CN110182797B - Preparation method of modified activated carbon material for capacitive deionization technology - Google Patents
Preparation method of modified activated carbon material for capacitive deionization technology Download PDFInfo
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Abstract
The invention disclosesA preparation method of a novel modified activated carbon material for capacitive deionization technology. The invention adopts cation exchange resin as an active carbon precursor and Ni (NO)3)2、ZnCl2As modifier, the treatment is carried out in different gas atmosphere. Target ions are uniformly attached to cation exchange resin through ion exchange for modification, and then are subjected to pretreatment, carbonization and activation for preparation, so that the basic structure and surface functional groups of the activated carbon are formed in the whole process, and meanwhile, the carbon yield is improved, and the high-performance mesoporous activated carbon material is prepared.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of a novel modified activated carbon material for a capacitive deionization technology.
Background
With the rapid development of the global social economy and the rapid increase of the population, the demand of water resources is increasing day by day, and the crisis of fresh water resources has been listed as the second of ten major problems facing mankind in the next 50 years. The existing forms of water resources are various, seawater and brackish water occupy most of the water resources (reaching 97 percent), and fresh water resources are only 3 percent, so that the seawater and brackish water desalination treatment is an important way for solving the shortage of the fresh water resources. The seawater desalination technology is developed to the present, the energy consumption is one of the important indexes for investigating whether each seawater desalination technology can be continuously developed, and the energy consumption of the capacitive deionization technology (CDI technology) for treating the brackish water is only 0.05-0.1kWh m-3Is far lower than the prior various seawater desalination technologies.
Generally, an excellent CDI electrode material must have the characteristics of high capacitance, high specific surface area, high heavy metal ion adsorption, good adsorption and desorption responsiveness and regeneration capacity, excellent electrochemical and chemical stability, simple preparation process, strong biological and organic pollution resistance, and the like. The carbon material has a developed pore structure, good conductivity and electrochemical and chemical stability, and is widely applied to CDI electrode materials, and the carbon materials which are widely applied at present mainly comprise carbon aerogel, activated carbon, mesoporous carbon, carbon nanotube graphene which is developed rapidly in recent years and the like. In the process of capacitive desalination, developed pore channels of activated carbon are needed to transport and adsorb metal ions, and at the moment, mesopores in the activated carbon have obvious advantages compared with micropores. However, activated carbon having a mesoporous structure cannot be obtained by a conventional activated carbon preparation method. At present, researchers prepare mesoporous carbon by methods such as nano-casting, carbonization of organic aerogel and high-molecular mixture. The preparation of mesoporous carbon through the nano-cast of the soft membrane plate and the hard membrane plate is a preparation method of a potential mesoporous carbon material. However, this method is costly, complicated, time consuming and must be done at the expense of the template. Therefore, it is not suitable for mass production and industrial application. Compared with the nano-casting method, the ion exchange method has certain advantages. The method takes common ion exchange resin as a raw material, loads transition metal through ion exchange, and prepares the active carbon through carbonization and activation treatment at a certain temperature. During carbonization and activation, the transition metal may form the corresponding oxide and become embedded in the carbonaceous matrix in the form of an internal template. When it is removed by acid washing, the number of mesopores in the activated carbon can be increased.
The invention innovatively provides a preparation method of a novel modified activated carbon material for capacitive deionization, and the activated carbon material with a mesoporous pore size structure is finally prepared.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a modified activated carbon material. The method can realize the low-cost, high-yield and high-efficiency preparation of the activated carbon material, and the prepared modified activated carbon material has the characteristics of high surface area, rich pore size distribution, various surface functional groups, good desalting effect, strong stability and the like.
The purpose of the invention is realized by the following scheme:
the invention provides a preparation method of a novel modified activated carbon material, which comprises the following steps: adopting cation exchange resin as active carbon precursor and Ni (NO)3)2、ZnCl2The modifier is treated in different gas atmospheres according to the following steps in sequence:
adding cation exchange resin to Ni (NO) at normal temperature3)2、ZnCl2Stirring the mixed solution (the concentration is 1mol/L) at a constant speed for a period of time, and carrying out ion exchange;
Ni(NO3)2、ZnCl2ni (NO) in solution3)2、ZnCl2The molar ratio of (1) to (0.5-20);
the ion exchange time is 5 min-8 h;
after the exchange is finished, filtering and drying the resin, and then pretreating the resin for a period of time at a certain temperature in an air atmosphere;
the drying temperature is controlled to be 20-110 ℃, and the drying time is 8 h;
the air pretreatment temperature is controlled to be 120-300 ℃, and the treatment time is 0.5-4 h;
step (3), carbonizing the product after air pretreatment for 2h at 800 ℃ in a nitrogen atmosphere;
and (4) activating the carbonized product at a certain temperature in a proper gas atmosphere, and cooling to obtain the modified activated carbon.
Suitable gas atmosphere is steam or CO2Gas atmosphere;
the activation temperature is controlled to be 550-850 ℃, and the activation time is controlled to be 0.5-5 h.
Eluting Ni, Zn, K and other ions of the sample activated in the step (5) by using 0.1M hydrochloric acid solution, and finally preparing the mesoporous carbon material.
The key technology for preparing the modified activated carbon by the method is the control of the loading process of the modified substance and the activation carbonization process. The specific principle is as follows:
target ions are uniformly attached to cation exchange resin through ion exchange for modification, and then are subjected to pretreatment, carbonization and activation for preparation, so that the basic structure and surface functional groups of the activated carbon are formed in the whole process, and meanwhile, the carbon yield is improved. Thereby preparing the mesoporous activated carbon material with high performance.
Compared with the prior art, the invention has the following advantages and beneficial effects: 1. in the preparation process of the modified activated carbon material adopted by the invention, target ions are attached to the carrier through ion exchange, and then carbonization and activation treatment are carried out, so that the modified activated carbon has high specific surface area and rich pore diameters (mainly mesoporous). 2. The modification method is in-situ growth, the prepared active carbon can fully exert the characteristics of the modified substances and the active carbon, overcomes the defects of activity reduction and loss caused by the fact that the modified substances occupy the original point positions of the active carbon, and has high desalting performance. 3. The method has simple process flow, environmental protection and short production period; in addition, the production raw materials are easy to obtain and low in price, the production cost is low, and the yield is high.
Drawings
FIG. 1(a) is a pore size distribution diagram of mesoporous activated carbon composite carbon material.
FIG. 1(b) is a TG graph showing the carbon yield of the mesoporous activated carbon composite carbon material.
Detailed Description
Detailed description of the inventionthe present invention is further analyzed by reference to the following specific examples.
Example 1
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2Stirring at constant speed, ion exchanging for 2 hr, filtering to obtain resin, drying at 20 deg.C, pretreating at 120 deg.C in air atmosphere for 2 hr, and dryingCarbonizing at 800 deg.C for 2h in nitrogen atmosphere, and treating with CO2Activating treatment is carried out for 2h at 550 ℃ in the atmosphere, acid washing is carried out, and finally the prepared activated carbon is used for desalting experiments. Different molar ratios of Ni (NO)3)2And ZnCl2The effect on desalting performance is shown in table 1.
TABLE 1 Ni (NO) in different molar ratios3)2And ZnCl2Effect on desalting Performance
Example 2
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2The molar ratio is 1:10, the mixture is stirred at a constant speed for ion exchange, after a certain time, the resin is filtered out and put into an environment with the temperature of 20 ℃ for drying, then the resin is pretreated for 2 hours at the temperature of 120 ℃ in the air atmosphere, then the product is carbonized for 2 hours at the temperature of 800 ℃ in the nitrogen atmosphere, and then the product is put into CO2Activating treatment is carried out for 2h at 550 ℃ in the atmosphere, acid washing is carried out, and finally the prepared modified activated carbon is used for desalting experiments. The effect of different ion exchange times on the desalting performance is shown in table 2.
TABLE 2 Effect of different ion exchange times on desalting Performance
Example 3
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2The mol ratio is 1:10, the mixture is stirred at a constant speed, and filtered out after ion exchange for 2 hoursDrying the resin in certain ambient temperature, pretreating the resin at 120 deg.C in air for 2h, carbonizing the product at 800 deg.C in nitrogen atmosphere for 2h, and treating the product with CO2Activating treatment is carried out for 2h at 550 ℃ in the atmosphere, acid washing is carried out, and finally the prepared modified activated carbon is used for desalting experiments. The effect of different drying temperatures on the desalting performance is shown in table 3.
TABLE 3 Effect of different drying temperatures on desalting Performance
Example 4
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2Stirring at constant speed, filtering out resin after 2h of ion exchange, drying the resin in an environment at 20 ℃, pretreating the resin for 2h at a certain temperature in an air atmosphere, carbonizing the product for 2h at 800 ℃ in a nitrogen atmosphere, and then putting the product in CO2Activating treatment is carried out for 2h at 550 ℃ in the atmosphere, acid washing is carried out, and finally the prepared modified activated carbon is used for desalting experiments. The effect of different air pretreatment temperatures on desalination performance is shown in table 4.
TABLE 4 Effect of different air pretreatment temperatures on desalination Performance
Example 5
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2The molar ratio is 1:10, and the mixture is stirred at constant speedStirring, ion exchanging for 2 hr, filtering to obtain resin, drying at 20 deg.C, pretreating at 120 deg.C in air atmosphere for a certain time, carbonizing at 800 deg.C in nitrogen atmosphere for 2 hr, and treating with CO2Activating treatment is carried out for 2h at 550 ℃ in the atmosphere, acid washing is carried out, and finally the prepared modified activated carbon is used for desalting experiments. The effect of different air pretreatment times on the desalination performance is shown in table 5.
TABLE 5 Effect of different air pretreatment times on desalination Performance
Example 6
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2The molar ratio is 1:10, stirring at constant speed, filtering out the resin after 2h of ion exchange, putting the resin into an environment of 20 ℃ for drying, then pretreating the resin at 120 ℃ for 2h in an air atmosphere, then carbonizing the product at 800 ℃ for 2h in a nitrogen atmosphere, and then putting the product in CO2Activating for 2 hours at a certain temperature in the atmosphere, pickling, and finally applying the prepared modified activated carbon to a desalting experiment. The effect of different activation temperatures on desalting performance is shown in table 6.
TABLE 6 Effect of different activation temperatures on desalting Performance
Example 7
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2Stirring at constant speed, filtering out resin after ion exchange for 2h, drying at 20 ℃, pretreating the resin at 120 ℃ for 2h in an air atmosphere, carbonizing the product at 800 ℃ for 2h in a nitrogen atmosphere, and then adding CO to the product2Activating treatment is carried out for a certain time at 550 ℃ in the atmosphere, and the prepared modified activated carbon is used for desalting experiments after acid washing. The effect of different activation times on desalting performance is shown in table 7.
TABLE 7 Effect of different activation times on desalting Performance
Example 8
Taking 10g of cation exchange resin (Mitsubishi chemical WK40L, highly porous polystyrene polymer resin), adding Ni (NO) at room temperature3)2And ZnCl2In the mixed solution of (1 mol/L), Ni (NO)3)2And ZnCl2The molar ratio is 1:10, stirring at a constant speed, filtering out resin after ion exchange for 2h, putting the resin into an environment with the temperature of 20 ℃ for drying, then pretreating the resin for 2h at the temperature of 120 ℃ in an air atmosphere, then carbonizing the product for 2h at the temperature of 800 ℃ in a nitrogen atmosphere, then activating the product for 2h at the temperature of 550 ℃ in a certain atmosphere, pickling, and finally using the prepared modified activated carbon for a desalting experiment. The effect of different activation atmospheres on the desalting performance is shown in table 8.
TABLE 8 Effect of different activation environments on desalting Performance
Fig. 1(a) is a pore size distribution diagram of the metal oxide-activated carbon composite material prepared as described above, and it can be seen from the diagram that the material has a mesoporous structure of 4nm or more. FIG. 1(b) is a TG graph showing the carbon yield of the mesoporous activated carbon composite carbon material.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (7)
1. A process for preparing modified activated carbon material used for capacitance deionizing technique features that the cation exchange resin is used as the precursor of activated carbon and Ni (NO) is used3)3、ZnCl2The modifier is treated in different gas atmospheres, and the following steps are carried out in sequence:
(1) adding cation exchange resin to Ni (NO) at room temperature3)3And ZnCl2Stirring the mixed solution at a constant speed for a period of time to perform ion exchange;
(2) after the exchange is finished, filtering and drying the resin, and then pretreating the resin for a period of time at a certain temperature in an air atmosphere;
(3) carbonizing the product pretreated by air at 800 deg.C in nitrogen atmosphere for 2h, and finally steaming or CO2Carrying out activation treatment at a certain temperature in a gas atmosphere, and cooling to obtain modified activated carbon;
(4) the carbonized product is put in steam or CO2Carrying out activation treatment at a certain temperature in a gas atmosphere, and cooling to obtain modified activated carbon;
(5) eluting Ni, Zn and K ions of the activated sample by using a hydrochloric acid solution, and finally preparing a mesoporous carbon material;
Ni(NO3)3and ZnCl2Ni (NO) in the mixed solution of (2)3)3And ZnCl2The molar ratio of (1) to (0.5-20).
2. The method according to claim 1, wherein the ion exchange time is 5 min-8 h.
3. The method for preparing a modified activated carbon material for capacitive deionization as claimed in claim 1, wherein the drying temperature is controlled to 20-110 ℃ and the drying time is 8 h.
4. The method for preparing the modified activated carbon material for capacitive deionization as claimed in claim 1, wherein the air pre-treatment temperature is controlled to be 120-300 ℃.
5. The method for preparing a modified activated carbon material for capacitive deionization as claimed in claim 1, wherein the air pretreatment time is controlled to be 0.5-4 h.
6. The method for preparing the modified activated carbon material for capacitive deionization as claimed in claim 1, wherein the activation temperature is controlled to be 550-850 ℃.
7. The method for preparing the modified activated carbon material for capacitive deionization as claimed in claim 1, wherein the activation time is controlled to be 0.5-5 h.
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