Inorganic-organic hybrid nanoporous material with nitrogen selective adsorptivity and method for separating nitrogen-containing gas mixture using the same

Patent metadata

Field	Value
Publication number	US-9687772-B2
Application number	US-201514866345-A
Country	US
Kind code	B2
Filing date	Sep 25, 2015
Priority date	Sep 25, 2014
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

The present invention relates to a nitrogen adsorbent having nitrogen selective adsorptivity by including an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore; and use thereof, such as a device separating nitrogen from a gas mixture containing nitrogen and methane, a pressure swing adsorption separation device and a temperature swing adsorption separation device for separating nitrogen provided, a method for separating nitrogen and methane from a gas mixture containing nitrogen and methane, a device for separating nitrogen, oxygen or argon, a method for separating nitrogen, oxygen or argon from a gas mixture containing nitrogen, oxygen or argon, and a method for preparing nitrogen or high purity inert gas all separated from a gas mixture containing nitrogen and inert gas.

First claim

What is claimed is:

1. A device for separating nitrogen from a gas mixture containing nitrogen and methane, the device comprising a hollow fiber or hollow fiber-formed nitrogen adsorbent separation membrane having nitrogen selective adsorptivity, wherein the membrane comprises an organic-inorganic hybrid nanoporous material that includes a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface, or pore.

2. The nitrogen separation device of claim 1 , wherein the gas mixture containing nitrogen and methane is natural gas or shale gas.

3. A method for preparing natural gas or shale gas in which nitrogen is removed or nitrogen content decreases, the method comprising removing nitrogen from a gas mixture containing nitrogen and methane using a nitrogen adsorbent having nitrogen selective adsorptivity, wherein the nitrogen adsorbent comprises an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore.

4. A method for preparing high purity liquefied methane or high purity liquefied nitrogen comprising:
separating nitrogen from a gas mixture containing nitrogen and methane using a nitrogen adsorbent having nitrogen selective adsorptivity, wherein the nitrogen adsorbent comprises an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore; and
liquefying the separated methane or separated nitrogen.

5. A device for separating nitrogen, oxygen or argon provided with a nitrogen adsorbent having nitrogen selective adsorptivity, wherein the nitrogen adsorbent comprises an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore and an oxygen adsorbent.

6. The device for separating nitrogen, oxygen or argon of claim 5 , wherein the nitrogen adsorbent and the oxygen adsorbent are arranged in consecutive order or in reverse order along the flow of a gas mixture.

7. A method for preparing high purity nitrogen, high purity oxygen or high purity argon all separated from a gas mixture containing nitrogen, oxygen or argon, the method comprising:
a first step of treating with a nitrogen adsorbent having nitrogen selective adsorptivity, wherein the nitrogen adsorbent comprises an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore; and
a second step of treating with an oxygen adsorbent,
wherein the first step and the second step are carried out either in consecutive order or in reverse order.

8. The preparation method of claim 7 , further comprising liquefying the separated high purity nitrogen, the separated high purity oxygen or the separated high purity argon.

9. A method for preparing nitrogen or high purity inert gas all separated from a gas mixture containing nitrogen and inert gas, the method comprising selectively adsorbing nitrogen at an adsorption temperature of −20° C. to 80° C. using a nitrogen adsorbent having nitrogen selective adsorptivity, wherein the nitrogen adsorbent comprises an organic-inorganic hybrid nanoporous material having a coordinatively unsaturated metal site with density of 0.2 mmol/g to 10 mmol/g in a skeleton, surface or pore.

10. The method for preparing separated nitrogen or separated high purity inert gas of claim 9 , wherein the inert gas is one or more selected from the group consisting of helium, neon, argon and hydrogen.

11. A method for preparing high purity argon separated from an argon-containing gas mixture including oxygen, nitrogen and mixtures thereof, the method comprising:
selectively adsorbing nitrogen and oxygen on an organic-inorganic hybrid nanoporous material MIL-100(Fe) containing iron as a central metal; and
collecting the permeated argon gas.

12. The nitrogen separation device of claim 1 , wherein the coordinatively unsaturated metal site is formed by removing a part or all of water, a solvent molecule other than water or a ligand included in the organic-inorganic hybrid nanoporous material.

13. The nitrogen separation device of claim 1 , wherein the device is a pressure swing or temperature swing adsorption separation device.

14. The nitrogen separation device of claim 1 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

15. The method of claim 3 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

16. The method of claim 4 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

17. The device of claim 5 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

18. The method of claim 7 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

19. The method of claim 9 , wherein the organic-inorganic hybrid nanoporous material having the coordinatively unsaturated metal site includes one or more metal ions selected from the group consisting of a trivalent chromium ion, a cobalt ion, a tungsten ion, a molybdenum ion, a ruthenium ion, a niobium ion, a manganese ion, a copper ion, a zinc ion, a titanium ion and a zirconium ion as a metal.

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Chang Jong-San
• Hwang Young Kyu
• Yoon Ji Woong
• Hong Do-Young
• Lee U-Hwang
• Lee Sukyung
• Cho Kyung Ho
• Hwang Dong Won
• Bae Youn-Sang
• Lee Seung-Joon

Classifications

• C10L3/105

  of nitrogen · CPC title

• B01D53/22

  by diffusion (manufacturing semi-permeable membranes B01D67/00; form, structure or properties of semi-permeable membranes B01D69/00; material for semi-permeable membranes B01D71/00) · CPC title

• C01B2210/0046

  Nitrogen · CPC title

• B01D2253/20

  Organic adsorbents · CPC title

• C01B2210/0015

  characterised by the adsorbent · CPC title