CN109806899B - Preparation method of solid catalyst capable of releasing acid in response to temperature - 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 solid catalyst capable of releasing acid in response to temperature. Dissolving aminoguanidine hydrochloride, silicon dioxide and water together, and evaporating water under the condition of heating and stirring to obtain dry solid particles; roasting the solid particles in a nitrogen atmosphere to obtain brown yellow solid powder; soaking the brown yellow solid powder in a hydrogen fluoride solution, filtering, and drying to obtain a mesoporous carbon and nitrogen material; and soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering, cleaning and drying to obtain the solid catalyst capable of releasing acid in response to temperature. 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 the carbon nitrogen material can recover the dilute acid at low temperature, thereby reducing the corrosion of equipment and the pollution of environment.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst capable of releasing acid in response to temperature, which is scientific, reasonable, simple and feasible, and the prepared solid catalyst capable of releasing acid in response to temperature can adsorb acid at low temperature and release acid at high temperature, has the characteristics of efficiently catalyzing cellulose directionally, and can realize the reutilization of the catalyst.
The preparation method of the solid catalyst for releasing acid in response to temperature comprises the following steps:
(1) preparation of mesoporous carbon-nitrogen material
Dissolving aminoguanidine hydrochloride, silicon dioxide and water together, and evaporating water under the condition of heating and stirring to obtain dry solid particles; grinding the solid particles, and roasting in a nitrogen atmosphere to obtain brown yellow solid powder; soaking the brown yellow solid powder in hydrogen fluoride solution to remove SiO2Then filtering, cleaning and drying to obtain a mesoporous carbon-nitrogen material;
(2) preparation of solid catalyst releasing acid in response to temperature
And soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering, cleaning and drying to obtain the solid catalyst capable of releasing acid in response to temperature.
The mass ratio of the aminoguanidine hydrochloride to the silicon dioxide in the step (1) is 1:0.1-10, and the preferable mass ratio is 1: 1.
the heating temperature in the step (1) is 80-90 ℃.
The roasting temperature in the step (1) is 200-.
The mass concentration of the hydrogen fluoride solution in the step (1) is 5-30%, preferably 10 wt%.
The drying temperature in the step (1) is 60-120 ℃, and the drying time is 10-12 hours.
The acidic solution in the step (2) 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 (2) is 0.1-10 mol/L.
The soaking time in the step (2) is 24-30 h.
The drying temperature in the step (2) is 60-120 ℃, and the drying time is 10-12 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.
According to the invention, aminoguanidine 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 an acid-releasing solid acid catalyst with temperature response, and then the catalytic effect of the acid-releasing solid acid catalyst is discussed through a catalytic reaction of converting cellulose into glucose and 5-hydroxymethylfurfural in one step.
The application of the solid catalyst for releasing acid in response to temperature prepared by the invention is as follows:
putting cellulose into water, adding the cellulose into a reaction kettle for pretreatment, then adding a solid catalyst which releases acid in response to temperature 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:
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. The invention utilizes the mesoporous carbon-nitrogen material with certain alkalinity, can chemically adsorb acid at low temperature, can release acid to catalyze cellulose hydrolysis at high temperature, and after the reaction is finished, the carbon-nitrogen material can recover the acid to prepare the solid catalyst capable of releasing the acid through temperature response, thereby effectively solving the separation problem of the catalyst and the product, being convenient for recycling, reducing the production cost and reducing the environmental pollution problem.
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.
FIG. 4 is a diagram showing the recycling of the catalyst in example 1.
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
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 0.5 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 500 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to remove SiO2Then filtering, washing for many times by using deionized water until the solution is washed by hydrofluoric acid, and finally drying in an oven at 70 ℃ for 10 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 7mol/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 solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 80%, the yield of reducing sugars was 53.4% (wherein the yield of glucose was 35.2%), and the yield of 5-hydroxymethylfurfural was 4.1%.
FIG. 1 is a graph of the catalyst temperature response to HCl release. As can be seen from the figure, the amount of HCl released by the solid catalyst adsorbing hydrochloric acid gradually increases with the increase of the temperature, and the release amount of HCl reaches 0.7mmol/g when the temperature is increased to 180 ℃, which proves that the catalyst can release hydrochloric acid at high temperature.
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 both have certain alkalinity and can carry out chemical adsorption on 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 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.
Fig. 4 is a catalyst recycling map. It can be seen from the figure that the catalyst still maintains good catalytic activity after four cycles of use. It has also been demonstrated that acid released at high temperatures can also be effectively recovered in low temperature processes.
Example 2
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 3, dissolving the mixture with water, and slowly evaporating water under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 500 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to removeSiO removal2Then filtering, washing for many times by using deionized water until the solution is washed by hydrofluoric acid, and finally drying in an oven at 80 ℃ for 12 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 7mol/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 80 ℃ for 12 h to obtain the solid catalyst capable of releasing acid in response to temperature.
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 0.4g of solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 82.5%, the yield of reducing sugars was 54.7% (wherein the yield of glucose was 36.2%), and the yield of 5-hydroxymethylfurfural was 6.2%.
Example 3
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 1 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 200 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to remove SiO2And (3) filtering the template, washing the template for multiple times by using deionized water until the template is washed by hydrofluoric acid, and finally drying the template in an oven at the temperature of 75 ℃ for 11 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 7mol/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 75 ℃ for 11 h to obtain the solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 72.6%, the yield of reducing sugars was 47.5% (wherein the yield of glucose was 25.6%), and the yield of 5-hydroxymethylfurfural was 4.3%.
Example 4
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 1 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 1000 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to remove SiO2And (3) filtering the template, washing the template for multiple times by using deionized water until the template is washed by hydrofluoric acid, and finally drying the template in an oven at 70 ℃ for 12 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 10mol/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 80 ℃ for 10 h to obtain the solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 68.3%, the yield of reducing sugars was 53.4% (wherein the yield of glucose was 25.9%), and the yield of 5-hydroxymethylfurfural was 4.2%.
Example 5
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 1 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 400 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to remove SiO2Then filtered and deionizedWashing with water for multiple times until the carbon nitride is washed with hydrofluoric acid, and finally drying in an oven at 80 ℃ for 10 hours to obtain the mesoporous carbon nitride material. Soaking the prepared carbon and nitrogen material in 7mol/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 solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 97.8%, the yield of reducing sugars was 60.1% (wherein the yield of glucose was 38.2%), and the yield of 5-hydroxymethylfurfural was 7.1%.
Example 6
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 1 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 500 ℃ in a nitrogen atmosphere (the heating rate is 2 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 5% HF solution to remove SiO2Then filtering, washing for many times by using deionized water until the solution is washed by hydrofluoric acid, and finally drying in an oven at 70 ℃ for 10 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 8mol/L formic acid for 24h, filtering, washing with deionized water for multiple times until redundant acid is washed, and finally drying in an oven at 80 ℃ for 12 h to obtain the solid catalyst which releases acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 81.6%, the yield of reducing sugars was 48.9% (wherein the yield of glucose was 32.6%), and the yield of 5-hydroxymethylfurfural was 5.2%.
Example 7
First, aminoguanidine hydrochloride and silica were mixed in a ratio of 1: 1 and water are dissolved together, and water is slowly evaporated under the condition of stirring at 80 ℃ to obtain solid particles; grinding the solid particles, and roasting at 500 ℃ in a nitrogen atmosphere (the heating rate is 5 ℃/min, and the temperature is kept for 1h) to obtain brown yellow solid powder. Soaking the brown yellow solid powder in 30% HF solution to remove SiO2And (3) filtering the template, washing the template for multiple times by using deionized water until the template is washed by hydrofluoric acid, and finally drying the template in an oven at the temperature of 75 ℃ for 10 hours to obtain the mesoporous carbon-nitrogen material. Soaking the prepared carbon and nitrogen material in 7mol/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 80 ℃ for 10 h to obtain the solid catalyst capable of releasing acid in response to temperature.
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 solid catalyst which releases acid in response to temperature is added into the reaction kettle, catalytic reaction is carried out for 6 hours in an oil bath kettle at 180 ℃, 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 64.6%, the yield of reducing sugars was 35.5% (wherein the yield of glucose was 23.4%), and the yield of 5-hydroxymethylfurfural was 3.9%.
Claims (9)
1. A preparation method of a solid catalyst capable of releasing acid in response to temperature is characterized by comprising the following steps:
(1) preparation of mesoporous carbon-nitrogen material
Dissolving aminoguanidine hydrochloride, silicon dioxide and water together, and evaporating water under the condition of heating and stirring to obtain dry solid particles; grinding the solid particles, and roasting in a nitrogen atmosphere to obtain brown yellow solid powder; mixing the above materialsSoaking yellow solid powder in hydrogen fluoride solution to remove SiO2Then filtering, cleaning and drying to obtain a mesoporous carbon-nitrogen material;
(2) preparation of solid catalyst releasing acid in response to temperature
Soaking the prepared mesoporous carbon nitrogen material in an acid solution, filtering, cleaning and drying to obtain a solid catalyst which responds to temperature and releases acid;
the acidic solution in the step (2) 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 a solid catalyst that releases acid in response to temperature according to claim 1, wherein the mass ratio of aminoguanidine hydrochloride to silica in step (1) is 1: 0.1-10.
3. The method for preparing a solid catalyst which releases an acid in response to temperature according to claim 1, wherein the heating temperature in the step (1) is 80 to 90 ℃.
4. The method for preparing a solid catalyst that releases acid in response to temperature as set forth in claim 1, wherein the calcination temperature in the step (1) is 200-1000 ℃.
5. The method for preparing a solid catalyst that releases an acid in response to temperature according to claim 1, wherein the hydrogen fluoride solution in the step (1) has a mass concentration of 5 to 30%.
6. The method for preparing a solid catalyst that releases an acid in response to temperature according to claim 1, wherein the drying temperature in step (1) is 60 to 120 ℃ and the drying time is 10 to 12 hours.
7. The method for preparing a solid catalyst that releases an acid in response to temperature according to claim 1, wherein the concentration of the acidic solution in the step (2) is 0.1 to 10 mol/L.
8. The method for preparing a solid catalyst that releases an acid in response to temperature according to claim 1, wherein the soaking time in the step (2) is 24 to 30 hours.
9. The method for preparing a solid catalyst that releases an acid in response to temperature according to claim 1, wherein the drying temperature in the step (2) is 60 to 120 ℃ and the drying time is 10 to 12 hours.
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