CN115990485B - Bimetallic composite biochar catalyst for sugar acid synthesis, sugar acid synthesis method and application - Google Patents
Bimetallic composite biochar catalyst for sugar acid synthesis, sugar acid synthesis method and application Download PDFInfo
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Abstract
The invention discloses a bimetallic composite biochar catalyst for sugar acid synthesis, which comprises the following steps: pulverizing biomass, and sieving to obtain biomass powder; adding biomass powder and platinum salt and/or zinc salt and alkali salt into an organic solvent for solvothermal reaction; and (3) washing the obtained material with absolute ethyl alcohol and ultrapure water, and drying to obtain the bimetallic composite biochar catalyst for sugar acid synthesis. The invention takes the straw as the raw material, thus realizing the recycling of the straw; the straw-based porous biochar material loaded with Pt and Zn bimetal is synthesized by a solvothermal method in one step, and the synthesis way is more green and safer; the polyol solution reduces part of platinum at high temperature, and meanwhile, transition metal zinc is introduced, so that the biomass derivative C5/C6 unit can be efficiently converted into sugar acid, and the reaction time is short and the selectivity is high. The catalyst of the invention is used as a catalyst, so that 100 percent of conversion rate and 65 to 88 percent of sugar acid yield are obtained.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis of sugar acid, and particularly relates to a bimetallic composite biochar catalyst for sugar acid synthesis, a sugar acid synthesis method and application.
Background
Fossil energy crisis and environmental problems are increasing, and lignocellulose biomass is used as a renewable resource and can be converted into liquid fuel, furfural and other C5/C6 chemicals with high added value. Wherein the oxidation product of the biomass derivative C5/C6 unit, namely gluconic acid/xylonic acid, is an important material for industries such as food, pharmacy, construction and the like. Compared with the problems of harsh conditions, long time and the like existing in the traditional methods of preparing the sugar acid by enzyme fermentation and the like, the metal heterogeneous catalysis system attracts more and more attention. However, the existing solid catalyst has the problems of complex synthesis process, harsh conditions, low activity and poor selectivity, and most of reaction systems need to be added with an alkali source and further acid treatment to finally obtain the sugar acid.
By searching, no patent publication related to the present patent application was found.
Disclosure of Invention
The invention aims to overcome the defects of complex synthesis process, harsh conditions and poor selectivity of a solid catalyst in the prior art, and provides a bimetallic composite biochar catalyst for sugar acid synthesis, a sugar acid synthesis method and application.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the bimetallic composite biochar catalyst for sugar acid synthesis comprises the following steps:
(1) Pulverizing biomass, and sieving to obtain biomass powder;
(2) Adding the biomass powder obtained in the step (1) and platinum salt and/or zinc salt and alkali salt into an organic solvent for solvothermal reaction to obtain a material;
(3) And (3) washing the material in the step (2) with absolute ethyl alcohol and ultrapure water, and drying to obtain the bimetallic composite biochar catalyst for sugar acid synthesis.
Further, the platinum salts in the step (2) are respectively platinum-containing inorganic salts, the zinc salts are zinc-containing inorganic salts, the alkali salts are hydroxides, and the organic solvent is polyalcohol. More preferably 1, 4-butanediol and ethylene glycol;
or, in the step (1), the biomass is one or more of rice straw, wheat straw, corn straw, peanut straw and sorghum straw;
or, during crushing, a crusher or a ball mill is used for crushing;
alternatively, the powder is crushed and sieved by a 60-mesh sieve.
Further, the amount of the substance of platinum atoms in the platinum salt in step (2): the amount of zinc atom in zinc salt is 1:4-8; amount of substance of platinum atom in platinum salt in step (2): the amount of the base salt material was 1:8-12. The mass ratio of the straw to the organic solution is 1:30-60; the mass ratio of the straw to the platinum atoms in the platinum salt is 1:2-5.
Further, the mass ratio of the straw to the organic solution is 1:55; the mass ratio of the straw to the platinum atoms in the platinum salt is 1:4.2; amount of platinum atom substance in platinum salt: the amount of zinc atom in zinc salt is 1:6-8, most preferably 1:6; amount of platinum atom substance in platinum salt: the amount of the base salt material was 1:10-12, most preferably 1:10.
further, when the biomass powder, the platinum salt, the zinc salt and the alkali salt are added into the organic solvent in the step (2), the platinum salt, the zinc salt and the alkali salt are magnetically stirred and dissolved in the polyol solution, and simultaneously the biomass powder is magnetically stirred and uniformly dispersed in the polyol solution, and the rotating speed of the magnetic stirring is 500-1000rpm; the rotation time is 0.5-4h;
or the solvothermal reaction in the step (2) is carried out at a temperature of 150-250 ℃ for 8-24h. The invention preferably controls the temperature of the solvothermal within the range, and the solvothermal temperature is too low, the metal loading is low, the temperature is too high, and the energy is wasted.
Or, the cleaning process in the step (3) specifically comprises the following steps: sequentially mixing the product obtained in the step (2) with absolute ethyl alcohol and ultrapure water, stirring and centrifuging; stirring for 5-10min at 200-300rmp, wherein the stirring mode is magnetic stirring, the times of washing with absolute ethyl alcohol are 2-3 times, and the times of washing with ultrapure water are 1-2 times; the rotation speed is 10000rpm during centrifugation, and the centrifugation time is 2min;
or the temperature of the drying in the step (3) is 55-80 ℃; the drying time is 10-24h.
Further, the rotation speed is 600-900rpm, most preferably 900rpm, and the rotation time is 1-2h, most preferably 1h;
the temperature of the solvothermal reaction is 180-220 ℃, most preferably 195 ℃; the solvothermal reaction time is 12-24 hours, most preferably 12 hours;
the drying temperature in the step (3) is 80 ℃; the drying time was 12h.
The application of the bimetal composite biochar catalyst in the catalytic oxidation of biomass derivatives.
The method for catalyzing and oxidizing biomass derivatives by using the bimetal composite biochar catalyst comprises the following steps:
the biomass derivative C5/C6 unit is added into water to prepare a reaction solution with the substrate mass concentration of 1-10%, the bimetallic composite biochar catalyst is used as a catalyst for sugar acid synthesis, oxygen is filled into a magnetic stirring high-pressure reaction kettle, then the reaction kettle is heated, after the reaction is finished, flowing water is used for cooling, and the upper liquid is taken out after the pressure is released, so that sugar acid is obtained.
Further, the sugar acid is gluconic acid or xylonic acid;
or the Pt content on the surface of the bimetallic composite biochar catalyst is 0.10-0.26mmol/g; the Zn content of the material surface is 0.30-0.77mmol/g.
Alternatively, the biomass derivative: the mass ratio of the catalyst is 1:1.5-10; the heating temperature is 50-120 ℃; heating for 0.1-8 h; the pressure of the oxygen is 0.2-2MPa; the present invention preferably controls the temperature and time of the oxidation reaction within the above-described ranges, which is advantageous in promoting complete oxidation of the biomass derivative C5/C6 units.
Or a reaction solution with a substrate mass concentration of 1-5%;
alternatively, the water is ultrapure water. In the present invention, the water only acts as a solvent and does not act as a catalyst. The source of the water is not particularly limited in the present invention, and products well known to those skilled in the art may be used.
Further, the Pt content on the surface of the bimetal composite biochar catalyst is 0.10-0.15mmol/g; the Zn content of the material surface is 0.30-0.46mmol/g;
the biomass derivative: the mass ratio of the catalyst is 1:2.5;
the heating temperature is 80-100 ℃; heating for 1-4h; the pressure of the oxygen is 0.2-1MPa;
alternatively, the magnetic stirring rate is 500-800rmp.
The invention has the advantages and positive effects that:
1. the invention takes the straw as the raw material, thus realizing the recycling of the straw; the straw-based porous biochar material loaded with Pt and Zn bimetal is synthesized by a solvothermal method in one step, and the synthesis way is more green and safer; the polyol solution reduces part of platinum at high temperature, meanwhile, transition metal zinc is introduced into the catalyst through a solvothermal process, and the material can not only efficiently convert biomass derivative C5/C6 units into sugar acid, but also has short reaction time and high selectivity. The results show that the bimetallic composite biochar catalyst for sugar acid synthesis prepared by the preparation method provided by the invention is used as a catalyst, and 100% of conversion rate and 65% -88% of sugar acid yield are obtained.
2. The method takes renewable biomass straw as a carbon source, prepares the bimetal composite biochar catalyst for synthesizing the sugar acid by carbonizing and reducing metal in one step by a solvothermal method, selectively catalyzes and oxidizes biomass derivative C5/C6 units in a neutral reaction system to synthesize the sugar acid, and provides a theoretical wide prospect for synthesizing the sugar acid by chemically catalyzing and converting agricultural wastes such as straw and the like.
3. The catalyst of the invention comprises platinum, zinc and oxygen-containing functional groups; the existence form of platinum is Pt 4+ 、Pt 2+ 、Pt 0 The zinc is present in the form of ZnO, and the oxygen-containing functional groups include hydroxyl functional groups and carboxyl functional groups.
4. The invention takes agricultural waste straw as a raw material, and prepares the bimetal composite biochar catalyst for synthesizing the sugar acid by carbonizing and reducing metal in one step by a solvothermal method, wherein the bimetal is platinum and zinc. The oxygen-containing functional group contained in the bimetallic composite biochar catalyst for synthesizing the sugar acid is beneficial to adsorption of a biomass derivative C5/C6 unit, promotes mass transfer of a reaction substrate, and platinum and zinc can promote oxidation products of the biomass derivative C5/C6 unit to be sugar acid, so that efficient catalytic reaction is realized.
Drawings
FIG. 1 is a TEM image of a product of the present invention; wherein, (a), (b) and (c) are the product patterns prepared in examples 1 to 3 in sequence; demonstrating successful loading of the metal on the carbon support;
FIG. 2 is an XPS diagram of a product of the invention; wherein, (a), (b) and (c) are the product patterns prepared in examples 1 to 3 in sequence; the surface of the material is proved to have metal, and part of platinum is reduced by an organic solvent;
FIG. 3 is a graph showing the yield and conversion rate of glucose produced by catalytic oxidation of biomass derivative C6 unit glucose for 1.5 hours at 100℃and 1MPa oxygen for the material prepared in the examples of the present invention;
FIG. 4 is a graph showing the yield of the material prepared in example 3 of the present invention in the catalytic oxidation of biomass derivative C6 glucose to gluconic acid at different reaction temperatures as a function of reaction time.
Detailed Description
The invention will now be further illustrated by reference to the following examples, which are intended to be illustrative, not limiting, and are not intended to limit the scope of the invention.
The various experimental operations involved in the specific embodiments are conventional in the art, and are not specifically noted herein, and may be implemented by those skilled in the art with reference to various general specifications, technical literature or related specifications, manuals, etc. before the filing date of the present invention.
The preparation method of the bimetallic composite biochar catalyst for sugar acid synthesis comprises the following steps:
(1) Pulverizing biomass, and sieving to obtain biomass powder;
(2) Adding the biomass powder obtained in the step (1) and platinum salt and/or zinc salt and alkali salt into an organic solvent for solvothermal reaction to obtain a material;
(3) And (3) washing the material in the step (2) with absolute ethyl alcohol and ultrapure water, and drying to obtain the bimetallic composite biochar catalyst for sugar acid synthesis.
Further, the platinum salts in the step (2) are respectively platinum-containing inorganic salts, the zinc salts are zinc-containing inorganic salts, the alkali salts are hydroxides, and the organic solvent is polyalcohol. More preferred are 1, 4-butanediol and ethylene glycol.
Or, in the step (1), the biomass is one or more of rice straw, wheat straw, corn straw, peanut straw and sorghum straw;
or, during crushing, a crusher or a ball mill is used for crushing;
alternatively, the powder is crushed and sieved by a 60-mesh sieve.
Preferably, the amount of material of platinum atoms in the platinum salt in step (2): the amount of zinc atom in zinc salt is 1:4-8; amount of substance of platinum atom in platinum salt in step (2): the amount of the base salt material was 1:8-12. The mass ratio of the straw to the organic solution is 1:30-60; the mass ratio of the straw to the platinum atoms in the platinum salt is 1:2-5.
Preferably, the mass ratio of the straw to the organic solution is 1:55; the mass ratio of the straw to the platinum atoms in the platinum salt is 1:4.2; amount of platinum atom substance in platinum salt: the amount of zinc atom in zinc salt is 1:6-8, most preferably 1:6; amount of platinum atom substance in platinum salt: the amount of the base salt material was 1:10-12, most preferably 1:10.
preferably, when the biomass powder, the platinum salt, the zinc salt and the alkali salt in the step (2) are added into the organic solvent, the platinum salt, the zinc salt and the alkali salt are magnetically stirred and dissolved in the polyol solution, and simultaneously the biomass powder is magnetically stirred and uniformly dispersed in the polyol solution, and the rotating speed of the magnetic stirring is 500-1000rpm; the rotation time is 0.5-4h;
or the solvothermal reaction in the step (2) is carried out at a temperature of 150-250 ℃ for 8-24h. The invention preferably controls the temperature of the solvothermal within the range, and the solvothermal temperature is too low, the metal loading is low, the temperature is too high, and the energy is wasted.
Or, the cleaning process in the step (3) specifically comprises the following steps: sequentially mixing the product obtained in the step (2) with absolute ethyl alcohol and ultrapure water, stirring and centrifuging; stirring for 5-10min at 200-300rmp, wherein the stirring mode is magnetic stirring, the times of washing with absolute ethyl alcohol are 2-3 times, and the times of washing with ultrapure water are 1-2 times; the rotation speed is 10000rpm during centrifugation, and the centrifugation time is 2min;
or the temperature of the drying in the step (3) is 55-80 ℃; the drying time is 10-24h.
Preferably, the rotation speed is 600-900rpm, most preferably 900rpm, and the rotation time is 1-2h, most preferably 1h;
the temperature of the solvothermal reaction is 180-220 ℃, most preferably 195 ℃; the solvothermal reaction time is 12-24 hours, most preferably 12 hours;
the drying temperature in the step (3) is 80 ℃; the drying time was 12h.
The application of the bimetal composite biochar catalyst in the catalytic oxidation of biomass derivatives.
The method for catalyzing and oxidizing biomass derivatives by using the bimetal composite biochar catalyst comprises the following steps:
the biomass derivative C5/C6 unit is added into water to prepare a reaction solution with the substrate mass concentration of 1-10%, the bimetallic composite biochar catalyst is used as a catalyst for sugar acid synthesis, oxygen is filled into a magnetic stirring high-pressure reaction kettle, then the reaction kettle is heated, after the reaction is finished, flowing water is used for cooling, and the upper liquid is taken out after the pressure is released, so that sugar acid is obtained.
Preferably, the sugar acid is gluconic acid or xylonic acid;
or the Pt content on the surface of the bimetallic composite biochar catalyst is 0.10-0.26mmol/g; the Zn content of the material surface is 0.30-0.77mmol/g.
Alternatively, the biomass derivative: the mass ratio of the catalyst is 1:1.5-10; the heating temperature is 50-120 ℃; heating for 0.1-8 h; the pressure of the oxygen is 0.2-2MPa; the present invention preferably controls the temperature and time of the oxidation reaction within the above-described ranges, which is advantageous in promoting complete oxidation of the biomass derivative C5/C6 units.
Or a reaction solution with a substrate mass concentration of 1-5%;
alternatively, the water is ultrapure water. In the present invention, the water only acts as a solvent and does not act as a catalyst. The source of the water is not particularly limited in the present invention, and products well known to those skilled in the art may be used.
Preferably, the Pt content on the surface of the bimetal composite biochar catalyst is 0.10-0.15mmol/g; the Zn content of the material surface is 0.30-0.46mmol/g;
the biomass derivative: the mass ratio of the catalyst is 1:2.5;
the heating temperature is 80-100 ℃; heating for 1-4h; the pressure of the oxygen is 0.2-1MPa;
alternatively, the magnetic stirring rate is 500-800rmp.
In the present invention, there is no particular requirement for the equipment of the pulverizing process, and a pulverizer or a ball mill well known to those skilled in the art may be used. In a specific embodiment of the present invention, the pulverizing apparatus is preferably a pulverizer.
After the solvothermal treatment is finished, the invention preferably filters, washes and dries the product after the solvothermal treatment in sequence to obtain the bimetallic composite biochar catalyst for sugar acid synthesis. The operation of the filtration, washing and drying is not particularly limited in the present invention, and washing and drying techniques well known to those skilled in the art may be employed.
The invention has no special requirement on the drying equipment, and adopts a common blast drying box in the field.
The invention has no special limitation on the mixing operation of the composite biochar catalyst, the biomass derivative C5/C6 unit and water and the oxygen filling operation, and adopts the technical scheme of mixing which is well known to the person skilled in the art.
Specifically, the related preparation and detection are as follows:
example 1
A preparation method of a platinum metal composite biochar catalyst for sugar acid synthesis comprises the following steps:
(1) 0.2g of chloroplatinic acid and 0.2g of sodium hydroxide are dissolved in 20ml of glycol solution; crushing rice straw, sieving with a 60-mesh sieve, adding 0.4g of crushed rice straw into the ethylene glycol solution, and uniformly mixing by magnetic stirring under the conditions of: the rotation speed is 900rpm, and the time is 1h;
(2) After the mixing is finished, the mixture is put into a high-temperature high-pressure reaction kettle for solvothermal reaction under the condition of: the heating temperature is 195 ℃ and the heating time is 12 hours. Taking out the carbonized bimetal composite material after the solvothermal treatment, washing the bimetal composite material with ethanol for 2-3 times, washing the bimetal composite material with ultrapure water for 1-2 times, centrifuging to obtain the carbonized material, and finally drying the carbonized material at 80 ℃ for 12 hours to obtain the straw-based platinum-containing porous biochar material (Pt/C).
Fig. 1 (a) is a TEM image of the product, demonstrating that the metallic platinum was successfully supported on the carbon support.
FIG. 2 (a) is an XPS diagram of the product, demonstrating the presence of platinum on the surface of the material, with a surface Pt content of preferably 0.05-0.10mmol/g.
The yield and conversion of glucose produced by catalytic oxidation of glucose for 1.5h at 100℃and 1MPa of oxygen for the material Pt/C prepared in example 1 are shown in FIG. 3.
Example 2
The preparation method of the zinc metal composite biochar catalyst for sugar acid synthesis comprises the following steps:
(1) 0.4g of zinc chloride and 0.2g of sodium hydroxide are dissolved in 20ml of glycol solution; crushing rice straw, sieving with a 60-mesh sieve, adding 0.4g of crushed rice straw into the ethylene glycol solution, and uniformly mixing by magnetic stirring under the conditions of: the rotation speed is 900rpm, and the time is 1h;
(2) After the mixing is finished, the mixture is put into a high-temperature high-pressure reaction kettle for solvothermal reaction under the condition of: the heating temperature is 195 ℃ and the heating time is 12 hours. Taking out the carbonized bimetal composite material after the solvothermal treatment, washing the bimetal composite material with ethanol for 2-3 times, washing the bimetal composite material with ultrapure water for 1-2 times, centrifuging to obtain the carbonized material, and finally drying the carbonized material at 80 ℃ for 12 hours to obtain the straw-based zinc-containing porous biochar material (Zn/C).
Fig. 1 (b) is a TEM image of the product, demonstrating that metallic zinc is uniformly supported on the carbon support.
FIG. 2 (b) is an XPS diagram of the product, demonstrating the presence of zinc on the surface of the material, with a surface Zn content of preferably 2.00-3.00mmol/g.
The yield and conversion of glucose produced by catalytic oxidation of glucose for 1.5h at 100℃and 1MPa of oxygen for the material Pt/C prepared in example 2 are shown in FIG. 3.
Example 3
The preparation process of bimetallic composite biochar catalyst for sugar acid synthesis includes the following steps:
(1) 0.2g of chloroplatinic acid, 0.4g of zinc chloride and 0.2g of sodium hydroxide are taken and dissolved in 20ml of glycol solution; crushing rice straw, sieving with a 60-mesh sieve, adding 0.4g of crushed rice straw into the ethylene glycol solution, and uniformly mixing by magnetic stirring under the conditions of: the rotation speed is 900rpm, and the time is 1h;
(2) After the mixing is finished, the mixture is put into a high-temperature high-pressure reaction kettle for solvothermal reaction under the condition of: the heating temperature is 195 ℃ and the heating time is 12 hours. Taking out the carbonized bimetal composite material after the solvothermal treatment, washing the bimetal composite material with ethanol for 2-3 times, washing the bimetal composite material with ultrapure water for 1-2 times, centrifuging the carbonized bimetal composite material to obtain the carbonized material, and finally drying the carbonized material at 80 ℃ for 12 hours to obtain the bimetal composite biochar catalyst (Pt/Zn/C) for sugar acid synthesis.
As calculated by XPS result, the Pt content in the bimetallic composite biochar catalyst for sugar acid synthesis prepared in the embodiment is preferably 0.10-0.26mmol/g, more preferably 0.10-0.15mmol/g; the surface Zn content of the material is preferably 0.30 to 0.77mmol/g, more preferably 0.30 to 0.46mmol/g.
Fig. 1 (c) is a TEM image of the product, demonstrating that the metal was successfully supported on the carbon support.
Fig. 2 (c) is an XPS diagram of the product, demonstrating the presence of platinum and zinc on the surface of the material, with part of the platinum being reduced by the polyol solution.
The yield and conversion of glucose produced by catalytic oxidation of glucose for 1.5h at 100℃and 1MPa oxygen for the material Pt/Zn/C prepared in example 3 are shown in FIG. 3.
FIG. 4 is a graph showing the yield of glucose produced by catalytic oxidation of glucose at various reaction temperatures as a function of reaction time for the material prepared in example 3.
Application example 1
A sugar acid synthesis method comprises the following steps:
taking and uniformly mixing 0.02g of the straw-based platinum-containing porous biochar material (Pt/C) prepared in the embodiment 1 with 0.05g of glucose and 5ml of ultrapure water to obtain a mixed solution (the mass concentration of the glucose in the mixed solution is 1 percent, and the mass ratio of the straw-based platinum-containing porous biochar catalyst to the glucose is 1:2.5), transferring the mixed solution into a high-pressure reaction kettle, filling 1MPa of oxygen, carrying out oxidation reaction at 100 ℃, and carrying out magnetic stirring at the stirring speed of 800rmp; after 1.5h, the reaction mixture was cooled rapidly with an ice-water bath, then filtered with a filter membrane, and the filtered solution was taken for liquid chromatography to determine the product, and the yield of gluconic acid was calculated.
Wherein, the conditions of the liquid chromatography are as follows: the column was Shodex SH1011, the mobile phase was 0.5ml/min sulfuric acid solution (5 mM), the column temperature was 50deg.C, and the sample injection amount was 10uL. The gluconic acid detector is an ultraviolet detector for measuring the sample components at 210nm, and the temperature of the detector is 25 ℃. The glucose detector was a differential detector with a detector temperature of 35 ℃.
The final yield of gluconic acid was 21.0% and the conversion of glucose was 28.7%.
Application example 2
A sugar acid synthesis method comprises the following steps:
mixing 0.02g of the straw-based zinc-containing porous biochar material (Zn/C) prepared in example 2 with 0.05g of glucose and 5ml of ultrapure water uniformly to obtain a mixed solution (the mass concentration of glucose in the mixed solution is 1%, and the mass ratio of the straw-based zinc-containing porous biochar catalyst to the glucose is 1:2.5), transferring the mixed solution into a high-pressure reaction kettle, filling 1MPa of oxygen, carrying out oxidation reaction at 100 ℃, and carrying out magnetic stirring at the stirring speed of 800rmp; after 1.5h, the reaction mixture was cooled rapidly with an ice-water bath, then filtered with a filter membrane, and the filtered solution was taken for liquid chromatography to determine the product, and the yield of gluconic acid was calculated.
Wherein, the conditions of the liquid chromatography are as follows: the column was Shodex SH1011, the mobile phase was 0.5ml/min sulfuric acid solution (5 mM), the column temperature was 50deg.C, and the sample injection amount was 10uL. The gluconic acid detector is an ultraviolet detector for measuring the sample components at 210nm, and the temperature of the detector is 25 ℃. The glucose detector was a differential detector with a detector temperature of 35 ℃.
The final yield of gluconic acid was 0.5% and the conversion of glucose was 4.2%.
Application example 3
A sugar acid synthesis method comprises the following steps:
taking 0.02g of the bimetallic composite biochar catalyst (Pt/Zn/C) for sugar acid synthesis prepared in example 3 and 0.05g of glucose, uniformly mixing 5ml of ultrapure water to obtain a mixed solution (the mass concentration of the glucose in the mixed solution is 1 percent, the mass ratio of the bimetallic composite biochar catalyst for sugar acid synthesis to the glucose is 1:2.5), transferring the mixed solution into a high-pressure reaction kettle, filling 1MPa of oxygen, carrying out oxidation reaction at 100 ℃, and carrying out magnetic stirring at the stirring speed of 800rmp; after 1.5h, the reaction mixture was cooled rapidly with an ice-water bath, then filtered with a filter membrane, and the filtered solution was taken for liquid chromatography to determine the product, and the yield of gluconic acid was calculated.
Wherein, the conditions of the liquid chromatography are as follows: the column was Shodex SH1011, the mobile phase was 0.5ml/min sulfuric acid solution (5 mM), the column temperature was 50deg.C, and the sample injection amount was 10uL. The gluconic acid detector is an ultraviolet detector for measuring the sample components at 210nm, and the temperature of the detector is 25 ℃. The glucose detector was a differential detector with a detector temperature of 35 ℃.
The final yield of gluconic acid was 88% and the conversion of glucose was 100%.
Application example 4
A sugar acid synthesis method comprises the following steps:
taking 0.02g of the bimetallic composite biochar catalyst (Pt/Zn/C) for sugar acid synthesis prepared in example 3 and 0.05g of xylose, uniformly mixing 5ml of ultrapure water to obtain a mixed solution (the mass concentration of xylose in the mixed solution is 1 percent, the mass ratio of the bimetallic composite biochar catalyst for sugar acid synthesis to the xylose is 1:2.5), transferring the mixed solution into a high-pressure reaction kettle, filling 1MPa of oxygen, carrying out oxidation reaction at 100 ℃, and carrying out magnetic stirring at the stirring speed of 800rmp; after 1.5h, the reaction mixture was cooled rapidly with an ice water bath, then filtered with a filter membrane, and the filtered solution was taken for liquid chromatography to determine the product, and the yield of xylonic acid was calculated.
Wherein, the conditions of the liquid chromatography are as follows: the column was Shodex SH1011, the mobile phase was 0.5ml/min sulfuric acid solution (5 mM), the column temperature was 50deg.C, and the sample injection amount was 10uL. The xylonic acid detector is an ultraviolet detector for measuring the sample components at 210nm, and the temperature of the detector is 25 ℃. The xylose detector was a differential detector with a detector temperature of 35 ℃.
The final yield of xylonic acid was 65% and the conversion of xylose was 100%.
The calculation formula of the yield in the above application example is:
yield of gluconic acid (mol%) =yield of gluconic acid (mol)/glucose unit (mol) ×100%
Xylitol yield (mol%) =xylitol yield (mol)/xylose unit (mol) ×100%.
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (6)
1. A bimetallic composite biochar catalyst for sugar acid synthesis is characterized in that: the preparation method of the catalyst comprises the following steps:
(1) Pulverizing biomass, and sieving to obtain biomass powder;
(2) Adding the biomass powder obtained in the step (1) and platinum salt, zinc salt and alkali salt into an organic solvent for solvothermal reaction to obtain a material;
(3) Washing the material in the step (2) with absolute ethyl alcohol and ultrapure water, and drying to obtain the bimetallic composite biochar catalyst for sugar acid synthesis;
the platinum salt in the step (2) is a platinum-containing inorganic salt, the zinc salt is a zinc-containing inorganic salt, the alkali salt is hydroxide, and the organic solvent is polyol;
the biomass in the step (1) is one or more of rice straw, wheat straw, corn straw, peanut straw and sorghum straw;
crushing by using a crusher or a ball mill during crushing;
pulverizing and sieving with 60 mesh sieve;
amount of substance of platinum atom in platinum salt in step (2): the amount of zinc atom in zinc salt is 1:4-8; amount of substance of platinum atom in platinum salt in step (2): the amount of the base salt material was 1:8-12; the mass ratio of the biomass powder to the organic solution is 1:30-60; the mass ratio of the biomass powder to the platinum atoms in the platinum salt is 1:2-5;
when the biomass powder, the platinum salt, the zinc salt and the alkali salt are added into the organic solvent in the step (2), magnetically stirring and dissolving the platinum salt, the zinc salt and the alkali salt in the polyol solution, and simultaneously, magnetically stirring and uniformly dispersing the biomass powder in the polyol solution, wherein the rotating speed of the magnetically stirring is 500-1000rpm; the rotation time is 0.5-4h;
the solvothermal reaction temperature in the step (2) is 150-250 ℃ and the reaction time is 8-24h;
the cleaning process in the step (3) specifically comprises the following steps: sequentially mixing the product obtained in the step (2) with absolute ethyl alcohol and ultrapure water, stirring and centrifuging; stirring for 5-10min at 200-300rmp, wherein the stirring mode is magnetic stirring, the times of washing with absolute ethyl alcohol are 2-3 times, and the times of washing with ultrapure water are 1-2 times; the rotation speed is 10000rpm during centrifugation, and the centrifugation time is 2min;
the drying temperature in the step (3) is 55-80 ℃; the drying time is 10-24 hours;
the rotating speed is 600-900rpm, and the rotating time is 1-2h.
2. The bimetallic composite biochar catalyst for sugar acid synthesis according to claim 1, wherein: the mass ratio of the straw to the organic solution is 1:55; the mass ratio of the straw to the platinum atoms in the platinum salt is 1:4.2; amount of platinum atom substance in platinum salt: the amount of zinc atom in zinc salt is 1:6-8; amount of platinum atom substance in platinum salt: the amount of the base salt material was 1:10-12;
the temperature of the solvothermal reaction in the step (2) is 180-220 ℃, and the time of the solvothermal reaction is 12-24 hours;
the drying temperature in the step (3) is 80 ℃; the drying time was 12h.
3. Use of the bimetallic composite biochar catalyst according to claim 1 or 2 in the catalytic oxidation of xylose or glucose.
4. A method for catalytic oxidation of xylose or glucose using the bimetallic composite biochar catalyst according to claim 1 or 2, characterized in that: the method comprises the following steps:
xylose or glucose is added into water to prepare a reaction solution with the substrate mass concentration of 1-10%, the bimetallic composite biochar catalyst for sugar acid synthesis is used as a catalyst, oxygen is filled into a magnetic stirring high-pressure reaction kettle to heat, flowing water is used for cooling after the reaction is finished, and the upper liquid is taken out after the pressure is released to obtain sugar acid; the sugar acid is gluconic acid or xylonic acid.
5. The method according to claim 4, wherein: the Pt content on the surface of the bimetal composite biochar catalyst is 0.10-0.26mmol/g; the Zn content of the material surface is 0.30-0.77mmol/g;
alternatively, the biomass derivative: the mass ratio of the catalyst is 1:1.5-10; the heating temperature is 50-120 ℃; heating for 0.1-8 h; the pressure of the oxygen is 0.2-2MPa;
or a reaction solution with a substrate mass concentration of 1-5%;
alternatively, the water is ultrapure water.
6. The method according to claim 5, wherein: the Pt content on the surface of the bimetal composite biochar catalyst is 0.10-0.15mmol/g; the Zn content of the material surface is 0.30-0.46mmol/g;
the biomass derivative: the mass ratio of the catalyst is 1:2.5;
the heating temperature is 80-100 ℃; heating for 1-4h; the pressure of the oxygen is 0.2-1MPa; alternatively, the magnetic stirring rate is 500-800rmp.
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