CN112517031A - Acrylic acid catalyst and preparation method and application thereof - Google Patents
Acrylic acid catalyst and preparation method and application thereof Download PDFInfo
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 40
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 40
- 239000004964 aerogel Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 17
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 90
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000009834 vaporization Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000010574 gas phase reaction Methods 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 28
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 229910020881 PMo12O40 Inorganic materials 0.000 description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000247 superabsorbent polymer Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000126 substance Substances 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
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an acrylic acid catalyst and a preparation method thereof. The catalyst takes anhydrous phosphotungstic acid or anhydrous phosphomolybdic acid as an active component,SiO2the catalyst comprises aerogel serving as a carrier, wherein the active component accounts for 10-30 wt% of the total mass of the catalyst, and the particle size is 20-40 meshes. The preparation method comprises the following steps: adding hydrous phosphotungstic acid or hydrous phosphomolybdic acid into distilled water until the solution is completely dissolved, and adding the obtained solution into SiO2Dipping the aerogel, stirring at room temperature until the aerogel is completely dipped, evaporating to remove redundant water, drying at 110-130 ℃, grinding, roasting at 350-550 ℃, tabletting and screening. The catalyst is environment-friendly, can keep the advantages of high activity and high selectivity at low temperature, and has better catalytic activity and higher selectivity; the preparation method has simple and rapid process, has strong capability of depositing the precursor under the condition that the catalyst has high loading capacity, and is suitable for large-scale preparation.
Description
Technical Field
The invention relates to an acrylic acid catalyst, a preparation method and application thereof, and belongs to the field of organic catalysis.
Background
Acrylic acid and its esters have unsaturated double bonds, and thus it is an important organic synthesis intermediate. It can be widely used in high molecular products, such as raw materials for producing water-soluble acrylate coating, Super Absorbent Polymer (SAP), adhesive, detergent and fiber. The method for synthesizing acrylic acid comprises an acetylene carbonylation method, a glycerol oxidation dehydration method and a propylene oxidation method. Among them, the technique of the propylene oxidation method is widely used in industrial production in various countries. However, propylene is expensive as a raw material for acrylic acid production and propylene is extracted from crude oil. Therefore, the process for synthesizing acrylic acid by the propylene oxidation method has high cost. On the other hand, because acetic acid and formaldehyde are easily available and mainly come from coal chemical products, the acetic acid and the formaldehyde conform to the national conditions of rich and poor coal in China, and the production cost can be reduced by synthesizing acrylic acid by using the aldol condensation reaction of the acetic acid and the formaldehyde. However, the preparation process of the catalyst used for synthesizing acrylic acid and esters thereof by formaldehyde and acetic acid is complex, the cost is high, and the yield of some catalysts is low.
Disclosure of Invention
An object of the present invention is to provide an acrylic acid catalyst. The specific technical scheme is as follows:
an acrylic acid catalyst is prepared from anhydrous phosphotungstic acid or anhydrous phosphomolybdic acid as active component and SiO2The catalyst comprises aerogel serving as a carrier, wherein the active component accounts for 10-30% of the total mass of the catalyst, and the particle size is 20-40 meshes.
The invention also aims to provide a preparation method of the acrylic acid catalyst. The specific technical scheme is as follows:
the preparation method of the acrylic acid catalyst comprises the following steps: weighing hydrated phosphotungstic acid or hydrated phosphomolybdic acid and SiO according to the weight of the anhydrous phosphotungstic acid or anhydrous phosphomolybdic acid accounting for 10-30 wt% of the total weight of the catalyst2Adding hydrous phosphotungstic acid or hydrous phosphomolybdic acid into distilled water until the solution is completely dissolved, and adding the obtained solution into SiO2Soaking in aerogel, stirring at room temperature until the aerogel is completely soaked, then evaporating to remove excessive water, drying the obtained product at 110-130 ℃ for 18-36 h, grinding, roasting at 350-550 ℃ for 2-5 h, tabletting under the pressure of 7-10 MPa, and sieving with a 20-40 mesh sieve to obtain the acrylic acid catalyst.
Preferably, the mass volume ratio of the hydrated phosphotungstic acid or the hydrated phosphomolybdic acid to the distilled water is 60-90 g: 1L.
Preferably, the stirring time at room temperature is 3-6 h.
Preferably, during the drying process, the product surface is continuously stirred before being dried.
The third purpose of the invention is to provide the application of the acrylic acid catalyst. The specific technical scheme is as follows:
the acrylic acid catalyst is applied to catalyzing formaldehyde and acetic acid to synthesize acrylic acid and ester thereof.
Preferably, the method of the specific application comprises the following steps: introducing trioxymethylene and acetic acid into a 280 ℃ vaporization chamber according to the molar ratio of 1:9, and carrying out gas phase reaction through a continuous fixed bed reactor loaded with the acrylic acid catalyst after vaporization, wherein the reaction temperature is 340-400 ℃.
More preferably, the fixed bed reactor is 20cm long and 0.5cm in inner diameter, quartz wool is placed in the fixed bed reaction tube, the injection flow rate of trioxymethylene and acetic acid is 8.4g/h, and the carrier gas N is2The flow rate was 20mL/min and the reaction was carried out at normal pressure.
The invention has the beneficial effects that:
the acrylic acid catalyst prepared by the isometric impregnation method is an environment-friendly supported catalyst, can keep the advantages of high activity and high selectivity at low temperature, and has better catalytic activity and higher selectivity (for H)3PW12O40/SiO2The catalyst has the total yield of acrylic acid and methyl acrylate of 51.7 percent when the reaction temperature is 400 ℃; for H3PMo12O40/SiO2When the reaction temperature is 360 ℃, the total yield of acrylic acid and methyl acrylate can reach 48.29 percent), the problems of corrosion and pollution of acid catalytic reaction are solved, and the catalyst can be repeatedly used. The preparation method provided by the invention is simple and rapid in process, has strong capability of depositing the precursor under the condition that the catalyst has high loading capacity, and is suitable for large-scale preparation of the catalyst.
Detailed Description
The invention will be further illustrated with reference to specific examples:
examples 1 and H3PW12O40/SiO2Preparation and use of catalysts
Preparation of the catalyst
H3PW12O40/SiO2The catalyst is prepared by an impregnation method, firstly, hydrated phosphotungstic acid (H) is weighed3PW12O40·19H2O)3.3563g, adding 40mL of distilled water for dissolving, weighing 7g of SiO2Aerogel to ensure the SiO2The amount of the aerogel is 30 wt% of the total mass of the catalyst according to the mass of the hydrated phosphotungstic acid, and the aerogel is added into the weighed SiO when the hydrated phosphotungstic acid is completely dissolved2Stirring the aerogel carrier for 4 hours at room temperature, drying the aerogel carrier for 24 hours in a drying oven at the temperature of 120 ℃, and continuously stirring the aerogel carrier before surface drying. Fully grinding, then roasting in a muffle furnace at 450 ℃ for 3h, then tabletting under a tablet press at the pressure of 8MPa, and screening to obtain the 20-40 mesh catalyst.
The prepared catalyst is used for catalyzing the condensation reaction of formaldehyde and acetic acid aldol to synthesize acrylic acid and ester thereof.
The reaction is carried out in a miniature continuous fixed bed reactor, and raw materials are gasified and then enter the fixed bed reactor (with the length of 20cm and the inner diameter of 0.5cm) for reaction; h3PW12O40/SiO2The loading of the catalyst was 3g, the raw material was fed into the vaporization chamber of the fixed bed reactor at a mass flow rate of 8.4g/h under normal pressure, vaporized at 280 ℃ and then fed into the reactor for reaction, and a carrier gas (N) was maintained2) The flow rate was 20mL/min, the reaction temperatures were considered to be 340 deg.C, 360 deg.C, 380 deg.C, 400 deg.C, the samples were continuously taken at the given temperatures for 1h, the products were collected by condensation, the collected products were analyzed by Agilent GC-7890A gas chromatograph, and the test results are calculated and listed in Table 1.
TABLE 1.H3PW12O40/SiO2Catalyst (H)3PW12O40The loading amount is 30 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Note: the loading referred to in the present invention is the mass of active component/mass of catalyst. The yield of acrylic acid (ester) in the present invention (conversion rate x (selectivity for acrylic acid + selectivity for methyl acrylate)) is the total yield of acrylic acid and methyl acrylate.
Example 2, H3PW12O40/SiO2Preparation and use of catalysts
Same as example 1, H in the catalyst was changed3PW12O40The loading capacity is correspondingly adjusted to hydrate phosphotungstic acid and SiO2Mass of aerogel, H3PW12O40The loading amount is 20 wt%, the formaldehyde and the acetic acid are catalyzed to react, and the test result is shown in table 2.
TABLE 2.H3PW12O40/SiO2Catalyst (H)3PW12O40The loading capacity is 20 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 3, H3PW12O40/SiO2Preparation and use of catalysts
Same as example 1, H in the catalyst was changed3PW12O40The loading capacity is correspondingly adjusted to hydrate phosphotungstic acid and SiO2Mass of aerogel, H3PW12O40The loading is 10 wt%, and the formaldehyde and the acetic acid are catalyzed to react, and the test results are shown in table 3.
TABLE 3.H3PW12O40/SiO2Catalyst (H)3PW12O40The loading amount is 10 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 4, H3PW12O40/SiO2Preparation and use of catalysts
Same as example 1, in H3PW12O40On the basis of the loading of 30 wt%, the reaction temperature during the preparation of the catalyst is changed to ensure that the catalyst is preparedThe calcination temperature of (2) was 350 ℃, and the formaldehyde was catalyzed to react with acetic acid, and the test results are shown in table 4.
TABLE 4.H3PW12O40/SiO2Catalyst (H)3PW12O40The loading amount is 30 wt%, the roasting temperature is 350 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 5, H3PW12O40/SiO2Preparation and use of catalysts
Same as example 1, in H3PW12O40On the basis of the loading amount of 30 wt%, the reaction temperature during the preparation of the catalyst was changed to 550 ℃ so as to catalyze the reaction of formaldehyde and acetic acid, and the test results are shown in table 5.
TABLE 5.H3PW12O40/SiO2Catalyst (H)3PW12O40The loading capacity is 30 wt%, the roasting temperature is 550 ℃) and the reaction test result of formaldehyde and acetic acid is catalyzed
Example 6, H3PMo12O40/SiO2Preparation and use of catalysts
Preparation of the catalyst
H3PMo12O40/SiO2The catalyst is prepared by an impregnation method. First, hydrated phosphomolybdic acid (H) is weighed3PMo12O40·29H2O)3.8581g, adding 60mL of distilled water for dissolving, weighing 7g of SiO2Aerogel to ensure the SiO2The aerogel accounts for 30 wt% of the total mass of the catalyst according to the mass of the hydrated phosphomolybdic acid, and the hydrated phosphomolybdic acid is added into the weighed SiO after being completely dissolved2Stirring in aerogel carrier at room temperature for 4 hr, and adding into aerogel carrier 120Drying in a drying oven at the temperature of 24h, and stirring continuously before surface drying. Fully grinding, then roasting in a muffle furnace at 450 ℃ for 3H, then tabletting under a tablet press at the pressure of 8MPa, and screening to obtain 20-40 mesh H3PMo12O40/SiO2A catalyst.
The prepared catalyst is used for catalyzing the condensation reaction of formaldehyde and acetic acid aldol to synthesize acrylic acid and ester thereof.
The reaction is carried out in a miniature continuous fixed bed reactor, and raw materials are gasified and then enter the fixed bed reactor (with the length of 20cm and the inner diameter of 0.5cm) for reaction; h3PMo12O40/SiO2The loading of the catalyst was 3g, the raw material was fed into the vaporization chamber of the fixed bed reactor at a mass flow rate of 8.4g/h under normal pressure, vaporized at 280 ℃ and then fed into the reactor for reaction, and a carrier gas (N) was maintained2) The flow rate was 20mL/min, the reaction temperatures were considered to be 340 deg.C, 360 deg.C, 380 deg.C, 400 deg.C, the samples were continuously taken at the given temperatures for 1h, the products were collected by condensation, the collected products were analyzed by Agilent GC-7890A gas chromatograph, and the test results are calculated and listed in Table 6.
TABLE 6.H3PMo12O40/SiO2Catalyst (H)3PMo12O40The loading amount is 30 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 7, H3PMo12O40/SiO2Preparation and use of catalysts
In the same manner as in example 6, H in the catalyst was changed3PMo12O40The loading of hydrated phosphomolybdic acid and SiO was adjusted accordingly2Mass of aerogel, H3PMo12O40The loading was 20wt% catalyzes the reaction of formaldehyde and acetic acid, and the test results are shown in Table 7.
TABLE 7.H3PMo12O40/SiO2Catalyst (H)3PMo12O40The loading capacity is 20 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 8, H3PMo12O40/SiO2Preparation and use of catalysts
In the same manner as in example 6, H in the catalyst was changed3PMo12O40The loading of hydrated phosphomolybdic acid and SiO was adjusted accordingly2Mass of aerogel, H3PMo12O40The loading is 10 wt%, and the formaldehyde and the acetic acid are catalyzed to react, and the test result is shown in table 8.
TABLE 8.H3PMo12O40/SiO2Catalyst (H)3PMo12O40The loading amount is 10 wt%, the roasting temperature is 450 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 9, H3PMo12O40/SiO2Preparation and use of catalysts
Same as example 6, in H3PMo12O40On the basis of the loading amount of 30 wt%, the reaction temperature during the preparation of the catalyst was changed to make the calcination temperature of the catalyst 350 ℃, and the formaldehyde and acetic acid were catalyzed to react, and the test results are shown in table 9.
TABLE 9.H3PMo12O40/SiO2Catalyst (H)3PMo12O40The loading amount is 30 wt%, the roasting temperature is 350 ℃) and catalyzes the formaldehyde and the reaction test result of acetic acid
Example 10, H3PMo12O40/SiO2Preparation and use of catalysts
Same as example 6, in H3PMo12O40On the basis of the loading amount of 30 wt%, the reaction temperature during the preparation of the catalyst was changed to 550 ℃ so as to catalyze the reaction of formaldehyde and acetic acid, and the test results are shown in table 10.
TABLE 10.H3PMo12O40/SiO2Catalyst (H)3PMo12O40The loading capacity is 30 wt%, the roasting temperature is 550 ℃) and the reaction test result of formaldehyde and acetic acid is catalyzed
For H3PW12O40/SiO2The catalyst has acrylic acid selectivity of 84.16% and methyl acrylate selectivity of 9.57% at a reaction temperature of 400 ℃, and the yield of acrylic acid (ester) can reach 51.70% at most (example 1); for H3PMo12O40/SiO2When the reaction temperature is 360 ℃, the selectivity of acrylic acid is 85.74%, the selectivity of methyl acrylate is 2.32%, and the yield of acrylic acid (ester) is the highest and reaches 48.29% (example 6). It was shown that the catalytic effect was best when the loading of the active component reached 30%.
Claims (8)
1. An acrylic acid catalyst is characterized in that anhydrous phosphotungstic acid or anhydrous phosphomolybdic acid is used as an active component, and SiO is used as a catalyst2The catalyst comprises aerogel serving as a carrier, wherein the active component accounts for 10-30 wt% of the total mass of the catalyst, and the particle size is 20-40 meshes.
2. The method for preparing an acrylic catalyst according to claim 1, comprising the steps of:
weighing hydrated phosphotungstic acid or hydrated phosphomolybdic acid and SiO according to the weight of the anhydrous phosphotungstic acid or anhydrous phosphomolybdic acid accounting for 10-30 wt% of the total weight of the catalyst2Adding hydrous phosphotungstic acid or hydrous phosphomolybdic acid into distilled water until the solution is completely dissolved, and adding the obtained solution into SiO2Soaking in aerogel, stirring at room temperature until the aerogel is completely soaked, then evaporating to remove excessive water, drying the obtained product at 110-130 ℃ for 18-36 h, grinding, roasting at 350-550 ℃ for 2-5 h, tabletting under the pressure of 7-10 MPa, and sieving with a 20-40 mesh sieve to obtain the acrylic acid catalyst.
3. The method for preparing the acrylic acid catalyst according to claim 2, wherein the mass-to-volume ratio of the hydrated phosphotungstic acid or the hydrated phosphomolybdic acid to the distilled water is 60 to 90g: 1L.
4. The method for preparing the acrylic acid catalyst according to claim 2, wherein the stirring time at room temperature is 3 to 6 hours.
5. The method for preparing an acrylic catalyst according to claim 2, wherein the surface of the product is dried with stirring during the drying process.
6. The acrylic acid catalyst as claimed in claim 1 is used for catalyzing formaldehyde and acetic acid to synthesize acrylic acid and its ester.
7. Method for application according to claim 6, characterized in that it comprises the following steps: introducing trioxymethylene and acetic acid into a 280 ℃ vaporization chamber according to the molar ratio of 1:9, and carrying out gas phase reaction through a continuous fixed bed reactor loaded with the acrylic acid catalyst after vaporization, wherein the reaction temperature is 340-400 ℃.
8. The method of claim 7, wherein the fixed bed reactor has a length of 20cm and an internal diameter of 0.5cm, and is used in a fluidized bed reactorQuartz cotton is placed in a fixed bed reaction tube, the sample injection flow rate of trioxymethylene and acetic acid is 8.4g/h, and the carrier gas is N2The flow rate was 20mL/min and the reaction was carried out at normal pressure.
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