# US 10,308,568 B2 · Selective poisoning of aromatization catalysts to increase catalyst activity and selectivity > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,308,568 B2 - Document ID: US10308568B2 - Status: Granted - Kind: B2 - Application number: 15/582,798 - Filed: 2017-05-01 - Published: 2018-11-01 - Granted: 2019-06-04 - Earliest claimed: 2017-05-01 - Assignees: Chevron Phillips Chemical Company LP - Applicants: Chevron Phillips Chemical Company LP - Inventors: Ryan W. Snell; Theresa E. Feltes; Cori A. Demmelmaier-Chang - Web page: https://patentgrep.com/patent/US10308568B2 ## CPC - C07C 5/417: {of the platinum group} - B01J 8/0214: {in a cylindrical annular shaped bed} - B01J 8/0411: {the beds being concentric} - B01J 8/0419: {the beds being placed in separate reactors} - C10G 35/09: Bimetallic catalysts in which at least one of the metals is a platinum group metal - C10G 35/095: containing crystalline alumino-silicates, e.g. molecular sieves {(C10G35/065 takes precedence)} - C10G 59/02: plural serial stages only - B01J 2208/025: Two or more types of catalyst - C07C 2529/62: Noble metals - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - 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 Spent aromatization catalysts containing a transition metal and a catalyst support are selectively poisoned in the disclosed reforming methods, resulting in improvements in overall aromatics yield and selectivity. ## Claims ### Claim 1 A reforming method comprising: (A) introducing a first hydrocarbon feed into a radial flow reactor comprising a catalyst bed, and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions to produce a first aromatic product; wherein: the catalyst bed comprises an outer reforming zone and an inner reforming zone; the outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support; and the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support; (B) performing step (A) for a time period sufficient to form a spent first aromatization catalyst in the outer reforming zone; (C) introducing a catalyst poisoning agent into the radial flow reactor and contacting at least a portion of the spent first aromatization catalyst to form a poisoned aromatization catalyst in the outer reforming zone; and (D) introducing a second hydrocarbon feed into the radial flow reactor comprising the catalyst bed, and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions to produce a second aromatic product; wherein: the spent first aromatization catalyst comprises from about 1 wt. % to about 10 wt. % carbon; the poisoned aromatization catalyst has an aromatics yield of less than 10 wt. %; and the catalyst poisoning agent comprises a heavy hydrocarbon, a sulfur-containing compound, a phosphorus-containing compound, an oxygen-containing compound, a bromine-containing compound, an iodine-containing compound, an organometallic lead compound, an organometallic arsenic compound, or any combination thereof. ### Claim 2 (depends on 1) The method of claim 1, wherein: the first aromatization catalyst comprises from about 0.3 wt. % to about 5 wt. % of the first transition metal; and the second aromatization catalyst comprises from about 0.3 wt. % to about 5 wt. % of the second transition metal. ### Claim 3 (depends on 1) The method of claim 1, wherein: the first transition metal and the second transition metal comprise platinum; the first catalyst support and the second catalyst support comprise a KL-zeolite and a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof; and the first aromatization catalyst and the second aromatization catalyst further comprise chlorine and fluorine. ### Claim 4 (depends on 1) The method of claim 1, wherein: the first aromatic product and the second aromatic product, independently, comprise benzene, toluene, or a combination thereof; and the first reforming conditions and the second reforming conditions, independently, comprise a reforming temperature in a range from about 350° C. to about 600° C. ### Claim 5 (depends on 1) The method of claim 1, wherein a weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in a range from about 1:1.5 to about 1:5. ### Claim 6 (depends on 3) The method of claim 3, wherein the first aromatization catalyst and the second aromatization catalyst, independently, comprise from about 0.5 wt. % to about 2 wt. % of platinum. ### Claim 7 (depends on 1) The method of claim 1, wherein the catalyst poisoning agent is introduced at a molar ratio, based on moles of the catalyst poisoning agent to moles of the first transition metal in the spent first aromatization catalyst, in a range from about 0.1:1 to about 0.75:1. ### Claim 8 (depends on 7) The method of claim 7, wherein: the first transition metal and the second transition metal comprise platinum; the first catalyst support and the second catalyst support comprise a KL-zeolite and a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof; and the first aromatization catalyst and the second aromatization catalyst further comprise chlorine and fluorine. ### Claim 9 (depends on 1) The method of claim 1, wherein: the aromatics yield of the second aromatization catalyst is greater than that of the spent first aromatization catalyst, under the same test conditions; and the aromatics selectivity of the second aromatization catalyst is greater than that of the spent first aromatization catalyst, under the same test conditions. ### Claim 10 (depends on 1) The method of claim 1, wherein an aromatics yield of the second aromatic product in step (D) is greater than a yield of the first aromatic product produced after step (B) and before step (C). ### Claim 11 (depends on 1) The method of claim 1, wherein an aromatics selectivity of the second aromatic product in step (D) is greater than an aromatics selectivity of the first aromatic product produced after step (B) and before step (C). ### Claim 12 A reforming method comprising: (a) providing a radial flow reactor comprising a catalyst bed, the catalyst bed comprising an outer reforming zone and an inner reforming zone; wherein: the outer reforming zone comprises a spent first aromatization catalyst comprising a first transition metal and a first catalyst support; and the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support; (b) introducing a catalyst poisoning agent into the radial flow reactor and contacting at least a portion of the spent first aromatization catalyst to form a poisoned aromatization catalyst in the outer reforming zone; and (c) introducing a hydrocarbon feed into the radial flow reactor comprising the catalyst bed, and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product; wherein: the spent first aromatization catalyst comprises from about 1 wt. % to about 10 wt. % carbon; the poisoned aromatization catalyst has an aromatics yield of less than 10 wt. %; and the catalyst poisoning agent comprises a heavy hydrocarbon, a sulfur-containing compound, a phosphorus-containing compound, an oxygen-containing compound, a bromine-containing compound, an iodine-containing compound, an organometallic lead compound, an organometallic arsenic compound, or any combination thereof. ### Claim 13 (depends on 12) The method of claim 12, wherein: an aromatics yield of the aromatic product in step (c) is greater than a yield of an aromatic product produced after step (a) and before step (b); and an aromatics selectivity of the aromatic product in step (c) is greater than an aromatics selectivity of an aromatic product produced after step (a) and before step (b). ### Claim 14 (depends on 13) The method of claim 13, wherein: the first transition metal and the second transition metal comprise platinum; the first catalyst support and the second catalyst support comprise a KL-zeolite and a binder comprising alumina, silica, a mixed oxide thereof, or a mixture thereof; and the spent first aromatization catalyst and the second aromatization catalyst further comprise chlorine and fluorine. ### Claim 15 (depends on 14) The method of claim 14, wherein: the spent first aromatization catalyst and the second aromatization catalyst, independently, comprise from about 0.3 wt. % to about 5 wt. % of platinum; and the aromatic product comprises benzene, toluene, or a combination thereof. ### Claim 16 (depends on 15) The method of claim 15, wherein the spent first aromatization catalyst comprises from about 1.5 wt. % to about 7 wt. % carbon. ### Claim 17 A reforming method comprising: (A) introducing a first hydrocarbon feed into a radial flow reactor comprising a catalyst bed, and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions to produce a first aromatic product; wherein: the catalyst bed comprises an outer reforming zone and an inner reforming zone; the outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support; and the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support; (B) performing step (A) for a time period sufficient to form a spent first aromatization catalyst in the outer reforming zone; (C) introducing a catalyst poisoning agent into the radial flow reactor and contacting at least a portion of the spent first aromatization catalyst to form a poisoned aromatization catalyst in the outer reforming zone; and (D) introducing a second hydrocarbon feed into the radial flow reactor comprising the catalyst bed, and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions to produce a second aromatic product; wherein: the spent first aromatization catalyst comprises from about 1 wt. % to about 10 wt. % carbon; the poisoned aromatization catalyst has an aromatics yield of less than 10 wt. %; the catalyst poisoning agent comprises a heavy hydrocarbon, a sulfur-containing compound, a phosphorus-containing compound, an oxygen-containing compound, a bromine-containing compound, an iodine-containing compound, an organometallic lead compound, an organometallic arsenic compound, or any combination thereof; an aromatics yield of the second aromatic product in step (D) is greater than a yield of the first aromatic product produced after step (B) and before step (C); and an aromatics selectivity of the second aromatic product in step (D) is greater than an aromatics selectivity of the first aromatic product produced after step (B) and before step (C). ### Claim 18 (depends on 17) The method of claim 17, wherein the first aromatization catalyst and the second aromatization catalyst, independently, comprise from about 0.5 wt. % to about 2 wt. % of platinum. ### Claim 19 (depends on 18) The method of claim 18, wherein: the first aromatic product and the second aromatic product, independently, comprise benzene, toluene, or a combination thereof; and the first catalyst support and the second catalyst support comprise a silica-bound KL-zeolite. ### Claim 20 (depends on 17) The method of claim 17, wherein: a weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in a range from about 1:1.5 to about 1:5; and the catalyst poisoning agent is introduced at a molar ratio, based on moles of the catalyst poisoning agent to moles of the first transition metal in the spent first aromatization catalyst, in a range from about 0.1:1 to about 0.75:1.