CN112479190A - Method for preparing graphene-like precursor from biomass - Google Patents
Method for preparing graphene-like precursor from biomass Download PDFInfo
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- CN112479190A CN112479190A CN202011397328.3A CN202011397328A CN112479190A CN 112479190 A CN112479190 A CN 112479190A CN 202011397328 A CN202011397328 A CN 202011397328A CN 112479190 A CN112479190 A CN 112479190A
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- 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
- C01B32/182—Graphene
- C01B32/184—Preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a method for preparing a graphene-like precursor by using biomass, which comprises the following steps: 1, firstly, crushing a biomass raw material to the particle size of less than 1mm, and drying the biomass raw material until the water content of the biomass raw material is less than 10%; step 2, placing the biomass and ethanol in a sealed pressure-resistant container with stirring equipment, heating to 260-310 ℃, boosting to 6-20 MPa, and keeping the state for 0.5-9 hours, wherein in the process, the stirring equipment is started to stir the substances in the container; and 3, cooling, filtering, and carrying out solid-liquid separation to obtain a solid which is a graphene-like precursor, wherein the solid conversion rate is 30-63%. According to the invention, supercritical ethanol is utilized to convert biomass into the graphene-like precursor, and the graphene-like precursor can be used for preparing graphene-like.
Description
Technical Field
The invention belongs to the technical field of new materials and the technical field of solid waste resource utilization, and particularly relates to a method for preparing a graphene-like precursor from biomass.
Background
Biomass is a diverse organism formed by photosynthesis, a persistent resource. Cellulosic biomass mainly includes agricultural cellulosic biomass, forestry cellulosic biomass, and the like. Agricultural cellulose biomass mainly comprises crop straws and agricultural product processing wastes. The crop straws comprise rice straws, corn straws, wheat straws and the like, wherein the rice straws, the corn straws and the wheat straws account for 84.3 percent; the agricultural product processing waste comprises rice hulls, corncobs, peanut shells, bagasse and the like. Forestry cellulose biomass is mainly firewood charcoal forest, forestry waste, stump shrubs and the like. The total amount of land forest biomass resources in China is more than 180 hundred million tons.
Graphene is a two-dimensional crystalline material formed by closely arranging carbon atoms of a hexagonal grid monomer structure. The graphene is the thinnest material at present, the thickness of single-layer graphene is only the diameter of one carbon atom, and the graphene belongs to a nano material. The thickness of the graphite sheet is about 0.34 nm, and the graphite sheet with the thickness of 1mm is formed by stacking about 300 ten thousand layers of graphene. It is a two-dimensional material with excellent mechanical, electrical and thermal properties. The graphene has super-strong mechanical strength which is 100 times of that of steel and is harder than diamond; the conductive material has ultrahigh conductivity, and the mobility of the conductive material is 100 times that of silicon; the material has excellent heat-conducting property, is superior to the carbon nano tube, and is expected to become a heat-radiating material of a future ultra-large-scale nano integrated circuit; has extremely high light transmittance; the material has extremely high specific surface area and is expected to become an energy storage material with huge potential and the like.
In recent years, scientists have paid more and more attention to the large-scale production of high-quality graphene. However, most current methods for synthesizing graphene rely primarily on pure chemical reagents, making scale-up expensive. How to prepare graphene or graphene-like substances by using biomass with low price and wide distribution becomes one of the main points of attention of domestic and foreign scientists.
The current graphene preparation technologies are largely divided into three categories: mainly comprises a micro-mechanical stripping method, a chemical vapor deposition method, graphite oxide reduction and the like. The micro-mechanical stripping method is simple to operate, but has poor controllability, low efficiency and high cost, and is not suitable for large-scale production. The thickness controllability of the graphene prepared by chemical vapor deposition is poor, the efficiency is not high, and the transfer process is complicated. The method for reducing the graphite oxide is simple to operate and low in preparation cost, can be used for preparing the graphene on a large scale, and becomes an effective way for preparing the graphene. But easily causes defects in the crystal structure of graphene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a graphene-like precursor from biomass.
The above object of the present invention is achieved by the following technical solutions:
a method for preparing a graphene-like precursor from biomass is characterized by comprising the following steps:
1, firstly, crushing a biomass raw material to the particle size of less than 1mm, and drying the biomass raw material until the water content of the biomass raw material is less than 10%;
step 2, placing the biomass and ethanol in a sealed pressure-resistant container with stirring equipment, heating to 260-310 ℃, boosting to 6-20 MPa, and keeping the state for 0.5-9 hours, wherein in the process, the stirring equipment is started to stir the substances in the container;
and 3, cooling, filtering, and carrying out solid-liquid separation to obtain a solid which is a graphene-like precursor, wherein the solid conversion rate is 30-63%.
Further: the biomass raw material in the step 1 is one or a mixture of a plurality of lignocellulose substances such as wood, bamboo, crop straw, fruit shells and the like.
Further: adding a catalyst into the step 2, wherein the dosage of the catalyst is as follows: 1-10 wt% of the total mass of the biomass raw material.
Further, the method comprises the following steps: the catalyst adopts potassium carbonate or sodium carbonate or potassium hydroxide.
Further: the purity of the ethanol added in the step 2 is 75-100 v/v%. The dosage of the ethanol is as follows: 1-15 ml of biomass raw material is used per 1 g.
The invention has the advantages and positive effects that:
1. according to the invention, the supercritical ethanol is utilized to convert the biomass into the graphene-like precursor, and the graphene-like precursor can be used for preparing graphene-like.
2. The invention selects supercritical ethanol as a reaction medium, and has lower critical temperature and critical pressure. Ethanol has the advantage of being non-toxic relative to other alcohols.
2. The method has the advantages of mild conditions and low requirements on reaction equipment.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following examples are given and detailed below. It should be noted that the present embodiment is illustrative, not restrictive, and the scope of the invention should not be limited thereby.
The invention discloses a method for preparing a graphene-like precursor by biomass, which comprises the following steps:
1, firstly, crushing to ensure that the granularity of the biomass raw material is less than 1mm, and if the granularity meets the requirement, crushing is not needed; and drying to make the water content of the biomass raw material less than 10%. The biomass material may be one or more of wood, bamboo, crop straw, fruit shell and other lignocellulose.
Step 2, placing the biomass and the ethanol into a sealed pressure-resistant container with stirring equipment, and preferably adding a certain amount of catalyst, wherein the catalyst is used in the following amount: 1-10 wt% of the total mass of the biomass raw material, wherein the catalyst can adopt potassium carbonate or sodium carbonate or potassium hydroxide; heating the container to 260-310 ℃, boosting the pressure to 6-20 MPa, keeping the state for 0.5-9 hours, and starting stirring equipment to stir the substances in the container in the process. Wherein the purity of the added ethanol is preferably 75-100 v/v%. The amount of ethanol used is preferably: 1-15 ml of biomass raw material is used per 1 g.
And 3, cooling, filtering, and carrying out solid-liquid separation to obtain a solid which is a graphene-like precursor, wherein the solid conversion rate is 30-63%. The graphene-like precursor is used for preparing a graphene-like nano composite material, and the graphene-like precursor is activated in a nitrogen environment at 800 ℃, pickled by a hydrochloric acid solution and dried to obtain the graphene-like.
Two examples are shown to illustrate the method for preparing the graphene-like precursor from biomass:
example 1: the method for preparing the graphene-like precursor by using the fir as the catalyst by using the supercritical ethanol and the potassium carbonate comprises the following steps of:
50g of fir sawdust which is dried by 20 meshes, 2.5g of potassium carbonate and 300ml of 96% ethanol are added into an autoclave, the autoclave is sealed and heated to 280 ℃, the pressure is increased to 12.1MPa, the autoclave is kept in the state for 5 hours, and filtration and solid-liquid separation are carried out after cooling, wherein the solid mass is 20g, and the solid conversion rate is 40%.
Example 2: method for preparing graphene-like precursor by using fir of supercritical ethanol
50g of fir sawdust which is dried by 20 meshes and 300ml of 96% ethanol are added into an autoclave, the autoclave is sealed and heated to 300 ℃, the pressure is increased to 14.5MPa, the state is kept for 5 hours, and the filtration and solid-liquid separation are carried out after cooling, wherein the solid mass is 19g, and the solid conversion rate is 38%.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (5)
1. A method for preparing a graphene-like precursor from biomass is characterized by comprising the following steps:
1, firstly, crushing a biomass raw material to the particle size of less than 1mm, and drying the biomass raw material until the water content of the biomass raw material is less than 10%;
step 2, placing the biomass and ethanol in a sealed pressure-resistant container with stirring equipment, heating to 260-310 ℃, boosting to 6-20 MPa, and keeping the state for 0.5-9 hours, wherein in the process, the stirring equipment is started to stir the substances in the container;
and 3, cooling, filtering, and carrying out solid-liquid separation to obtain a solid which is a graphene-like precursor, wherein the solid conversion rate is 30-63%.
2. The method for preparing the graphene-like precursor from the biomass as claimed in claim 1, wherein: the biomass raw material in the step 1 is one or a mixture of a plurality of lignocellulose substances such as wood, bamboo, crop straw, fruit shells and the like.
3. The method for preparing the graphene-like precursor from the biomass as claimed in claim 1, wherein: adding a catalyst into the step 2, wherein the dosage of the catalyst is as follows: 1-10 wt% of the total mass of the biomass raw material.
4. The method for preparing the graphene-like precursor from the biomass as claimed in claim 3, wherein: the catalyst adopts potassium carbonate or sodium carbonate or potassium hydroxide.
5. The method for preparing the graphene-like precursor from the biomass as claimed in claim 1, wherein: the purity of the ethanol added in the step 2 is 75-100 v/v%. The dosage of the ethanol is as follows: 1-15 ml of biomass raw material is used per 1 g.
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| CN202011397328.3A CN112479190A (en) | 2020-12-03 | 2020-12-03 | Method for preparing graphene-like precursor from biomass |
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| CN202011397328.3A CN112479190A (en) | 2020-12-03 | 2020-12-03 | Method for preparing graphene-like precursor from biomass |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687315A (en) * | 2005-04-19 | 2005-10-26 | 华东理工大学 | Supercritical liquefaction method for biomass |
| KR20090039470A (en) * | 2007-10-18 | 2009-04-22 | 대한민국(관리부서 : 산림청 국립산림과학원장) | Saccharification of woody biomasses using supercritical water in presence of acid catalysts |
| CN105950274A (en) * | 2016-05-06 | 2016-09-21 | 华南农业大学 | Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose |
| CN107987862A (en) * | 2017-11-13 | 2018-05-04 | 华南农业大学 | The method that a kind of Asia/supercritical methanol liquified cellulosic prepares primary biomass platform chemicals |
| CN109336080A (en) * | 2018-08-21 | 2019-02-15 | 浙江工业大学 | A kind of preparation method of adjustable grading porous foam Carbon Materials |
| CN111533111A (en) * | 2020-05-10 | 2020-08-14 | 西南石油大学 | Preparation method of biomass graphene hydrogen storage material |
-
2020
- 2020-12-03 CN CN202011397328.3A patent/CN112479190A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687315A (en) * | 2005-04-19 | 2005-10-26 | 华东理工大学 | Supercritical liquefaction method for biomass |
| KR20090039470A (en) * | 2007-10-18 | 2009-04-22 | 대한민국(관리부서 : 산림청 국립산림과학원장) | Saccharification of woody biomasses using supercritical water in presence of acid catalysts |
| CN105950274A (en) * | 2016-05-06 | 2016-09-21 | 华南农业大学 | Method for preparation of bio-oil by hydroxyl donor coordinated sub/super-critical ethanol liquefaction of straw cellulose |
| CN107987862A (en) * | 2017-11-13 | 2018-05-04 | 华南农业大学 | The method that a kind of Asia/supercritical methanol liquified cellulosic prepares primary biomass platform chemicals |
| CN109336080A (en) * | 2018-08-21 | 2019-02-15 | 浙江工业大学 | A kind of preparation method of adjustable grading porous foam Carbon Materials |
| CN111533111A (en) * | 2020-05-10 | 2020-08-14 | 西南石油大学 | Preparation method of biomass graphene hydrogen storage material |
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