CN111533125A - Preparation method of nitrogen-doped hierarchical pore carbon material - Google Patents

Preparation method of nitrogen-doped hierarchical pore carbon material Download PDF

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CN111533125A
CN111533125A CN202010426509.8A CN202010426509A CN111533125A CN 111533125 A CN111533125 A CN 111533125A CN 202010426509 A CN202010426509 A CN 202010426509A CN 111533125 A CN111533125 A CN 111533125A
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nitrogen
carbon material
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solid waste
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闫秀玲
武晋雄
吴雨鑫
安瑜
刘天宝
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Ili Normal University
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    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B32/342—Preparation characterised by non-gaseous activating agents
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract

The invention discloses a preparation method of a nitrogen-doped hierarchical pore carbon material, which comprises the following steps of (1) carrying out acid washing treatment on organic solid waste and then drying the organic solid waste for later use; (2) fully mixing the organic solid waste obtained in the step (1), an activating agent and a nitrogen source according to the mass ratio of 1 (1-3) to (1-3), and grinding and drying after mixing; (3) transferring the product obtained in the step (2) into a porcelain boat, and placing the porcelain boat in a tube furnace for heat preservation treatment; (4) and (4) carrying out acid washing treatment on the product obtained in the step (3) again, and drying the product until the weight is constant to obtain the nitrogen-doped hierarchical porous carbon material. The method realizes the preparation of the graded porous carbon material by the organic solid waste, has the advantages of simple method, low cost and easy operation, changes waste residues into valuables, and has high economic benefit and remarkable social benefit; the carbon material prepared by the method not only increases the porosity and the specific surface area of the material, but also increases the active adsorption sites, can effectively remove pollutants in environmental wastewater, and realizes resource utilization.

Description

Preparation method of nitrogen-doped hierarchical pore carbon material
Technical Field
The invention relates to the field of resource utilization of organic solid wastes, in particular to a preparation method of a nitrogen-doped hierarchical porous carbon material and application of the nitrogen-doped hierarchical porous carbon material.
Background
With the acceleration of the industrialization process, various organic solid wastes such as: the accumulation of plant straws, lavender residues, municipal sludge and the like is also getting bigger and bigger. Not only occupies land resources, but also pollutes the environment, and the waste gas generated by long-term accumulation fermentation is diffused in the air to seriously affect the life of people. The traditional treatment methods mainly comprise an incineration method, a landfill method, a digestion treatment method and the like. When the temperature is raised to 1000 ℃, the conversion of nitrogen oxides in the material is also greatly improved, and the smoke contains chlorine-containing substances such as dioxin, hydrochloric acid and the like, which are converted into carcinogenic substances to threaten human health, so that the incineration method is widely prohibited. The organic solid waste is directly buried without being treated, the degradation is slow, and the heavy metal is leached out to pollute the soil. In order to reduce pollution, the Chinese patent application No. CN201911186775.1 discloses a sludge anaerobic digestion method and application thereof, relating to the technical field of sludge treatment. The anaerobic digestion method of the sludge comprises anaerobic digestion of the sludge with the water content of 88-92 wt% at the temperature of 39-42 ℃. The anaerobic digestion method of the sludge can improve the degradation rate of organic matters and improve the yield of the biogas. However, the period is long, and the digestion reaction is not easily caused by overhigh or overlow temperature, so the implementation difficulty is high. The content of organic matters remained in the solid can reach 70 percent, and if the organic matters are not properly treated, the environment is polluted, and resources are wasted.
The carbon material is an ideal environment-friendly adsorbent, and has high adsorption efficiency and easy recovery. Chinese patent application No. 201911302933.5 discloses a nitrogen-oxygen co-doped porous carbon material and a preparation method thereof, wherein oxygen-containing organic molecules and nitrogen-containing organic molecules are subjected to high-temperature roasting under the action of a nano oxide template agent to obtain the nitrogen-oxygen co-doped porous carbon material. The particle size of the prepared nitrogen-oxygen co-doped porous carbon material is 0.5-30 mu m, the mesoporous size is 20-500nm, the nitrogen-oxygen doping amount is 5-25%, the removal rate of rose bengal, nickel ions and suspended impurities can reach 99%, but dangerous chemicals are required to be used for removing the nano oxide template agent, and the preparation cost is increased. According to the invention, the organic solid waste is used as a raw material, and is converted into the nitrogen-doped hierarchical porous carbon material by adding a nitrogen source alkali activation mode, so that the porosity and the specific surface area of the material are increased, the active adsorption sites are increased, and the organic solid waste is comprehensively and comprehensively utilized as a waste water adsorbent, so that the aim of changing waste into valuable is fulfilled.
Disclosure of Invention
The invention aims to provide a high-efficiency preparation method of a nitrogen-doped hierarchical pore carbon material aiming at the difficulty in organic solid waste treatment. According to the invention, the organic solid waste is converted into the nitrogen-doped hierarchical porous carbon material in a nitrogen source alkali activation mode, so that the porosity and the specific surface area of the material are increased, nitrogen doping is performed to a certain degree, active adsorption sites are increased, and the organic solid waste is comprehensively and comprehensively utilized as a wastewater adsorbent, so that the aim of changing waste into valuable is fulfilled. High operability, can realize large-scale continuous industrial production and solve the existing environmental problems.
In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a nitrogen-doped hierarchical pore carbon material comprises the following steps:
(1) carrying out acid pickling treatment on the organic solid waste, and then drying the organic solid waste;
(2) fully mixing the organic solid waste obtained in the step (1), an activating agent and a nitrogen source according to the mass ratio of 1 (1-3) to 1-3, and grinding and drying after mixing;
(3) transferring the product obtained in the step (2) into a porcelain boat, and placing the porcelain boat in a tube furnace for heat preservation treatment;
(4) and (4) carrying out acid washing treatment on the product obtained in the step (3) again, and drying the product until the weight is constant to obtain the nitrogen-doped hierarchical porous carbon material.
Preferably, the organic solid waste is one or a combination of two of lavender residue and straw.
Preferably, the activating agent comprises one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate, and the nitrogen source comprises one or more of urea, melamine, dicyandiamide, oleylamine, oleic acid and pyrrolidone.
Preferably, the step (1) of acid washing treatment is to wash and remove silicate by using acid washing solution, and the step (4) of acid washing treatment is to wash and remove alkaline substances by using acid washing solution; and washing the washed product to be neutral by using ionized water.
Preferably, the acid washing solution comprises one or more of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, and the pH value of the acid washing solution is 1-2.
Preferably, the grinding treatment is to grind the mixture for 0.5 to 1 hour, and the drying treatment is to keep the temperature in an oven at 80 to 120 ℃ for 1 to 5 hours.
Preferably, the heat preservation treatment is to place the dried product in a tubular furnace for heat preservation at 500-1000 ℃ for 2-4 h.
Preferably, the tube furnace is filled with inert gas, and the inert gas comprises one of nitrogen and argon.
Preferably, the drying treatment is drying in a vacuum drying oven at 80-200 ℃.
Preferably, the application is a solid adsorbent for wastewater, and the wastewater contains one or more of heavy metal ions and organic dyes.
Compared with the prior art, the invention has the beneficial effects that:
1. the method realizes the preparation of the graded porous carbon material by the organic solid waste, has the advantages of simple method, low cost and easy operation, changes waste residues into valuables, and has high economic benefit and remarkable social benefit;
2. the carbon material prepared by the method not only increases the porosity and the specific surface area of the material, but also increases the active adsorption sites, can effectively remove pollutants in environmental wastewater, and realizes resource utilization.
Drawings
FIG. 1 is a schematic view of a process for preparing a nitrogen-doped hierarchical porous carbon material;
FIG. 2 is an XPS survey of a nitrogen-doped nanoporous carbon material produced in example 7;
FIG. 3 is an XPS N1 s spectrum of a nitrogen-doped multi-level pore carbon material prepared in example 7;
FIG. 4 is a BET specific surface area graph of a nitrogen-doped hierarchical porous carbon material produced in example 7;
FIG. 5 is a BJH pore size distribution diagram of a nitrogen-doped multi-level pore carbon material produced in example 7;
FIG. 6 is a graph of the adsorption capacity and distribution coefficient of the nitrogen-doped hierarchical porous carbon material prepared by the method for adsorbing Cr (VI) at different pH values;
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited by the specific examples, which are defined by the claims. In addition, any modification or change that can be easily made by a person having ordinary skill in the art without departing from the technical solution of the present invention will fall within the scope of the claims of the present invention.
As shown in fig. 1, a method for preparing a nitrogen-doped hierarchical porous carbon material comprises the following steps:
(1) carrying out acid pickling treatment on the organic solid waste, and then drying the organic solid waste;
(2) fully mixing the organic solid waste obtained in the step (1), an activating agent and a nitrogen source according to the mass ratio of 1 (1-3) to 1-3, and grinding and drying after mixing;
(3) transferring the product obtained in the step (2) into a porcelain boat, and placing the porcelain boat in a tube furnace for heat preservation treatment;
(4) and (4) carrying out acid washing treatment on the product obtained in the step (3) again, and drying the product until the weight is constant to obtain the nitrogen-doped hierarchical porous carbon material.
Preferably, the organic solid waste is one or a combination of two of lavender residue and straw.
Preferably, the activating agent comprises one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate, and the nitrogen source comprises one or more of urea, melamine, dicyandiamide, oleylamine, oleic acid and pyrrolidone.
Preferably, the step (1) of acid washing treatment is to wash and remove silicate by using acid washing solution, and the step (4) of acid washing treatment is to wash and remove alkaline substances by using acid washing solution; and washing the washed product to be neutral by using ionized water.
Preferably, the acid washing solution comprises one or more of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, and the pH value of the acid washing solution is 1-2.
Preferably, the grinding treatment is to grind the mixture for 0.5 to 1 hour, and the drying treatment is to keep the temperature in an oven at 80 to 120 ℃ for 1 to 5 hours.
Preferably, the heat preservation treatment is to place the dried product in a tubular furnace for heat preservation at 500-1000 ℃ for 2-4 h.
Preferably, the tube furnace is filled with inert gas, and the inert gas comprises one of nitrogen and argon.
Preferably, the drying treatment is drying in a vacuum drying oven at 80-200 ℃.
Preferably, the application is a solid adsorbent for wastewater, and the wastewater contains one or more of heavy metal ions and organic dyes.
Example 1
(1) Weighing 100g of lavender residues, washing the lavender residues for several times by using nitric acid, washing the lavender residues to be neutral by using deionized water, and drying the lavender residues for later use;
(2) mixing the lavender residue with potassium hydroxide and urea according to the weight ratio of 1:1:1, and fully grinding for 0.5 h; keeping the obtained solid mixture at 100 ℃ in an oven for 5 h;
(3) transferring the solid obtained in the step (3) into a porcelain boat, placing the porcelain boat in a tubular furnace filled with nitrogen, slowly heating to the target temperature of 800 ℃, and preserving heat for 3 hours;
(4) and (4) washing the product obtained in the step (3) with nitric acid again, washing the product with deionized water to be neutral, and drying the product in a vacuum drying oven at the temperature of 80 ℃ to be constant in weight to obtain the nitrogen-doped hierarchical porous carbon material.
Example 2
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:1:2, and fully grinding for 0.5 h; the other conditions were the same as in example 1.
Example 3
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:1:3, and fully grinding for 0.5 h; the rest of the procedure was the same as in example 1.
Example 4
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:2:1, and fully grinding for 0.5 h; the rest of the procedure was the same as in example 1.
Example 5
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:2:2, and fully grinding for 0.5 h; the rest of the procedure was the same as in example 1.
Example 6
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:2:3, and fully grinding for 0.5 h; the rest of the procedure was the same as in example 1.
Example 7
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:3:2, and fully grinding for 0.5 h; the rest of the procedure was the same as in example 1.
Example 8
The procedure of example 1 was repeated except that the lavender residue was mixed with potassium hydroxide and urea at a weight ratio of 1:3:3, and sufficiently ground for 0.5 h.
Example 9
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:3:2, and fully grinding for 0.5 h; the temperature was slowly raised to the target temperature of 500 ℃ and the rest was the same as in example 1.
Example 10
Mixing the lavender residue, potassium hydroxide and urea according to the weight ratio of 1:3:2, and fully grinding for 0.5 h; the temperature was slowly raised to the target temperature of 1000 ℃ and the rest was the same as in example 1.
The yields of the porous biochar prepared through the above examples 1-8 were calculated as follows:
Figure BDA0002498862240000071
in summary, in examples 1 to 10, the nitrogen-doped hierarchical pore carbon material is prepared by performing heat preservation treatment on the lavender residues, the potassium hydroxide and the urea at different weight ratios and different temperatures, and the yield is the highest when the weight ratio of the lavender residues, the potassium hydroxide and the urea is 1:3:2 and the heat preservation treatment temperature is 800 ℃; weighing, and processing the organic solid waste by the steps to obtain 20g of the nitrogen-doped hierarchical porous carbon material, wherein the yield reaches 37.3% (the yield is obtained by calculating the mass ratio of the nitrogen-doped hierarchical porous carbon material to the dried organic solid waste after acid washing); as shown in FIGS. 2 and 3, C, N, O elements in the carbon material are uniformly distributed on the surface of the carbon material, the N content is as high as 7.29 at%, as shown in FIGS. 4 and 5, the specific surface area can reach 2071.59cm2/g, and the calculated pore diameter of BJH is about 25.40nm, so the carbon material is an ideal adsorbing material. The invention changes the organic solid waste into valuable and solves the problems of difficult accumulation and treatment of the organic solid waste and environmental pollution.
The weight ratio of the organic solid waste residue, the activating agent and the nitrogen source is 1: (1-3): (1-3), the temperature of high-temperature activation is within the range of 500-1000 ℃, and the roasting time is within the range of 2-4 h.
Example 11
The prepared hierarchical porous carbon material was subjected to the hexavalent chromium adsorption test according to the method of example 7, specifically including the steps of adding 0.005g of the prepared charcoal adsorbent to 30mL of 50mg/L hexavalent chromium solution, which had pH values of 2, 4, 6, 8, 10, and 12, respectively. The absorbance of the multi-stage porous carbon material is tested at 540nm by using a diphenylcarbonyldihydrazide spectrophotometric method, and the measurement result is shown in fig. 6, when the pH value of the multi-stage porous carbon material is 2, the adsorption capacity is maximum, the solution can fade in a short time, the adsorption balance is achieved, the distribution coefficient is larger than 104, therefore, a very strong adsorption acting force exists, the adsorption is easy to carry out, the maximum adsorption capacity can reach 276.2mg/g, and the removal rate can reach 92.9%.

Claims (10)

1. The preparation method of the nitrogen-doped hierarchical pore carbon material is characterized by comprising the following steps of:
(1) carrying out acid pickling treatment on the organic solid waste, and then drying the organic solid waste;
(2) fully mixing the organic solid waste obtained in the step (1), an activating agent and a nitrogen source according to the mass ratio of 1 (1-3) to 1-3, and grinding and drying after mixing;
(3) transferring the product obtained in the step (2) into a porcelain boat, and placing the porcelain boat in a tube furnace for heat preservation treatment;
(4) and (4) carrying out acid washing treatment on the product obtained in the step (3) again, and drying the product until the weight is constant to obtain the nitrogen-doped hierarchical porous carbon material.
2. The method for preparing the nitrogen-doped hierarchical porous carbon material according to claim 1, wherein the organic solid waste is one or a combination of two of lavender residues and straws.
3. The method for preparing the nitrogen-doped hierarchical pore carbon material according to claim 1, wherein the activating agent comprises one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate, and the nitrogen source comprises one or more of urea, melamine, dicyandiamide, oleylamine, oleic acid and pyrrolidone.
4. The method for preparing nitrogen-doped hierarchical pore carbon material according to claim 1, wherein the step (1) of acid washing treatment is to wash and remove silicate by using acid washing solution, and the step (4) of acid washing treatment is to wash and remove alkaline substance by using acid washing solution; and washing the washed product to be neutral by using ionized water.
5. The method as claimed in claim 4, wherein the acid washing solution comprises one or more of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, and has a pH of 1-2.
6. The method for preparing the nitrogen-doped hierarchical porous carbon material according to claim 1, wherein the grinding treatment is to grind the mixture for 0.5-1h, and the drying treatment is to keep the temperature in an oven at 80-120 ℃ for 1-5 h.
7. The method as claimed in claim 1, wherein the heat-preservation treatment is to place the dried product in a tubular furnace at 500-1000 ℃ for 2-4 h.
8. The method as claimed in claim 7, wherein the tube furnace is filled with an inert gas, and the inert gas includes one of nitrogen and argon.
9. The method for preparing nitrogen-doped hierarchical porous carbon material according to claim 1, wherein the drying treatment is drying in a vacuum drying oven at 80-200 ℃.
10. Use of a nitrogen-doped hierarchical pore carbon material prepared according to any one of claims 1 to 9 as a solid adsorbent for wastewater containing one or more of heavy metal ions, organic dyes.
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN112062128A (en) * 2020-09-10 2020-12-11 中国矿业大学 Preparation method and application of nitrogen-doped porous carbon material based on crop straws
CN112138699A (en) * 2020-09-25 2020-12-29 拉萨波玛拉生物科技有限公司 Preparation method of N-rich hydrothermal carbon material
CN113184845A (en) * 2021-06-01 2021-07-30 浙江红狮环保股份有限公司 Method for co-processing organic nitrogen-containing compound in cement kiln
CN114395410A (en) * 2022-01-20 2022-04-26 中国科学院大学 Preparation method of biochar with high adsorption capacity, biochar and application
CN115445574A (en) * 2022-10-11 2022-12-09 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water
CN115520864A (en) * 2022-09-28 2022-12-27 山西大学 Preparation method of sulfur-nitrogen in-situ doped porous carbon material
CN116102167A (en) * 2023-01-16 2023-05-12 浙江科技学院 Preparation method, product and application of bimetal magnetic modified nitrogen-enriched sewage peat
CN116768207A (en) * 2023-08-03 2023-09-19 广东省科学院生物与医学工程研究所 Preparation method and application of duck feather biochar with nitrogen-doped hierarchical graphene structure

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CN111017927A (en) * 2020-01-08 2020-04-17 浙江大学 Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112062128A (en) * 2020-09-10 2020-12-11 中国矿业大学 Preparation method and application of nitrogen-doped porous carbon material based on crop straws
CN112138699A (en) * 2020-09-25 2020-12-29 拉萨波玛拉生物科技有限公司 Preparation method of N-rich hydrothermal carbon material
CN113184845A (en) * 2021-06-01 2021-07-30 浙江红狮环保股份有限公司 Method for co-processing organic nitrogen-containing compound in cement kiln
CN113184845B (en) * 2021-06-01 2022-08-12 浙江红狮环保股份有限公司 Method for co-processing organic nitrogen-containing compound in cement kiln
CN114395410A (en) * 2022-01-20 2022-04-26 中国科学院大学 Preparation method of biochar with high adsorption capacity, biochar and application
CN115520864A (en) * 2022-09-28 2022-12-27 山西大学 Preparation method of sulfur-nitrogen in-situ doped porous carbon material
CN115445574A (en) * 2022-10-11 2022-12-09 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water
CN115445574B (en) * 2022-10-11 2024-01-16 中国科学院东北地理与农业生态研究所 Preparation method of N, S co-doped hydrothermal carbon and application thereof in removing Cr (VI) in water
CN116102167A (en) * 2023-01-16 2023-05-12 浙江科技学院 Preparation method, product and application of bimetal magnetic modified nitrogen-enriched sewage peat
CN116768207A (en) * 2023-08-03 2023-09-19 广东省科学院生物与医学工程研究所 Preparation method and application of duck feather biochar with nitrogen-doped hierarchical graphene structure

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Application publication date: 20200814

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