CN116351405A - Gas-phase capillary column using UiO-66 as adsorbent and manufacturing method and application thereof - Google Patents
Gas-phase capillary column using UiO-66 as adsorbent and manufacturing method and application thereof Download PDFInfo
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- CN116351405A CN116351405A CN202310412862.4A CN202310412862A CN116351405A CN 116351405 A CN116351405 A CN 116351405A CN 202310412862 A CN202310412862 A CN 202310412862A CN 116351405 A CN116351405 A CN 116351405A
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 55
- 239000003463 adsorbent Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012808 vapor phase Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 239000001282 iso-butane Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 14
- 230000005526 G1 to G0 transition Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000013259 porous coordination polymer Substances 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- -1 zirconium ions Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 11
- 239000000306 component Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- KOWXKIHEBFTVRU-UHFFFAOYSA-N nga2 glycan Chemical compound CC.CC KOWXKIHEBFTVRU-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 3
- 208000034486 Multi-organ failure Diseases 0.000 description 2
- FDTGUDJKAXJXLL-UHFFFAOYSA-N acetylene Chemical compound C#C.C#C FDTGUDJKAXJXLL-UHFFFAOYSA-N 0.000 description 2
- LFKIGTZUWPXSIH-UHFFFAOYSA-N but-1-ene;2-methylprop-1-ene Chemical compound CCC=C.CC(C)=C LFKIGTZUWPXSIH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
-
- 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
- B01D53/025—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 with wetted adsorbents; Chromatography
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3092—Packing of a container, e.g. packing a cartridge or column
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/84—Capillaries
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/56—Packing methods or coating methods
- G01N2030/562—Packing methods or coating methods packing
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
The invention discloses a gas-phase capillary column taking UiO-66 as an adsorbent, and a manufacturing method and application thereof, wherein the manufacturing method comprises the following steps: s1: adding zirconium tetrachloride and terephthalic acid into N, N-dimethylformamide, uniformly mixing, and transferring into a closed container; s2: filling the UiO-66 solution into a capillary column, reacting at constant pressure and constant temperature, and cooling to room temperature after the reaction is finished; s3: filling inert gas into the capillary column treated in the step S2 until liquid in the capillary column is blown out; s4: and (3) loading the capillary column treated in the step (S3) into a gas chromatograph, introducing inert gas, aging, and cooling to room temperature. The invention discloses a gas-phase capillary column taking UiO-66 as an adsorbent, a manufacturing method and application thereof, wherein terephthalic acid is taken as an organic molecule, and a porous coordination polymer generated by taking tetravalent zirconium ions as coordinated metal ions is taken as a capillary column stationary phase, so that the separation effect of the capillary column on lower alkane is improved.
Description
Technical Field
The invention relates to the technical field of capillary columns, in particular to a gas-phase capillary column taking UiO-66 as an adsorbent, and a manufacturing method and application thereof.
Background
The chromatographic column is a core component of gas chromatography and has wide application in the fields of petroleum, chemical industry, biochemistry, medicine and health, food industry, environmental protection and the like. The gas chromatographic stationary phase is used as the filling of the chromatographic column, is the part where the components of the mixed gas are separated, and is also the core material for forming the gas chromatographic column. The gas chromatography column may be packed/coated with different fixatives/adsorbents to obtain a number of different chromatography columns. The method can be divided into two main types of filling columns and capillary columns according to different manufacturing modes. The current gas chromatographic column for separating lower alkane is mainly PLOT-Al 2 O 3 The capillary column is a packed column packed with gamma-alumina.
The Metal Organic Framework (MOF) material is a crystalline organic-inorganic hybrid framework material formed by coordination self-assembly of organic ligands and metal ions, has the advantages of uniform pore structure, high specific surface area, adjustable pore structure and pore chemical environment and the like, and has wide application prospects in the fields of gas storage and separation, catalysis, sensing, drug transmission and the like. Meanwhile, the metal organic framework material is also a potential gas chromatography stationary phase material, and has good application prospect in the analysis of multi-component gases such as alkane/alkene, hydrogen/methane, oxygen/nitrogen and the like.
However, most MOFs are less stable, which greatly limits the development of MOFs. The zirconium (Zr) -based metal organic framework material UiO-66 is formed by coordination connection of a regular octahedron Zr and 12 organic ligands terephthalic acid. The UiO-66 not only has the thermal stability which can still keep a stable structure under 813K, but also has certain acid and alkali resistance, is one of the materials with the best stability in the current metal-organic framework materials, and attracts attention. However, at present, the Metal Organic Framework (MOF) material is mostly in the form of a packed column as a chromatographic stationary phase, and the research of taking zirconium (Zr) based metal organic framework material UiO-66 as a capillary column stationary phase has not been reported yet.
Disclosure of Invention
The invention aims to provide a gas-phase capillary column taking zirconium-based metal organic framework material UiO-66 as an adsorbent, a manufacturing method and application thereof, terephthalic acid is taken as an organic bridging molecule, tetravalent zirconium ions are taken as porous coordination polymers generated by coordinated metal ions, and the polymers are taken as a capillary column stationary phase, so that the separation effect of the capillary column on lower alkane is improved.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method for preparing a vapor capillary column with UiO-66 as an adsorbent, comprising the steps of:
s1: adding zirconium tetrachloride and terephthalic acid into N, N-dimethylformamide, uniformly mixing, and transferring the mixed solution into a closed container for standby;
s2: filling the mixed solution prepared in the step S1 into a capillary column, reacting for 24 hours under the conditions of constant pressure of 0.1Mpa and temperature of 120-150 ℃, and cooling to room temperature after the reaction is finished;
s3: filling inert gas into the capillary column treated in the step S2, so that the mixed liquid blows out the liquid in the capillary column at a constant speed of 20-30cm/min in the capillary, and continuing to fill the inert gas for 2 hours;
s4: and (3) loading the capillary column treated in the step (S3) into a gas chromatograph, introducing inert gas, setting the front pressure of the capillary column to be 0.15-0.2 Mpa, setting the aging temperature to be 100 ℃ for 1h, then heating to 300 ℃ at the heating rate of 20 ℃/min, preserving heat for 4h at 300 ℃, and cooling to room temperature.
Further, the weight ratio of zirconium tetrachloride to terephthalic acid is 0.2332:0.1661.
further, the mixed solution also comprises cerium trichloride, wherein the weight ratio of the cerium trichloride to the zirconium tetrachloride to the terephthalic acid is 0.21:0.02:0.1661.
Further, in step S2, the specific method for filling the capillary column with the UiO-66 solution is as follows: inserting the capillary column into the closed container, and keeping the pipe orifice of the capillary column below the liquid level of the mixed liquid; and then introducing inert gas into the closed container until the mixed liquid completely fills the capillary column.
Further, in step S1, the mixed liquor is sonicated for 20-30min before transferring the mixed liquor to a closed vessel.
Further, the inert gases used in the step S3 and the step S4 are high-purity nitrogen.
In order to achieve the above purpose, the present invention provides the following technical solutions: the gas-phase capillary column with the UiO-66 as the adsorbent is obtained by adopting the preparation method of the gas-phase capillary column with the UiO-66 as the adsorbent.
In order to achieve the above purpose, the present invention provides the following technical solutions: the application of the gas-phase capillary column taking the UiO-66 as the adsorbent in separating lower alkane.
Further, the application of the gas-phase capillary column with the UiO-66 as the adsorbent in separating liquefied gas, wherein the analysis and detection conditions for separating methane, ethane, ethylene, acetylene, propane, propylene, propyne, 1, 3-butadiene, fumaric acid, n-butene, isobutene, maleic acid, n-butane and isobutane in the liquefied gas are as follows: adopting a flame ionization detector, keeping the temperature of a column box at 120 ℃, keeping 1min, heating to 230 ℃ at 20 ℃/min, keeping for 30min, keeping the temperature of a vaporization chamber at 250 ℃, keeping the temperature of a detection chamber at 260 ℃, and keeping the chromatographic column split ratio at 40:1, column flow rate 1ml/min.
In summary, the invention has the following beneficial effects:
first, terephthalic acid is used as organic bridgeThe molecule, tetravalent zirconium ion is used as porous coordination polymer UiO-66 generated by coordination metal ion, uiO-66 is used as capillary column stationary phase for the first time, uiO-66 material is fixed on the inner wall of capillary while in situ synthesized in capillary column, uiO-66 material is microporous, the specific surface area and aperture of the material are reduced to a certain extent, and the traditional PLOT-Al is solved 2 O 3 The capillary column is needed to synthesize the stationary phase through chemical reaction outside the capillary column, and then the stationary phase is filled into the capillary column for physical coating, because the aluminum oxide cannot be adhered to the surface of the glass, and the aluminum oxide is needed to form hydrogen bonds on the surface of the glass by means of inorganic adhesive, the main component of the glass is the problem that the aluminosilicate and the aluminum oxide do not form hydrogen bonds, and the UiO-66 molecule contains hydrogen atoms, so that the aluminum oxide can directly react inside the column.
Secondly, the zirconium-based metal organic framework material UiO-66 prepared by the method is not easy to fall off, has high separation efficiency, and provides a thought for taking the zirconium (Zr) -based metal organic framework material UiO-66 as a capillary column stationary phase.
The gas-phase capillary column prepared by the method provided by the application and taking the zirconium-based metal organic framework material UIO-66 as an adsorbent has a good separation effect on lower alkane, and the principle is that the molecular form of UIO-66 is a space reticular structure taking terephthalic acid as a bracket and metal ions as nodes. Has the property of a screen and has certain polarity. The structure of the screen can screen hydrocarbon molecules according to the size, namely the number of carbon atoms. The polarity can be used for screening hydrocarbons with the same carbon number, different structures and different saturation degrees.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is an SEM image of UiO-66 prepared according to example 1;
FIG. 2 is a diagram showing the state of change of the solution for preparing the UiO-66 solution in this example 1;
FIG. 3 is a view showing the construction of the external appearance of a vapor phase capillary column based on UiO-66 as an adsorbent, which was prepared in example 1;
FIG. 4 is an SEM image of a vapor phase capillary column based on UIO-66 as an adsorbent prepared in example 1;
FIG. 5 is an SEM image of modified UiO-66 prepared according to example 2;
FIG. 6 is a solution change state diagram of the modified UiO-66 solution prepared in this example 2;
FIG. 7 is a view showing the construction of the external appearance of a vapor phase capillary column based on modified UiO-66 as an adsorbent, which was prepared in this example 2;
FIG. 8 is an SEM image of a vapor phase capillary column based on modified UiO-66 as an adsorbent prepared in example 2;
FIG. 9 is a gas chromatograph of a liquid gas separated by using the UiO-66 material prepared in example 1 as a capillary column stationary phase;
FIG. 10 is a gas chromatograph of a modified UiO-66 material prepared in example 2 as a capillary column stationary phase for separating liquefied gas;
fig. 11 is a gas chromatograph of a capillary column for separating liquefied gas provided in a comparative example.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 to 11 in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Parameters of the capillary tube to which the present application relates: the length is 30-100m, the material is glass, and the outer diameter is 0.32mm.
Table 1 raw materials according to the present application
| Raw materials | Source |
| Zirconium tetrachloride | The purity of the macllin reagent is 99% |
| Terephthalic acid | The purity of the macllin reagent is 99% |
| N, N-dimethylformamide | Tianjin family Miou reagent |
| Cerium trichloride | The purity of the macllin reagent is 99% |
Examples
Example 1
A method for preparing a vapor capillary column with UiO-66 as an adsorbent, comprising the steps of:
s1: 0.2332g of zirconium tetrachloride (10026-11-6), 0.1661g of terephthalic acid (CAS: 100-21-0) were each weighed out and added to 50ml of N, N-Dimethylformamide (DMF). And placing the mixed reaction liquid into an ultrasonic cleaner for ultrasonic treatment for 20min. The mixture was transferred to a clean glass bottle, which was plugged with a rubber stopper.
S2: the capillary column is inserted into the glass bottle through the rubber plug, and the pipe orifice of the capillary column is inserted below the liquid level of the reaction liquid. Then a stainless steel tube is inserted, and the stainless steel tube is not contacted with the reaction liquid. Continuously introducing high-purity nitrogen into the glass bottle through the stainless steel tube, and pressing the mixed liquid in the glass bottle into the capillary column until the reaction liquid is completely filled in the capillary column. And taking out the capillary column, putting the capillary column into a constant temperature drying oven, connecting two ends of the capillary column to a constant pressure device, taking high-purity nitrogen as constant pressure gas, and ensuring the constant pressure in the capillary column to be 0.1Mpa. The temperature of the constant temperature drying oven was set to 120℃and the reaction time was kept at 24 hours.
After the reaction is finished, waiting for cooling to room temperature;
s3: and (3) taking out the capillary column treated in the step (S2), introducing high-purity nitrogen, blowing out the liquid in the capillary column at a constant speed of 20-30cm/min in the capillary, and then continuously introducing the high-purity nitrogen for 2 hours.
S4: and (3) introducing the capillary column treated in the step (S3) into a gas chromatograph, and introducing high-purity nitrogen. Setting the capillary column front pressure to 0.15Mpa-0.2Mpa, setting the aging temperature to 100 ℃ for 1 hour, then heating to 300 ℃ at the heating rate of 20 ℃/min, keeping 300 ℃ for 4 hours, and naturally cooling to room temperature to obtain the gas-phase capillary column taking UIO-66 as the adsorbent.
FIG. 1 is an SEM image of the preparation of UiO-66 of example 1.
FIG. 2 is a diagram showing the state of change of the solution for preparing the UiO-66 solution in this example 1.
FIG. 3 is a view showing the construction of the external appearance of a vapor phase capillary column based on UiO-66 as an adsorbent, which was prepared in example 1;
FIG. 4 is a vapor phase capillary column coated with UiO-66 prepared in this example 1;
it can be seen from FIG. 3 that many break points occur in the vapor capillary column, and from FIG. 4 that the capillary inner wall has very little crystals, is mostly smooth, and the smooth portion proves to be uncoated with UiO-66; as can be seen from fig. 3 and 4, the solvent is volatilized at different speeds due to the influence of ambient temperature and pressure during the process of preparation, so that the suspended matters in the solvent are stored in the chromatographic column after being volatilized and have inconsistent thickness.
Example 2
A method for preparing a vapor capillary column with modified UiO-66 as an adsorbent, comprising the steps of:
s1: separately, 0.21g of cerium trichloride (7790-86-5), 0.02g of zirconium tetrachloride (10026-11-6), and 0.1661g of terephthalic acid (CAS: 100-21-0) were weighed out. To 50ml of N, N-Dimethylformamide (DMF). And putting the mixed reaction liquid into an ultrasonic cleaner for ultrasonic treatment for 30min. The reaction solution was transferred to a clean glass bottle, which was closed with a rubber stopper.
S2: the capillary column is inserted into the glass bottle through the rubber plug, and the pipe orifice of the capillary column is inserted below the liquid level of the reaction liquid. Then a stainless steel tube is inserted, and the stainless steel tube is not contacted with the reaction liquid. Continuously introducing high-purity nitrogen into the glass bottle through the stainless steel tube, and pressing the mixed liquid in the glass bottle into the capillary column until the reaction liquid is completely filled in the capillary column. And taking out the capillary column, putting the capillary column into a constant temperature drying oven, connecting two ends of the capillary column to a constant pressure device, taking high-purity nitrogen as constant pressure gas, and ensuring the constant pressure in the capillary column to be 0.1Mpa. The temperature of the constant temperature drying oven was set at 150℃and the reaction time was kept at 24 hours.
After the reaction is finished, waiting for cooling to room temperature;
s3: as in example 1;
s4: a vapor phase capillary column with modified UiO-66 as adsorbent was prepared as in example 1.
FIG. 5 is an SEM image of the preparation of modified UiO-66 of example 2.
FIG. 6 is a diagram showing the state of change in the solution for preparing the modified UiO-66 solution in this example 2.
FIG. 7 is a diagram showing the external appearance of a vapor phase capillary column based on modified UiO-66 as an adsorbent, which was prepared in example 2.
FIG. 8 is a vapor phase capillary column coated with modified UiO-66 prepared in this example 2.
As can be seen from fig. 7, the raw materials are uniformly distributed in the solution so that the reaction also occurs uniformly in the chromatographic column. The reaction solution is non-volatile, and the solvent is simply extracted after the reaction is finished. Therefore, the distribution of reaction products in the capillary column is not affected, no break point exists in the gas-phase capillary column, and the thickness of raw materials in the chromatographic column is uniform.
As can be seen from fig. 8, there are no break points on the capillary tube wall of the gas phase coated with modified UiO-66 and the crystals are uniformly distributed on the capillary tube wall, further demonstrating the uniform thickness of the feedstock in the column.
It can be seen in connection with examples 1-2, figures 1-8 that the product was changed before and after modification, indicating that the modified process was effective without the same product.
Comparative example: plot Al sold in the market 2 O 3 A vapor phase capillary column.
Test examples
Test example 1
The capillary column prepared in example 1 was tested for separation performance of liquefied gas, and the results are shown in fig. 9 and table 2.
The testing method comprises the following steps: and (5) connecting the prepared capillary column into an Agilent gas chromatograph, wherein the chromatograph model is 5890.
The gas chromatograph configuration and conditions of use are as follows:
vaporization chamber temperature: 250 DEG C
FID detector temperature: 260 DEG C
Column box temperature: the temperature is raised to 230 ℃ at 120 ℃ and kept for 1min at 20 ℃/min, and the temperature is kept for 30min.
Chromatographic column split ratio 40:1, column flow rate 1mL/min.
Sample: liquefied gas
Sample injection amount 0.1ml
TABLE 2
| Retention time | Component name | Symmetry factor | Peak width | Number of trays | Degree of separation |
| 3.267411 | Methane | 0.948923 | 0.025364 | 91927.39 | |
| 3.427888 | Acetylene + ethylene | 0.911487 | 0.022864 | 124476.2 | 3.909717 |
| 3.55423 | Ethane (ethane) | 0.774806 | 0.022699 | 135746.1 | 3.258155 |
| 4.329263 | Propyne+propylene | 0.598972 | 0.025567 | 158638.8 | 18.86767 |
| 4.777063 | Propane | 0.340068 | 0.042049 | 71333.05 | 7.781614 |
| 5.869953 | 1, 3-butadiene + fumaric acid | 0.448237 | 0.026548 | 270516 | 18.72 |
| 6.259119 | N-butene | 0.370011 | 0.038403 | 146921.8 | 7.040197 |
| 6.527285 | Isobutene+cis | 0.367846 | 0.042917 | 127955 | 3.874774 |
| 6.835855 | N-butane | 0.30826 | 0.048327 | 110673.5 | 3.973627 |
| 7.216219 | Isobutane | 0.28466 | 0.064656 | 68949.64 | 3.955684 |
As can be seen by combining fig. 9 and table 2, the gas capillary column of example 1 of the present application can separate 14 components in liquefied gas, the chromatogram has a flat base line and no obvious tailing phenomenon of the chromatographic peak shape, and the overall analysis time is short, but two pairs of peaks of acetylene, ethylene, propyne, propylene, 1, 3-butadiene, isobutylene, and maleic isomers cannot be separated well.
Test example 2
The capillary column prepared in example 2 was tested for separation performance of liquefied gas, and the results are shown in fig. 10 and table 3.
The testing method comprises the following steps: the same as in test example 1.
TABLE 3 Table 3
| Retention time | Component name | Symmetry factor | Peak width | Number of trays | Degree of separation |
| 3.252315 | Methane | 0.961263 | 0.022917 | 111594.4 | |
| 3.355632 | Acetylene (acetylene) | 0.934224 | 0.021425 | 135916 | 2.737795 |
| 3.414921 | Ethylene | 0.951994 | 0.020833 | 148858.9 | 1.648534 |
| 3.546339 | Ethane (ethane) | 0.930466 | 0.02 | 174135.5 | 3.781613 |
| 4.050492 | Propyne | 0.860373 | 0.019583 | 236847.5 | 14.9654 |
| 4.336392 | Propylene | 0.764068 | 0.020151 | 256380.6 | 8.454402 |
| 4.810369 | Propane | 0.651422 | 0.024294 | 217013.6 | 12.53044 |
| 5.666896 | 1, 3-butadiene | 0.57184 | 0.026395 | 255041.3 | 19.8546 |
| 5.859321 | Fumaric acid | 0.399965 | 0.036849 | 139862.6 | 3.575001 |
| 6.134289 | N-butene | 0.48654 | 0.037985 | 159637.1 | 3.69846 |
| 6.272911 | Isobutene (i-butene) | 0.425029 | 0.035427 | 173486.9 | 3.52376 |
| 6.529941 | Maleic anhydride | 0.357172 | 0.042365 | 131452.2 | 3.882298 |
| 6.866976 | N-butane | 0.324698 | 0.041771 | 149530.1 | 4.706862 |
| 7.26025 | Isobutane | 0.449582 | 0.048333 | 124908.2 | 5.128478 |
As can be seen from fig. 10 and table 3, the vapor capillary column of example 2 of the present application can completely realize baseline separation of 14 components in liquefied gas, and has a good separation effect. The improved gas phase capillary column solves the problem of poor separation effect of acetylene, ethylene, propyne, propylene, 1, 3-butadiene, fumaric acid, isobutene and maleic acid isomers, all components are separated by a base line, the base line of a chromatogram is straight, no obvious tailing phenomenon exists in the shape of the chromatographic peak, and the whole analysis time is short.
Test example 3
The capillary column prepared in example 3 was tested for separation performance of liquefied gas, and the results are shown in fig. 11 and table 4.
The testing method comprises the following steps: the same as in test example 1.
TABLE 4 Table 4
| Retention time | Component name | Peak width | Number of trays | Degree of separation |
| 3.404 | Methane | 0.026645 | 90428 | |
| 3.607 | Ethane (ethane) | 0.026033 | 106333 | 0.05954 |
| 3.909 | Ethylene | 0.028628 | 103297 | 0.1484 |
| 4.342 | Propane | 0.031154 | 107598 | 0.2755 |
| 6.022 | Propylene | 0.080508 | 30993 | 0.769 |
| 6.68 | Isobutane | 0.057708 | 74233 | 0.9624 |
| 7.098 | N-butane | 0.059813 | 78024 | 1.085 |
| 8.222 | Acetylene (acetylene) | 0.083479 | 53737 | 1.415 |
| 10.355 | Fumaric acid | 0.082159 | 88002 | 2.042 |
| 10.667 | N-butene | 0.081831 | 94131 | 2.134 |
| 11.233 | Isobutene (i-butene) | 0.087258 | 91816 | 2.3 |
| 11.584 | Maleic anhydride | 0.087811 | 96260 | 2.403 |
| 13.792 | 1, 3-butadiene | 0.11046 | 86371 | 3.052 |
| 14.821 | Propyne | 0.1031 | 114473 | 3.354 |
As can be seen from a combination of Table 4 and FIG. 11, the use of Plot Al 2 O 3 When analyzing a liquefied gas sample, although all components gave a baselineSeparation, but the chromatogram base line is not flat and the chromatogram peak shape has obvious tailing phenomenon.
As can be seen in combination with tables 1-3 and FIGS. 9-11, due to the Plot Al 2 O 3 The final peak-out time is 14.821min, the average tray number of all peaks is 86835, the final peak-out time of the capillary column provided by the invention is 7.26min, and the average tray number of all peaks is 172476. The peak time of the capillary column provided by the invention is the commodity Plot Al 2 O 3 The capillary column has half of the peak time and double theoretical plate number, so that the capillary chromatographic column prepared by the method of the embodiment 1-2 of the application greatly shortens the analysis time. The average plate number is also higher than that of Plot Al 2 O 3 The gas phase capillary column is high.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A method for preparing a vapor capillary column with UiO-66 as an adsorbent, comprising the steps of:
s1: adding zirconium tetrachloride and terephthalic acid into N, N-dimethylformamide, uniformly mixing to obtain a mixed solution, and transferring the mixed solution into a closed container for standby;
s2: filling the mixed solution prepared in the step S1 into a capillary column, reacting for 24 hours under the conditions of constant pressure of 0.09-0.11Mpa and temperature of 120-150 ℃, and cooling to room temperature after the reaction is finished;
s3: filling inert gas into the capillary column treated in the step S2, so that the mixed liquid moves at a constant speed of 20-30cm/min in the capillary column until all the liquid flows out of the capillary column;
s4: and (3) loading the capillary column treated in the step (S3) into a gas chromatograph, introducing inert gas, setting the front pressure of the capillary column to be 0.15-0.2 Mpa, setting the aging temperature to be 100 ℃ for 1h, then heating to 300 ℃ at the heating rate of 20 ℃/min, preserving heat for 4h at 300 ℃, and cooling to room temperature.
2. The method for preparing a vapor phase capillary column with UiO-66 as an adsorbent according to claim 1, wherein the weight ratio of zirconium tetrachloride to terephthalic acid is 0.2332:0.1661.
3. the method according to claim 1, wherein in the step S1, cerium trichloride is further contained in the mixed solution, and the weight ratio of cerium trichloride to zirconium tetrachloride to terephthalic acid is 0.21:0.02:0.1661.
4. The method for preparing a vapor phase capillary column using UiO-66 as an adsorbent according to claim 1, wherein in step S2, the specific method for filling the capillary column with the mixed solution is as follows: inserting the capillary column into the closed container, and keeping the pipe orifice of the capillary column below the liquid level of the mixed liquid; and then introducing inert gas into the closed container until the mixed liquid completely fills the capillary column.
5. The method for preparing a vapor phase capillary column using UiO-66 as an adsorbent according to claim 1, wherein the mixed solution is sonicated for 20-30min before transferring the mixed solution to a closed vessel in step S1.
6. The method for preparing a vapor phase capillary column using UiO-66 as an adsorbent according to claim 1, wherein the inert gas used in step S3 and step S4 is high purity nitrogen.
7. A vapor-phase capillary column having UiO-66 as an adsorbent, which is obtained by the method for producing a vapor-phase capillary column using UiO-66 as an adsorbent according to any one of claims 1 to 6.
8. Use of a vapor phase capillary column with UiO-66 as adsorbent according to claim 7 for separating lower alkanes.
9. The use according to claim 8, wherein the use of a capillary column in the vapor phase of UiO-66 as an adsorbent for separating liquefied gas from methane, ethane, ethylene, acetylene, propane, propylene, propyne, 1, 3-butadiene, fumaric acid, n-butene, isobutene, maleic acid, n-butane, isobutane under the following analytical detection conditions: adopting a flame ionization detector, keeping the temperature of a column box at 120 ℃, keeping 1min, heating to 230 ℃ at 20 ℃/min, keeping for 30min, keeping the temperature of a vaporization chamber at 250 ℃, keeping the temperature of a detection chamber at 260 ℃, and keeping the chromatographic column split ratio at 40:1, column flow rate 1ml/min.
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