Hydrocarbon conversion process

Patent metadata

Field	Value
Publication number	US-9260357-B2
Application number	US-201314397492-A
Country	US
Kind code	B2
Filing date	Jun 21, 2013
Priority date	Jul 6, 2012
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

The invention relates to methods and equipment for converting C 3+ olefin to, e.g., one or more of di-C 3+ olefin, oligomers and polymers of C 3+ olefin, branched C 4+ -aldehydes, C 4+ -carboxylic acids, and C 4+ oxygenates. The invention encompasses producing methyl tert-butyl ether and diisobutylene, and converting methyl tert-butyl ether to isobutylene.

First claim

What is claimed is:

1. An olefin upgrading method comprising:
(a) providing a first portion of a first olefin mixture and a first process fluid, the first olefin mixture comprising ≧1.0 wt. % of C 3+ iso-olefins based on the weight of the first olefin mixture, and the first process fluid comprising ≧10.0 wt. % alcohol based on the weight of the first process fluid;
(b) reacting the first portion of the first olefin mixture and the first process fluid in a first reactor to produce a first reaction mixture, the first reaction mixture comprising ether and di-C 3+ olefin and having a di-C 3+ olefin: ether molar ratio ≧1.0;
(c) separating from the first reaction mixture a second olefin mixture and a first product, wherein (A) the second olefin mixture comprises at least a portion of any unreacted first olefin mixture present in the first reaction mixture and (B) the first product (i) comprises at least a portion of the first reaction mixture's di-C 3+ olefin and at least a portion of the first reaction product's ether and (ii) has a di-C 3+ olefin: ether molar ratio ≧1.0;
(d) providing a third olefin mixture and a second process fluid, wherein the third olefin mixture comprises (i) a second portion of the first olefin mixture or a fourth olefin mixture, the fourth olefin mixture comprising ≧1.0 wt. % of C 3+ iso-olefins based on the weight of the fourth olefin mixture, and (ii) at least a portion of the second olefin mixture, and wherein the second process fluid comprises ≧10.0 wt. % alcohol based on the weight of the second process fluid; and
(e) reacting the third olefin mixture and the second process fluid in a second reactor to produce a second reaction mixture, the second reaction mixture comprising ether and having di-C 3+ olefin : ether molar ratio <1.0,
wherein (i) the first olefin mixture comprises ≧50.0 wt. % of C 4 monoolefins based on the weight of the first olefin mixture, (ii) the third olefin mixture comprises ≧50.0 wt. % of C 4 monoolefins based on the weight of the third olefin mixture, and (iii) the third olefin mixture has a higher C 3+ monoolefins concentration than the second olefin mixture.

2. The method of claim 1 , wherein (i) the first process fluid comprises ≧50.0 wt . % methanol based on the weight of the first process fluid, (ii) the second process fluid comprises ≧50.0 wt. % methanol based on the weight of the second process fluid, and (iii) the third olefin mixture comprises ≧10.0 wt. % of the second olefin mixture and ≧10.0 wt. % of the second portion of the first olefin mixture.

3. The method of claim 1 , wherein the reacting of step (b) is carried out in a first reactor, the reacting of step (e) is carried out in a second reactor, and further comprising conducting at least a portion of the second reaction mixture to a third reactor for reacting at least a portion of any unreacted third olefin mixture and at least a portion of any unreacted second process fluid in the presence of the second reaction mixture to produce a third reaction mixture; wherein the third reaction mixture comprises ether and has (i) a di-C 3+ olefin: ether molar ratio <1.0 and (ii) a non-oligomerized C 3+ monoolefin : ether molar ratio <10.

4. The method of claim 3 , further comprising separating from the third reaction mixture a second product and a first byproduct, the second product comprising ether and the first byproduct comprising alcohol and non-oligomerized monoolefins.

5. The method of claim 3 , further comprising separating from the first product (i) a second byproduct comprising ether and (ii) a third product comprising di-C 3+ olefin; the second byproduct having a di-C 3+ olefin : ether molar ratio <0.10 and the third product having tri-C 3+ olefin : di-C 3+ olefin molar ratio <1.0.

6. The method of claim 5 , further comprising separating from the third product a first portion comprising ≧90.0 wt. % di-C 3+ olefin based on the weight of the first portion and a second portion comprising ≧50.0 wt. % oligomer of order 3 of di-C 3+ olefin based on the weight of the second portion.

7. The method of claim 4 , wherein the separation of the second olefin mixture and the first product is carried out in a separator 1 A, the separation of the third product and the second byproduct is carried out in a separator 1 B, the separation of the first byproduct and the second product is carried out in a separator 2 , and the third reactor and the separator 2 are each components of a catalytic distillation tower; and further comprising:
conducting away from the process at least a first portion of the second product;
conducting at least a second portion of the second product to separator 1 B, for separating ether from the second product; and conducting at least a portion of the second byproduct to the first reactor to lessen the production of ether in the first reactor.

8. The method of claim 4 , further comprising (f) providing a third process fluid, the third process fluid comprising ≧50.0 wt. % water based on the weight of the third process fluid and (g) contacting at least a portion of the first byproduct with the third process fluid to separate (i) a first raffinate comprising ≧50.0 wt. % non-oligomerized monoolefins based on the weight of the first raffinate and (ii) a first extract comprising water and ≧90.0 wt. % of the first byproduct's alcohol based on the weight of the first byproduct.

9. The method of claim 2 , further comprising producing the first and second portions of the first olefin mixture by dividing the first olefin mixture into the first and second portion using valve means.

10. The method of claim 3 , wherein the first olefin mixture comprises ≧90.0 wt. % of C 4 monoolefin based on the weight of the first olefin mixture, the third olefin mixture comprises ≧90.0 wt. % of C 4 monoolefin based on the weight of the third olefin mixture, the first process fluid comprises ≧65.0 wt. % methanol based on the weight of the first process fluid, the second process fluid comprises ≧65.0 wt. % methanol based on the weight of the second process fluid, the first product's di-C 3+ olefin comprises ≧90.0 wt. % diisobutylene based on the weight of the first product's di-C 3+ olefin, the first product's ether comprises ≧90.0 wt. % MTBE based on the weight of the first product's ether, and the first reaction mixture's ether comprising ≧90.0 wt. % MTBE based on the weight of the first reaction mixture's ether.

11. The method of claim 4 , wherein (i) the second product comprises ≧90.0 wt. % ether based on the weight of the second product (ii) the ether of the second product comprises ≧90.0 wt. % MTBE based on the weight of the second product's ether, (iii) the first byproduct's alcohol comprises ≧90.0 wt. % methanol based on the weight of the first byproduct's alcohol, and (iv) the first byproduct's non-oligomerized monoolefin comprises ≧90.0 wt. % C 4 monoolefin, based on the weight of the first byproduct's monoolefin.

12. The method of claim 5 , wherein (i) ≧90.0 wt. % of the second byproduct's ether comprises MTBE based on the weight of the second byproduct's ether and (ii) the third product comprises ≧50.0 wt. % diisobutadiene based on the weight of the third product.

13. The method of claim 6 , wherein (i) the first portion of the third product comprises ≧90.0 wt. % diisobutylene based on the weight of the first portion and the second portion of the third product comprises ≧50.0 wt. % of oligomers of order 3 of C 3+ olefin based on the weight of the second portion.

14. The method of claim 6 , wherein
(i) the first product comprises ≧20.0 wt. % of the first reaction mixture and the second olefin mixture comprises ≦80.0 wt. % of t

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Yarrison Matthew B
• Srivastava Alok
• Jindal Roshni
• Then Chee Keong
• Smith Rodney S

Classifications

• C07C1/24

  by elimination of water · CPC title

• C07C2/20 Primary

  Acids of halogen; Salts thereof {; Complexes thereof with organic compounds} · CPC title

• C07C11/09

  Isobutene · CPC title

• C07C2/864

  the non-hydrocarbon is an alcohol · CPC title

• C08F110/10

  Isobutene · CPC title