CN110615437A - Comprehensive utilization method of lignite - Google Patents
Comprehensive utilization method of lignite Download PDFInfo
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Abstract
The invention discloses a method for comprehensively utilizing lignite, which comprises the steps of crushing lignite into powder, cleaning and drying; extracting humic acid in lignite by using KOH and urea as a composite extracting agent; then, through chemical activation, KOH activates and remoldes the pore channels of the extraction residues, and simultaneously uses urea as a nitrogen source to carry out nitrogen doping modification on the porous carbon to prepare the N-doped porous carbon composite lithium battery cathode material; in addition, neutralizing the waste liquid in the extraction and preparation processes to prepare a nitrogen, phosphorus and potassium compound fertilizer; the invention creates a new green process method for comprehensive utilization of lignite, and the humic acid and N-doped porous carbon composite lithium battery cathode material can be prepared by the process method; in addition, waste liquid generated in the whole process is prepared into a nitrogen, phosphorus and potassium compound fertilizer; thereby realizing the conversion of the lignite into high-quality products to the maximum extent and basically realizing zero emission.
Description
Technical Field
The invention relates to the field of lignite processing and utilization, in particular to a comprehensive lignite utilization method.
Background
Lignite resources in China are rich, and reserves account for more than 55% of the total reserves of coal; the storage amount of lignite in the inner Mongolia autonomous region is the largest, and accounts for 77% of the national lignite resource amount; wherein, the content of total humic acid in the inner Mongolia red peak lignite is 31.6 percent, the content of free humic acid is 24.9 percent, the content of ash is 14.53 percent, and the content of water is 27.8 percent; humic acid is mainly an organic high molecular polymer formed and accumulated by animal and plant remains through microbial decomposition, transformation and a series of geophysical and chemical reactions, and widely exists in carbonaceous sedimentary rocks such as water, soil, peat, lignite, weathered coal, shale and the like; the humic acid structure contains rich active oxygen-containing functional groups such as carboxyl, phenolic hydroxyl, carbonyl, sulfonic group, methoxy group and the like, and has important influence on the acidity, ion exchange property, colloid property and complexing property; the method is widely applied to various fields of agriculture, forestry, pasture, petroleum, chemical industry, building materials, medicine, health, environmental protection and the like; particularly, ecological agricultural construction, pollution-free agricultural production, green food, pollution-free and environment-friendly properties and the like are advocated at present, and the humic acid is more advocated; lignite contains rich humic acid and is a main resource for utilizing the humic acid on a large scale; compared with soil humic acid, the lignite humic acid has higher carbon content, lower nitrogen content and higher hydrogen content, and shows that the chemical activity and the substitution performance are better; researchers at home and abroad extract humic acid in lignite by using an alkali solution acid precipitation method, an acid extraction agent method, a microorganism dissolution method and the like, and the extraction rate of the humic acid reaches more than 80 percent; at least more than 25% of organic matters in the residue after the humic acid is extracted are not fully utilized; if the organic matters are carbonized and activated to prepare the N-doped porous carbon composite lithium battery cathode material, the method has great significance for realizing the clean, efficient and high-added-value utilization of the lignite; at present, the prior art has not been researched and reported in this respect.
Therefore, the comprehensive utilization clean production process capable of converting the lignite into high-quality products to the maximum extent is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a method for comprehensively utilizing lignite, which comprises the steps of crushing lignite into powder, cleaning and drying the powder; extracting humic acid in lignite by using KOH and urea as a composite extracting agent; then, through chemical activation, KOH activates and remoldes the pore channels of the extraction residues, and simultaneously uses urea as a nitrogen source to carry out nitrogen doping modification on the porous carbon to prepare the N-doped porous carbon composite lithium battery cathode material; in addition, the waste liquid in the extraction and preparation processes is neutralized and processed to prepare the nitrogen, phosphorus and potassium compound fertilizer, and the lignite is converted into high-quality products to the maximum extent by the method.
The technical scheme adopted by the invention is as follows: a method for comprehensively utilizing lignite comprises the following steps:
s1: preparing a lignite raw material: pulverizing lignite into powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the processing of the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 0.5-1: 2.5; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 5-1: 30; the mass fraction of the KOH solution is 0.5 to 4.5 percent; then, cooking the prepared solid-liquid mixture for 70-100 min at the temperature of 70-100 ℃; cooling, stirring with a magnetic stirrer for reaction, and centrifuging with a centrifuge to separate residue and extractive solution;
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating at the temperature of 410-720 ℃ for 0.4-2.2 h to obtain a carbonized and activated product;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a dilute acid solution, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
in the step S3.2, the dilute acid solution for soaking the carbonized and activated product is a nitric acid solution or a phosphoric acid solution, and the concentration is 0.2-3.0 mol/L;
s4: preparing humic acid:
carrying out acid precipitation on the extracting solution obtained in the step S2 by using a dilute acid solution to ensure that the pH value of the solution is less than 4, and filtering the obtained precipitate to obtain humic acid after vacuum drying;
the diluted acid solution used in the acid precipitation process in the step S4 is a phosphoric acid solution or a nitric acid solution, and the concentration is 0.3-2.5 mol/L.
Further, the brown coal used in step S1 of the present invention is brown coal in the red peak area of inner mongolian city.
In a preferred embodiment, the dilute acid solution used for immersing the carbonized activation product in step S3.2 of the present invention is a nitric acid solution, and the dilute acid solution used in the acid precipitation process in step S4 is a phosphoric acid solution; then the waste liquid generated in the steps S2, S3 and S4 is collected together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
In another preferred embodiment, the diluted acid solution used for immersing the carbonization activation product in step S3.2 of the invention is phosphoric acid solution, and the diluted acid solution used in the acidification process in step S4 is nitric acid solution; then the waste liquid generated in the steps S2, S3 and S4 is collected together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
The invention has the beneficial effects that: the invention provides a method for comprehensively utilizing lignite, which comprises the steps of crushing lignite into powder, cleaning and drying; extracting humic acid in lignite by using KOH and urea as a composite extracting agent; then, through chemical activation, KOH activates and remoldes the pore channels of the extraction residues, and simultaneously uses urea as a nitrogen source to carry out nitrogen doping modification on the porous carbon to prepare the N-doped porous carbon composite lithium battery cathode material; in addition, the waste liquid in the extraction and preparation processes is neutralized and processed to prepare the nitrogen, phosphorus and potassium compound fertilizer.
The invention creates a new green process method for comprehensive utilization of lignite, and the humic acid and N-doped porous carbon composite lithium battery cathode material can be prepared by the process method; in addition, waste liquid generated in the whole process is prepared into a nitrogen, phosphorus and potassium compound fertilizer; thereby realizing the conversion of the lignite into high-quality products to the maximum extent and basically realizing zero emission.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Fig. 2 is an SEM image of the negative electrode material of the N-doped porous carbon composite lithium battery prepared by the method of embodiment 1 of the present invention.
Fig. 3 is a cycle performance diagram of the negative electrode material of the N-doped porous carbon composite lithium battery prepared by the method in embodiment 1 of the invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and examples, which are set forth below for illustrating the technical solutions of the present invention only and are not limited thereto.
As shown in fig. 1, a method for comprehensively utilizing lignite, which comprises the steps of crushing lignite into powder, cleaning and drying the powder; extracting humic acid in lignite by using KOH and urea as a composite extracting agent; then, through chemical activation, KOH activates and remoldes the pore channels of the extraction residues, and simultaneously uses urea as a nitrogen source to carry out nitrogen doping modification on the porous carbon to prepare the N-doped porous carbon composite lithium battery cathode material; in addition, the waste liquid in the extraction and preparation processes is neutralized and processed to prepare the nitrogen, phosphorus and potassium compound fertilizer, and the lignite is converted into high-quality products to the maximum extent by the method.
A method for comprehensively utilizing lignite comprises the following steps:
s1: preparing a lignite raw material: pulverizing lignite into powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material; the lignite used in the method of the invention is preferably lignite in the red peak area of inner Mongolia; impurities mixed in the lignite and silt on the surface can be removed by repeatedly cleaning the lignite with distilled water;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the processing of the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 0.5-1: 2.5; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 5-1: 30; the mass fraction of the KOH solution is 0.5 to 4.5 percent; then, cooking the prepared solid-liquid mixture for 70-100 min at the temperature of 70-100 ℃; cooling, stirring with a magnetic stirrer for reaction, and centrifuging with a centrifuge to separate residue and extractive solution; after the treatment of the step, the humic acid is separated from the lignite particles and dissolved in the extracting solution, porous holes are formed on the surfaces of the lignite particles, the specific surface area of the lignite particles is increased, the residues have certain adsorption capacity, and the holes on the surfaces provide embeddable regions for adsorbed ions.
Firstly, preparing an N-doped porous carbon composite lithium battery anode material by utilizing separated residues, and specifically comprising the following steps:
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating at the temperature of 410-720 ℃ for 0.4-2.2 h to obtain a carbonized and activated product;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a dilute acid solution, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
in the step S3.2, the dilute acid solution for soaking the carbonized and activated product is a nitric acid solution or a phosphoric acid solution, and the concentration is 0.2-3.0 mol/L;
meanwhile, humic acid can be prepared by utilizing the separated extracting solution; the method comprises the following specific steps:
s4: preparing humic acid:
carrying out acid precipitation on the extracting solution obtained in the step S2 by using a dilute acid solution to ensure that the pH value of the solution is less than 4, and filtering the obtained precipitate to obtain humic acid after vacuum drying;
the diluted acid solution used in the acid precipitation process in the step S4 is a phosphoric acid solution or a nitric acid solution, and the concentration is 0.3-2.5 mol/L.
In order to further realize the maximum conversion of the lignite into high-quality products and reduce the emission; in the technical scheme, the waste liquid generated by the process is collected together for preparing the nitrogen, phosphorus and potassium compound fertilizer, and the specific steps are as follows:
s5: preparing a nitrogen, phosphorus and potassium compound fertilizer:
collecting the waste liquid generated in the steps S2, S3 and S4 together for neutralization treatment to obtain a nitrogen, phosphorus and potassium compound fertilizer; in order to prepare the nitrogen, phosphorus and potassium compound fertilizer, when the dilute acid solution for soaking the carbonization activation product in the step S3.2 is a nitric acid solution, the dilute acid solution used in the acidification process in the step S4 is a phosphoric acid solution; or when the dilute acid solution used for soaking the carbonization activation product in the step S3.2 is a phosphoric acid solution, the dilute acid solution used in the acidification process in the step S4 is a nitric acid solution.
The main advantages of the invention are: a new green process method for comprehensive utilization of lignite is created, and the humic acid and N-doped porous carbon composite lithium battery cathode material can be prepared by the process method; in addition, waste liquid generated in the whole process is prepared into a nitrogen, phosphorus and potassium compound fertilizer; thereby realizing the conversion of the lignite into high-quality products to the maximum extent and basically realizing zero emission.
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Example 1
S1: preparing a lignite raw material: adopting lignite in the red peak area of inner Mongolia, crushing the lignite into 60-mesh powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 1; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 20; the mass fraction of the KOH solution is 2 percent; then, the prepared solid-liquid mixture is cooked for 90min in a water bath with the temperature of 90 ℃; taking out, cooling, stirring with a magnetic stirrer for reaction, centrifuging with a centrifuge, and separating to obtain residue and extractive solution;
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1h at the temperature of 600 ℃;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a dilute nitric acid solution with the concentration of 2.0mol/L, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
s4: preparing humic acid:
performing acid precipitation on the extracting solution obtained in the step S2 by using 1.5mol/L phosphoric acid solution to enable the pH value of the solution to reach 2, filtering the obtained precipitate, and performing vacuum drying to obtain humic acid;
s5: preparing a nitrogen, phosphorus and potassium compound fertilizer:
and (4) collecting the waste liquid generated in the steps S2, S3 and S4 together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
Fig. 2 is an SEM image of the negative electrode material of the N-doped porous carbon composite lithium battery prepared in the present example, wherein (a) is a low-power SEM image, (b) is a high-power SEM image, and (c) is an EDS surface scan image; as can be seen from the graphs (a) and (b), the material has a remarkable pore structure and a larger specific surface area, and more pores can relieve the volume expansion when lithium ions are de-intercalated and prevent pulverization; the transmission of lithium ions can be accelerated, and the conductivity of the material is improved; in addition, the larger specific surface area provides more attachment sites for lithium ions, and increases the specific capacity of the material. In addition, it can be seen from the graph (c) that nitrogen is uniformly distributed in the material, which can improve the conductivity of the material, and thus improve the electrochemical performance of the material.
Fig. 3 is a graph showing the cycle performance of the negative electrode material of the N-doped porous carbon composite lithium battery prepared by the method in example 1 of the present invention; the traditional graphite lithium battery cathode only has the specific capacity of 375mA/g, while the specific capacity of the material prepared by the embodiment reaches 1072mA/g, which is nearly 3 times of that of the existing graphite lithium battery cathode.
Table 1 below shows the chemical composition analysis table of the nitrogen, phosphorus, and potassium compound fertilizer prepared in this example; the contents of nitrogen, phosphorus and potassium are changed along with the addition of KOH, urea, phosphoric acid solution and the like; the chemical components of the prepared nitrogen, phosphorus and potassium compound fertilizer have different contents due to different addition amounts.
Table 1 chemical composition of nitrogen phosphorus potassium compound fertilizer prepared in example 1
The content of other components is less than 0.01%.
Example 2
S1: preparing a lignite raw material: adopting lignite in the red peak area of inner Mongolia, crushing the lignite into 60-mesh powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 2; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 20; the mass fraction of the KOH solution is 1 percent; then, the prepared solid-liquid mixture is cooked for 70min in a water bath with the temperature of 80 ℃; taking out, cooling, stirring with a magnetic stirrer for reaction, centrifuging with a centrifuge, and separating to obtain residue and extractive solution;
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 1h at the temperature of 600 ℃;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a phosphoric acid solution with the concentration of 3.0mol/L, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
s4: preparing humic acid:
carrying out acid precipitation on the extracting solution obtained in the step S2 by using a 2.0mol/L nitric acid solution to enable the pH value of the solution to reach 1.5, filtering the obtained precipitate, and drying the filtered precipitate in vacuum to obtain humic acid;
s5: preparing a nitrogen, phosphorus and potassium compound fertilizer:
and (4) collecting the waste liquid generated in the steps S2, S3 and S4 together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
The pore structure of the N-doped porous carbon composite lithium battery cathode material prepared in the embodiment is basically the same as that of the embodiment 1, and the conductivity is similar; the chemical components of the prepared nitrogen, phosphorus and potassium compound fertilizer are basically the same and have different contents.
Example 3
S1: preparing a lignite raw material: pulverizing lignite into powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 0.5; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 5; the mass fraction of the KOH solution is 0.5 percent; then, the prepared solid-liquid mixture is cooked for 70min at the temperature of 70 ℃; cooling, stirring with magnetic stirrer, centrifuging, and separating residue and extractive solution.
Firstly, preparing an N-doped porous carbon composite lithium battery anode material by utilizing separated residues, and specifically comprising the following steps:
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating for 0.4h at the temperature of 410 ℃ to obtain a carbonized and activated product;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a nitric acid solution, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
the concentration of the nitric acid solution for soaking the carbonized and activated product in the step S3.2 is 0.2 mol/L;
meanwhile, humic acid can be prepared by utilizing the separated extracting solution; the method comprises the following specific steps:
s4: preparing humic acid:
performing acid precipitation on the extracting solution obtained in the step S2 by using a phosphoric acid solution to ensure that the pH value of the solution reaches 2, and filtering the obtained precipitate to obtain humic acid after vacuum drying;
the concentration of the phosphoric acid solution used in the acid-out process in step S4 was 0.3 mol/L.
Example 4
S1: preparing a lignite raw material: pulverizing lignite into powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 2.5; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 30; the mass fraction of the KOH solution is 4.5 percent; then, the prepared solid-liquid mixture is cooked for 100min at the temperature of 100 ℃; cooling, stirring with magnetic stirrer, centrifuging, and separating residue and extractive solution.
Firstly, preparing an N-doped porous carbon composite lithium battery anode material by utilizing separated residues, and specifically comprising the following steps:
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carrying out carbonization and activation for 2.2h at the temperature of 720 ℃ to obtain a carbonization and activation product;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a nitric acid solution, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
the concentration of the nitric acid solution for soaking the carbonized and activated product in the step S3.2 is 3.0 mol/L;
meanwhile, humic acid can be prepared by utilizing the separated extracting solution; the method comprises the following specific steps:
s4: preparing humic acid:
performing acid precipitation on the extracting solution obtained in the step S2 by using a phosphoric acid solution to ensure that the pH value of the solution reaches 2, and filtering the obtained precipitate to obtain humic acid after vacuum drying;
the concentration of the phosphoric acid solution used in the acid-out process in step S4 was 2.5 mol/L.
In the above examples, example 1 was the most preferable example obtained by comparative experiments, in which the extraction rate of humic acid was the largest in the experiments, so that more pores were formed on the surface of the lignite particles and the specific capacity was also the largest in the experiments.
Although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to one skilled in the art that various changes in the embodiments and/or modifications of the embodiments and/or portions thereof may be made, and all changes, equivalents, and modifications that fall within the spirit and scope of the invention are therefore intended to be embraced by the appended claims.
Claims (5)
1. A method for comprehensively utilizing lignite is characterized by comprising the following steps:
s1: preparing a lignite raw material: pulverizing lignite into powder, cleaning the powder by using distilled water, and drying the powder in the sun to prepare a clean lignite raw material;
s2: alkali extraction of KOH and urea: weighing the clean lignite raw material obtained by the processing of the step S1, and mixing the clean lignite raw material with urea, wherein the mass ratio of the lignite raw material to the urea is 1: 0.5-1: 2.5; mixing the mixture with a KOH solution to prepare a mixture, wherein the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 5-1: 30; the mass fraction of the KOH solution is 0.5 to 4.5 percent; then, cooking the prepared solid-liquid mixture for 70-100 min at the temperature of 70-100 ℃; cooling, stirring with a magnetic stirrer for reaction, and centrifuging with a centrifuge to separate residue and extractive solution;
s3: preparing an N-doped porous carbon composite lithium battery negative electrode material:
s3.1: putting the residue obtained in the step S2 into a tubular furnace with nitrogen as protective gas, and carbonizing and activating at the temperature of 410-720 ℃ for 0.4-2.2 h to obtain a carbonized and activated product;
s3.2: soaking the carbonized and activated product prepared in the step S3.1 in a dilute acid solution, performing suction filtration, washing with deionized water, and drying in a forced air drying oven to obtain the N-doped porous carbon composite lithium battery cathode material;
in the step S3.2, the dilute acid solution for soaking the carbonized and activated product is a nitric acid solution or a phosphoric acid solution, and the concentration is 0.2-3.0 mol/L;
s4: preparing humic acid:
carrying out acid precipitation on the extracting solution obtained in the step S2 by using a dilute acid solution to ensure that the pH value of the solution is less than 4, and filtering the obtained precipitate to obtain humic acid after vacuum drying;
the diluted acid solution used in the acid precipitation process in the step S4 is a phosphoric acid solution or a nitric acid solution, and the concentration is 0.3-2.5 mol/L.
2. The comprehensive lignite utilization method according to claim 1, wherein the comprehensive lignite utilization method comprises the following steps: the lignite used in the step S1 is lignite in the red peak area of inner mongolian city.
3. The comprehensive lignite utilization method according to claim 1 or 2, wherein the comprehensive lignite utilization method comprises the following steps: the dilute acid solution for soaking the carbonization activation product in the step S3.2 is a nitric acid solution, and the dilute acid solution used in the acidification process in the step S4 is a phosphoric acid solution; then the waste liquid generated in the steps S2, S3 and S4 is collected together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
4. The comprehensive lignite utilization method according to claim 1 or 2, wherein the comprehensive lignite utilization method comprises the following steps: the dilute acid solution for soaking the carbonization activation product in the step S3.2 is phosphoric acid solution, and the dilute acid solution used in the acidification process in the step S4 is nitric acid solution; then the waste liquid generated in the steps S2, S3 and S4 is collected together for neutralization treatment to obtain the nitrogen, phosphorus and potassium compound fertilizer.
5. The comprehensive lignite utilization method according to claim 2, wherein the comprehensive lignite utilization method comprises the following steps:
in step S1, the lignite is pulverized into 60 mesh powder;
in the step S2, the mass ratio of the lignite raw material to the urea is 1: 1; the solid-to-liquid ratio (g: mL) of the mixture to the KOH solution is 1: 20; the mass fraction of the KOH solution is 2 percent; then, the prepared solid-liquid mixture is cooked for 90min in a water bath with the temperature of 90 ℃;
in the step S3.1, under the condition that the temperature is 600 ℃, carbonization and activation are carried out for 1 h;
in the step S3.2, soaking the substrate by using a dilute nitric acid solution with the concentration of 2.0 mol/L;
in step S4, the solution is acidified with 1.5mol/L phosphoric acid solution to reach pH 2, and the precipitate obtained by filtration is dried in vacuum to obtain humic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111548235A (en) * | 2020-05-12 | 2020-08-18 | 锡林郭勒职业学院 | Method for extracting humic acid from lignite companion |
| CN114180571A (en) * | 2020-09-14 | 2022-03-15 | 华中科技大学 | Nitrogen-doped carbon-based lithium storage material and preparation method and application thereof |
| CN115109321A (en) * | 2022-08-12 | 2022-09-27 | 内蒙古科技大学 | Humic acid based nano-superporous aerogel and preparation method thereof |
| WO2023116261A1 (en) * | 2021-12-24 | 2023-06-29 | 宁波中车新能源科技有限公司 | Method for preparing nitrogen-doped porous carbon material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016346A (en) * | 2015-07-09 | 2015-11-04 | 大连海事大学 | Green method for comprehensively utilizing biomass ash |
| CN106395816A (en) * | 2016-09-05 | 2017-02-15 | 中国矿业大学 | Method for extracting humic acid from lignite and then using residues to prepare adsorbent |
| US20180050914A1 (en) * | 2016-08-18 | 2018-02-22 | Nanotek Instruments, Inc. | Process for Producing Highly Oriented Humic Acid Films and Highly Conducting Graphitic Films Derived Therefrom |
| CN109517189A (en) * | 2018-11-29 | 2019-03-26 | 内蒙古科技大学 | A kind of method that lignite produces primary humic acid and methane gas |
-
2019
- 2019-09-28 CN CN201910928117.9A patent/CN110615437A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016346A (en) * | 2015-07-09 | 2015-11-04 | 大连海事大学 | Green method for comprehensively utilizing biomass ash |
| US20180050914A1 (en) * | 2016-08-18 | 2018-02-22 | Nanotek Instruments, Inc. | Process for Producing Highly Oriented Humic Acid Films and Highly Conducting Graphitic Films Derived Therefrom |
| CN106395816A (en) * | 2016-09-05 | 2017-02-15 | 中国矿业大学 | Method for extracting humic acid from lignite and then using residues to prepare adsorbent |
| CN109517189A (en) * | 2018-11-29 | 2019-03-26 | 内蒙古科技大学 | A kind of method that lignite produces primary humic acid and methane gas |
Non-Patent Citations (3)
| Title |
|---|
| ROBLES, I. ET AL.: ""Adsorption study of mercury on lignite in the presence of different anions"", 《SUSTAINABLE ENVIRONMENT RESEARCH》 * |
| 刘靖等: ""兰炭特性及应用研究进展"", 《洁净煤技术》 * |
| 杭波等: ""利用尿素复合溶液从风化煤中提取水溶腐植酸和生成腐植酸络合酰胺态氮的研究"", 《腐植酸》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548235A (en) * | 2020-05-12 | 2020-08-18 | 锡林郭勒职业学院 | Method for extracting humic acid from lignite companion |
| CN114180571A (en) * | 2020-09-14 | 2022-03-15 | 华中科技大学 | Nitrogen-doped carbon-based lithium storage material and preparation method and application thereof |
| CN114180571B (en) * | 2020-09-14 | 2023-06-16 | 华中科技大学 | Nitrogen-doped carbon-based lithium storage material and preparation method and application thereof |
| WO2023116261A1 (en) * | 2021-12-24 | 2023-06-29 | 宁波中车新能源科技有限公司 | Method for preparing nitrogen-doped porous carbon material |
| CN115109321A (en) * | 2022-08-12 | 2022-09-27 | 内蒙古科技大学 | Humic acid based nano-superporous aerogel and preparation method thereof |
| CN115109321B (en) * | 2022-08-12 | 2023-03-21 | 内蒙古科技大学 | Humic acid based nano-superporous aerogel and preparation method thereof |
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