CN109734449B - Preparation method of integral porous carbon material with high strength and high wear resistance - Google Patents
Preparation method of integral porous carbon material with high strength and high wear resistance Download PDFInfo
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Abstract
A preparation method of an integral porous carbon material with high strength and high wear resistance comprises the steps of preparing the integral porous carbon material with high strength and high wear resistance at one time through a sol-gel process, a curing process and a carbonization and pyrolysis process; the method comprises the steps of taking a phenolic compound and an aldehyde compound as raw materials, taking water or ethanol as a solvent, taking a small amount of alkaline compound as a catalyst, taking an acidic nitrogen-containing organic compound as a modifier, adding a proper amount of curing agent to promote polymerization and crosslinking of reactants, preparing a block polymer, drying and carbonizing to obtain the integral porous carbon material with high strength and high wear resistance. The representative sample synthesized by the method has the advantages of high specific surface, multi-level pore channels, high mechanical strength, good chemical inertness, especially excellent wear resistance, and wide application prospect in catalyst carriers, adsorbents, chromatographic column fillers and electrode materials. The method has mild reaction conditions and simple operation, and avoids the problem that the high strength, the wear resistance, the high specific surface and the porosity of the porous carbon material can not be considered at the same time.
Description
Technical Field
The invention relates to a simple preparation method of an integral porous carbon material with high strength and high wear resistance.
Background
The porous carbon is a porous carbon-containing substance, has a developed pore structure, good chemical stability, thermal stability, water vapor resistance and electrical conductivity, and is widely applied to the fields of catalysis, adsorption and electrochemical energy storage. However, the porous carbon material prepared and synthesized at present is powdery, and in order to meet the requirements of practical application, the porous carbon material needs to be formed by a binder, so that the mechanical strength and the wear resistance are improved. The porosity of the shaped porous carbon is significantly reduced due to the presence of the binder. The pore enlargement is usually further activated, but this reduces the mechanical strength and wear resistance of the shaped carbon (clean coal technology, 2008,14, 23; new carbon materials, 2000,15: 6-10). The direct preparation of self-supporting monolithic porous carbon has received great attention from enterprises, and in recent years, documents and patents are continuously reported (CN 200910220488.8; CN 201710406263.6). The preparation of the integral porous carbon basically takes phenolic aldehyde alkaline polymer as a precursor and is obtained through a sol-gel process and a carbonization process. Although the self-supporting integral porous carbon has rich pore structures and certain compressive strength, the wear resistance is poor, the powder falling phenomenon is serious, the abrasion rate is high, and the industrial requirements cannot be met. Therefore, a new preparation process needs to be explored, and the wear resistance and mechanical strength of the self-supporting integral porous carbon are improved on the basis of not influencing the specific surface area and the pore structure of the carbon material.
Disclosure of Invention
The invention aims to overcome the defects of low strength, easy pulverization and the like of the existing formed activated carbon material, and prepares the high-strength and high-wear-resistance integral porous carbon by taking acidic nitrogen-containing organic matters as a modifier based on phenolic aldehyde polymerization reaction. The method can solve the technical problem that the porous carbon material has high strength, high wear resistance, high specific surface area and high porosity.
The technical scheme of the invention is as follows:
a preparation method of an integral porous carbon material with high strength and high wear resistance comprises the steps of preparing the integral porous carbon material with high strength and high wear resistance at one time through a sol-gel process, a curing process and a carbonization and pyrolysis process; the method comprises the steps of taking a phenolic compound and an aldehyde compound as raw materials, taking water or ethanol as a solvent, taking a small amount of alkaline compound as a catalyst, taking an acidic nitrogen-containing organic compound as a modifier, adding a proper amount of curing agent to promote polymerization and crosslinking of reactants, preparing a block polymer, drying and carbonizing to obtain the integral porous carbon material with high strength and high wear resistance.
The method comprises the following steps:
(1) adding an acidic nitrogen-containing organic compound into a formaldehyde solution, adding a basic compound solution, stirring at room temperature until the acidic nitrogen-containing organic compound is completely dissolved to obtain a transparent colorless solution marked as a solution A, wherein the molar ratio of the acidic nitrogen-containing organic compound to formaldehyde is 0.1: 1-0.5: 1, the molar ratio of the basic compound to acidic nitrogen-containing organic substances is not more than 0.05:1, and the concentration of the basic compound is controlled to be 1-5 mol/l;
preferably, the molar ratio of the acidic nitrogen-containing organic compound to formaldehyde is 0.1:1, and the molar ratio of the basic compound to the acidic nitrogen-containing organic compound is 0.038: 1.
(2) Preparing a resorcinol solution with the concentration of 0.2-1.0 g/ml, and marking as a solution B;
(3) pouring the solution B into the solution A, and stirring at room temperature for 10-60 min to obtain a clear transparent solution, wherein the molar ratio of resorcinol to formaldehyde is 0.5: 1-1.25: 1;
(4) adding a curing agent in a stirring state, stirring until the curing agent is completely dissolved, and marking as a solution C, wherein the using amount of the curing agent is 0.5-5 wt% of the total mass of all reactants;
(5) pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling and taking out, and drying for 24h at 50 ℃ to obtain a dried block polymer;
(6) carbonizing: and (3) placing the polymer obtained in the step (5) in an argon atmosphere, heating to 600-1100 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 2 hours to obtain the integral porous carbon with high strength and high wear resistance.
Wherein the solid content of the reaction system is controlled, namely the content of the non-volatile substances in the solution is 20-50 wt.%.
The acidic nitrogen-containing organic compound is one or more of aspartic acid, glutamic acid, cyanuric acid, pyrrole and guanidine hydrochloride.
The curing agent is one or the mixture of more than two of hexamethylenetetramine, paraformaldehyde, benzene sulfonyl chloride and methyl benzene sulfonyl chloride.
The solvent of the reaction system is water or ethanol.
The alkaline compound is one or more of potassium carbonate, potassium hydroxide and sodium hydroxide.
The resorcinol can be replaced by phenol or phloroglucinol.
The formaldehyde may be replaced by glyoxal or terephthalaldehyde.
The invention has the beneficial effects that: the invention takes weak acidic nitrogenous organic matter as a modifier, and prepares the integral porous carbon with high strength and high wear resistance based on phenolic aldehyde polymerization reaction, and the integral porous carbon has rich pore structure. The representative sample synthesized by the method has the advantages of high specific surface, multi-level pore channels, high mechanical strength, good chemical inertness, especially excellent wear resistance, and wide application prospect in catalyst carriers, adsorbents, chromatographic column fillers and electrode materials. The method has mild reaction conditions and simple operation, and effectively solves the problem that the high strength, the wear resistance, the high specific surface and the porosity of the porous carbon material can not be considered at the same time.
Drawings
FIG. 1 is a nitrogen adsorption curve for example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1 (guanidine hydrochloride as acidic modifier)
Adding 2.6g of guanidine hydrochloride into 4ml of glyoxal solution with the concentration of 50mmol/l, stirring at room temperature until the guanidine hydrochloride is completely dissolved, and marking the solution as A; 2.930g of resorcinol were dissolved in 3ml of deionized water at room temperature, the solution being labeled B; pouring the solution B into the solution A, adding hexamethylenetetramine, stirring at room temperature until the hexamethylenetetramine is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 700 ℃ at a heating rate of 2 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 44.3%, and the specific surface area was about 600m2(iv)/g, radial compressive strength of about 600N/cm, and test abrasion rate of 1.7 wt.%.
Example 2 (aspartic acid as acidic modifier)
0.573g of aspartic acid is added into 6ml of formaldehyde solution and stirred at room temperatureAll dissolved, the solution is marked as A; 2.237g of phenol were dissolved in 4ml of ethanol at room temperature, the solution being marked B; pouring the solution B into the solution A, adding paraformaldehyde, stirring at room temperature until the solution is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 800 ℃ at a heating rate of 1 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 50.6%, the specific surface area was 670m2(iv)/g, radial compressive strength of about 400N/cm, and test abrasion rate of 1.4 wt.%.
Example 3 (guanidine hydrochloride as acidic modifier)
Adding 0.687g of guanidine hydrochloride into 4ml of formaldehyde solution, adding 40 mu l of 5mol/l potassium carbonate solution, stirring at room temperature until the guanidine hydrochloride is completely dissolved, and marking the solution as A; 2.930g of resorcinol were dissolved in 4ml of deionized water at room temperature, the solution being labeled B; pouring the solution B into the solution A, adding hexamethylenetetramine, stirring at room temperature until the hexamethylenetetramine is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 1000 ℃ at a heating rate of 2 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 45.7%, and the specific surface area was about 630m2(iv) a radial compressive strength of about 1000N/cm, a test abrasion rate of only 0.5 wt.%.
Example 4 (cyanuric acid as acidic modifier)
Adding 0.918g of cyanuric acid into 6ml of formaldehyde solution, adding 20 mu l of 3mol/l potassium carbonate solution, stirring at room temperature until the cyanuric acid is completely dissolved, and marking the solution as A; 4.395g of resorcinol were dissolved in 6ml of ethanol at room temperature, the solution being marked B; pouring the solution B into the solution A, adding paraformaldehyde, stirring at room temperature until the solution is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 600 ℃ at a heating rate of 5 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 50.3%, and the specific surface area was about 750m2G, radial compressive strengthAbout 550N/cm, test abrasion 1.8 wt.%
Example 5 (pyrrole as acidic modifier)
Dissolving 0.357g pyrrole in 5ml ethanol, adding 5ml formaldehyde solution, adding 100 μ l of 2mol/l potassium carbonate solution, and stirring at room temperature, wherein the solution is marked as A; 4.395g of resorcinol were dissolved in 4ml of ethanol at room temperature, the solution being marked B; pouring the solution B into the solution A, adding paraformaldehyde, stirring at room temperature until the solution is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 46.8%, and the specific surface area was about 645m2A radial compressive strength of about 450N/cm, a test abrasion of 2.1wt. -%)
Example 6 (glutamic acid as acidic modifier)
Adding 0.112g of glutamic acid into 4ml of formaldehyde solution, adding 40 mu l of 5mol/l potassium hydroxide solution, stirring at room temperature until the glutamic acid is completely dissolved, and marking the solution as A; 2.930g of resorcinol were dissolved in 4ml of deionized water at room temperature, the solution being labeled B; pouring the solution B into the solution A, adding benzenesulfonyl chloride, stirring at room temperature until the solution is completely dissolved, and marking the solution as C; pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling, taking out a product, and drying; placing the obtained polymer in an argon atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 47.2%, and the specific surface area was about 630m2(iv)/g, radial compressive strength of about 670N/cm, and test abrasion rate of 1.2 wt.%.
Example 7 (without addition of acid modifier, for comparison)
0.078g of 1, 6-hexanediamine was added to 10ml of 50mmol/l terephthalaldehyde solution in a water-ethanol mixture at a water/alcohol ratio of 1:1 by volume. Stirring at room temperature until the solution is completely dissolved, and marking the solution as A; 2.930g of resorcinol were dissolved in 4ml of deionized water at room temperature, the solution being labeled B; pouring the solution B into the solution A, stirring at room temperature until the solution B is completely dissolved, and marking the solution as C; mixing the solutionC, pouring the mixture into a reactor, reacting for 4 hours at 90 ℃, cooling, and taking out a product to be dried; placing the obtained polymer in an argon atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min with a flow rate of 100ml/min, preserving heat for 2 hours, cooling to room temperature, and taking out. The sample yield was 46.1%, and the specific surface area was about 650m2The radial compressive strength is about 300N/cm, and the test abrasion rate rises to 3.4 wt.%.
Example 8 (commercial shaped carbon, for comparison)
Commercially available phi 4 columnar activated carbon with a specific surface area of about 1100m2(iv) a radial compressive strength of about 170N/cm, a test abrasion rate of up to 5.7 wt.%.
Claims (7)
1. A preparation method of an integral porous carbon material with high strength and high wear resistance is characterized by comprising the following steps:
(1) adding an acidic nitrogen-containing organic compound into a formaldehyde solution, adding a basic compound solution, stirring at room temperature until the acidic nitrogen-containing organic compound is completely dissolved to obtain a transparent colorless solution marked as a solution A, wherein the molar ratio of the acidic nitrogen-containing organic compound to formaldehyde is 0.1: 1-0.5: 1, the molar ratio of the basic compound to the acidic nitrogen-containing organic compound is not more than 0.05:1, and the concentration of the basic compound solution is controlled to be 1-5 mol/L; the acidic nitrogen-containing organic compound is guanidine hydrochloride; the alkaline compound is potassium carbonate;
(2) preparing a resorcinol solution with the concentration of 0.2-1.0 g/mL, and marking as a solution B;
(3) pouring the solution B into the solution A, and stirring at room temperature for 10-60 min to obtain a clear transparent solution, wherein the molar ratio of resorcinol to formaldehyde is 0.5: 1-1.25: 1;
(4) adding a curing agent in a stirring state, stirring until the curing agent is completely dissolved, and marking as a solution C, wherein the using amount of the curing agent is 0.5-5 wt% of the total mass of all reactants;
(5) pouring the solution C into a reactor, reacting for 4h at 90 ℃, cooling and taking out, and drying for 24h at 50 ℃ to obtain a dried block polymer;
(6) carbonizing: placing the polymer obtained in the step (5) in an argon atmosphere, heating to 600-1100 ℃ at a heating rate of 0.5-10 ℃/min, and preserving heat for 2 hours to obtain high-strength and high-wear-resistance integral porous carbon;
wherein the solid content of the reaction system is controlled, namely the content of the non-volatile substances in the solution is 20-50 wt.%.
2. The method according to claim 1, wherein the molar ratio of the acidic nitrogen-containing organic compound to formaldehyde is 0.1:1, and the molar ratio of the basic compound to the acidic nitrogen-containing organic compound is 0.038: 1.
3. The production method according to claim 1 or 2,
the curing agent is one or a mixture of more than two of hexamethylenetetramine, paraformaldehyde, benzene sulfonyl chloride and methyl benzene sulfonyl chloride;
the solvent of the reaction system is water or ethanol.
4. The method according to claim 1 or 2, wherein the resorcinol is replaced with phenol or phloroglucinol.
5. The method according to claim 3, wherein the resorcinol is replaced with phenol or phloroglucinol.
6. The method according to claim 1, 2 or 5, wherein the formaldehyde is replaced with glyoxal or terephthalaldehyde.
7. The method according to claim 3, wherein the formaldehyde is replaced with glyoxal or terephthalaldehyde.
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