CN112076778A - Catalyst raw powder, catalyst, preparation method and application - Google Patents
Catalyst raw powder, catalyst, preparation method and application Download PDFInfo
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- CN112076778A CN112076778A CN202011051863.3A CN202011051863A CN112076778A CN 112076778 A CN112076778 A CN 112076778A CN 202011051863 A CN202011051863 A CN 202011051863A CN 112076778 A CN112076778 A CN 112076778A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000000843 powder Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UATRONWBYDQKSQ-UHFFFAOYSA-N 3-methyl-1-(3-methylbut-2-enoxy)but-2-ene Chemical compound CC(C)=CCOCC=C(C)C UATRONWBYDQKSQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 50
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 44
- 239000011780 sodium chloride Substances 0.000 description 22
- 239000000376 reactant Substances 0.000 description 20
- 239000012044 organic layer Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 4
- NFIYTPYOYDDLGO-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].OP(O)(O)=O NFIYTPYOYDDLGO-UHFFFAOYSA-N 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a catalyst raw powder, a catalyst, a preparation method and an application, wherein the catalyst raw powder is prepared from a triblock copolymer, a phosphoric acid solution, sodium tungstate and tetraethoxysilane, and the mass percentages of the triblock copolymer, the phosphoric acid solution, the sodium tungstate and the tetraethoxysilane are respectively 20%, 48-49%, 2-3% and 28-3%; the granular catalyst is prepared by the catalyst raw powder and silica sol. The catalyst has the advantages that the triblock copolymer is used as a carrier, so that active components are uniformly dispersed, the using amounts of phosphoric acid solution and sodium tungstate can be reduced, the stability of the catalyst can be improved, the catalyst is green and environment-friendly, the catalyst has higher catalytic activity and selectivity of a target product for the single-ring oxidation of the dimethyl allyl ether, the catalyst still has higher catalytic activity after being recycled and calcined and regenerated, the preparation cost of the catalyst can be further reduced, and the economic benefit can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of oxidation catalysts, and particularly relates to a catalyst raw powder, a catalyst, a preparation method and an application.
Background
The catalyst for single-ring oxidation of dimethyl allyl ether mainly comprises heteropoly acid quaternary ammonium salt and TS-1. However, the applicant found that: the catalyst is not easy to recover, so that the cost is high; and although the recovery rate of TS-1 is higher, the catalytic performance of the TS-1 is not high, and the catalytic performance after recovery is obviously reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for the monoepoxy of dimethyl allyl ether and a preparation method of the catalyst for the monoepoxy of dimethyl allyl ether.
High catalytic performance, easy recovery and recovery
In order to solve the technical problems, the invention adopts the following technical scheme:
the catalyst raw powder is prepared from a triblock copolymer, a phosphoric acid solution, sodium tungstate and ethyl orthosilicate, wherein the mass percentage ranges of the triblock copolymer, the phosphoric acid solution, the sodium tungstate and the ethyl orthosilicate are 20%, 48-49%, 2-3% and 28-30% respectively.
Further, the triblock copolymer is a triblock surfactant P123.
A preparation method of catalyst raw powder specifically comprises the following steps:
a1. adding the triblock copolymer and a phosphoric acid solution into a polytetrafluoroethylene reaction kettle, adding deionized water, and stirring in a constant-temperature water bath kettle until the triblock copolymer is completely dissolved;
a2. adding sodium tungstate into a polytetrafluoroethylene reaction kettle, uniformly stirring, adding tetraethoxysilane, and continuously stirring to obtain a reaction solution;
a3. pouring the reaction liquid obtained in the step a2 into a sealed tank lined with polytetrafluoroethylene, and then putting the sealed tank into an oven for crystallization;
a4. cooling and filtering after crystallization, washing with deionized water to weak acidity, drying and roasting in sequence after filtering to obtain P-WO3Catalyst base powder of SBA-15.
Further, the temperature of the constant-temperature water bath in the step a1 is 38 ℃, and the stirring time is 1 h; in the step a2, the temperature of the constant-temperature water bath is 38 ℃, and the stirring time is 6 hours.
Further, the temperature of the oven in the step a3 is 105 ℃, and the crystallization time is 48 h.
Further, the step a4, namely "washing with deionized water to weak acidity" includes: and washing with deionized water for 3-4 times to make the pH value between 5.5-7.
A catalyst in the form of particles, which is obtained from the catalyst raw powder according to claim 1 or 2 and silica sol.
Further, the mass ratio of the catalyst raw powder to the silica sol is 4: 1.
A method for preparing a catalyst, comprising the steps of mixing the catalyst raw powder according to claim 1 or 2 and silica sol according to a ratio, and then sequentially stirring, granulating and baking to obtain a granular catalyst.
Further, the baking is specifically baking in an oven at 80 ℃ for 8 hours.
The catalyst is used for the single-ring oxidation of dimethyl allyl ether.
The invention mainly has the following beneficial effects:
according to the catalyst, the triblock copolymer is used as the carrier, and due to the dispersion effect of the carrier, the active components are uniformly dispersed, so that the using amounts of a phosphoric acid solution and sodium tungstate can be reduced, the stability of the catalyst can be improved, the catalyst is green and environment-friendly, the catalyst has high catalytic activity for the single-ring oxidation of the dimethyl allyl ether and the selectivity of a target product, the catalyst also has high catalytic activity after being recycled, calcined and regenerated, the preparation cost of the catalyst can be further reduced, and the economic benefit can be effectively improved.
Drawings
FIG. 1 is a schematic flow chart of an example of a method for preparing a raw catalyst powder according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The catalyst is prepared from a triblock copolymer, a phosphoric acid solution, sodium tungstate and tetraethoxysilane, wherein the mass percentage ranges of the triblock copolymer, the phosphoric acid solution, the sodium tungstate and the tetraethoxysilane are respectively 20%, 48-49%, 2-3% and 28-30%. Among them, the triblock copolymer is preferably a triblock surfactant P123.
As shown in fig. 1, a method for preparing a catalyst raw powder specifically includes the following steps:
s100, adding the triblock copolymer and a phosphoric acid solution into a polytetrafluoroethylene reaction kettle, adding deionized water, and stirring in a constant-temperature water bath kettle until the triblock copolymer is completely dissolved; wherein the temperature of the constant-temperature water bath is preferably 38 ℃, and the stirring time is preferably 1 h.
S200, adding sodium tungstate into a polytetrafluoroethylene reaction kettle, uniformly stirring, adding tetraethoxysilane, and continuously stirring to obtain a reaction solution; wherein the temperature of the constant-temperature water bath is preferably 38 ℃, and the stirring time is preferably 6 h.
S300, pouring the reaction liquid obtained in the step S200 into a sealed tank lined with polytetrafluoroethylene, and then putting the sealed tank into an oven for crystallization; wherein the temperature of the oven is preferably 105 ℃, and the crystallization time is preferably 48 h.
S400, cooling and filtering after crystallization is finished, washing with deionized water to be weakly acidic, and drying and roasting sequentially after filtering to obtain catalyst raw powder (P-WO)3Catalyst raw powder of SBA-15); wherein the step of washing with deionized water to weak acidity specifically comprises the following steps: and washing with deionized water for 3-4 times to make the pH value between 5.5-7.
Preparing the catalyst raw powder and silica sol into a granular catalyst, wherein the mass ratio of the catalyst raw powder to the silica sol is 4:1 (namely the mass percentage of the silica sol is 20%); the preparation method of the granular catalyst specifically comprises the following steps: mixing the raw catalyst powder and silica sol according to a ratio, and then sequentially stirring, granulating and baking to obtain a granular catalyst; wherein the baking is specifically baking in an oven at 80 ℃ for 8 hours.
In addition, the catalyst of the invention is used for the monoepoxy of dimethyl allyl ether.
According to the catalyst, the triblock copolymer is used as the carrier, and due to the dispersion effect of the carrier, the active components are uniformly dispersed, so that the using amounts of a phosphoric acid solution and sodium tungstate can be reduced, the stability of the catalyst can be improved, the catalyst is green and environment-friendly, the catalyst has high catalytic activity for the single-ring oxidation of the dimethyl allyl ether and the selectivity of a target product, the catalyst still has high catalytic activity after being recycled, calcined and regenerated, the preparation cost of the catalyst can be further reduced, and the economic benefit can be effectively improved.
The catalyst of the present invention and the use of the catalyst in the monoepoxy of dimethylallyl ether are further illustrated by the specific examples below.
The conversion of dimethylallyl ether in the examples defines the formula:
the target product selectivity in the examples is defined by the formula:
example 1:
the weight percentages are as follows:
| triblock copolymers | Phosphoric acid | Sodium tungstate | Tetraethoxysilane |
| 20％ | 48％ | 2％ | 30％ |
Example 2:
the weight percentages are as follows:
| triblock copolymers | Phosphoric acid | Sodium tungstate | Tetraethoxysilane |
| 20％ | 48％ | 3％ | 29％ |
Example 3:
the weight percentages are as follows:
| triblock copolymers | Phosphoric acid | Sodium tungstate | Tetraethoxysilane |
| 20％ | 49％ | 2％ | 29％ |
Example 4:
the weight percentages are as follows:
| triblock copolymers | Phosphoric acid | Sodium tungstate | Tetraethoxysilane |
| 20％ | 49％ | 3％ | 28％ |
Example 5:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 40 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 6:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 45 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 7:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 8:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 55 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 9:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 4 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 10:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 6 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 11:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 7 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 12:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 1.07g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 13:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: 50g of dimethyl allyl ether, 1.07g of catalyst and 1.79g of NaCl are added into a 250mL four-neck flask, then the four-neck flask is placed into a water bath kettle, 21.59g of 50% hydrogen peroxide is slowly dripped under stirring, the reaction temperature is controlled to be 50 ℃, after dripping is finished, the temperature is continuously controlled and stirred for 5 hours, and finally after the reaction is finished, the reaction solution is centrifuged, and an upper organic layer is taken.
Example 14:
according to the mass ratio of 1:0.8 of dimethyl allyl ether to 50% of hydrogen peroxide, the dosage of the catalyst accounts for 1.5% of the total mass of the two reactants, and NaCl accounts for 0.5% of the total mass of the two reactants. The specific implementation process comprises the following steps: adding 50g of dimethyl allyl ether, 1.07g of catalyst and 0.36g of NaCl into a 250mL four-neck flask, then placing the four-neck flask into a water bath, slowly dropwise adding 21.59g of 50% hydrogen peroxide while stirring, controlling the reaction temperature to be 50 ℃, continuing stirring for 5 hours at a controlled temperature after dropwise adding, centrifuging the reaction solution after the reaction is finished, taking an upper organic layer, finally recovering the catalyst, drying, repeating the experiment for 3 times with the same amount of the catalyst, then taking the catalyst recovered for the last time, calcining for 4 hours in a muffle furnace at 550 ℃, repeating the reaction for one time, and taking the upper organic layer.
The results of gas-phase analysis of the organic layers obtained in examples 1 to 14 were as follows:
examples 1-4, raw powders prepared in different mass percentages were mixed with silica sol and then molded, the appearance and strength of which were approximately the same. The results are shown in Table 1, under the same reaction conditions.
TABLE 1 shaped catalyst reaction results for the preparation of raw powders at different mass percentages
| Examples | Hydrogen peroxide conversion/%) | Target product selectivity/%) |
| 1 | 95.34 | 90.51 |
| 2 | 98.75 | 96.05 |
| 3 | 97.52 | 92.64 |
| 4 | 98.71 | 95.97 |
The results of analyzing the organic layers obtained in examples 5 to 8 under the conditions of different reaction temperatures are shown in Table 2.
TABLE 2 Effect of reaction temperature on epoxidation
| Examples | Hydrogen peroxide conversion/%) | Target product selectivity/%) |
| 5 | 78.56 | 97.21 |
| 6 | 85.94 | 96.43 |
| 7 | 98.75 | 96.05 |
| 8 | 99.24 | 71.70 |
The results of analyzing the organic layers obtained in examples 7 and 9 to 11 under the conditions of different reaction times are shown in Table 3.
TABLE 3 Effect of reaction time on epoxidation
| Examples | Hydrogen peroxide conversion/%) | Target product selectivity/%) |
| 9 | 91.82 | 95.65 |
| 7 | 98.75 | 96.05 |
| 10 | 98.86 | 85.34 |
| 11 | 98.91 | 52.36 |
The results of analyzing the organic layers of examples 7, 12 and 13 with different amounts of NaCl are shown in Table 4.
TABLE 4 Effect of different amounts of NaCl on epoxidation
| Examples | Hydrogen peroxide conversion/%) | Target product selectivity/%) |
| 7 | 98.75 | 96.05 |
| 12 | 82.86 | 85.43 |
| 13 | 56.45 | 68.91 |
Example 14, the results of analysis of catalyst recovery, performance of the repeat experiment and regeneration performance are shown in Table 5.
TABLE 5 comparison of catalyst repetition and regeneration Performance
| Experimental group number | Hydrogen peroxide conversion/%) | Target product selectivity/%) |
| Procatalyst | 98.75 | 96.05 |
| Repeating for the first time | 98.13 | 96.26 |
| Repeating for the second time | 97.94 | 96.32 |
| Repeating for the third time | 96.88 | 96.72 |
| Regenerated catalyst | 98.52 | 96.31 |
From the analytical structures of examples 1 to 14, it can be seen that:
(1) the catalyst (modified mesoporous molecular sieve SBA-15 catalyst) has high catalytic activity and basically meets the requirements;
(2) in the catalyst (modified mesoporous molecular sieve SBA-15 catalyst) disclosed by the invention, the modified elements are uniformly dispersed on the carrier, so that the loss of active substances is reduced;
(3) the catalyst (modified mesoporous molecular sieve SBA-15 catalyst) can be effectively recovered and regenerated, so that the production cost is effectively reduced;
(4) the catalyst (the modified mesoporous molecular sieve SBA-15 catalyst) has sufficient stability and strength, and the pore structure is not changed after multiple reactions are finished.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The catalyst raw powder is characterized by being prepared from a triblock copolymer, a phosphoric acid solution, sodium tungstate and tetraethoxysilane, wherein the mass percentage ranges of the triblock copolymer, the phosphoric acid solution, the sodium tungstate and the tetraethoxysilane are respectively 20%, 48-49%, 2-3% and 28-30%.
2. The catalyst base powder according to claim 1, wherein the triblock copolymer is a triblock surfactant P123.
3. The preparation method of the catalyst raw powder is characterized by comprising the following steps:
a1. adding the triblock copolymer and a phosphoric acid solution into a polytetrafluoroethylene reaction kettle, adding deionized water, and stirring in a constant-temperature water bath kettle until the triblock copolymer is completely dissolved;
a2. adding sodium tungstate into a polytetrafluoroethylene reaction kettle, uniformly stirring, adding tetraethoxysilane, and continuously stirring to obtain a reaction solution;
a3. pouring the reaction liquid obtained in the step a2 into a sealed tank lined with polytetrafluoroethylene, and then putting the sealed tank into an oven for crystallization;
a4. cooling and filtering after crystallization, washing with deionized water to weak acidity, drying and roasting in sequence after filtering to obtain P-WO3Catalyst base powder of SBA-15.
4. The preparation method according to claim 3, wherein the temperature of the constant temperature water bath in the step a1 is 38 ℃, and the stirring time is 1 h; the temperature of the constant-temperature water bath in the step a2 is 38 ℃, and the stirring time is 6 hours; the temperature of the oven in the step a3 is 105 ℃, and the crystallization time is 48 h.
5. The preparation method according to claim 3, wherein the step a4 of washing with deionized water to weak acidity includes: and washing with deionized water for 3-4 times to make the pH value between 5.5-7.
6. A catalyst which is a particulate catalyst and is obtained from the catalyst raw powder according to claim 1 or 2 and silica sol.
7. The catalyst according to claim 6, wherein the mass ratio of the raw catalyst powder to the silica sol is 4: 1.
8. A process for producing a catalyst, characterized by mixing the catalyst raw powder according to claim 1 or 2 and silica sol in a certain proportion, followed by stirring, granulating and baking in this order to obtain a granular catalyst.
9. The preparation method according to claim 8, wherein the baking is specifically baking in an oven at 80 ℃ for 8 h.
10. Use of a catalyst according to claim 6 or 7 for the monoepoxy of dimethylallyl ether.
Priority Applications (1)
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| CN114702463A (en) * | 2022-03-29 | 2022-07-05 | 浙江皇马科技股份有限公司 | Method for preparing methyl epichlorohydrin |
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| CN114702463A (en) * | 2022-03-29 | 2022-07-05 | 浙江皇马科技股份有限公司 | Method for preparing methyl epichlorohydrin |
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