Ethylene and ethane adsorbing separation method based on ultramicroporous metal organic framework material

A metal-organic framework, adsorption separation technology, applied in separation methods, adsorption purification/separation, organic chemistry, etc., can solve the problems of high adsorption capacity and high adsorption selectivity, pollution, high energy consumption for regeneration, and achieve enhanced Molecular recognition ability, high adsorption capacity, effect of high adsorption capacity

Active Publication Date: 2019-05-14
ZHEJIANG UNIV +1
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  • Abstract
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  • Application Information

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Problems solved by technology

However, the existing ethylene / ethane selective adsorbents often have the disadvantages of high adsorption capacity and high adsorption selectivity, poor material stability, etc.
For example, the all-silicon molecular sieve ITQ-55 (Science, 2017, 358(6366): 1068-1071.) exhibits high kinetic selectivity to ethylene / ethane, but its ethylene adsorption capacity is low. Only 1.5mmol g -1 ; Mg-MOF-74 (Langmuir,2011,27(22):13554-13562.) has an adsorption capacity of up to 7.5mmol g for ethylene -1 (1bar, 298K), but its separation selectivity to equimolar ethylene / ethane mixture is no more than 10; based on transition metal ion-based adsorbents such as molecular sieve AgA (Journal of the American Chemical Society, 2012,134(36):14635 -14637.), organic porous material PAF-1-SO 3 Although Ag (Journal of the American Chemical Society, 2014, 136 (24): 8654-8660.), CuCl-loaded alumina (CN 1048010C) and the like can selectively recognize ethylene through π complexation, these materials are susceptible to Polluted by moisture and sulfur-containing compounds in raw gas, poor stability, short service life, and high regeneration energy consumption, it is not suitable for industrial applications

Method used

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  • Ethylene and ethane adsorbing separation method based on ultramicroporous metal organic framework material
  • Ethylene and ethane adsorbing separation method based on ultramicroporous metal organic framework material
  • Ethylene and ethane adsorbing separation method based on ultramicroporous metal organic framework material

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Embodiment 1

[0044] Using the method reported in the literature (Angewandte Chemie, 2012,124(8):1862-1865.), with phosphoric acid, Zn(OH) 2 · 2ZnCO 3 Synthesis of ultramicroporous metal-organic framework Zn-Atz-PO with 3-amino-1,2,4-triazole as raw material 4 . Utilize X-ray powder diffraction to analyze material, result ( figure 1 ) is consistent with the literature report, the size of the narrowest part of the material pore diameter is Zn-Atz-PO 4 The thermogravimetric curve of the material is as figure 2 As shown, the data show that it has high thermal stability, and its decomposition temperature is close to 420 °C.

[0045] Measurement of Zn-Atz-PO 4 The adsorption isotherms and dynamic adsorption curves of materials for ethylene and ethane at 273K and 298K, the results are as follows Figure 3-6 shown. The results show that the synthesized Zn-Atz-PO 4 The equilibrium adsorption capacity of the material for ethylene and the diffusion rate of ethylene in its pores are signif...

Embodiment 2

[0048] CoCO 3 、Na 3 VO 4 and 3-chloro-1,2,4-triazole were added into a water / methanol mixed solvent with a volume ratio of 1:1 at a mass ratio of 1:1:4 and stirred evenly, and hydrochloric acid was added to adjust the pH of the reaction solution to 8.5, It was then placed in an oven at 120° C. for 48 hours to react. After the reaction, the obtained solid product was collected by suction filtration, washed several times with methanol, and then activated for 12 hours at 100°C in a vacuum environment to obtain the metal organic framework material Co-Cltz-VO 4 .

[0049] The resulting Co-Cltz-VO 4 The product was loaded into a 5cm fixed-bed adsorption column, and ethylene / ethane mixed gas (volume ratio 90:10) was passed into the bed at 298K and 8bar at a flow rate of 2.0mL / min for fixed-bed breakthrough experiments. Due to the weak interaction between the ethane component and the ultramicroporous material and the slow diffusion rate in its pores, it preferentially penetrates ...

Embodiment 3

[0051] With the Zn-Atz-PO of embodiment 1 gained 4 The material was loaded into a 5cm fixed-bed adsorption column, and ethylene / ethane mixed gas (volume ratio 50:50) was passed into the bed at 273K and 1bar at a flow rate of 0.5mL / min for fixed-bed breakthrough experiments. Such as Figure 8 As shown, after 27 minutes of adsorption, the ethane component preferentially penetrates the adsorption column, and high-purity ethane gas (99.999%) can be obtained from the outlet of the adsorption column. The ethylene component is enriched in the adsorption column and only penetrates the bed after about 70 minutes. After the adsorption column reaches equilibrium, stop the air intake, use the ethylene product gas obtained in Example 2 to sweep the bed for 10 minutes (0.5mL / min), and then vacuumize (<0.05bar) and heat (65°C) to The adsorption column is desorbed to obtain ethylene gas with a purity of 99%, and the regeneration of the adsorption column is completed at the same time.

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Abstract

The invention discloses an ethylene and ethane adsorbing separation method based on an ultramicroporous metal organic framework material. The ethylene and ethane adsorbing separation method comprisesthe following steps: contacting mixed gas of ethylene and ethane with the ultramicroporous metal organic framework material to adsorb ethylene in the mixed gas so as to separate the ethylene from theethane, wherein the ultramicroporous metal organic framework material adopts a chemical formula of [M3L3A] infinite, in which M is a metal cation, L is an organic ligand and A is an oxygen-containinginorganic anion; the organic ligand is 1,2,4-triazole and a derivative thereof; the metal cation is one of Cu<2+>, Zn<2+>, Co<2+> and Ni<2+>; the oxygen-containing inorganic anion is PO4<3-> or VO4<3->. When the mixed gas of the ethylene and the ethane contacts the ultramicroporous metal organic framework material, significant differences in the diffusion rates and the adsorption capacities of thetwo in a material pore are caused by differences in molecular sizes and hydrogen bond acidity of the ethylene / the ethane, so that selective adsorption of the ethylene is achieved, and high-purity ethylene gas and high-purity ethane gas are obtained.

Description

technical field [0001] The invention belongs to the technical field of chemical industry separation, and in particular relates to a method for using an ultramicroporous metal organic framework material for ethylene / ethane separation. Background technique [0002] As one of the most produced chemicals in the world, ethylene is the core of the petrochemical industry and an important symbol to measure a country's petrochemical development level. The downstream products of ethylene mainly include polyethylene, polyvinyl chloride, ethylene oxide, ethylene glycol, vinyl acetate, etc., accounting for more than 75% of petrochemical products, and are widely used in various national economic industries such as plastics, pharmaceuticals, textiles, and coatings. At present, naphtha is mainly used as raw material in industry, which is cracked into a variety of low-carbon hydrocarbon mixtures, and then ethylene is separated and extracted from it. Ethylene and ethane have similar molecula...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C7/12C07C11/04C07C9/06B01J20/22B01J20/28B01J20/30B01D53/02
CPCB01D53/02B01J20/22B01J20/28B01J20/30C07C7/12B01D2253/204B01D2256/24B01D2257/7022B01D2253/308C07C9/06
Inventor 邢华斌丁琦崔希利
Owner ZHEJIANG UNIV
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