CN116408105A - Preparation of carbon-based solid acid catalyst and method for preparing methyl levulinate by using same in glucose alcoholysis - Google Patents

Preparation of carbon-based solid acid catalyst and method for preparing methyl levulinate by using same in glucose alcoholysis Download PDF

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CN116408105A
CN116408105A CN202111680232.2A CN202111680232A CN116408105A CN 116408105 A CN116408105 A CN 116408105A CN 202111680232 A CN202111680232 A CN 202111680232A CN 116408105 A CN116408105 A CN 116408105A
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catalyst
glucose
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alcoholysis
carbon
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冯君锋
范腾
潘晖
童乐
张荣花
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Nanjing Forestry University
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Nanjing Forestry University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention discloses a method for preparing a difunctional carbon-based solid acid catalyst and a research method for preparing methyl levulinate by using the difunctional carbon-based solid acid catalyst in glucose alcoholysis. The preparation method of the bifunctional catalyst comprises the steps of introducing a metal component Cr with Lewis acidic sites on the basis of taking sulfonic acid as the Bronsted acidic sites, and synthesizing the bifunctional 300-AC-SO through high-temperature carbonization, hydrothermal sulfonation and metal impregnation 3 The catalyst is a catalyst of H-Cr,the bifunctional catalyst is then applied to the reaction of preparing methyl levulinate by glucose alcoholysis. The invention utilizes acid sites and introduces metal active sites on the basis of the acid sites, thereby not only improving the dehydration reaction activity, but also effectively improving the isomerization reaction activity from glucose to fructose and from methyl glucoside to methyl fructoside. The catalyst has the characteristics of simple and economical preparation, high catalytic activity, easy separation and the like, and has good catalytic performance in the reaction of preparing methyl levulinate by glucose alcoholysis.

Description

Preparation of carbon-based solid acid catalyst and method for preparing methyl levulinate by using same in glucose alcoholysis
Technical Field
The invention relates to the technical field of catalysts and applications, in particular to a carbon-based solid acid 300-AC-SO 3 H-Cr catalyst, and a preparation method and application thereof.
Background
Lignocellulose is the most abundant clean renewable resource on earth and mainly consists of cellulose, hemicellulose and lignin, and from these raw materials, various chemicals and fuels with high added value can be prepared through a certain technological means, wherein levulinate is a very important platform compound, and can be applied to various fields of perfumes, organic solvents, adhesives, fuel additives, medicines and the like.
At present, three processes for preparing levulinate from biomass resources at home and abroad are mainly adopted: 1) Levulinic acid esterification process. The method has the advantages that the reaction is relatively easy to carry out and no byproducts are produced, but the substrate levulinic acid is synthesized by converting biomass, so that the cost is high; 2) Furfuryl alcohol alcoholysis. The levulinate prepared by the method can also obtain ideal yield, and has the defects of complex reaction load, high energy consumption, high-pressure hydrogenation for converting furfural into furfuryl alcohol and high equipment requirement; 3) Biomass is directly hydrolyzed. Compared with the two preparation processes, the biomass direct alcoholysis method has the advantages of wide raw material sources, short process route and environmental friendliness, and has great prospect in industrial industrialization, wherein the most critical is the preparation of the efficient and practical catalyst. At present, the catalytic systems for preparing levulinate are divided into two types, wherein the homogeneous catalytic systems such as liquid acid, metal salt and ionic liquid have better catalytic performance but obvious defects, such as difficult separation and high corrosiveness. Heterogeneous catalytic systems are receiving increasing attention from researchers due to their advantages of reusability, ease of separation and recovery, and reduced environmental pollution. The carbon-based solid acid has the characteristics of low material cost, chemical inertia, good mechanical property, thermal stability and the like, and shows better performance in acid-catalyzed biomass utilization reaction.
The preparation of levulinate by glycolysis of glucose is a relatively complex reaction requiring the synergy of the Bronsted acid and the Lewis acid. In order to realize efficient alcoholysis of glucose, a catalyst with dual functions is critical to the whole reaction process.
Disclosure of Invention
The invention relates to a carbon-based solid acid catalyst 300-AC-SO 3 The preparation of H-Cr and the research method for preparing methyl levulinate by alcoholysis of glucose aim at solving the problems in the prior art, and the preparation of the double-function catalyst which is beneficial to dehydration reaction and isomerization reaction is realized, and the product and the catalyst are easy to separate, have high stability and can be recycled.
The technical solution of the invention is as follows: carbon-based solid acid catalyst 300-AC-SO 3 The research method for preparing H-Cr and preparing methyl levulinate by alcoholysis of glucose is characterized by comprising the following steps:
1) Taking a certain amount of microcrystalline cellulose in a tube furnace, and pyrolyzing the microcrystalline cellulose in a nitrogen atmosphere to generate active carbon;
2) Placing the activated carbon in the step 1 and a certain amount of concentrated sulfuric acid into a hydrothermal reaction kettle, and aging the activated carbon and the concentrated sulfuric acid in an oven at a certain temperature for a period of time.
3) After the reaction in the step 2 is completed, washing the obtained sulfonated carbon with deionized water until the PH=7, and then drying in an oven;
4) Mixing the solid obtained in the step 3 with a certain amount of CrCl 3 ·6H 2 O is dissolved in deionized water, and the final catalyst is obtained after stirring, filtering and drying.
5) Glucose, a solvent and a catalyst are added into a high-pressure reaction kettle to form a reaction system, wherein the amount of the added glucose is 0.3g, the amount of the catalyst is 0.05 g-0.25 g, and the amount of the catalyst is 20ml.
2. The preparation method according to claim 1, wherein the pyrolysis temperature of the tube furnace is 300 ℃, the heating rate is 5 ℃/min, the holding time is 5h, and the nitrogen flow rate is 40ml/min.
3. The method according to claim 1, wherein the ratio of activated carbon to concentrated sulfuric acid is 1g: 20ml.
4. The preparation method according to claim 1, wherein the hydrothermal temperature is 150 ℃ and the hydrothermal time is 10 hours.
5. The process of claim 1, wherein the temperature of the dried catalyst is 105 ℃ for a period of time of 12 hours or more.
6. The process according to claim 1, wherein the stirring speed is 600 to 800rpm and the stirring time is 6 to 8 hours.
7. The method according to claim 1, wherein the Cr loading is 5% -15%.
8. 300-AC-SO of a carbon-based solid acid prepared as claimed in claim 1 3 The H-Cr catalyst is used for an experiment for preparing methyl levulinate by glucose alcoholysis and is characterized by comprising the following steps.
9. The carbon-based solid acid 300-AC-SO of claim 1 3 The H-Cr catalyst, glucose and solvent are added into a high-pressure reaction kettle to form a reaction system, the amount of the added glucose is 0.3g, the dosage of the catalyst is 0.05 g-0.25 g, and the dosage of the methanol is 20ml.
10. And (3) reacting for 3-7h at 180-220 ℃, and separating the catalyst after the reaction is finished to obtain a target product.
11. The invention has the advantages that: the carbon-based solid acid catalyst provided by the invention has the advantages of simple preparation mode, low material cost and high activity. The catalyst is a heterogeneous catalyst, so that the catalyst is convenient to recycle.
Drawings
FIG. 1 catalyst X-ray diffraction pattern (XRD)
FIG. 2 Raman spectrum of catalyst (Raman)
FIG. 3 catalyst 300-AC-SO 3 Stability test of H-Cr
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, it being understood that these examples are provided for the purpose of illustrating the invention only and are not intended to limit the scope of the invention. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the invention, and that such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
0.3g of glucose and 0.15g of 300-AC-SO were weighed out 3 The H-Cr catalyst and 20ml of methanol are reacted in a high-pressure reaction kettle for 5 hours at 200 ℃, after the reaction is finished, the reaction is cooled to room temperature, and products are respectively analyzed by gas phase and liquid phase, and the glucose conversion rate is 99.6% and the yields of methyl levulinate and levulinate are 43.06% through quantitative analysis.
Example 2
The reaction procedure was exactly the same as in example 1, except that: in the catalyst preparation step, 200-AC-SO was prepared 3 H-Cr. The glucose conversion was 95.5%, and the yield of the main product methyl levulinate was 30.2%.
Example 3
The reaction procedure was exactly the same as in example 1, except that: in the catalyst preparation step, 400-AC-SO was prepared 3 H-Cr. The glucose conversion was 98.5%, and the yield of the main product methyl levulinate was 37.1%.
Example 4
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the reaction time of the alcoholysis of glucose is 3 hours, the conversion rate of glucose is 97.3 percent, and the yields of main products of methyl levulinate and levulinate are 35.69 percent.
Example 5
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the reaction time of the alcoholysis of glucose is 4 hours, the conversion rate of glucose is 97.5%, and the yields of main products of methyl levulinate and levulinic acid are 38.1%.
Example 6
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the reaction time of the alcoholysis of glucose is 6 hours, the conversion rate of glucose is 99.6 percent, and the yields of main products of methyl levulinate and levulinic acid are 40.1 percent.
Example 7
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the reaction time of the alcoholysis of glucose is 7 hours, the conversion rate of glucose is 99.7 percent, and the yields of main products of methyl levulinate and levulinic acid are 36.77 percent.
Example 8
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the temperature of the alcoholysis reaction of glucose is 180 ℃, the conversion rate of glucose is 82.6%, and the yields of main products of methyl levulinate and levulinate are 23.6%.
Example 9
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the temperature of the alcoholysis reaction of glucose is 190 ℃, the conversion rate of glucose is 94.9%, and the yields of main products of methyl levulinate and levulinate are 29.79%.
Example 10
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the temperature of the alcoholysis reaction of glucose is 210 ℃, the conversion rate of glucose is 99.8%, and the yields of main products of methyl levulinate and levulinate are 37.1%.
Example 11
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the temperature of the alcoholysis reaction of glucose is 220 ℃, the conversion rate of glucose is 99.8%, and the yields of main products of methyl levulinate and levulinate are 32.1%.
Example 12
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the dosage of the catalyst for the alcoholysis reaction of glucose is 0.05g, the conversion rate of glucose is 96.7%, and the yields of the main products of methyl levulinate and levulinic acid are 28.5%.
Example 13
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the dosage of the catalyst for the alcoholysis reaction of glucose is 0.10g, the conversion rate of glucose is 98.8%, and the yields of the main products of methyl levulinate and levulinate are 35.65%.
Example 14
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the dosage of the catalyst for the alcoholysis reaction of glucose is 0.20g, the conversion rate of glucose is 99.8%, and the yields of the main products of methyl levulinate and levulinic acid are 42.2%.
Example 15
The catalyst preparation is exactly the same as in example 1, except that: in the reaction step, the dosage of the catalyst for the alcoholysis reaction of glucose is 0.25g, the conversion rate of glucose is 99.8%, and the yields of the main products of methyl levulinate and levulinate are 39.46%.
FIG. 1 is an XRD pattern of the carbon-based solid acid catalyst prepared in example 1. It can be seen from the figure that 2 theta is 10-30 deg. and 35-50 deg diffraction peaks are the (002) and (101) crystal planes of amorphous carbon. Compared with AC, AC-SO 3 H and 300-AC-SO 3 The diffraction peak of H-Cr shifted from 17.8℃to 24℃indicating that sulfuric acid treatment resulted in further carbonization of the AC and increased the resulting AC-SO 3 H and 300-AC-SO 3 Degree of graphitization of H-Cr.
FIG. 2 is a Raman spectrum of the catalyst showing two prominent peaks at 1320 and 1590cm-1, corresponding to the D and G bands. 300-AC-SO was found by the D-band to G-band intensity ratio (ID/IG) 3 H-Cr(1.01)＜AC-SO 3 H (1.18) < AC (1.26), indicating an increase in graphitic carbon extent after sulfonation, consistent with XRD results.
FIG. 3 is a stability test of the catalyst prepared in example 1, and the yield of methyl levulinate can be maintained at about 30% after three repetitions.
Table 1 shows the effect of the carbon-based solid acid catalyst obtained in examples 1 to 3 on the alcoholysis reaction of glucose, and it can be seen from Table 1 that the reaction was best at a carbonization temperature of 300 ℃.
Table 2 shows the effect of different reaction times for example 1 and examples 4-7. As can be seen from the table, the catalyst performance was best with a glucose conversion of 99.6% and yields of levulinic acid and methyl levulinate of 43.06% when the reaction time was 5 h.
Table 3 shows the effect of different reaction temperatures in case 1 and cases 8 to 11. As can be seen from the table, the catalyst performs best when the reaction time is 200 ℃.
Table 4 shows the effect of the different catalyst amounts in case 1 and in cases 12 to 15. As can be seen from the table, the catalyst performance was best when the catalyst amount was 0.15 g.
Table 1 shows the effect of the alcoholysis of glucose at different carbonization temperatures during the preparation of the catalysts of examples 1 to 3.
Figure RE-GSB0000198862540000061
Table 2 shows the effects of different reaction times for example 1 and examples 4-7
Figure RE-GSB0000198862540000062
Table 3 shows the effects of different reaction temperatures for example 1 and examples 8-11
Figure RE-GSB0000198862540000063
Figure RE-GSB0000198862540000071
Table 4 shows the effect of the different catalyst amounts in case 1, cases 12 to 15
Figure RE-GSB0000198862540000072
The embodiments described above are embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (9)

1. Carbon-based solid acid catalyst 300-AC-SO 3 The research method for preparing H-Cr and preparing methyl levulinate by alcoholysis of glucose is characterized by comprising the following steps: the catalyst is prepared by adding Cr metal favorable for isomerization reaction on the basis of taking sulfuric acid as a Bronsted acidic site according to the methods of high-temperature carbonization, hydrothermal sulfonation and metal impregnation. The preparation method comprises the following steps:
1) Taking a certain amount of microcrystalline cellulose in a tube furnace, and pyrolyzing the microcrystalline cellulose in a nitrogen atmosphere to generate active carbon;
2) Placing the activated carbon in the step 1 and a certain amount of concentrated sulfuric acid into a hydrothermal reaction kettle, and aging the activated carbon and the concentrated sulfuric acid in an oven at a certain temperature for a period of time.
3) After the reaction in the step 2 is completed, washing the obtained sulfonated carbon with deionized water until the PH=7, and then drying in an oven;
4) Mixing the solid obtained in the step 3 with a certain amount of CrCl 3 ·6H 2 O is dissolved in deionized water, and the final catalyst is obtained after stirring, filtering and drying.
2. The preparation method according to claim 1, wherein the pyrolysis temperature of the tube furnace is 300 ℃, the heating rate is 5 ℃/min, the holding time is 5h, and the nitrogen flow rate is 40ml/min.
3. The method according to claim 1, wherein the ratio of the activated carbon to the concentrated sulfuric acid is 1 g/20 ml.
4. The preparation method according to claim 1, wherein the hydrothermal temperature is 150 ℃ and the hydrothermal time is 10 hours.
5. The process of claim 1, wherein the temperature of the dried catalyst is 105 ℃ for a period of time of 12 hours or more.
6. The process according to claim 1, wherein the stirring speed is 600 to 800rpm and the stirring time is 6 to 8 hours.
7. The method according to claim 1, wherein the Cr loading is 5% -15%.
8. The method for preparing methyl levulinate by catalyzing glucose alcoholysis is characterized in that biomass derivatives such as glucose are taken as substrates, methanol is taken as a solvent, and the carbon-based solid acid catalyst as claimed in claim 1 is taken as a reaction catalyst to realize the glucose alcoholysis reaction.
9. The method of claim 8, wherein when glucose is used as a substrate, the preparing step comprises the steps of: glucose, the carbon-based solid acid catalyst and methanol are added into a high-pressure reaction kettle, the mass ratio of the substrate to the catalyst is 1-2:1, the reaction temperature is 180-220 ℃, and the reaction time is 3-7h.
CN202111680232.2A 2021-12-31 2021-12-31 Preparation of carbon-based solid acid catalyst and method for preparing methyl levulinate by using same in glucose alcoholysis Pending CN116408105A (en)

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