CN111558369B - Perovskite substrate solid acid catalyst and preparation method and application thereof - Google Patents
Perovskite substrate solid acid catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a perovskite substrate solid acid catalyst and a preparation method and application thereof, wherein the perovskite substrate solid acid catalyst is obtained by acid-washing calcium titanate with a nitric acid solution with the concentration of 0.1-0.5mol/l, or strontium manganate with a nitric acid solution with the concentration of 0.02-0.3mol/l, or lanthanum ferrite with an acetic acid solution with the concentration of 0.02-0.2 mol/l. The perovskite substrate solid acid catalyst is prepared by taking a perovskite compound as a substrate and acid-washing the perovskite compound by using low-concentration acid, has good stability, has small corrosion to a reactor, greatly reduces the reaction difficulty when being used for cellulose hydrolysis, can hydrolyze cellulose at the reaction temperature of 50 ℃, has the conversion rate of the cellulose of 32.4 percent, and can be easily separated from a product by a suction filtration separation method, thereby realizing the recycling of the cellulose.
Description
Technical Field
The invention relates to the technical field of biomass conversion and recycling, in particular to a perovskite substrate solid acid catalyst and a preparation method and application thereof.
Background
To date, various forms of energy systems have been developed as alternatives to petrochemical resources, such as solar, wind, biomass, nuclear, hydroelectric, and geothermal energy. Among these different sources of energy, biomass is currently the only renewable organic carbon source on earth, and is the best feedstock alternative for energy and chemicals production.
Biomass is a generic term for carbohydrates fixed by green plants on earth through photosynthesis, such as grasses, trees, crop straws and other agricultural wastes. The first generation of biofuels were ethanol obtained by fermentation of sugars or starches and biodiesel produced from vegetable oils, however, the production of these fuels competed with human beings for valuable food resources, while the production of these feedstocks was limited by limited land resources. The research of the second generation biofuel mainly focuses on the application of lignocellulose, which is mainly derived from non-edible parts of food crops and other plants, so that people do not compete for food resources, and many energy plants can grow on barren land.
Green plants on earth synthesize about 2200 million tons of dry matter each year, here 70-95% lignocellulose. Lignocellulose is mainly composed of 3 substances, namely cellulose (40-50%), hemicellulose (25-30%) and lignin (18-28%) (the content of each component is different in biomass from different sources). Among these biopolymers, cellulose is the most valuable, glucose is obtained by depolymerization of cellulose, and ethanol is obtained by fermentation, or 5-Hydroxymethylfurfural (HMF) and other platform molecules are formed by dehydration.
Currently, the most common method of cellulose hydrolysis is by cellulase hydrolysis, which has been in commercial use for more than 30 years to date. Although the degradation mechanism of cellulases has not been completely elucidated, cellulases have been widely used and recognized in various industries. However, due to various problems such as production process and production efficiency, the method has low efficiency and high cost. There are also many studies on the conversion of glucose from cellulose by hydrolysis with mineral acids, of which the study on sulfuric acid is the most. However, the large-scale use of acid-hydrolyzed cellulose has many problems such as corrosion of equipment, difficulty in recovering the catalyst, and generation of a large amount of waste water.
Disclosure of Invention
In view of the above, the present invention aims to provide a perovskite-based solid acid catalyst to solve the problems that the existing mineral acid for hydrolyzing cellulose is easy to corrode equipment, difficult to recover and easy to generate a large amount of wastewater.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the perovskite substrate solid acid catalyst is obtained by acid-washing calcium titanate with a nitric acid solution with the concentration of 0.1-0.5mol/l, or strontium manganate with a nitric acid solution with the concentration of 0.02-0.3mol/l, or lanthanum ferrite with an acetic acid solution with the concentration of 0.02-0.2 mol/l.
A second object of the present invention is to provide a method for preparing the above perovskite-based solid acid catalyst, which comprises the steps of:
1) performing ball milling on calcium oxide and titanium dioxide, or strontium oxide and manganese dioxide, or ferric oxide and lanthanum oxide by adopting a mechanical ball milling process to respectively obtain calcium titanate, strontium manganate and lanthanum ferrite;
2) dispersing the calcium titanate in a nitric acid solution with the concentration of 0.1-0.5mol/l, stirring and reacting for a period of time under the condition of water bath, or dispersing the strontium manganate in a nitric acid solution with the concentration of 0.02-0.3mol/l, stirring and reacting for a period of time at room temperature, or dispersing the lanthanum ferrite in an acetic acid solution with the concentration of 0.02-0.2mol/l, stirring and reacting for a period of time under the condition of water bath, and after the stirring and reacting are finished, performing suction filtration, washing and drying to obtain the perovskite substrate solid acid catalyst.
Optionally, in the step 1), the molar ratio of calcium oxide to titanium dioxide, or strontium oxide to manganese dioxide, or iron trioxide to lanthanum trioxide is 1: 1.
Optionally, the ball milling rotation speed of the ball milling in the step 1) is 500-.
Optionally, the calcium titanate is dispersed in nitric acid solution with concentration of 0.1-0.5mol/l in the step 2), and the reaction is stirred for a period of time under the condition of water bath, and the method comprises the following steps:
dispersing the calcium titanate in nitric acid solution with the concentration of 0.1-0.5mol/l, and stirring and reacting for 6-24h at the stirring speed of 10-30rpm under the water bath condition of 25-80 ℃.
Optionally, the step 2) of dispersing the strontium manganate in a nitric acid solution with a concentration of 0.02-0.3mol/l, and stirring and reacting at room temperature for a period of time, wherein the reaction comprises:
dispersing the strontium manganate into a nitric acid solution with the concentration of 0.02-0.3mol/l, and stirring and reacting for 5-20min at room temperature by adopting a stirring speed of 10-30 rpm.
Optionally, the lanthanum ferrite is dispersed in an acetic acid solution with the concentration of 0.02-0.2mol/l in the step 2), and the reaction is stirred for a period of time under the condition of water bath, and the method comprises the following steps:
dispersing the lanthanum ferrite in an acetic acid solution with the concentration of 0.02-0.2mol/l, and stirring and reacting for 6-24h at the stirring speed of 10-30rpm under the condition of a water bath with the temperature of 25-80 ℃.
Optionally, the content of the calcium titanate in the step 2) is 0.5-1.5g per 100ml of nitric acid solution; the content of the strontium manganate in 100ml of nitric acid solution is 0.5-1.5 g; the content of the lanthanum ferrite in each 100ml of acetic acid solution is 0.5-1.5 g.
The third purpose of the invention is to provide the application of the perovskite substrate solid acid catalyst in the catalytic hydrolysis of cellulose, which comprises the following steps:
dispersing cellulose and a perovskite substrate solid acid catalyst in water, reacting for 6-24 hours under the condition of a water bath at 25-80 ℃, and performing suction filtration to obtain a water-soluble organic matter.
Optionally, the mass ratio of the cellulose and the perovskite-based solid acid catalyst is from 1: 9 to 1: 3, and the total addition of the cellulose and the perovskite-based solid acid catalyst per 100ml of water is from 2 to 8 g.
Compared with the prior art, the perovskite substrate solid acid catalyst has the following advantages:
1. the perovskite substrate solid acid catalyst is prepared by taking a perovskite compound as a substrate and acid-washing the perovskite compound by using low-concentration acid, has good stability, has small corrosion to a reactor, greatly reduces the reaction difficulty when being used for cellulose hydrolysis, can hydrolyze cellulose at the reaction temperature of 50 ℃, has the conversion rate of the cellulose of 32.4 percent, and can be easily separated from a product by a suction filtration separation method, thereby realizing the recycling of the cellulose.
2. The preparation method is simple, the perovskite matrix solid acid catalyst can be obtained by adopting a mechanical ball milling method and a low-concentration nitric acid pickling method, the production efficiency is greatly increased, the reaction condition is mild, a large amount of wastewater is not generated in the production process, the production cost is low, the whole production process is green and economic, and the preparation method has wide industrial application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows CaO and TiO according to example 1 of the present invention2XRD pattern of the dry-milled product of (a);
FIG. 2 is a graph of cellulose conversion for perovskite-based solid acid catalysts of examples 1-5 of the present invention;
FIG. 3 shows SrO and MnO in example 7 of the present invention2XRD pattern of the dry-milled product of (a);
FIG. 4 is a graph of cellulose conversion for perovskite-based solid acid catalysts of examples 7-11 of the present invention;
FIG. 5 shows La of example 13 of the present invention2O3And Fe2O3XRD pattern of the dry-milled product of (a);
FIG. 6 is a graph of cellulose conversion for perovskite-based solid acid catalysts of examples 13-16 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A perovskite matrix solid acid catalyst is prepared by the following method:
1) putting calcium oxide and titanium dioxide into a ball milling tank according to the molar ratio of 1: 1 by adopting a mechanical ball milling process, ball milling for 3 hours under the condition of 700rpm, and reacting to generate calcium titanate;
2) dispersing calcium titanate in nitric acid solution with the concentration of 0.2mol/l, wherein the content of the calcium titanate in each 100ml of nitric acid solution is 1g, stirring and reacting for 24 hours under the water bath condition at the temperature of 50 ℃, the stirring speed is 20rpm, after the stirring and reacting are finished, performing suction filtration, washing and drying to obtain the perovskite substrate solid acid catalyst, namely the calcium titanate solid acid catalyst.
The perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, which specifically included the following steps: the cellulose and the calcium titanate solid acid catalyst of the embodiment are dispersed in water, the mass ratio of the cellulose to the calcium titanate solid acid catalyst is 1: 3, the added solids, namely the cellulose and the calcium titanate solid acid catalyst, are stirred and reacted for 12 hours in 100ml of water at the stirring speed of 20rpm under the water bath condition of 50 ℃, and after the stirring and reaction are finished, the water-soluble organic matter is obtained by suction filtration.
The calcium titanate obtained in this example was subjected to XRD measurement and compared with calcium titanate obtained at 100rpm and 400rpm, and the results are shown in FIG. 1.
As can be seen from FIG. 1, when the rotation speed of the ball mill was 100rpm, the characteristic peaks of the dry-milled product were almost all the characteristic peaks of the two raw material substances, and when the rotation speed reached 400rpm, CaO and TiO were present2The characteristic peaks of the two raw materials disappear gradually, only the characteristic peak of the calcium titanate is left when the rotating speed reaches 700rpm, and the strength is good, which shows that when the ball milling rotating speed is 700rpm and the ball milling time is 3 hours, the raw materials CaO and TiO2Can be completely reacted to generate stable calcium titanate solid with good crystal structure.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 2.
As is clear from fig. 2, the conversion of cellulose under the conditions of this example was 13.8%.
Example 2
This example differs from example 1 in that: when the perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, the temperature of the hydrolysis reaction was 25 ℃.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 2.
As is clear from fig. 2, the conversion of cellulose under the conditions of this example was 10.4%.
Example 3
This example differs from example 1 in that: when the perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, the temperature of the hydrolysis reaction was 40 ℃.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 2.
As is clear from fig. 2, the conversion of cellulose under the conditions of this example was 12.8%.
Example 4
This example differs from example 1 in that: when the perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, the temperature of the hydrolysis reaction was 60 ℃.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 2.
As can be seen from fig. 2, the conversion of cellulose under the conditions of this example was 13.82%.
Example 5
This example differs from example 1 in that: when the perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, the temperature of the hydrolysis reaction was 80 ℃.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 2.
As is clear from fig. 2, the conversion of cellulose under the conditions of this example was 13.5%.
Example 6
This example differs from example 1 in that: when the perovskite-based solid acid catalyst (calcium titanate solid acid catalyst) of the present example was used for hydrolysis of cellulose, the mass ratio of cellulose to the calcium titanate solid acid catalyst was 1: 6.
The perovskite-based solid acid catalyst of this example was tested for hydrolysis efficiency in hydrolyzing cellulose.
From the test, the conversion of cellulose under the conditions of this example was 18.5%.
Example 7
A perovskite matrix solid acid catalyst is prepared by the following method:
1) putting strontium oxide and manganese dioxide into a ball milling tank according to the molar ratio of 1: 1 by adopting a mechanical force ball milling process, and carrying out ball milling for 2 hours under the condition of 600rpm to generate strontium manganate through reaction;
2) dispersing strontium manganate into a nitric acid solution with the concentration of 0.05mol/l, wherein the content of the strontium manganate in each 100ml of the nitric acid solution is 1g, stirring and reacting for 15 minutes at the temperature of 20 ℃, the stirring speed is 20rpm, after the stirring and reacting are finished, performing suction filtration, washing and drying to obtain the perovskite substrate solid acid catalyst, namely the strontium manganate solid acid catalyst.
The perovskite-based solid acid catalyst (strontium manganate solid acid catalyst) of the present example was used for hydrolysis of cellulose, and specifically included the following steps: the cellulose and the strontium manganate solid acid catalyst of the embodiment are dispersed in water, the mass ratio of the cellulose to the strontium manganate solid acid catalyst is 1: 4, the added solids, namely the cellulose and the strontium manganate solid acid catalyst, are 2.5g per 100ml of water, and are stirred and reacted for 6 hours in a water bath condition at 50 ℃, the stirring speed is 20rpm, and after the stirring and reaction are finished, the water-soluble organic matter is obtained by suction filtration.
The strontium manganate obtained in this example was subjected to XRD test and compared with strontium manganate obtained at 100rpm and 400rpm, and the test results are shown in fig. 3.
As can be seen from FIG. 3, when the rotation speed of the ball mill was 100rpm, the characteristic peaks of the dry-milled product were almost all the characteristic peaks of the two raw material substances, and when the rotation speed reached 400rpm, SrO and MnO2The characteristic peaks of the two raw materials disappear gradually, SrMnO3The characteristic peak of the strontium manganate is gradually obvious, when the rotating speed reaches 600rpm, only the characteristic peak of the strontium manganate is remained, and the strength is good, which indicates that when the ball milling rotating speed is 600rpm and the ball milling time is 2 hours, the raw materials SrO and MnO are2Can completely react to generate the strontium manganate solid with stability and good crystal structure.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 4.
As is clear from fig. 4, the cellulose conversion rate was 5.8% under the conditions of this example.
Example 8
This example differs from example 7 in that: when the perovskite (strontium manganate) of the present example was dispersed in a nitric acid solution and reacted to produce a perovskite-based solid acid catalyst (strontium manganate solid acid catalyst), the concentration of the nitric acid solution was 0.02 mol/l.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 4.
As is clear from fig. 4, the conversion of cellulose under the conditions of this example was 1.6%.
Example 9
This example differs from example 7 in that: when the perovskite (strontium manganate) of the present example was dispersed in a nitric acid solution and reacted to produce a perovskite-based solid acid catalyst (strontium manganate solid acid catalyst), the concentration of the nitric acid solution was 0.1 mol/l.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 4.
As is clear from fig. 4, the cellulose conversion rate was 4.8% under the conditions of this example.
Example 10
This example differs from example 7 in that: when the perovskite (strontium manganate) of the present example was dispersed in a nitric acid solution and reacted to produce a perovskite-based solid acid catalyst (strontium manganate solid acid catalyst), the concentration of the nitric acid solution was 0.2 mol/l.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 4.
As is clear from fig. 4, the cellulose conversion rate was 4.5% under the conditions of this example.
Example 11
This example differs from example 7 in that: when the perovskite (strontium manganate) of the present example was dispersed in a nitric acid solution and reacted to produce a perovskite-based solid acid catalyst (strontium manganate solid acid catalyst), the concentration of the nitric acid solution was 0.3 mol/l.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown in fig. 4.
As is clear from fig. 4, the conversion of cellulose under the conditions of this example was 4.2%.
Example 12
This example differs from example 7 in that: when the perovskite-based solid acid catalyst (strontium manganate solid acid catalyst) of this example was used for hydrolysis of cellulose, the mass ratio of cellulose to calcium titanate solid acid catalyst was 1: 8.
The perovskite-based solid acid catalyst of this example was tested for hydrolysis efficiency in hydrolyzing cellulose.
From the test, the conversion of cellulose under the conditions of this example was 9.2%.
Example 13
A perovskite matrix solid acid catalyst is prepared by the following method:
1) putting ferric oxide and lanthanum oxide into a ball milling tank according to the molar ratio of titanium to lanthanum oxide of 1: 1 by adopting a mechanical force ball milling process, and carrying out ball milling for 2 hours under the condition of 600rpm to generate lanthanum ferrite;
2) dispersing lanthanum ferrite in an acetic acid solution with the concentration of 0.1mol/l, wherein the content of the lanthanum ferrite in each 100ml of the acetic acid solution is 1g, carrying out stirring reaction for 12 hours under the water bath condition with the temperature of 50 ℃, wherein the stirring speed is 20rpm, and after the stirring reaction is finished, carrying out suction filtration, washing and drying to obtain the lanthanum ferrite solid acid catalyst.
The perovskite matrix solid acid catalyst (lanthanum ferrite solid acid catalyst) of the embodiment is used for the hydrolysis of cellulose, and specifically comprises the following steps: the cellulose and the lanthanum ferrite solid acid catalyst of the embodiment are dispersed in water, the mass ratio of the cellulose to the lanthanum ferrite solid acid catalyst is 1: 5, the added solids, namely the cellulose and the lanthanum ferrite solid acid catalyst, are 2g in each 100ml of water, and are stirred and reacted for 16 hours under the water bath condition of 50 ℃, the stirring speed is 20rpm, and after the stirring and reaction are finished, the water-soluble organic matter is obtained by suction filtration.
The lanthanum ferrite obtained in this example was subjected to XRD measurement and compared with lanthanum ferrite obtained at 100rpm and 400rpm, and the results are shown in FIG. 5.
As can be seen from FIG. 5, when the rotation speed of the ball mill was 100rpm, the characteristic peaks of the dry-milled product were almost all the characteristic peaks of the two raw material substances, and when the rotation speed reached 400rpm, Fe2O3And La2O3The characteristic peaks of the two raw materials gradually disappear, and LaFeO3The characteristic peak of the lanthanum ferrite is gradually obvious, when the rotating speed reaches 600rpm, only the characteristic peak of the lanthanum ferrite is left, and the strength is good, which shows that when the ball milling rotating speed is 600rpm and the ball milling time is 2 hours, the raw material Fe2O3And La2O3Can be completely reacted to generate the stable lanthanum ferrite solid with good crystal structure.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown as a in fig. 6.
As is clear from fig. 6, the conversion of cellulose under the conditions of this example was 24.8%.
Example 14
This example differs from example 13 in that: when the perovskite-based solid acid catalyst (lanthanum ferrite solid acid catalyst) of this example was used for hydrolysis of cellulose, the mass ratio of cellulose to lanthanum ferrite solid acid catalyst was 1: 8.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown as B in fig. 6.
As is clear from fig. 6, the conversion of cellulose under the conditions of this example was 28.4%.
Example 15
This example differs from example 13 in that: when the perovskite-based solid acid catalyst (lanthanum ferrite solid acid catalyst) of this example was used for hydrolysis of cellulose, the mass ratio of cellulose to lanthanum ferrite solid acid catalyst was 1: 10.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown as C in fig. 6.
As is clear from fig. 6, the conversion of cellulose under the conditions of this example was 32.4%.
Example 16
This example differs from example 13 in that: when the perovskite-based solid acid catalyst (lanthanum ferrite solid acid catalyst) of this example was used for hydrolysis of cellulose, the mass ratio of cellulose to lanthanum ferrite solid acid catalyst was 1: 12.
The perovskite-based solid acid catalyst of the present example was tested for hydrolysis efficiency of cellulose, and the test results are shown as D in fig. 6.
As is clear from fig. 6, the conversion of cellulose under the conditions of this example was 32.5%.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. Use of a perovskite-based solid acid catalyst for the catalytic hydrolysis of cellulose, comprising the steps of:
dispersing cellulose and a perovskite substrate solid acid catalyst in water, reacting for 6-24 hours under the condition of a water bath at 25-80 ℃, and performing suction filtration to obtain a water-soluble organic matter;
the perovskite substrate solid acid catalyst is obtained by pickling calcium titanate for 6-24h through a nitric acid solution with the concentration of 0.1-0.5mol/L under the water bath condition of 25-80 ℃, or pickling strontium manganate for 5-20min through a nitric acid solution with the concentration of 0.02-0.3mol/L at room temperature, or pickling lanthanum ferrite for 6-24h through an acetic acid solution with the concentration of 0.02-0.2mol/L under the water bath condition of 25-80 ℃.
2. Use of the perovskite-based solid acid catalyst according to claim 1 for the catalytic hydrolysis of cellulose, wherein the mass ratio of the cellulose and the perovskite-based solid acid catalyst is from 1: 9 to 1: 3 and the total addition of the cellulose and the perovskite-based solid acid catalyst per 100mL of water is from 2 to 8 g.
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