Method for adsorption separation of propylene and propyne

Patent metadata

Field	Value
Publication number	US-2019010102-A1
Application number	US-201716067576-A
Country	US
Kind code	A1
Filing date	May 10, 2017
Priority date	May 17, 2016
Publication date	Jan 10, 2019
Grant date	—

Abstract

A method for the adsorption separation of propylene and propyne, comprising selectively adsorbing propyne from a mixed gas of propylene and propyne using an anion-containing metal-organic framework material as an adsorbing agent so as to obtain a purified propylene gas. The anion-containing metal-organic framework material is used as an adsorbing agent in the method, and the adsorbing agent is a kind of highly ordered microporous organic-inorganic hybrid material, with the pore size thereof being adjustable within the range of 0.4-1.2 nm, and the pore volume thereof being adjustable within the range of 0.1-1.2 cm3/g. A large number of anionic active sites and a highly ordered spatial arrangement thereof allow the adsorbing agent to exhibit excellent propyne adsorption properties. Thus, the adsorbing agent has a very high propyne selectivity and adsorption volume.

First claim

1 . A method of separating propyne from propene using metal-organic framework materials, wherein the anion-containing metal-organic framework are the adsorbents, selectively adsorbing propyne from propyne/propene mixed gases, thus achieving propene with ultralow amount of propyne.

2 . The method of separating propyne from propene using metal-organic framework materials according to claim 1 , wherein the anion-containing metal-organic framework materials comprise one class of the following four kinds:
first-class materials being firstly coordinated by a metal ion M1 and an organic ligand L1 to form two-dimensional frameworks, and then bridged by an inorganic ligand L2 to form the three-dimensional framework; wherein the metal ion M1 can comprise one or more of Zn 2+ , Cu 2+ , Ni 2+ , co 2+ , Mg 2+ , Al 2+ ; wherein the inorganic ligand L2 can comprise one or more of SiF 6 2− , TiF 6 2− , SnF 6 2− , ZrF 6 2− , GeF 6 2− ; wherein the organic ligand L1 is selected from any of the following:

wherein R is selected from any of following groups;

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are selected from the groups H, F, Cl, Br, I, CH 3 , NH 2 , OH, SO 3 H, COOH, and CF 3 ,
second-class materials being porous framework materials formed by the metal ion M1, a bio-organic ligand L3, and an inorganic anion L2;
wherein the organic ligand L3 is selected from any of the following:

third class of materials being porous frameworks firstly coordinated by the metal ion M1 and an organic ligand L4, then further coordinated with Mg(X1) 2 , obtained the metal-organic frameworks with organic anions X1 in the pores;
wherein the organic ligand L4 is selected from any of the following:

the organic anion X1 is selected from any of the following:

fourth-class of material being coordinated by the metal ion M1 and the organic ligand L4 to form the porous framework materials, and then this material were oxidized to convert divalent metal ion M1 to trivalent, and further by introducing anion X2 to coordinate with trivalent metal ion M1;
wherein the anion X2 is selected from any of the following: Cl − , Br − , I − , COO − , CH 3 COO − , NTf 2 − , BF 4 − , PF 6 − , SiF 6 2− , TiF 6 2− , and N(CN) 2 − .

3 . The method of separating propyne from propene using metal-organic framework materials according to claim 2 , wherein anion-containing metal-organic framework materials are the first class of materials, among which:
the metal ion M1 comprises one or more of Zn 2+ , Cu 2+ , Ni 2+ ; the inorganic ligand L2 comprises one or more of SiF 6 2− , TiF 6 2− , SnF 6 2− ; the organic ligand L1 comprises one or more of pyrazine, 4,4′-dipyridylacetylene, and 4,4′-bipyridine.

4 . The method of separating propyne from propene using metal-organic framework materials according to claim 3 , wherein the L2 is SiF 6 2− .

5 . The method of separating propyne from propene using metal-organic framework materials according to claim 2 , wherein anion-containing metal-organic framework materials are the second-class materials, among which:
the metal ion M1 comprises one or more of Zn 2+ , Cu 2+ , Ni 2+ ; the bio-organic ligand L3 is adenine; and the inorganic anion ligand L2 comprises one or more of SiF 6 2− and TiF 6 2− .

6 . The method of separating propyne from propene using metal-organic framework materials according to claim 2 , wherein anion-containing metal-organic framework materials are the third-class or the fourth-class materials, among which:
the metal ion M1 comprises one or more of Mg 2+ and Fe 2+ , the organic ligand L4 is one or more of 2,5-dihydroxyterephthalic acid, 4,4′-dihydroxy-3,3′-dicarboxylic acid.

7 . The method of separating propyne from propene using metal-organic framework materials according to claim 2 , wherein anion-containing metal-organic framework materials are the fourth-class of materials, among which the anion X2 is selected from any of the following: Cl − , Br − , I − , COO − , CH 3 COO − .

8 . The method of separating propyne from propene using metal-organic framework materials according to claim 1 , wherein the concentration of propyne in the obtained propyene is below 1 ppm, and the regeneration of adsorbents includes vacuum, heating, or heating with inert gas flow.

9 . The method of separating propyne from propene using metal-organic framework materials according to claim 1 , wherein the adsorption temperature is between 0-40° C.

10 . The method of separating propyne from propene using metal-organic framework materials according to claim 9 , wherein the pressure for the adsorption and separation is 0.5-10 atom.

Assignees

• Univ Zhejiang

Inventors

• Xing Huabin
• Cui Xili
• Yang Lifeng
• Bao Zongbi
• Yang Qiwei
• Ren Qilong

Classifications

• B01J20/28069

  Pore volume, e.g. total pore volume, mesopore volume, micropore volume · CPC title

• B01J20/226 Primary

  Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• C07C7/12 Primary

  by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers · CPC title

• B01J20/223

  containing metals, e.g. organo-metallic compounds, coordination complexes · CPC title