Organic-inorganic hybrid nanoporous material containing intramolecular acid anhydride functional group, composition for adsorption comprising the same, and use thereof for separation of hydrocarbon gas mixture

Patent metadata

Field	Value
Publication number	US-11285455-B2
Application number	US-201716342937-A
Country	US
Kind code	B2
Filing date	Oct 17, 2017
Priority date	Oct 17, 2016
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

The present invention relates to an organic-inorganic hybrid nanoporous material, maintaining a nanoporous skeleton structure formed by coordination of an organic ligand containing an aromatic compound to a trivalent central metal ion, and further having an intramolecular acid anhydride functional group modified on the aromatic compound of the nanoporous skeleton structure, and thereby exhibits selectivity for olefins, and an adsorbent comprising the same. Specifically, the organic-inorganic hybrid nanoporous material of the present invention exhibits an excellent olefin-selective adsorption capacity through differences in adsorption equilibrium and adsorption rate, and thus can be usefully employed in the separation of C2-C4 hydrocarbons. Further, the olefins adsorbed to the organic-inorganic hybrid nanoporous material can be desorbed by purging of an inert gas which is not liquefied by way of mild vacuum conditions or compression, and thus, the organic-inorganic hybrid nanoporous material can be used to prepare olefins by separating C2-C4 hydrocarbon mixtures.

First claim

The invention claimed is:

1. An organic-inorganic hybrid nanoporous material comprising:
a nanoporous skeleton structure having an aromatic portion, the nanoporous skeleton structure including coordinate bonds between organic ligands containing aromatic portions to central metal ions, at least some of the aromatic portions being bonded to intramolecular acid anhydride functional groups in which an independent COOH functional group, which is not coordinated to a metal ion, in a benzenetricarboxylic acid organic ligand coordinated to a trivalent central metal ion is present and which contains the composition of Chemical Formula 2, or a hydrate or solvate thereof:
A x B y C z   [Chemical Formula 2]

A={M 4 (μ 2 -OH) 4 [(CO 2 ) 2 C 6 H 3 COOH] 4 }
B={M 4 (μ 2 -OH) 4 [C 6 H 4 (CO 2 ) 2 ] 4 }
C={M 4 (μ 2 -O) d (μ 2 -OH) e [(CO 2 )C 6 H 3 (CO) 2 O] 4 }

in Chemical Formula 2, M=a trivalent metal ion; x+y+z=1; x>0; y≥0; z≥0 (with the proviso that y=z=0 is excluded); 0≤d≤4; 0≤e≤4; and d, e, x, y, and z are rational numbers.

2. The organic-inorganic hybrid nanoporous material of claim 1 ,
wherein at least a portion of the skeleton structure is represented by Chemical Formula 1 below, or a hydrate or solvate thereof:
{[C 6 H 3 (CO 2 )C 2 O 3 ] a M 4 (O) b (OH) c }  [Chemical Formula 1]

in Chemical Formula 1, M is a trivalent metal ion, and a, b, and c are each independently a rational number from 0 to 4.

3. The organic-inorganic hybrid nanoporous material of claim 1 , wherein the organic-inorganic hybrid nanoporous material represented by Chemical Formula 2 is prepared by synthesizing a hybrid nanoporous material using a trivalent metal ion salt and a 1,2,4-benzenetricarboxylic acid ligand as reaction raw materials and allowing for heat treatment at a temperature of 100° C. to 450° C.

4. An apparatus for adsorption separation of C 2-4 hydrocarbons, comprising the organic-inorganic hybrid nanoporous material of claim 1 as an adsorbent.

5. A method for separating olefins and paraffins having the same number of carbon atoms, comprising:
contacting a mixture of olefins and paraffins having the same number of carbon atom in C 2-4 hydrocarbons with the organic-inorganic hybrid nanoporous material of claim 1 ,
wherein the adsorption-desorption temperature is from −30° C. to 150° C. and the adsorption-desorption pressure is from 0.1 bar to 35 bar.

6. The method for separating olefins and paraffins having the same number of carbon atoms of claim 5 ,
wherein the organic-inorganic hybrid nanoporous material of claim 1 is the organic-inorganic hybrid nanoporous material of claim 2 .

7. A method for separating hydrocarbons having a different number of carbon atoms, comprising:
contacting a mixture containing C 1-4 hydrocarbons having a different number of carbon atoms with the organic-inorganic hybrid nanoporous material of claim 1 ,
wherein the adsorption-desorption temperature is from −30° C. to 150° C. and the adsorption-desorption pressure is from 0.1 bar to 35 bar.

8. The method for separating hydrocarbons having a different number of carbon atoms of claim 7 ,
wherein the organic-inorganic hybrid nanoporous material of claim 1 is the organic-inorganic hybrid nanoporous material of claim 2 .

9. A method for separating olefin and paraffin gases from a mixed hydrocarbon gas, comprising:
contacting a mixed C 1-4 hydrocarbon gas with the organic-inorganic hybrid nanoporous material of claim 1 ,
wherein the adsorption-desorption temperature is from −30° C. to 150° C. and the adsorption-desorption pressure is from 0.1 bar to 35 bar.

10. The method for separating olefin and paraffin gases from a mixed hydrocarbon gas of claim 9 ,
wherein the organic-inorganic hybrid nanoporous material of claim 1 is the organic-inorganic hybrid nanoporous material of claim 2 .

11. A method for preparing C 2-4 olefins, comprising:
a first step of adsorbing olefins in C 2-4 hydrocarbons to an adsorbent including the organic-inorganic hybrid nanoporous material of claim 1 ; and
a second step of purging the adsorbent to which C 2-4 olefins are adsorbed with an inert gas.

12. The method for preparing C 2-4 olefins of claim 11 ,
wherein the inert gas in the second step is nitrogen, helium, argon, or a mixed gas thereof.

13. The method for preparing C 2-4 olefins of claim 11 ,
wherein the organic-inorganic hybrid nanoporous material of claim 1 is the organic-inorganic hybrid nanoporous material of claim 2 .

14. A method for preparing the organic-inorganic hybrid nanoporous material of claim 1 , comprising:
a first step of preparing a mixed solution of a trivalent metal ion-containing metal precursor, an organic ligand containing an aromatic compound substituted with two or more carboxylic acid functional groups, and a nitrogen-containing basic compound in a reaction vessel;
a second step of placing the reaction vessel in a pressure reactor and allowing to react at 100° C. to 200° C. for 10 to 20 hours; and

a third step of heat-treating the solid product obtained from the previous step at a temperature of 350° C. to 500° C.

15. An organic-inorganic hybrid porous material comprising:
a porous skeleton structure including a trivalent central metal ion and organic ligand coordination compound, the coordination compound including an aromatic portion, and an intramolecular acid anhydride functional group being bonded to the aromatic portion represented by the composition of Chemical Formula 2, or a hydrate or solvate thereof:
A x B y C z   [Chemical Formula 2]

A={M 4 (μ 2 -OH) 4 [(CO 2 ) 2 C 6 H 3 COOH] 4 }; B={M 4 (μ 2 -OH) 4 [C 6 H 4 (CO 2 ) 2 ] 4 }; C={M 4 (μ 2 -O) d (μ 2 -OH) e [(CO 2 )C 6 H 3 (CO) 2 O] 4 }; M=a trivalent ion; x+y+z=1; x>0; y≥0; z≥0 (with the proviso that y=z=0 is excluded); 0≤d≤4; 0≤e≤4; and d, e, x, y, and z are rational numbers.

16. The organic-inorganic hybrid porous material of claim 15 wherein the trivalent central metal ion is an aluminum ion.

17. The organic-inorganic hybrid nanoporous material of claim 2 wherein the trivalent central metal ions are Al 3+ .

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Yoon Ji Woong
• Chang Jong San
• Hwang Young Kyu
• Cho Kyung Ho
• Lee U Hwang
• Lee Su Kyung
• Lee Ji Sun

Classifications

• B01D53/047

  Pressure swing adsorption · 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

• B01J20/223 Primary

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

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title