CN109759112B - Preparation method of temperature response solid catalyst for biomass upgrading - Google Patents
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a temperature response solid catalyst for biomass upgrading. Mixing glucosamine hydrochloride and silicon dioxide, dissolving in water, heating, stirring and evaporating to dryness to obtain solid particles; grinding the solid particles, and roasting in a nitrogen atmosphere to obtain black solid powder; soaking black solid powder in a hydrogen fluoride solution, filtering, and drying to obtain a mesoporous carbon-nitrogen material; and soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering and drying to obtain the temperature response solid catalyst for biomass upgrading. According to the invention, the mesoporous carbon-nitrogen material has certain alkalinity, can chemically adsorb acid at low temperature, can release acid to catalyze cellulose hydrolysis at high temperature, and can recover the acid after the reaction is finished, so that the biomass raw material is finally converted into an energy chemical product with high added value.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a temperature response solid catalyst for biomass upgrading.
Background
Cellulose is renewable non-edible carbohydrate with the most abundant source in nature, and the directional conversion of the cellulose to prepare chemicals has important significance. However, natural cellulose has a stable crystal structure and strong intermolecular hydrogen bonding, which makes it very difficult to dissolve and degrade cellulose to obtain chemicals. At present, the methods for converting cellulose mainly include a biological enzyme method, a thermochemical method and a chemical conversion method. The biological enzyme method has low efficiency, high cost and difficult recycling of enzyme; thermochemical processes have high reaction temperatures, poor selectivity, and complex products, and thus chemical conversion of cellulose to chemicals has received increasing attention.
Hydrolysis of cellulose is a process of breaking 1, 4-glycosidic bonds in cellulose under the catalysis of Bronsted acids to produce oligosaccharides or glucose. Catalysts for cellulose hydrolysis are divided into two classes, one being homogeneous and the other heterogeneous. Homogeneous catalysts such as hydrochloric acid, sulfuric acid, heteropoly acid, ionic liquid and the like are widely used due to the characteristics of convenient use, high conversion efficiency and the like, but have various problems of equipment corrosion, acid recovery and the like, and limit further application of the homogeneous catalysts in cellulose hydrolysis. Heterogeneous catalysts such as sulfonated carbon, H-type molecular sieves, and the like. Heterogeneous catalysis has received more and more attention from researchers in recent years due to its unique advantages of easy product separation, reusable catalyst, less corrosion, less environmental pollution, etc. However, due to the solid-solid phase contact between the cellulose and the catalyst, high catalyst/substrate ratios, high reaction temperatures and long reaction times are generally required. Thus, efficient contact between the cellulose molecules and the catalyst becomes critical for efficient catalytic hydrolysis.
Chinese patent CN105080608A proposes a polyacid catalyst for catalyzing cellulose hydrolysis to prepare glucose, according to the fact that polyacid with a Dawson structure has high proton content, a polyacid compound and a surfactant are mixed according to a molar ratio to obtain a precipitate, and the precipitate is roasted by a muffle furnace to obtain the catalyst.
Chinese patent CN102532206A proposes a method for preparing levoglucosenone by catalytic pyrolysis of cellulose with solid phosphoric acid. Solid phosphoric acid is used as a catalyst, the solid phosphoric acid is mechanically mixed with cellulose, fast pyrolysis is carried out at 280-450 ℃ under the anaerobic condition, pyrolysis gas is condensed, and a liquid product rich in levoglucosenone can be obtained, wherein the yield of levoglucosan is about 20% according to determination.
The above patents all refer to heterogeneous catalysts, and the solid-solid phase contact is adopted between the cellulose and the catalyst, and the solid-solid reaction still has the problem of mass transfer.
At present, there is a need to provide a solid catalyst which is reusable, less corrosive and less polluting to the environment.
Disclosure of Invention
The invention aims to provide a preparation method of a temperature response solid catalyst for biomass upgrading, which is scientific, reasonable, simple and feasible, and the prepared temperature response solid catalyst for biomass upgrading can adsorb acid at low temperature and release acid at high temperature, so that cellulose can be efficiently and directionally catalyzed, and the catalyst can be recycled.
The invention relates to a preparation method of a temperature response solid catalyst for biomass upgrading, which comprises the following steps:
(1) mixing glucosamine hydrochloride and silicon dioxide, dissolving in water, heating, stirring and evaporating to dryness to obtain solid particles;
(2) grinding the solid particles, and roasting in a nitrogen atmosphere to obtain black solid powder;
(3) soaking black solid powder in a hydrogen fluoride solution to remove silicon dioxide, filtering, cleaning and drying to obtain a mesoporous carbon-nitrogen material;
(4) and soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering, cleaning and drying to obtain the temperature response solid catalyst for biomass upgrading.
The mass ratio of the glucosamine hydrochloride to the silicon dioxide in the step (1) is 1: 0.5-12, preferably in a mass ratio of 1: 1.
the heating temperature in the step (1) is 75-90 ℃.
The roasting temperature in the step (2) is 400-600 ℃, the preferred roasting temperature is 450 ℃, the heating rate is 1-10 ℃/min, and the preferred heating rate is 5 ℃/min.
The mass concentration of the hydrogen fluoride solution in the step (3) is 5-20%, and is preferably 12%.
The drying temperature in the step (3) is 70-80 ℃, and the drying time is 10-12 hours.
The acidic solution in the step (4) is one of a hydrochloric acid solution, a sulfuric acid solution, a phosphoric acid solution, a phosphotungstic acid solution or a formic acid solution.
The concentration of the acidic solution in the step (4) is 0.3-12 mol/L.
The soaking time in the step (4) is 15-25 h.
The drying temperature in the step (4) is 70-80 ℃, and the drying time is 9-15 hours.
The strong acid with trace concentration has little corrosion to equipment, so a weak alkaline solid and trace inorganic strong acid combined catalytic high-efficiency cellulose hydrolysis system is constructed. The invention provides a research idea of utilizing carbon-nitrogen materials to adsorb acid at low temperature and release acid at high temperature for catalytic reaction, and constructs heterogeneous cellulose directional conversion guided by an N-doped carbon solid catalyst with multiple catalytic active centers.
The invention not only overcomes the problems that the traditional heterogeneous catalyst and the cellulose solid-solid reaction mass transfer need high catalyst/substrate ratio, higher reaction temperature and long reaction time, but also utilizes the dilute acid to hydrolyze the cellulose and recover the dilute acid.
According to the invention, glucosamine hydrochloride and silicon dioxide are used as precursors, a carbon-nitrogen material is prepared after roasting, the silicon dioxide is removed to adsorb acid to obtain the acid-releasing solid acid catalyst with temperature response, and then the catalytic effect of the acid-releasing solid acid catalyst is discussed through the catalytic reaction of converting cellulose into glucose and 5-hydroxymethylfurfural in one step.
The application of the temperature response solid catalyst for biomass upgrading prepared by the invention is as follows:
putting cellulose into water, adding the cellulose into a reaction kettle for pretreatment, then adding a temperature response solid catalyst for biomass upgrading into the reaction kettle, carrying out catalytic reaction in an oil bath kettle, measuring reducing sugar by using an ultraviolet analyzer, and measuring glucose and 5-hydroxymethylfurfural in the product by using high performance liquid chromatography.
The invention has the following beneficial effects:
according to the invention, the mesoporous carbon-nitrogen material has certain alkalinity, can chemically adsorb acid at low temperature, can release acid to catalyze cellulose hydrolysis at high temperature, and can recover the acid after the reaction is finished, so that the biomass raw material is finally converted into an energy chemical product with high added value.
Drawings
FIG. 1 is a graph of the temperature response to HCl evolution for the catalyst of example 1.
FIG. 2 is a graph showing the nitrogen content of the carbon-nitrogen material and the types and contents of different types of nitrogen in the XPS analysis of example 1, wherein A is an XPS full graph of the carbon-nitrogen material and B is an XPS peak profile of the N element.
FIG. 3 is example 1CO2TPD measures the alkaline bitmap of the carbon-nitrogen material.
Detailed Description
The present invention is further described below with reference to examples.
The percentages in the following examples are by weight unless otherwise specified.
Example 1
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 0.5 mixing, dissolving in water, and slowly evaporating water under stirring at 80 deg.C to obtain solid granule.
(2) Grinding the solid particles, and roasting at 500 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the heat preservation is carried out for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 5% HF solution to remove silicon dioxide, filtering, washing with deionized water for multiple times until hydrofluoric acid is washed, and finally drying in a 70 ℃ oven for 10 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 6mol/L hydrochloric acid for 24h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 70 ℃ for 10 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 77.2%, the yield of reducing sugars was 46.9% (wherein the yield of glucose was 30.7%), and the yield of 5-hydroxymethylfurfural was 5.2%.
FIG. 1 is a graph of the catalyst temperature response to HCl release. It can be seen from the figure that the amount of HCl released from the solid catalyst adsorbed with hydrochloric acid gradually increased with increasing temperature, and when the temperature increased to 190 ℃, the amount of HCl released reached 0.6mmol/g, demonstrating that the catalyst can release hydrochloric acid at high temperature, and that acid chemisorbed on the surface of the catalyst during low temperature, demonstrating that the catalyst releasing acid in response to temperature is feasible.
FIG. 2 is a graph showing the nitrogen content of a carbon-nitrogen material analyzed by XPS, and the types and contents of different types of nitrogen. As can be seen from the figure, the material has high nitrogen content, the nitrogen types mainly include pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, and the pyridine nitrogen and the pyrrole nitrogen are main nitrogen types which are also important nitrogen types for the catalyst to chemisorb acid.
FIG. 3 is CO2TPD measures the alkaline bitmap of the carbon-nitrogen material. As can be seen from the figure, the carbon-nitrogen material has a wide absorption peak between 150 ℃ and 200 ℃, which indicates that the carbon-nitrogen material has certain weak alkaline sites and can adsorb CO at low temperature2Can be desorbed at high temperature, and has certain consistency with the principle of releasing HCl at high temperature in figure 1.
Example 2
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 5, dissolving the mixture in water, and slowly evaporating water under stirring at 86 ℃ to obtain solid particles.
(2) Grinding the solid particles, and roasting at 400 ℃ in a nitrogen atmosphere (the heating rate is 8 ℃/min, and the temperature is kept for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 8% HF solution to remove silicon dioxide, filtering, washing with deionized water for multiple times until hydrofluoric acid is washed, and finally drying in a 75 ℃ oven for 12 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 6mol/L hydrochloric acid for 25h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in a 75 ℃ oven for 15h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 71.9%, the yield of reducing sugars was 43.7% (wherein the yield of glucose was 27.5%), and the yield of 5-hydroxymethylfurfural was 4.4%.
Example 3
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 1, dissolving in water after mixing, and slowly evaporating water under stirring at 80 ℃ to obtain solid particles.
(2) Grinding the solid particles, and roasting at 600 ℃ in a nitrogen atmosphere (the heating rate is 6 ℃/min, and the heat preservation is carried out for 1h) to obtain black solid powder.
(3) And (3) soaking the black solid powder in 10% HF solution to remove the silicon dioxide template, then filtering, washing for multiple times by using deionized water until the silicon dioxide template is cleaned by hydrofluoric acid, and finally drying in a 72 ℃ oven for 11 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 10mol/L hydrochloric acid for 15h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in a 75 ℃ oven for 9 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 74.9%, the yield of reducing sugars was 45.3% (wherein the yield of glucose was 28.6%), and the yield of 5-hydroxymethylfurfural was 4.7%.
Example 4
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 10, and dissolving in water, and slowly evaporating water under stirring at 78 deg.C to obtain solid granules.
(2) Grinding the solid particles, and roasting at 550 ℃ in a nitrogen atmosphere (the heating rate is 10 ℃/min, and the heat is preserved for 1h) to obtain black solid powder.
(3) And (3) soaking the black solid powder in 7% HF solution to remove the silicon dioxide template, then filtering, washing for multiple times by using deionized water until the silicon dioxide template is cleaned by hydrofluoric acid, and finally drying in an oven at 78 ℃ for 10 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 3mol/L hydrochloric acid for 20h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 70 ℃ for 12 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 64.4%, the yield of reducing sugars was 34.5% (wherein the yield of glucose was 21.6%), and the yield of 5-hydroxymethylfurfural was 3.2%.
Example 5
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 1, dissolving in water after mixing, and slowly evaporating water under stirring at 80 ℃ to obtain solid particles.
(2) Grinding the solid particles, and roasting at 450 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the heat preservation is carried out for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 8% HF solution to remove silicon dioxide, filtering, washing with deionized water for multiple times until hydrofluoric acid is washed, and finally drying in an oven at 80 ℃ for 10 hours to obtain the mesoporous carbon-nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 6mol/L hydrochloric acid for 22h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 80 ℃ for 11 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 82.6%, the yield of reducing sugars was 51.4% (wherein the yield of glucose was 30.1%), and the yield of 5-hydroxymethylfurfural was 5.7%.
Example 6
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 6 dissolving in water after mixing, and slowly evaporating water under stirring at 75 ℃ to obtain solid particles.
(2) Grinding the solid particles, and roasting at 450 ℃ in a nitrogen atmosphere (the heating rate is 1 ℃/min, and the temperature is kept for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 6% HF solution to remove silicon dioxide, filtering, washing with deionized water for multiple times until hydrofluoric acid is washed, and finally drying in a 75 ℃ oven for 12 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 9mol/L formic acid for 18h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 78 ℃ for 10 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 70.2%, the yield of reducing sugars was 40.6% (wherein the yield of glucose was 25.6%), and the yield of 5-hydroxymethylfurfural was 3.8%.
Example 7
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 5 mixing, dissolving in water, and slowly evaporating water under stirring at 90 deg.C to obtain solid granule.
(2) Grinding the solid particles, and roasting at 480 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 10% HF solution to remove the silicon dioxide template, then filtering, washing with deionized water for multiple times until the silicon dioxide template is cleaned by hydrofluoric acid, and finally drying in an oven at 80 ℃ for 11 hours to obtain the mesoporous carbon-nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 6mol/L hydrochloric acid for 24h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 70 ℃ for 12 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 71.2%, the yield of reducing sugars was 41.1% (wherein the yield of glucose was 24.9%), and the yield of 5-hydroxymethylfurfural was 4.1%.
Example 8
(1) Mixing glucosamine hydrochloride and silicon dioxide in a ratio of 1: 2, dissolving the mixture in water, and slowly evaporating water under stirring at 75 ℃ to obtain solid particles.
(2) Grinding the solid particles, and roasting at 450 ℃ in a nitrogen atmosphere (the heating rate is 1 ℃/min, and the temperature is kept for 1h) to obtain black solid powder.
(3) Soaking black solid powder in 6% HF solution to remove silicon dioxide, filtering, washing with deionized water for multiple times until hydrofluoric acid is washed, and finally drying in a 75 ℃ oven for 12 hours to obtain the mesoporous carbon nitrogen material.
(4) Soaking the prepared carbon and nitrogen material in 9mol/L phosphotungstic heteropoly acid for 18h, filtering, washing with deionized water for many times until redundant acid is cleaned, and finally drying in an oven at 78 ℃ for 10 h to obtain the temperature response solid catalyst for biomass upgrading.
Analysis and test of catalytic performance:
0.1g of cellulose is put into 10ml of water and added into a reaction kettle for pretreatment for 2 hours, then 0.2g of temperature response solid catalyst for biomass upgrading is added into the reaction kettle, catalytic reaction is carried out for 5 hours at 190 ℃ in an oil bath kettle, reducing sugar is measured by an ultraviolet analyzer, and glucose and 5-hydroxymethylfurfural in the product are measured by high performance liquid chromatography.
It was found that the conversion of cellulose was 74.8%, the yield of reducing sugars was 44.6% (wherein the yield of glucose was 28.1%), and the yield of 5-hydroxymethylfurfural was 4.5%.
Claims (9)
1. A preparation method of a temperature response solid catalyst for biomass upgrading is characterized by comprising the following steps:
(1) mixing glucosamine hydrochloride and silicon dioxide, dissolving in water, heating, stirring and evaporating to dryness to obtain solid particles;
(2) grinding the solid particles, and roasting in a nitrogen atmosphere to obtain black solid powder;
(3) soaking black solid powder in a hydrogen fluoride solution to remove silicon dioxide, filtering, cleaning and drying to obtain a mesoporous carbon-nitrogen material;
(4) soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering, cleaning and drying to obtain a temperature response solid catalyst for biomass upgrading;
the acidic solution in the step (4) is one of a hydrochloric acid solution, a sulfuric acid solution, a phosphoric acid solution, a phosphotungstic acid solution or a formic acid solution.
2. The method for preparing the temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the mass ratio of glucosamine hydrochloride to silica in step (1) is 1: 0.5-12.
3. The method for preparing a temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the heating temperature in step (1) is 75-90 ℃.
4. The method for preparing the temperature-responsive solid catalyst for biomass upgrading as claimed in claim 1, wherein the calcination temperature in the step (2) is 400-600 ℃.
5. The method for preparing the temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the mass concentration of the hydrogen fluoride solution in the step (3) is 5-20%.
6. The method for preparing a temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the drying temperature in the step (3) is 70-80 ℃ and the drying time is 10-12 hours.
7. The method for preparing a temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the concentration of the acidic solution in the step (4) is 0.3-12 mol/L.
8. The method for preparing a temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the soaking time in the step (4) is 15-25 h.
9. The method for preparing a temperature-responsive solid catalyst for biomass upgrading according to claim 1, characterized in that the drying temperature in the step (4) is 70-80 ℃ and the drying time is 9-15 hours.
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