CN110817868A - Preparation method of high-strength mesoporous carbon - Google Patents
Preparation method of high-strength mesoporous carbon Download PDFInfo
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- CN110817868A CN110817868A CN201911282742.7A CN201911282742A CN110817868A CN 110817868 A CN110817868 A CN 110817868A CN 201911282742 A CN201911282742 A CN 201911282742A CN 110817868 A CN110817868 A CN 110817868A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
Abstract
The invention discloses a preparation method of high-strength mesoporous carbon, which adopts petroleum asphalt as a raw material to react with phenol and aldehyde to obtain asphalt resin; asphalt resin is used as a binding agent, petroleum coke powder is used as an aggregate, a cross-linking agent and a pore-foaming agent are added, and the mixture is crushed, blended, molded, carbonized and activated to prepare the modified asphalt with the BET specific surface area of 300-600 m2A total pore volume of 0.3-0.7 cm3The columnar carbon has a mesoporous rate of 60-90% and a strength of more than or equal to 95%. According to the invention, the high-temperature resistant bonding agent with excellent bonding property with the petroleum coke powder is obtained by controlling the condensation reaction parameters of the petroleum asphalt, phenol and aldehyde, and the cross-linking agent further promotes the condensation of the asphalt resin bonding agent and the surface of the petroleum coke powder to prepare the high-strength columnar carbon; under the dual functions of pore-forming agent and activation, the high-strength mesoporous carbon is obtained. The invention widens the source of the raw material of the active carbon and improves the added value of the petroleum asphalt and the petroleum coke.
Description
Technical Field
The invention belongs to the technical field of preparation of activated carbon, and particularly relates to a preparation method of high-strength mesoporous carbon.
Background
The active carbon is a porous functional carbon material with developed pore structure, has large specific surface area and low manufacturing cost, and is widely applied to the fields of adsorption, gas separation, energy storage and the like. The active carbon in the current market mainly comprises micropores and is used for adsorbing small molecular gases and liquids, the adsorption effect of some polymers and inorganic macromolecules is poor, and the application effect in the fields of preparation of catalyst carriers, electrode materials of double electric layer capacitors and the like is not ideal, so that higher requirements are put forward on the pore structure of the active carbon, and mesoporous active carbon with developed mesopores, large specific surface area and low price is urgently needed.
The commonly used mesoporous carbon regulation and control method comprises the following steps: the catalytic activation method utilizes the gasification catalysis of metal activators on carbon, but the method can cause metal elements to remain in the activated carbon; the most important disadvantage of the method is that the treatment of removing the template is required, which is costly and time-consuming.
At present, the precursors for preparing the active carbon mainly comprise petroleum coke, phenolic resin, coal, biomass, blue carbon powder and the like. Petroleum coke is a solid carbon product formed by thermal processing and condensation of heavy oil, so that high-quality petroleum coke is widely applied, the utilization rate of medium-low grade petroleum coke is low, and the petroleum coke is only used as fuel for heat supply in industry, so that a large amount of petroleum coke resources are wasted, and the environment is seriously influenced. The petroleum coke has the characteristics of high fixed carbon content, low ash content and volatile content, high strength, high resistivity and the like, and is a potential high-quality precursor for preparing the molded activated carbon. The petroleum asphalt is used as heavy component residual oil left in the petroleum refining industry and has the characteristics of complex structure, high viscosity and the like.
Disclosure of Invention
The invention aims to overcome the defects of the mesoporous carbon regulation and control method, fully utilizes petroleum processing byproducts, namely low-grade petroleum coke and petroleum asphalt, and provides a preparation method of mesoporous carbon with a mesoporous rate of 60-90% and strength of more than or equal to 95%.
Aiming at the purposes, the scheme adopted by the invention comprises the following steps:
1. condensation reaction
Mixing petroleum asphalt, phenol and aldehyde according to the mass ratio of 100 (2-30) to (5-40), heating to 80-130 ℃, adding a catalyst accounting for 0.1-2% of the mass of the asphalt under the stirring reflux state, keeping the reflux temperature of the system constant, and carrying out reflux reaction for 1-6 hours under normal pressure; and after the reflux reaction is finished, distilling for 0.5-5 hours at the temperature of 130-180 ℃ and under the pressure of-0.0960-0 MPa to obtain the pitch resin binder.
2. Shaping of
Grinding the asphalt resin binder and the petroleum coke obtained in the step (1) to below 160 meshes respectively, then putting the petroleum coke powder, the asphalt resin binder, the cross-linking agent, the pore-forming agent and the water into a kneading machine according to the mass ratio of 100 (20-100) to (0.1-2) to (5-20), uniformly kneading, extruding and molding at 30-70 ℃, and standing at normal temperature for 30-80 hours to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 500-800 ℃ at the speed of 2-10 ℃/min under the protection of nitrogen, and keeping the temperature for 2-4 hours to obtain the columnar carbon.
4. Activation of
And (3) under the protection of nitrogen, continuously heating the columnar carbon obtained in the step (3) to 750-950 ℃, introducing water vapor at the flow rate of 0.3-0.8 mL/min, and performing activation treatment for 2-6 hours to obtain the high-strength mesoporous carbon.
In the step 1, preferably mixing petroleum asphalt, phenol and aldehyde according to the mass ratio of 100 (12-20) to (15-30), heating to 90-120 ℃, adding a catalyst with the mass of 0.5-1.5% of that of the asphalt under the stirring reflux state, keeping the reflux temperature of the system constant, and carrying out reflux reaction at normal pressure for 2-5 hours; after the reflux reaction is finished, distilling for 1.5-3 hours at the temperature of 145-165 ℃ and the pressure of-0.06-0.03 MPa.
In the step 1, the petroleum asphalt, the phenol and the aldehyde are further preferably mixed according to the mass ratio of 100 (15-18) to (20-25), the mixture is heated to 100-110 ℃, a catalyst with the mass of 0.8-1.2% of that of the asphalt is added under the stirring reflux state, the reflux temperature of the system is kept constant, and the normal pressure reflux reaction is carried out for 3-4 hours; after the reflux reaction is finished, distilling for 2.0-2.5 hours at the temperature of 150-160 ℃ and the pressure of-0.05-0.04 MPa.
The petroleum asphalt is any one of atmospheric residue, vacuum residue, extract oil and deoiled asphalt, preferably any one of atmospheric residue, vacuum residue and deoiled asphalt; the phenol is any one of phenol, cresol, xylenol and nonyl phenol, phenol or nonyl phenol; the aldehyde is any one of formaldehyde, paraformaldehyde, acetaldehyde and benzaldehyde, and preferably formaldehyde or paraformaldehyde; the catalyst is any one of oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, citric acid and maleic acid, and preferably any one of hydrochloric acid, sulfuric acid and maleic acid.
In the step 2, preferably, the asphalt resin binder and the petroleum coke obtained in the step 1 are respectively ground to below 160 meshes, then the petroleum coke powder, the asphalt resin binder, the cross-linking agent, the pore-foaming agent and the water are put into a kneading machine according to the mass ratio of 100 (50-70) (0.5-1.5) (10-15), and are uniformly kneaded, extruded and molded at the temperature of 45-55 ℃, and placed for 45-65 hours at normal temperature.
The cross-linking agent is ZnCl2、Zn(NO3)2ZnS, preferably ZnCl2Or Zn (NO)3)2(ii) a The pore-forming agent is any one of polyethylene glycol, hydroxymethyl cellulose, polyurethane and polybutylece butyl ester, preferably any one of polyethylene glycol, hydroxymethyl cellulose and polyurethane.
In the step 3, preferably, the columnar blank obtained in the step 2 is put into a tubular resistance furnace, heated to 600-700 ℃ at a speed of 5-7 ℃/min under the protection of nitrogen, and kept at the constant temperature for 2.5-3.5 hours.
In the step 4, preferably under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 800-900 ℃, water vapor is introduced at the flow rate of 0.4-0.7 mL/min, and the activation treatment is carried out for 3-5 hours.
The invention has the following beneficial effects:
the invention obtains the high temperature resistant asphalt resin binder with excellent binding property with the petroleum coke powder by controlling the condensation reaction parameters of the petroleum asphalt, the phenol and the aldehyde,the cross-linking agent further promotes the cross-linking condensation of the asphalt resin binder and the surface of the petroleum coke powder to prepare high-strength columnar carbon; the method utilizes the weak connection point of the interface of petroleum coke powder and asphalt resin bonding agent, and obtains the high-strength mesoporous carbon through the activation reaction of water vapor and boundary carbon, pore formation and further pore expansion of pore-forming agent, wherein the BET specific surface area of the high-strength mesoporous carbon is 300-600 m2A total pore volume of 0.3-0.7 cm3The ratio of mesoporous is 60-90%, and the strength is more than or equal to 95%. The invention widens the source of the raw material of the active carbon and improves the added value of the petroleum asphalt and the petroleum coke.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
In the following examples, the BET specific surface area of activated carbon was measured using a full-automatic rapid specific surface area and porosity analyzer model ASAP-2020M, Michmark (micromeritics), N277K. The sample was treated at 250 ℃ for 8h (10-2Torr) under vacuum before measurement. The strength of the activated carbon is measured by using a GB/T7702.3-2008 coal granular activated carbon test method.
Example 1
1. Condensation reaction
Adding 1000g of atmospheric residue, 20g of phenol and 400g of formaldehyde atmospheric residue into a three-neck flask, heating the system to 80 ℃ within 30min under the condition of stirring, adding 1g of oxalic acid under the condition of stirring reflux, and carrying out atmospheric reflux reaction for 6 hours; replacing the reflux device with a distillation device, and distilling at 130 ℃ for 5 hours under the distillation pressure of-0.0960 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 200g of asphalt resin binder and 1g of ZnCl250g of polyethylene glycol and 50g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 30 ℃, and placed for 30 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 500 ℃ at the speed of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, continuously heating the columnar carbon obtained in the step 3 to 750 ℃, introducing water vapor at the flow rate of 0.3mL/min, and performing activation treatment for 6 hours to obtain the columnar carbon with the BET specific surface area of 360m2Per g, total pore volume of 0.35cm3The mesoporous carbon has a mesoporous rate of 70 percent and a strength of more than or equal to 98 percent.
Example 2
1. Condensation reaction
Adding 1000g of atmospheric residue, 60g of phenol and 350g of formaldehyde atmospheric residue into a three-neck flask, heating the system to 90 ℃ within 30min under the condition of stirring, adding 5g of acetic acid under the condition of stirring reflux, and carrying out atmospheric reflux reaction for 5 hours; replacing the reflux device with a distillation device, and distilling at 130 ℃ for 4 hours under the distillation pressure of-0.0720 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 300g of asphalt resin binder and 1g of ZnCl2And 70g of polyethylene glycol and 70g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 35 ℃, and placed for 40 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 550 ℃ at the speed of 3 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 775 ℃, water vapor is introduced at the flow rate of 0.4mL/min, and the activation treatment is carried out for 5.5 hours to obtain the BET specific surface area of 380m2Per g, total pore volume of 0.36cm3(ii) a mesoporous carbon having a mesoporous rate of 77% and a strength of 98% or more.
Example 3
1. Condensation reaction
Adding 1000g of vacuum residue, 100g of cresol and 300g of paraformaldehyde atmospheric residue into a three-neck flask, heating the system to 100 ℃ within 30min under the condition of stirring, adding 5g of acetic acid under the condition of stirring reflux, and carrying out normal pressure reflux reaction for 4.5 hours; replacing the reflux device with a distillation device, and distilling at 145 ℃ for 3 hours under the distillation pressure of-0.0720 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 400g of asphalt resin binder and 5g of ZnCl290g of hydroxymethyl cellulose and 90g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 40 ℃, and placed for 45 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 600 ℃ at the speed of 4 ℃/min under the protection of nitrogen, and keeping the temperature for 2 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, continuously heating the columnar carbon obtained in the step 3 to 800 ℃, introducing water vapor at the flow rate of 0.45mL/min, and performing activation treatment for 5 hours to obtain the BET specific surface area of 400m2Per g, total pore volume of 0.50cm3The mesoporous carbon has a mesoporous rate of 83 percent and a strength of more than or equal to 96 percent.
Example 4
1. Condensation reaction
Adding 1000g of vacuum residue, 140g of cresol and 250g of paraformaldehyde atmospheric residue into a three-neck flask, heating the system to 100 ℃ within 30min under the condition of stirring, adding 10g of hydrochloric acid under the condition of stirring reflux, and carrying out normal pressure reflux reaction for 4 hours; replacing the reflux device with a distillation device, and distilling at 150 ℃ for 2 hours under the distillation pressure of-0.0720 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Mixing the asphalt resin binder obtained in the step 1 with stoneGrinding the oil coke to below 160 meshes respectively, and then adding 1000g of petroleum coke powder, 500g of pitch resin binder and 5g of Zn (NO)3)2And 110g of hydroxymethyl cellulose and 110g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 45 ℃, and placed for 50 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 650 ℃ at the speed of 5 ℃/min under the protection of nitrogen, and keeping the temperature for 3 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 825 ℃, water vapor is introduced at the flow rate of 0.5mL/min, and the activation treatment is carried out for 4.5 hours to obtain the BET specific surface area of 550m2Per g, total pore volume of 0.62cm3The mesoporous carbon has a mesoporous rate of 85 percent and a strength of more than or equal to 98 percent.
Example 5
1. Condensation reaction
Adding 1000g of vacuum residue, 180g of cresol and 200g of paraformaldehyde atmospheric residue into a three-neck flask, heating the system to 110 ℃ within 30min under the condition of stirring, adding 10g of hydrochloric acid under the condition of stirring reflux, and carrying out normal pressure reflux reaction for 3 hours; the reflux device is replaced by a distillation device, and the distillation is carried out for 2 hours at the temperature of 160 ℃, and the distillation pressure is-0.0480 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 700g of asphalt resin binder and 15g of Zn (NO)3)2140g of hydroxymethyl cellulose and 140g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 55 ℃, and placed for 60 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 650 ℃ at the speed of 7 ℃/min under the protection of nitrogen, and keeping the temperature for 3 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, continuously heating the columnar carbon obtained in the step 3 to 875 ℃, introducing water vapor at the flow rate of 0.6mL/min, and performing activation treatment for 3.5 hours to obtain the BET specific surface area of 560m2Per g, total pore volume of 0.65cm3The mesoporous carbon has a mesoporous rate of 84% and a strength of more than or equal to 96%.
Example 6
1. Condensation reaction
Adding 1000g of extract oil, 220g of xylenol and 150g of acetaldehyde atmospheric residue into a three-neck flask, heating the system to 110 ℃ within 30min under the condition of stirring, adding 15g of sulfuric acid under the condition of stirring reflux, and carrying out atmospheric reflux reaction for 2.5 hours; the reflux device is replaced by a distillation device, and the distillation is carried out for 3 hours at 165 ℃ under the distillation pressure of-0.0480 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 800g of asphalt resin binder and 15g of Zn (NO)3)2160g of polyurethane and 160g of water are filled into a kneading machine, uniformly kneaded, extruded and molded at 60 ℃, and placed for 65 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 700 ℃ at the speed of 8 ℃/min under the protection of nitrogen, and keeping the temperature for 4 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 900 ℃, water vapor is introduced at the flow rate of 0.65mL/min, and the activation treatment is carried out for 3 hours to obtain the BET specific surface area of 590m2Per g, total pore volume of 0.67cm3The mesoporous carbon has a mesoporous rate of 84% and a strength of more than or equal to 95%.
Example 7
1. Condensation reaction
Adding 1000g of extract oil, 260g of xylenol and 100g of acetaldehyde atmospheric residue into a three-neck flask, heating the system to 120 ℃ within 30min under the condition of stirring, adding 15g of sulfuric acid under the condition of stirring reflux, and carrying out atmospheric reflux reaction for 2 hours; replacing the reflux device with a distillation device, and distilling at 170 deg.C for 4 hr under-0.0240 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, then putting 1000g of petroleum coke powder, 900g of asphalt resin binder, 20g of ZnS, 180g of polyurethane and 180g of water into a kneading machine, uniformly kneading, extruding and molding at 65 ℃, and standing at normal temperature for 70 hours to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 750 ℃ at the speed of 9 ℃/min under the protection of nitrogen, and keeping the temperature for 4 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 925 ℃, water vapor is introduced at the flow rate of 0.7mL/min, and the activation treatment is carried out for 2.5 hours to obtain the BET specific surface area of 580m2Per g, total pore volume of 0.65cm3The mesoporous carbon has a mesoporous rate of 83 percent and a strength of more than or equal to 95 percent.
Example 8
1. Condensation reaction
Adding 1000g of deoiled asphalt, 300g of nonyl phenol and 50g of benzaldehyde atmospheric residue into a three-neck flask, heating the system to 130 ℃ within 30min under the stirring condition, adding 20g of citric acid under the stirring reflux state, and carrying out atmospheric reflux reaction for 1 hour; replacing the reflux device with a distillation device, and distilling at 180 ℃ for 5 hours under the distillation pressure of 0 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, then putting 1000g of petroleum coke powder, 1000g of asphalt resin binder, 20g of ZnS, 200g of polybutylece butyl ester and 200g of water into a kneading machine, uniformly kneading, extruding and molding at 70 ℃, and standing for 80 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 800 ℃ at the speed of 10 ℃/min under the protection of nitrogen, and keeping the temperature for 4 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, continuously heating the columnar carbon obtained in the step 3 to 950 ℃, introducing water vapor at the flow rate of 0.8mL/min, and performing activation treatment for 2 hours to obtain the BET specific surface area of 579m2Per g, total pore volume of 0.64cm3The mesoporous carbon has a mesoporous rate of 83 percent and a strength of more than or equal to 95 percent.
Example 9
1. Condensation reaction
Adding 1000g of deoiled asphalt, 150g of nonyl phenol and 230g of benzaldehyde atmospheric residue into a three-neck flask, heating the system to 130 ℃ within 30min under the stirring condition, adding 10g of maleic acid under the stirring reflux state, and carrying out atmospheric reflux reaction for 3.5 hours; the reflux device is replaced by a distillation device, and the distillation is carried out for 2.5 hours at the temperature of 155 ℃, and the distillation pressure is-0.0450 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, then putting 1000g of petroleum coke powder, 600g of asphalt resin binder, 10g of ZnS, 125g of polybutylece butyl ester and 125g of water into a kneading machine, uniformly kneading, extruding and molding at 50 ℃, and standing for 55 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 650 ℃ at the speed of 6 ℃/min under the protection of nitrogen, and keeping the temperature for 3 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 850 ℃, water vapor is introduced at the flow rate of 0.55mL/min, and the activation treatment is carried out for 4 hours to obtain the BET specific surface area of 600m2Per g, total pore volume of 0.7cm3(ii) g, the mesoporous rate is 85%, and the strength is more than or equal to 98%Mesoporous carbon.
Example 10
1. Condensation reaction
Adding 1000g of vacuum residue, 200g of cresol and 230g of paraformaldehyde atmospheric residue into a three-neck flask, heating the system to 100 ℃ within 30min under the condition of stirring, adding 10g of hydrochloric acid under the condition of stirring reflux, and carrying out normal pressure reflux reaction for 3.5 hours; the reflux device is replaced by a distillation device, and the distillation is carried out for 2.5 hours at the temperature of 155 ℃, and the distillation pressure is-0.0450 MPa; and after the reaction is finished, closing the vacuum pump, discharging and cooling to obtain the asphalt resin binder.
2. Shaping of
Respectively grinding the asphalt resin binder and the petroleum coke obtained in the step 1 to below 160 meshes, and then respectively grinding 1000g of petroleum coke powder, 600g of asphalt resin binder and 10g of Zn (NO)3)2125g of hydroxymethyl cellulose and 125g of water are filled into a kneading machine to be kneaded uniformly, and the mixture is extruded and molded at 40 ℃ and is placed for 55 hours at normal temperature to obtain a columnar blank.
3. Charring
And (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 700 ℃ at the speed of 6 ℃/min under the protection of nitrogen, and keeping the temperature for 3 hours to obtain columnar carbon.
4. Activation of
Under the protection of nitrogen, the columnar carbon obtained in the step 3 is continuously heated to 825 ℃, water vapor is introduced at the flow rate of 0.55mL/min, and the activation treatment is carried out for 4 hours to obtain the BET specific surface area of 590m2Per g, total pore volume of 0.68cm3The mesoporous carbon has a mesoporous rate of 85 percent and a strength of more than or equal to 98 percent.
Claims (8)
1. The preparation method of the high-strength mesoporous carbon is characterized by comprising the following steps of:
(1) condensation reaction
Mixing petroleum asphalt, phenol and aldehyde according to the mass ratio of 100 (2-30) to (5-40), heating to 80-130 ℃, adding a catalyst accounting for 0.1-2% of the mass of the asphalt under the stirring reflux state, keeping the reflux temperature of the system constant, and carrying out reflux reaction for 1-6 hours under normal pressure; after the reflux reaction is finished, distilling for 0.5-5 hours at the temperature of 130-180 ℃ and under the pressure of-0.0960-0 MPa to obtain the pitch resin binder;
the petroleum asphalt is any one of atmospheric residue oil, vacuum residue oil, extract oil and deoiled asphalt; the phenol is any one of phenol, cresol, xylenol and nonyl phenol; the aldehyde is any one of formaldehyde, paraformaldehyde, acetaldehyde and benzaldehyde; the catalyst is any one of oxalic acid, acetic acid, hydrochloric acid, sulfuric acid, citric acid and maleic acid;
(2) shaping of
Grinding the asphalt resin binder and the petroleum coke obtained in the step (1) to below 160 meshes respectively, then putting the petroleum coke powder, the asphalt resin binder, the cross-linking agent, the pore-forming agent and water into a kneading machine according to the mass ratio of 100 (20-100): (0.1-2): (5-20): 5-20), kneading uniformly, extruding and molding at 30-70 ℃, and standing at normal temperature for 30-80 hours to obtain a columnar blank;
the cross-linking agent is ZnCl2、Zn(NO3)2And ZnS; the pore-foaming agent is any one of polyethylene glycol, hydroxymethyl cellulose, polyurethane and polybutylece butyl ester;
(3) charring
Putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 500-800 ℃ at the speed of 2-10 ℃/min under the protection of nitrogen, and keeping the temperature for 2-4 hours to obtain columnar carbon;
(4) activation of
And (3) under the protection of nitrogen, continuously heating the columnar carbon obtained in the step (3) to 750-950 ℃, introducing water vapor at the flow rate of 0.3-0.8 mL/min, and performing activation treatment for 2-6 hours to obtain the high-strength mesoporous carbon.
2. The method for preparing high-strength mesoporous carbon according to claim 1, wherein: in the step (1), mixing petroleum asphalt, phenol and aldehyde according to a mass ratio of 100 (12-20) to (15-30), heating to 90-120 ℃, adding a catalyst with the mass of 0.5-1.5% of that of the asphalt under a stirring reflux state, keeping the reflux temperature of the system constant, and carrying out reflux reaction at normal pressure for 2-5 hours; after the reflux reaction is finished, distilling for 1.5-3 hours at the temperature of 145-165 ℃ and the pressure of-0.06-0.03 MPa.
3. The method for preparing high-strength mesoporous carbon according to claim 1, wherein: in the step (1), mixing petroleum asphalt, phenol and aldehyde according to a mass ratio of 100 (15-18) to (20-25), heating to 100-110 ℃, adding a catalyst with the mass of 0.8-1.2% of that of the asphalt under a stirring reflux state, keeping the reflux temperature of the system constant, and carrying out reflux reaction at normal pressure for 3-4 hours; after the reflux reaction is finished, distilling for 2.0-2.5 hours at the temperature of 150-160 ℃ and the pressure of-0.05-0.04 MPa.
4. The method for preparing high-strength mesoporous carbon according to any one of claims 1 to 3, wherein: the petroleum asphalt is any one of atmospheric residue, vacuum residue and deoiled asphalt, the phenol is phenol or nonyl phenol, the aldehyde is formaldehyde or paraformaldehyde, and the catalyst is any one of hydrochloric acid, sulfuric acid and maleic acid.
5. The method for preparing high-strength mesoporous carbon according to claim 1, wherein: in the step (2), the asphalt resin binder and the petroleum coke obtained in the step (1) are respectively ground to below 160 meshes, then the petroleum coke powder, the asphalt resin binder, the cross-linking agent, the pore-foaming agent and the water are put into a kneading machine according to the mass ratio of 100 (50-70) (0.5-1.5) (10-15), and are uniformly kneaded, extruded and molded at the temperature of 45-55 ℃, and placed for 45-65 hours at normal temperature.
6. The method for preparing high-strength mesoporous carbon according to claim 1 or 5, wherein: the cross-linking agent is ZnCl2Or Zn (NO)3)2The pore-foaming agent is any one of polyethylene glycol, hydroxymethyl cellulose and polyurethane.
7. The method for preparing high-strength mesoporous carbon according to claim 1, wherein: and (3) putting the columnar blank obtained in the step (2) into a tubular resistance furnace, heating to 600-700 ℃ at the speed of 5-7 ℃/min under the protection of nitrogen, and keeping the temperature for 2.5-3.5 hours.
8. The method for preparing high-strength mesoporous carbon according to claim 1, wherein: in the step (4), under the protection of nitrogen, the columnar carbon obtained in the step (3) is continuously heated to 800-900 ℃, water vapor is introduced at the flow rate of 0.4-0.7 mL/min, and the activation treatment is carried out for 3-5 hours.
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| CN116354741A (en) * | 2022-12-21 | 2023-06-30 | 中国人民解放军96901部队23分队 | Method for preparing low-density hierarchical pore isostatic pressing graphite material by template method |
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