CN114618559A - Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation - Google Patents
Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation Download PDFInfo
- Publication number
- CN114618559A CN114618559A CN202210372495.5A CN202210372495A CN114618559A CN 114618559 A CN114618559 A CN 114618559A CN 202210372495 A CN202210372495 A CN 202210372495A CN 114618559 A CN114618559 A CN 114618559A
- Authority
- CN
- China
- Prior art keywords
- kit
- catalyst
- solid acid
- acid catalyst
- valerolactone
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 195
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000011973 solid acid Substances 0.000 title claims abstract description 75
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006114 decarboxylation reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- 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 49
- 239000007790 solid phase Substances 0.000 claims abstract description 28
- 238000005470 impregnation Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000001665 trituration Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- 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
- B01J35/617—500-1000 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
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/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
- 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
- C07C1/2078—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by a transformation in which at least one -C(=O)-O- moiety is eliminated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a solid acid catalyst, a preparation method thereof and application thereof in catalyzing decarboxylation of gamma-valerolactone to prepare butene. The invention introduces Al into the KIT-6 molecular sieve framework by an impregnation method or a solid phase grinding method respectively to form corresponding solid acid sites. The gamma-valerolactone and 10 wt.% of catalyst are added into a high-pressure reaction kettle, and the yield of the butene can reach 94% after the reaction is carried out for 4 hours under the conditions of normal pressure, 300 ℃ and 700 r/min. The catalyst disclosed by the invention has the advantages that: the catalyst has simple preparation process and can be synthesized in large batch; the prepared catalyst has larger specific surface area and pore diameter; the catalytic reaction condition is mild, the yield of the butene is still high at a lower reaction temperature, the catalytic stability is excellent, and more ideas and methods are provided for the development and utilization of biomass energy.
Description
Technical Field
The invention relates to a catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, in particular to a preparation method and application of a solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, which is a biomass platform compound, and has the advantages of large specific surface area and mild catalytic reaction conditions, and belongs to the field of development of renewable clean energy.
Background
Butene is used as a basic chemical raw material and is commonly used in the fields of fuel preparation, chemical processing and the like. At present, the industrial production of butenes still derives from the traditional petroleum cracking technology, not only having a strong dependency on fossil energy, but also causing serious environmental damage. Along with the awakening of global environmental awareness and the progress of science and technology, people gradually abandon the concept of producing butylene by stone energy such as petroleum and the like, and seek a butylene preparation process which is environment-friendly and low in cost.
The biomass energy is a renewable carbon source which can replace fossil energy and can be converted into liquid or gaseous fuel and other chemical raw materials, and has the advantages of neutral carbon, low sulfur content, high hydrogen content and the like. The biomass resource has little pollution to the environment, can make up the current situation of insufficient fossil fuel to a great extent, and relieves the passive situation that the petroleum resource depends on import to a great extent. Gamma-valerolactone is a biomass platform compound with high boiling point, high flash point, low toxicity and low melting point, which can be directly used as fuel and produce various chemicals. The catalyst is used for catalyzing the decarboxylation of gamma-valerolactone to prepare butene, which is a brand new biomass conversion idea. However, the harsh reaction conditions, complex catalyst preparation process, and high production costs have always limited the widespread use of this technology.
The research team (Science,2010,327,1110) of university of Wisconsin in 2 months 2010 adopts cheap SiO for the first time2/Al2O3The catalyst catalyzes gamma-valerolactone aqueous solution to carry out decarboxylation reaction under the high-temperature and high-pressure state (375 ℃, 36bar), and high-yield and high-purity butene is obtained by separating generated gas, but the development of the technology is limited by higher reaction temperature and reaction pressure and harsh requirements on production equipment.
Aimee Kellicutt et al, Jesse Bond group, in 2014 prepared 5 amorphous silica-alumina (ASA) catalysts with different silica to alumina ratios by a sol-gel process. The proper pore structure and the proper amount are found for the first timeThe site is a key element of the decarboxylation reaction, has a large pore size and Lewis acid sites at 350 ℃ and has a relatively high deprotonation energyThe stability of the acid site catalyst is highest.
In 2019, Wang et al reduced the reaction temperature to 300 ℃ based on the former, and increased the reaction pressure and reaction time to 2MPa and 4.5h, respectively, and conducted decarboxylation reaction on GVL in a batch reactor using a purchased Nabeta-5 catalyst, and obtained a considerable yield of butene (98%). The research reduces the reaction temperature to a certain extent, saves the reaction energy consumption and provides possibility for the industrial production of the reaction for preparing the butylene by the GVL decarboxylation.
Recently, Hongtao Wang et al, university of Wuhan, developed a two-stage integrated system with SiO2-Al2O3Combined with HZSM-5, to give C in 57.6% yield via the butene intermediate5+Hydrocarbons, the mechanism of GVL ring opening and decarboxylation is explained in detail.
At present, few reports about catalysts for catalyzing decarboxylation of gamma-valerolactone to prepare butene are reported, and no report about introducing Al into a KIT-6 matrix for catalyzing preparation of the gamma-valerolactone to prepare the butene through a simple impregnation method or a solid-phase grinding method is provided.
Disclosure of Invention
In order to solve the problems of complex production process, higher cost, poor stability, deficient varieties and the like in the existing catalyst for preparing butylene by decarboxylation of gamma-valerolactone, the invention provides a synthesis method of an Al-KIT-6 solid acid catalyst, which is simple, convenient and beneficial to mass production. The obtained catalyst not only has larger specific surface area and ordered mesoporous structure, but also has good catalytic activity and excellent catalytic stability for the decarboxylation of gamma-valerolactone to prepare butene at lower temperature.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a solid acid catalyst is Al-KIT-6 formed by introducing Al into a KIT-6 mesoporous molecular sieve framework by taking a KIT-6 mesoporous molecular sieve as a matrix; wherein, the Al atomic mass is 1-10% of the mass of KIT-6 mesoporous molecular sieve.
Preferably, the solid acid catalyst has a pore diameter of 4.5-7.6 nm and a specific surface area of 440.22-820.64 m2·g-1The total pore volume is 0.74-1.20 cm3·g-1。
A method for preparing a solid acid catalyst comprises the following steps:
1) preparation of KIT-6 mesoporous molecular sieve: adding P123 template agent to H2O and concentrated hydrochloric acid solution, and stirring vigorously until P123 is completely dissolved; slowly dropwise adding n-butanol, reacting for 1h in a water bath at 35 ℃, then slowly dropwise adding tetraethyl orthosilicate, and continuously stirring and reacting for 24h in a water bath at 35 ℃; transferring the obtained reaction mixture into an autoclave, and carrying out hydrothermal treatment at 95 ℃ for 24 h; filtering, washing, drying, and finally roasting at 550 ℃ for 8h to obtain a KIT-6 mesoporous molecular sieve;
2) preparation of Al-KIT-6: mixing an aluminum-containing compound with a KIT-6 mesoporous molecular sieve by an impregnation method or a solid phase grinding method at room temperature, and finally calcining at 550 ℃ for 5 hours to obtain a target product.
Preferably, in the above preparation method, step 2), the impregnation method is: dissolving an aluminum-containing compound in a solvent by magnetic stirring at room temperature, adding a KIT-6 mesoporous molecular sieve under stirring, stirring for 4h, placing in a water bath at 60 ℃, evaporating the solvent to dryness, drying the obtained product, and calcining at 550 ℃ for 5h to obtain Al-KIT-6.
Preferably, in the above preparation method, step 2), the solid phase milling method is: at room temperature, after an aluminum-containing compound is fully subjected to solid phase grinding in an agate mortar, a KIT-6 mesoporous molecular sieve is added, no or a small amount of solvent is added, solid phase grinding is continued at room temperature until the mixture is uniformly mixed, and the obtained product is calcined for 5 hours at 550 ℃ to obtain Al-KIT-6.
Preferably, in the above preparation method, the aluminum-containing compound is selected from AlCl3、AlCl3·6H2O、Al(NO3)3·9H2O、Al2O3、Al2(SO4)3And C9H21AlO3。
Preferably, in the above preparation method, the solvent is one or two of methanol, ethanol or water.
Preferably, in the above preparation method, the ratio by mass of the aluminum-containing compound to KIT-6 mesoporous molecular sieve is 0.02 to 0.67: 1.
The solid acid catalyst provided by the invention is applied to catalyzing decarboxylation of gamma-valerolactone to prepare butene.
Preferably, the method comprises the following steps of adding gamma-valerolactone and a solid acid catalyst into a high-temperature high-pressure reaction kettle, filling nitrogen into the reaction kettle for protection, and reacting at 260-350 ℃ under normal pressure.
Preferably, the mass ratio of the gamma-valerolactone to the solid acid catalyst is 1: 0.05-0.15.
When the Al-KIT-6 catalyst provided by the invention is applied to catalyzing decarboxylation of gamma-valerolactone to prepare butylene, the powder state can be maintained or the catalyst can be prepared into the conventional catalyst shape in the field of catalysts, such as granular, strip-shaped or sheet-shaped shapes.
The invention has the beneficial effects that:
1. the solid acid catalyst Al-KIT-6 provided by the invention is simple in preparation method and can be produced in large batch.
2. The solid acid catalyst Al-KIT-6 provided by the invention not only has larger specific surface area and ordered mesoporous structure, but also has good catalytic activity and excellent catalytic stability for the reaction of preparing butylene by decarboxylating gamma-valerolactone, and is suitable for industrial production.
3. The solid acid catalyst Al-KIT-6 provided by the invention can catalyze the reaction of preparing butylene by decarboxylation of gamma-valerolactone under normal pressure, and the reaction condition is mild.
Drawings
FIG. 1 is a graph showing the temperature dependence of the activity of the solid acid catalyst S (1) obtained in example 1 for catalyzing the decarboxylation of gamma-valerolactone to produce butene.
FIG. 2 is a graph showing the reaction activity of the solid acid catalyst S (1) obtained in example 1 for catalyzing the decarboxylation of gamma-valerolactone to prepare butene according to the number of catalyst cycles.
FIG. 3 is N of catalysts obtained in examples 1, 2, 3, 4, 5 and comparative example 12Adsorption-desorption isotherms and pore size distribution curves.
Detailed Description
In order that those skilled in the art may more fully understand the present invention, the present invention will now be described in more detail by way of the following non-limiting examples and comparative examples, which are not intended to limit the invention in any way.
EXAMPLE 1 impregnation preparation of solid acid catalyst S (1) for the decarboxylation of gamma-valerolactone to butene
The method comprises the following steps:
1. preparation of KIT-6 mesoporous molecular sieve
Adding 4.0g P123 template agent to 120g H2Violently stirring a mixed solution of O and 20mL of concentrated hydrochloric acid until P123 is completely dissolved, slowly dripping 4.0g of n-butyl alcohol at one time, stirring the mixed solution in a water bath at the temperature of 35 ℃ for reaction for 1 hour, slowly dripping 8.6g of tetraethyl orthosilicate at one time, and continuously stirring the mixed solution in the water bath at the temperature of 35 ℃ for reaction for 24 hours; transferring the obtained reaction mixture into an autoclave, and carrying out hydrothermal treatment at 95 ℃ for 24 h; filtering, washing and drying to obtain a product at 55Roasting at 0 deg.c for 8 hr to obtain KIT-6 mesoporous molecular sieve.
2. Preparation of Al-KIT-6
0.0445g of AlCl was stirred magnetically at room temperature3Dissolved in 4.2mL of absolute ethanol, 0.3g of KIT-6 mesoporous molecular sieve was added with stirring, and stirring was continued at room temperature for 4 h. Placing the obtained mixture in a water bath kettle at 60 deg.C, completely evaporating ethanol, and drying the obtained product in an oven at 50 deg.C for 12 hr. And finally, putting the dried sample into a muffle furnace, and calcining for 5h at 550 ℃ to obtain an Al-KIT-6 solid acid catalyst with the Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve, which is named as a 3 wt% Al-KIT-6-J catalyst and is marked as a catalyst S (1).
EXAMPLE 2 impregnation preparation of solid acid catalyst S (2) for catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0148g of AlCl was used3Instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 1% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 1 wt% Al-KIT-6-J catalyst and marked as catalyst S (2).
EXAMPLE 3 impregnation preparation of solid acid catalyst S (3) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0296g of AlCl is added3Instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 2% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 2 wt% Al-KIT-6-J catalyst and marked as catalyst S (3).
EXAMPLE 4 impregnation preparation of solid acid catalyst S (4) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0592g AlCl was used3Instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 4 wt% Al-KIT-6-J catalyst and marked as catalyst S (4).
EXAMPLE 5 impregnation preparation of solid acid catalyst S (5) for the decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0741g of AlCl was used3Instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with the Al atomic mass of 5 percent of the mass of the KIT-6 mesoporous molecular sieve is obtained and named as 5wt percent Al-KIT-6-J catalyst and is marked as catalyst S (5).
COMPARATIVE EXAMPLE 1 preparation of solid acid catalyst B (1) catalyzing decarboxylation of gamma-valerolactone to butene by impregnation
The procedure is as in example 1. Except that in step 2, no AlCl was added3And absolute ethyl alcohol, calcining the KIT-6 mesoporous molecular sieve at 550 ℃ for 5h to obtain the Al-KIT-6 solid acid catalyst with the Al atomic mass of 0% of that of the KIT-6 mesoporous molecular sieve, which is named as 0 wt% Al-KIT-6-J catalyst and is marked as catalyst B (1).
EXAMPLE 6 impregnation preparation of solid acid catalyst B (2) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0804g of AlCl was used3·6H2O instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 3 wt% Al-KIT-6 catalyst and marked as catalyst B (2).
EXAMPLE 7 preparation of solid acid catalyst B (3) by impregnation catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.1251g of Al (NO) was used3)3·9H2O instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 3 wt% Al-KIT-6 catalyst and marked as catalyst B (3).
EXAMPLE 8 preparation of solid acid catalyst B (4) catalyzing decarboxylation of gamma-valerolactone to butene by impregnation
The procedure is as in example 1. Except that in step 2, 0.0570g of Al was used2(SO4)3Instead of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 3 wt% Al-KIT-6 catalyst and marked as catalyst B (4).
EXAMPLE 9 impregnation preparation of solid acid catalyst B (5) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except in step 2, at 0.0681g C9H21AlO3(aluminum isopropoxide) in place of 0.0445g AlCl in example 13The Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 3 wt% Al-KIT-6 catalyst and marked as catalyst B (5).
Example 10 impregnation preparation of solid acid catalyst B (6) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0445g of AlCl was added3Dissolving in 4.2mL of methanol solution to obtain Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of KIT-6 mesoporous molecular sieve, named 3 wt% Al-KIT-6 catalyst and marked as catalyst B (6).
EXAMPLE 11 impregnation preparation of solid acid catalyst B (7) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0445g of AlCl was added3Dissolving in 4.2mL of aqueous solution to obtain an Al-KIT-6 solid acid catalyst with the Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve, which is named as 3 wt.% Al-KIT-6 catalyst and is marked as catalyst B (7).
EXAMPLE 12 impregnation preparation of solid acid catalyst B (8) catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 1. Except that in step 2, 0.0445g of AlCl was added3Dissolving in 4.2mL of 50% ethanol water solution to obtain Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of KIT-6 mesoporous molecular sieve, named 3 wt% Al-KIT-6 catalyst and marked as catalyst B (8).
Example 13 preparation of solid acid catalyst S (6) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The method comprises the following steps:
1. preparation of KIT-6 mesoporous molecular sieve: the same as in example 1.
2. Preparation of Al-KIT-6:
0.0592g AlCl is added at room temperature3Fully in an agate mortarAfter solid phase grinding, 0.3g of KIT-6 mesoporous molecular sieve is added, and solid phase grinding is continued for 0.5h at room temperature until the two phases are uniformly mixed. And putting the obtained product into a muffle furnace, and calcining for 5 hours at 550 ℃ to obtain an Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve, which is named as 4 wt% Al-KIT-6-Y catalyst and is marked as catalyst S (6).
Example 14 preparation of solid acid catalyst S (7) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.0148g of AlCl was used3Instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 1% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 1 wt% Al-KIT-6-Y catalyst and marked as catalyst S (7).
Example 15 solid phase Mill method for preparing solid acid catalyst S (8) for catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 13. Except that in step 2, 0.0296g of AlCl is added3Instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 2% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 2 wt% Al-KIT-6-Y catalyst and marked as catalyst S (8).
Example 16 preparation of solid acid catalyst S (9) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.0445g of AlCl was used3Instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 3% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 3 wt% Al-KIT-6-Y catalyst and marked as catalyst S (9).
Example 17 solid phase Mill method for preparing solid acid catalyst S (10) for catalyzing decarboxylation of gamma-valerolactone to butene
The procedure is as in example 13. Except that in step 2, 0.0741g of AlCl was used3Instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with the Al atomic mass of 5% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 5 wt% Al-KIT-6-Y catalyst and marked as catalyst S (10).
Example 18 preparation of solid acid catalyst B (9) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.1072g of AlCl was used3·6H2O instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 4 wt% Al-KIT-6 catalyst and marked as catalyst B (9).
Example 19 preparation of solid acid catalyst B (10) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.1669g of Al (NO) was added3)3·9H2O instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of the mass of the KIT-6 mesoporous molecular sieve is obtained and named as 4 wt% Al-KIT-6 catalyst and is marked as catalyst B (10).
Example 20 preparation of solid acid catalyst B (11) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.076g of Al was used2(SO4)3Instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 4 wt% Al-KIT-6 catalyst and marked as catalyst B (11).
EXAMPLE 21 solid phase Mill preparation of solid acid catalyst B (12) for the decarboxylation of gamma-valerolactone to butene
The procedure is as in example 13. Except in step 2, at 0.0908g C9H21AlO3(aluminum isopropoxide) instead of 0.0592g AlCl in example 133The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 4 wt% Al-KIT-6 catalyst and marked as catalyst B (12).
EXAMPLE 22 preparation of solid acid catalyst B (13) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 13. Except that in step 2, 0.0227g of Al was used2O3Alternative example 130.0592g AlCl3The Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve is obtained, named as 4 wt% Al-KIT-6 catalyst and marked as catalyst B (13).
EXAMPLE 23 preparation of solid acid catalyst B (14) catalyzing decarboxylation of gamma-valerolactone to butene by solid phase trituration
The procedure is as in example 12. Except that in step 2, before the solid phase grinding is started, 1mL of absolute ethyl alcohol is additionally added to obtain the Al-KIT-6 solid acid catalyst with Al atomic mass of 4% of that of the KIT-6 mesoporous molecular sieve, which is named as 4 wt% Al-KIT-6 catalyst and is marked as catalyst B (14).
EXAMPLE 24 determination of Activity of the catalyst prepared in example 1 for catalyzing decarboxylation of gamma-valerolactone to butene production at different temperatures
1g of gamma-valerolactone and 0.1g of the catalyst S (1) prepared in example 1 were added into a 100mL high-temperature high-pressure reaction kettle, and then reacted for 4 hours at 260 ℃, 280 ℃, 300 ℃, 320 ℃, 340 ℃ and 700r/min under normal pressure after nitrogen protection was filled into the reaction kettle. After the reaction is finished, putting the reaction kettle into cold water for quenching, and after the temperature of a reaction system is reduced to room temperature, collecting a gas product generated by the reaction by using an aluminum foil gas collecting bag, and reserving the gas product for gas chromatography/gas chromatography-mass spectrometry analysis; the liquid in the reaction kettle is collected by a disposable syringe, diluted by solvent and filtered into a sample bottle for gas chromatography/gas chromatography-mass spectrometry analysis. The butene yield and the gamma-valerolactone conversion were calculated.
The reaction system is a closed system, and the mass is conserved before and after the reaction. According to the law of conservation of mass, the yield of butenes and the conversion of gamma valerolactone can be calculated by the following formula:
the formula (1) is a calculation formula of the yield of the butene. Yield of butene using Y(C4)Is represented by m0Is the total mass of gamma-valerolactone initially charged into the system, m1Is the total mass of liquid remaining in the system after gas release. Wherein the gas released in the system consists of butenes and carbon dioxide in equal amounts.
The formula (2) is a calculation formula of the conversion rate of gamma-valerolactone. The conversion of gamma valerolactone was conv.(GVL)Is represented by m0Is the total mass of gamma-valerolactone initially charged into the system, m2The mass of gamma valerolactone in the remaining liquid product obtained was calculated for the external standard method.
FIG. 1 is a graph showing the relationship between the yield of butene and the temperature change in the process of catalyzing the decarboxylation of gamma-valerolactone to produce butene in the catalyst S (1) prepared by the impregnation method in example 1. As can be seen from fig. 1, when the reaction pressure was atmospheric, the amount of the catalyst was 10 wt.% of the reactant γ -valerolactone, and the reaction was continued for 4 hours. As the reaction temperature increases, the butene yield also increases. And reached a maximum at 320 c, at which point the butene yield was about 96.27%. Subsequently, as the reaction temperature continues to increase, the conversion of the reactants in the system is nearly complete and there is no significant increase in butene yield. This result shows that the temperature has a great influence on the reaction for catalyzing the preparation of butene from gamma-valerolactone, and the highest efficiency of the catalyst can be achieved only at a proper reaction temperature. In addition, the catalyst obtained in the example 1 has great application potential in the aspect of catalyzing gamma-valerolactone to prepare butene.
EXAMPLE 25 determination of Activity of catalyst prepared by impregnation method for catalyzing decarboxylation of gamma-valerolactone to butene
The performance of the catalysts obtained in examples 1 to 12 and comparative example 1 was measured. 13 parts of 1g of gamma-valerolactone and 0.1g of the catalyst obtained in examples 1 to 12 and comparative example 1 are respectively added into a 100mL high-temperature high-pressure reaction kettle, and the reaction kettle is filled with nitrogen for protection and then reacts for 4h at normal pressure, 300 ℃ and 700 r/min. After the reaction is finished, putting the reaction kettle into cold water for quenching, and after the temperature of a reaction system is reduced to room temperature, collecting a gas product generated by the reaction by using an aluminum foil gas collecting bag, and reserving the gas product for gas chromatography/gas chromatography-mass spectrometry analysis; the liquid in the reaction kettle is collected by a disposable syringe, diluted by solvent and filtered into a sample bottle for gas chromatography/gas chromatography-mass spectrometry analysis. Butene yields and gamma valerolactone conversions were calculated and the results are shown in table 1.
TABLE 1 yield of butene obtained after 4h reaction at 300 deg.C and 700r/min for the catalysts obtained in each example and comparative example prepared by impregnation
As can be seen from Table 1, at the same reaction temperature, initial pressure, rotation speed and reaction time, the comparison of catalysts S (1) -S (5) shows that, under the condition of consistent aluminum source and solvent, the yield of butene tends to increase and decrease with the increase of Al content in the catalyst, wherein the catalytic activity of the catalyst S (1) is the highest. On the premise of ensuring the consistent Al content, the catalyst S (1) is compared with the catalysts B (2) -B (5), and the catalyst S (1) has the highest conversion rate of catalyzing the decarboxylation of gamma-valerolactone to prepare butene. That is, AlCl, an aluminum compound is used3The aluminum source is more favorable for improving the performance of the catalyst. Comparing the catalysts S (1) and the catalysts B (6) to B (8), it was found that the four catalysts exhibited different catalytic activities when the Al source and the Al content were the same but the solvents used were different. The catalyst S (1) adopting absolute ethyl alcohol as a solvent has better performance for catalyzing the reaction of preparing the butylene by decarboxylation of gamma-valerolactone, and the prepared butylene is the highest.
EXAMPLE 26 determination of Activity in decarboxylation of Gamma-valerolactone, a catalyst prepared by solid phase trituration method, to butene
The catalytic activities of the catalysts obtained in examples 13 to 23 were measured in accordance with the method described in example 25, and the results are shown in Table 2.
TABLE 2 yield of butene obtained by reaction of the catalysts obtained in examples and comparative examples prepared by solid phase milling at 300 ℃ and 700r/min for 4 hours
As shown in Table 2, the yields of butenes were different for different catalysts at the same catalyst loading and reaction conditions. Comparison of the catalysts S (6) to S (10) with AlCl without addition of solvent3In the case of aluminum sources, the Al content also has a greater influence on the butene yield. Among them, the yield of butene corresponding to the catalyst S (6) is the highest. In addition, solid phase grinding method is adopted to use AlCl3Catalyst S (6) prepared from aluminum source and AlCl prepared by adopting impregnation method3The catalyst S (1) prepared for the aluminum source has similar Al content, and the comparison shows that the catalyst S (6) has slightly lower catalytic activity than the catalyst S (1), and the corresponding butene yield is lower. But the preparation method is simpler, so that the catalyst S (6) has a great application prospect. When comparing the catalyst S (6) with the catalysts B (9) to B (13), it is understood that catalysts prepared using different aluminum sources have different catalytic activities when the Al content is the same. The aluminum source also influences the performance of the catalyst prepared by the solid phase grinding method, and an aluminum-containing compound AlCl is adopted3The catalyst S (6) prepared by taking the aluminum source has the best performance for the reaction of preparing butylene by decarboxylation of gamma-valerolactone.
Example 27 test for cyclic regeneration of catalyst obtained in example 1
The catalyst obtained in example 1 was measured for catalytic activity by the method described in example 25, but after the test, the catalyst after the reaction was collected and activated for 1 hour under a tubular furnace air flow at 600 ℃, and then the above-mentioned activity test operation was repeated to conduct a cyclic reaction test. The results are shown in FIG. 2.
As can be seen from FIG. 2, the catalyst S (1) can still maintain the yield of butene of more than 80% after 5 times of cyclic tests, and can also maintain the yield of butene of more than 62% after 9 times of cyclic reactions, which indicates that the catalyst has good stability and has the prospect of industrial production.
Example 28N of catalysts obtained in examples 1 to 5 and comparative example 12Physical adsorption assay
The catalysts S (1) -S (5) and B (1) obtained in examples 1, 2, 3, 4, 5 and comparative example 1 were selected for N2Adsorption-desorption isotherms and pore size distribution curves were determined as shown in figure 3. As shown in FIG. 3 (A), the catalystS (1) -S (5) have IV-type adsorption-desorption isotherms and H1-type hysteresis loops similar to those of the catalyst B (1) (pure KIT-6), which shows that the catalysts S (1) -S (5) and B (1) have good mesoporous structures, and the introduction of the aluminum source does not cause great damage to the mesoporous structures of the catalysts. When the Al content in the catalyst was increased from 0 to 5 wt.%, the specific surface areas of the catalysts B (1), S (2), S (1), S (3), S (4) and S (5) were found to be from 673.22m as calculated by the BET method2·g-1Reduced to 574.61m2·g-1. As shown in fig. 3 (B), the pore size distributions of catalysts B (1) and S (1) -S (5) are typical mesoporous pore size distributions, and the pore size distributions are narrow. The total pore volume of the four catalysts calculated according to the BJH model is from 0.92m3·g-1Reduced to 0.78m3·g-1The pore diameter is 5.6 nm.
Claims (10)
1. A solid acid catalyst is characterized in that the solid acid catalyst is Al-KIT-6 formed by taking KIT-6 mesoporous molecular sieve as a matrix and introducing Al into the framework of the KIT-6 mesoporous molecular sieve; wherein, the Al atomic mass is 1-10% of the mass of KIT-6 mesoporous molecular sieve.
2. The solid acid catalyst according to claim 1, wherein the solid acid catalyst has a pore size of 4.5 to 7.6nm and a specific surface area of 440.22 to 820.64m2·g-1The total pore volume is 0.74-1.20 cm3·g-1。
3. A method of preparing a solid acid catalyst as claimed in claim 1 or 2, characterized in that the method comprises:
1) preparation of KIT-6 mesoporous molecular sieve: adding P123 template agent to H2O and concentrated hydrochloric acid solution, and stirring vigorously until P123 is completely dissolved; slowly dropwise adding n-butyl alcohol, reacting for 1h in a water bath at 35 ℃, then slowly dropwise adding tetraethyl orthosilicate, and continuously stirring and reacting for 24h in the water bath at 35 ℃; transferring the obtained reaction mixture into an autoclave, and carrying out hydrothermal treatment at 95 ℃ for 24 h; filtering, washing, drying, and finally roasting at 550 ℃ for 8h to obtain KIT-6 mesoporousA molecular sieve;
2) preparation of Al-KIT-6: mixing an aluminum-containing compound with a KIT-6 mesoporous molecular sieve by an impregnation method or a solid phase grinding method at room temperature, and finally calcining at 550 ℃ for 5 hours to obtain a target product.
4. The method according to claim 3, wherein in step 2), the impregnation method is: dissolving an aluminum-containing compound in a solvent by magnetic stirring at room temperature, adding a KIT-6 mesoporous molecular sieve under stirring, stirring for 4h, placing in a water bath at 60 ℃, evaporating the solvent to dryness, drying the obtained product, and calcining at 550 ℃ for 5h to obtain Al-KIT-6.
5. The method according to claim 3, wherein in step 2), the solid phase milling method is: at room temperature, after an aluminum-containing compound is fully subjected to solid phase grinding in an agate mortar, a KIT-6 mesoporous molecular sieve is added, no or a small amount of solvent is added, solid phase grinding is continued at room temperature until the mixture is uniformly mixed, and the obtained product is calcined for 5 hours at 550 ℃ to obtain Al-KIT-6.
6. The method of claim 3, 4 or 5, wherein the aluminum-containing compound is selected from AlCl3、AlCl3·6H2O、Al(NO3)3·9H2O、Al2O3、Al2(SO4)3And C9H21AlO3。
7. The method according to claim 4 or 5, wherein the solvent is one or two of methanol, ethanol, and water.
8. The preparation method according to claim 3, 4 or 5, wherein the aluminum-containing compound, KIT-6 mesoporous molecular sieve, is 0.02-0.67: 1 by mass ratio.
9. Use of the solid acid catalyst of claim 1 or 2 for catalyzing the decarboxylation of gamma valerolactone to butene.
10. The application of the gamma-valerolactone and the solid acid catalyst are added into a high-temperature high-pressure reaction kettle, nitrogen is filled into the reaction kettle for protection, and then the reaction is carried out at the normal pressure and the temperature of 260-350 ℃; preferably, the mass ratio of the gamma-valerolactone to the solid acid catalyst is 1: 0.05-0.15.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210372495.5A CN114618559A (en) | 2022-04-11 | 2022-04-11 | Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210372495.5A CN114618559A (en) | 2022-04-11 | 2022-04-11 | Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114618559A true CN114618559A (en) | 2022-06-14 |
Family
ID=81905780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210372495.5A Pending CN114618559A (en) | 2022-04-11 | 2022-04-11 | Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114618559A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115155553A (en) * | 2022-08-03 | 2022-10-11 | 辽宁大学 | Preparation method of amorphous aluminosilicate solid acid catalyst and application of amorphous aluminosilicate solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150005558A1 (en) * | 2013-06-27 | 2015-01-01 | Wisconsin Alumni Research Foundation | Selective catalytic production of linear alpha olefins from lactones and unsaturated carboxylic acids |
CN107930674A (en) * | 2017-10-17 | 2018-04-20 | 太原理工大学 | A kind of catalyst and preparation method and application for preparing dimethyl carbonate |
-
2022
- 2022-04-11 CN CN202210372495.5A patent/CN114618559A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150005558A1 (en) * | 2013-06-27 | 2015-01-01 | Wisconsin Alumni Research Foundation | Selective catalytic production of linear alpha olefins from lactones and unsaturated carboxylic acids |
CN107930674A (en) * | 2017-10-17 | 2018-04-20 | 太原理工大学 | A kind of catalyst and preparation method and application for preparing dimethyl carbonate |
Non-Patent Citations (1)
Title |
---|
周一思等: ""乙醇-盐酸辅助脱模制备Ni/Al-KIT-6介孔催化剂及其正庚烷异构性能"", 《石油学报(石油加工)》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115155553A (en) * | 2022-08-03 | 2022-10-11 | 辽宁大学 | Preparation method of amorphous aluminosilicate solid acid catalyst and application of amorphous aluminosilicate solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Catalytic conversion of glucose to 5-hydroxymethylfurfural over nano-sized mesoporous Al2O3–B2O3 solid acids | |
WO2018171251A1 (en) | Solid-supported metalloporphyrin catalyst and application thereof in preparation of maleic acid | |
CN105968075B (en) | A kind of method that photochemical catalytic oxidation HMF prepares DFF | |
CN110385142B (en) | Catalyst for isobutane normal structuring reaction and preparation method and application thereof | |
CN103143381B (en) | Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method | |
CN113101964B (en) | Mesoporous cerium oxide photocatalyst and preparation method and application thereof | |
CN111875566A (en) | Method for preparing 2, 5-dimethylfuran | |
CN114618559A (en) | Solid acid catalyst, preparation method thereof and application of solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation | |
Liu et al. | Gold and silver nanoparticles supported on metal-organic frameworks: A highly active catalyst for three-component coupling reaction | |
CN112958146B (en) | MFI molecular sieve nanosheet-loaded zirconium-based catalyst and application thereof in butadiene preparation reaction | |
CN100402485C (en) | Method for reaction rectification coupling continuous preparation of and series acetate | |
CN111978516B (en) | Preparation and catalytic application of donor-acceptor type ion porous polymer | |
CN111203267B (en) | Solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, and preparation method and application thereof | |
CN115155553A (en) | Preparation method of amorphous aluminosilicate solid acid catalyst and application of amorphous aluminosilicate solid acid catalyst in catalyzing decarboxylation of gamma-valerolactone to butene preparation | |
CN110240197B (en) | Ultrathin nanosheet self-assembled multilayer BiOCl microsphere and application thereof in photocatalytic coupling of benzylamine to imine | |
CN104310413B (en) | A kind of preparation method and application preparing the thin layer nano-sheet silica zeolite of hexanolactam | |
CN106866985B (en) | A kind of metal-organic framework materials and preparation method thereof separated for acetylene and methane adsorption | |
Li et al. | Preparation of 5-hydroxymethylfurfural using magnetic Fe 3 O 4@ SiO 2@ mSiO 2-TaOPO 4 catalyst in 2-pentanol | |
CN103709010A (en) | Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water | |
CN114011467A (en) | Mercaptopropionic acid-linked titanium dioxide covalent organic framework composite material and preparation method and application thereof | |
CN114405538A (en) | Hierarchical pore Fe/ZSM-5 molecular sieve and preparation method and application thereof | |
CN114797949B (en) | Solid acid catalyst based on MCM-41 mesoporous molecular sieve, and preparation method and application thereof | |
Gu et al. | PPRODUCTION OF AROMATIC ALDEHYDE BY MICROWAVE CATALYTIC OXIDATION OF A LIGNIN MODEL COMPOUND WITH La-CONTAINING SBA-15/H2O2 SYSTEMS | |
CN108946751B (en) | Preparation method and application of boron hexa-oxygen | |
CN103570071A (en) | Method for preparing mesoporous manganese-aluminum spinel material by using simple dual-template agent |
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 |