CN110787841A - Super-strong solid acid material containing nitrogen MOFs and application thereof - Google Patents
Super-strong solid acid material containing nitrogen MOFs and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011973 solid acid Substances 0.000 title claims abstract description 61
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000010992 reflux Methods 0.000 claims abstract description 20
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 13
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- -1 sultone compound Chemical class 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
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- 238000005406 washing Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010335 hydrothermal treatment Methods 0.000 description 10
- QSQLTHHMFHEFIY-UHFFFAOYSA-N methyl behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OC QSQLTHHMFHEFIY-UHFFFAOYSA-N 0.000 description 10
- 229930182555 Penicillin Natural products 0.000 description 9
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
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- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
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- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 5
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 5
- 229910007926 ZrCl Inorganic materials 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 5
- 229940073769 methyl oleate Drugs 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 4
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 4
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000013140 multifunctional metal-organic framework Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001047746 Homo sapiens Lamina-associated polypeptide 2, isoform alpha Proteins 0.000 description 1
- 101001047731 Homo sapiens Lamina-associated polypeptide 2, isoforms beta/gamma Proteins 0.000 description 1
- 102100023981 Lamina-associated polypeptide 2, isoform alpha Human genes 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000013309 porous organic framework Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/30—Non-coordinating groups comprising sulfur
- B01J2540/32—Sulfonic acid groups or their salts
- B01J2540/325—Sulfonic acid groups or their salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional groups
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- B01J2540/40—Non-coordinating groups comprising nitrogen
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Abstract
The invention discloses a super-strong solid acid material containing nitrogen MOFs and application thereof, wherein the super-strong solid acid material is prepared by the following method: 1. uniformly mixing a nitrogen-containing MOFs material, a sulfolactone compound and a solvent A, and reacting under a reflux condition to obtain an intermediate product; 2. and (3) uniformly mixing the intermediate product, trifluoromethanesulfonic acid and a solvent B, and then carrying out an ion exchange reaction to obtain the ultra-strong solid acid material containing the nitrogen MOFs. The superstrong solid acid material has high thermal stability, simple preparation method and low preparation cost, can be used for catalyzing ester exchange reaction and esterification reaction, and can improve the conversion rate and selectivity of the ester exchange reaction and the esterification reaction.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a super-strong solid acid material containing nitrogen MOFs and application thereof.
Background
In recent years, with the relative shortage of petroleum and coal resources on the earth, multiple constraints such as 'carbon emission' and 'high pollution' are also faced, so that the development of low-carbon economy becomes a focus of attention of countries in the world. Biological energy has attracted extensive research interest as a novel energy industry with great potential. In 1983, the american scientist Graham Quicki prepared methyl linolenate for the first time by transesterification and defined it as biodiesel, and then developed a systematic study around the synthesis method of fatty acid methyl esters and gradually formed the first generation biodiesel products represented by fatty acid methyl esters. In the transesterification reaction process, the acid catalyst plays a crucial role, and the conventional acid catalysts are classified into liquid acid catalysts and solid acid catalysts. The liquid acidic catalyst mainly comprises hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, and the solid acidic catalyst mainly comprises a molecular sieve, a metal oxide, a novel multifunctional MOFs solid acid material and the like. In the esterification reaction process, although the liquid acid catalyst has an excellent catalytic effect, the liquid acid catalyst is not beneficial to the separation of a product and the catalyst, so that the operation is complex and the cost is high in the post-treatment process, and meanwhile, the environment is seriously polluted. While the solid acid catalyst can solve the problems well, the molecular sieve and the metal oxide are not high in cost but have insignificant catalytic effect for some special esterification reactions.
Therefore, novel multifunctional MOFs solid acid materials are designed in a targeted manner. MOFs is oneA porous organic framework crystalline material comprising metal nodes and organic linkers. The pore size and shape of the material can be adjusted by selecting different metals and organic ligands, and the material has the characteristics of high porosity, low density, large specific surface area, regular pore channels, adjustable pore size, diversity and tailorability of topological structures and the like. Therefore, the MOFs material has wide application in the aspects of energy storage, gas adsorption and separation, catalysis and the like. The MOFs material with acidic catalytic property is prepared and synthesized through a post-modification strategy and is used for catalytically converting various vegetable oils, but the MOFs material has the problems of low acid content, weak acid strength and the like, and how to improve the acid content and strength of the MOFs material is a great challenge. The introduction of the B acid is difficult in the early modification process of the MOFs material, so that the B acid is introduced after the MOFs material is synthesized, the modification method has high success rate, and the stability, the large specific surface area and the regular pore path of the crystal structure of the MOFs material can be kept, so that the catalytic efficiency of the MOFs material can be greatly improved. For example, after MOF-808 is successfully synthesized by the composition of the American Yaghi project, sulfonic acid groups are further introduced on the MOF-808, so that the acid strength and the acid content of the MOF-808 are improved, but the acid strength of the MOF-808 is still lower,31the chemical shift of P is only 69ppm and the acid density is not high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a super-strong solid acid material containing nitrogen MOFs and an application thereof.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
the super-strong solid acid material containing the nitrogen MOFs is prepared by the following method:
1. uniformly mixing a nitrogen-containing MOFs material, a sultone compound and a solvent A, and reacting under a reflux condition to obtain an intermediate product;
2. and (3) uniformly mixing the intermediate product, trifluoromethanesulfonic acid and a solvent B, and then carrying out an ion exchange reaction to obtain the ultra-strong solid acid material containing the nitrogen MOFs.
Further, the sultone compound is 1, 3-propane sultone or 1, 4-butane sultone, and the mass volume ratio of the intermediate product to the trifluoromethanesulfonic acid is 0.5g-1 g: 50 to 100. mu.l.
Furthermore, the solvent A is toluene, and the solvent B is dichloromethane.
Further, the mass ratio of the nitrogen-containing MOFs material to 1, 3-propane sultone is 1-10:1, the reflux temperature is 80-110 ℃, and the reflux time is 20-28 h.
Further, after the reflux is finished, performing centrifugal separation on the obtained product, washing the obtained filter cake with N, N-dimethylformamide, and performing vacuum drying at the temperature of 110-150 ℃ for 12-24h to obtain an intermediate product.
Further, stirring was carried out while refluxing, and the rotation speed of stirring was 200-500 rmp.
Further, the ion exchange reaction is carried out for 20-30h under the ice bath condition, after the reaction is finished, the obtained product is subjected to centrifugal separation, the obtained filter cake is washed clean by dichloromethane and dried, and the super-strong solid acid material containing the nitrogen MOFs is obtained.
An application of super-strong solid acid material containing nitrogen MOFs in catalyzing ester exchange reaction and esterification reaction.
Compared with the prior art, the invention has the beneficial effects and advantages that:
1. the preparation method of the super-strong solid acid material is simple, the process conditions are simple and easy to control, the industrial production is easy to realize, and the application prospect is wide.
2. The synthetic surface area of the super-strong solid acid material is as high as 300-500m2The catalyst has excellent catalytic activity, can be used for catalyzing ester exchange reaction and esterification reaction, particularly catalyzing the reaction of vegetable oil and methanol, and greatly improves the selectivity and the conversion rate.
3. When the super-strong solid acid material is prepared, other active components are not required to be loaded or added, and only sulfonic acid groups are required to be introduced to the nitrogen-containing MOFs material skeleton, so that the acid strength and the acid density of the MOFs are enhanced.
4. The superstrong solid acid material is also beneficial to being separated from a product after the reaction is finished, and the separated superstrong solid acid material is washed clean by methanol and then acidified by trifluoromethanesulfonic acid, so that the superstrong solid acid material can be recycled.
Drawings
FIG. 1 is a graph of adsorption isotherms of ultra-strong solid acid materials containing nitrogen MOFs prepared in examples 1-3.
FIG. 2 is an SEM image of nitrogen-containing MOFs material prepared in example 3.
FIG. 3 is an SEM image of the ultra-strong solid acid materials containing nitrogen MOFs prepared in example 3.
FIG. 4 is an infrared spectrum of the ultra-strong solid acid materials containing nitrogen MOFs prepared in examples 1 to 5.
FIG. 5 is a 31P-1H two-dimensional nuclear magnetic spectrum of the ultra-strong solid acid material containing nitrogen MOFs prepared in example 3.
Detailed Description
Example 1
1. 0.45g of ZrCl was weighed4Adding 0.45g of 2-amino terephthalic acid into a reaction kettle, adding 50ml of DMF and 10ml of hydrochloric acid, performing ultrasonic treatment for 10min until all solid solvents are dissolved, heating the reaction kettle to 100 ℃, keeping the temperature, performing hydrothermal treatment at 100 ℃ for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, performing suction filtration, washing with DMF, soaking for three days with ethanol, filtering, and performing vacuum drying on the obtained filter cake at 150 ℃ for 12h to obtain the nitrogen-containing MOFs material UiO-66-NH2；
2. 1g of UiO-66-NH2Adding 0.1g of 1, 3-propane sultone into 30mL of toluene, uniformly stirring, refluxing at a stirring speed of 200rmp and a reflux temperature of 130 ℃ for 24h, performing suction filtration, washing with DMF (dimethyl formamide), and performing vacuum drying at 120 ℃ for 18h to obtain an intermediate product;
3. adding 0.1g of intermediate product and 100 mul of trifluoromethanesulfonic acid into dichloromethane, stirring uniformly, performing ion exchange reaction for 24h under ice bath condition, washing with dichloromethane, and drying to obtain super-strong solid acid material containing nitrogen MOFs, wherein the mark is super-strong solid acid material containing nitrogen MOFsUiO-66-[C3NH2][CF3SO3]-Ⅰ。
Example 2
1. 0.45g of ZrCl was weighed4Adding 0.45g of 2-amino terephthalic acid into a reaction kettle, adding 50ml of DMF and 10ml of hydrochloric acid, performing ultrasonic treatment for 10min until all solid solvents are dissolved, heating the reaction kettle to 100 ℃, keeping the temperature, performing hydrothermal treatment at 100 ℃ for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, performing suction filtration, washing with DMF, soaking for three days with ethanol, filtering, and performing vacuum drying on the obtained filter cake at 150 ℃ for 12h to obtain the nitrogen-containing MOFs material UiO-66-NH2；
2. 1g of UiO-66-NH2Adding 0.2g of 1, 3-propane sultone into 30mL of toluene, uniformly stirring, refluxing for 24h at the stirring speed of 200rmp and the reflux temperature of 130 ℃, washing with DMF (dimethyl formamide), and drying in vacuum for 18h at 120 ℃ to obtain an intermediate product;
3. adding 0.1g of intermediate product and 100 mul of trifluoromethanesulfonic acid into dichloromethane, stirring uniformly, performing ion exchange reaction for 24h under ice bath condition, washing with dichloromethane, and drying to obtain super-strong solid acid material containing nitrogen MOFs, wherein the mark is UiO-66- [ C3NH2][CF3SO3]-Ⅱ。
Example 3
1. 0.45g of ZrCl was weighed4Adding 0.45g of 2-amino terephthalic acid into a reaction kettle, adding 50ml of DMF and 10ml of hydrochloric acid, performing ultrasonic treatment for 10min until all solid solvents are dissolved, heating the reaction kettle to 100 ℃, keeping the temperature, performing hydrothermal treatment at 100 ℃ for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, performing suction filtration, washing with DMF, soaking for three days with ethanol, filtering, and performing vacuum drying on the obtained filter cake at 150 ℃ for 12h to obtain the nitrogen-containing MOFs material UiO-66-NH2；
2. 1g of UiO-66-NH2Adding 0.5g of 1, 3-propane sultone into 30mL of toluene, uniformly stirring, refluxing for 24h at the stirring speed of 200rmp and the reflux temperature of 130 ℃, washing with DMF (dimethyl formamide), and drying in vacuum for 18h at 120 ℃ to obtain an intermediate product;
3. 0.1g of intermediate and 100. mu.l of trifluoromethanesulfonic acid were added to the di-tert-butyl acetateUniformly stirring in chloromethane, carrying out ion exchange reaction for 24h under the ice bath condition, washing with dichloromethane, and drying to obtain super-strong solid acid material containing nitrogen MOFs, marked as UiO-66- [ C3NH2][CF3SO3]-Ⅲ。
Example 4
1. 0.45g of ZrCl was weighed4Adding 0.45g of 2-amino terephthalic acid into a reaction kettle, adding 50ml of DMF and 10ml of hydrochloric acid, performing ultrasonic treatment for 10min until all solid solvents are dissolved, heating the reaction kettle to 100 ℃, keeping the temperature, performing hydrothermal treatment at 100 ℃ for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, performing suction filtration, washing with DMF, soaking for three days with ethanol, filtering, and performing vacuum drying on the obtained filter cake at 150 ℃ for 12h to obtain the nitrogen-containing MOFs material UiO-66-NH2；
2. 1g of UiO-66-NH2Adding 0.1g of 1, 3-propane sultone into 30mL of toluene, uniformly stirring, refluxing at a stirring speed of 200rmp and a reflux temperature of 130 ℃ for 24h, performing suction filtration, washing with DMF (dimethyl formamide), and performing vacuum drying at 120 ℃ for 18h to obtain an intermediate product;
3. adding 0.1g of intermediate product and 50 mul of trifluoromethanesulfonic acid into dichloromethane, stirring uniformly, performing ion exchange reaction for 24h under ice bath condition, washing with dichloromethane, and drying to obtain super-strong solid acid material containing nitrogen MOFs, wherein the mark is UiO-66- [ C3NH2][CF3SO3]-Ⅳ。
Example 5
1. 0.45g of ZrCl was weighed4Adding 0.45g of 2-amino terephthalic acid into a reaction kettle, adding 50ml of DMF and 10ml of hydrochloric acid, performing ultrasonic treatment for 10min until all solid solvents are dissolved, heating the reaction kettle to 100 ℃, keeping the temperature, performing hydrothermal treatment at 100 ℃ for 12h, naturally cooling to room temperature after the hydrothermal treatment is finished, performing suction filtration, washing with DMF, soaking for three days with ethanol, filtering, and performing vacuum drying on the obtained filter cake at 150 ℃ for 12h to obtain the nitrogen-containing MOFs material UiO-66-NH2；
2. 1g of UiO-66-NH2And 0.5g of 1, 3-propane sultone were added to 30mL of toluene, stirred uniformly, and then stirred at a rotation speed of 200rmp at a reflux temperature of 130 deg.CRefluxing for 24h, performing suction filtration, washing with DMF, and vacuum drying at 120 ℃ for 18h to obtain an intermediate product;
3. adding 0.1g of intermediate product and 50 mul of trifluoromethanesulfonic acid into dichloromethane, stirring uniformly, performing ion exchange reaction for 24h under ice bath condition, washing with dichloromethane, and drying to obtain super-strong solid acid material containing nitrogen MOFs, wherein the mark is UiO-66- [ C3NH2][CF3SO3]-Ⅴ。
The ultra-strong solid acid materials containing nitrogen MOFs prepared in examples 1 to 3 were used as N2The adsorption isotherms and pore size distribution profiles obtained by performing the test analysis on physical adsorption and calculating the specific surface area by the BET method are shown in fig. 1, and as can be seen from fig. 1, the adsorption and desorption isotherms of the super-strong solid acid materials of examples 1 to 3 are type I, which indicates that the micro-porous structures exist in the super-strong solid acid materials of examples 1 to 3. It can be seen that the super-strong solid acid materials prepared in examples 1 to 3 according to the present invention further ensure the structural integrity while introducing acidic sites.
Physical properties such as specific surface area and average pore diameter of the ultra-strong solid acid materials containing nitrogen MOFs prepared in examples 1 to 3 are shown in table 1:
TABLE 1
The UiO-66-NH prepared in example 32And UiO-66- [ C3NH2][CF3SO3]-1.5 scanning with a scanning electron microscope, the SEM images obtained are shown in FIGS. 2 and 3, in which FIG. 2 is UiO-66-NH2FIG. 3 is a drawing of UiO-66- [ C ]3NH2][CF3SO3]SEM photograph of-1.5, comparing FIGS. 2 and 3, it can be seen that UiO-66- [ C ]3NH2][CF3SO3]Morphology of-1.5 with UiO-66-NH2Is substantially consistent, thereby further reducing the profile ofThe shape and the structure of the super-strong solid acid material prepared by the invention are still regular.
Infrared spectrum analysis is carried out on the ultra-strong solid acid materials containing the nitrogen MOFs prepared in the examples 1 to 5, the obtained infrared spectrograms are shown in FIG. 4, and as can be seen from FIG. 4, the infrared spectrums of the ultra-strong solid acid materials of the examples 1 to 5 are all 1190cm in the infrared spectrum-1、1038cm-1And a stretching vibration peak appears, which is a characteristic peak of the sulfonic acid group, and the sulfonic acid group is successfully grafted into the super-strong solid acid material.
TMPO was adsorbed on the super strong solid acid material prepared in example 3, and then tested by a 400M solid NMR spectrometer, and the resulting material was analyzed by31P-1The H two-dimensional nuclear magnetic spectrum is shown in FIG. 5, and as can be seen from FIG. 5, the super-strong solid acid material of example 3 is super-strong acid,31the chemical shift of P can reach 88 ppm.
Experiment I, experiment of effect of the super-strong solid acid material containing nitrogen MOFs in catalyzing ester exchange reaction
The test method comprises the following steps:
respectively adding 6 parts of 0.5mL sunflower seed oil into 6 penicillin bottles with 10mL, respectively adding 25mg of the superstrong solid acid material and the sulfuric acid prepared in the examples 1-5 into 6 penicillin bottles, respectively adding 2mL of methanol into 6 penicillin bottles, respectively heating the 6 penicillin bottles to 85 ℃, preserving the temperature, reacting for 12 hours at 85 ℃, after the reaction is finished, performing centrifugal separation, and testing and analyzing the products in the penicillin bottles by using an Shimadzu GCMS-2010PLUS gas chromatograph-mass spectrometer equipped with a mass spectrometer, wherein the testing conditions are as follows: the injection inlet temperature is 270 ℃, the initial column temperature is 140 ℃, the temperature is raised to 270 ℃ at a heating rate of 10 ℃/min, and the temperature of the detector is 280 ℃.
And (3) test results:
the main products of this reaction are as follows: methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl behenate, and calculating the conversion rates of the methyl palmitate, the methyl stearate, the methyl oleate, the methyl linoleate and the methyl behenate according to the detection results (A solution-free, one-step synthesis of sulfuric acid group-functionalized methanol with ultra-high acid concentrations and excellent cationic activities for calculation of the conversion rates);
the conversion of the main products is shown in table 2 below:
TABLE 2 Effect of different catalysts in transesterification of sunflower oil
As can be seen from the above table, the super-strong solid acid materials prepared in examples 1 to 5 catalyze the sunflower seed oil exchange reaction, which has a high conversion rate, the conversion rate of methyl palmitate can reach 79.5 to 89.7%, the conversion rate of methyl stearate can reach 81.8 to 86.6%, the conversion rate of methyl oleate can reach 71.9 to 89.1%, the conversion rate of methyl linoleate can reach 75.4 to 86.0%, and the conversion rate of methyl behenate can reach 69.1 to 81.4%. And conventional H2SO4Compared with the catalyst, under the same reaction conditions, UiO-66- [ C3NH2][CF3SO3]The catalytic effect of-III is better than that of H2SO4The conversion rates of methyl palmitate (89.7%), methyl oleate (89.1%) and methyl behenate (77.9%) are obviously higher than the catalytic effect of sulfuric acid under the same conditions.
Experiment II, experiment of catalytic stability of the nitrogen-containing MOFs super-strong solid acid material
1. Adding 0.5mL of sunflower seed oil into a 10mL penicillin bottle, adding 25mg of the superstrong solid acid material prepared in the embodiment 3 into the penicillin bottle, then adding 2mL of methanol into the Xilin bottle, respectively heating the penicillin bottles, heating to 85 ℃, preserving heat, reacting at 85 ℃ for 12 hours, after the reaction is finished, performing centrifugal separation, and testing and analyzing products in the penicillin bottles by using an Shimadzu GCMS-2010PLUS gas chromatograph-mass spectrometer equipped with a mass spectrometer, wherein the test conditions are as follows: the injection port temperature is 270 ℃, the initial column temperature is 140 ℃, then the temperature is increased to 270 ℃ at the heating rate of 10 ℃/min, and the temperature of the detector is 280 ℃;
2. washing the filter cake obtained after the centrifugal separation with methanol, then drying in vacuum at 60 ℃ for 12h to obtain a recovered catalyst, activating a dichloromethane solution of trifluoromethanesulfonic acid with the volume fraction of 1% of the catalyst for 12h, and drying the catalyst for later use after the activation is completed;
3. repeating the step 1 on the catalyst obtained in the step 2 to perform a sunflower seed oil catalysis test;
4. repeating the step 2-3 times;
and (3) test results:
the main products of each transesterification reaction of the sunflower seed oil are as follows: the conversion rates of the methyl palmitate, the methyl stearate, the methyl oleate, the methyl linoleate and the methyl behenate are calculated according to the detection result of each time;
for each transesterification reaction catalyzed by sunflower seed oil, the conversion of the main product is shown in table 3 below:
TABLE 3 Effect of recycling the catalyst of example 3 for catalyzing transesterification of sunflower seed oil
As can be seen from table 3, after the super-strong solid acid material prepared in example 3 is recycled for many times, the catalytic effect is hardly reduced, and the effect of the super-strong solid acid material used for the first time is almost the same, and it can be seen that the super-strong solid acid material of the present invention has high catalytic stability.
Claims (8)
1. The super-strong solid acid material containing the nitrogen MOFs is characterized by being prepared by the following method:
1.1, uniformly mixing a nitrogen-containing MOFs material, a sultone compound and a solvent A, and reacting under a reflux condition to obtain an intermediate product;
1.2, uniformly mixing the intermediate product, trifluoromethanesulfonic acid and a solvent B, and then carrying out an ion exchange reaction to obtain the super-strong solid acid material containing the nitrogen MOFs.
2. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 1, wherein: the sulfolactone compound is 1, 3-propane sultone or 1, 4-butane sultone, and the mass volume ratio of the intermediate product to the trifluoromethanesulfonic acid is 0.1g-1 g: 50 to 100. mu.l.
3. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 1, wherein: the solvent A is toluene, and the solvent B is dichloromethane.
4. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 1, wherein: the mass ratio of the nitrogen-containing MOFs material to 1, 3-propane sultone is 1-10:1, the reflux temperature is 80-110 ℃, and the reflux time is 20-28 h.
5. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 3, wherein: after the reflux is finished, the obtained product is centrifugally separated, the obtained filter cake is washed by N, N-dimethylformamide and then is dried in vacuum for 12-24h at the temperature of 110-150 ℃ to obtain an intermediate product.
6. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 1, wherein: stirring was carried out while refluxing, with a stirring speed of 200-500 rmp.
7. The ultra-strong solid acid materials containing nitrogen MOFs according to claim 1, wherein: the ion exchange reaction is carried out for 20-30h under the ice bath condition, after the reaction is finished, the obtained product is centrifugally separated, the obtained filter cake is washed clean by dichloromethane and then dried, and the super-strong solid acid material containing the nitrogen MOFs is obtained.
8. Use of the ultra-strong solid acid materials containing nitrogen MOFs according to claim 1 for catalyzing transesterification and esterification reactions.
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