CN114733571B - Catalyst for preparing methacrolein and preparation method thereof - Google Patents
Catalyst for preparing methacrolein and preparation method thereof Download PDFInfo
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- CN114733571B CN114733571B CN202210546030.7A CN202210546030A CN114733571B CN 114733571 B CN114733571 B CN 114733571B CN 202210546030 A CN202210546030 A CN 202210546030A CN 114733571 B CN114733571 B CN 114733571B
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of catalytic materials, and provides a catalyst for preparing methacrolein and a preparation method thereof. The preparation method of the catalyst comprises the following steps: s1, mixing resin, glycidyl methacrylate, ammonium persulfate and dimethylformamide to react under protective gas to obtain modified resin; s2, mixing the modified resin, the grafting reagent and dimethylformamide to react to obtain grafted resin; and S3, mixing the grafted resin and an acetic acid aqueous solution for an acidification reaction to obtain the catalyst for preparing the methacrolein. The preparation method is simple and short in steps, and the prepared catalyst has higher catalytic activity.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a catalyst for preparing methacrolein and a preparation method thereof.
Background
Methacrolein is an important intermediate for the production of methacrylic acid and methyl methacrylate. Methyl Methacrylate (MMA) is an important monomer for polymerization and chemical raw material, is commonly used for producing polymethyl methacrylate (organic glass) and acrylic resin materials, and is also widely applied to producing plastics, coatings, adhesives and various industrial aids. In recent years, with the development of economy, the demand for MMA is on a rapid increase trend, and a situation of short supply and demand has arisen.
The preparation of MMA firstly needs to prepare methacrolein, and the existing preparation process of methacrolein mainly comprises a selective oxidation method of isobutene or tert-butyl alcohol catalyzed by Mo-Bi binary oxide and a condensation reaction process of propionaldehyde and formaldehyde aldol catalyzed by diethylamine. However, it is difficult to ensure a high selectivity even at a high conversion rate by the selective oxidation method, and it is also necessary to prevent excessive oxidation. The condensation reaction process is complicated in steps and needs to be carried out at different temperatures. At present, although a plurality of technical schemes for preparing catalysts for methacrolein are disclosed, for example, patent nos. CN109438201A, CN104003856A, CN104557490A, CN112638856A, CN114302869A, CN113248359A, CN110882722A, CN105722814A, CN104311403A, CN102659542A and CN101074192, the catalysts prepared by the above technical schemes still have the technical problems of low catalyst activity, poor selectivity, easy deactivation, difficult separation and recovery, etc. during use.
Therefore, how to provide a catalyst for preparing methacrolein, which has a simple preparation process, high activity and good selectivity, is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a catalyst for preparing methacrolein and a preparation method thereof. The preparation method is simple and short in steps, and the prepared catalyst has higher catalytic activity. The catalyst effectively solves the technical problems of low activity, poor selectivity, easy inactivation, difficult separation and recovery and the like of the catalyst prepared by the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a catalyst for preparing methacrolein, which comprises the following steps:
s1, under protective gas, mixing resin, glycidyl methacrylate, ammonium persulfate and dimethylformamide to react to obtain modified resin;
s2, mixing the modified resin, the grafting reagent and dimethylformamide for reaction to obtain grafted resin;
and S3, mixing the grafted resin and an acetic acid aqueous solution for an acidification reaction to obtain the catalyst for preparing the methacrolein.
Further, the protective gas is nitrogen, argon or helium;
the resin is D301, D311, D314 or D330.
Further, the mass ratio of the resin to the ammonium persulfate is 100: 1.5-2.5, wherein the volume ratio of the glycidyl methacrylate to the dimethylformamide is 1: 5-8, wherein the mass volume ratio of the resin to the dimethylformamide is 1-5 g: 70-100 mL.
Further, the reaction temperature in the step S1 is 50-70 ℃, and the reaction time is 15-30 h.
Further, the grafting reagent is tetraethylenepentamine or pentaethylenehexylamine;
in the step S2, the volume ratio of the grafting reagent to dimethylformamide is 1: 1-2;
the mass volume ratio of the modified resin to the grafting reagent is 1-5 g:5 to 10mL.
Further, the reaction temperature in the step S2 is 80-100 ℃, and the reaction time is 10-30 h.
Further, the mass volume ratio of the grafted resin to the acetic acid aqueous solution is 1-5 g: 10-20 mL;
the mass fraction of the acetic acid aqueous solution is 40-60%.
Further, the time of the acidification reaction is 10-30 h.
The present invention provides a catalyst for preparing methacrolein prepared by the above preparation method.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the catalyst for preparing methacrolein prepared by the invention has more active sites, and has higher catalytic activity under the same mass compared with the existing catalyst;
2. according to the invention, acetate of tetraethylenepentamine or pentaethylenehexylamine is grafted on the resin, so that the catalyst is easier to separate and recover;
3. according to the invention, secondary amine groups in tetraethylenepentamine or pentaethylenehexylamine are subjected to acetic acid acidification, so that the alkalinity of the tetra-ethylenepentylamine or pentaethylenehexylamine can be weakened, and the occurrence of side reactions can be effectively inhibited;
4. the preparation method of the catalyst is simple, short in steps, wide in raw material source and capable of realizing large-scale production.
Detailed Description
The invention provides a preparation method of a catalyst for preparing methacrolein, which comprises the following steps:
s1, under protective gas, mixing resin, glycidyl methacrylate, ammonium persulfate and dimethylformamide to react to obtain modified resin;
s2, mixing the modified resin, the grafting reagent and dimethylformamide to react to obtain grafted resin;
and S3, mixing the grafted resin and an acetic acid aqueous solution for an acidification reaction to obtain the catalyst for preparing the methacrolein.
In the present invention, the protective gas is nitrogen, argon or helium, preferably nitrogen or argon, and more preferably nitrogen; the resin is D301, D311, D314 or D330, preferably D301 or D314, more preferably D301.
In the invention, the mass ratio of the resin to the ammonium persulfate is 100:1.5 to 2.5, preferably 100:1.8 to 2.4, more preferably 100:2.0 to 2.2; the volume ratio of the glycidyl methacrylate to the dimethylformamide is 1:5 to 8, preferably 1:6 to 7, more preferably 1:6; the mass volume ratio of the resin to the dimethylformamide is 1-5 g:70 to 100mL, preferably 2 to 4g:75 to 90mL, more preferably 3g: 80-85 mL.
In the present invention, the temperature of the reaction in the step S1 is 50 to 70 ℃, preferably 55 to 65 ℃, and more preferably 58 to 60 ℃; the time is 15 to 30 hours, preferably 18 to 28 hours, and more preferably 20 to 25 hours.
In the invention, after the reaction in step S1 is finished, the reaction product is washed and dried to obtain the modified resin, the solvent for washing is acetone, and the time is 1 to 10min, preferably 2 to 8min, and more preferably 5 to 6min; the drying temperature is 60-100 ℃, preferably 70-90 ℃, and more preferably 80-85 ℃; the drying time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 to 26 hours.
In the invention, the grafting reagent is tetraethylenepentamine or pentaethylenehexylamine, preferably tetraethylenepentamine;
in the step S2, the volume ratio of the grafting reagent to dimethylformamide is 1:1 to 2, preferably 1:1.2 to 1.8, more preferably 1:1.4 to 1.6;
the mass volume ratio of the modified resin to the grafting reagent is 1-5 g:5 to 10mL, preferably 2 to 4g:6 to 9mL, more preferably 3g:7mL.
In the present invention, the temperature of the reaction in the step S2 is 80 to 100 ℃, preferably 85 to 95 ℃, and more preferably 90 ℃; the time is 10 to 30 hours, preferably 12 to 28 hours, and more preferably 15 to 20 hours.
In the invention, after the reaction in the step S2 is finished, washing and drying the reaction product to obtain the grafted resin, wherein the washed solvent is ethanol and water, and the ethanol is firstly used for washing and then the water is used for washing; the washing time is independently 1-10 min, preferably 2-8 min, and more preferably 5-6 min; the drying temperature is 60-100 ℃, preferably 70-90 ℃, and further preferably 80-85 ℃; the drying time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 to 26 hours.
In the invention, the mass volume ratio of the grafted resin to the acetic acid aqueous solution is 1-5 g:10 to 20mL, preferably 2 to 4g:12 to 18mL, more preferably 3g: 14-16 mL;
the mass fraction of the acetic acid aqueous solution is 40 to 60%, preferably 45 to 55%, and more preferably 50%.
In the present invention, the time for the acidification reaction is 10 to 30 hours, preferably 12 to 26 hours, and more preferably 15 to 24 hours.
In the invention, after the acidification reaction in step S3 is finished, the reaction product is washed and dried to obtain the catalyst for preparing methacrolein, the solvent for washing is water, and the time is 1 to 10min, preferably 2 to 8min, and more preferably 5 to 6min; the drying temperature is 60-100 ℃, preferably 70-90 ℃, and more preferably 80-85 ℃; the drying time is 20 to 30 hours, preferably 22 to 28 hours, and more preferably 24 to 26 hours.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Under the nitrogen atmosphere, 1g of D301 resin, 0.02g of ammonium persulfate, 16mL of glycidyl methacrylate and 80mL of DMF are mixed and then react at 60 ℃ for 24h, the reaction product is washed with propanol for 5min and then dried in vacuum at 80 ℃ for 24h to obtain modified resin;
mixing 1g of modified resin, 5mL of tetraethylenepentamine and 5mL of DMF, reacting for 20h at 90 ℃, washing the reaction product with ethanol and deionized water for 5min respectively, and then drying for 24h under vacuum at 80 ℃ to obtain grafted resin;
and (2) putting 1g of the grafted resin into 10mL of acetic acid solution with the mass fraction of 40%, acidifying and reacting for 20h, washing the reaction product with deionized water for 5min, and then drying in vacuum at 80 ℃ for 24h to obtain the catalyst Cat-1 for preparing the methacrolein.
Example 2
Under the nitrogen atmosphere, 1g of D311 resin, 0.015g of ammonium persulfate, 12mL of glycidyl methacrylate and 80mL of DMMF are mixed and then react for 24h at 70 ℃, the reaction product is washed for 7min by propanol, and then vacuum drying is carried out for 26h at 70 ℃ to obtain modified resin;
mixing 1g of modified resin, 5mL of pentaethylenehexylamine and 10mL of DMF, reacting at 95 ℃ for 20h, washing the reaction product with ethanol and deionized water for 3min respectively, and then drying at 90 ℃ for 22h in vacuum to obtain grafted resin;
placing 1g of the grafted resin in 10mL of acetic acid solution with the mass fraction of 60% for acidification reaction for 20h, washing the reaction product with deionized water for 5min, and then drying the reaction product in vacuum at 80 ℃ for 24h to obtain the catalyst Cat-2 for preparing the methacrolein.
Example 3
Under the nitrogen atmosphere, 1g of D314 resin, 0.025g of ammonium persulfate, 10mL of glycidyl methacrylate and 80mL of DMMF are mixed and reacted at 50 ℃ for 24h, the reaction product is washed with propanol for 4min and then dried under vacuum at 75 ℃ for 25h to obtain modified resin;
mixing 1g of modified resin, 5mL of tetraethylenepentamine and 5mL of DMMF, reacting at 100 ℃ for 20h, washing the reaction product with ethanol and deionized water for 3min respectively, and then drying at 90 ℃ in vacuum for 22h to obtain grafted resin;
and (3) placing 1g of the grafted resin in 10mL of acetic acid solution with the mass fraction of 50% for acidification reaction for 20h, washing the reaction product with deionized water for 5min, and then performing vacuum drying at 85 ℃ for 23h to obtain a catalyst Cat-3 for preparing methacrolein.
Example 4
Under the nitrogen atmosphere, 1g of D330 resin, 0.02g of ammonium persulfate, 14mL of glycidyl methacrylate and 80mL of DMMF are mixed and reacted at 60 ℃ for 24h, the reaction product is washed with propanol for 5min and then dried under vacuum at 80 ℃ for 25h to obtain modified resin;
mixing 1g of modified resin, 5mL of pentaethylenehexylamine and 10mL of DMF, reacting at 95 ℃ for 20h, washing the reaction product with ethanol and deionized water for 4min respectively, and then drying at 85 ℃ in vacuum for 22h to obtain grafted resin;
and (2) putting 1g of the grafted resin into 10mL of acetic acid solution with the mass fraction of 40% for acidification reaction for 20h, washing the reaction product with deionized water for 5min, and then drying the reaction product in vacuum at 85 ℃ for 20h to obtain the catalyst Cat-4 for preparing the methacrolein.
Example 5
Mixing 1g of D301 resin, 0.015g of ammonium persulfate, 10mL of glycidyl methacrylate and 80mL of DMMF in a nitrogen atmosphere, reacting at 50 ℃ for 24h, washing the reaction product with propanol for 5min, and then drying in vacuum at 80 ℃ for 21h to obtain modified resin;
mixing 1g of modified resin, 5mL of tetraethylenepentamine and 5mL of DMMF, reacting at 90 ℃ for 20h, washing the reaction product with ethanol and deionized water for 5min respectively, and then drying in vacuum at 85 ℃ for 22h to obtain grafted resin;
placing 1g of the grafted resin in 10mL of acetic acid solution with the mass fraction of 50% for acidification reaction for 20h, washing the reaction product with deionized water for 5min, and then drying the reaction product in vacuum at 80 ℃ for 20h to obtain the catalyst Cat-5 for preparing the methacrolein.
Example 6
Mixing 1g of D301 resin, 0.015g of ammonium persulfate, 10mL of glycidyl methacrylate and 80mL of DMMF in a nitrogen atmosphere, reacting at 50 ℃ for 24h, washing the reaction product with propanol for 5min, and then drying in vacuum at 80 ℃ for 21h to obtain modified resin;
mixing 1g of modified resin, 5mL of pentaethylenehexylamine and 5mL of TMMF, reacting for 20h at 90 ℃, washing the reaction product with ethanol and deionized water for 5min respectively, and then drying for 22h at 80 ℃ in vacuum to obtain grafted resin;
and (3) placing 1g of the grafted resin in 10mL of acetic acid solution with the mass fraction of 50% for acidification reaction for 20h, washing the reaction product with deionized water for 5min, and then performing vacuum drying at 80 ℃ for 20h to obtain a catalyst Cat-6 for preparing methacrolein.
Performance testing
Test 1: the activity test tests of the catalysts prepared in examples 1 to 6 were carried out on a fixed bed reactor, with a catalyst loading of 1mL and a propanal/formaldehyde molar ratio of 1:2, the space velocity is 2h -1 The reaction temperature was 80 ℃ and the test results are shown in Table 1.
Table 1 results of activity test of catalysts of examples 1 to 6
And (3) testing 2: the activity test tests of the catalysts prepared in examples 1 to 6 were carried out on a fixed bed reactor, with a catalyst loading of 1mL and a propanal/formaldehyde molar ratio of 1:1, space velocity of 1h -1 The reaction temperature was 70 ℃ and the test results are shown in Table 2.
Table 2 results of activity test of catalysts of examples 1 to 6
| Catalyst and process for preparing same | Methylacrolein generation rate/(mmol/gCat/h) -1 ) | Selectivity/%) |
| Cat-1 | 7.2 | 99.3 |
| Cat-2 | 5.4 | 99.8 |
| Cat-3 | 8.6 | 99.1 |
| Cat-4 | 6.4 | 99.4 |
| Cat-5 | 10.2 | 99.6 |
| Cat-6 | 16.9 | 99.7 |
And (3) testing: the activity test of the catalysts prepared in examples 1 to 6 was carried out on a fixed bed reactor, the catalyst loading was 1mL, the propionaldehyde/formaldehyde molar ratio was 1 -1 The reaction temperature was 70 ℃ and the test results are shown in Table 3.
Table 3 results of activity test of catalysts of examples 1 to 6
| Catalyst and process for producing the same | Methylacrolein generation rate/(mmol/gCat/h) -1 ) | Selectivity/%) |
| Cat-1 | 8.3 | 100 |
| Cat-2 | 6.7 | 100 |
| Cat-3 | 9.7 | 100 |
| Cat-4 | 7.5 | 100 |
| Cat-5 | 11.6 | 100 |
| Cat-6 | 18.9 | 100 |
And (4) testing: the activity test tests of the catalysts prepared in examples 1 to 6 were carried out in a fixed bed reactor, with a catalyst loading of 1mL, a propanal/formaldehyde molar ratio of 1.5, and a space velocity of 1h -1 The reaction temperature was 70 ℃ and the test results are shown in Table 4.
Table 4 results of activity test of catalysts of examples 1 to 6
As can be seen from tables 1 to 4, the selectivity of the catalyst for preparing methacrolein prepared by the invention is high and can reach 100%; the formation rate of methacrolein is high, which shows that the catalyst prepared by the invention has high catalytic activity.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing a catalyst for use in the preparation of methacrolein, comprising the steps of:
s1, under protective gas, mixing resin, glycidyl methacrylate, ammonium persulfate and dimethylformamide to react to obtain modified resin;
s2, mixing the modified resin, the grafting reagent and dimethylformamide for reaction to obtain grafted resin;
s3, mixing the grafted resin and an acetic acid aqueous solution for an acidification reaction to obtain a catalyst for preparing methacrolein;
the grafting reagent is tetraethylenepentamine or pentaethylenehexylamine;
in the step S2, the volume ratio of the grafting reagent to dimethylformamide is 1:1 to 2;
the mass volume ratio of the modified resin to the grafting reagent is 1-5 g: 5-10 mL.
2. The method of claim 1, wherein the protective gas is nitrogen, argon, or helium;
the resin is D301, D311, D314 or D330.
3. The preparation method according to claim 2, wherein the mass ratio of the resin to the ammonium persulfate is 100: 1.5-2.5, wherein the volume ratio of the glycidyl methacrylate to the dimethylformamide is 1: 5-8, wherein the mass volume ratio of the resin to the dimethylformamide is 1-5 g: 70-100 mL.
4. The method according to claim 2 or 3, wherein the reaction in step S1 is carried out at a temperature of 50 to 70 ℃ for 15 to 30 hours.
5. The process according to any one of claims 1 to 3, wherein the reaction in step S2 is carried out at a temperature of 80 to 100 ℃ for a period of 10 to 30 hours.
6. The preparation method according to claim 5, wherein the mass-to-volume ratio of the grafted resin to the aqueous acetic acid solution is 1 to 5g: 10-20 mL;
the mass fraction of the acetic acid aqueous solution is 40-60%.
7. The method according to claim 1, 2, 3 or 6, wherein the time for the acidification reaction is 10 to 30 hours.
8. A catalyst for producing methacrolein prepared by the method of any one of claims 1 to 7.
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| CN101074192A (en) * | 2007-06-20 | 2007-11-21 | 天津大学 | Production of methyl a-methacrylate with methanal as raw material |
| CN109438201A (en) * | 2018-12-07 | 2019-03-08 | 中国科学院过程工程研究所 | A method of preparing methacrolein |
| KR20210067425A (en) * | 2019-11-29 | 2021-06-08 | 롯데케미칼 주식회사 | Method for preparing isobutenol |
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