CN112110445B - Preparation method of lignin-based porous carbon material - Google Patents
Preparation method of lignin-based porous carbon material Download PDFInfo
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Abstract
The invention belongs to the field of carbon material preparation, and particularly relates to a preparation method of a lignin-based porous carbon material. Under the oxidation action of low-concentration hydrogen peroxide, ozone gas blowing and low-temperature carbonization carbon burning processes during low-temperature carbonization are combined, the order and regularity of lignin molecules are increased, the oxidation of unsaturated bonds of lignin is promoted, and then activation of melamine pyrophosphate serving as an activating agent is performed, so that the aims of quickly removing small molecules, reducing the carbon forming time and increasing the yield of a carbon material can be fulfilled during high-temperature cracking, and the performance of the obtained carbon material is more excellent.
Description
Technical Field
The invention belongs to the field of carbon material preparation, and particularly relates to a preparation method of a lignin-based porous carbon material.
Background
Lignin (Lig) is an amorphous polymer formed by connecting three phenylpropane as basic units through ester bonds and carbon-carbon bonds, the carbon chain and the benzene ring of the polymer contain functional groups such as hydroxyl, carboxyl, methoxyl, carbonyl, carbon-carbon double bonds, benzene ring and the like, and the existence of the active functional groups enables the lignin to have various chemical properties and to perform various reactions such as alcoholysis, reduction, oxidation, hydrolysis, acylation, alkylation, polycondensation, copolymerization and the like. At present, the application fields of lignin in China mainly focus on the industrial fields of resin products, concrete preparation, hydrogels, pesticides and the like. As the only polymer containing a benzene ring structure in plant resources, the lignin has the potential of replacing industrial high molecular materials.
The porous carbon material has high specific surface area, high porosity, good electrical conductivity and thermal conductivity, and adjustable pore size and surface performance, and meanwhile, the preparation and application progress of the lignin-based mesoporous carbon material is more and more important in the wide application of the fields of supercapacitors, catalyst carriers, adsorption, drug sustained release and the like.
At present, the publicly reported preparation of the porous carbon material usually adopts a chemical activation method, and KOH, NaOH and ZnCl are selected2、H3PO4The activating agent is mixed with the carbonaceous precursor according to a certain proportion, and the mixture is heated to 600-1000 ℃ for activation, so that the activated carbon material with higher specific surface area and developed pores can be obtained. Although the method has a certain industrial production scale, a plurality of problems which are not ignored exist, such as the introduction of heavy metal, and the serious pollution of the heavy metal to the environment caused by improper subsequent treatment; a large amount of acid and alkali are consumed in the preparation process, and the damage to equipment and environment cannot be avoided. Therefore, the search for a new preparation method has important significance for further meeting the market demand on the porous carbon material.
Disclosure of Invention
The invention aims to provide a preparation method of a lignin-based porous carbon material, which is simple to operate and low in cost, under the oxidation action of low-concentration hydrogen peroxide, combines ozone gas blowing and low-temperature carbonization carbon burning processes during low-temperature carbonization, increases the order and regularity of lignin molecules, promotes the oxidation of unsaturated bonds of lignin, and is activated by an activator melamine pyrophosphate, so that the aims of quickly removing small molecules, reducing the carbon formation time and increasing the yield of a carbon material can be achieved during high-temperature cracking, and the performance of the obtained carbon material is more excellent. The method has the advantages of simple operation, reduced energy consumption, and greatly improved utilization value due to large storage and wide source of the raw material lignin.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a lignin-based porous carbon material comprises the following specific steps:
(1) dissolving lignin in low-concentration strong alkali solution, and adding H2O2Melamine pyrophosphate, magnetic stirring and ultrasound;
the lignin is pure lignin, the strong base is sodium hydroxide, the mass concentration of a sodium hydroxide solution is more than 4% and more than 1%, and the concentration of the lignin in an alkali solution is 1-10%;
H2O2the mass concentration of the lignin in the alkali solution is 0.3-1%, and the mass ratio of the lignin to the melamine pyrophosphate is 1-3: 2-6, magnetically stirring for 6 hours at normal temperature, and carrying out ultrasonic conditions: the ultrasonic intensity is 70% at 25 ℃, and the time is 1-2 h.
(2) Performing spray drying on the solution subjected to the ultrasonic treatment in the step (1), putting the obtained powder into a tubular furnace, blowing air into the tubular furnace by using an odor generator, and carbonizing at low temperature;
the inlet temperature of spray drying is 150 ℃, the outlet temperature is 60-100 ℃, the rotating speed of an atomizer is 25000rpm, and the water evaporation capacity is 5 kg/h.
The ozone blowing time is 0-40 min, the ozone outlet concentration is 12-20 mg/L, and the ozone output is 5 g/h.
And the low-temperature carbonization process adopts nitrogen protection, the constant-temperature low-temperature carbonization temperature range is 150-350 ℃ in the carbonization process, and the carbonization time is 1-4 h.
The ozone blowing is used for promoting the lignin to oxidize unsaturated bonds in lignin molecules during low-temperature carbonization, promoting the removal of small molecules, and enabling the lignin to be carbonized in a ring form at high temperature under the action of hydrogen peroxide and melamine pyrophosphate, so that the yield is increased, and the carbonization time is shortened.
(3) Calcining the powder carbonized in the step (2) at high temperature in an inert gas atmosphere to obtain a carbon block, pickling and washing the carbon block, and crushing the carbon block by using an ultramicro wet crusher; and finally, drying for 12 hours in vacuum to obtain the final product carbon material.
The temperature rise rate in the carbonization treatment process is 5-10 ℃/min, the high-temperature carbonization temperature range is 650-950 ℃, and the time is 30-120 min.
The post-treatment sequence of the carbon block comprises grinding, acid washing and water washing, the carbon block is crushed by an ultramicro wet crusher and is dried in vacuum for 12 hours to obtain the porous carbon material.
Wherein, the porous carbon material is washed for 1 to 3 times by using a hydrochloric acid solution with the mass fraction of 10 to 30 percent, and washed for 3 to 5 times by using distilled water
The invention has the following beneficial effects:
1. according to the invention, lignin is used as a carbon material precursor, hydrogen peroxide is used as a carbon promoting agent, melamine pyrophosphate is used as a carbon forming agent, ozone blowing gas is used for low-temperature carbonization in a tubular furnace, and inert gas is used for protecting high-temperature calcination to prepare the porous carbon material, so that a complex activation process is avoided, carbonization and activation are carried out simultaneously, and compared with the existing preparation method of firstly carbonizing and then activating, the method effectively reduces the carbon preparation cost and avoids environmental pollution.
2. The ozone blowing of the invention aims to promote the unsaturated bond oxidation of lignin during low-temperature carbonization, promote the removal of small molecules, and enable the lignin to be carbonized in a ring form at high temperature under the action of hydrogen peroxide and melamine pyrophosphate, thereby increasing the yield and reducing the carbonization time.
3. The method takes the lignin as the raw material to prepare the porous carbon material, has simple preparation process, technically uses a spray drying method and an ultramicro wet type crushing method, technically helps to improve the yield, and simultaneously effectively improves the utilization value of the lignin.
Drawings
FIG. 1 is a Raman plot of carbon materials prepared under different ozone low temperature carbonization conditions.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto. The lignin used in the embodiments 1 to 6 is pure lignin, and a lignin alkali solution is prepared by a conventional method.
Example 1
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent and AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then carrying out spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace by using an odor generator for 40 minutes (with the ozone content of about 3.33g), carbonizing at the low temperature of 190 ℃ for 2 hours, and heating to calcine at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 17% and a high-temperature carbonization time of 55 min.
Example 2
Preparing 100mL of alkali solution by adding water into 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (the concentration is 30 percent, AR), adding 6g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (the outlet temperature is 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (the ozone content is about 3.33g) by using an odor generator, carbonizing at the low temperature of 190 ℃ for 2 hours, heating and calcining at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 26.8% and a high-temperature carbonization time of 20 min.
Example 3
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent, AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 20 minutes (with the ozone content of about 3.33g) by using an odor generator, carbonizing at the low temperature of 190 ℃ for 2 hours, and heating to calcine at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 10% and a high-temperature carbonization time of 60 min.
Example 4
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent and AR) into water, adding 2g of melamine pyrophosphate into the alkali solution, placing the alkali solution into a three-neck flask, magnetically stirring the alkali solution for 6 hours, ultrasonically dispersing the alkali solution for 1 hour, performing spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (with the ozone content of about 3.33g) by using an odor generator, carbonizing the powder at the low temperature of 350 ℃ for 2 hours, and heating the powder to be calcined at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 10.8% and a high-temperature carbonization time of 30 min.
Example 5
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent and AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then carrying out spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (with the ozone content of about 3.33g) by using an odor generator, carbonizing at the low temperature of 190 ℃ for 2 hours, and heating to calcine at the high temperature in a nitrogen atmosphere at the temperature of 750 ℃. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 11.5% and a high-temperature carbonization time of 40 min.
Example 6
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 3g of hydrogen peroxide (the concentration is 30 percent, AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (the outlet temperature is 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (the ozone content is about 3.33g) by using an odor generator, carbonizing at the low temperature of 190 ℃ for 2 hours, heating and calcining at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 9.4% and a high-temperature carbonization time of 50 min.
Example 7
1g of sodium hydroxide, 1g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent and AR) are added with water to prepare 100mL of alkaline solution, 3g of melamine pyrophosphate is added, the solution is placed in a three-neck flask for magnetic stirring for 6 hours, ultrasonic dispersion is carried out for 1 hour, spray drying is carried out (the outlet temperature is 100 ℃), the obtained powder is placed in a tube furnace, an odor generator is used for blowing air into the tube furnace for 40min (the ozone content is about 3.33g), the powder is carbonized at the low temperature of 260 ℃ for 2 hours, and the temperature is raised and the high-temperature calcination is carried out in the nitrogen atmosphere at the temperature of 950 ℃. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 19.6% and a high-temperature carbonization time of 35 min.
Example 8
Preparing 100mL of alkali solution by adding water into 4g of sodium hydroxide, 10g of lignin and 1g of hydrogen peroxide (the concentration is 30 percent, AR), adding 15g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (the outlet temperature is 60 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (the ozone content is about 3.33g) by using an odor generator, carbonizing at the low temperature of 150 ℃ for 4 hours, heating and calcining at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 16.3% and a high-temperature carbonization time of 25 min.
Comparative example 1 (one-step carbonization)
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent and AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then carrying out spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (with the ozone content of about 3.33g) by using an odor generator in the temperature rising process, and directly carbonizing at high temperature in one step, wherein the carbonization temperature is 850 ℃. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 9% and a high-temperature carbonization time of 120 min.
Comparative example 2 (No ozone)
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent, AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, carbonizing at 190 ℃ for 2 hours under the nitrogen atmosphere, and heating to calcine at 850 ℃ under the nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 13.5% and a high-temperature carbonization time of 70 min.
Comparative example 3 (alkali activation)
Adding 9g of potassium hydroxide alkali activator into 3g of lignin, adding 100mL of distilled water to prepare a lignin solution, adding 1g of hydrogen peroxide (with the concentration of 30 percent and AR), placing the lignin solution into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, then performing spray drying (with the outlet temperature of 100 ℃), placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (with the ozone content of about 3.33g) by using an odor generator, carbonizing at the low temperature of 190 ℃ for 2 hours, and heating to perform high-temperature calcination in a nitrogen atmosphere at the temperature of 850 ℃. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 7% and a high-temperature carbonization time of 65 min.
Comparative example 4 (vacuum drying)
Preparing 100mL of alkali solution by adding 3g of sodium hydroxide, 3g of lignin and 1g of hydrogen peroxide (with the concentration of 30 percent, AR) into water, adding 2g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6 hours, ultrasonically dispersing for 1 hour, drying for 12 hours at 100 ℃ in a vacuum oven, placing the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40 minutes (with the ozone content of about 3.33g) by using an odor generator, carbonizing for 2 hours at the low temperature of 190 ℃, heating and calcining at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 15.7% and a high-temperature carbonization time of 60 min.
Comparative example 5 (non-dioxygen water)
Taking 3g of sodium hydroxide and 3g of lignin, adding water to prepare 100mL of alkali solution, adding 2g of melamine pyrophosphate, putting the solution into a three-neck flask, magnetically stirring the solution for 6h, ultrasonically dispersing the solution for 1h, then carrying out spray drying (outlet temperature is 100 ℃), putting the obtained powder into a tubular furnace, blowing air into the tubular furnace for 40min (ozone content is about 3.33g) by using an odor generator, carbonizing the powder at the low temperature of 190 ℃ for 2h, heating the powder and calcining the powder at the high temperature of 850 ℃ in a nitrogen atmosphere. And (3) pickling and washing the obtained carbon block with water, crushing the carbon block by using an ultramicro wet crusher, and finally drying the carbon block for 12 hours in vacuum to obtain a final product carbon material. The carbon material obtained in this example had a yield of 13.6% and a high-temperature carbonization time of 55 min.
The performance test method comprises the following steps: adopting BELSORP-max specific surface area and pore analyzer, and using high purity N at 77K2For adsorbates, the specific surface area and pore volume of the sample were determined. The samples were all at 200 c prior to testing,<degassing pretreatment for more than 2h under the condition of 4 mmHg. Preparing methyl violet solution at room temperature, 20mg/L, and testing the adsorption performance of the carbon material. The specific capacitance of the carbon material was measured with the Shanghai Chenghua electrochemical workstation 660 e.
Table 1 shows the BET specific surface area, the adsorption performance for methyl violet, the pore volume, and the specific capacitance of the obtained lignin-based carbon material.
TABLE 1
Table 2 shows X-ray spectroscopy data of lignin-based carbon materials obtained in optimal formulation example 2
TABLE 2
| Element name | C | O | N | P |
| Content of element (%) | 96.8 | 2.3 | 0.6 | 0.3 |
As can be seen from Table 1, the carbon material obtained in example 2 with a 2:3 ratio of melamine pyrophosphate to lignin exhibited the best adsorption performance: 284.5mg of methyl violet can be adsorbed to 1g of the carbon material. The specific surface area is the largest and is as high as 1389m2G, pore volume 2.73cm3The specific capacitance is up to 991 mAh/g. The obtained carbon material has the maximum yield and the shortest carbonization time.
Table 2 shows the X-electron spectroscopy data of the lignin-based carbon material of example 2, which shows that the obtained activated carbon contains a small amount of N and P elements, wherein the content of N is slightly higher than that of O element, and the main component is C, which is as high as 96.8%.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (1)
1. The preparation method of the lignin-based porous carbon material is characterized by comprising the following steps: preparing 100mL of aqueous alkali by taking 3g of sodium hydroxide, 3g of lignin and 1g of 30% hydrogen peroxide and adding water, adding 6g of melamine pyrophosphate, placing the mixture into a three-neck flask, magnetically stirring for 6h, ultrasonically dispersing for 1h, then carrying out spray drying, placing the obtained powder into a tubular furnace at the outlet temperature of 100 ℃, blowing air into the tubular furnace for 40min by using an odor generator, wherein the ozone content is about 3.33g, carbonizing at the low temperature of 190 ℃ for 2h, heating the mixture to be calcined at the high temperature of 850 ℃ in a nitrogen atmosphere, carrying out high-temperature carbonization for 20min, pickling and washing the obtained carbon block, crushing the carbon block by using an ultramicro wet crusher, and finally carrying out vacuum drying for 12h to obtain the final product carbon material.
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