CN112916024A - Solid super acidic catalyst and its preparation method and use - Google Patents
Solid super acidic catalyst and its preparation method and use Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000007787 solid Substances 0.000 title claims abstract description 47
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000013207 UiO-66 Substances 0.000 claims abstract description 17
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 89
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 24
- 239000008103 glucose Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 6
- 239000003930 superacid Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000007598 dipping method Methods 0.000 claims 2
- 238000006735 epoxidation reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000007848 Bronsted acid Substances 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- 150000007517 lewis acids Chemical class 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 description 28
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
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- 229930091371 Fructose Natural products 0.000 description 1
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
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- 150000002148 esters Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a solid super acidic catalyst, a preparation method and application thereof, relating to the technical field of solid super acidic catalysts. The preparation method provided by the invention uses aluminum isopropoxide as an aluminum source and UiO-66 as a zirconium source to prepare the solid super acidic catalyst so as to avoid the sintering phenomenon, and the prepared solid super acidic catalyst has high BET specific surface area, contains Bronsted acid sites and Lewis acid sites, and has higher catalytic reaction efficiency.
Description
Technical Field
The invention relates to the technical field of solid super acidic catalysts, in particular to a solid super acidic catalyst and a preparation method and application thereof.
Background
As an important chemical intermediate, ethyl levulinate is generally synthesized by using carbohydrates (cellulose, glucose and fructose) as a raw material through methods such as levulinic acid esterification derived from acid-catalyzed alcoholysis of the carbohydrates, alcoholysis conversion of furfuryl alcohol of furfural and derivatives thereof, and the like. Compared with the problems of equipment corrosion, environmental pollution and the like caused by the use of traditional inorganic liquid acids (such as sulfuric acid, hydrochloric acid, phosphoric acid and the like), the solid super acid is paid more and more attention by researchers due to the characteristics of low corrosivity, environmental protection, easiness in recycling and the like.
The solid superacid is an acid which is stronger than 100% sulfuric acid, i.e.an acid having a Hammett function H0. ltoreq.12. Wherein sulfated zirconia (SO)4 2-/ZrO2) Has the advantages of super strong acidity and good catalytic activity, and can be widely applied to hydrocarbon isomerization, alkylation, ester exchange and other reactions. Currently, most of zirconium sources for synthesizing sulfated zirconia include zirconium hydroxide, zirconium oxychloride, zirconium oxide, zirconium n-propoxide, and the like, but sulfated zirconia synthesized from these raw materials is likely to cause a sintering phenomenon, which affects catalytic activity.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a solid super acidic catalyst, a preparation method and application thereof. The preparation method provided by the invention avoids the caking phenomenon, and the prepared solid super acidic catalyst has high BET specific surface area, contains Bronsted acid sites and Lewis acid sites, and has higher catalytic reaction efficiency.
The invention is realized by the following steps:
in one aspect, the present invention provides a method for preparing a solid super acidic catalyst, comprising:
performing primary calcination on a mixture containing a zirconium source and an aluminum source to obtain a calcined product of alumina-coated zirconia; the aluminum source is aluminum isopropoxide, aluminum sulfate or aluminum nitrate, and the zirconium source is zirconium-based MOFs; the zirconium-based MOFs is UiO-66.
The calcined product was subjected to a second calcination after surface treatment with a sulfidizing agent to obtain the solid super acid catalyst (sulfated alumina-coated zirconia product).
The presence of hydroxyl groups and surface defects makes the surface structure of zirconium octahedra in zirconium-based MOFs (UiO-66) similar to amorphous zirconium hydroxide. And the content of UiO-66 carbon is high, and the metal node density is high.
The invention adopts UiO-66 as a zirconium source for the first time and adopts aluminum isopropoxide, aluminum sulfate or aluminum nitrate as an aluminum source to prepare the novel solid super acidic catalyst, which can effectively avoid the caking phenomenon. The presence of hydroxyl groups and surface defects makes the surface structure of zirconium octahedra in zirconium-based MOFs (UiO-66) similar to amorphous zirconium hydroxide. And the content of UiO-66 carbon is high, and the metal node density is high. By carrying out thermal decomposition on the catalyst, the caking phenomenon is avoided, and the catalytic reaction efficiency is improved. The prepared solid super acidic catalyst has high BET specific surface area reaching 301-330 m2The catalyst contains Bronsted acid sites and Lewis acid sites, and can effectively improve the catalytic reaction efficiency. The invention provides a foundation for developing a customized mesoporous zirconia type solid super acidic catalyst material.
It should be noted that UiO-66 can be obtained commercially or synthesized by the method of the present invention.
Optionally, in some embodiments of the invention, the sulfiding agent is selected from any one of ammonium sulfate, ammonium persulfate and sulfuric acid.
The sulfiding agent of the present invention may be selected as desired, including but not limited to ammonium sulfate, ammonium persulfate, and sulfuric acid.
Optionally, in some embodiments of the invention, the sulfiding agent is ammonium sulfate.
Optionally, in some embodiments of the present invention, the concentration of the ammonium sulfate is 1 to 3mol/L, and the amount of the ammonium sulfate is as follows: 15-25ml of the ammonium sulfate is used per 1g of the aluminum source.
Alternatively, in some embodiments of the invention, the mixture is prepared by:
step (a): dissolving the aluminum source in deionized water, ethanol or isopropanol to obtain an aluminum source solution;
step (b): dispersing the zirconium source in water through ultrasonic treatment, adding CTAB, and mixing to obtain a zirconium source dispersion solution; CTAB mainly acts to keep the zirconium source dispersed and not aggregated and to reduce the surface energy to stabilize it.
Step (c): adding the aluminum source solution to the zirconium source dispersion solution and mixing to obtain the mixture.
Optionally, in some embodiments of the present invention, in step (b), the sonication time is 5-30min and the frequency is 45-55 KHZ.
Alternatively, in some embodiments of the invention, in step (b), 2.5 to 3.5g CTAB, preferably 3g CTAB, are added per 1g of zirconium source.
Optionally, in some embodiments of the present invention, in step (b), the mixing is performed by stirring for 3-15 min.
In the step (c), the zirconium source dispersion solution is stirred, filtered and dried after the aluminum source solution is added, so that the mixture is obtained.
Alternatively, in some embodiments of the invention, in step (c), the stirring time is from 3 to 8 hours.
Optionally, in some embodiments of the present invention, in the step (c), the drying is performed at a temperature of 80 to 120 ℃ for 6 to 12 hours.
Optionally, in some embodiments of the invention, the mass ratio of the zirconium source to the aluminum source is from 1:3 to 7.
Optionally, in some embodiments of the invention, the mass ratio of the zirconium source to the aluminum source is 1: 5.
Optionally, in some embodiments of the present invention, the first calcination is performed at a calcination temperature of 300-.
Optionally, in some embodiments of the present invention, the second calcination is performed at a calcination temperature of 300 to 600 ℃ for 1 to 4 hours.
Alternatively, in some embodiments of the invention, the calcined product is surface treated with the sulfiding agent in the manner of: impregnating the calcined product in the sulfiding agent.
In other embodiments of the present invention, the surface treatment may be selected to adhere the sulfiding agent to the surface or in the voids of the calcined product by spraying.
Optionally, in some embodiments of the invention, the vulcanizing agent is stirred during impregnation; the impregnation temperature is 25-35 deg.C, and the impregnation time is 0.5-3.5 h.
Optionally, in some embodiments of the invention, the preparation method further comprises: before the second calcination and after the impregnation, drying the calcined product at 80-120 ℃ for 6-12 h.
In another aspect, the present invention provides a solid super acidic catalyst prepared by the preparation method as described in any one of the above.
The solid super acidic catalyst provided by the invention has a higher BET specific surface area which reaches 301-330 m2(ii)/g; and contains both Bronsted acid sites and Lewis acid sites. The catalyst has higher catalytic efficiency when being used for catalytic reaction such as the catalytic alcoholysis of glucose to prepare ethyl levulinate.
In another aspect, the present invention provides the use of a solid super acid catalyst as described above in acid catalysis.
In another aspect, the invention provides the use of the solid super acidic catalyst as described above in the preparation of ethyl levulinate by catalyzing the hydrolysis of glucitol.
The solid super acidic catalyst is used for catalyzing alcoholysis of glucose to prepare ethyl levulinate, so that the method has the advantages of high efficiency, environmental protection and recycling, the yield of ethyl levulinate is improved, and the yield of ethyl levulinate can reach 35-38 mol%.
Optionally, in some embodiments of the invention, it comprises: glucose, the solid super acidic catalyst and absolute ethyl alcohol are mixed according to the mass ratio: adding the mixture into a micro high-pressure reaction kettle in a ratio of 1: 0.2-1.1: 11, and reacting for 1-10 h at 150-240 ℃, preferably 180-220 ℃ in an inert gas atmosphere to obtain the ethyl levulinate.
Optionally, in some embodiments of the invention, the inert gas is N2The pressure is 0.1-0.5 MPa.
Optionally, in some embodiments of the invention, the stirring speed is 300-600 r.min-1The reaction was carried out in the state of (1).
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows a solid super acidic SO prepared in example 5 of the present invention4 2-/ZrO2@Al2O3NH of (2)3-TPD map.
FIG. 2 shows the solid super acidic SO prepared in example 5 of the present invention4 2-/ZrO2@Al2O3Pyridine infrared diagram of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. It should be noted that the scope of the present application is not limited to these examples.
Furthermore, the reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Synthesis of UiO-66: first, 1.16g (4.97mmol) of zirconium chloride and 0.825g (4.97mmol) of terephthalic acid (H) were introduced2BDC) was dissolved in 60mL of N, N-Dimethylformamide (DMF) and 20mL of acetic acid. Then, the solution was homogenized by ultrasonic treatment for 30min, and after the ultrasonic treatment was completed, the reaction was carried out at 120 ℃ for 24 hours. After the reaction was completed, the mixture was centrifuged, washed 3 times with N, N-Dimethylformamide (DMF) and methanol, and dried at 120 ℃ for 6h to obtain UiO-66 nanocrystals.
Example 2
Sulfated zirconia (SO)4 2-/ZrO2) The synthesis of (2): the UiO-66 was calcined at 500 ℃ for 3 hours (heating rate 1 ℃/min) to obtain ZrO2. 1g at 30 ℃: ZrO 2 in a proportion of 15mL2Immersing in ammonium sulfate solution (3mol/L) for 1h, filtering, drying at 100 deg.C for 6h, calcining at 500 deg.C and holding for 3h (heating rate of 1 deg.C/min) to obtain SO4 2-/ZrO2。
Example 3
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The preparation method comprises the following steps:
0.5g of aluminum isopropoxide was dissolved in 20mL of ethanol and stirred for 3h to form a clear solution for later use. Dispersing 100mg of UiO-66 nano-crystal in 30mL of deionized water, carrying out ultrasonic treatment for 10min, adding 0.3g of CTAB, and stirring for 5 min. Then slowly adding the aluminum isopropoxide solution into the UiO-66 dispersoid, stirring for 3h, carrying out reduced pressure suction filtration, washing for 3-5 times by using 95% ethanol and deionized water, and drying for 6h at 100 ℃ to obtain a product of the UiO-66 coated with aluminum hydroxide, which is recorded as UiO-66@ Al (OH)3. Mixing UiO-66@ Al (OH)3Calcining at 500 ℃ for 3h to obtain a calcined product of the alumina-coated zirconia, which is marked as ZrO2@Al2O3Then, the mixture was immersed in an ammonium sulfate solution (1mol/L) at 30 ℃ for 1 hour with stirring (amount: 1g of UiO-66: 15mL of the ammonium sulfate solution), filtered, and dried at 100 ℃ for 6 hours. Finally, the solid super acidic catalyst (marked as SO) of the embodiment is obtained by calcining the mixture for 3 hours at 500 ℃ at the heating rate of 1 ℃/min4 2-/ZrO2@Al2O3-1M). The sintering phenomenon does not occur in the preparation process. The BET specific surface area of the solid super acidic catalyst of this example was determined to be: 287m2The desorption amount of ammonia is as follows: 82.5cm3/g STP。
Example 4
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The same procedure as in example 3 was repeated, except that the ammonium sulfate solution was used in a concentration of 2 mol/L.
The solid super acidic catalyst obtained is marked as SO4 2-/ZrO2@Al2O3-2M. The sintering phenomenon does not occur in the preparation process. The BET specific surface area of the solid super acidic catalyst of this example was determined to be: 301m2The desorption amount of ammonia is as follows: 90.8cm3/g STP。
Example 5
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The same procedure as in example 3 was repeated, except that the ammonium sulfate solution was used in a concentration of 3 mol/L.
The solid super acidic catalyst obtained is marked as SO4 2-/ZrO2@Al2O3-3M. The sintering phenomenon does not occur in the preparation process. The BET specific surface area of the solid super acidic catalyst of this example was determined to be: 330m2The desorption amount of ammonia is as follows: 109cm3/g STP。
For SO of this example4 2-/ZrO2@Al2O3Characterization by-3M, FIG. 1 for SO prepared4 2-/ZrO2@Al2O3NH of 3M catalyst3TPD plot from which the SO synthesized can be seen4 2-/ZrO2@Al2O3The 3M catalyst has super acidic sites, and the BET specific surface area of the solid super acidic catalyst of the present example is determined as follows: 330m2The desorption amount of ammonia is as follows: 109cm3And/g STP. Meanwhile, FIG. 2 is madePreparation of SO4 2-/ZrO2@Al2O3The pyridine infrared diagram of the 3M catalyst, from which it can be found that the prepared catalyst has both Bronsted acid sites and Lewis acid sites, this property making it possible to better catalyze the reaction of glucose to ethyl levulinate.
Example 6
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) Substantially the same as in example 5, except that the mass ratio of the zirconium source to the aluminum source used was 1: 4.
Example 7
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) Substantially the same as in example 5, except that the mass ratio of the zirconium source to the aluminum source was 1: 6.
Example 8
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The same procedure as in example 5 was repeated, except that the ammonium sulfate solution was immersed in the solution for a stirring time of 2 hours.
Example 9
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The same procedure as in example 5 was repeated, except that the ammonium sulfate solution was immersed and stirred for 3 hours.
Example 10
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) The procedure of (1) was substantially the same as in example 5, except that the aluminum source used was aluminum sulfate.
Example 11
The solid super acidic catalyst (SO) provided in this example4 2-/ZrO2@Al2O3) Substantially the same as in example 5, except thatThe aluminum source is aluminum nitrate.
Example 12
The catalyst SO obtained in example 3 was used4 2-/ZrO2@Al2O3-1M is used to catalyze the reaction of glucitol hydrolysis to produce ethyl levulinate. The catalytic reaction is carried out in a 25mL micro high-pressure reaction kettle, 0.12g of glucose and 90mg of catalyst are added into a quartz lining of the reaction kettle which is added with 14mL of absolute ethyl alcohol in advance, then the quartz lining is replaced by nitrogen for 3 times, then 0.2Mpa nitrogen is introduced again, the reaction kettle is heated to 200 ℃ under the condition of 500r/min, and the reaction kettle is heated for 5 hours at constant temperature. After the reaction, the catalyst was separated by centrifugation, and the reaction solution was filtered through a 0.22 μm filter and then checked by gas chromatography to obtain a product in which the yield of ethyl levulinate was 30.5 mol%.
Example 13
Catalyst SO obtained in example 4 was measured by the method in reference example 124 2-/ZrO2@Al2O3The activity of-2M on catalyzing the glucose to prepare ethyl levulinate, after the reaction for 5 hours at 200 ℃, the yield of the ethyl levulinate is 33 mol%.
Example 14
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3Activity of-3M on catalyzing glucose to prepare ethyl levulinate, yield of ethyl levulinate after 5h of reaction at 200 ℃ was 37.5 mol%.
Comparative example 1
Blank test: the catalytic reaction is carried out in a 25mL micro high-pressure reaction kettle, 0.12g of glucose is added into a quartz lining of the reaction kettle which is added with 14mL of absolute ethyl alcohol in advance, then the quartz lining is replaced by nitrogen for 3 times, then 0.2Mpa nitrogen is introduced again, the reaction kettle is heated to 200 ℃ under the condition of 500r/min, and the reaction kettle is heated for 5 hours at constant temperature. After the reaction, the catalyst was separated by centrifugation, and the reaction mixture was filtered through a 0.22 μm filter and the product was detected by gas chromatography, and ethyl levulinate was not detected.
Comparative example 2
The activity of the catalyst UiO-66 for catalyzing the preparation of ethyl levulinate from glucose was measured by referring to the method in example 12, and the yield of ethyl levulinate after 5 hours of reaction at 200 ℃ was 12.5 mol%.
Comparative example 3
Catalyst SO determination by the method of reference example 124 2-/ZrO2The activity of catalyzing the glucose to prepare the ethyl levulinate is that the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 9.8 mol%.
Example 15
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3-3M activity on catalyzing glucose to prepare ethyl levulinate, the yield of ethyl levulinate after 5h of reaction at 180 ℃ is 22.3 mol%.
Example 16
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3Activity of-3M on catalyzing glucose to prepare ethyl levulinate, yield of ethyl levulinate after 5h of reaction at 220 ℃ was 32.3 mol%.
Example 17
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3Activity of 3M on catalysis of glucose to ethyl levulinate, yield of ethyl levulinate 28.1 mol% when catalyst addition was 30 mg.
Example 18
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3Activity of 3M on catalysis of glucose to ethyl levulinate, yield of ethyl levulinate was 34.7 mol% when catalyst addition was 60 mg.
Example 19
Catalyst SO obtained in example 5 was measured by the method in reference example 124 2-/ZrO2@Al2O3Activity of 3M on catalysis of glucose to Ethyl levulinate, yield of Ethyl levulinate 36.6mol when catalyst addition was 120mg％。
Example 20
Catalyst SO obtained in example 6 was measured by the method in reference example 124 2-/ZrO2@Al2O3For the activity of catalyzing the glucose to prepare the ethyl levulinate, the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 33 mol%.
Example 21
Catalyst SO obtained in example 7 was measured by the method in reference example 124 2-/ZrO2@Al2O3For the activity of catalyzing the glucose to prepare the ethyl levulinate, the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 35 mol%.
Example 22
Catalyst SO obtained in example 8 was measured by the method in reference example 124 2-/ZrO2@Al2O3The activity of catalyzing the glucose to prepare the ethyl levulinate is that the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 33.5 mol%.
Example 23
Catalyst SO obtained in example 9 was measured by the method in reference example 124 2-/ZrO2@Al2O3For the activity of catalyzing the glucose to prepare the ethyl levulinate, the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 34 mol%.
Example 24
Catalyst SO obtained in example 10 was measured by the method in reference example 124 2-/ZrO2@Al2O3For the activity of catalyzing the glucose to prepare the ethyl levulinate, the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 35.4 mol%.
Example 25
Catalyst SO obtained in example 11 was measured by the method in reference example 124 2-/ZrO2@Al2O3The activity of catalyzing the glucose to prepare the ethyl levulinate is that the yield of the ethyl levulinate after the reaction for 5 hours at 200 ℃ is 33.1 mol%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a solid super acidic catalyst is characterized by comprising the following steps:
performing primary calcination on a mixture containing a zirconium source and an aluminum source to obtain a calcined product of alumina-coated zirconia; the aluminum source is aluminum isopropoxide, aluminum sulfate or aluminum nitrate, and the zirconium source is zirconium-based MOFs; the zirconium-based MOFs is UiO-66;
and carrying out surface treatment on the calcined product by using a vulcanizing agent, and then carrying out secondary calcination to obtain the solid super acidic catalyst.
2. The production method according to claim 1, wherein the vulcanizing agent is selected from any one of ammonium sulfate, ammonium persulfate and sulfuric acid;
preferably, the vulcanizing agent is ammonium sulfate;
preferably, the concentration of the ammonium sulfate is 1-3 mol/L, and the dosage of the ammonium sulfate is as follows: 15-25ml of the ammonium sulfate is used per 1g of the aluminum source.
3. The method according to claim 1 or 2, wherein the mixture is prepared by:
step (a): dissolving the aluminum source in deionized water, ethanol or isopropanol to obtain an aluminum source solution;
step (b): dispersing the zirconium source in water through ultrasonic treatment, adding CTAB, and mixing to obtain a zirconium source dispersion solution;
step (c): adding the aluminum source solution to the zirconium source dispersion solution to mix to obtain the mixture;
preferably, in step (b), the time of ultrasonic treatment is 5-30min, and the frequency is 45-55 KHZ;
preferably, in step (b), 2.5-3.5g CTAB per 1g of zirconium source is added;
preferably, in the step (b), the mixing is carried out in a stirring manner, and the stirring time is 3-15 min;
preferably, in step (c), the zirconium source dispersion solution is stirred, filtered and dried after the aluminum source solution is added to obtain the mixture;
preferably, in step (c), the stirring time is 3-8 h;
preferably, in the step (c), the drying is carried out at a temperature of 80-120 ℃ for 6-12 h.
4. The method according to claim 3, wherein the mass ratio of the zirconium source to the aluminum source is 1:3 to 7, preferably 1: 5.
5. The preparation method according to claim 1 or 2, characterized in that the calcination temperature for the first calcination is 300-600 ℃, and the calcination time is 1-4 h;
the calcination temperature for the second calcination is 300-600 ℃, and the calcination time is 1-4 h.
6. The production method according to claim 1 or 2, characterized in that the calcined product is surface-treated with the vulcanizing agent in such a manner that: impregnating the calcined product in the sulfiding agent;
preferably, the vulcanizing agent is stirred during impregnation; the dipping temperature is 25-35 ℃, and the dipping time is 0.5-3.5 h;
preferably, the preparation method further comprises: before the second calcination and after the impregnation, drying the calcined product at 80-120 ℃ for 6-12 h.
7. A solid super acidic catalyst, which is obtained by the production method according to any one of claims 1 to 6.
8. Use of the solid super acid catalyst of claim 7 in a chemical reaction comprising: isomerization, alkylation, esterification or epoxidation.
9. The use of the solid super acid catalyst of claim 7 in catalyzing the hydrolysis of glucose to produce ethyl levulinate.
10. Use according to claim 9, characterized in that it comprises: glucose, the solid super acidic catalyst and absolute ethyl alcohol are mixed according to the mass ratio: adding the mixture into a micro high-pressure reaction kettle in a ratio of 1: 0.2-1.1: 11, and reacting for 1-10 h at 150-240 ℃ in an inert gas atmosphere to obtain ethyl levulinate;
preferably, the inert gas is N2The pressure is 0.1-0.5 Mpa;
preferably, the stirring speed is 300 to 600 r.min-1The reaction was carried out in the state of (1).
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