# US 10,865,164 B2 · Process for oligomerization with stage-customized exchange of the oligomerization catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,865,164 B2 - Document ID: US10865164B2 - Status: Granted - Kind: B2 - Application number: 16/711,012 - Filed: 2019-12-11 - Published: 2020-06-18 - Granted: 2020-12-15 - Earliest claimed: 2018-12-13 - Assignees: Evonik Operations GmbH - Applicants: Evonik Operations GmbH - Inventors: Stephan Peitz; Dietrich Maschmeyer; Helene Reeker; Guido Stochniol; Markus Winterberg; Andreas Beckmann - Web page: https://patentgrep.com/patent/US10865164B2 ## CPC - C07C 2/10: with metal oxides - C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation - B01J 38/02: Heat treatment - B01J 38/485: {Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements} - C07C 7/04: by distillation - B01J 8/02: with stationary particles, e.g. in fixed beds - B01J 8/04: the fluid passing successively through two or more beds - B01J 8/0419: {the beds being placed in separate reactors} - B01J 19/1818: {in series} - B01J 19/1825: {in parallel} - B01J 19/1837: {Loop-type reactors} - B01J 19/24: Stationary reactors without moving elements inside (B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02) - B01J 19/2415: {Tubular reactors} - B01J 19/242: {in series} - B01J 19/2425: {in parallel} - C07C 7/005: {Processes comprising at least two steps in series} - C07C 2521/12: Silica and alumina - C07C 2523/78: with alkali- or alkaline earth metals or beryllium - Y02P 20/584: Recycling of catalysts - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - 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 - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A method includes at least two-stage process for the oligomerization of short-chain olefins in the presence of a catalyst, wherein the regeneration of the catalyst is stage-customized. ## Claims ### Claim 1 A process for oligomerization of C3- to C6-olefins, the process comprising: reacting a starting mixture comprising C3- to C6-olefins, from which nitrogen-, oxygen- and/or sulfur-containing impurities that act as catalyst poisons have been at least partially removed, in at least two successive reaction stages, wherein each reaction stage comprises at least one reactor and at least one distillation column, wherein each reaction stage uses an oligomerization catalyst, having a composition of 15 to 40% by weight NiO, 5 to 30% by weight Al2O3, 55 to 80% by weight SiO2, and 0.01 to 2.5% by weight of an alkali metal oxide, wherein the at least one reactor of the first reaction stage is operated isothermally, exchanging the oligomerization catalyst in the first reaction stage for a fresh oligomerization catalyst at the latest after 47 months, and exchanging the oligomerization catalyst in the second reaction stage for a fresh oligomerization catalyst at the earliest after 48 months to at the latest after 72 months. ### Claim 2 (depends on 1) The process according to claim 1, wherein the exchanging the oligomerization catalyst in the first reaction stage for the fresh oligomerization catalyst occurs at the earliest after 6 months. ### Claim 3 (depends on 1) The process according to claim 1, wherein the process comprises three, four or five reaction stages. ### Claim 4 (depends on 3) The process according to claim 3, wherein the oligomerization catalyst of the second and all subsequent reaction stages are exchanged at the same time. ### Claim 5 (depends on 1) The process according to claim 1, wherein the at least one reactor in each reaction stage is operated isothermally. ### Claim 6 (depends on 1) The process according to claim 1, wherein the volume of the reactor of the second reaction stage and, if present, the volume of the reactor of each subsequent reaction stage is equal to or smaller than the volume of the preceding reaction stage. ### Claim 7 (depends on 1) The process according to claim 1, wherein the fresh oligomerization catalyst is a newly produced oligomerization catalyst or a regenerated oligomerization catalyst. ### Claim 8 (depends on 7) The process according to claim 7, wherein the fresh oligomerization catalyst is a regenerated oligomerization catalyst produced by: A) burning off an oligomerization catalyst used for the oligomerization, and B) impregnating the oligomerization catalyst burnt off in A) with a solution of a transition metal compound and subsequent calcination. ### Claim 9 (depends on 8) The process according to claim 8, wherein in B), the impregnated oligomerization catalyst is dried at temperatures between 100 and 250° C. and at standard pressure or under reduced pressure prior to the calcination. ### Claim 10 (depends on 1) The process according to claim 1, wherein the oligomerization is carried out at a temperature in the range of 50 to 200° C. and at a pressure of 10 to 70 bar. ### Claim 11 (depends on 1) The process according to claim 1, wherein the oligomerization catalyst in the first reaction stage is exchanged at the latest after 45 months. ### Claim 12 (depends on 1) The process according to claim 1, wherein the oligomerization catalyst in the first reaction stage is exchanged at the latest after 43 months. ### Claim 13 (depends on 1) The process according to claim 1, wherein the C3- to C6-olefins are purified by completely removing the nitrogen-, oxygen- and/or sulfur-containing impurities from the starting mixture comprising the C3- to C6-olefins. ### Claim 14 A system for oligomerization of C3- to C6-olefins, the system comprising: a starting mixture comprising the C3- to C6-olefins, wherein nitrogen-, oxygen- and/or sulfur-containing impurities that act as catalyst poisons are at least partially removed from the starting mixture, at least two reaction stages, each of which comprises at least one reactor and at least one distillation column, and an oligomerization catalyst, comprising 15 to 40% by weight NiO, 5 to 30% by weight Al2O3, 55 to 80% by weight SiO2, and 0.01 to 2.5% by weight of an alkali metal oxide, wherein the at least one reactor of the first reaction stage is operated isothermally, wherein the oligomerization catalyst in the first reaction stage is exchanged with a fresh oligomerization catalyst at the latest after 47 months, and wherein the oligomerization catalyst in the second reaction stage is exchanged with a fresh oligomerization catalyst at the earliest after 48 months to at the latest after 72 months.