CN116355229B - Application of metal-organic framework material in separation of tetramethylsilane and isopentane - Google Patents
Application of metal-organic framework material in separation of tetramethylsilane and isopentane Download PDFInfo
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000926 separation method Methods 0.000 title claims abstract description 30
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- VWAIZPYLEYEEFK-UHFFFAOYSA-N adamantane-1,3,5,7-tetracarboxylic acid Chemical compound C1C(C2)(C(O)=O)CC3(C(O)=O)CC1(C(=O)O)CC2(C(O)=O)C3 VWAIZPYLEYEEFK-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- -1 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid tetramethyl ester Chemical compound 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- UCXRPFYLIDYANL-UHFFFAOYSA-N 2,6,6,7-tetramethyl-8,9-dioxobicyclo[3.3.1]nonane-1,2,5,7-tetracarboxylic acid Chemical compound O=C1C2(C(O)=O)C(C)(C)C(C)(C(O)=O)C(=O)C1(C(O)=O)C(C(O)=O)(C)CC2 UCXRPFYLIDYANL-UHFFFAOYSA-N 0.000 claims description 4
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- WLHBDEBAVNPAJE-UHFFFAOYSA-N tetramethyl 2,6-dioxoadamantane-1,3,5,7-tetracarboxylate Chemical compound C1C(C2=O)(C(=O)OC)CC3(C(=O)OC)CC2(C(=O)OC)CC1(C(=O)OC)C3=O WLHBDEBAVNPAJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 150000005837 radical ions Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- JZKNMIIVCWHHGX-UHFFFAOYSA-N adamantane-1,2,2,3-tetracarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)C(C(O)=O)(C(O)=O)C2(C(O)=O)C3 JZKNMIIVCWHHGX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the field of gas adsorption separation, and particularly relates to application of a metal-organic framework material in separation of tetramethylsilane and isopentane. By utilizing the characteristic that MOFs pore canal is adjustable, MOFs suitable for TMS separation and purification can be accurately synthesized, so that the purity of the separation product is improved. The invention provides a scheme for separating TMS and isopentane based on copper-based MOF constructed by adamantane tetracarboxylic acid ligand. The invention provides the method for separating the TMS and isopentane mixture generated in industrial production by using the ATC-Cu, fills the gap of MOF in the separation application, and simultaneously separates by using the ATC-Cu, so that TMS with extremely high purity can be obtained, the separation effect is better than that of zeolite molecular sieve, and the energy is saved than that of a rectification method.
Description
Technical Field
The invention belongs to the field of gas adsorption separation, and particularly relates to application of a metal-organic framework material in separation of tetramethylsilane and isopentane.
Background
Tetramethylsilane (TMS) may be a suitable precursor for low dielectric constant amorphous nitrogen doped silicon carbide (SiCNH) barriers used in the fabrication of very large scale integrated circuits. There are two pathways for TMS to be available at present: a method for converting organic silicon and a method for separating organic silicon low-boiling-point substances. The low boiling point substance separation method of the organic silicon refers to the separation of TMS from a low boiling point residue (hereinafter referred to as LBR) obtained in industrial production. In the industrial process of synthesizing methylchlorosilanes by the direct method, a large amount of LBR is produced, and about 40% of TMS is contained in LBR. With the increasing production scale of methylchlorosilanes, there is also an increasing number of LBR obtained in this process. LBR is a byproduct in industrial production and is low in price, so that the high-purity TMS obtained from the LBR has great economic value. LBR is mainly composed of TMS, isopentane, etc. with boiling point below 313K. The separation methods commonly used at present are as follows: a rectification method and an adsorption method.
And (3) rectifying: a method for separating components by utilizing the difference in boiling points of the components in a mixture. The rectification method requires that the components to be separated have obvious boiling point differences, and substances with small boiling point differences are difficult to separate. For example, TMS has a boiling point of 299.7K and isopentane has a boiling point of 300.7K, which are very close to each other, and a high theoretical plate number rectifying tower is needed for separating and purifying TMS from LBR by a rectifying method, and the method has high energy consumption and high cost.
Adsorption method: and (3) using a porous material as a fixed bed adsorbent to selectively adsorb the gas, and then desorbing at a certain temperature and pressure to obtain a target product. The adsorption method is simple to operate, the adsorbent can be generally recycled, the method is environment-friendly and economical, and the method is proved to be an effective method (S.Qiu,M.Xue,G.Zhu,Metal-organic framework membranes:from synthesis to separation application[J].Chem.Soc.Rev.2014,43,6116-6140.;J.-R.Li,R.J.Kuppler,H.-C.Zhou,Selective gas adsorption and separation in metal-organic frameworks[J].Chem.Soc.Rev.2009,38,1477-1504.;Z.Kang,L.Fan,D.Sun,Recent advances and challenges ofmetal–organic framework membranes for gas separation[J].J.Mater.Chem.A.2017,5,10073-10091.). for separating TMS and isopentane by the adsorption method, in the research on separating TMS and isopentane by the adsorption method, the zeolite molecular sieve is selected to separate and purify TMS (X.Chang,Y.Wan,X.Zhao,Z.Yuan,X.Zhao,Y.Li,S.Guo,D.Yan,Adsorptive separation ofhigh purity tetramethylsilane on zeolites from low-boiling residues ofdimethyldichlorosilane synthesis[J].Mater.Chem.Phys.2020,254,123522.). in summary, and the adsorption method is simple, convenient and quick to separate, is convenient for industrialization, and has great significance in the deep research.
Disclosure of Invention
The technical problems in the prior art are that the adsorption method has small energy consumption and simple process, and is convenient for industrial separation operation. However, the molecular sieve commonly used in the industry is made of rigid materials, the pore size is not adjustable, the application range is limited, and functional sites cannot be introduced, so that the molecular sieve has poor separation effect and a proper adsorption separation material needs to be further explored.
For the defects that the energy consumption of the rectification method is high and the separation purpose cannot be achieved, the TMS can be purified by an adsorption method. In view of the current few studies in this direction, it is of great importance to develop a novel adsorbent material with good TMS and isopentane separation properties. Metal-organic framework Materials (MOFs) are novel porous materials spanning multiple disciplines of organic, inorganic, materials, crystal engineering, supermolecular chemistry, topology, coordination chemistry, etc., greatly facilitating the development of adsorbent materials. The diversity and designability of MOFs building blocks allow precise control over atomic dimensions less than 0.05nm, thus allowing identification of small differences between gas molecules. By utilizing the characteristic that MOFs pore canal can be regulated, MOFs suitable for TMS separation and purification can be accurately synthesized, so that the purity of the separation product is improved.
In order to solve the technical problems, the application provides the following technical scheme:
the invention provides the use of a metal-organic framework material, obtained by heating 1,3,5, 7-adamantane tetracarboxylic acid and copper salt in an alkaline aqueous solution, for separating Tetramethylsilane (TMS) and isopentane.
Preferably, the molar ratio of 1,3,5, 7-adamantane tetracarboxylic Acid (ATC) to copper salt is 1:2-6.
Preferably, the copper salt is copper nitrate or a hydrate of copper nitrate.
Preferably, the temperature of the heating reaction is 140-240 ℃.
Preferably, the heating reaction time is 14-24 hours.
Preferably, the metal-organic framework material is degassed under vacuum prior to separation of Tetramethylsilane (TMS) and isopentane.
Preferably, the temperature of the degassing is 140-240 ℃.
Preferably, the degassing time is 4-20 hours.
Preferably, the 1,3,5, 7-adamantane tetracarboxylic acid is prepared by the following steps:
S1: dimethyl malonate, formaldehyde, diethylamine and methanol are mixed and reacted to obtain tetramethyl 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid;
S2: reacting the 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid tetramethyl ester with dibromomethane to obtain 2, 6-dioxoadamantane-1, 3,5, 7-tetracarboxylic acid tetramethyl ester;
S3: and (3) reacting the tetramethyl 2, 6-dioxoadamantane-1, 3,5, 7-tetracarboxylic acid with hydrazine hydrate in a sodium methoxide solution to obtain the 1,3,5, 7-adamantane tetracarboxylic acid.
Further, in the step S3, the reaction method is that the reaction is carried out for 0.5 to 1.5 hours at 180 to 220 ℃ and then for 6 to 10 hours at 230 to 250 ℃.
Specifically, the metal-organic framework material (ATC-Cu) is prepared by the following steps:
H 4 ATC is dissolved in 5 multiplied by 10 -5 to 0.05mol/L dilute sodium hydroxide solution, then Cu (NO 3)2·3H2 O) is added, after uniform mixing, the solution is transferred into a high-pressure reaction kettle, and the temperature is heated to 200 ℃ and kept for 18 hours, so that blue-green hydrated ATC-Cu crystals are obtained.
Compared with the prior art, the technical scheme of the invention has the following advantages:
The invention provides a scheme for separating TMS and isopentane based on copper-based MOF constructed by adamantane tetracarboxylic acid ligand. According to the scheme, the TMS and isopentane mixture generated in industrial production is separated by using ATC-Cu, so that the gap of MOF in the separation application is filled, and meanwhile, the ATC-Cu is used for separation, so that the TMS with ultra-high purity can be obtained, the separation effect is better than that of zeolite molecular sieve, and the energy is saved than that of a rectification method.
Drawings
FIG. 1 is a molecular minimal cross-sectional view; a is TMS molecule and b is isopentane molecule.
FIG. 2 is a schematic diagram of the channel structure of ATC-Cu.
FIG. 3 is an adsorption diagram of ATC-Cu to TMS and isopentane at 298K; (a) Isothermal adsorption curve, (b) Ideal Adsorption Solution Theory (IAST) curve.
FIG. 4 is a schematic diagram of the synthesis of the ligand 1,3,5, 7-adamantane tetracarboxylic acid.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1 Synthesis of 1,3,5, 7-adamantane tetracarboxylic Acid (ATC)
Synthesis of tetramethyl 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid (a): diethylamine was added to a mixture of dimethyl malonate and formaldehyde solution. The viscous colorless solution was then diluted with methanol to give a clear colorless solution. After a period of reaction at 25 ℃, the temperature was raised to 40 ℃ and finally the stirring was stopped and cooled to 0 ℃, the aqueous layer was removed and the organic residue was washed three times with sulfuric acid and water in sequence. The remaining viscous liquid was freed from unreacted dimethyl malonate under vacuum. To the product was added sodium methoxide solution and the reaction was refluxed for 4 hours. Methanol was removed in vacuo and the residue was treated with ice water. Adding hydrochloric acid solution to obtain white solid, recrystallizing with methanol to obtain 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetramethyl tetracarboxylic acid tetramethyl ester light rose prismatic crystal with yield 75％.1HNMR(400MHz,DMSO-d6)δ11.98(s,1H),3.74(s,3H),3.68(s,3H),2.83(d,1H),2.67(d,1H),2.30(s,1H).;IR(KBr)3400,3000,1740,1622cm-1.
Synthesis of tetramethyl 2, 6-dioxoadamantane-1, 3,5, 7-tetracarboxylic acid (b): tetramethyl 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid (a) was dissolved in 3M sodium methoxide solution and then CH 2Br2 was added. The clear solution was transferred to an autoclave and heated overnight. After cooling at room temperature (25.+ -. 5 ℃ C.), the crystalline solid obtained is filtered off and washed with methanol and a large amount of water. Drying to obtain 2, 6-dioxoadamantane-1, 3,5, 7-tetramethyl tetracarboxylic acid, and the yield is 30%; 1H NMR(400MHz,DMSO-d6)δ3.68(s,3H),2.92(s,2H).;IR(KBr)1734,1710,3000,2850cm-1.
Synthesis of 1,3,5, 7-adamantane tetracarboxylic acid (c): b, hydrazine hydrate and 3M sodium methoxide solution are added into a high-pressure degassing reaction kettle. The temperature was maintained at 200℃for one hour and heating was continued until the temperature reached 240℃and then maintained for 8 hours. After cooling, acidify with hydrochloric acid to weak acidity, cool, filter to obtain white powder of c in 90% yield. 1H NMR (400 MHz, DMSO-d 6) delta 12.45 (s, 4H), 1.80 (s, 12H); IR (KBr) 3105 (wide), 1709, 1450, 1398, 1194cm -1.
EXAMPLE 2 Synthesis of ATC-Cu Crystal
The synthesis method of Cu 2(ATC)(2H2O)·5H2 O is as follows:
A proper amount of H 4 ATC is dissolved in 0.01mol/L sodium hydroxide solution, cu (the mol ratio of NO 3)2·3H2O(H4 ATC to Cu (NO 3)2·3H2 O: 1:2) is added, the solution is transferred into a high-pressure reaction kettle after being uniformly mixed, the solution is heated to 220 ℃ and kept for 18 hours, and blue-green hydrated ATC-Cu crystals are obtained, wherein the yield is 60%.
Example 3 vapor sorption test
Prior to testing the vapor adsorption analysis, the samples were degassed under high vacuum conditions (less than 5 μmhg) at 200 ℃ for 12 hours, changing the color of the samples from blue-green to deep-violet. After the ATC-Cu activation was completed, adsorption isotherms of ATC-Cu on both vapors were collected using an adsorption analyzer (micromeritics SAP 2020 Plus).
Effect evaluation 1
Due to TMS moleculesAnd isopentane molecule/>There is a slight gap in the size of the isopentane molecule, and an effective design strategy is to select MOFs with binding sites in the pore channels and pore diameters close to the size of the isopentane molecule to specifically capture the isopentane molecule, so that TMS with higher purity is obtained.
And combining the above elements, and selecting ATC-Cu to separate the two substances. The MOF is synthesized by taking 1,3,5, 7-adamantane tetracarboxylic acid (H 4 ATC) as a ligand and copper nitrate as metal salt through hydrothermal reaction. As shown in FIG. 1, the H 4 ATC ligand was used as a tetrahedral linker to connect to 4 copper-paddle wheel secondary building blocks to construct a channel with rectangular shape (window size) Is a three-dimensional frame of (c). The TMS molecule is larger than the pore size of the MOF, and isopentane is similar to the MOF, so that the MOF allows isopentane to pass through the channel, but TMS cannot pass through the channel, and screening of the two substances by ATC-Cu is achieved.
The adsorption of the single component vapors of TMS and isopentane by ATC-Cu is shown in FIG. 3a below, and the experimental results show that at 298K, the adsorption capacity of the ATC-Cu for two substances is significantly different. The selectivity of the TMS and isopentane mixture with the same mole of ATC-Cu at 298K and 100kPa is as high as 146.7 calculated by adopting an Ideal Adsorption Solution Theory (IAST), and the material is a good isopentane and TMS separation material.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The use of a metal-organic framework material for separating tetramethylsilane from isopentane, wherein the metal-organic framework material is Cu 2(ATC)(2H2O)·5H2 O, and wherein ATC is the acid radical ion from which 1,3,5, 7-adamantane tetracarboxylic acid has been stripped of four hydrogens; the metal-organic framework material is prepared by heating 1,3,5, 7-adamantane tetracarboxylic acid and copper salt in alkaline aqueous solution for reaction.
2. The use according to claim 1, wherein the molar ratio of 1,3,5, 7-adamantane tetracarboxylic acid to copper salt is 1:2-6.
3. The use according to claim 1, wherein the copper salt is copper nitrate or a hydrate of copper nitrate.
4. The use according to claim 1, wherein the temperature of the heating reaction is 140-240 ℃.
5. The use according to claim 1, wherein the heating reaction is for a period of 14-24 h.
6. Use according to claim 1, wherein the metal-organic framework material is degassed under vacuum before separation of tetramethylsilane and isopentane.
7. The use according to claim 6, wherein the temperature of the degassing is 140-240 ℃.
8. The use according to claim 6, wherein the degassing is carried out for a period of time of 4 to 20 h.
9. The use according to claim 1, wherein the 1,3,5, 7-adamantane tetracarboxylic acid is prepared by the steps of:
S1: dimethyl malonate, formaldehyde, diethylamine and methanol are mixed and reacted to obtain tetramethyl 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid;
S2: reacting the 2, 6-dioxobicyclo (1.3.3) -nonane-1, 3,5, 7-tetracarboxylic acid tetramethyl ester with dibromomethane to obtain 2, 6-dioxoadamantane-1, 3,5, 7-tetracarboxylic acid tetramethyl ester;
S3: and (3) reacting the tetramethyl 2, 6-dioxoadamantane-1, 3,5, 7-tetracarboxylic acid with hydrazine hydrate in a sodium methoxide solution to obtain the 1,3,5, 7-adamantane tetracarboxylic acid.
10. The use according to claim 9, wherein in step S3 the reaction is carried out at 180-220 ℃ and then at 230-250 ℃ after 0.5-1.5 h and then at 6-10 h.
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| Dense packing of xenon in an ultra-microporous metal–organic framework for benchmark xenon capture and separation;Qiang Liu等;《Chemical Engineering Journal 》;20221019;第453卷;文献号139849（1-9） * |
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