CN114653343A - Anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and preparation method thereof - Google Patents

Anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and preparation method thereof Download PDF

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CN114653343A
CN114653343A CN202210206807.5A CN202210206807A CN114653343A CN 114653343 A CN114653343 A CN 114653343A CN 202210206807 A CN202210206807 A CN 202210206807A CN 114653343 A CN114653343 A CN 114653343A
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adsorbent
pillared
anion
ultramicropore
nitrate
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褚效中
王心悦
翟海荣
朱立文
宣霆锋
王飞
吴飞跃
程志鹏
朱凤霞
赵宜江
徐继明
景钰晨
贝中军
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Huaiyin Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D59/00—Separation of different isotopes of the same chemical element
    • B01D59/22—Separation by extracting
    • B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores

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Abstract

The invention discloses an anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and a preparation method thereof, wherein an organic ligand bipyridyl alkane or bipyridyl alkene or bipyridyl alkyne, pillared anion ligand hydrocarbyl disulfonate and nitrate are used as raw materials to prepare a novel ultramicropore adsorbent; the specific synthetic process is as follows: dissolving an organic ligand, a pillared anion ligand and nitrate in methanol or N, N' -dimethylformamide according to a certain molar ratio, stirring for reaction, precipitating, filtering, and drying in vacuum to obtain the ultra-microporous adsorbent. The invention uses cheap organic ligand and anion ligand to react with nitrate to prepare novel anion pillared ultramicropore adsorbent, which has easily adjustable pore diameter, higher adsorption selectivity, better separation effect on hydrogen isotope gas and potential application prospect.

Description

Anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and preparation method thereof
Technical Field
The invention relates to an adsorbent and a preparation method thereof, in particular to an anion pillared ultramicropore adsorbent for hydrogen isotope gas separation and a preparation method thereof.
Background
The hydrogen isotope gas is widely applied to the fields of nuclear industry, energy, materials, medical treatment, detection and the like, and the purity of the deuterium gas determines the controllable nuclear fusion reaction efficiency and the performance of the deuterated materials. However, D is generated in the process of preparing deuterium gas by electrolyzing heavy water2HD and H2The mixed gas must be separated to obtain high-purity D2(ii) a Furthermore, D2And T2As a raw material of a nuclear fusion reactor, the conversion rate is less than 10%, tritium has radioactivity, and unreacted D discharged from a plasma chamber is considered from the aspects of economy, safety and environmental protection of a fusion reactor2And T2Needs to be separated for reuse, which is a problem that needs to be solved in the nuclear fuel circulation process of the fusion reactor.However, hydrogen isotope gas molecules have extremely similar size, shape and thermodynamic properties, and how to efficiently separate hydrogen isotope gas has become one of the most challenging issues in the research of separation technology. The separation method of hydrogen isotope gas mainly includes low-temperature rectification method, thermal diffusion method, chromatography, metal hydride method and adsorption method. Among many methods, the adsorption method has been widely studied because of its advantages of high selectivity, low energy consumption, and easy regeneration of the adsorbent. The pore diameter of the ultramicropore material of the anion pillared is easy to adjust, and the ultramicropore material can form a hydrogen bond or a metal hydrogen bond with a hydrogen isotope to strengthen the separation process, so that the novel ultramicropore adsorbent of the anion pillared has important scientific significance and market application prospect when being used for efficiently separating hydrogen isotope gas.
Disclosure of Invention
The purpose of the invention is: the preparation method of the ultra-microporous adsorbent comprises the steps of preparing the ultra-microporous adsorbent by using an organic ligand, a pillared anion ligand and nitrate as raw materials, fully utilizing the cheap organic ligand and anion ligand, having mild reaction conditions, easily adjusting the pore diameter of the adsorbent, having high adsorption selectivity, having a good separation effect on hydrogen isotope gas and having a potential application prospect.
The technical solution of the invention is as follows: an anion pillared ultramicropore adsorbent for separating hydrogen isotope gas is prepared by taking an organic ligand, a pillared anion ligand and nitrate as raw materials; the method is characterized in that: the organic ligand is dipyridyl alkane, dipyridyl alkene or dipyridyl alkyne with the general formula
Figure BDA0003531354170000011
R is different alkane, alkene or alkyne; the pillared anionic ligand is alkyl disulfonate with the general formula
Figure BDA0003531354170000012
R1Are different hydrocarbyl groups; the pore diameter of the ultra-microporous adsorbent is between
Figure BDA0003531354170000013
Wherein the organic ligand
Figure BDA0003531354170000014
The alkane R is methylene, ethyl, propyl or corresponding alkenyl or alkynyl, pillared anionic ligand
Figure BDA0003531354170000015
The hydrocarbyl is methylene, ethyl, propyl, phenyl, ethenyl, or ethynyl.
Dissolving an organic ligand, a pillared anion ligand and a nitrate in methanol or N, N' -dimethylformamide according to a certain molar ratio, stirring for reaction, precipitating, filtering, and drying in vacuum to obtain the ultramicropore adsorbent; the method is characterized in that: first, an organic ligand is added
Figure BDA0003531354170000021
And pillared anionic ligands
Figure BDA0003531354170000022
Dissolving in methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain solution A; secondly, dissolving nitrate in methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain solution B; thirdly, slowly dripping the solution B into the solution A under the stirring condition, and heating and reacting for a certain time; fourthly, stopping stirring, precipitating, filtering, and drying the filtered product in vacuum to obtain the ultramicropore adsorbent.
Wherein the molar ratio of the two ligands is 0.5-2: 1, organic ligands
Figure BDA0003531354170000023
The molar ratio of the nitrate to the nitrate is 0.5-3: 1, the reaction temperature is 20-160 ℃, the reaction time is 0.5-48h, the stirring speed is 50-200r/min, and the vacuum drying temperature is 80 ℃.
Further, two areThe optimal molar ratio of the various ligands is 1:1, organic ligands
Figure BDA0003531354170000024
The optimum molar ratio to nitrate was 1.5: 1, the optimal reaction temperature is 80 ℃, and the optimal reaction time is 8 h.
The invention has the following advantages:
1. the organic ligand and the anion ligand used by the ultra-microporous adsorbent with the anion pillared prepared by the method are cheap, and the reaction condition is mild.
2. The pore diameter of the adsorbent is easy to adjust, and the realization of the adsorption
Figure BDA0003531354170000025
And (4) precisely adjusting the step length.
3. The pore diameter of the prepared adsorbent can be adjusted to
Figure BDA0003531354170000026
And the device is suitable for separating small molecule gas mixtures.
4. The adsorbent has high adsorption selectivity to hydrogen isotope gas, and the molar ratio of the hydrogen isotope gas to the hydrogen isotope gas is 1:1H at 77K2/D2The separation factor of the mixed gas by a penetration method can reach 4.5, and the application prospect is good.
5. The pore diameter of the adsorbent is between
Figure BDA0003531354170000027
When the device is used for the adsorption separation of the hydrogen isotope gas, the device has better separation effect.
Drawings
FIG. 1 is a graph showing the volumetric measurement of H at 77K2And D2Adsorption isotherms of (a);
FIG. 2 is a fixed bed breakthrough method for H determination2/D2A mixed gas breakthrough curve;
Detailed Description
The present invention is described in detail below by way of examples, it being necessary to note that the examples are provided for illustration of the invention only and are not to be construed as a limitation of the inventionDue to the limitations described above, those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the embodiments described herein. In the examples, the measurement of H at 77K was carried out by the volumetric method2And D2Adsorption isotherm of (2), determination of H by means of the breakthrough method2/D2Breakthrough curve of the gas mixture in the fixed bed.
Example 1: firstly, dissolving organic ligand dipyridyl methane and anion ligand methylene disulfonic acid sodium in methanol according to a molar ratio of 0.5 to obtain a solution A; secondly, dissolving nickel nitrate (the molar ratio of the organic ligand to the nitrate is 0.5) in methanol to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 50r/min, and then heating the reaction system to 20 ℃ for reaction for 0.5 h; fourthly, stopping stirring, precipitating, washing and filtering, and drying the filtered product in vacuum to obtain the adsorbent with the pore diameter of
Figure BDA0003531354170000028
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 4.0.
Example 2: firstly, dissolving organic ligand dipyridyl ethane and anion ligand ethyl disulfonic acid sodium in N, N' -dimethylformamide according to a molar ratio of 1 to obtain a solution A; secondly, dissolving zinc nitrate (the molar ratio of the organic ligand to the nitrate is 1.5) in N, N' -dimethylformamide to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 100r/min, and then heating the reaction system to 80 ℃ for reacting for 8 hours; fourthly, stopping stirring, precipitating, washing and filtering, and drying the filtered product in vacuum to obtain the adsorbent with the pore diameter of
Figure BDA0003531354170000031
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 4.5.
Example 3: first, the organic ligand dipyridyl ethyleneAnd anionic ligand propyl disulfonic acid sodium are dissolved in methanol according to the molar ratio of 1.3 to obtain solution A; secondly, dissolving nitrate (the molar ratio of the organic ligand to the nitrate is 1.0) in methanol to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 150r/min, and then heating the reaction system to 100 ℃ for reaction for 12 hours; fourthly, stopping stirring, precipitating, washing and filtering, and drying the filtered product in vacuum to obtain the adsorbent with the pore diameter of
Figure BDA0003531354170000032
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 3.2.
Example 4: firstly, dissolving organic ligand bipyridyl propylene and anionic ligand phenyl disulfonic acid sodium in N, N' -dimethylformamide according to the molar ratio of 1.8 to obtain a solution A; secondly, dissolving cobalt nitrate (the molar ratio of the organic ligand to the nitrate is 2.2) in N, N' -dimethylformamide to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 180r/min, and then heating the reaction system to 120 ℃ to react for 24 hours; fourthly, stopping stirring, precipitating, washing and filtering, and drying the filtered product in vacuum to obtain the adsorbent with the pore diameter of
Figure BDA0003531354170000033
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 3.4.
Example 5: firstly, dissolving organic ligand bipyridyl acetylene and anion ligand ethylene disulfonic acid sodium in methanol according to a molar ratio of 1 to obtain a solution A; secondly, dissolving aluminum nitrate (the molar ratio of the organic ligand to the nitrate is 2.6) in methanol to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 200r/min, and then heating the reaction system to 140 ℃ for reacting for 36 hours; fourthly, stopping stirring, precipitating, washing and filtering, andvacuum drying the filtered product to obtain adsorbent with pore diameter of
Figure BDA0003531354170000034
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 3.2.
Example 6: firstly, dissolving organic ligand dipyridyl butane and anion ligand acetylene disulfonic acid sodium in N, N' -dimethylformamide according to a molar ratio of 1.5 to obtain a solution A; secondly, dissolving ferrous nitrate (the molar ratio of the organic ligand to the nitrate is 3) in N, N' -dimethylformamide to obtain a solution B; thirdly, slowly dripping the solution B into the solution A under the condition that the stirring speed is 100r/min, and then heating the reaction system to 160 ℃ for reaction for 48 hours; fourthly, stopping stirring, precipitating, washing and filtering, and drying the filtered product in vacuum to obtain the adsorbent with the pore diameter of
Figure BDA0003531354170000035
Finally, the penetration method is used to determine H at 77K2/D2The breakthrough curve of the gas mixture (molar ratio 1:1) in the fixed bed has a separation factor of 2.8.

Claims (5)

1. An anion pillared ultramicropore adsorbent for hydrogen isotope gas separation is prepared by taking an organic ligand, a pillared anion ligand and nitrate as raw materials; the method is characterized in that: the organic ligand is dipyridyl alkane, dipyridyl alkene or dipyridyl alkyne with the general formula
Figure FDA0003531354160000011
R is different alkane, alkene or alkyne; the pillared anionic ligand is alkyl disulfonate with the general formula
Figure FDA0003531354160000012
R1Are different hydrocarbyl groups; ultra-microporous adsorbent having pore size between
Figure FDA0003531354160000013
2. The anion-pillared ultramicropore adsorbent for hydrogen isotope gas separation according to claim 1, wherein: organic ligands
Figure FDA0003531354160000014
The alkane R is methylene, ethyl, propyl or corresponding alkenyl or alkynyl, and the anion ligand
Figure FDA0003531354160000015
The hydrocarbyl is methylene, ethyl, propyl, phenyl, ethenyl, or ethynyl.
3. Dissolving an organic ligand, a pillared anion ligand and nitrate in methanol or N, N' -dimethylformamide according to a certain molar ratio, stirring for reaction, precipitating, filtering, and drying in vacuum to obtain the ultramicropore adsorbent; the method is characterized in that: first, an organic ligand is added
Figure FDA0003531354160000016
And pillared anionic ligands
Figure FDA0003531354160000017
Dissolving the mixture in a methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain a solution A; secondly, dissolving nitrate in methanol or N, N' -dimethylformamide solvent according to a certain molar ratio to obtain solution B; thirdly, slowly dripping the solution B into the solution A under the condition of stirring, and heating for reacting for a certain time; fourthly, stopping stirring, precipitating, filtering, and drying the filtered product in vacuum to obtain the ultramicropore adsorbent.
4. Isotope of hydrogen for use according to claim 3The preparation method of the anion pillared ultramicropore adsorbent for gas separation is characterized by comprising the following steps: the molar ratio of the two ligands is 0.5-2: 1, organic ligands
Figure FDA0003531354160000018
The molar ratio of the nitrate to the nitrate is 0.5-3: 1, the reaction temperature is 20-160 ℃, the reaction time is 0.5-48h, the stirring speed is 50-200r/min, and the vacuum drying temperature is 80 ℃.
5. The method for producing an anion-pillared ultramicropore adsorbent for hydrogen isotope gas separation according to claim 4, comprising: the optimal molar ratio of the two ligands is 1:1, organic ligands
Figure FDA0003531354160000019
The optimum molar ratio to nitrate was 1.5: 1, the optimal reaction temperature is 80 ℃, and the optimal reaction time is 8 h.
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