CN114479096B - Double-ligand metal organic framework material and preparation method and application thereof - Google Patents
Double-ligand metal organic framework material and preparation method and application thereof Download PDFInfo
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- CN114479096B CN114479096B CN202011170710.0A CN202011170710A CN114479096B CN 114479096 B CN114479096 B CN 114479096B CN 202011170710 A CN202011170710 A CN 202011170710A CN 114479096 B CN114479096 B CN 114479096B
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- 239000003446 ligand Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 69
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 45
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 230000009977 dual effect Effects 0.000 claims description 16
- -1 monocarboxylic acid compound Chemical class 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001879 copper Chemical class 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011593 sulfur Substances 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000012452 mother liquor Substances 0.000 description 22
- 238000001179 sorption measurement Methods 0.000 description 19
- 238000006477 desulfuration reaction Methods 0.000 description 17
- 230000023556 desulfurization Effects 0.000 description 17
- 239000013084 copper-based metal-organic framework Substances 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 239000013148 Cu-BTC MOF Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
-
- 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
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Abstract
The invention discloses a dual-ligand hierarchical pore metal organic framework material, a preparation method and application thereof. The dual-ligand hierarchical pore metal organic framework material provided by the invention comprises metal ions and ligands, wherein the metal ions comprise copper ions, and the ligands comprise trimesic acid and imidazole; the dual-ligand hierarchical pore metal organic framework material has a polyhedral prismatic structure. The double-ligand hierarchical pore metal organic framework material is used as an adsorbent to effectively remove thiophene sulfides, has the characteristics of high removal rate and high sulfur capacity, and is mild in reaction condition, low in production cost and low in hydrogen consumption.
Description
Technical Field
The invention relates to the field of adsorption desulfurization, in particular to a double-ligand metal organic framework material, a preparation method thereof and application thereof in adsorption desulfurization.
Background
Today, environmental protection work is increasingly emphasized, and no matter the application of traditional fossil energy or new energy, the problem of reducing the sulfur content in oil products is still to be solved.
Sulfur compounds in fuel oils such as finished gasoline mainly include mercaptans, sulfides, disulfides, thiophenes and derivatives thereof, while thiophenic sulfur compounds account for more than 85% of the total sulfur in gasoline. Wherein the sulfur atoms of mercaptans, sulfides and disulfides have a higher electron cloud density and the carbon-sulfur bonds are weaker and can be removed by conventional hydrodesulfurization processes. Thiophene and its derivatives are difficult to remove by hydrodesulfurization because of the stable conjugated structure formed between the lone pair electron on the sulfur atom and pi electron on the thiophene ring.
In recent years, selective adsorption desulfurization is gradually considered as the most promising new technology of fine desulfurization and deep desulfurization due to the advantages of mild operation conditions, simplicity, low equipment requirements, easy regeneration and the like. The Metal Organic Frameworks (MOFs) material has a great specific surface area, a flexible and adjustable framework and pore channel structure, and has a wide application prospect in the field of selective adsorption desulfurization of hydrocarbon mixtures. CN105561929B discloses a preparation method of bimetallic MOFs, and the zn@pcn-10 material capable of effectively removing dibenzothiophene is obtained through coordination and connection of proper ligands and bimetallic. The sulfur capacity of the material is limited to a certain extent, raw materials are not fully utilized, the preparation period is long, and the material is unfavorable for realizing industrial application in the later period.
Disclosure of Invention
The invention solves the technical problems of low removal rate of thiophene and derivatives thereof, small sulfur capacity and the like in the prior art, and also has the defects of harsh reaction conditions, high production cost, high hydrogen consumption and the like. The invention provides a double-ligand hierarchical pore metal organic framework material, a preparation method and application thereof, wherein the double-ligand hierarchical pore metal organic framework material can be used as an adsorbent for effectively removing thiophene sulfides, has the characteristics of high removal rate, high sulfur capacity and long service life, and is mild in reaction condition, low in production cost and low in hydrogen consumption.
The invention provides a dual-ligand hierarchical pore metal organic framework material, which comprises metal ions and ligands, wherein the metal ions comprise copper ions, and the ligands comprise trimesic acid and imidazole; the dual-ligand hierarchical pore metal organic framework material has a polyhedral prismatic structure.
In the technical scheme, the dual-ligand hierarchical pore metal organic framework material is provided with micropores, mesopores and/or macropores.
In the technical proposal, the specific surface area of the dual-ligand hierarchical pore metal organic framework material is 950-1700m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The total pore volume is 0.3-0.95cm 3 ·g -1 The micropore volume is 0.29-0.55cm 3 ·g -1 Mesoporous volume of 0.01-0.5cm 3 ·g -1 The mesoporous aperture is 2-30nm; preferably, the specific surface area of the dual-ligand hierarchical pore metal organic framework material is 1100-1400m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume of 0.6-0.95cm 3 ·g -1 Mesoporous volume of 0.15-0.50cm 3 ·g -1 The mesoporous aperture is 5-20nm.
In the technical scheme, the mass content of the framework metal Cu element in the dual-ligand hierarchical pore metal organic framework material is 15% -60%; the molar ratio of trimesic acid to imidazole is 1:0.1-6.
In the above technical solution, the dual-ligand hierarchical pore metal organic framework material has a polyhedral prismatic structure, preferably a hexagonal prism; the prism section comprises a hexagon, but is not limited to a hexagon, the side length of the section polygon is 1-7 mu m, the surface of the crystal is provided with a triangular hole-shaped structure, and the side length of the triangle is 50-300nm.
The second aspect of the invention provides a preparation method of a dual-ligand hierarchical pore metal organic framework material, which comprises the following steps:
s1: copper salt and trimesic acid are dissolved in a first solvent to form a reaction solution, and organic alkali is added in batches under the condition of ultrasonic and continuous intense stirring;
s2: dissolving imidazole into a second solvent, adding the S1 solution, dropwise injecting a single-coordination ligand under stirring, reacting, centrifuging and drying.
In the above technical scheme, the copper salt in step S1 is selected from inorganic salts of copper, preferably copper nitrate.
In the above technical solution, the first solvent in step S1 includes one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methanol, ethanol, acetonitrile, deionized water, and dimethyl sulfoxide.
In the above technical solution, the organic base in step S1 includes one or more of methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine, diethylamine, triethylamine, aniline, acetamide, and urea, preferably triethylamine.
In the technical scheme, the molar ratio of the trimesic acid to the imidazole is 1: (0.1-6).
In the above technical scheme, the molar ratio of the copper salt to trimesic acid in step S1 is 1: (0.2-5); the dosage ratio of the first solvent to the copper salt in the step S1 is 5-200mL of solvent/1.0 g of metal salt; the volume ratio of the organic base to the solvent is 1:25-300.
In the technical scheme, the mixture in the step S1 is subjected to water bath ultrasonic treatment, the ultrasonic power is 200-1000W, and the ultrasonic treatment time is 20-300min.
In the above technical scheme, the total addition amount of the organic base in step S1 can be batched for 2-5 times, and the addition amounts of each batch are the same.
In the technical scheme, the mixture in the step S1 is vigorously stirred at 400-1000rpm.
In the above technical solution, the second solvent in step S2 includes one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methanol, ethanol, acetonitrile, deionized water, and dimethyl sulfoxide.
In the above technical solution, the second solvent in step S2 and the first solvent in step S1 may be the same or different.
In the above technical solution, the monodentate ligand in step S2 is a monocarboxylic acid compound including one or more of acetic acid, benzoic acid, and lauric acid; and/or the volume ratio of the monocarboxylic acid compound to the second solvent in S2 is 1:0.5-50.
In the above technical scheme, the dosage ratio of the second solvent to imidazole in the step S2 is 5-50mL of solvent/1.0 g of ligand.
In the above technical solution, the reaction in step S2 is performed in a reaction kettle, preferably the reaction kettle is provided with a high temperature resistant material, preferably the high temperature resistant material is selected from polytetrafluoroethylene; the high-temperature resistant material is in a rod shape, a strip shape or a plate shape.
In the technical scheme, the reaction conditions in the step S2 comprise a reaction temperature of 30-150 ℃ and a reaction time of 3-48h; the drying in the step S2 is carried out in two stages, wherein the temperature of the first stage is 50-100 ℃, the time is 1-24h, the drying temperature of the second stage is 100-200 ℃, and the time is 1-24h.
In the technical scheme, the prepared dual-ligand hierarchical pore metal organic framework material is provided with micropores and mesoporous and/or macroporous hierarchical pore channels.
In the technical proposal, the specific surface area of the dual-ligand hierarchical pore metal organic framework material is 950-1700m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The total pore volume is 0.3-0.95cm 3 ·g -1 The micropore volume is 0.29-0.55cm 3 ·g -1 Mesoporous volume of 0.01-0.5cm 3 ·g -1 The mesoporous aperture is 2-30nm; preferably, the specific surface area of the dual-ligand hierarchical pore metal organic framework material is 1100-1400m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Pore volume of 0.6-0.95cm 3 ·g -1 Mesoporous volume of 0.15-0.50cm 3 ·g -1 The mesoporous aperture is 5-20nm.
In the technical scheme, the prepared dual-ligand hierarchical pore metal organic framework material has a polyhedral prismatic structure, and is preferably a hexagonal prism; the prism section comprises a hexagon, but is not limited to a hexagon, the side length of the section polygon is 1-7 mu m, the surface of the crystal is provided with a triangular hole-shaped structure, and the side length of the triangle is 50-300nm.
In a third aspect, the present invention provides a method for removing sulfides, comprising contacting the dual ligand hierarchical pore metal organic framework material provided in the first aspect or the dual ligand hierarchical pore metal organic framework material obtained by the preparation method in the second aspect with a dibenzothiophene-containing material.
In the technical proposal, the concentration of the dibenzothiophene in the dibenzothiophene-containing material is 0.5 to 5mgS/g, and the airspeed is 0.1 to 5h -1 。
The invention has the following beneficial effects:
1. the dual-ligand hierarchical pore metal organic framework material provided by the invention has special crystal morphology and rich special pore channel properties, so that the dual-ligand hierarchical pore metal organic framework material can adsorb sulfides with larger molecular weight, the adsorption rate is improved, desorption is easy, and the service life of the material is prolonged.
2. At present, crystals formed by certain ligands and metal ions are difficult to grow in the prior art, and the method of the invention takes MOFs easy to grow as a crystal nucleus substrate and adopts single ligand adjustment as a means to grow new MOFs on the basis of the substrate. In the preparation process of the dual-ligand synergistic growth hierarchical porous metal-organic framework material, MOFs are quickly nucleated by ultrasonic treatment, injection of organic base and vigorous stirring. Wherein ultrasound generates a large number of local hot spots at a nanoscale instantaneous high temperature and high pressure, provides an environment for rapid nucleation and growth, and the shear force provided by intense stirring plays a role in slightly reducing solubility, and the organic base deprotonates the ligand and rapidly nucleates the skeleton. The imidazole added in the step S2 is difficult to nucleate with metal ions, but the MOF substrate grows in the early stage, and then the adjusting function of the single ligand is added, so that the dual-ligand synergistic growth hierarchical pore metal-organic framework material can be prepared. In addition, the monodentate ligand reversibly competes with the bridging ligand for metal sites, affecting the kinetics of crystal growth and changing the morphology of the MOF.
Drawings
FIG. 1 is an SEM image of a dual ligand hierarchical pore metal-organic framework material of example 1 at different magnifications;
FIG. 2 is an SEM image of a dual ligand hierarchical pore metal-organic framework material of example 2;
FIG. 3 is an SEM image of a dual ligand hierarchical pore metal-organic framework material of example 3;
FIG. 4 is an SEM image of a metal-organic framework material of comparative example 1;
FIG. 5 is an SEM image of a metal-organic framework material of comparative example 3;
FIG. 6 is an SEM image of a metal-organic framework material of comparative example 4;
FIG. 7 is an XRD pattern for the dual ligand hierarchical pore metal organic framework material of example 1 and the metal organic framework material of comparative example 1;
FIG. 8 is a graph of adsorption rates for the dual ligand hierarchical pore metal organic framework material of example 1 and the metal organic framework material of comparative example 1.
Detailed Description
The technical scheme of the invention is further illustrated by examples below, but the protection scope of the invention is not limited by the examples. In the invention, the weight percent is the mass fraction.
In the present invention, the pore diameter property of the sample was analyzed by ASAP2020 (Micrometrics) nitrogen adsorption-desorption isotherms of the test material were obtained at 77K. The specific surface area of the sample was calculated by Brunauer-Emmett-Teller (BET) equation, and the micropore volume (V) of the material was obtained by using the T-plot micropore analysis method micro ) Acquisition of the total pore volume (V) of the material by single point adsorption branching of the adsorption isotherm total ) And (3) obtaining the mesoporous aperture by adopting BJH (Barrett-Joyner-Halenda) desorption branch calculation.
In the present invention, a Scanning Electron Microscope (SEM) photograph of a sample is taken on a Hitachi S-4800 type II scanning electron microscope. The accelerating voltage of the instrument is 15kV, and the samples are subjected to chromium plating treatment before analysis.
In the present invention, the test conditions of XRD patterns of samples are as follows: obtained by using a Japanese national science Rigaku-Ultima X-ray diffractometer and subjected to MOFs crystalline phase analysis. Cukα radiation, wavelength λ= 0.15432nm. X-ray diffraction pattern scan range 2θ=3-75 °, scan speed 5 °/min, step size 0.02 °.
Example 1
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 0.5mL is added, and stirring is carried out vigorously for 20min. Ultrasonic again for 30min, add triethylamine 0.5mL, stir vigorously for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
3.0g of imidazole was weighed and dissolved in 30mL of deionized water, after which it was added to the copper-based MOF mother liquor 1 described above, vigorously stirred at 700rpm for 60 minutes, and 9mL of acetic acid was added dropwise, in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. Then dried at 60℃for 8 hours and at 130℃for 10 hours to give sample 1, the copper content was found to be 24.3%.
The data of specific surface area and pore properties of sample 1 are shown in Table 1, and the specific surface area of sample 1 is smaller than that of comparative sample 1, but has larger total pore volume, so that the specific surface area is reduced due to the generation of mesopores. SEM images of sample 1 are shown in fig. 1. Fig. 1 (a) shows a hexagonal prism-like crystal, and triangular-shaped channels on the crystal surface can be seen under a high power mirror. The side length of the cross section polygon is 2-6 μm, and the side length of the triangle is 50-300nm.
The XRD pattern of sample 1 is shown in FIG. 7, and it can be seen from FIG. 7 that the characteristic peaks of seed crystal HKUST-1 at 2θ=5.4°,9.4 °,11.62 °,17.4 °,19 °,29.3 ° are consistent with the characteristic peak report of document HKUST-1. At 2θ=7.5°,21 °, a new diffraction peak appears at 24 °, indicating that the crystal structure has changed.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
The relationship of the removal rate of model oil with time at a lower sulfur concentration was examined by a static adsorption method, and the obtained adsorption rate graph is shown in FIG. 8, in which the concentration of dibenzothiophene is 400ppm. As can be seen from fig. 8, the sample 1 dual ligand porous MOF material reached adsorption equilibrium faster and the desulfurization rate was higher, reaching 99.6%, and the desulfurization rate of comparative example 1 was 96.1% as compared to the seed MOF comparative example 1.
Example 2
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 0.5mL is added, and stirring is carried out vigorously for 20min. Ultrasonic again for 30min, add triethylamine 0.5mL, stir vigorously for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
3.0g of imidazole was weighed and dissolved in 30mL of deionized water, after which it was added to the copper-based MOF mother liquor 1 described above, vigorously stirred at 700rpm for 60 minutes, and acetic acid 15mL was added dropwise, in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. Then dried at 60℃for 8 hours and at 130℃for 10 hours to give sample 2, the copper content was found to be 26.2%.
The specific surface area and pore properties of sample 2 are shown in Table 1. The SEM image of sample 2 is shown in fig. 2, and the crystal has a hexagonal prism shape as shown in fig. 2. It can be seen that holes are also present on the crystal surface. The side length of the cross section polygon is 1-7 mu m, and the side length of the triangle is 50-300nm. The XRD pattern of sample 2 is the same as that of sample 1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Example 3
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 0.5mL is added, and stirring is carried out vigorously for 20min. Ultrasonic again for 30min, add triethylamine 0.5mL, stir vigorously for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
Imidazole 6.0g was weighed and dissolved in 30mL deionized water, after which it was added to the copper-based MOF mother liquor 1 described above, vigorously stirred at 700rpm for 60min, and acetic acid 9mL was added dropwise, in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. Then dried at 60℃for 8 hours and at 130℃for 10 hours to give sample 3, the copper content was found to be 22.9%. The specific surface area and pore properties of sample 3 are shown in Table 1. The SEM image of sample 3 is shown in fig. 3, and as shown in fig. 3, the crystal has a hexagonal prism shape, and the existence of holes on the surface of the crystal can be seen. The side length of the cross section polygon is 1-6 mu m, and the side length of the triangle is 50-300nm. The XRD pattern of sample 3 is the same as that of sample 1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Example 4
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 2mL is added, and stirring is carried out vigorously for 20min. Again sonicated for 30min, triethylamine 2mL was added and vigorously stirred for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
3.0g of imidazole was weighed and dissolved in 30mL of deionized water, after which it was added to the copper-based MOF mother liquor 1 described above, vigorously stirred at 700rpm for 60 minutes, and 9mL of acetic acid was added dropwise, in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. After drying at 60 ℃ for 8 hours and at 130 ℃ for 10 hours, sample 4 was obtained, and the copper content was measured to be 27.1%.
The specific surface area and pore properties of sample 4 are shown in Table 1, SEM image is the same as that of sample 1, the side length of the cross-sectional polygon is 1-6 μm, and the side length of the triangle is 50-300nm. The XRD pattern is the same as sample 1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Comparative example 1
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20min. The ultrasonic power is 300W, the ultrasonic treatment is carried out for 30min, and the stirring is carried out vigorously for 20min. Again sonicated for 30min and vigorously stirred for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. After drying at 60℃for 8 hours and 130℃for 10 hours, comparative example 1 was obtained, and the copper content was found to be 28.2%. The data of the specific surface area, pore properties, etc. of comparative example sample 1 are shown in Table 1, and since the sample is basically microporous, there are few mesopores, so that the mesopore diameter is small. SEM pictures are seen in FIG. 4. As can be seen from FIG. 4, the sample exhibits an octahedron, which is consistent with the morphology of seed MOF-HKUST-1. The edge length of the octahedron is 1-6 μm. XRD patterns are shown in FIG. 7-seed crystal HKUST-1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Comparative example 2
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 90min, and copper-based MOF mother liquor 1 is obtained.
3.0g of imidazole was weighed and dissolved in 30mL of deionized water, after which it was added to the copper-based MOF mother liquor 1 described above, vigorously stirred at 700rpm for 60 minutes, and 9mL of acetic acid was added dropwise, in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. After drying at 60℃for 8 hours and 130℃for 10 hours, comparative example 2 was obtained, and the copper content was found to be 23.6%. The data of the specific surface area and pore properties of comparative sample 2 are shown in Table 1, and SEM images are similar to those of sample 1, the side length of the cross-sectional polygon is 1-6 μm, and the side length of the triangle is 50-300nm. The XRD pattern is similar to sample 1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Comparative example 3
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 0.5mL is added, and stirring is carried out vigorously for 20min. Ultrasonic again for 30min, add triethylamine 0.5mL, stir vigorously for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
3.0g of imidazole was weighed and dissolved in 30mL of deionized water, then added to the copper-based MOF mother liquor 1, vigorously stirred at 700rpm for 60 minutes, then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a separator, and reacted at 95℃for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. After drying at 60℃for 8 hours and 130℃for 10 hours, comparative example 3 was obtained, and the copper content was found to be 25.6%.
The data of the specific surface area and pore properties of comparative example 3 are shown in Table 1.SEM images of comparative example 3 are shown in fig. 5, and it is seen from fig. 5 that the crystal morphology is changed compared to the seed MOF, because another ligand is added. However, the crystal morphology is irregular in morphology change due to no regulation and control effect of the acetic acid single ligand, the side length of the cross section polygon is 1-8 mu m, and the surface aperture is 50-300nm. The XRD pattern of comparative example 3 was the same as that of sample 1.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
Comparative example 4
3.5g of trimesic acid is weighed and added into a mixed solution of 80mL of absolute ethyl alcohol and 40mLN, N-dimethylformamide, and the mixture is fully stirred for 20min. 11.2g of copper nitrate trihydrate was weighed out and dissolved in 30mL of deionized water, after which the two solutions were mixed and stirred for 20min. Ultrasonic power is 300W, ultrasonic is carried out for 30min, triethylamine 0.5mL is added, and stirring is carried out vigorously for 20min. Ultrasonic again for 30min, add triethylamine 0.5mL, stir vigorously for 20min. The total of 3 times was carried out to obtain copper-based MOF mother liquor 1.
Acetic acid 9mL was added dropwise and the reaction was performed in three portions. Then transferred to a stainless steel autoclave lined with polytetrafluoroethylene with a baffle plate, and reacted at 95 ℃ for 1 hour. And standing and naturally cooling to room temperature. The mother liquor was removed by centrifugation and washed several times with ethanol. After drying at 60℃for 8 hours and 130℃for 10 hours, comparative example 4 was obtained, and the copper content was found to be 27.8%. The data of the specific surface area and pore properties of comparative example 4 are shown in Table 1.SEM images are shown in fig. 6, and the crystal morphology is changed compared to the seed MOF due to the kinetic process of crystal growth affected by the presence of acetic acid, but the morphology presented by sample 1 is also greatly different from that presented by the second ligand, with the sides of the cross-sectional polygon being 1-6 μm. The XRD pattern of the sample was similar to comparative sample 1, but the peak intensity was weaker.
And (5) carrying out desulfurization performance evaluation through a fixed bed dibenzothiophene adsorption device. The concentration of the dibenzothiophene in the raw material is 2mgS/g, and the airspeed is set to be 4h -1 The breakthrough sulfur capacity was measured and is shown in table 2.
TABLE 1 specific surface area and pore Property parameters of samples obtained in examples 1 to 4 and comparative examples 1 to 4
Note that: [ a ]]S BET Represents the BET specific surface area calculated from the Brunauer-Emmett-Teller (BET) formula; [ b ]]V t Representing the total pore volume; [ c ]]V micro Represents micropore volume; [ d ]]V meso Represents mesoporous volume; [ e ]]D meso Representing mesoporous pore size.
TABLE 2 desulfurization Properties of samples obtained in examples and comparative examples
Claims (15)
1. A dual-ligand hierarchical pore metal organic framework material, comprising metal ions and ligands, wherein the metal ions comprise copper ions, and the ligands comprise trimesic acid and imidazole; the dual-ligand hierarchical pore metal organic framework material has a polyhedral prismatic structure;
the preparation method of the dual-ligand hierarchical pore metal organic framework material comprises the following steps:
s1: copper salt and trimesic acid are dissolved in a first solvent to form a reaction solution, and organic alkali is added in batches under the condition of ultrasonic and continuous intense stirring;
s2: dissolving imidazole into a second solvent, adding the mixed solution obtained in the step S1, dropwise injecting a single ligand under stirring, reacting, centrifuging and drying to obtain a double-ligand hierarchical pore metal organic framework material;
the monodentate ligand in step S2 is a monocarboxylic acid compound.
2. The dual ligand hierarchical pore metal organic framework material of claim 1 wherein the dual ligand hierarchical pore metal organic framework material has micropores and mesopores and/or macropores.
3. The dual ligand hierarchical pore metal organic framework material of claim 1 wherein the dual ligand hierarchical pore metal organic framework material has a specific surface area of 950-1700m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The total pore volume is 0.3-0.95cm 3 ·g -1 The micropore volume is 0.29-0.55cm 3 ·g -1 Mesoporous volume of 0.01-0.5cm 3 ·g -1 The mesoporous aperture is 2-30nm.
4. The dual-ligand hierarchical pore metal-organic framework material according to claim 1, wherein the mass content of framework metal Cu element in the dual-ligand hierarchical pore metal-organic framework material is 15% -60%; the molar ratio of trimesic acid to imidazole is 1:0.1-6.
5. The dual ligand hierarchical pore metal organic framework material of claim 1 wherein the dual ligand hierarchical pore metal organic framework material is a hexagonal prism; the prism section comprises a hexagon, the side length of the section polygon is 1-7 mu m, the surface of the crystal is provided with a triangular hole-shaped structure, and the side length of the triangle is 50-300nm.
6. The preparation method of the dual-ligand hierarchical pore metal organic framework material comprises the following steps:
s1: copper salt and trimesic acid are dissolved in a first solvent to form a reaction solution, and organic alkali is added in batches under the condition of ultrasonic and continuous intense stirring;
s2: dissolving imidazole into a second solvent, adding the mixed solution obtained in the step S1, dropwise injecting a single ligand under stirring, reacting, centrifuging and drying to obtain a double-ligand hierarchical pore metal organic framework material;
the monodentate ligand in step S2 is a monocarboxylic acid compound.
7. The method according to claim 6, wherein in step S1 the copper salt is selected from the group consisting of inorganic salts of copper; the first solvent in the step S1 comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methanol, ethanol, acetonitrile, deionized water and dimethyl sulfoxide; the organic base in the step S1 comprises one or more of methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine, diethylamine, triethylamine, aniline, acetamide and urea.
8. The method according to claim 6, wherein the copper salt in step S1 is copper nitrate; the organic base is triethylamine.
9. The method according to claim 6, wherein the molar ratio of trimesic acid to imidazole is 1:0.1-6.
10. The method according to claim 6, wherein the molar ratio of copper salt to trimesic acid in step S1 is 1:0.2-5; the dosage ratio of the solvent to the copper salt in the step S1 is 5-200mL of solvent/1.0 g of metal salt; the volume ratio of the organic base to the first solvent is 1:25-300.
11. The method of claim 6, wherein the second solvent in step S2 comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methanol, ethanol, acetonitrile, deionized water, and dimethylsulfoxide.
12. The method of claim 6, wherein the monodentate ligand in step S2 comprises one or more of acetic acid, benzoic acid, lauric acid; and/or the volume ratio of the monocarboxylic acid compound to the second solvent in the step S2 is 1:0.5-50.
13. The method according to claim 6, wherein the reaction conditions of step S2 include a reaction temperature of 30 to 150 ℃ and a reaction time of 3 to 48 hours; the drying in the step S2 is carried out in two stages, wherein the temperature of the first stage is 50-100 ℃, the time is 1-24h, the drying temperature of the second stage is 100-200 ℃, and the time is 1-24h.
14. A method for removing sulfides, comprising contacting the dual ligand hierarchical pore metal organic framework material according to any one of claims 1 to 5 or the dual ligand hierarchical pore metal organic framework material obtained by the preparation method according to any one of claims 6 to 13 with a dibenzothiophene-containing material.
15. The process according to claim 14, wherein the dibenzothiophene-containing material has a concentration of 0.5 to 5mgS/g and a space velocity of 0.1 to 5h -1 。
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