	US 12,215,075 B2
	Method for the production of MTBE and 1-butene from a C₄feed stream
Mohammad Al-Somali, Jubail (SA); Ewa Gebauer-Henke, Geleen (NL); Aäron Vandeputte, Geleen (NL); Christian Okolo, Geleen (NL); and Rasim Yagan, Geleen (NL)
Assigned to SABIC GLOBAL TECHNOLOGIES B.V., Bergen op Zoom (NL)
Appl. No. 17/273,217
Filed by SABIC GLOBAL TECHNOLOGIES B.V., Bergen op Zoom (NL)
PCT Filed Sep. 3, 2019, PCT No. PCT/IB2019/057424 § 371(c)(1), (2) Date Mar. 3, 2021, PCT Pub. No. WO2020/049463, PCT Pub. Date Mar. 12, 2020.
Claims priority of provisional application 62/728,593, filed on Sep. 7, 2018.
Prior Publication US 2021/0347717 A1, Nov. 11, 2021
Int. Cl. C07C 41/06 (2006.01); C07C 5/25 (2006.01); C07C 7/04 (2006.01); C07C 41/42 (2006.01)

CPC C07C 41/06 (2013.01) [C07C 5/2506 (2013.01); C07C 7/04 (2013.01); C07C 41/42 (2013.01)]

19 Claims

1. A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising:

distilling a crude C₄hydrocarbon 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.

2. A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising:

distilling a crude C₄hydrocarbon 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;

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 C₄hydrocarbon 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.

6. A method of producing methyl tertiary butyl ether (MTBE) and/or 1-butene, the method comprising:

distilling a crude C₄hydrocarbon 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;

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