CN111790351A - Preparation method of graded porous carbon material with toluene adsorption effect - Google Patents

Preparation method of graded porous carbon material with toluene adsorption effect Download PDF

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CN111790351A
CN111790351A CN202010586166.1A CN202010586166A CN111790351A CN 111790351 A CN111790351 A CN 111790351A CN 202010586166 A CN202010586166 A CN 202010586166A CN 111790351 A CN111790351 A CN 111790351A
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袁明
陈东辉
安昭辉
安志浩
曾珂
马晶莹
段方蕾
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Shanghai Institute of Technology
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Abstract

The invention relates to a preparation method of a graded porous carbon material with toluene adsorption effect, which comprises the steps of uniformly mixing F127, HCl and ethanol, adding tetraethoxysilane and resol, and obtaining a carbon precursor after continuous stirring, standing for volatilization, heating and polymerization; then, crushing, screening, carbonizing and calcining the carbon precursor, soaking the carbon precursor in NaOH solution to remove silicon, and filtering, washing and drying the carbon precursor to obtain a carbon material; and finally, dissolving the carbon material and an activating agent in an ethanol solution, and sequentially drying, roasting, soaking, filtering and washing to be neutral to obtain the graded porous carbon material. Compared with the prior art, the method has the advantages of easiness in control, low cost, simplicity and convenience in method and the like, and the prepared carbon material has the characteristics of hierarchical porosity, large specific surface area, good adsorption performance and the like, and has a great potential application value in the fields of adsorption, electrode materials, separation, sensing, gas storage, catalyst carriers and the like.

Description

Preparation method of graded porous carbon material with toluene adsorption effect
Technical Field
The invention belongs to the technical field of biomass carbon materials, and relates to a preparation method of a graded porous carbon material with a toluene adsorption effect.
Background
Most Volatile Organic Compounds (VOCs) are highly toxic, carcinogenic, and hazardous. In confined spaces, VOCs can irritate the eyes, nose and throat, and more seriously, can cause dizziness, headache, memory and visual impairment, and even death. In addition to human damage, VOCs are also a major contributor to stratospheric ozone depletion and regional ozone formation. The vaporized alkanes, aromatics and alkenes will react photochemically in the appropriate climates, and the species with the greatest potential for ozone formation, including m/p-xylene, toluene, o-xylene and ethylbenzene, make up 30% of the total VOCs emitted and 69% of the total potential for ozone formation. Since VOCs can pose serious threats to the ecological environment and human health, the development of a method and a material for treating VOCs is of great significance to human and natural environments.
In recent years, as the amount of VOCs discharged continues to increase, more and more researchers are studying techniques for degrading VOCs. Among them, the adsorption technology uses the adsorption material to perform physical and chemical interactions with the VOCs in the exhaust gas, which is an effective method for enriching and separating VOCs, and the adsorption material can be reused by thermal desorption or vacuum desorption. Thus, adsorption technology is considered an effective and economical control strategy because it allows for the recycling of adsorbent materials and the efficient disposal of VOCs.
The activated carbon is the most widely used adsorbing material because of its advantages of rich pore structure, large specific surface area, high porosity and the like. The active carbon material mainly takes a microporous structure as a main part, has shown good adsorption performance in the adsorption research of VOCs, but just because of abundant irregular microporous structure, causes pore channel blockage easily again in the adsorption process, makes the mass transfer resistance increase, is unfavorable for the desorption process.
Ordered Mesoporous Carbon (OMC), as a novel carbon material, has been widely used in various fields such as adsorption, catalysis, energy storage, etc. due to a series of advantages such as large BET surface area, adjustable pore size, high pore volume, good chemical inertness and mechanical strength. The OMC has mesoporous channels with uniform and orderly arranged channels, so that the OMC shows higher adsorption mass transfer efficiency in adsorption application, and simultaneously, the OMC makes up the problems of large mass transfer resistance, difficult desorption and the like of an activated carbon material mainly comprising micropores. Therefore, OMC has certain application prospect in the adsorption of VOCs theoretically.
Disclosure of Invention
The invention aims to provide a preparation method of a graded porous carbon material with a toluene adsorption effect, which is used for solving the problem that the existing ordered mesoporous carbon material has poor adsorption capacity on VOCs.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graded porous carbon material with toluene adsorption effect comprises the following steps:
1) uniformly mixing F127, an HCl solution and ethanol to obtain a mixed solution;
2) adding tetraethoxysilane and a resol solution into the mixed solution, and sequentially carrying out continuous stirring, standing, volatilizing, self-assembling and heating polymerization processes to obtain a carbon precursor;
3) sequentially carrying out crushing screening, carbonization and calcination processes on the carbon precursor to obtain a carbon-silicon composite material, then soaking the carbon-silicon composite material in a NaOH solution to remove silicon, and sequentially carrying out filtering, washing and drying to obtain a carbon material;
4) dissolving a carbon material and an activating agent in an ethanol solution, and sequentially drying, roasting, soaking, filtering and washing to be neutral to obtain the graded porous carbon material.
Further, in the step 1), the mass ratio of the F127 to the HCl solution to the ethanol is (2-4) to (1-3) to (6-8), and the concentration of the HCl solution is 0.1-0.3 mol/L.
Further, in the step 1), the mixing process is to stir for 0.5 to 1.5 hours at the temperature of between 30 and 50 ℃.
Further, in step 2), the preparation method of the resol solution comprises: uniformly stirring and mixing the molten phenol and the NaOH aqueous solution at 40-45 ℃, adding the formaldehyde aqueous solution, heating to 60-80 ℃, continuously stirring for 0.5-1.5h, cooling the solution to room temperature, adjusting the pH value to be neutral, and finally performing vacuum drying and ethanol dilution to obtain the resol solution.
Furthermore, the mass ratio of the phenol to the NaOH aqueous solution is (4-6) to (0.5-1.5), and the mass concentration of the NaOH aqueous solution is 15-25 wt%;
the mass ratio of the phenol to the formaldehyde aqueous solution is (4-6) to (8-10), and the mass concentration of the formaldehyde aqueous solution is 35-40 wt%;
in the vacuum drying, the drying temperature is 40-50 ℃, and the drying time is 10-15 h.
Further, in the step 2), the mass ratio of the mixed solution, the tetraethoxysilane and the resol solution is (10-12) to (3-5) to (8-12), and the mass concentration of the resol solution is 10-20 wt%.
Further, in the step 2), in the standing volatilization process, the standing time is 5-8h, and the standing temperature is room temperature; in the heating polymerization process, the polymerization temperature is 90-110 ℃, and the polymerization time is 20-28 h.
Further, in the step 3), in the crushing and screening process, the screening mesh number is 40-60 meshes; in the carbonization and calcination process, the temperature rise speed is 2-10 ℃/min, the calcination temperature is 750-850 ℃, and the calcination time is 1-3 h.
Further, in the step 3), the concentration of the NaOH solution is 2-4mol/L, the dipping temperature is 60-80 ℃, and the dipping time is 20-24 h.
Further, in the step 4), the mass ratio of the carbon material to the activating agent is 1 (1-5), and the activating agent comprises KOH and H3PO4And Na2CO3The calcination ofIn the process, the temperature rising speed is 1-5 ℃/min, the roasting temperature is 700-.
As a preferable technical scheme, in the step 4), when the activating agent is KOH, the soaking solution used in the soaking process is 0.8-1.2mol/L HCl solution.
Preferably, in the step 4), after the washing process, the product is dried at 80-105 ℃ to obtain the graded porous carbon material.
As a preferable technical scheme, the carbonization and calcination process in step 3) and the calcination process in step 4) are performed under the protection of an inert gas, wherein the inert gas includes one or more of nitrogen, helium, neon, argon, krypton, or xenon.
As a further preferable technical scheme, the carbonization and calcination process in the step 3) and the calcination process in the step 4) are started after inert gas is filled for 15-20 min.
The preparation method adopts a solvent volatilization induction self-assembly method in a soft template method, and HCl plays a role in regulating the PH value and playing a role of a polymerization catalyst in the preparation process. F127 is a nonionic surfactant and is a mesoporous template. Tetraethoxysilane is used as a micropore template. The phenolic resin serves to provide a carbon source.
Compared with the prior art, the invention has the following characteristics:
1) the invention is based on the soft template method to prepare the hierarchical porous carbon material, compared with the hard template, the method can obviously simplify the experimental steps;
2) the invention proves the promoting effect of the micropore-mesopore hierarchical pore structure on adsorption, and the prepared material combines the structural advantages of micropores and mesopores, so that the adsorption effect can be improved and the adsorption rate can be improved;
3) according to the invention, phenolic resin is used as a carbon source to prepare the high-surface-area activated carbon material with the hierarchical porous characteristic, and the specific activation temperature and the heat preservation time are controlled to greatly influence the surface area and the pore structure of the material, so that the material with high adsorption performance on VOCs is prepared, and the application range of the carbon material is expanded;
4) the method has the advantages of easy control, low cost, simple and convenient method and the like, and the prepared carbon material has the characteristics of hierarchical porosity, large specific surface area, good adsorption performance and the like, and has great potential application value in the fields of adsorption, electrode materials, separation, sensing, gas storage, catalyst carriers and the like.
Drawings
FIG. 1 is a schematic view of the structure of an adsorption test apparatus used in example 6;
FIG. 2 is a graph of toluene sorption breakthrough for the carbon material prepared in example 1 and the graded porous carbon material prepared in example 2;
FIG. 3 is a graph showing toluene adsorption saturation amounts of the carbon material prepared in example 1 and the hierarchical porous carbon material prepared in example 2;
FIG. 4 is a graph of toluene sorption breakthrough for the carbon material prepared in example 1 and the graded porous carbon material prepared in example 3;
FIG. 5 is a graph showing toluene adsorption saturation amounts of the carbon material prepared in example 1 and the hierarchical porous carbon material prepared in example 3;
FIG. 6 is a graph of toluene sorption breakthrough for the carbon material prepared in example 1 and the graded porous carbon material prepared in example 4;
FIG. 7 is a graph showing toluene adsorption saturation amounts of the carbon material prepared in example 1 and the hierarchical porous carbon material prepared in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
A preparation method of a graded porous carbon material with toluene adsorption effect comprises the following steps:
1) mixing F127, 0.1-0.3mol/L HCl solution and absolute ethyl alcohol according to the mass ratio of (2-4) to (1-3) to (6-8), and stirring for 0.5-1.5h at 30-50 ℃ to obtain a mixed solution;
2) adding tetraethoxysilane and 10-20 wt% of resol solution into the mixed solution, stirring for 1-3h at 30-50 ℃, standing and volatilizing for 5-8h at room temperature, and heating and polymerizing for 20-28h at 90-110 ℃ to obtain a carbon precursor; wherein the mass ratio of the mixed solution to the ethyl orthosilicate to the resol solution is (10-14) to (3-5) to (8-12);
3) crushing the carbon precursor, sieving by using a 40-60-mesh sieve, carbonizing and calcining for 1-3h at the temperature of 750-850 ℃ (the heating speed is 2-10 ℃/min in the heating process) to obtain a carbon-silicon composite material, then soaking the carbon-silicon composite material in 2-4mol/L NaOH solution at the temperature of 60-80 ℃ for 20-24h to remove silicon, and then sequentially filtering, washing and drying at the temperature of 100-110 ℃ to obtain a carbon material;
4) dissolving a carbon material and an activator in 40-60 wt% ethanol solution according to the mass ratio of 1 (1-5), drying at 80-105 ℃, roasting (the temperature rise speed is 1-5 ℃/min, the roasting temperature is 700 ℃ and 900 ℃, the roasting time is 2-4H), soaking, filtering, washing to be neutral, and drying at 80-105 ℃ to obtain the hierarchical porous carbon material, wherein the activator comprises KOH and H3PO4And Na2CO3，
Wherein, in the step 2), the preparation method of the resol solution comprises the following steps: stirring molten phenol and 15-25 wt% of NaOH aqueous solution for 10-15min at 40-45 ℃, adding 35-40 wt% of formaldehyde aqueous solution, heating to 60-80 ℃, continuing stirring for 0.5-1.5h, cooling the solution to room temperature, adjusting the pH to be neutral by using 1-3mol/L HCl solution, then carrying out vacuum drying for 10-15h at 40-50 ℃ to obtain a viscous liquid of the resol, diluting the viscous liquid by using ethanol until the mass fraction is 10-20 wt%, and obtaining the resol solution. Wherein the mass ratio of the phenol to the formaldehyde aqueous solution is (4-6) to (8-10).
As a preferable technical scheme, in the step 4), when the activating agent is KOH, the soaking solution used in the soaking process is 0.8-1.2mol/L HCl solution.
As a preferable technical scheme, the carbonization and calcination process in step 3) and the calcination process in step 4) are performed under the protection of an inert gas, wherein the inert gas includes one or more of nitrogen, helium, neon, argon, krypton, or xenon.
As a further preferable technical scheme, the carbonization and calcination process in the step 3) and the calcination process in the step 4) are started to heat up after inert gas is filled for 15-20 min.
The following examples are given in detail to illustrate the embodiments and specific procedures of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
this example was used to prepare carbon material OMC-1, comprising the following steps:
1) putting 5g of phenol in a 100mL beaker, heating the phenol to 42 ℃ through a water bath to melt the phenol, slowly adding 1.06g of 20 wt% NaOH aqueous solution, stirring the mixture for 10min, then adding 8.85g of 37 wt% formaldehyde aqueous solution, heating the mixture to 70 ℃, continuing stirring the mixture for 1h, stopping stirring the mixture, slowly cooling the solution to room temperature, adjusting the pH to be neutral by using 2mol/L HCl solution, then carrying out vacuum drying on the mixed solution at 45 ℃ for 12h to obtain a viscous liquid of resol, diluting the viscous liquid by using ethanol until the mass fraction is 20 wt%, and then placing the viscous liquid in a refrigerator for low-temperature storage;
2) 3.2g F127, 2.0g of 0.2mol/L HCl solution and 6g of absolute ethyl alcohol are mixed in a 100mL beaker and stirred for 1h at 40 ℃ to obtain a mixed solution;
3) adding 4.16g of tetraethoxysilane and 10g of 20 wt% resol solution into the mixed solution, then magnetically stirring for 2 hours at 40 ℃, then transferring to an evaporation dish, standing and volatilizing for 6 hours at room temperature to evaporate ethanol, and then carrying out polymerization reaction for 24 hours in an oven at 100 ℃ to obtain a carbon precursor;
4) crushing the carbon precursor by using a crusher, screening the crushed carbon precursor into small particles by using a sieve with 50 meshes, placing the particles in a tubular furnace, introducing 100mL/min of high-purity nitrogen for stabilization for 15min to discharge air in the tube, carbonizing and calcining the particles at 800 ℃ for 2h (the heating speed is 8 ℃/min in the heating process) to obtain a carbon-silicon composite material, soaking the carbon-silicon composite material in 4mol/L NaOH solution at 60 ℃ for 24h to remove silicon dioxide, filtering the solution, washing the solution with deionized water to be neutral, and drying the solution at 105 ℃ to obtain the carbon material OMC-1.
Example 2:
this example uses carbon material OMC-1 prepared in example 1 as a raw material and H3PO43, preparing a hierarchical porous carbon material as an activating agent, wherein the specific preparation processes are respectively as follows:
1) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 1g of H were sequentially added3PO4Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 700 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tube furnace, sequentially soaking, filtering and washing to be neutral, and drying at 105 ℃ overnight to obtain a hierarchical porous carbon material which is marked as POMC-1-700;
2) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 3g of H were sequentially added3PO4Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 800 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tube furnace, sequentially soaking, filtering and washing to be neutral, and drying at 105 ℃ overnight to obtain a hierarchical porous carbon material, which is marked as POMC-3-800;
3) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 5g of H were sequentially added3PO4Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 900 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally taking the activated biomass activated carbon out of the tube furnace, soaking, filtering and washing the activated biomass activated carbon to be neutral in sequence, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain the graded porous carbon material which is recorded as POMC-5-900。
Example 3:
in this example, the carbon material OMC-1 prepared in example 1 is used as a raw material, KOH is used as an activator, and 3 hierarchical porous carbon materials are prepared, specifically, the preparation processes are respectively as follows:
1) placing 1g of carbon material OMC-1 in a 30mL nickel crucible, sequentially adding 10mL of 50 wt% ethanol solution and 1g of KOH for full dissolution, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tubular furnace, introducing 20min100mL/min high-purity nitrogen, exhausting air in the tubular furnace, then heating to 700 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tube furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain a graded porous carbon material which is recorded as KOMC-1-700;
2) placing 1g of carbon material OMC-1 in a 30mL nickel crucible, sequentially adding 10mL of 50 wt% ethanol solution and 3g of KOH for full dissolution, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tubular furnace, introducing 20min100mL/min high-purity nitrogen, exhausting air in the tubular furnace, then heating to 800 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tube furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain a graded porous carbon material which is recorded as KOMC-3-800;
3) placing 1g of carbon material OMC-1 in a 30mL nickel crucible, sequentially adding 10mL of 50 wt% ethanol solution and 5g of KOH for full dissolution, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tubular furnace, introducing 20min100mL/min high-purity nitrogen, exhausting air in the tubular furnace, then heating to 900 ℃ at a heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; and finally taking the activated biomass activated carbon out of the tube furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain the hierarchical porous carbon material which is recorded as KOMC-5-900.
Example 4:
this example uses carbon material OMC-1 prepared in example 1 as a raw material and Na2CO33, preparing a hierarchical porous carbon material as an activating agent, wherein the specific preparation processes are respectively as follows:
1) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 1g of Na were sequentially added2CO3Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 700 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tubular furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain a graded porous carbon material which is recorded as NaOMC-1-700;
2) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 3g of Na were sequentially added2CO3Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 800 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; finally, taking the activated biomass activated carbon out of the tubular furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain a graded porous carbon material which is recorded as NaOMC-3-800;
3) 1g of carbon material OMC-1 was placed in a 30mL nickel crucible, and 10mL of 50 wt% ethanol solution and 5g of Na were sequentially added2CO3Fully dissolving, then placing the nickel crucible in an oven at 80 ℃ for drying, then placing the nickel crucible in a tube furnace, introducing 20min100mL/min high-purity nitrogen, exhausting the air in the tube furnace, then heating to 900 ℃ at the heating rate of 1 ℃/min, preserving heat for 2h, and carrying out chemical activation; and finally taking the activated biomass activated carbon out of the tubular furnace, sequentially soaking the activated biomass activated carbon for 6 hours in 1mol/L HCl solution, filtering and washing the activated biomass activated carbon to be neutral, and drying the activated biomass activated carbon at 105 ℃ overnight to obtain the graded porous carbon material which is recorded as NaOMC-5-900.
Example 5:
this example was used to perform physical property tests on the carbon materials prepared in examples 1 to 4 and the graded porous carbon material, and the test results are shown in table 1.
TABLE 1
Figure BDA0002554713750000081
Figure BDA0002554713750000091
Phosphoric acid activation mechanism the activation temperature can be lowered by adding phosphoric acid, which is dispersed in the carbon material, and after activation, washing away the phosphoric acid leaves pores in the carbon material, but the main generation of phosphoric acid activation is mesopores. For the KOH activation process involving two activation reaction mechanisms, namely, a medium temperature radial activation mechanism and a high temperature transverse activation mechanism, K was discovered2O、—O—K+and-CO2—K+Is an activator active component of a medium-temperature activation section mainly activated in the radial direction, and K in a molten state+O-、K+It is the catalytically active component of the high temperature activation section that is predominantly laterally activated, and the KOH activation process produces a large surface area while forming predominantly micropores. Na (Na)2CO3Can be oxidized and decomposed at high temperature to obtain CO2，CO2CO is produced by reaction with carbon at high temperature, and adsorption of CO on the active sites of carbon hinders the progress of the reaction, thus resulting in non-uniform pores and larger pore diameters. The molecular diameter of toluene is about 0.7nm, and the pore diameter generated after KOH activation is 0.6-1.0nm in the micropore. The adsorption effect on toluene after KOH activation is the best in terms of adsorption theory through the pores.
From table 1, it can be seen that the structure of the material is greatly changed after activation by the activator, and the surface area, the micropore volume and the mesopore volume of the material before non-activation are relatively small. The surface area, the micropore volume and the mesopore volume of the material are relatively increased after the material is activated by the activating agent. Compared with an activating agent, the surface area and the micropore volume of the activated KOH are obviously increased, wherein the specific surface area and the micropore volume of the KOMC-3-800 are the largest, and the KOH activation plays a favorable role in preparing high specific surface area hierarchical porous materials.
Example 6:
this example was used to test the toluene adsorption efficiency of the carbon materials prepared in examples 1 to 4 and the graded porous carbon material, the adsorption test apparatus is shown in fig. 1, and the test procedure is as follows:
the test uses a dynamic gas distribution method, i.e. toluene gas is prepared by a bubbling method (see the documents Huiping Zhou, Shaomin Gao, Wenwen Zhang, Zhaohui An, Donghui Chen. dynamic adaptation of the phase on amino-functional SBA-15type of waterborne medicine silicon. RSC Advance.2019: 7196-7202.). High-purity nitrogen is used as carrier gas, wherein one path of high-purity nitrogen passes through a bubbler filled with toluene liquid, the flow rate is 9ml/min, the other path of high-purity nitrogen is used as diluent gas, the flow rate is 51ml/min, and the two paths of gas are directly introduced into a mixing tank, and finally the two paths of gas are uniformly mixed in the mixing tank. The bubbler is placed in a constant-temperature ice-water bath, a 3mm stainless steel pipe is adopted as a gas circulation pipeline of the whole system, and the temperature is kept at 60 ℃. The initial concentration of toluene was controlled by controlling the gas flow rate into the bubbler and the gas flow rate of the dilution gas by adjusting a gas mass flow Meter (MFC). The mixed gas reaches the purpose of carrying out an adsorption experiment through a U-shaped pipe filled with an adsorbent, the finally adsorbed gas directly enters a Gas Chromatography (GC) for analysis and detection, the concentration of toluene is 4mg/L, and 4 groups of experiments are carried out on the material. The test results are shown in fig. 2-7, respectively.
It can be seen from the adsorption breakthrough curves of toluene (as shown in fig. 2, 4 and 6) that the adsorption breakthrough time after activation is significantly longer, since the adsorption breakthrough time reflects the effect of the adsorbent to some extent, and the longer the breakthrough time, the better the adsorption effect, and it can be seen from the graphs that the adsorption breakthrough time after activation with activated KOH is significantly longer than that after activation with the other two activators, wherein the breakthrough curve time of KOMC-3-800 is the longest. Referring again to the saturation adsorption amount (as shown in fig. 3, 5 and 7), it was also found that the adsorption amount after activation of the activator was significantly increased, and it was also found that the adsorption amount after activation of KOH was significantly increased. The saturated adsorption capacity of KPMC-3-800 is the greatest as in the breakthrough curve. Shows that the three activators have promotion effect on the toluene adsorption of the material after activation, wherein the KOH effect is the best.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a graded porous carbon material with toluene adsorption effect is characterized by comprising the following steps:
1) uniformly mixing F127, an HCl solution and ethanol to obtain a mixed solution;
2) adding ethyl orthosilicate and a resol solution into the mixed solution, and sequentially carrying out continuous stirring, standing volatilization and heating polymerization processes to obtain a carbon precursor;
3) sequentially carrying out crushing, screening, carbonization and calcination processes on the carbon precursor, soaking the carbon precursor in NaOH solution, and sequentially carrying out filtering, washing and drying on the carbon precursor to obtain a carbon material;
4) dissolving a carbon material and an activating agent in an ethanol solution, and sequentially carrying out drying, roasting, soaking, filtering and washing processes to obtain the graded porous carbon material.
2. The method according to claim 1, wherein in the step 1), the mass ratio of the F127 to the HCl solution to the ethanol is (2-4) to (1-3) to (6-8), and the concentration of the HCl solution is 0.1-0.3 mol/L.
3. The method for preparing a hierarchical porous carbon material with toluene adsorbing effect according to claim 1, wherein in the step 1), the mixing process is stirring at 30-50 ℃ for 0.5-1.5 h.
4. The method according to claim 1, wherein the step 2) of preparing the resol solution comprises: uniformly stirring and mixing the molten phenol and the NaOH aqueous solution at 40-45 ℃, adding the formaldehyde aqueous solution, heating to 60-80 ℃, continuously stirring for 0.5-1.5h, cooling the solution to room temperature, adjusting the pH value to be neutral, and finally performing vacuum drying and ethanol dilution to obtain the resol solution.
5. The method for preparing a hierarchical porous carbon material with toluene adsorbing effect as claimed in claim 4, wherein the mass ratio of phenol to NaOH aqueous solution is (4-6): (0.5-1.5), the mass concentration of NaOH aqueous solution is 15-25 wt%;
the mass ratio of the phenol to the formaldehyde aqueous solution is (4-6) to (8-10), and the mass concentration of the formaldehyde aqueous solution is 35-40 wt%;
in the vacuum drying, the drying temperature is 40-50 ℃, and the drying time is 10-15 h.
6. The method for preparing a hierarchical porous carbon material having an effect of adsorbing toluene according to claim 1, wherein in the step 2), the mass ratio of the mixed solution, tetraethoxysilane and resol solution is (10-12), (3-5), (8-12), and the mass concentration of the resol solution is 10-20 wt%.
7. The method for preparing a hierarchical porous carbon material with toluene adsorbing effect according to claim 1, wherein in the step 2), the standing time is 5-8h and the standing temperature is room temperature during the standing volatilization; in the heating polymerization process, the polymerization temperature is 90-110 ℃, and the polymerization time is 20-28 h.
8. The method for preparing a hierarchical porous carbon material with toluene adsorbing effect as claimed in claim 1, wherein in the step 3), the crushing and screening process has a screen mesh number of 40-60 meshes; in the carbonization and calcination process, the temperature rise speed is 2-10 ℃/min, the calcination temperature is 750-850 ℃, and the calcination time is 1-3 h.
9. The method for preparing a hierarchical porous carbon material with toluene adsorbing effect according to claim 1, wherein in step 3), the concentration of NaOH solution is 2-4mol/L, the dipping temperature is 60-80 ℃, and the dipping time is 20-24 h.
10. The method according to claim 1, wherein in step 4), the mass ratio of the carbon material to the activating agent is 1 (1-5), and the activating agent comprises KOH and H3PO4And Na2CO3In the roasting process, the temperature rising speed is 1-5 ℃/min, the roasting temperature is 700-900 ℃, and the roasting time is 2-4 h.
CN202010586166.1A 2020-06-24 2020-06-24 Preparation method of graded porous carbon material with toluene adsorption effect Pending CN111790351A (en)

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Application publication date: 20201020