A meoh-bifunctional zirconium-based heteropoly acid catalytic system, a preparation method and application thereof
The MeOH-bifunctional zirconium-based heteropolyacid catalytic system efficiently catalyzes the conversion of glucose to pyruvate under mild conditions, solving the problems of harsh catalytic conditions and difficult preparation in existing technologies. It achieves high catalytic efficiency and easily separable products, and is suitable for biomass reactions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGDONG UNIV OF TECH
- Filing Date
- 2026-03-06
- Publication Date
- 2026-06-19
AI Technical Summary
Existing technologies for catalyzing the conversion of glucose to pyruvate require harsh catalytic conditions, are difficult to prepare, are not efficient enough, and are difficult to apply industrially.
A MeOH-bifunctional zirconium-based heteropolyacid catalytic system, consisting of a heteropolyacid catalyst and a methanol solvent, is used to catalyze the conversion of glucose to pyruvate in a one-step process under mild conditions. The catalyst is easy to prepare and can be recycled.
It achieves efficient and selective catalytic conversion of glucose to pyruvate under mild conditions, with easy product separation, saving manpower and resources, high catalytic efficiency, and applicable to reactions such as biomass.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer catalysis technology, and more specifically to a catalytic system based on MeOH-bifunctional zirconium-based heteropolyacids, its preparation method, and its application. Background Technology
[0002] The depletion of fossil resources and global warming have sparked great interest in renewable and sustainable alternatives to fuels and chemicals. Biomass, an important renewable carbon resource, boasts advantages such as abundant reserves, easy access, and the ability to be utilized without altering the existing carbon balance of ecosystems, making it the only promising renewable non-fossil-based carbon resource.
[0003] Glucose is a very important and versatile compound in the chemical field. It has wide applications in industrial production and laboratory research. It can be used to produce ethanol, butanol, antibiotics, amino acids, and to synthesize vitamin C, sorbitol, mannitol, gluconic acid, etc. Glucose is widely and abundantly sourced, and its conversion is particularly important in the field of biomass conversion. Pyruvic acid is a multifunctional chemical raw material that plays a key role in many industries. It is not only widely used in the petrochemical industry, but also holds an irreplaceable position in the cosmetics, fragrance, polymer crosslinking agents, and pharmaceutical industries. Therefore, finding efficient production methods to convert glucose into pyruvic acid has become an important issue for industry development.
[0004] Natalia Sobus et al. used synthetic zeolite BEA as a matrix to convert biomass glucose into pyruvate with the participation of Na-BEA zeolite. The highest pyruvate yield was achieved when treated with 0.1 g and 0.6 g Na-BEA catalysts for 1-5 hours at 200-250℃. Luo et al. optimized the fermentation process using gene editing combined with glucose as the main carbon source, strictly controlling dissolved oxygen and pH during fermentation to maintain efficient cell production. In the optimized fermenter scale, pyruvate yield reached approximately 65 g / L with a high sugar-acid conversion rate. Hädrich et al. used engineered Vibrionatriegens for fermentation, confirming that pyruvate was generated during high-intensity production using high-growth strains. While these studies achieved good results, the catalytic conditions were demanding, the preparation was difficult, and the efficiency was not high.
[0005] Therefore, developing a catalytic system that can be easily prepared and can efficiently and selectively catalyze under mild conditions is key to converting D-glucose into pyruvate for industrial production. Summary of the Invention
[0006] In view of this, the present invention provides a MeOH-bifunctional zirconium-based heteropolyacid catalytic system, its preparation method, and its application. This method uses methanol as the main solvent and heteropolyacid as the catalyst to prepare a heteropolyacid catalytic system based on MeOH as the solvent. The system exhibits excellent catalytic performance, is simple to prepare, and can be recycled.
[0007] The heteropolyacid catalytic system of this invention is mainly composed of a heteropolyacid catalyst and MeOH as a solvent.
[0008] One objective of this invention is to provide a method for preparing a MeOH-bifunctional zirconium-based heteropolyacid catalytic system, the specific steps of which are as follows:
[0009] S1. Prepare aqueous solutions of sodium tungstate and sodium metasilicate respectively. Within 10 min, add hydrochloric acid solution and sodium metasilicate solution to the aqueous solution of sodium tungstate in sequence. After adjusting the pH value, let it stand. After standing, add potassium chloride to the reaction solution, stir at room temperature, filter and collect the precipitate, and further purify to obtain SiW-1.
[0010] S2. Dissolve SiW-1 in deionized water, filter to remove insoluble matter, then adjust the pH value with potassium carbonate aqueous solution and let stand. After standing, add potassium chloride to the reaction solution, stir the reaction, filter and collect the precipitate to obtain SiW.
[0011] S3. Dissolve SiW in deionized water, adjust the pH of the SiW aqueous solution with hydrochloric acid, then add zirconium oxychloride aqueous solution, continue to adjust the pH, add cesium chloride, stir the reaction, filter and collect the precipitate, recrystallize the precipitate in water at 60℃, dry and grind it into Cs. 10 [(γ-SiW 10 O 36 The catalyst powder was added to MeOH to obtain the MeOH-bifunctional zirconium-based heteropolyacid catalytic system.
[0012] Preferably, in step S1, the concentration of the sodium tungstate aqueous solution is 0.6-0.7 g / mL, and the concentration of the sodium metasilicate aqueous solution is 0.11 g / mL; the volume ratio of the sodium tungstate aqueous solution to the sodium metasilicate aqueous solution is 3 mL:1 mL, and the concentration of the hydrochloric acid solution is 4 mol·L⁻¹. -1 The volume ratio of the hydrochloric acid solution to the sodium metasilicate aqueous solution is 1.65 mL: 1 mL.
[0013] Preferably, in step S1, the pH value is adjusted to 5.0-6.0, and the standing time is 100 minutes.
[0014] Preferably, in step S1, the mass ratio of sodium metasilicate to potassium chloride in the sodium metasilicate aqueous solution is 11g:90g.
[0015] In a further preferred embodiment, in step S1, the further purification operation is as follows: the precipitate is dissolved in 800 mL of deionized water, and the insoluble matter is removed by vacuum filtration; then 80 g of potassium chloride is added to the filtrate, and a large amount of precipitate is generated again. The precipitate is collected by vacuum filtration to obtain SiW-1.
[0016] Preferably, in step S2, the solid-liquid ratio of SiW-1 to deionized water is 1g:2mL, and the mass ratio of SiW-1 to potassium chloride is 1g:6g.
[0017] Preferably, in step S2, the concentration of the potassium carbonate aqueous solution is 2 mol·L⁻¹. -1 The pH value is adjusted to 8.8-9.0, and the standing time is 16 minutes; the stirring time at room temperature is 15-20 minutes.
[0018] Preferably, in step S3, the solid-liquid ratio of SiW to deionized water is 1 g: 15 mL, and the concentration of the hydrochloric acid solution is 1 mol·L⁻¹. -1 The hydrochloric acid solution is used to adjust the pH of the SiW aqueous solution to 4.0-4.1;
[0019] The concentration of the zirconium oxychloride aqueous solution is 22.6 mg / mL, and the volume ratio of the SiW aqueous solution to the zirconium oxychloride aqueous solution is 3 mL: 1 mL.
[0020] Preferably, in step S3, the pH value is adjusted to 2.0-2.1, the mass ratio of SiW to cesium chloride is 1g:0.56g, the stirring reaction is carried out for 20min, and the solid-liquid ratio of the catalyst powder to MeOH is 25mg:10mL.
[0021] The second objective of this invention is to provide a MeOH-bifunctional zirconium-based heteropolyacid catalytic system obtained by the above method.
[0022] The third objective of this invention is to provide an application of the MeOH-bifunctional zirconium-based heteropolyacid catalytic system, specifically: D-glucose and the MeOH-bifunctional zirconium-based heteropolyacid catalytic system are simultaneously added to a high-pressure reactor and stirred for 1-4 hours under conditions of 1MPa-2.5MPa oxygen and 110-150℃.
[0023] As can be seen from the above technical solution, compared with the prior art, the technical effects achieved by the present invention are as follows:
[0024] 1. The preparation and application of this invention have low equipment requirements, are easy to implement and operate, and the products are easier to separate compared with traditional reaction systems, saving manpower and resources.
[0025] 2. The heteropolyacid catalytic system of the present invention is mainly composed of zirconium-based heteropolyacid catalyst and methanol as solvent. The catalytic system has excellent catalytic efficiency, can be recycled, saves manpower and material resources in the catalytic process, and produces products with high catalytic activity and high catalytic efficiency.
[0026] 3. This invention breaks away from the traditional reaction system of a single metal catalyst + water solvent, using methanol, which has a relatively low boiling point, as the solvent. It achieves a one-step catalytic cracking of D-glucose into PA in oxygen, without requiring gas switching during the reaction. It can be applied to reactions such as the catalytic cracking of biomass. Attached Figure Description
[0027] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.
[0028] Figure 1 The structural formula of PA, the product of this invention;
[0029] Figure 2 The liquid chromatogram of Application Example 1;
[0030] Figure 3 The liquid chromatogram of Application Example 2;
[0031] Figure 4 The liquid chromatogram of Application Example 3;
[0032] Figure 5 The liquid chromatogram of Application Example 4;
[0033] Figure 6 The liquid chromatogram of Application Example 5;
[0034] Figure 7 The liquid chromatogram of Example 6 is used;
[0035] Figure 8 The liquid chromatogram of Application Example 7;
[0036] Figure 9 The liquid chromatogram of Example 8 is used;
[0037] Figure 10 The liquid chromatogram of Example 9 is used;
[0038] Figure 11 The liquid chromatogram of Application Example 10;
[0039] Figure 12 The liquid chromatogram of Application Example 11;
[0040] Figure 13 The liquid chromatogram of Comparative Example 1;
[0041] Figure 14 This is the liquid chromatogram of Comparative Example 2. Detailed Implementation
[0042] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0043] Example 1
[0044] 1. Weigh 182 g of sodium tungstate and dissolve it in 300 mL of deionized water; weigh 11 g of sodium metasilicate and add it to 100 mL of deionized water until completely dissolved; within 10 min, add 165 mL of 4 mol·L⁻¹ sodium sulfate to the sodium tungstate aqueous solution. -1 A hydrochloric acid solution was prepared, followed by the addition of an aqueous sodium metasilicate solution; then 4 mol·L⁻¹ was used. -1 The pH was adjusted to 5-6 with hydrochloric acid and maintained for 100 min. After 100 min, 90 g of potassium chloride was added, which produced a large amount of white precipitate. The white precipitate was collected by vacuum filtration. For further purification, the white precipitate was dissolved in 800 mL of deionized water and the insoluble matter was removed by vacuum filtration. Then, 80 g of potassium chloride was added to the filtrate, which again produced a large amount of precipitate. The precipitate was collected by vacuum filtration to obtain SiW-1.
[0045] 2. Dissolve 15 g of SiW-1 in 30 mL of deionized water, and remove insoluble matter by suction filtration; then use 2 mol·L⁻¹ water. -1 The pH of the potassium carbonate aqueous solution was adjusted to 9.0 and maintained for 16 min; 90 g of potassium chloride was added, which produced a large amount of white precipitate; stirring was continued for about 15 min, and the white precipitate SiW was collected by vacuum filtration.
[0046] 3. Weigh 1 g of SiW and dissolve it in 15 mL of deionized water; weigh 113 mg of zirconium oxychloride and dissolve it in 5 mL of deionized water; use 1 mol·L⁻¹ -1 The pH of the SiW aqueous solution was adjusted to 4.0 with hydrochloric acid, then zirconium oxychloride aqueous solution was added, and the pH was further adjusted to 2.0. After 3 min, 0.56 g of cesium chloride was added, producing a large amount of white precipitate. The mixture was stirred at room temperature for 20 min. Finally, the precipitate was collected by vacuum filtration and recrystallized in water at 60 °C. The precipitate was then dried in a forced-air oven to obtain white crystals. After grinding, 25 mg of Cs was taken... 10[(γ-SiW 10 O 36 The powder of Zr(H2O)2(µOH)2]·18H2O was added to 10 mL of MeOH to obtain a heteropolyacid catalytic system.
[0047] Application Example 1
[0048] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 110 °C (600 rpm) for 3 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 2 As shown.
[0049] Application Example 2
[0050] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the reaction was carried out at 120 °C with stirring (600 rpm) for 3 h. After the reaction was completed, the remaining liquid volume of the reaction system was accurately measured first, and then 1 mL of liquid sample was taken for liquid chromatography characterization. Figure 3 As shown.
[0051] Application Example 3
[0052] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 130 °C (600 rpm) for 3 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 4 As shown.
[0053] Application Example 4
[0054] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 140 °C (600 rpm) for 3 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 5 As shown.
[0055] Application Example 5
[0056] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 150 °C (600 rpm) for 3 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 6 As shown.
[0057] Application Example 6
[0058] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 130 °C (600 rpm) for 1 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 7 As shown.
[0059] Application Example 7
[0060] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 130 °C (600 rpm) for 2 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 8 As shown.
[0061] Application Example 8
[0062] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1 MPa, and the mixture was stirred at 130 °C (600 rpm) for 4 h. After the reaction, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 9 As shown.
[0063] Application Example 9
[0064] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 1.5 MPa, and the reaction was carried out at 130 °C with stirring (600 rpm) for 3 h. After the reaction was completed, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 10 As shown.
[0065] Application Example 10
[0066] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 2.0 MPa, and the reaction was carried out at 130 °C with stirring (600 rpm) for 3 h. After the reaction was completed, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 11 As shown.
[0067] Application Example 11
[0068] 200 mg (1.1 mmol) of D-glucose and the heteropolyacid catalytic system from Example 1 were simultaneously added to a high-pressure reactor, oxygen was introduced at 2.5 MPa, and the reaction was carried out at 130 °C with stirring (600 rpm) for 3 h. After the reaction was completed, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of liquid sample was taken for liquid chromatography characterization. Figure 12 As shown.
[0069] Comparative Example 1
[0070] 200 mg (1.1 mmol) of D-glucose was added to a high-pressure reactor, oxygen was introduced at 2.5 MPa, and the mixture was stirred at 130 °C (600 rpm) for 3 h. After the reaction was complete, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 13 As shown.
[0071] Comparative Example 2
[0072] 200 mg (1.1 mmol) of D-glucose and silicotungstic acid were simultaneously added to a high-pressure reactor, oxygen was introduced at 2.5 MPa, and the mixture was stirred at 130 °C (600 rpm) for 3 h. After the reaction was complete, the remaining liquid volume of the reaction system was accurately measured, and then 1 mL of the liquid sample was taken for liquid chromatography characterization. Figure 14 As shown.
[0073] Table 1 shows the catalytic activity of the catalytic systems used in Examples 1-11 for the catalytic cracking of D-glucose to pyruvate (PA).
[0074]
[0075] Table 1 shows the catalytic activity of the catalytic systems used in Application Examples 1-11 for the catalytic cracking of D-glucose to pyruvate (PA). As can be seen from Table 1, compared to Comparative Example 1, the conversion rate of D-glucose was improved in all reactions using the catalyst. Most of the products were concentrated in PA and GA, with the intermediate product GAP occasionally appearing, but in yields all below 10%. The yield of PA reached 40% or higher, indicating that the present invention exhibits excellent catalytic effect on D-glucose and can efficiently promote its reaction. Among these, under the reaction conditions of Application Example 3, using Example 1 as the catalytic system, the highest PA yield reached 56.0%.
[0076] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not 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
1. A process for the preparation of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system, characterized by, The specific steps are as follows: S1. Prepare aqueous solutions of sodium tungstate and sodium metasilicate respectively. Within 10 min, add hydrochloric acid solution and sodium metasilicate solution to the aqueous solution of sodium tungstate in sequence. After adjusting the pH value, let it stand. After standing, add potassium chloride to the reaction solution, stir at room temperature, filter and collect the precipitate, and further purify to obtain SiW-1. S2. Dissolve SiW-1 in deionized water, filter to remove insoluble matter, then adjust the pH value with potassium carbonate aqueous solution and let stand. After standing, add potassium chloride to the reaction solution, stir the reaction, filter and collect the precipitate to obtain SiW. S3. Dissolve SiW in deionized water, adjust the pH of the SiW aqueous solution with hydrochloric acid solution, then add zirconium oxychloride aqueous solution, continue to adjust the pH, add cesium chloride, stir the reaction, filter and collect the precipitate, recrystallize the precipitate, dry and grind it, add the powder to MeOH to obtain the MeOH-bifunctional zirconium-based heteropolyacid catalytic system.
2. The method for preparing a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S1, the concentration of the sodium tungstate aqueous solution is 0.6-0.7 g / mL, and the concentration of the sodium metasilicate aqueous solution is 0.11 g / mL; the volume ratio of the sodium tungstate aqueous solution to the sodium metasilicate aqueous solution is 3 mL:1 mL, and the concentration of the hydrochloric acid solution is 4 mol·L⁻¹. -1 The volume ratio of the hydrochloric acid solution to the sodium metasilicate aqueous solution is 1.65 mL: 1 mL.
3. The process for the preparation of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S1, the pH value is adjusted to 5.0-6.0, and the standing time is 100 minutes.
4. The process for the preparation of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S1, the mass ratio of sodium metasilicate to potassium chloride in the sodium metasilicate aqueous solution is 11g:90g.
5. The process for the preparation of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S2, the solid-liquid ratio of SiW-1 to deionized water is 1g:2mL, and the mass ratio of SiW-1 to potassium chloride is 1g:6g.
6. The process for the preparation of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S2, the concentration of the potassium carbonate aqueous solution is 2 mol·L⁻¹. -1 The pH value is adjusted to 8.8-9.0, and the standing time is 16 minutes; the stirring time at room temperature is 15-20 minutes.
7. The method for preparing a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S3, the solid-liquid ratio of SiW to deionized water is 1 g: 15 mL, and the concentration of the hydrochloric acid solution is 1 mol·L⁻¹. -1 The hydrochloric acid solution is used to adjust the pH of the SiW aqueous solution to 4.0-4.1; The concentration of the zirconium oxychloride aqueous solution is 22.6 mg / mL, and the volume ratio of the SiW aqueous solution to the zirconium oxychloride aqueous solution is 3 mL: 1 mL.
8. The method for preparing a MeOH-bifunctional zirconium-based heteropolyacid catalytic system according to claim 1, characterized in that, In step S3, the pH value is adjusted to 2.0-2.1, the mass ratio of SiW to cesium chloride is 1g:0.56g, the stirring reaction is carried out for 20min, and the solid-liquid ratio of the powder to MeOH is 25mg:10mL.
9. The MeOH-bifunctional zirconium-based heteropolyacid catalytic system obtained by any one of the methods described in claims 1-8.
10. An application of a MeOH-bifunctional zirconium-based heteropolyacid catalytic system, characterized in that, Specifically, D-glucose and the MeOH-bifunctional zirconium-based heteropolyacid catalytic system described in claim 9 are simultaneously added to a high-pressure reactor and stirred for 1-4 hours under conditions of 1MPa-2.5MPa oxygen and 110-150℃.