CN115999638A - Immobilized trifluoromethyl sulfonic acid and preparation method thereof - Google Patents
Immobilized trifluoromethyl sulfonic acid and preparation method thereof Download PDFInfo
- Publication number
- CN115999638A CN115999638A CN202211647318.XA CN202211647318A CN115999638A CN 115999638 A CN115999638 A CN 115999638A CN 202211647318 A CN202211647318 A CN 202211647318A CN 115999638 A CN115999638 A CN 115999638A
- Authority
- CN
- China
- Prior art keywords
- sba
- trifluoromethanesulfonic acid
- immobilized
- zirconium dioxide
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 37
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 238000006237 Beckmann rearrangement reaction Methods 0.000 abstract description 4
- 230000010933 acylation Effects 0.000 abstract description 2
- 238000005917 acylation reaction Methods 0.000 abstract description 2
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 230000006315 carbonylation Effects 0.000 abstract description 2
- 238000005810 carbonylation reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012876 carrier material Substances 0.000 abstract 2
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000005809 transesterification reaction Methods 0.000 abstract 1
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an immobilized trifluoromethanesulfonic acid and a preparation method thereof, which are characterized in that a mesoporous silica molecular sieve SBA-15 is synthesized by adopting a conventional hydrothermal synthesis method, zirconium dioxide is coated on the inner surface of a pore canal of the SBA-15 by adopting an ammonia/steam induced hydrolysis method, SBA-15 carrier materials with different loading amounts of zirconium dioxide are obtained after a solvent is removed, toluene is taken as the solvent, the trifluoromethanesulfonic acid is loaded on the carrier materials by a wet impregnation method in a nitrogen atmosphere, and free trifluoromethanesulfonic acid is removed by washing, soxhlet extraction and low-temperature roasting, so that the immobilized trifluoromethanesulfonic acid is obtained stably. The immobilized trifluoromethanesulfonic acid product provided by the invention can be used for acid catalytic reactions, such as esterification, transesterification, beckmann rearrangement, acylation, polymerization, alkylation, carbonylation and the like, and has wide application in the fields of chemical industry and fine chemical synthesis.
Description
Technical Field
The invention belongs to the field of immobilized liquid acid products, and in particular relates to immobilized trifluoromethanesulfonic acid and a preparation process thereof. The immobilized trifluoro methyl sulfonic acid material is prepared by taking mesoporous molecular sieve SBA-15 as a carrier, coating a zirconium dioxide thin layer on the surface, taking the zirconium dioxide thin layer as the carrier, taking trifluoro methyl sulfonic acid as a sulfonic acid grafting reagent and adopting an impregnation method.
Background
Trifluoromethanesulfonic acid is one of the strongest organic acids, and is considered to be a "stronger" acid than concentrated sulfuric acid. The trifluoromethanesulfonic acid and its conjugate base have extremely high thermal stability and oxidation-reduction resistance, and even if a strong nucleophile exists, no fluoride ion is provided. Thus, trifluoromethanesulfonic acid is a highly efficient homogeneous catalyst and is widely used in many organic reactions, such as Koch carbonylation, acylation, polymerization, alkylation reactions. However, recovery of trifluoromethanesulfonic acid from the reaction mixture generates a large amount of waste, increases costs, and pollutes the environment. Therefore, the solid supported trifluoromethyl sulfonic acid is a reliable solution for solving the problem of the homogeneous catalyst, and accords with the concept of green chemistry and sustainable development.
In the study of immobilized trifluoromethanesulfonic acid, the choice of the support material is particularly important, which relates to the grafting amount of the trifluoromethanesulfonic acid groups. The existing carrier is mainly selected from silica gel, molecular sieve, zirconium dioxide, titanium dioxide, polydivinylbenzene, attapulgite powder, active carbon, MOF and the like. Among them, solid acids prepared from zirconium dioxide as a support material often exhibit excellent properties, and the loading of the trifluoromethanesulfonic acid thereof tends to reach a very high level. However, conventionally prepared zirconium dioxide has relatively low specific surface area and porosity, and introduction of mesopores is one way of improving catalytic activity. Accordingly, many researchers have focused on the investigation of mesoporous zirconium dioxide having a uniform pore structure with a specific surface area. However, mesoporous zirconia prepared by the synthetic methods reported in the literature has thermal instability and collapses upon calcination at high temperatures. The silicon oxide is loaded on the mesoporous silicon dioxide material with high specific surface area, the thermal stability of the silicon oxide can reach 900 ℃, and the silicon oxide is another method for improving the dispersion of zirconium dioxide and increasing the specific surface area of zirconium dioxide. However, at higher zirconia loadings, the mesopores of the material can become plugged, resulting in a severe decrease in catalytic activity due to mass transfer difficulties.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the immobilized trifluoromethanesulfonic acid.
The invention also aims to provide a preparation method of the immobilized trifluoromethanesulfonic acid.
The technical scheme for realizing the technical purpose of the invention is as follows:
(1) Preparing a mesoporous molecular sieve SBA-15 by a hydrothermal method;
(2) Loading a zirconium precursor on the prepared mesoporous molecular sieve by a wet impregnation method;
(3) Hydrolyzing the precursor by adopting an ammonia/steam induced hydrolysis method and baking at a low temperature to prepare zirconium dioxide coated SBA-15;
(4) Toluene is used as a solvent, the trifluoromethyl sulfonic acid is loaded by an immersion method under the nitrogen atmosphere, acetone is used for washing, and the methylene dichloride and the absolute ethyl ether are used for Soxhlet extraction to remove unreacted trifluoromethyl sulfonic acid, so that a stable immobilized trifluoromethyl sulfonic acid product is obtained.
In the step (1), for preparing the mesoporous molecular sieve SBA-15 by a hydrothermal method, the specific operation is as follows: according to the molar ratio TEOS to HCl to P123 (EO 20 PO 70 EO 20 , Mav=5800): H 2 O=1:5.8:0.017:165, 4 g of P123 was weighed and dissolved in 125 g of 1.9M hydrochloric acid solution at room temperature, heated to 40 ℃,8.5 g of TEOS was added dropwise to the above solution, stirred at 40 ℃ for 24 h, then transferred to a polytetrafluoroethylene bottle, left to stand at 100 ℃ for crystallization for 24 h, filtered, washed, dried at 100 ℃ overnight, and then the solid was put in a muffle furnace for calcination at 500 ℃ for 5 h to obtain SBA-15.
The specific operation steps of the step (2) are as follows: 1 g of SBA-15 was dispersed in 20 n-hexane (mL), stirred for 1 h, and 20% by weight (mZrO) 2 /m SBA-15)ZrO 2 Adding equivalent zirconium n-butoxide into the above system, wet impregnating into SBA-15 pore, stirring at room temperature for 1 h, rotary evaporating to remove solvent n-hexane, drying at 120deg.C for 6 h, and repeating the above impregnation drying steps to obtain 40wt%, 60wt% and 80wt% ZrO 2 Equivalent amounts of impregnated precursor.
In the step (3), the ammonia/water vapor induced hydrolysis method comprises the following specific operations: the SBA-15 powder of 0.5 g loaded zirconia precursor is placed in an open glass vial of 10 mL and placed in a polytetrafluoroethylene liner containing 10 mL of 14wt% ammonia solution without direct contact with ammonia, placed in a high pressure reactor, the sample is heated at 60 ℃ for 1-5 hours, and then taken out and dried at 120 ℃ for 12 h. The low-temperature baking condition is 120-200 ℃.
In the step (4), the specific operation of the impregnation method is as follows: firstly, putting the zirconium dioxide coated SBA-15 obtained in the step (3) into a three-neck flask, and introducing N at 150 DEG C 2 2 h to thoroughly remove moisture. And weighing 5-30wt% of supported trifluoromethyl sulfonic acid, dispersing in 20-40 mL of anhydrous toluene, dropwise adding the anhydrous toluene into the solid, and stirring and refluxing for 2-6 h at 90 ℃. After the reaction, the mixture was filtered, washed with a large amount of acetone, and dried under vacuum at 40℃for 6 h. The saidThe amounts of dichloromethane and dehydrated ether used were 100 mL dichloromethane and 100 mL dehydrated ether per 1 g material. The extraction mode is Soxhlet extraction 24 h. Drying at room temperature, and baking at 160deg.C for 8 h, and thoroughly removing solvent, extractant and free trifluoromethanesulfonic acid.
The beneficial effects of the invention are as follows:
(1) According to the invention, zirconium dioxide is coated on the surface of the SBA-15 pore canal by virtue of the high specific surface area and rich pore canal structure of the SBA-15 through an ammonia/steam induced hydrolysis method, so that the zirconium dioxide is uniformly dispersed in the mesoporous silica pore canal, the loading capacity of the zirconium dioxide is improved, the pore canal is not blocked, and the mass transfer is facilitated.
(2) According to the invention, the trifluoromethyl sulfonic acid is grafted on the surface of zirconium dioxide, and the trifluoromethyl sulfonic acid can be immobilized to the maximum extent by means of the strong interaction between hydroxyl groups on the surface of zirconium dioxide and the trifluoromethyl sulfonic acid.
(3) The prepared immobilized trifluoromethyl sulfonic acid product has large specific surface area, high acidity and easy recovery, is used for liquid-phase Beckmann rearrangement reaction of cyclohexanone oxime, and has high activity and selectivity and good repeated use performance.
Drawings
FIG. 1 (a) is SBA-15, zrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 Small angle XRD pattern of @ SBA-15.
FIG. 1 (b) is SBA-15, zrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 Large angle XRD pattern of @ SBA-15.
FIG. 2 is SBA-15, zrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-20 @SBA-15、TFA 30 /ZrO 2-40 FT-IR spectral diagram of @ SBA-15.
FIG. 3 is SBA-15, zrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 NH of @ SBA-15 3 -TPD map.
Detailed Description
The invention is further illustrated in the following figures and examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
Synthesis of SBA-15: according to the molar ratio TEOS to HCl to P123 (EO 20 PO 70 EO 20 , Mav=5800): H 2 O=1:5.8:0.017:165, 4 g of P123 was weighed and dissolved in 125 g of 1.9M hydrochloric acid solution at room temperature, heated to 40 ℃,8.5 g of TEOS was added dropwise to the above solution, stirred at 40 ℃ for 24 h, then transferred to a polytetrafluoroethylene bottle, left to stand at 100 ℃ for crystallization for 24 h, filtered, washed, dried at 100 ℃ overnight, and then the solid was put in a muffle furnace for calcination at 500 ℃ for 5 h to obtain SBA-15.
Coating of zirconium dioxide: 1 g of SBA-15 was dispersed in 20 mL n-hexane, stirred at room temperature under a closed condition for 1 h, then 1.557 g of zirconium n-butoxide solution (80 wt%) was weighed, stirred at room temperature under a closed condition for 1 h, then the n-hexane was removed by rotary evaporation, and dried at 120℃for 6 h. Repeating the above steps twice to obtain 60wt% ZrO 2 Equivalent of precursor. The 0.5 g zirconium dioxide precursor loaded SBA-15 powder was placed in a 10 mL open glass vial, then placed in a polytetrafluoroethylene liner containing 10 mL of 14wt% aqueous ammonia solution (5 mL deionized water+5 mL commercial ammonia) without direct contact with the ammonia, placed in a hydrothermal reaction kettle, the sample was heated at 60℃to 1 h, then removed and dried at 120℃to 12 h. Then baking at 150deg.C for 5 h to obtain ZrO 2-60 @SBA-15。
Load of trifluoromethanesulfonic acid: 1 g of ZrO was weighed out 2-60 @ SBA-15 was placed in a 50 mL three-necked flask, and N was introduced at 150 ℃C 2 2 h. 0.3. 0.3 g triflic acid was weighed and dispersed in 20 mL anhydrous toluene, added dropwise to the carrier, and refluxed with stirring at 90 ℃ for 2 h. After the reaction, the mixture was centrifuged, filtered, washed with a large amount of acetone, and dried under vacuum at 40℃for 6 h. 100 mL methylene dichloride and 100 mL anhydrous diethyl ether are mixed as an extractant for each 1 g solid material, and 24 h of Soxhlet extraction is carried out. Drying at room temperature, and baking at 160deg.C for 8 h to obtain TFA -30 /ZrO 2-60 @SBA-15 。
As shown in FIG. 1 (a) SBA-15, zrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 The small angle XRD spectra of @ SBA-15 show the characteristic diffraction of (100), (110), (200)ZrO with hexagonal mesoporous peak 2 These structures are retained but the strength is reduced, indicating that the immobilization of the trifluoromethanesulfonic acid slightly reduces the framework structure and long range order of the support material. As shown in FIG. 1 (b), SBA-15 and ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 Large-angle XRD spectra of @ SBA-15 in which no ZrO was observed 2 Tetragonal phase of (C) illustrating ZrO 2 Is well confined within the pores of SBA-15.
As shown in FIG. 2, SBA-15 and ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-20 @SBA-15、TFA 30 /ZrO 2-40 FT-IR spectrum of @ SBA-15, TFA compared to SBA-15 and ZrO2@SBA-15 30 /ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-20 @SBA-15、TFA 30 /ZrO 2-40 The absorption peak of @ SBA-15 at 1240 cm-1,1180 cm-1 can be categorized as a tensile vibration peak of the S=O bond, a bending vibration peak of the C-F bond at 649 cm-1, and a tensile vibration peak of the C-S bond at 587 cm-1, indicating successful immobilization of the trifluoromethanesulfonic acid. In addition, different ZrO 2 The loading also affects the TFA immobilization, 40wt% ZrO 2 The characteristic peak type of the load as a carrier is more obvious. ZrO (ZrO) 2 Too much loading can otherwise block the channels, and too little loading provides fewer trifluoromethanesulfonic acid grafting sites.
As shown in FIG. 3, SBA-15 and ZrO 2-60 @SBA-15、TFA 30 /ZrO 2-60 NH of @ SBA-15 3 TPD pattern, zrO-coated 2 The acidity of SBA-15 is improved, and the acid strength and the acid quantity are improved. After the trifluoro methyl sulfonic acid is immobilized, the peak area of the ammonia desorption peak is larger, which indicates that the acid quantity of the trifluoro methyl sulfonic acid is improved, and the peak area of the desorption peak of the medium strong acid is higher than Wen Yidong, which indicates that the immobilized trifluoro methyl sulfonic acid improves the acid quantity and the acid strength.
Example 2
Dispersing 1 g SBA-15 into 20 mL n-hexane, stirring at room temperature under sealed condition for 1 h, weighing 1.557 g zirconium n-butoxide solution (80 wt%) and stirring at room temperature under sealed condition for 1 h, and rotary evaporating to removeN-hexane and then dried at 120℃for 6 h. Repeating the above steps once to obtain 40wt% ZrO 2 Equivalent of precursor. The 0.5 g zirconium dioxide precursor loaded SBA-15 powder was placed in a 10 mL open glass vial, then placed in a polytetrafluoroethylene liner containing 10 mL of 14wt% aqueous ammonia solution (5 mL deionized water+5 mL commercial ammonia) without direct contact with the ammonia, placed in a hydrothermal reaction kettle, the sample was heated at 60℃to 1 h, then removed and dried at 120℃to 12 h. Then baking at 150deg.C for 5 h to obtain ZrO 2-40 @SBA-15。
Example 3
Weighing ZrO 2-60 15 g of @ SBA-15 g is put into a 50 mL three-neck flask and N is introduced at 150 DEG C 2 2 h. 0.2. 0.2 g of trifluoromethanesulfonic acid was weighed, dispersed in 20 mL of anhydrous toluene, added dropwise to the carrier, and refluxed with stirring at 90℃of 2 h. After the reaction, the mixture was centrifuged, filtered, washed with a large amount of acetone, and dried under vacuum at 40℃for 6 h. 100 mL methylene dichloride and 100 mL anhydrous diethyl ether are mixed as an extractant for each 1 g solid material, and 24 h of Soxhlet extraction is carried out. Drying at room temperature, and baking at 160deg.C for 8 h to obtain TFA 20 /ZrO 2-60 @SBA-15。
Example 4
Weighing ZrO 2-40 15 g of @ SBA-15 g is put into a 50 mL three-neck flask and N is introduced at 150 DEG C 2 2 h. 0.3. 0.3 g triflic acid was weighed and dispersed in 20 mL anhydrous toluene, added dropwise to the carrier, and refluxed with stirring at 90 ℃ for 2 h. After the reaction, the mixture was centrifuged, filtered, washed with a large amount of acetone, and dried under vacuum at 40℃for 6 h. 100 mL methylene dichloride and 100 mL anhydrous diethyl ether are mixed as an extractant for each 1 g solid material, and 24 h of Soxhlet extraction is carried out. Drying at room temperature, and baking at 160deg.C for 8 h to obtain TFA 30 /ZrO 2-40 @SBA-15。
Application examples
Immobilized trifluoromethyl sulfonic acid TFA 30 /ZrO 2-40 The @ SBA-15 was used for Beckmann rearrangement of cyclohexanone oxime: 0.1 g of cyclohexanone oxime, 0.15 g of immobilized trifluoromethanesulfonic acid and 20 mL of solvent benzonitrile are weighed and placed in a 50 mL three-neck flask with a condenser tube. First pass N 2 30 minAir and water vapor in the system were removed, and the reaction was carried out at 130℃for 8 h. After the reaction is finished, centrifuging, taking supernatant, performing gas chromatography analysis, taking n-heptane as an internal standard substance, calculating the mass of cyclohexanone oxime, cyclohexanone and caprolactam in the reaction liquid by adopting an internal standard method, and then calculating the conversion rate of the cyclohexanone oxime, the selectivity of the cyclohexanone and the yield and the selectivity of the caprolactam. To thoroughly collect the product, the lower layer of immobilized trifluoromethanesulfonic acid was taken, washed with 10 mL of 10wt% NaOH solution, centrifuged, the supernatant was taken, extracted three times with 60 mL chloroform, and the extract was analyzed by gas chromatography to calculate the total caprolactam yield.
The final cyclohexanone oxime conversion rate can reach 100%, the caprolactam yield is 64%, and the solid acid product has better catalytic performance in Beckmann rearrangement application of the cyclohexanone oxime.
Further combinations of the features of the above embodiments are possible, and for brevity, all of the possible combinations of features in the above embodiments are not described, however, they should be considered as being within the scope of the description provided herein, as long as there is no contradiction between these features.
The above examples merely represent a few embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (8)
1. The immobilized trifluoromethanesulfonic acid is characterized by comprising mesoporous silica, zirconium dioxide and trifluoromethanesulfonic acid, wherein the mesoporous silica is mesoporous molecular sieve SBA-15, zirconium dioxide is loaded on the pore channel surface of SBA-15, the trifluoromethanesulfonic acid is a sulfonating reagent, and the trifluoromethanesulfonic acid groups are grafted on the surface of zirconium dioxide in the pore channel of SBA-15.
2. A process for the preparation of immobilized trifluoromethanesulfonic acid according to claim 1, comprising the steps of:
preparing a mesoporous silica molecular sieve SBA-15 by a hydrothermal synthesis method; dispersing SBA-15 in n-hexane, adding zirconium n-butoxide as a zirconium dioxide precursor, and loading different amounts of zirconium precursor onto the SBA-15 through a step-by-step dipping-drying step; preparing SBA-15 loaded with zirconium dioxide by hydrolyzing a zirconium precursor by adopting an ammonia gas and water vapor induced hydrolysis method; toluene is used as a solvent, trifluoromethanesulfonic acid is loaded by a wet impregnation method under nitrogen atmosphere, acetone is used for washing after the reaction is finished, dichloromethane and diethyl ether are used as extractant, free trifluoromethanesulfonic acid is removed by Soxhlet extraction, and a stable immobilized trifluoromethanesulfonic acid product is obtained after low-temperature baking.
3. The method according to claim 2, wherein the zirconia is supported in an amount of 20 to 60wt% of mZrO 2 /m SBA-15。
4. The method according to claim 2, wherein the step of stepwise impregnation-drying comprises dispersing SBA-15 in n-hexane, stirring in a closed state for 1 h, loading 20wt% equivalent of zirconium dioxide precursor, stirring at 60 ℃ for 1 h, removing n-hexane by rotary evaporation, drying at 120 ℃ for 6 h, and repeating the above steps to prepare impregnated precursors with different loadings.
5. The method according to claim 2, wherein the concentration of ammonia water is 14-wt%, the induced hydrolysis is carried out by placing SBA-15 loaded with zirconium dioxide precursor in a glass bottle, placing the glass bottle in a polytetrafluoroethylene lining containing the ammonia water, and not directly contacting with the ammonia water, heating at 60 ℃ for 1-5 h, and drying at 120 ℃ for 12-h after placing at room temperature for 2-h.
6. The preparation method of claim 2, wherein the load of the triflic acid loaded by the impregnation method is 5wt% -30 wt%.
7. The preparation method of claim 2, wherein the dosage of dichloromethane and anhydrous diethyl ether is 100 mL dichloromethane and 100 mL anhydrous diethyl ether for each 1 g immobilized trifluoromethanesulfonic acid.
8. The method of claim 2, wherein the low temperature baking condition is 8 h at 160 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211647318.XA CN115999638A (en) | 2022-12-21 | 2022-12-21 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211647318.XA CN115999638A (en) | 2022-12-21 | 2022-12-21 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115999638A true CN115999638A (en) | 2023-04-25 |
Family
ID=86027588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211647318.XA Pending CN115999638A (en) | 2022-12-21 | 2022-12-21 | Immobilized trifluoromethyl sulfonic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115999638A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853778A (en) * | 2005-04-26 | 2006-11-01 | 中国科学院生态环境研究中心 | Synthesis of SBA-15-SO3II solid-phase catalyst and Beckmann rearrangement, esterification catalytic performances |
| CN101862675A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Catalyst loaded with zinc trifluoromethanesulfonate, preparation method and application |
| CN102039178A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst prepared by loading zinc trifluoromethanesulfonate on macroporous-mesoporous material, and preparation method and use thereof |
| CN105107547A (en) * | 2015-09-22 | 2015-12-02 | 河南工业大学 | High hydrophobic high-temperature-resistant solid acid catalyst |
| WO2016202076A1 (en) * | 2015-06-16 | 2016-12-22 | 武汉凯迪工程技术研究总院有限公司 | Support for selective synthesis of high-quality kerosene fraction from synthesis gas, catalyst thereof, and preparation method therefor |
| CN106311345A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Acid-base bifunctional solid catalyst and preparation method thereof |
| CN108355709A (en) * | 2018-02-11 | 2018-08-03 | 嘉兴学院 | Purposes of the Bismuth triflate as Beckmann rearrangement catalyst |
| CN112044473A (en) * | 2019-11-20 | 2020-12-08 | 榆林学院 | High-activity bifunctional catalyst, preparation method and application thereof |
| CN113289644A (en) * | 2021-05-28 | 2021-08-24 | 太原理工大学 | Solid acid material applied to catalytic synthesis of biodiesel and preparation method thereof |
-
2022
- 2022-12-21 CN CN202211647318.XA patent/CN115999638A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853778A (en) * | 2005-04-26 | 2006-11-01 | 中国科学院生态环境研究中心 | Synthesis of SBA-15-SO3II solid-phase catalyst and Beckmann rearrangement, esterification catalytic performances |
| CN101862675A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Catalyst loaded with zinc trifluoromethanesulfonate, preparation method and application |
| CN102039178A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst prepared by loading zinc trifluoromethanesulfonate on macroporous-mesoporous material, and preparation method and use thereof |
| WO2016202076A1 (en) * | 2015-06-16 | 2016-12-22 | 武汉凯迪工程技术研究总院有限公司 | Support for selective synthesis of high-quality kerosene fraction from synthesis gas, catalyst thereof, and preparation method therefor |
| CN105107547A (en) * | 2015-09-22 | 2015-12-02 | 河南工业大学 | High hydrophobic high-temperature-resistant solid acid catalyst |
| CN106311345A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Acid-base bifunctional solid catalyst and preparation method thereof |
| CN108355709A (en) * | 2018-02-11 | 2018-08-03 | 嘉兴学院 | Purposes of the Bismuth triflate as Beckmann rearrangement catalyst |
| CN112044473A (en) * | 2019-11-20 | 2020-12-08 | 榆林学院 | High-activity bifunctional catalyst, preparation method and application thereof |
| CN113289644A (en) * | 2021-05-28 | 2021-08-24 | 太原理工大学 | Solid acid material applied to catalytic synthesis of biodiesel and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KAMLESH N. TAYADE ET AL.: "Zirconium triflate grafted on SBA‐15 as a highly efficient solid acid catalyst for ring opening of epoxides by amines and alcohols", 《CHINESE JOURNAL OF CATALYSIS》, vol. 38, 5 April 2017 (2017-04-05), pages 758 - 766, XP029991102, DOI: 10.1016/S1872-2067(17)62794-3 * |
| 刘鹏 等: "Zr-SBA-15-SO_3H固体酸催化剂的制备、表征及催化酯交换制备生物柴油", 《中国油脂》, vol. 45, no. 1, 31 December 2020 (2020-12-31), pages 82 - 87 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10293335B2 (en) | Rh-C3N4 heterogeneous catalyst for preparing acetic acid by carbonylation reaction | |
| Jaenicke et al. | Organic–inorganic hybrid catalysts for acid-and base-catalyzed reactions | |
| CN107759796A (en) | The preparation method of a kind of porous super cross-linked polymer | |
| Tao et al. | A green and efficient hydration of alkynes catalyzed by hierarchically porous poly (ionic liquid) s solid strong acids | |
| CN107626341B (en) | Solid acid catalyst for preparing p-xylene and preparation method and application thereof | |
| CN106311345A (en) | Acid-base bifunctional solid catalyst and preparation method thereof | |
| CN105854942A (en) | Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction | |
| CN101172240B (en) | Method for preparing propylene by butylene disproportionation | |
| CN107868226B (en) | Preparation method of narrow-distribution diisocyanate trimer | |
| WO2021169028A1 (en) | Method for preparing hierarchical pore zsm-5 molecular sieve and method for preparing bis-(5-formylfurfuryl)ether | |
| Kraleva et al. | Solid acid catalysts for dehydration of glycerol to acrolein in gas phase | |
| CN102698811A (en) | Solid basic catalyst, preparation method of solid basic catalyst and application of solid basic catalyst in ester exchange reaction | |
| CN110090664B (en) | Acidic ionic liquid @ COF material and preparation method and application thereof | |
| CN103785451A (en) | Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst | |
| CN115999638A (en) | Immobilized trifluoromethyl sulfonic acid and preparation method thereof | |
| CN106955690B (en) | Solid alkaline catalyst for preparing butanol by catalyzing ethanol and preparation method thereof | |
| CN107262140B (en) | 2, 6-dimethylnaphthalene catalyst prepared from 2-methylnaphthalene, preparation and application thereof | |
| CN109678174A (en) | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method and application | |
| CN111592010B (en) | Method for preparing hierarchical porous Fe-MFI molecular sieve by secondary crystallization | |
| CN105289746B (en) | A kind of preparation method of modified graphene oxide catalyst for Beckmann rearrangement reactions | |
| CN109836320A (en) | A kind of method that dehydrating glycerin prepares methacrylaldehyde | |
| CN112844453A (en) | ZSM-5 catalyst, and preparation method and application thereof | |
| CN114425440B (en) | Modified mesoporous catalyst and preparation method and application thereof | |
| CN112076786B (en) | Preparation method of catalyst for preparing methacrylic acid by catalyzing isobutyraldehyde | |
| CN115591586B (en) | Application of super-crosslinked polymer supported metal catalyst in synthesis of cyclic carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |