# US 11,896,963 B1 · Mesoporous ZSM-5 for steam enhanced catalytic cracking of crude oil > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,896,963 B1 - Document ID: US11896963B1 - Status: Granted - Kind: B1 - Application number: 17/952,757 - Filed: 2022-09-26 - Granted: 2024-02-13 - Earliest claimed: 2022-09-26 - Assignees: Saudi Arabian Oil Company - Applicants: Saudi Arabian Oil Company - Inventors: Aaron Chi Akah; Veera Venkata Ramakrishna Tammana - Web page: https://patentgrep.com/patent/US11896963B1 ## CPC - B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively - B01J 29/041: {Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41} - B01J 35/615: {100-500 m2/g} - B01J 35/617: {500-1000 m2/g} - B01J 35/633: {less than 0.5 ml/g} - B01J 35/643: {less than 2 nm} - B01J 35/647: {2-50 nm} - B01J 35/69: bimodal - C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves - C10G 11/20: by direct contact with inert heated gases or vapours - B01J 2229/14: to alter the inside of the molecular sieve channels - B01J 2229/34: Reaction with organic or organometallic compounds - B01J 2229/38: Base treatment - B01J 2229/40: Special temperature treatment, i.e. other than just for template removal - C10G 2300/1033: Oil well production fluids - C10G 2300/308: Gravity, density, e.g. API - C10G 2300/4006: Temperature - C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV - C10G 2300/4025: Yield - C10G 2300/70: Catalyst aspects - C10G 2400/20: C2-C4 olefins - C10G 2400/30: Aromatics - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - 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 A process for upgrading a hydrocarbon feed includes contacting the hydrocarbon feed with steam in the presence of a cracking catalyst at reaction conditions sufficient to cause at least a portion of hydrocarbons in the hydrocarbon feed to undergo one or more cracking reactions to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both. The cracking catalyst is hierarchical mesoporous ZSM-5 zeolite. The hierarchical mesoporous ZSM-5 zeolite is made by providing a starting ZSM-5 zeolite, disintegrating the a portion of the starting ZSM-5 in the presence of a surfactant using sodium hydroxide, and then recrystallizing the zeolite constituents in the presence of the surfactant to produce recrystallized ZSM-5 zeolite. The recrystallized ZSM-5 zeolite is then recovered and calcined to produce the hierarchical mesoporous ZSM-5 zeolite. ## Claims ### Claim 1 A process for upgrading a hydrocarbon feed, the process comprising: contacting the hydrocarbon feed with steam in the presence of a cracking catalyst at reaction conditions sufficient to cause at least a portion of hydrocarbons in the hydrocarbon feed to undergo one or more cracking reactions to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both, where: the light olefins are selected from the group consisting of ethylene, propylene, butenes, and combinations thereof; the light aromatic compounds are selected from the group consisting of benzene, toluene, ethylbenzene, xylenes, and combinations thereof; the cracking catalyst consists essentially of a hierarchical mesoporous ZSM-5 zeolite; and the hierarchical mesoporous ZSM-5 zeolite comprises a molar ratio of silica to alumina of from 10 to 40. ### Claim 2 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-5 zeolite has a crystal size of from 50 nanometers to 600 nanometers. ### Claim 3 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-zeolite comprises a hierarchical pore structure comprising mesopores and micropores. ### Claim 4 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-zeolite has a total BET surface area of from 500 m2/g to 600 m2/g, and a mesoporous BET surface area of from 300 m2/g to 400 m2/g, where the mesoporous BET surface area is a surface area of internal surfaces of the mesopores as determined by the BET method. ### Claim 5 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-zeolite has a mesoporous BET surface area that is greater than a microporous BET surface area, where the mesoporous BET surface area is a surface area of internal surfaces of mesopores of the hierarchical mesoporous ZSM-zeolite as determined by the BET method, and the microporous BET surface area is a surface area of internal surface of micropores of the hierarchical mesoporous ZSM-zeolite as determined by the BET method. ### Claim 6 (depends on 5) The process of claim 5, where the mesoporous BET surface area of the hierarchical mesoporous ZSM-zeolite is greater than or equal to 50% of a total BET surface area of the hierarchical mesoporous ZSM-zeolite. ### Claim 7 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-zeolite has a total pore volume of from 0.4 cm3/g to 0.5 cm3/g, where the total pore volume includes a mesopore volume and a micropore volume of the hierarchical mesoporous ZSM-zeolite. ### Claim 8 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-zeolite has a mesopore volume that is greater than a micropore volume, where the mesopore volume is a pore volume of mesopores of the hierarchical mesoporous ZSM-zeolite, and the micropore volume is a pore volume of micropores of the hierarchical mesoporous ZSM-zeolite. ### Claim 9 (depends on 8) The process of claim 8, where the mesopore volume of the hierarchical mesoporous ZSM-zeolite is greater than or equal to 60% of the total pore volume of the hierarchical mesoporous ZSM-zeolite. ### Claim 10 (depends on 1) The process of claim 1, where the hierarchical mesoporous ZSM-5 zeolite is prepared by a method comprising: providing a starting ZSM-5 zeolite; disintegrating at least a portion of the ZSM-5 zeolite in a first mixture comprising the starting ZSM-5 zeolite, sodium hydroxide, and a surfactant at a temperature of 100° C. for a first time period; after the disintegrating the at least a portion of the ZSM-5 zeolite, recrystallizing zeolite constituents in the presence of the surfactant to produce a recrystallized ZSM-5 zeolite; recovering the recrystallized ZSM-5 zeolite; and calcining the recrystallized ZSM-5 zeolite, where the calcining removes the surfactant from the recrystallized ZSM-5 zeolite to produce the hierarchical mesoporous ZSM-5 zeolite having a hierarchical pore structure. ### Claim 11 (depends on 10) The process of claim 10, further comprising, after calcining, treating the hierarchical mesoporous ZSM-5 zeolite with 0.25 N ammonium nitrate twice at 80° C. for 5 hours, where the treating with the ammonium nitrate ion-exchanges the hierarchical mesoporous ZSM-5 zeolite to produce the hierarchical mesoporous ZSM-5 zeolite in hydrogen form. ### Claim 12 (depends on 10) The process of claim 10, where disintegrating the at least a portion of the starting ZSM-5 zeolite comprises: combining the starting ZSM-5 zeolite, the sodium hydroxide, and the surfactant to form the first mixture; heating the first mixture to a temperature of 100° C. while stirring; and maintaining the first mixture at the temperature of 100° C. and stirring for a period of from 10 hours to 30 hours. ### Claim 13 (depends on 10) The process of claim 10, where recrystallizing the ZSM-5 zeolite constituents comprises: cooling the first mixture to a temperature of from 20° C. to 50° C.; adjusting the pH of the first mixture to a pH of 9.0 to produce a second mixture; stirring the second mixture for a second time period of from 10 hours to 30 hours; and hydrothermally treating the second mixture by increasing the temperature to 100° C. and stirring for a third period of from 10 hours to 30 hours, where stirring for the second time period and hydrothermally treating the second mixture for the third period recrystallizes the zeolite constituents in the presence of the surfactant to produce the recrystallized ZSM-5 zeolite. ### Claim 14 (depends on 10) The process of claim 10, where the surfactant comprises cetyltrimethylammonium bromide (CTAB), and the concentration of the CTAB in the first mixture is from 4 weight percent to 5 weight percent based on the total weight of the first mixture. ### Claim 15 (depends on 1) The process of claim 1, where the hydrocarbon feed comprises a whole crude oil having an API gravity between 25 and 50. ### Claim 16 (depends on 1) The process of claim 1, where the steam catalytic cracking effluent comprises olefins and the olefins comprise one or more of ethylene, propylene, butenes, or combinations of these. ### Claim 17 (depends on 1) The process of claim 1, comprising contacting the hydrocarbon feed with the steam in the presence of the cracking catalyst in a cracking reactor, where the cracking reactor comprises one or more fixed bed reactors, fluidized bed reactor, batch reactor, moving bed catalytic cracking reactor, fluidized catalytic cracking (FCC) reactor, or combinations of these. ### Claim 18 (depends on 1) The process of claim 1, comprising contacting the hydrocarbon feed with the steam in the presence of the cracking catalyst at a reaction temperature of from 500° C. to 800° C., a mass ratio of steam to hydrocarbons of from 0.2 to less than 1, a weight ratio of cracking catalyst to hydrocarbon from 3 to 40, or combinations of these. ### Claim 19 (depends on 1) The process of claim 1, comprising contacting the hydrocarbon feed with the steam in the presence of the cracking catalyst for a residence time of from 1 second to 60 seconds. ### Claim 20 A process for upgrading a hydrocarbon feed, the process comprising: contacting the hydrocarbon feed with steam in the presence of a cracking catalyst at reaction conditions sufficient to cause at least a portion of hydrocarbons in the hydrocarbon feed to undergo one or more cracking reactions to produce a steam catalytic cracking effluent comprising light olefins, light aromatic compounds, or both, where: the light olefins are selected from the group consisting of ethylene, propylene, butenes, and combinations thereof, the light aromatic compounds are selected from the group consisting of benzene, toluene, ethylbenzene, xylenes, and combinations thereof, the cracking catalyst consists essentially of a hierarchical mesoporous ZSM-5 zeolite; and the hydrocarbon feed comprises a whole crude oil having an API gravity between 25 and 50.