CN112973746A - Preparation method of supported vanadium phosphorus oxygen catalyst, catalyst prepared by preparation method and application of catalyst - Google Patents
Preparation method of supported vanadium phosphorus oxygen catalyst, catalyst prepared by preparation method and application of catalyst Download PDFInfo
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- CN112973746A CN112973746A CN201911294622.9A CN201911294622A CN112973746A CN 112973746 A CN112973746 A CN 112973746A CN 201911294622 A CN201911294622 A CN 201911294622A CN 112973746 A CN112973746 A CN 112973746A
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- acetic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 307
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 219
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
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- 239000004005 microsphere Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000012159 carrier gas Substances 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 239000012018 catalyst precursor Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000006004 Quartz sand Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002149 hierarchical pore Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 22
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000012876 carrier material Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 37
- 239000000203 mixture Substances 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 238000006482 condensation reaction Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- JCGCKSUCGVTMNB-UHFFFAOYSA-N acetic acid;formaldehyde Chemical compound O=C.CC(O)=O JCGCKSUCGVTMNB-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 239000007790 solid phase Substances 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
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- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- 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
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a supported vanadium phosphorus oxygen catalyst for preparing acrylic acid and methyl acrylate by condensing acetic acid and formaldehyde, and a preparation method and application thereof, wherein ammonium metavanadate is used as a vanadium source, phosphoric acid is used as a phosphorus source, and water is used as a solvent medium, and the supported vanadium phosphorus oxygen catalyst is loaded on a silicon-based carrier material (MCM-41, SBA-15, gas-phase SiO by a simple deposition method2And hierarchical porous SiO2Microspheres) and then calcined under air atmosphere to obtain the final catalyst. The dispersion state, the surface phosphorus-vanadium ratio and the vanadium valence of active species of the catalyst are regulated and controlled by controlling the type of the carrier, the vanadium-phosphorus loading capacity and preparation parameters, so that the acidity-basicity and the catalytic reaction performance of the surface of the catalyst are regulated and controlled. The invention is applied to acetic acidThe catalyst for preparing acrylic acid (ester) by formaldehyde condensation has the advantages of simple preparation, green and environment-friendly process (no use of a large amount of organic solvent or corrosive strong acid), high catalytic efficiency and less by-products, and the selectivity of a target product (acrylic acid and methyl acrylate) based on fed acetic acid is 90 percent.
Description
Technical Field
The invention relates to a supported vanadium phosphorus oxygen catalyst, a preparation method thereof and application thereof in preparing acrylic acid (ester) by condensation reaction of acetic acid and formaldehyde.
Background
Acrylic acid is an important basic chemical raw material, and is widely applied to synthesis of various chemicals and production of various resins. The industrial production process of acrylic acid mainly comprises a chlorohydrin method, a cyanoethanol method, a Reppe method, an ketene method, an acrylonitrile hydrolysis method, a propylene two-step oxidation method and a propane one-step oxidation method in sequence. The most widely used process for the production of acrylic acid in industry today is the two-step oxidation of propylene, accounting for about 85% of the total yield of acrylic acid.
The above-described processes are all based on petrochemical feedstocks. Combining the current energy structure situation of rich coal, poor oil and less gas in China, people are prompted to actively research and explore a new way for preparing acrylic acid. The route for preparing acrylic acid by reacting acetic acid, a downstream product of bulk coal chemical industry, with formaldehyde has attracted extensive attention and is one of the most promising approaches for solving the problem of acrylic acid production in the near future. At present, the method for preparing acrylic acid by reacting acetic acid and formaldehyde is still in a laboratory stage, and mainly aims at improving the performance of a catalyst. The reactants of the invention are limited to acetic acid instead of acetate except formaldehyde, and the acetic acid is used as the reactant, so that the requirement on the catalyst is higher.
Vanadium phosphorus oxide catalyst or VPO catalyst is one of the most complex catalysts. It is well known that the structure, composition and catalytic performance are greatly influenced by the preparation chemistry, including the kind of solvent/reducing agent, the amount added, the temperature of calcination activation and the carrier. The addition of the carrier in the preparation process of the catalyst can adjust the appearance and crystallinity of the catalyst, the reactivity of lattice oxygen and the surface V5+/V4+Ratios, etc., thereby significantly altering the reaction behavior of the catalyst. The classical preparation method of VPO catalyst is an organic phase reduction method, which firstly carries out V2O5Reducing into V in benzyl alcohol or benzyl alcohol/isobutyl alcohol mixed organic solvent4 +Then adding phosphoric acid as a phosphorus source to prepare a catalyst precursor VOHPO4·0.5H2The VPO catalyst prepared by the method has the characteristics of controllable phase and high conversion rate to target reaction, but has sensitive property, harsh preparation conditions, high cost (reduction temperature is 140 ℃, organic matter is used as a solvent), and safety consideration in the preparation process (so that the VPO catalyst with different phases is obtained by activating the precursor in different atmospheres)Using a butane-containing mixed gas as the activating gas), and the like. Therefore, the invention provides a preparation method of a supported vanadium phosphorus oxygen catalyst, which comprises the following specific steps: firstly, dissolving ammonium metavanadate in a certain amount of deionized water, then adding phosphoric acid serving as a phosphorus source according to a measured P/V ratio, reacting for a certain time, evaporating water to obtain a supported catalyst precursor, and finally roasting and activating in a flowing air atmosphere to obtain a corresponding catalyst. The preparation method used in the invention has the advantages of simple process, no use of a large amount of organic solvents or additives, environmental protection and the like.
In the present invention, the catalyst precursor is deposited on a silicon-based carrier having a large specific surface area and various pore structures, including MCM-41, SBA-15, gas phase SiO by a simple process2Or hierarchical porous SiO2The microsphere (Silica-HP) can simultaneously regulate the dispersion state of VPO species, the P/V ratio of the catalyst, the valence state of vanadium species and the acidity and alkalinity of the surface of the catalyst, thereby obviously regulating the catalytic performance of the catalyst on target reaction.
The silicon-based carrier has the following characteristics:
MCM-41 is a silicon oxide with two-dimensional regular hexagonal pore canals and large specific surface area (>800m2In terms of/g), the pore size distribution is narrow (3-5 nm).
SBA-15 is silicon oxide with two-dimensional regular hexagonal pore canals, and the specific surface area of the silicon oxide is 500-600m2In terms of/g) and a pore size distribution of 6 to 11 nm.
Gas phase SiO2Is a compound with a large specific surface area (400 m)2Silica in a specific proportion/g) without an inner pore structure.
Hierarchical porous SiO2The microspheres (Silica-HP) are Silica microspheres with a hierarchical pore distribution and a specific surface area of 166m2The particle size is 3-5 μm, and the pore size distribution is wide (0.5-60 nm).
Disclosure of Invention
The invention is based on aldol condensation reaction, takes acetic acid and formaldehyde (formalin) as raw materials, uses a supported VPO catalyst, and prepares acrylic acid and methyl acrylate through one-step reaction. The reaction can be realized at a lower temperature, and reactants are chemical raw materials with low cost. Based on the difference of the specific surface area and the pore structure of the silicon-based carrier, the invention mainly aims at changing the VPO loading capacity and the dispersion state and regulating and controlling the P/V ratio of the surface of the catalyst, the valence state of vanadium species and the acidity and alkalinity of the surface of the catalyst by selecting different carrier materials, thereby obviously regulating and controlling the performance of the catalyst.
The technical scheme of the invention is as follows:
a process for the preparation of a supported VPO catalyst comprising the steps of:
step 1, dissolving 1 part by mass of ammonium metavanadate in 34-43 parts by mass of deionized water, and adding one of the following silicon-based carriers according to different silicon-phosphorus molar ratios (0-9): MCM-41, SBA-15, gas phase SiO2(fumed silica) or hierarchical pore SiO2Microsphere (Silica-HP)]Stirring for 6H, adding 85% phosphoric acid (H) according to the molar ratio of phosphorus to vanadium of 13PO4) Continuously stirring for 10-60 min, and evaporating water from the obtained suspension to obtain a supported catalyst precursor;
step 2. activation of catalyst precursor: and (2) heating the catalyst precursor from room temperature to 400 ℃ at the heating rate of 2-10 ℃/min in a flowing air atmosphere (60-150 mL/min), and keeping the temperature at 400 ℃ for 10-16h to obtain a corresponding supported catalyst: VPO/MCM-41, VPO/SBA-15, VPO/fumed SiO2Or VPO/Silica-HP.
The results of the invention show that the change of the carrier, the change of the loading amount and the change of the activation atmosphere have the effects on the phase composition, the surface P/V ratio and the surface V of the catalyst5+/V4+The ratio and the acidity and alkalinity of the catalyst have obvious influence, and the influence on the reaction behavior of the catalyst is obvious.
A supported VPO catalyst prepared according to the catalyst preparation method described above.
The supported VPO catalyst is applied to the preparation of acrylic acid (ester) by condensing acetic acid and formaldehyde.
The method for preparing acrylic acid (ester) by condensing acetic acid and formaldehyde by using the supported VPO catalyst is characterized in that the reaction temperature is 360 ℃, the reaction liquid consists of acetic acid and formaldehyde (formalin), the molar ratio of the acetic acid to the formaldehyde is 2-3: 1, and the sample injection rate of liquid-phase reactants is 6.1-24.4 mmol/h-1The method comprises the following steps of (calculated by formaldehyde), taking oxygen as a carrier gas, namely 2.3-6.8 vol.% of mixed gas of nitrogen, controlling the flow rate of the carrier gas to be 30-50 mL by a mass flow meter, introducing the mixed gas into a reactor, injecting a liquid-phase material into the reactor by a sample injection pump, preheating the carrier gas and a liquid-phase reactant through a quartz sand layer at the front section of a catalyst bed layer, gasifying the liquid-phase reactant, mixing, and then introducing the mixture into the catalyst bed layer for reaction to obtain the acrylic acid and methyl acrylate products.
The catalyst applied to the preparation of acrylic acid (ester) by acetic acid-formaldehyde condensation has the advantages of simple preparation, green and environment-friendly process (no use of a large amount of organic solvent or corrosive strong acid), high catalytic efficiency and less byproducts, and the selectivity of a target product (acrylic acid and methyl acrylate) based on the fed acetic acid is 90 percent.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
3.51g of ammonium metavanadate is dissolved in 150g of deionized water, stirred for 6 hours, added with 85 percent of phosphoric acid according to the P/V molar ratio of 1, continuously stirred for 20 minutes, and rotated and evaporated to dryness to obtain the catalyst precursor. Tabletting and crushing the precursor into particles of 20-40 meshes, putting 3.00g of the precursor into a fixed bed reaction tube with the diameter of 20mm, adding 5.0g of quartz sand, raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in an air atmosphere of 60mL/min, and maintaining for 16 hours to obtain the unsupported VPO catalyst (the Si/P molar ratio is 0) applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The above calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at normal pressure, with 2.3 vol.% oxygen/nitrogen as a reaction carrier gas, with a mixture of acetic acid and formaldehyde (provided by formalin) (molar ratio 2.5:1) as a reaction material, with a sample rate of 6.1mmol/h (based on formaldehyde), a carrier gas flow rate of 40.0mL/min, and after 2.5 hours, sampling analysis showed that the yield of the target product (acrylic acid + methyl acrylate) was 37.5% (based on formaldehyde) and the selectivity was 81.4% (based on acetic acid).
Example 2
2.34g of ammonium metavanadate is dissolved in 100g of deionized water, SBA-15 is added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 30 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 33% -VPO/SBA-15 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 4.5 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 3:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 61.1% (based on formaldehyde) and the selectivity was 71.0% (based on acetic acid).
Example 3
2.34g of ammonium metavanadate is dissolved in 100g of deionized water, porous silicon oxide microspheres (Silica-HP) are added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 20 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere of 150mL/min, and maintaining for 16 hours to obtain the 33% -VPO/Silica-HP catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample rate of 18.3mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 51.0% (based on formaldehyde) and the selectivity was 89.8% (based on acetic acid).
Example 4
2.81g of ammonium metavanadate is dissolved in 120g of deionized water, stirred for 6 hours, added with 85 percent of phosphoric acid according to the P/V molar ratio of 1, continuously stirred for 20 minutes, and rotated and evaporated to dryness to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. The temperature is raised to 400 ℃ at the temperature raising rate of 2 ℃/min in 150mL/min air atmosphere, and the temperature is maintained for 16h, so that the unsupported VPO catalyst (the Si/P molar ratio is 0) applied to the preparation of acrylic acid (ester) by the condensation of acetic acid and formaldehyde is obtained.
The above calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at normal pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample introduction of 18.3mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 39.8% (based on formaldehyde) and a selectivity of 90.5% (based on acetic acid).
Example 5
2.34g of ammonium metavanadate is dissolved in 80g of deionized water, SBA-15 is added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 60 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere of 150mL/min, and maintaining for 16 hours to obtain the 33% -VPO/SBA-15 catalyst applied to the preparation of acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 2.3 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 53.4% (based on formaldehyde) and the selectivity was 55.9% (based on acetic acid).
Example 6
3.98g of ammonium metavanadate is dissolved in 170g of deionized water, MCM-41 is added according to the Si/P molar ratio of 2, the mixture is continuously stirred for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, the mixture is continuously stirred for 40min, and the catalyst precursor is obtained by rotary evaporation. Tabletting and crushing the precursor into 20-40 mesh particles, loading 3.00g of the precursor into a fixed bed reaction tube with the diameter of 20mm, and adding a certain amount of quartz sand. Raising the temperature to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere of 150mL/min, and maintaining for 10h to obtain the 33% -VPO/MCM-41 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 1.1 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 3:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 62.3% (based on formaldehyde) and the selectivity was 67.9% (based on acetic acid).
Example 7
2.34g of ammonium metavanadate was dissolved in 90g of deionized water, and fumed SiO was added in a Si/P molar ratio of 22And continuously stirring for 6 hours, adding 85% phosphoric acid according to the molar ratio of P/V of 1, continuously stirring for 20min, and rotationally evaporating to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere of 150mL/min, and maintaining for 16 hours to obtain 33% -VPO/fumed SiO applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde2A catalyst.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample rate of 18.3mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 39.5% (based on formaldehyde) and a selectivity of 83.4% (based on acetic acid).
Example 8
2.34g of ammonium metavanadate is dissolved in 100g of deionized water, MCM-41 is added according to the Si/P molar ratio of 1, the mixture is continuously stirred for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, the mixture is continuously stirred for 30 minutes, and the catalyst precursor is obtained by rotary evaporation. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 15 hours to obtain the 50% -VPO/MCM-41 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 2.3 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2.5:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 35.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 70.1% (based on formaldehyde) and the selectivity was 70.4% (based on acetic acid).
Example 9
2.34g of ammonium metavanadate is dissolved in 100g of deionized water, MCM-41 is added according to the Si/P molar ratio of 2, the mixture is continuously stirred for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, the mixture is continuously stirred for 20 minutes, and the catalyst precursor is obtained by rotary evaporation. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 33% -VPO/MCM-41 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 6.8 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2.5:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 70.1% (based on formaldehyde) and a selectivity of 49.3% (based on acetic acid).
Example 10
2.50g of ammonium metavanadate is dissolved in 95g of deionized water, SBA-15 is added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 30 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 33% -VPO/SBA-15 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 6.8 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 3:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde) and a carrier gas flow rate of 50.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of 68.4% (based on formaldehyde) and a selectivity of 43.2% (based on acetic acid) for the desired product (acrylic acid + methyl acrylate).
Example 11
2.34g of ammonium metavanadate is dissolved in 100g of deionized water, SBA-15 is added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 20 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 33% -VPO/SBA-15 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample rate of 12.2mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 66.9% (based on formaldehyde) and a selectivity of 70.1% (based on acetic acid)
Example 12
2.81g of ammonium metavanadate is dissolved in 120g of deionized water, stirred for 6 hours, added with 85 percent of phosphoric acid according to the P/V molar ratio of 1, continuously stirred for 20 minutes, and rotated and evaporated to dryness to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. The temperature is raised to 400 ℃ at the temperature raising rate of 2 ℃/min in the air atmosphere of 60mL/min, and the temperature is maintained for 16h, so that the unsupported VPO catalyst (the Si/P molar ratio is 0) applied to the preparation of acrylic acid (ester) by the condensation of acetic acid and formaldehyde is obtained.
The above calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at normal pressure, with 4.5 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 3:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde) and a carrier gas flow rate of 30.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 45.8% (based on formaldehyde) and the selectivity was 76.8% (based on acetic acid).
Example 13
2.58g of ammonium metavanadate was dissolved in 100g of deionized water, and fumed SiO was added in a Si/P molar ratio of 22And continuously stirring for 6 hours, adding 85% phosphoric acid according to the molar ratio of P/V of 1, continuously stirring for 20min, and rotationally evaporating to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the temperature rise rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain 33% -VPO/fumed SiO applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde2A catalyst.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 2.3 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2.5:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of 54.2% (based on formaldehyde) and a selectivity of 50.5% (based on acetic acid) for the desired product (acrylic acid + methyl acrylate).
Example 14
2.34g of ammonium metavanadate was dissolved in 100g of deionized water, and fumed SiO was added in a Si/P molar ratio of 22And continuously stirring for 6 hours, adding 85% phosphoric acid according to the molar ratio of P/V of 1, continuously stirring for 30min, and rotationally evaporating to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the temperature rise rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain 33% -VPO/fumed SiO applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde2A catalyst.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample rate of 18.3mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 32.6% (based on formaldehyde) and a selectivity of 75.7% (based on acetic acid).
Example 15
3.04g of ammonium metavanadate is dissolved in 120g of deionized water, porous silicon oxide microspheres (Silica-HP) are added according to the Si/P molar ratio of 9, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 30 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 10% -VPO/Silica-HP catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 2.3 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2.5:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 30.0 mL/min. After 2.5 hours, a sample was taken and analyzed, and the yield of the desired product (acrylic acid + methyl acrylate) was 45.6% (based on formaldehyde) and the selectivity was 47.5% (based on acetic acid).
Example 16
3.75g of ammonium metavanadate is dissolved in 150g of deionized water, porous silicon oxide microspheres (Silica-HP) are added according to the Si/P molar ratio of 4, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 50 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 12 hours to obtain the 20% -VPO/Silica-HP catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 2.3 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 2.5:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of the desired product (acrylic acid + methyl acrylate) of 60.5% (based on formaldehyde) and a selectivity of 56.1% (based on acetic acid).
Example 17
2.34g of ammonium metavanadate is dissolved in 90g of deionized water, SBA-15 is added according to the Si/P molar ratio of 2, stirring is continued for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, stirring is continued for 30 minutes, and rotary evaporation is carried out to obtain the catalyst precursor. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at a heating rate of 10 ℃/min in an air atmosphere of 150mL/min, and maintaining for 16 hours to obtain the 33% -VPO/SBA-15 catalyst applied to the preparation of acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with a reaction carrier gas of 3.9 vol.% oxygen/nitrogen, with a reaction mass of acetic acid-formaldehyde (provided by formalin) mixture (molar ratio 2.5:1), with a sample rate of 24.4mmol/h (based on formaldehyde), and a carrier gas flow rate of 40.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of 50.2% (based on formaldehyde) and a selectivity of 79.4% (based on acetic acid) for the desired product (acrylic acid + methyl acrylate).
Example 18
4.21g of ammonium metavanadate is dissolved in 150g of deionized water, MCM-41 is added according to the Si/P molar ratio of 2, the mixture is continuously stirred for 6 hours, 85 percent phosphoric acid is added according to the P/V molar ratio of 1, the mixture is continuously stirred for 40min, and the catalyst precursor is obtained by rotary evaporation. The precursor is tabletted and crushed into 20-40 mesh particles, 3.00g of the precursor is loaded into a fixed bed reaction tube with the diameter of 20mm, and 5.0g of quartz sand is added. Raising the temperature to 400 ℃ at the heating rate of 2 ℃/min in 60mL/min air atmosphere, and maintaining for 16h to obtain the 33% -VPO/MCM-41 catalyst applied to preparing acrylic acid (ester) by condensing acetic acid and formaldehyde.
The calcined catalyst was directly subjected to a gas-solid phase condensation reaction of acetic acid and formaldehyde in a fixed bed reactor at 360 ℃, at atmospheric pressure, with 4.5 vol.% oxygen/nitrogen as reaction carrier gas, with a mixture of acetic acid-formaldehyde (provided by formalin) (molar ratio 3:1) as reaction feed, at a sample rate of 6.1mmol/h (based on formaldehyde), and at a carrier gas flow rate of 50.0 mL/min. After 2.5 hours, a sample was taken and analyzed, giving a yield of 49.7% (based on formaldehyde) and a selectivity of 69.6% (based on acetic acid) for the desired product (acrylic acid + methyl acrylate).
Claims (5)
1. A preparation method of a supported VPO catalyst is characterized by comprising the following steps:
step 1, dissolving 1 part by mass of ammonium metavanadate in 34-43 parts by mass of deionized water, and adding one of the following silicon-based carriers according to different silicon-phosphorus molar ratios (0-9): MCM-41, SBA-15, gas phase SiO2(fumed silica) or hierarchical pore SiO2Microsphere (Silica-HP)]Stirring for 6H, adding 85% phosphoric acid (H) according to the molar ratio of phosphorus to vanadium of 13PO4) Continuously stirring for 10-60 min, and evaporating water from the obtained suspension to obtain a supported catalyst precursor;
step 2. activation of catalyst precursor: heating the catalyst precursor from room temperature to 400 ℃ at a heating rate of 2-10 ℃/min in a flowing air atmosphere of 60-150 mL/min, and keeping the temperature at 400 ℃ for 10-16h to obtain a corresponding supported catalyst: VPO/MCM-41, VPO/SBA-15, VPO/fumed SiO2Or VPO/Silica-HP.
2. A supported VPO catalyst prepared according to the supported VPO catalyst preparation method of claim 1.
3. Use of the supported VPO catalyst of claim 2 in the condensation of acetic acid and formaldehyde to make acrylic acid (esters).
4. A method for preparing acrylic acid (ester) by condensing acetic acid and formaldehyde by using the supported VPO catalyst of claim 2, which is characterized by comprising the following steps: the method is characterized in that at the reaction temperature of 360 ℃, the reaction liquid consists of acetic acid and formaldehyde aqueous solution, the molar ratio of the acetic acid to the formaldehyde aqueous solution is 2-3: 1, and the sample injection rate of liquid-phase reactants is 6.1-24.4 mmol/h in terms of formaldehyde-1The carrier gas is mixed gas of 2.3-6.8 vol.% of nitrogen, the flow rate of the carrier gas is 30-50 mL, the mixed gas is controlled by a mass flow meter to be introduced into the reactor, liquid-phase materials are injected into the reactor by a sample injection pump, the carrier gas and the liquid-phase reactants enter the catalyst bed layer for reaction after being preheated by a quartz sand layer at the front section of the catalyst bed layer, gasified and mixed, and then the acrylic acid and methyl acrylate products are prepared.
5. The process for producing acrylic acid (ester) by condensing acetic acid with formaldehyde according to claim 4, wherein: the formaldehyde aqueous solution is formalin.
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| CN113457700A (en) * | 2021-06-24 | 2021-10-01 | 浙江大学 | Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof |
| CN114210352A (en) * | 2022-01-24 | 2022-03-22 | 吉林大学 | Preparation method and application of transition metal doped aluminum phosphate catalyst |
| CN114394893A (en) * | 2022-01-06 | 2022-04-26 | 北京大学 | Method for directly preparing acrylic acid from methyl acetate and catalyst |
| CN115888777A (en) * | 2022-10-27 | 2023-04-04 | 潍坊科技学院 | Enhanced modified VPO catalyst and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113457700A (en) * | 2021-06-24 | 2021-10-01 | 浙江大学 | Vanadium-phosphorus-oxygen catalyst for aldol condensation and preparation method and application thereof |
| CN114394893A (en) * | 2022-01-06 | 2022-04-26 | 北京大学 | Method for directly preparing acrylic acid from methyl acetate and catalyst |
| CN114210352A (en) * | 2022-01-24 | 2022-03-22 | 吉林大学 | Preparation method and application of transition metal doped aluminum phosphate catalyst |
| CN114210352B (en) * | 2022-01-24 | 2024-03-22 | 吉林大学 | Preparation method and application of transition metal doped aluminum phosphate catalyst |
| CN115888777A (en) * | 2022-10-27 | 2023-04-04 | 潍坊科技学院 | Enhanced modified VPO catalyst and preparation method and application thereof |
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