# US 12,215,075 B2 · Method for the production of MTBE and 1-butene from a C4 feed stream > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,215,075 B2 - Document ID: US12215075B2 - Status: Granted - Kind: B2 - Application number: 17/273,217 - Filed: 2019-09-03 - Published: 2021-11-11 - Granted: 2025-02-04 - Earliest claimed: 2018-09-07 - Assignees: Sabic Global Technologies B.V. - Applicants: Sabic Global Technologies B.V. - Inventors: Mohammad Al-Somali; Ewa Gebauer-Henke; Aäron Vandeputte; Christian Okolo; Rasim Yagan - Web page: https://patentgrep.com/patent/US12215075B2 ## CPC - C07C 41/06: by addition of organic compounds only - C07C 5/2506: {Catalytic processes} - C07C 7/04: by distillation - C07C 41/42: by distillation - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Systems and methods for producing MTBE and 1-butene are disclosed. A crude C4 hydrocarbon stream is obtained by removing butadiene from a C4 hydrocarbon mixture of a hydrocarbon cracking unit. The crude C4 hydrocarbon stream is then distilled to form (a) a first distillate stream comprising isobutylene, isobutane, 1-butene, or combinations thereof and (b) a first bottom stream comprising 2-butene, n-butane, a deactivating compound for catalyst of MTBE synthesis. The first distillate stream is then flowed to a MTBE synthesis unit to produce via reaction with methanol. The raffinate from the MTBE synthesis unit comprising isobutane and 1-butene is further separated in a distillation column to produce 1-butene. ## Claims ### Claim 1 A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising: distilling a crude C4 hydrocarbon stream that comprises n-butane, 1-butene, 2-butene, isobutane and isobutene, one or more of 1,2-butadiene and 1,3-butadiene, and a catalyst deactivating compound capable of deactivating the catalyst for MTBE synthesis to produce: (1) a distillate stream comprising isobutene, isobutane, and 1-butene; and (2) a bottom stream comprising 2-butene, n-butane, and the catalyst deactivating compound; reacting the isobutene of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tertiary butyl ether and an unreacted portion of the distillate stream; separating the methyl tertiary butyl ether from the unreacted portion of the distillate stream, the unreacted portion comprising isobutane and 1-butene; and flowing the bottom stream to an olefins conversion technology unit, and reacting at least some of the 2-butene of the bottom stream with ethylene in the olefins conversion technology unit to form an effluent containing propylene and a liquified petroleum gas stream; distilling the unreacted portion of the distillate stream to produce a second distillate stream comprising isobutane and a second bottom stream comprising primarily 1-butene; wherein the catalyst deactivating compound is selected from the group consisting of dimethylformamide, n-methyl-2-pyrrolidone, acetonitrile, furfural, methoxy-propionitrile, or combinations thereof; wherein the MTBE is separated at a recovery rate of 95 to 100 wt. % in the separating step; and wherein distilling the unreacted portion of the distillate stream is carried out under operating conditions including a bottom boiling range of 40 to 70° C., an overhead boiling range of 30 to 60° C., a molar reflux ratio in a range of 55 to 100, and a number of theoretical plates in a range of 85 to 120. ### Claim 2 A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising: distilling a crude C4 hydrocarbon stream that comprises n-butane, 1-butene, 2-butene, isobutane, isobutene, one or more of 1,2-butadiene and 1,3-butadiene, and a catalyst deactivating compound capable of deactivating the catalyst for MTBE synthesis to produce: (1) a distillate stream comprising isobutene, isobutane, and 1-butene; and (2) a bottom stream comprising 2-butene, n-butane, and the catalyst deactivating compound; reacting the isobutene of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tertiary butyl ether and an unreacted portion of the distillate stream; separating the methyl tertiary butyl ether from the unreacted portion of the distillate stream, the unreacted portion comprising isobutane and 1-butene; isomerizing, in an isomerization unit, at least some of the 2-butene in the bottom stream to form an isomerized recycle stream comprising 1-butene, non-isomerized 2-butene, and n-butane; combining the isomerized recycle stream with the crude C4 hydrocarbon stream for the distilling step; and distilling the unreacted portion of the distillate stream to produce a second distillate stream comprising isobutane and a second bottom stream comprising primarily 1-butene; wherein the MTBE is separated at a recovery rate of 95 to 100 wt. % in the separating step; and wherein the isomerizing is carried out at a pressure of 15 to 40 bar and distilling the unreacted portion of the distillate stream is carried out under operating conditions including a bottom boiling range of 40 to 70° C., an overhead boiling range of 30 to 60° C., a molar reflux ratio in a range of 55 to 100, and a number of theoretical plates in a range of 85 to 120. ### Claim 3 (depends on 2) The method of claim 2, wherein the isomerization unit comprises a catalyst selected from the group consisting of iridium pincer complex catalysts, or supported catalysts containing at least one noble metal from Group VIII, selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum, or nickel, and the catalyst is processed by a sulfur-containing compound, then by hydrogen prior to being used. ### Claim 4 (depends on 2) The method of claim 2, wherein the catalyst deactivating compound is selected from the group consisting of dimethylformamide, acetonitrile n-methyl-2-pyrrolidone, furfural, methoxy-propionitrile, or combinations thereof. ### Claim 5 (depends on 2) The method of claim 2, wherein the isomerizing is carried out at a pressure of 20 to 40 bar. ### Claim 6 A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising: distilling a crude C4 hydrocarbon stream that comprises one or more of n-butane, 1-butene, 2-butene, isobutane, isobutene, 1,2-butadiene, 1,3-butadiene, and a catalyst deactivating compound capable of deactivating the catalyst for MTBE synthesis to produce: (1) a distillate stream comprising isobutene, isobutane, and 1-butene; and (2) a bottom stream comprising 2-butene, n-butane, and the catalyst deactivating compound; reacting the isobutene of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tertiary butyl ether and an unreacted portion of the distillate stream; separating the methyl tertiary butyl ether from the unreacted portion of the distillate stream, the unreacted portion comprising isobutane and 1-butene; flowing the bottom stream to an olefins conversion technology unit; reacting at least some of the 2-butene of the bottom stream with ethylene in the olefins conversion technology unit to form an effluent comprising propylene and liquefied petroleum gas; distilling the unreacted portion of the distillate stream to produce a second distillate stream comprising isobutane and a second bottom stream comprising primarily 1-butene; wherein the catalyst deactivating compound is selected from the group consisting of dimethylformamide, acetonitrile, n-methyl-2-pyrrolidone, furfural, methoxy-propionitrile, or combinations thereof; wherein the MTBE is separated at a recovery rate of 95 to 100% in the separating step; wherein the olefins conversion technology unit is operated at a temperature of 100 to 500° C.; and wherein distilling the unreacted portion of the distillate stream is carried out under operating conditions including a bottom boiling range of 40 to 70° C., an overhead boiling range of 30 to 60° C., a molar reflux ratio in a range of 55 to 100, and a number of theoretical plates in a range of 85 to 120. ### Claim 7 (depends on 6) The method of claim 6, wherein the olefins conversion technology unit contains a catalyst selected from the group consisting of Schrock catalysts, tungsten oxide on silica or alumina support, molybdenum oxide on silica or alumina support, rhenium oxide on silica or alumina support, cobalt molybdate on alumina, and combinations thereof. ### Claim 8 (depends on 4) The method of claim 4, wherein the catalyst deactivating compound comprises dimethylformamide, acetonitrile n-methyl-2-pyrrolidone, methoxy-propionitrile, or combinations thereof. ### Claim 9 (depends on 1) The method of claim 1, wherein the distilling of the crude C4 hydrocarbon stream is carried out under operating conditions including a bottom boiling range of 50 to 100° C., an overhead boiling range of 30 to 60° C., a molar reflux ratio in a range of 0.5 to 100, and a number of theoretical plates in a range of 25 to 120. ### Claim 10 (depends on 1) The method of claim 1, wherein the distilling of the crude C4 hydrocarbon stream is carried out at a pressure of 3 to 10 bar. ### Claim 11 (depends on 1) The method of claim 1, wherein distilling the unreacted portion is carried out under operating conditions including a bottom boiling range of 40 to 70° C., an overhead boiling range of 30 to 60° C., a molar reflux ratio in a range of 60 to 100, and a number of theoretical plates in a range of 90 to 120. ### Claim 12 (depends on 1) The method of claim 1, wherein distilling the unreacted portion is carried out at a pressure of 3 to 10 bar. ### Claim 13 (depends on 1) The method of claim 1, wherein the second bottom stream comprises 95 to 99.9 wt. % 1-butene. ### Claim 14 (depends on 1) The method of claim 1, wherein the crude C4 hydrocarbon stream comprises 0 to 1 wt. % catalyst deactivating compound. ### Claim 15 (depends on 1) The method of claim 1, wherein the distillate stream further comprises 0.1 to 10 ppm of the catalyst deactivating compound. ### Claim 16 (depends on 1) The method of claim 1, wherein the catalyst deactivating compound is dimethylformamide (DMF). ### Claim 17 (depends on 1) The method of claim 1, wherein the catalyst deactivating compound is n-methyl-2-pyrrolidone (NMP). ### Claim 18 (depends on 1) The method of claim 1, wherein the catalyst deactivating compound is furfural. ### Claim 19 (depends on 1) The method of claim 1, wherein the catalyst deactivating compound is methoxy-propionitrile (MOPN).