# US 11,028,332 B2 · Integrated selective hydrocracking and fluid catalytic cracking process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,332 B2 - Document ID: US11028332B2 - Status: Granted - Kind: B2 - Application number: 16/033,613 - Filed: 2018-07-12 - Published: 2019-02-07 - Granted: 2021-06-08 - Earliest claimed: 2011-07-29 - Assignees: Saudi Arabian Oil Company - Applicants: Saudi Arabian Oil Company - Inventors: Omer Refa Koseoglu - Web page: https://patentgrep.com/patent/US11028332B2 ## CPC - C10G 69/02: plural serial stages only - C10G 2300/1096: Aromatics or polyaromatics - C10G 2300/202: Heteroatoms content, i.e. S, N, O, P - C10G 2300/44: Solvents - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES ## Abstract An integrated process and system for conversion of a heavy crude oil to produce transportation fuels is provided. The process includes separating the hydrocarbon feed into an aromatic-lean fraction and an aromatic-rich fraction. The aromatic-rich fraction is hydrocracked under relatively high pressure to convert at least a portion of refractory aromatic organosulfur and organonitrogen compounds and to produce a hydrocracked product stream. Unconverted bottoms effluent is recycled to the aromatic separation step. The aromatic-lean fraction is cracked in a fluidized catalytic cracking reaction zone to produce a cracked product stream, a light cycle oil stream and a heavy cycle oil stream. In certain embodiments the aromatic-lean fraction can be hydrotreated prior to fluidized catalytic cracking. ## Claims ### Claim 1 An integrated process for conversion of a feedstock to produce hydrocracked product and fluidized catalytically cracked product, the process comprising: a. separating, in an aromatic separation zone, a hydrocarbon feed and an unconverted bottoms recycle stream, into an aromatic-lean fraction that contains labile organosulfur compounds and an aromatic-rich fraction that contains refractory aromatic organosulfur and/or organonitrogen compounds, wherein feed to the aromatic separation zone comprises the unconverted bottoms recycle stream and the hydrocarbon feed, wherein the hydrocarbon feed is selected from the group consisting of straight run gas oil, vacuum gas oil, deasphalted oil or demetalized oil obtained from a solvent deasphalting process, light coker or heavy coker gas oil obtained from a coker process, gas oil obtained from a visbreaking process, and a combination comprising two or more of the foregoing; b. passing the aromatic-rich fraction to a hydrocracking reaction zone operating at a hydrogen partial pressure of at least about 60 Kg/cm2 to convert at least a portion of refractory aromatic organosulfur and/or organonitrogen compounds and to produce hydrocracked product and an unconverted bottoms effluent; c. recycling at least a portion of the unconverted bottoms effluent to the aromatic separation step as the unconverted bottoms recycle stream in step (a); and d. passing a fluid catalytic cracking feed to a fluid catalytic cracking reaction zone to produce cracked product, a light cycle oil stream and a heavy cycle oil stream, wherein the fluid catalytic cracking feed consists essentially of the aromatic-lean fraction or wherein the fluid catalytic cracking feed consists essentially of the aromatic-lean fraction in combination with a portion of the unconverted bottoms effluent. ### Claim 2 (depends on 1) The process of claim 1, wherein the fluid catalytic cracking feed consists essentially of the aromatic-lean fraction in combination with a portion of the unconverted bottoms effluent. ### Claim 3 (depends on 1) The process of claim 1, further comprising conveying a portion of the light cycle oil to the hydrocracking reaction zone. ### Claim 4 (depends on 1) The process of claim 1, further comprising conveying a portion of the heavy cycle oil to the hydrocracking reaction zone. ### Claim 5 (depends on 1) The process of claim 1, the hydrocarbon feed having an aromatic content and a non-aromatic content, wherein separating the hydrocarbon feed into an aromatic-lean fraction and an aromatic-rich fraction comprises: subjecting the hydrocarbon feed and an effective quantity of extraction solvent to an extraction zone to produce an extract containing a major proportion of the aromatic content of the hydrocarbon feed and a portion of the extraction solvent and a raffinate containing a major proportion of the non-aromatic content of the hydrocarbon feed and a portion of the extraction solvent; separating at least substantial portion of the extraction solvent from the raffinate and retaining the aromatic-lean fraction; and separating at least substantial portion of the extraction solvent from the extract and retaining the aromatic-rich fraction. ### Claim 6 (depends on 5) The process of claim 5, wherein the extraction solvent is selected from the group consisting of furfural, N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, phenol, nitrobenzene, sulfolanes, acetonitrile, and glycols. ### Claim 7 (depends on 5) The process of claim 5, wherein the extraction zone is a stage-type extractor. ### Claim 8 (depends on 5) The process of claim 5, wherein the extraction zone is a differential extractor. ### Claim 9 (depends on 1) The process of claim 1, wherein the aromatic-rich fraction includes benzothiophene, alkylated derivatives of benzothiophene, dibenzothiophene, alkyl derivatives of dibenzothiophene, benzonaphtenothiophene, and alkyl derivatives of benzonaphtenothiophene. ### Claim 10 (depends on 1) The process of claim 1, wherein the aromatic-rich fraction includes pyrrole, quinoline, acridines, carbazoles and their derivatives. ### Claim 11 (depends on 1) The process of claim 1, wherein the fluid catalytic cracking reaction zone includes a downflow reactor. ### Claim 12 (depends on 11) The process of claim 11, wherein the downflow reactor operates with catalyst and under conditions effective to promote formation of olefins and minimize olefin-consuming reactions including hydrogen-transfer reactions, said conditions including reaction temperature of from about 550° C. to about 650° C., reaction pressure of from about 1 Kg/cm2 to about 20 Kg/cm2, contact time (in the reactor) of from about 0.1 seconds to about 30 seconds; a catalyst to feed ratio of from about 10:1 to about 40:1; and use of a catalyst mixture containing base cracking catalyst and additive, the base cracking catalyst in the catalyst mixture in a range of 60 to 95 W % and the additive in the catalyst mixture in a range of 5 to 40 W %, wherein the base cracking catalyst is selected from the group consisting of natural zeolites, synthetic zeolites, Y-zeolite, kaolin, montmorilonite, halloysite, bentonite, porous alumina oxide, porous silica oxide, porous boria oxide, porous chromia oxide, porous magnesia oxide, porous zirconia oxide, porous titania oxide, and porous silica-alumina oxide, and wherein the additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, and pentasil-type aluminosilicates. ### Claim 13 (depends on 1) The process of claim 1, wherein the fluid catalytic cracking reaction zone includes a riser reactor. ### Claim 14 (depends on 13) The process of claim 13, wherein the riser reactor operates with catalyst and under conditions effective to promote formation of olefins and minimize olefin-consuming reactions including hydrogen-transfer reactions, said conditions including reaction temperature of from about 480° C. to about 650° C.; reaction pressure of from about 1 Kg/cm2 to about 20 Kg/cm2; contact time (in the reactor) of from about 0.7 seconds to about 10 seconds, and a catalyst to feed ratio of from about 8:1 to about 20:1; and use of a catalyst mixture containing base cracking catalyst and additive, the base cracking catalyst in the catalyst mixture in a range of 60 to 95 W % and the additive in the catalyst mixture in a range of 5 to 40 W %, wherein the base cracking catalyst is selected from the group consisting of natural zeolites, synthetic zeolites, Y-zeolite, kaolin, montmorilonite, halloysite, bentonite, porous alumina oxide, porous silica oxide, porous boria oxide, porous chromia oxide, porous magnesia oxide, porous zirconia oxide, porous titania oxide, and porous silica-alumina oxide, and wherein the additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, and pentasil-type aluminosilicates. ### Claim 15 (depends on 1) The process of claim 1, wherein step (d) comprises conveying a fluidized cracking catalyst mixture including a fluidized cracking base catalyst and a catalyst additive. ### Claim 16 (depends on 1) The process of claim 1, wherein feed to the aromatic separation zone consists essentially of the unconverted bottoms recycle from step (c) and the hydrocarbon feed. ### Claim 17 (depends on 1) The process of claim 1, wherein the hydrocarbon feed is straight run gas oil. ### Claim 18 (depends on 1) The process of claim 1, wherein the fluid catalytic cracking feed consists essentially of the aromatic-lean fraction. ### Claim 19 An integrated process for conversion of a feedstock to produce hydrocracked product and fluidized catalytically cracked product, the process comprising: a. separating, in an aromatic separation zone, a hydrocarbon feed and an unconverted bottoms recycle stream to an aromatic-lean fraction that contains labile organosulfur and/or organonitrogen compounds and an aromatic-rich fraction that contains sterically hindered refractory aromatic organosulfur compounds, wherein feed to the aromatic separation zone comprises the unconverted bottoms recycle stream and the hydrocarbon feed, wherein the hydrocarbon feed is selected from the group consisting of straight run gas oil, vacuum gas oil, deasphalted oil or demetalized oil obtained from a solvent deasphalting process, light coker or heavy coker gas oil obtained from a coker process gas oil obtained from a visbreaking process and a combination comprising two or more of the foregoing; b. passing the aromatic-rich fraction to a hydrocracking reaction zone operating at a hydrogen partial pressure of at least about 60 Kg/cm2 to convert at least a portion of refractory aromatic organosulfur and/or organonitrogen compounds and to produce a hydrocracked product stream and an unconverted bottoms effluent; c. recycling at least a portion of the unconverted bottoms effluent to the aromatic separation step as the unconverted bottoms recycle stream in step (a); d. passing the aromatic-lean fraction to a hydrotreating reaction zone operating at a pressure in the range of about 20.4 Kg/cm2 to about 61.2 Kg/cm2 to desulfurize at least a portion of aromatic-lean fraction and to produce a hydrotreated stream; and e. passing a fluid catalytic cracking feed to a fluid catalytic cracking reaction zone to produce cracked product, a light cycle oil stream and a heavy cycle oil stream, wherein the fluid catalytic cracking feed consists essentially of the hydrotreated stream or wherein the fluid catalytic cracking feed consists essentially of the hydrotreated stream in combination with a portion of the unconverted bottoms effluent. ### Claim 20 (depends on 19) The process of claim 19, wherein the fluid catalytic cracking feed consists essentially of the hydrotreated stream in combination with a portion of the unconverted bottoms effluent. ### Claim 21 (depends on 19) The process of claim 19, further comprising conveying a portion of the light cycle oil to the hydrocracking reaction zone. ### Claim 22 (depends on 19) The process of claim 19, further comprising conveying a portion of the heavy cycle oil to the hydrocracking reaction zone. ### Claim 23 (depends on 19) The process of claim 19, the hydrocarbon feed having an aromatic content and a non-aromatic content, wherein separating the hydrocarbon feed into an aromatic-lean fraction and an aromatic-rich fraction comprises: subjecting the hydrocarbon feed and an effective quantity of extraction solvent to an extraction zone to produce an extract containing a major proportion of the aromatic content of the hydrocarbon feed and a portion of the extraction solvent and a raffinate containing a major proportion of the non-aromatic content of the hydrocarbon feed and a portion of the extraction solvent; separating at least substantial portion of the extraction solvent from the raffinate and retaining the aromatic-lean fraction; and separating at least substantial portion of the extraction solvent from the extract and retaining the aromatic-rich fraction. ### Claim 24 (depends on 23) The process of claim 23, wherein the extraction solvent is selected from the group consisting of furfural, N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, phenol, nitrobenzene, sulfolanes, acetonitrile, and glycols. ### Claim 25 (depends on 23) The process of claim 23, wherein the extraction zone is a stage-type extractor. ### Claim 26 (depends on 23) The process of claim 23, wherein the extraction zone is a differential extractor. ### Claim 27 (depends on 19) The process of claim 19, wherein the aromatic-rich fraction includes benzothiophene, alkylated derivatives of benzothiophene, dibenzothiophene, alkyl derivatives of dibenzothiophene, benzonaphtenothiophene, and alkyl derivatives of benzonaphtenothiophene. ### Claim 28 (depends on 19) The process of claim 19, wherein the aromatic-rich fraction includes pyrrole, quinoline, acridines, carbazoles and their derivatives. ### Claim 29 (depends on 19) The process of claim 19, wherein the fluid catalytic cracking reaction zone includes a downflow reactor. ### Claim 30 (depends on 29) The process of claim 29, wherein the downflow reactor operates with catalyst and under conditions effective to promote formation of olefins and minimize olefin-consuming reactions including hydrogen-transfer reactions, said conditions including reaction temperature of from about 550° C. to about 650° C., reaction pressure of from about 1 Kg/cm2 to about 20 Kg/cm2, contact time (in the reactor) of from about 0.1 seconds to about 30 seconds; a catalyst to feed ratio of from about 10:1 to about 40:1; and use of a catalyst mixture containing base cracking catalyst and additive, the base cracking catalyst in the catalyst mixture in a range of 60 to 95 W % and the additive in the catalyst mixture in a range of 5 to 40 W %, wherein the base cracking catalyst is selected from the group consisting of natural zeolites, synthetic zeolites, Y-zeolite, kaolin, montmorilonite, halloysite, bentonite, porous alumina oxide, porous silica oxide, porous boria oxide, porous chromia oxide, porous magnesia oxide, porous zirconia oxide, porous titania oxide, and porous silica-alumina oxide, and wherein the additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, and pentasil-type aluminosilicates. ### Claim 31 (depends on 19) The process of claim 19, wherein the fluid catalytic cracking reaction zone includes a riser reactor. ### Claim 32 (depends on 31) The process of claim 31, wherein the riser reactor operates with catalyst and under conditions effective to promote formation of olefins and minimize olefin-consuming reactions including hydrogen-transfer reactions, said conditions including reaction temperature of from about 480° C. to about 650° C.; reaction pressure of from about 1 Kg/cm2 to about 20 Kg/cm2; contact time (in the reactor) of from about 0.7 seconds to about 10 seconds, and a catalyst to feed ratio of from about 8:1 to about 20:1; and use of a catalyst mixture containing base cracking catalyst and additive, the base cracking catalyst in the catalyst mixture in a range of 60 to 95 W % and the additive in the catalyst mixture in a range of 5 to 40 W %, wherein the base cracking catalyst is selected from the group consisting of natural zeolites, synthetic zeolites, Y-zeolite, kaolin, montmorilonite, halloysite, bentonite, porous alumina oxide, porous silica oxide, porous boria oxide, porous chromia oxide, porous magnesia oxide, porous zirconia oxide, porous titania oxide, and porous silica-alumina oxide, and wherein the additive comprises a shape-selective zeolite selected from the group consisting of ZSM-5 zeolite, zeolite omega, SAPO-5 zeolite, SAPO-11 zeolite, SAPO34 zeolite, and pentasil-type aluminosilicates. ### Claim 33 (depends on 19) The process of claim 19, wherein step (e) comprises conveying a fluidized cracking catalyst mixture including a fluidized cracking base catalyst and a catalyst additive. ### Claim 34 (depends on 19) The process of claim 19, wherein a feed to the aromatic separation zone consists essentially of the unconverted bottoms recycle from step (c) and the hydrocarbon feed. ### Claim 35 (depends on 19) The process of claim 19, wherein the hydrocarbon feed is straight run gas oil. ### Claim 36 (depends on 19) The process of claim 19, wherein the fluid catalytic cracking feed consists essentially of the hydrotreated stream.