Heterogenized catalyst for acetylene dimerization

Patent metadata

Field	Value
Publication number	US-2019118169-A1
Application number	US-201816221316-A
Country	US
Kind code	A1
Filing date	Dec 14, 2018
Priority date	Jun 22, 2016
Publication date	Apr 25, 2019
Grant date	—

Abstract

A catalyst and a process for using the catalyst are presented. The catalyst is a heterogeneous catalyst and includes active metal halides bonded to functional groups. The functional groups are bonded to a polymeric backbone to form the structure supporting the catalyst. The catalyst is useful for the dimerization of acetylene to convert the acetylene to a larger hydrocarbon, and in particular to dimerize acetylene to vinylacetylene.

First claim

1 . A catalyst for the dimerization of acetylene under dimerization conditions comprising:
an ion exchange resin with an exchangeable anion (hydroxide or halide ion) to form an exchanged resin including the halide; and the exchanged resin is compounded with a metal halide.

2 . The catalyst of claim 1 wherein the halide compound is selected from the group consisting of amines, phosphines, and mixtures thereof.

3 . The catalyst of claim 2 wherein the amine has the form of NR1R2R3, and the phosphine has the form PR1R2R3.

4 . The catalyst of claim 3 wherein the R1, R2, R3 groups are selected from the group consisting of hydrogen, alkyl groups, aryl groups, and mixtures thereof.

5 . The catalyst of claim 4 wherein the R1, R2, R3 groups are the same alkyl group or the same aryl group.

6 . The catalyst of claim 1 wherein the metal halide is selected from the group consisting of cuprous chloride (CuCl), silver chloride (AgCl), ferrous chloride (FeCl 2 ), ferric chloride (FeCl 3 ), nickel chloride (NiCl 2 ), chlorides of gold (AuCl and AuCl 3 ), or mixtures thereof.

7 . The catalyst of claim 6 wherein the metal halide is cuprous chloride.

8 . The catalyst of claim 1 wherein the ion exchange resin comprises a polymer backbone selected from the group consisting of styrene, divinylbenzene, styrene-divinylbenzene co-polymer, polyethylene, polyamine-epichlorohyrdin-NH 3 condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, cellulose and mixtures thereof.

9 . A catalyst comprising:
a polymer backbone with a plurality of functional groups, wherein the functional groups are selected phosphonium chlorides and amine chlorides; and the functional groups are ion exchanged with metal chlorides.

10 . The catalyst of claim 9 wherein the polymer backbone is selected from the group consisting of styrene, divinylbenzene, styrene-divinylbenzene co-polymer, polyethylene, polyamine-epichlorohyrdin-NH 3 condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, cellulose and mixtures thereof.

11 . The catalyst of claim 9 wherein the amine in the amine chloride has the form of NR1R2R3, and the phosphine in the phosphonium chloride has the form PR1R2R3.

12 . The catalyst of claim 11 wherein the R1, R2, R3 groups are selected from the group consisting of hydrogen, alkyl groups having from 1 to 4 carbon atoms, aryl groups and mixtures thereof.

13 . The catalyst of claim 11 wherein R1, R2, R3 are selected from the group consisting of H, CH 3 , C 2 H 5 , or mixtures thereof.

14 . The catalyst of claim 9 wherein the metal chloride is selected from the group consisting of cuprous chloride (CuCl), silver chloride (AgCl), ferrous chloride (FeCl 2 ), ferric chloride (FeCl 3 ), nickel chloride (NiCl 2 ), chlorides of gold (AuCl and AuCl 3 ), or mixtures thereof.

15 . The catalyst of claim 14 wherein the metal chloride is cuprous chloride.

16 . The catalyst of claim 9 wherein the polymer backbone is selected from the group consisting of styrene, divinylbenzene, styrene-divinylbenzene co-polymer, polyethylene, polyamine-epichlorohyrdin-NH 3 condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, cellulose and mixtures thereof.

17 . A process for the production of 1,3 butadiene, comprising:
dimerizing a first process stream comprising acetylene, under dimerization conditions, in the presence of a catalyst comprising a polymer backbone with a plurality of functional groups affixed to the polymer backbone wherein the functional groups have a positive charge and a charge balancing anion, and at least one of the anions is ion exchanged with a metal halide, that is converted to anion form, to generate a polymer with metal halide groups ionically bonded to the functional groups, to generate a second process stream comprising vinylacetylene, wherein the functional groups are selected from the group consisting of amines, phosphines and mixtures thereof; hydrogenating the vinylacetylene in the second process stream to generate a third process stream comprising 1,3 butadiene.

18 . The process of claim 17 wherein the metal is selected from the group consisting of copper, iron, silver and mixtures thereof.

19 . The process of claim 17 wherein the hydrogenating of vinyl acetylene is performed in a reactor with a selective hydrogenation catalyst.

20 . The process of claim 17 wherein the polymer backbone is selected from the group consisting of styrene, divinylbenzene, styrene-divinylbenzene co-polymer, polyethylene, polyamine-epichlorohyrdin-NH 3 condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, melamine-formaldehyde condensate, polyamine-phenol-formaldehyde condensate, and mixtures thereof.

Assignees

• Uop Llc

Inventors

• Voskoboynikov Timur V
• Bhattacharyya Alakananda
• Adonin Nikolay Y
• Timofeeva Mariya N
• Prikhodko Sergey A
• Parmon Valentin N

Classifications

• B01J41/13

  obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• B01J47/016

  Modification or after-treatment of ion-exchangers · CPC title

• B01J41/10

  Inorganic material · CPC title

• B01J31/08 Primary

  Ion-exchange resins · CPC title

• C07C11/28

  containing carbon-to-carbon double bonds and carbon-to-carbon triple bonds · CPC title