLt/Lt
• hydrocracking system Any standard hydrocracking system may be used including single reactors, multiple reactors operated in series, fixed bed reactors, ebullated bed reactors, and so forth.
• a catalyst is used in the hydrocracking process, preferably the catalyst incorporated by reference supra.
• the catalyst contains from about 2% to about 40% by weight of active metal, a total pore volume of from about 0.3 to about 1.5 cc/g, a total surface area of from about 200 to about 450 m 2 /g, and an average pore diameter of at least 50 angstroms.
• metals from Group VI, VII or VIIIB are preferred, and may include one or more of Co, Ni, W, and Mo. While it is not required to do so, the catalysts are generally incorporated on a support, such as alumina, silica, a zeolite or a zeolite modified by, e.g., steam, ammonia, acid washing and/or insertion of transition metals into its structure.
• the asphalt portion of the crude oil is gasified in a gasification chamber, e.g., a membrane wall type reactor, preferably at a temperature of from about 900°C to about 1700°C, and a pressure of from about 20 bars to about 100 bars.
• Gasification takes place in the presence of an O 2 containing gas, which may be, e.g., pure O 2 or more preferably, atmospheric gas.
• Means may be provided to control the amounts of asphalt and oxygen entering the gasification reactor. Such means are well known to the skilled artisan and need not reiterated here. It is preferred t control the amounts of asphalt and O 2 , so that a stoichiometric balance permitting partial combustion ensues. This can be determined via determining the hydrocarbon content of the crude oil, such as was done in the example, supra. Preferably, the amounts are selected such that the oxygen:carbon ratio ranges from about 0.2:1.0 to about 5:0.1 by weight.
• steam may be added to the gasification chamber.
• it is, it too is added in an amount based upon the carbon content of the crude oil, and is preferably presented at a ratio of from about 0.1:1.0 to about 100:1.0 by weight.
• Gasification results in a product sometimes referred to as "syngas" consisting essentially of hydrogen and carbon monoxide.
• the syngas produced by gasification is transmitted to a water gas shift reaction chamber and treated to produce H 2 and CO 2 , after which H 2 is separated.
• the resulting, pure H 2 may be channeled to the hydrocracking reaction.
• the process by which the syngas is treated may include treatment at a temperature of from about 150°C to about 400°C, and a pressure of from about 1 to about 60 bars.
• gas content can be measured at any point in the process described here.
• water can be added to the reaction chamber, preferably at a molar ratio with CO of from about 3 : 1 to about 5:1.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Hydrogen, Water And Hydrids (AREA)
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• 2013
  • 2013-05-29 WO PCT/US2013/043055 patent/WO2013184462A1/en active Application Filing
  • 2013-05-29 US US13/904,545 patent/US20130319910A1/en not_active Abandoned
  • 2013-05-29 EP EP13730395.4A patent/EP2855639A1/en not_active Ceased
  • 2013-05-29 SG SG11201408000XA patent/SG11201408000XA/en unknown
  • 2013-05-29 CN CN201380029767.0A patent/CN104540926A/zh active Pending
  • 2013-05-29 JP JP2015516064A patent/JP5991562B2/ja active Active
  • 2013-05-29 KR KR1020157000070A patent/KR101716986B1/ko active IP Right Grant

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