CN114308007A - Preparation method of solid acid catalyst for preparing dimethyl dodecanedioate - Google Patents

Preparation method of solid acid catalyst for preparing dimethyl dodecanedioate Download PDF

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CN114308007A
CN114308007A CN202011070649.2A CN202011070649A CN114308007A CN 114308007 A CN114308007 A CN 114308007A CN 202011070649 A CN202011070649 A CN 202011070649A CN 114308007 A CN114308007 A CN 114308007A
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solid acid
acid catalyst
catalyst
drying
preparing
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CN114308007B (en
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魏开轩
黄冬
逯贵广
曾志强
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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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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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method of a solid acid catalyst for preparing dimethyl dodecanedioate, belonging to the field of catalysts. During preparation of the catalyst, 20-40% of charcoal particles and 10-30% of SnCl are weighed according to mass fraction4·5H2Adding O and 30-70% of diatomite into certain deionized water, and neutralizing, stirring and extruding to obtain a precursor; h of the precursor at 1-5 mol/L2SO4Soaking in solution, drying, and adding N2Under the protection of (3), calcining at 400-650 ℃ to obtain the solid acid catalyst. When the catalyst is applied to the preparation of dimethyl dodecanedioate, the catalyst has high conversion rate and selectivity and can be recycled.

Description

Preparation method of solid acid catalyst for preparing dimethyl dodecanedioate
Technical Field
The invention relates to a preparation method of a solid acid catalyst for preparing dimethyl dodecanedioate, belonging to the technical field of catalysts.
Background
Dimethyl dodecanedioate is an important fine chemical product and is widely applied to the industries of medicines, plastics, polyurethane and coatings.
The current synthesis methods mainly comprise a biological fermentation method and a cyclohexanone oxidation method.
The fermentation method has the problems of long process time and many impurities, and cannot be popularized in the fields of spices, medicines and the like.
The cyclohexanone oxidation method has problems of high cost and low yield because a large amount of hydrogen peroxide is consumed as an oxidizing agent.
CN1670010A discloses a method for preparing dimethyl dodecanedioate by oxidizing cyclohexanone, which adopts methanol as a solvent, the cyclohexanone as a raw material, and hydrogen peroxide as an oxidant to prepare peroxide of the cyclohexanone through a quaternary ammonium salt, crown ether and other phase transfer catalysts, and then the dimethyl dodecanedioate is obtained through ring-opening dimerization. The consumption of the hydrogen peroxide is 45-60% of that of the cyclohexanone, and the final yield is about 72%.
Dodecanedioic acid is used as a raw material, the reaction steps are reduced by directly carrying out esterification reaction on the dodecanedioic acid and methanol through an acid catalyst, the reaction selectivity is high, and the method is a feasible scheme for preparing the dimethyl dodecanedioic acid.
The traditional homogeneous acid catalyst has the problems of difficult separation and easy corrosion of equipment, so that the application of the traditional homogeneous acid catalyst in the chemical field is limited.
The heterogeneous solid acid catalyst gradually becomes a hotspot of research in the field of catalysts by virtue of the characteristics of strong acidity, easy separation, no corrosion to equipment and reusability.
Carbonaceous solid acid catalysts were first proposed by the Japanese scholars Masakazu Toda, Atsushi Takagaki et al. The biomass solid acid catalyst is obtained by taking cellulose as a raw material and performing carbonization and sulfonation, and has high acidity and low cost. However, the carbonized sulfonated solid acid catalyst still has the problems of easy pulverization and low mechanical strength when in use, and the large-scale application of the carbonized sulfonated solid acid catalyst is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a composite solid acid catalyst, which takes cheap and easily-obtained charcoal particles as active site carriers and compounds SnO2With diatomsThe solid acid catalyst prepared by the method has the advantages of excellent catalytic performance, high mechanical strength and low cost. When the method is used for preparing dimethyl dodecanedioate, the conversion rate is higher, and the method can be repeatedly used.
The main technical scheme of the invention is that the preparation method of the solid acid catalyst for preparing the dodecanedioic acid dimethyl ester is characterized in that charcoal particles are used as active site carriers, and SnO is passed through2Compounding with diatomite to obtain the catalyst.
In general, the preparation method of the invention comprises the following steps:
(1) weighing 20-40% of charcoal particles and 10-30% of SnCl4·5H2Adding O and 30-70% of diatomite into certain deionized water, and stirring to obtain a stable suspension;
(2) dropwise adding concentrated ammonia water, adjusting the pH value of the suspension to 6, performing suction filtration and drying, adding 5-10% of a binder into the product, uniformly mixing, extruding and drying to obtain a catalyst precursor;
(3) weighing a certain amount of precursor in 1-5 mol/L H2SO4Soaking the precursor in the solution for acidic activation, and drying at 80-130 ℃ after soaking;
(4) the activated sample is placed in N2And calcining at 400-650 ℃ under protection to finally obtain the composite solid acid catalyst.
The preparation method of the solid acid catalyst for preparing the dimethyl dodecanedioate is characterized in that charcoal particles can be obtained by crushing white carbon, black carbon, activated carbon and machine-made carbon.
The preparation method of the solid acid catalyst for preparing the dimethyl dodecanedioate is characterized in that the mesh number of the selected diatomite is 80-200 meshes.
The preparation method of the solid acid catalyst for preparing the dimethyl dodecanedioate is characterized in that the addition amount of the binder is 5-10%.
The preparation method of the solid acid catalyst for preparing the dimethyl dodecanedioate is characterized in that the drying temperature is 80-130 ℃.
The invention relates to a preparation method of a solid acid catalyst for preparing dimethyl dodecanedioate, which is characterized in that H is2SO4The soaking time of the solution is 3-24 h.
The solid acid catalyst prepared by the preparation method is used for preparing dimethyl dodecanedioate by reacting dodecanedioic acid with methanol.
The reaction material is dodecanedioic acid and methanol, the ratio of the amount of the alkyd substance is 1-20, the reaction temperature is 60-120 ℃, the conversion rate of the dodecanedioic acid is 71-88%, and the selectivity of the dimethyl dodecanedioic acid is 84-93%.
Effects of the invention
The solid acid catalyst prepared by the method takes cheap and easily available diatomite and carbon-based particles as carriers to prepare the solid acid catalyst with strong catalytic activity and high selectivity by chemical doping and modification, and the catalyst can be repeatedly used.
Detailed Description
The present invention will be described in detail with reference to the following examples
Example 1
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 1mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 71 91
4 80 82 87
10 100 83 85
Example 2
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 2mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 73 91
4 80 83 88
10 100 83 84
Example 3
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 3mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 78 92
4 80 85 92
10 100 86 84
Example 4
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 4mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 81 93
4 80 87 92
10 100 88 90
Example 5
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 5mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 81 93
4 80 88 93
10 100 88 91
Example 6
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 5mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining at 550 ℃ for 6h under protection to obtain the final solid acid catalyst. Weighing 16g of dodecanedioic acid and 27g of methanol, adding a certain proportion of catalyst, and reacting on a reflux reaction device for a certain timeAfter suction filtration, the reaction results are detected by gas chromatography as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 80 92
4 80 86 91
10 100 84 89
Example 7
20g of charcoal particles, 10g of SnCl4·5H2Adding 70g of diatomite and O into 250g of deionized water, stirring for 2h, dropwise adding concentrated ammonia water to adjust the pH value to 6, carrying out suction filtration and drying, adding 10% of a binder, extruding and drying to obtain a precursor. Soaking the precursor in 5mol/L H2SO4Drying the solution after 12h, and putting the product in N2Calcining for 6h at 450 ℃ under protection to obtain the final solid acid catalyst. Weighing dodecanedioic acid 16g and 27g of methanol, adding 4% of catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
number of times of catalyst use Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
1 80 86 91
2 80 85 90
3 80 82 90
4 80 82 89
5 80 81 89
Comparative example 1
Weighing 16g of dodecanedioic acid and 27g of methanol, adding a commercial amberlyst15 solid acid catalyst, reacting for a certain time on a reflux reaction device, and detecting the reaction result by gas chromatography after suction filtration as follows:
(catalyst/acid)/%) Reaction temperature/. degree.C Conversion rate/% Selectivity/%)
2 60 67 85
4 80 71 82
10 100 73 82
。
It can be seen from the above examples and comparative examples that the solid acid catalyst prepared by the invention has high conversion rate and good selectivity when used for catalytically synthesizing dimethyl dodecanedioate, and has a certain commercial application prospect.

Claims (10)

1. A process for preparing the solid acid catalyst used to prepare dimethyl dodecanedioate features that the charcoal particles are used as the carrier of active sites and SnO is used2Compounding with diatomite to obtain the catalyst.
2. The method of claim 1, wherein the method comprises the steps of:
(1) 20-40% of charcoal particles and 10-30% of SnCl4·5H2Adding O and 30-70% of diatomite into deionized water, and stirring to obtain a stable suspension;
(2) dropwise adding concentrated ammonia water, adjusting the pH value of the suspension to 6, performing suction filtration and drying, adding a binder into the product, uniformly mixing, extruding and drying to obtain a catalyst precursor;
(3) taking a precursor, and adding the precursor into 1-5 mol/L H2SO4Soaking the precursor in the solution for acidic activation, and drying after soaking;
(4) the treated product is placed in N2And calcining at 400-650 ℃ under protection to finally obtain the composite solid acid catalyst.
3. The method of claim 1 or 2, wherein the charcoal particles are one of white charcoal, black charcoal, activated charcoal and machine-made charcoal, which is obtained by pulverizing.
4. The method of claim 2, wherein the diatomaceous earth has a mesh size of 80-200 mesh.
5. The method for preparing a solid acid catalyst for preparing dimethyl dodecanedioate according to claim 2,
the adhesive is characterized in that the addition amount of the adhesive is 5-10%.
6. The method for preparing a solid acid catalyst for preparing dimethyl dodecanedioate according to claim 2,
the method is characterized in that the drying temperature is 80-130 ℃.
7. The method of claim 2, wherein H is H, the solid acid catalyst is selected from the group consisting of dimethyl dodecandioate, and dimethyl dodecandioate2SO4The soaking time of the solution is 3-24 h.
8. The solid acid catalyst prepared by the preparation method of claim 1, which is used for preparing dimethyl dodecanedioate by reacting dodecanedioic acid with methanol.
9. The solid acid catalyst prepared by the preparation method of claim 8, wherein the reaction materials are dodecanedioic acid and methanol, the ratio of the amount of the alkyd material is 1-20, and the reaction temperature is 60-120 ℃.
10. The solid acid catalyst prepared by the preparation method of claim 8, wherein the conversion rate of dodecanedioic acid is 71-88%, and the selectivity of dimethyl dodecanedioic acid is 84-93%.
CN202011070649.2A 2020-10-09 2020-10-09 Method for preparing solid acid catalyst for preparing dodecanedioic acid dimethyl ester Active CN114308007B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932306A (en) * 1973-01-17 1976-01-13 Imi (Tami) Institute For Research & Development Solid catalyst for heterogeneous reactions
CN1613559A (en) * 2004-09-28 2005-05-11 北京化工大学 Preparation for hydrophobic solid acid catalyst
CN104028294A (en) * 2014-06-26 2014-09-10 江南大学 Solid acid catalyst suitable for microwave-assisted reaction and preparation method of solid acid catalyst
CN106732673A (en) * 2016-11-10 2017-05-31 常州大学 A kind of construction method of the solid acid catalyst with montmorillonite as carrier

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932306A (en) * 1973-01-17 1976-01-13 Imi (Tami) Institute For Research & Development Solid catalyst for heterogeneous reactions
CN1613559A (en) * 2004-09-28 2005-05-11 北京化工大学 Preparation for hydrophobic solid acid catalyst
CN104028294A (en) * 2014-06-26 2014-09-10 江南大学 Solid acid catalyst suitable for microwave-assisted reaction and preparation method of solid acid catalyst
CN106732673A (en) * 2016-11-10 2017-05-31 常州大学 A kind of construction method of the solid acid catalyst with montmorillonite as carrier

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈丹云;邹雪艳;何建英: "SO42-/SnO2-硅藻土型固体酸的制备及其对正丁酸与异戊醇的催化酯化" *

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