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Metal organic framework material reinforcing methane adsorption separation and preparation and application thereof

An organic framework, adsorption separation technology, applied in separation methods, alkali metal compounds, dispersed particle separation, etc., can solve the problems of MOFs material adsorption selectivity without obvious advantages, complex synthesis process, harsh conditions, etc., to increase development. The effect of utilization, high surface area, large pore volume

Inactive Publication Date: 2015-02-25
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] Based on the results of the above reports, there are two major defects in the current MOFs materials as adsorbents for the separation and purification of unconventional natural gas: (1) most of the reported MOFs materials have complicated synthesis processes or harsh conditions; (2) the use of CH 4 / N 2 The adsorption selectivity of the isolated MOFs material has no obvious advantage
However, the CH of MOFs materials reported in the current literature 4 / N 2 The adsorption and separation selectivities are all less than 5, especially the CH 4 / N 2 Adsorption separation selectivity prediction is only about 2.9

Method used

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  • Metal organic framework material reinforcing methane adsorption separation and preparation and application thereof

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Effect test

Embodiment 1

[0050] Embodiment 1: Atmospheric pressure synthesis Cu x Zn 1-x -BTC

[0051] Weigh 5g copper acetate (Cu(CH 3 COO) 2 ·H 2 O), 1g zinc acetate (Zn(CH 3 COO) 2 ·H 2 O) and 8g trimesic acid (H 3 BTC) was dissolved in 300ml of water-ethanol (water:ethanol = 1:1 weight ratio), stirred for 30min until uniform; heated to 80°C, stirred for 8h, cooled down naturally, and centrifuged to separate the obtained solid; respectively, water (500ml) , ethanol (250ml), and acetone 200mL to wash the solid successively for 60 minutes; dry the solid powder at 80°C to obtain 7.8g of solid.

[0052] N 2 The specific surface area is 872.04m 2 / g (determined by Langmuir method);

[0053] The obtained adsorbent is at 298K, between 0-1Mpa, CH 4 / N 2 The equilibrium adsorption separation factor is between 5 and 6, CO 2 / CH 4 The equilibrium adsorption separation factor is between 6-7.

Embodiment 2

[0054] Embodiment 2: Atmospheric pressure synthesis Cu-BTC

[0055] Weigh 5g copper acetate (Cu(CH 3 COO) 2 ·H 2 O) and 6.9g trimesic acid (H 3 BTC) was dissolved in 240ml of water-ethanol (water:ethanol=2:3 weight ratio), stirred for 30min until uniform; heated to 80°C, stirred for 4h, cooled down naturally, and centrifuged to separate the obtained solid; respectively, water (500ml) , ethanol (250ml), and acetone 200mL to wash the solid for 45 minutes in sequence. The solid powder was dried at 80°C to obtain 6.2 g of solid.

[0056] N 2 The specific surface area is 1213.04m 2 / g (determined by Langmuir method);

[0057] The obtained adsorbent is at 298K, between 0-1Mpa, CH 4 / N 2 The equilibrium adsorption separation factor is between 6 and 8, CO 2 / CH 4The equilibrium adsorption separation factor is between 8-9.

Embodiment 3

[0058] Embodiment 3: high pressure synthesis Cu (bdc) (dabco) 0.5

[0059] Weigh 9g copper acetate (Cu(CH 3 COO) 2 ·H 2 O), 6.8g terephthalic acid (H 2 BDC) and 2.3g triethylenediamine (DABCO) were dissolved in 450ml DMF, stirred for 30min until homogeneous, and a mixed solution was obtained; the mixed solution was transferred to a 1000ml autoclave with a Teflon liner and sealed tightly, placed in React in an oven at 110°C for 48h, and then cool down naturally. The resulting solid was separated by centrifugation; washed with DMF (2 x 150ml) for 2 hours and ether (2 x 150ml) for 40 minutes; the solid was dried overnight at 110°C to yield 10g.

[0060] N 2 The specific surface area is 1283.2m 2 / g (as determined by the Langmuir method).

[0061] The obtained adsorbent is at 298K, between 0-1Mpa, CH 4 / N 2 The equilibrium adsorption separation factor is between 4 and 6, CO 2 / CH 4 The equilibrium adsorption separation factor is between 5-9.

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Abstract

The invention discloses a porous metal organic framework material reinforcing methane adsorption separation and preparation and application thereof, the porous metal organic framework material is a supramolecular porous network structural compound prepared from metal ions at least containing CuII and at least one organic compound which can be coordinated with the CuII and at least is provided with two teeth. The CuII-containing porous metal organic framework material can be synthesized by co precipitation, hydrothermal, microwave, ball milling and other different methods, the biggest feature of the porous metal organic framework material is to improve the methane adsorption separation performance by use of effect of weakly polar or nonpolar solvents on the surface in the preparation process of. The CuII-containing porous metal organic framework material has excellent CH4 adsorption selectivity in the separation process of CH4 and N2, the equilibrium adsorption selectivity can reach more than 6, and the material is particularly suitable for use in oil field gas, shale gas, coal seam gas and biogas development and utilization process.

Description

technical field [0001] The invention belongs to the technical field of chemical material synthesis and mixed gas adsorption and separation engineering, and specifically relates to a metal organic framework material, preparation and application for strengthening methane adsorption and separation. Background technique [0002] As the cleanest fossil energy recognized in the world, natural gas is playing an increasingly important role in the energy consumption structure of various countries. The national energy strategy proposes that by 2020, my country's natural gas consumption will account for more than 12% of energy consumption, increasing to 400 billion cubic meters. At present, the proportion of natural gas in my country's energy consumption is less than 4%, which is far from the target of 12%. It can be seen that the contradiction between the supply and demand of natural gas in my country will become increasingly acute. my country has huge reserves of unconventional natu...

Claims

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Application Information

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IPC IPC(8): B01J20/22B01J20/28B01J20/30B01D53/02C10L3/10
CPCB01D53/02B01J20/226B01J20/28054C10L3/104C10L3/105Y02C20/40
Inventor 王树东孙天军任新宇胡江亮
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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