Processes and systems for C3+ monoolefin conversion

Patent metadata

Field	Value
Publication number	US-11845707-B2
Application number	US-202017611342-A
Country	US
Kind code	B2
Filing date	Jun 10, 2020
Priority date	Jun 12, 2019
Publication date	Dec 19, 2023
Grant date	Dec 19, 2023

Abstract

Processes and systems for C 3+ monoolefin conversion. In some examples, the process can include reacting a first mixture that includes C 3+ monoolefins and a first oxygenate to produce a first effluent that includes a first ether and <1 wt. % of any first di-C 3+ olefin. A first product that includes the first ether and a first byproduct that includes at least a portion of any first di-C 3+ olefin and unreacted C 3+ monoolefins can be separated from the first effluent. A second olefin mixture, at least a portion of the first byproduct, and a second oxygenate can be combined to produce a second mixture. The second mixture can be reacted to produce a second effluent that includes a second ether and a second di-C 3+ olefin. The reaction of the second mixture can produce a greater amount, on a mole basis, of the second di-C 3+ olefin than the second ether.

First claim

What is claimed is:

1. A process for C 3+ monoolefin conversion, comprising:
providing a first mixture comprising a first process fluid and a first olefin mixture,
catalytically reacting at least a portion of the first mixture's first process fluid with at least a portion of the first mixture's first olefin mixture to produce a first effluent comprising a first ether and unreacted first olefin mixture, wherein the first olefin mixture comprises ≥1 wt. % of a first C 3+ monoolefin, wherein the first process fluid comprises ≥1 wt. % of a first oxygenate, and wherein the first effluent comprises <1 wt. % of a first di-C 3+ olefin or is free of any first di-C 3+ olefin;
separating a first product and a first byproduct from the first effluent, wherein the first product comprises at least a portion of the first ether, and wherein the first byproduct comprises at least a portion of the unreacted first olefin mixture;
combining a second olefin mixture, at least a portion of the first byproduct, and a second process fluid to produce a second mixture, wherein (i) the second olefin mixture comprises ≥1 wt. % of a second C 3+ monoolefin, and (ii) the second process fluid comprises ≥1 wt. % of a second oxygenate; and
catalytically reacting two or more of (i) at least a portion of the second mixture's second process fluid, (ii) at least a portion of the second mixture's second olefin mixture, and (iii) at least a portion of the second mixture's first byproduct to produce a second effluent comprising a second di-C 3+ olefin and a second ether, wherein the reaction produces a greater amount, on a mole basis, of the second di-C 3+ olefin than that of the second ether, wherein the second effluent further comprises unreacted first C3+ monoolefin, unreacted second C3+ monoolefin, or a mixture thereof,
reacting at least a portion of any unreacted first C 3+ monoolefin, at least a portion of any unreacted second C 3+ monoolefin, or both in a third reactor to produce a third effluent comprising a third di-C 3+ olefin, a third ether;
obtaining a second product, a third product, and a recycle from the third effluent, and
mixing a portion of the recycle with the first byproduct, the second olefin mixture, the second mixture, the second effluent, or a combination of two or more thereof.

2. The process of claim 1 , wherein the first oxygenate comprises a first alcohol.

3. The process of claim 1 , wherein the first oxygenate comprises methanol, ethanol, n-propanol, n-butanol, n-amylalcohol, or a mixture thereof.

4. The process of claim 1 , wherein the first olefin mixture and the second olefin mixture each further comprise but-1-ene, cis-p-butylene, trans-R-butylene, n-butane, or a mixture thereof.

5. The process of claim 1 , wherein the first ether, the second oxygenate, and the second ether each comprise methyl tert-butyl ether, and wherein the first di-C 3+ olefin and the second di-C 3+ olefin each comprise diisobutylene.

6. The process of claim 1 , wherein the first product comprises ≥98 wt. % of methyl tert-butyl ether, based on the weight of the first product.

7. The process of claim 1 , wherein the first mixture is reacted in the presence of a first catalyst to produce the first effluent, and wherein the second mixture is reacted in the presence of a second catalyst to produce the second effluent.

8. The process of claim 1 , further comprising separating a second product and a second byproduct from the second effluent, wherein the second product comprises at least a portion of any first di-C 3 olefin and at least a portion of the second di-C 3 + olefin.

9. The process of claim 1 , wherein:
the third di-C3+ olefin comprises diisobutylene,
the third ether comprises methyl tert-butyl ether, methyl sec-butyl ether, or a mixture thereof,
the second product comprises >60 wt. % of diisobutylene based on the weight of the second product;
the third product comprises >90 wt. % of one or more tri-C4+ olefins based on the weight of the third product,
the second byproduct comprises but-1-ene, cis-β-butylene, trans-β-butylene, n-butane, or a mixture thereof,
the recycle comprises methyl tert-butyl ether, methyl sec-butyl ether, or a mixture thereof, and
the second process fluid comprises a portion of the recycle.

10. The process of claim 9 , wherein the second by-product comprises no greater than 1 wt % of isobutylene, based on the total weight of the second byproduct.

11. The process of claim 1 , wherein the recycle comprises about 75 wt. % to about 90 wt. % of methyl tert-butyl ether based on a total weight of the recycle.

12. The process of claim 11 , wherein the recycle comprises about 10 wt. % to about 20 wt. % of methyl sec-butyl ether based on a total weight of the recycle.

13. The process of claim 1 , wherein the first olefin mixture and the second olefin mixture are the same.

14. The process of claim 1 , wherein at least a portion of the first byproduct is supplied into the third reactor.

15. The process of claim 1 , wherein:
the third reactor comprises a reactive distillation column, and a second byproduct comprising unreacted second mixture is produced from the third reactor.

16. The process of claim 1 , wherein the third effluent further comprises unreacted second mixture; and the process further comprises:
separating a second byproduct comprising at least a portion of the unreacted second mixture and a fourth effluent from the third effluent; and
separating a second product, a third product, and a recycle from the fourth effluent.

17. A process for C 3+ monoolefin conversion, comprising:
combining a first olefin mixture and a first process fluid to produce a first mixture, wherein the first olefin mixture comprises ≥1 wt. % of a first C 3+ monoolefin, and wherein the first process fluid comprises ≥1 wt. % of a first alcohol;
reacting the first mixture in the presence of a first catalyst to produce a first effluent comprising a first ether and unreacted first olefin mixture, wherein the first effluent comprises <1 wt. % of a first di-C 3+ olefin or is free of any first di-C 3+ olefin;
separating a first product and a first byproduct from the first effluent, wherein the first product comprises at least a portion of the first ether, and wherein the first byproduct comprises at least a portion of the unreacted first olefin mixture;
combining a second olefin mixture, at least a portion of the first byproduct, and a second process fluid to produce a second mixture, wherein the second olefin mixture comprises ≥1 wt. % of a second C 3+ olefin;
reacting the second mixture in the presence of a second catalyst to produce a second effluent comprising a second di-C 3+ olefin, a second ether, unreacted first olefin mixture, and unreacted second olefin mixture, wherein reacting the second mixture produces a greater amount, on a mole basis, of the second di-C 3+ olefin than the second ether;
combining the second effluent and a third process fluid to produce a third mixture, wherein the third process fluid comprises ≥1 wt. % of a second alcohol;
reacting the third mixture in a third reactor in the presence of a third catalyst to produce a third effluent comprising a third ether, a third di-C 3+ olefin, unreacted first olefin mixture, and unreacted second olefin mixture; and
separating a second product and a recycle from the third effluent, wherein the second product comprises at least a portion of any first di-C 3+ olefin, at least a portion of the second di-C 3+ olefin, and at least a portion of the third di-C 3+ olefin, wherein the recycle comprises at least a porti

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Smith Rodney S
• Jindal Roshni
• Hietpas Julie D

Classifications

• C07C2/28 Primary

  with ion-exchange resins · CPC title

• C07C2/864 Primary

  the non-hydrocarbon is an alcohol · CPC title

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C1/24

  by elimination of water · CPC title

• C07C2/08

  Catalytic processes · CPC title