CN113044829A - Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt - Google Patents
Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt Download PDFInfo
- Publication number
- CN113044829A CN113044829A CN202110326414.3A CN202110326414A CN113044829A CN 113044829 A CN113044829 A CN 113044829A CN 202110326414 A CN202110326414 A CN 202110326414A CN 113044829 A CN113044829 A CN 113044829A
- Authority
- CN
- China
- Prior art keywords
- biochar
- solid waste
- mixing
- biomass
- macroporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt, which specifically comprises the following steps: taking biomass solid waste generated in the production process of agriculture and forestry as a raw material, cleaning, drying in the sun, crushing, screening by a screen, drying by an oven and dehydrating; mixing and grinding the obtained biomass powder and metal mixed salt, carrying out carbonization reaction in an inert gas atmosphere, cooling to room temperature after the reaction is finished, and separating and grinding to obtain the charcoal powder; and washing the obtained charcoal powder with ultrapure water until the pH of the solution is nearly neutral, and removing salt impurities remained on the surface to obtain the charcoal with the nanosheet self-assembly structure. The method for preparing the biochar can convert biomass of solid waste into the biochar with a macroporous/mesoporous hybrid pore structure at relatively low temperature, and keeps rich surface functional groups. The invention can realize the resource utilization of the agriculture and forestry solid waste biomass and generate carbon materials with higher added values.
Description
Technical Field
The invention relates to the field of resource utilization of solid waste biomass and preparation of carbon materials, in particular to a method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt.
Background
The biochar is a solid substance which is prepared from biological residues through high-temperature pyrolysis or hydrothermal carbonization under the condition of oxygen deficiency or low oxygen content and is infusible, stable, high in aromatizing degree and rich in carbon content. The biochar can be applied to the fields of adsorption, separation, purification, energy storage and the like of substances. The raw material sources of the biochar are wide, such as wood, dead branches, straws, fruit peels, shells and kernels and the like. The prepared biochar can be used for recycling biomass waste generated in the production process of agriculture and forestry, and can be converted into a material with higher value.
However, the high temperature pyrolysis and hydrothermal methods generally used have some disadvantages. First, the high-temperature pyrolysis method used for the production of activated carbon often requires a high temperature of 800 ℃ or higher, and has a problem of large energy consumption. The hydrothermal method is accompanied by high pressure hidden trouble, has higher requirements on equipment and is not beneficial to industrial over-amplification. In addition, the biochar prepared by the method often only has one of the following characteristics, and two or more characteristics are not easy to be considered at the same time: (1) high specific surface area, (2) rich pore structure, (3) rich surface functional groups.
According to the invention, the biochar is prepared by adopting a biomass molten salt mixing and melting mode, not only has a special macroporous/mesoporous hybrid pore structure, but also contains rich functional groups, can effectively play the physical and chemical adsorption roles, is beneficial to expanding the application of carbon materials in various fields, and can be used as a means for recycling solid waste biomass.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt.
The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt is characterized by comprising the following steps:
1) taking biomass solid waste generated in the production process of agriculture and forestry as a raw material, cleaning, drying in the sun, crushing, screening by a screen of 60-200 meshes, and further drying and dehydrating by an oven;
2) mixing and grinding the biomass powder obtained in the step 1) and a pre-prepared metal mixed salt, performing a carbonization reaction at a lower temperature in an inert gas atmosphere, controlling the heating rate, keeping the temperature for a constant time, cooling to room temperature after the reaction is finished, separating and grinding to obtain charcoal powder, wherein the metal mixed salt is two or more than two of chloride, sulfate or phosphate in any ratio;
3) washing the charcoal powder obtained in the step 2) with ultrapure water until the pH of the solution is nearly neutral, and removing salt impurities remained on the surface to obtain the macroporous/mesoporous structure hybrid charcoal
Further, in the step 1), the biomass solid waste is pericarp, hull and core, straw and branch; the drying and dehydrating temperature is 100-120 ℃, and the drying time is 3-12 h.
Further, in step 2), the metal mixed salt refers to a mixture of two or more kinds, and is ball-milled through a 500-mesh screen.
Further, in step 2), the inert gas refers to one of nitrogen, argon, helium and neon.
Further, in the step 2), the lower temperature is 300-780 ℃.
Further, in the step 2), the temperature rise is controlled to be 2-10 ℃/min.
Further, in the step 2), the constant temperature time is controlled to be 1-6 h.
Furthermore, in the step 3), 0.1-0.5M hydrochloric acid solution is adopted for soaking and ultrasonic washing.
The biochar prepared by the method has a special pore structure with mixed macropores and mesopores, has rich surface functional groups, and can play a better role in adsorption and energy storage.
The beneficial effects obtained by the invention are as follows:
1) the invention can realize the resource utilization of agriculture and forestry solid waste biomass at lower temperature through biomass molten salt mixing and melting, and successfully realize waste-to-material conversion.
2) According to the invention, by regulating and controlling reaction conditions and adopting a simple preparation method, the carbon material spontaneously forms a specific nanosheet self-assembly structure to form a special macroporous and mesoporous hybrid pore structure. Besides the specific physical and chemical adsorption function of the carbon material, the carbon material can also play a role in filling pores, thereby effectively improving the adsorption and storage capacity of the carbon material.
Drawings
FIG. 1 is an SEM image of a biochar sample 1 prepared in example 1;
FIG. 2 is an SEM image of biochar sample 2 prepared in example 2;
FIG. 3 is an SEM image of biochar sample 3 prepared in example 3;
FIG. 4 is a graph of pore size distribution of biochar for samples 1, 2, 3;
FIG. 5 is a FT-IR chart of biochar of samples 1, 2, and 3.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1 method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt, comprising the following steps:
1) the method comprises the following steps of (1) taking biomass solid waste banana peel generated in the production process of agriculture and forestry as a raw material, washing with tap water, exposing in the sun for 4 hours, crushing, screening with a 100-mesh screen, and keeping in an oven for 4 hours at 100 ℃ to achieve the purpose of further drying and dewatering;
2) preparing metal mixed salt, adding KCl: k2SO4：Na2SO4According to the following steps of 3: 1: mixing according to the weight ratio of 6, ball-milling for 1 hour, sieving by a 500-mesh sieve, and collecting for later use;
3) mixing and grinding the biomass powder prepared in the steps 1) and 2) with metal mixed salt, carrying out carbonization reaction at 500 ℃ under the protection of nitrogen atmosphere, controlling the heating rate at 5 ℃/min, keeping the temperature for 2h at constant temperature, cooling to room temperature after the reaction is finished, and transferring the product into a glass container;
4) soaking the product prepared in the step 3) in 0.2M hydrochloric acid solution, ultrasonically washing, filtering, leaching with deionized water (the pH of the washing solution is nearly neutral) and ethanol (the water content of the product is favorably reduced), and placing in a vacuum drying oven to dry overnight at 65 ℃ to obtain the macroporous/mesoporous structure hybrid biochar material.
Fig. 1 is an SEM image of biochar sample 1 prepared in example 1. From fig. 1, it can be seen that the biochar prepared in the example 1 is formed by self-assembly of ultrathin nanosheets into a unique macroporous structure, and the pore diameter is tens to hundreds of nanometers. Furthermore, as can be seen from FIG. 4, the sample 1 material has a mesoporous characteristic of about 4nm and has a relatively rich volume (up to 0.12 cm)3In terms of/g). In addition, the biochar material prepared by the method has abundant surface functional groups, such as aromatic ring, -COOH, -OH and-NH2Etc., see fig. 5 for details.
Embodiment 2 a method for preparing a macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt, comprising the following steps:
1) taking biomass solid waste peanut shells generated in the production process of agriculture and forestry as raw materials, washing by tap water, exposing in the sun for 2 hours, crushing and screening by a 100-mesh screen, and keeping in an oven for 4 hours at 100 ℃ to achieve the aim of further drying and dewatering;
2) preparing metal mixed salt, adding KCl: k2SO4：Na2SO4According to the following steps: 1: mixing according to the weight ratio of 8, ball-milling for 1 hour, sieving by a 500-mesh sieve, and collecting for later use;
3) mixing and grinding the biomass powder prepared in the steps 1) and 2) with metal mixed salt, carrying out carbonization reaction at 550 ℃ under the protection of nitrogen atmosphere, controlling the heating rate at 3 ℃/min, keeping the temperature for 2h at constant temperature, cooling to room temperature after the reaction is finished, and transferring the product into a glass container;
4) soaking the product prepared in the step 3) in 0.2M hydrochloric acid solution, ultrasonically washing, filtering, leaching with deionized water (the pH of the washing solution is nearly neutral) and ethanol (the water content of the product is favorably reduced), and placing in a vacuum drying oven to dry overnight at 65 ℃ to obtain the macroporous/mesoporous structure hybrid biochar material.
Fig. 2 is an SEM image of biochar sample 2 prepared in example 2. From fig. 2, it can be seen that the biochar prepared in the example 2 is formed by self-assembly of ultrathin nanosheets into a unique macroporous structure, and the pore diameter is tens to hundreds of nanometers. Furthermore, as can be seen from FIG. 4, the sample 2 material has a mesoporous characteristic of about 3.5nm and has a certain volume (up to 0.06 cm)3In terms of/g). In addition, the biochar material prepared by the method has abundant surface functional groups, such as aromatic ring, -COOH, -OH and-NH2Etc., see fig. 5 for details.
Embodiment 3 a method for preparing a macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt, comprising the following steps:
1) cleaning dead branches of biomass solid waste generated in the production process of agriculture and forestry as raw materials by tap water, exposing the raw materials in the sun for 6 hours, crushing the raw materials by a 100-mesh screen, and keeping the crushed raw materials in an oven for 4 hours at 100 ℃ to achieve the aim of further drying and dewatering;
2) preparing a metal mixed salt, mixing LiCl: ZnCl2According to the following steps: mixing according to the weight ratio of 1, ball-milling for 1 hour, sieving by a 500-mesh sieve, and collecting for later use;
3) mixing and grinding the biomass powder prepared in the steps 1) and 2) with metal mixed salt, carrying out carbonization reaction at 600 ℃ under the protection of nitrogen atmosphere, controlling the temperature rise rate at 2 ℃/min, keeping the temperature for 2h at constant temperature, cooling to room temperature after the reaction is finished, and transferring the product into a glass container;
4) soaking the product prepared in the step 3) in 0.2M hydrochloric acid solution, ultrasonically washing, filtering, leaching with deionized water (the pH of the washing solution is nearly neutral) and ethanol (the water content of the product is favorably reduced), and placing in a vacuum drying oven to dry overnight at 65 ℃ to obtain the macroporous/mesoporous structure hybrid biochar material.
5) Fig. 3 is an SEM image of biochar sample 3 prepared in example 3. From fig. 3, it can be seen that the biochar prepared in the example 3 is formed by self-assembly of ultrathin nanosheets into a unique macroporous structure, and the pore diameter is tens to hundreds of nanometers. Furthermore, as can be seen from FIG. 4, the material of sample 3 has a mesoporous characteristic of about 3.2nm and has a certain volume (up to 0.07 cm)3In terms of/g). In addition, the biochar material prepared by the method has abundant surface functional groups, such as aromatic ring, -COOH, -OH and-NH2Etc., see fig. 5 for details.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (7)
1. A method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt is characterized by comprising the following steps:
taking biomass solid waste generated in the production process of agriculture and forestry as a raw material, cleaning, drying in the sun, crushing, screening by a screen of 60-200 meshes, and further drying and dehydrating by an oven;
mixing and grinding the biomass powder obtained in the step 1) and a pre-prepared metal mixed salt, performing a carbonization reaction at a lower temperature in an inert gas atmosphere, controlling the heating rate, keeping the temperature for a constant time, cooling to room temperature after the reaction is finished, separating and grinding to obtain charcoal powder, wherein the metal mixed salt is two or more than two of chloride, sulfate or phosphate in any ratio;
washing the charcoal powder obtained in the step 2) with ultrapure water until the pH of the solution is nearly neutral, and removing salt impurities remained on the surface to obtain the macroporous/mesoporous structure hybrid charcoal
The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass and molten salt as claimed in claim 1, wherein in the step 1), the biomass solid waste is pericarp, putamen, straw and branch; the drying and dehydrating temperature is 100-120 ℃, and the drying time is 3-12 h.
2. The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting the solid waste biomass molten salt according to claim 1, wherein in the step 2), the metal mixed salt refers to a mixture of two or more than two types, and the mixture is ball-milled and screened by a 500-mesh screen.
3. The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting the solid waste biomass and the molten salt according to claim 1, wherein in the step 2), the inert gas refers to one of nitrogen, argon, helium and neon.
4. The method for preparing the macroporous/mesoporous structure hybrid biochar through mixing and melting solid waste biomass molten salt according to claim 1, wherein in the step 2), the lower temperature is 300-780 ℃.
5. The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt according to claim 1, wherein in the step 2), the temperature rise is controlled to be 2-10 ℃/min.
6. The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt according to claim 1, wherein in the step 2), the constant temperature time is controlled to be 1-6 h.
7. The method for preparing the macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt according to claim 1, wherein in the step 3), 0.1-0.5M hydrochloric acid solution is adopted for soaking and ultrasonic washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110326414.3A CN113044829A (en) | 2021-03-26 | 2021-03-26 | Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110326414.3A CN113044829A (en) | 2021-03-26 | 2021-03-26 | Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113044829A true CN113044829A (en) | 2021-06-29 |
Family
ID=76515611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110326414.3A Pending CN113044829A (en) | 2021-03-26 | 2021-03-26 | Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113044829A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247433A (en) * | 2021-12-20 | 2022-03-29 | 中新国际联合研究院 | Method for treating organic waste salt and agricultural and forestry wastes and preparing biochar by molten salt method |
| CN115259131A (en) * | 2022-06-23 | 2022-11-01 | 长江水利委员会长江科学院 | Green method for preparing multifunctional biochar from sludge and application of biochar |
| CN115709980A (en) * | 2022-11-23 | 2023-02-24 | 浙江工业大学 | Biochar material rich in microporous structure and adjustable in pore volume and preparation method and application thereof |
| CN115709053A (en) * | 2022-11-23 | 2023-02-24 | 浙江工业大学 | Biochar with specific surface area regulated by cations in molten salt medium and preparation method and application thereof |
| CN115818615A (en) * | 2022-11-23 | 2023-03-21 | 浙江工业大学 | Carbon-based material carbon dioxide capture agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104709905A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院兰州化学物理研究所 | Method for preparing supercapacitor-dedicated active carbon by using mixed molten salts as activator |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN110734348A (en) * | 2019-10-08 | 2020-01-31 | 浙江工业大学 | biochar, biochar-based multifunctional soil remediation agent and preparation method thereof |
-
2021
- 2021-03-26 CN CN202110326414.3A patent/CN113044829A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104709905A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院兰州化学物理研究所 | Method for preparing supercapacitor-dedicated active carbon by using mixed molten salts as activator |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN110734348A (en) * | 2019-10-08 | 2020-01-31 | 浙江工业大学 | biochar, biochar-based multifunctional soil remediation agent and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247433A (en) * | 2021-12-20 | 2022-03-29 | 中新国际联合研究院 | Method for treating organic waste salt and agricultural and forestry wastes and preparing biochar by molten salt method |
| CN114247433B (en) * | 2021-12-20 | 2024-01-09 | 中新国际联合研究院 | Method for simultaneously preparing biochar by treating organic waste salt and agricultural and forestry waste through molten salt method |
| CN115259131A (en) * | 2022-06-23 | 2022-11-01 | 长江水利委员会长江科学院 | Green method for preparing multifunctional biochar from sludge and application of biochar |
| CN115259131B (en) * | 2022-06-23 | 2024-04-30 | 长江水利委员会长江科学院 | Green method for preparing multifunctional biochar by utilizing sludge and application of biochar |
| CN115709980A (en) * | 2022-11-23 | 2023-02-24 | 浙江工业大学 | Biochar material rich in microporous structure and adjustable in pore volume and preparation method and application thereof |
| CN115709053A (en) * | 2022-11-23 | 2023-02-24 | 浙江工业大学 | Biochar with specific surface area regulated by cations in molten salt medium and preparation method and application thereof |
| CN115818615A (en) * | 2022-11-23 | 2023-03-21 | 浙江工业大学 | Carbon-based material carbon dioxide capture agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113044829A (en) | Method for preparing macroporous/mesoporous structure hybrid biochar by mixing and melting solid waste biomass molten salt | |
| WO2015106720A1 (en) | Method for producing super activated charcoal from biomass power plant ash | |
| WO2016072932A1 (en) | Activated carbon, hydrochar and processes for making same | |
| US20170007980A1 (en) | Process for the production of high-quality activated carbons as well as activated carbons produced according to the process | |
| CN108128773B (en) | Method for preparing electrode carbon material for electrochemical capacitor by using peanut shells | |
| CN107628597B (en) | By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method | |
| KR20150100636A (en) | Electrode material for secondary batteries, method for producing same, and secondary battery | |
| CN111408376A (en) | Preparation method and application of multifunctional biochar with heavy metal adsorption and organic matter degradation functions | |
| CN111408343B (en) | Preparation method of three-dimensional biochar and application of three-dimensional biochar in heavy metal adsorption | |
| CN101439280B (en) | Expanded graphite-based composite material and preparation method thereof | |
| CN113233462A (en) | Preparation method of lignite-based activated carbon with high specific surface area | |
| Sharath et al. | Production of activated carbon from solid waste rice peel (husk) using chemical activation | |
| CN110482544B (en) | Activated carbon and preparation method and application thereof | |
| CN104888708B (en) | Corn scytoblastema three-dimensional multistage pore structure carbon material and preparation method thereof | |
| CN109158083B (en) | Preparation method and application of biomass-based carbon material | |
| CN109160514B (en) | Bean curd reaming method, bean curd powder preparation method, bean curd graded porous activated carbon and preparation method thereof | |
| CN113351162B (en) | Preparation method and application of carbon-based phosphorus-doped ferrihydrite | |
| CN111725506B (en) | Porous carbon/carbon nitride composite material and preparation method thereof | |
| CN115106059A (en) | High-specific-surface-area magnesium oxide/magnesium hydroxide load and preparation method thereof | |
| CN109841825B (en) | Method for preparing lithium ion battery cathode material by recycling tin in electroplating sludge | |
| CN114956074A (en) | Seaweed-based three-dimensional porous carbon sieve and preparation method thereof | |
| CN115084483A (en) | Walnut shell derived porous carbon/nickel/sulfur composite material and battery anode material prepared from same | |
| CN114275782B (en) | Method for preparing full-microporous activated carbon by low-temperature alkali melting method | |
| CN117361529A (en) | Preparation method of sulfur-doped porous carbon-based carbon dioxide adsorbent | |
| CN108298535A (en) | A kind of continuous production method of Sargassum horneri mesopore activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |