CN116654912A - Preparation method and application of rice hull-based porous graphene - Google Patents
Preparation method and application of rice hull-based porous graphene Download PDFInfo
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- KHOMMWHGIAOVKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;nickel Chemical compound [Ni].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KHOMMWHGIAOVKF-UHFFFAOYSA-N 0.000 claims description 4
- ACOUVIAARVCJGT-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate;cobalt Chemical compound [Co].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O ACOUVIAARVCJGT-UHFFFAOYSA-N 0.000 claims description 4
- NVGQLLICICOXGV-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate;manganese Chemical compound [Mn].CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O NVGQLLICICOXGV-UHFFFAOYSA-N 0.000 claims description 4
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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
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01B32/194—After-treatment
- C01B32/196—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a preparation method of rice hull-based porous graphene, which comprises the steps of firstly cleaning rice hulls, drying, crushing, sieving, secondly mixing and ball milling a catalyst with rice hull powder, thirdly performing catalytic pyrolysis graphene treatment to obtain a graphene-containing product, fourthly performing acid washing to remove metal components to obtain porous graphene, and fifthly, recovering the metal components to obtain a regenerated catalyst; according to the invention, the organic catalyst and the carbon source are mixed by mechanical ball milling, the organic ligand catalyst directly converts the carbonaceous material into the graphene material at the medium temperature of 700-1000 ℃, and the catalyst metal component is recycled and then converted into the catalyst for repeated use, so that the yield of the graphene product reaches 40-50%; the process has the advantages of relatively mild reaction condition, reusable catalyst and low production cost.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a preparation method and application of rice hull-based porous graphene.
Background
In recent years, with the continuous and deep research of different allotropes of ordered carbon, graphene materials are widely accepted in the market; the graphene material can be used as an adsorbent for adsorbing pollutants in water environment, can be used as a catalyst for advanced oxidation technology, promotes degradation of organic pollutants, and can be used as an electrode material for application in the field of electrochemical energy storage; the existing preparation methods of graphene mainly comprise mechanical stripping, chemical vapor deposition, oxidation reduction and the like, but the methods have the problems of low yield, high cost, complex procedures, high preparation temperature and the like. And mainly uses non-renewable mineral-derived graphite or other carbonaceous organic compounds as production raw materials. Practical limitations are imposed on the sustainable development of the graphene industry.
In the prior art, as disclosed in the publication No. CN115594170A, the graphene powder prepared by the method is not easy to agglomerate and has good electrochemical capacitance behavior; in addition, as disclosed in the publication No. CN106744918A, the biological carbon precursor is first carbonized into carbon powder in a vacuum carbonizing machine at vacuum degree of 5X 10-2-5X 10-4Pa and 900-1300 deg.c; (2) adding carbon powder into acid solution, stirring uniformly, and reacting for 48-72h, wherein the acid solution is HF aqueous solution and HCl aqueous solution; (3) placing the purified carbon powder into a baking oven for baking; (4) keeping the temperature of the dried carbon powder at 2700-3000 ℃, and cooling to room temperature to obtain graphitized carbon; in addition, as disclosed in the publication No. CN110171818B, the method for extracting graphene from corn stalks has the advantages of high cellulose effective extraction rate, high carbon-containing gas recovery rate, capability of converting more graphene through water washing gas, and high impurity content of the prepared graphene; the biomass graphene disclosed by the publication number CN112919451B and the preparation method thereof not only improve the utilization rate of waste biomass resources and the conversion benefit of kitchen waste hydrolysis residues, but also provide a sustainable method and the like for preparing a catalyst in an advanced oxidation process.
At present, biomass resources are converted to graphene products, a certain research result is obtained, but the following problems are needed to be solved in order to realize industrial application: 1) The condition of converting biomass into graphene is harsh, and high-temperature and high-pressure harsh reaction conditions are needed; 2) The catalyst has poor stability, is not easy to recycle after reaction, and pollutes the environment; 3) The selectivity of biomass conversion products is not high, the quality of the products is not high, and the yield is low.
In combination with the existing technology for preparing graphene by biomass, when no catalyst is adopted, the energy consumption is extremely high; the catalytic graphitization process taking the metal chloride catalyst as the leading has the problems of catalyst treatment, equipment corrosion and the like; the supported catalyst requires a carbon precursor having a certain adsorptivity and a long impregnation time; most biomass graphene products in the market have low specific surface area and high defect degree; the catalyst separation and reuse problems exist in the metal ion removal process, the sustainable preparation of products is limited, and biomass-based graphene products with high quality cannot be obtained under the low temperature condition below 1000 ℃, so that the invention provides a preparation method and application of rice hull-based porous graphene to solve the problems in the prior art.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of rice hull-based porous graphene, which mixes an organic catalyst and a carbon source by mechanical ball milling, and the organic ligand catalyst directly converts a carbonaceous raw material into a graphene material under the medium temperature condition of 700-1000 ℃, so that the yield of the graphene reaches 40-50%; and the catalyst metal component is converted into a catalyst again for repeated use after being recovered; the process has the advantages of relatively mild reaction conditions, low production cost and environment-friendly process, and provides a feasible technical scheme for macro, low-cost and sustainable preparation of graphene.
In order to achieve the purpose of the invention, the invention is realized by the following technical scheme: the preparation method of the rice hull-based porous graphene comprises the following steps of:
firstly, preprocessing rice hulls, namely cleaning surface soil by using clean water, drying, crushing by using a crusher, and sieving and storing to obtain rice hull powder;
step two, mixing materials, namely adding rice hull powder and a catalyst into a ball mill for ball milling and mixing to obtain mixed powder;
step three, carrying out graphene treatment, namely placing the obtained mixed powder in an atmosphere furnace, and carrying out catalytic graphene treatment under the condition of introducing inert gas to protect the atmosphere to obtain a graphene-containing product;
step four, acid washing treatment, namely sequentially treating graphene-containing products obtained by catalytic pyrolysis by adopting oxalic acid tetraacetic acid and deionized water until the pH value is neutral, and drying to obtain rice hull-based porous graphene;
and fifthly, recovering, namely adjusting the pH value of the ethylenediamine tetraacetate solution obtained after the acid washing reaction in the step four to 6-8, then carrying out distillation concentration, adding an ethanol solution into the concentrated solution, and filtering to obtain the crystalline ethylenediamine tetraacetate catalyst.
The further improvement is that: and in the first step, when the rice hull powder is dried, the rice hull powder is dried for 12 hours at the temperature of 80-120 ℃ to ensure that the water content of the raw materials is less than 5 percent, and after the rice hull powder is dried, the rice hull powder is crushed and sieved by using a 200-mesh screen, and the unqualified rice hull powder is continuously returned to a crusher to be crushed and sieved repeatedly.
The further improvement is that: the catalyst in the second step is one or a mixture of more than one of ferric ethylenediamine tetraacetate, cobalt ethylenediamine tetraacetate, nickel ethylenediamine tetraacetate and manganese ethylenediamine tetraacetate, and the mixing mass ratio of the rice hull powder to the catalyst is 0.25-3:1, preferably 0.5-2.5:1.
The further improvement is that: in the second step, the ball-milling mixing time is 0.5-8.0 h, preferably 1-4 h, wherein the ball-material ratio is 8:1-2:1, preferably 4:1-2:1.
The further improvement is that: the temperature of the catalytic graphitization process in the step three is 700-1000 ℃, preferably 800-950 ℃, the heating speed is controlled to be 1-15 ℃/min, preferably 1-10 ℃/min, the heat preservation time is 0.5-3 h, and nitrogen is introduced as protective gas in the process.
The further improvement is that: the carbon content of the rice hull-based porous graphene prepared in the fourth step is 96% -98%; the concentration of the ethanol solution added in the step five is 95-99%.
The application of rice hull-based porous graphene in the production of conductive agents, heat conductive agents, material reinforcing auxiliary products and materials.
The beneficial effects of the invention are as follows: according to the invention, the organic catalyst and the carbon source are mixed by mechanical ball milling, the organic ligand catalyst directly converts the carbonaceous raw material into the graphene material under the mild condition of 700-1000 ℃, and the catalyst metal component is recycled and then converted into the catalyst for repeated use, so that the yield of the graphene product reaches 40-50%; the process has the advantages of relatively mild reaction conditions, reusable catalyst and low production cost;
and the process is environment-friendly, and a feasible technical scheme is provided for macro, low-cost and sustainable preparation of graphene.
Drawings
FIG. 1 is a flow chart of the preparation method of example 1 of the present invention.
FIG. 2 is a Raman spectrum of a graphene product of examples 2-5 of the present invention.
Fig. 3 is an XRD pattern of the graphene product of example 5 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following examples, which are only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
According to the embodiment shown in fig. 1, the preparation method of the rice hull-based porous graphene is provided, and comprises the following steps:
firstly, preprocessing rice hulls, namely cleaning the collected waste rice hulls into biomass raw materials by using clean water, then placing the raw materials in an environment of 80-120 ℃ for drying for 12 hours to ensure that the water content of the raw materials is less than 5%, and then sieving and storing the raw materials by using a 200-mesh screen after crushing by using a crusher to obtain rice hull powder;
wherein, the unqualified rice hull powder is continuously returned to the pulverizer to be repeatedly pulverized and sieved.
Mixing materials, namely adding rice hull powder and a catalyst into a ball mill for ball milling and mixing to obtain mixed powder, wherein the mixing mass ratio of the rice hull powder to the catalyst is 0.5-2.5:1;
wherein the catalyst is one or a mixture of more of ferric ethylenediamine tetraacetate, cobalt ethylenediamine tetraacetate, nickel ethylenediamine tetraacetate and manganese ethylenediamine tetraacetate;
ball-milling is carried out for 0.5-8.0 h with the ball-material ratio of 4:1-2:1.
Step three, carrying out graphene treatment, namely placing the obtained mixed powder in an atmosphere furnace, catalyzing the graphene under the condition of introducing nitrogen as a protective gas and at the temperature of 800-950 ℃, controlling the heating speed to be 1-10 ℃/min, and carrying out pyrolysis calcination for 0.5-3 h to obtain a graphene-containing product;
step four, acid washing treatment, namely sequentially treating graphene-containing products obtained by catalytic pyrolysis by adopting oxalic acid tetraacetic acid and deionized water until the pH value is neutral, and drying to obtain rice hull-based porous graphene, wherein the carbon content of the rice hull-based porous graphene is 96% -98%;
and fifthly, recycling, namely adjusting the pH value of the ethylenediamine tetraacetate solution obtained after the acid washing reaction in the step four to 6-8, then carrying out distillation concentration, adding 95% -99% ethanol solution into the concentrated solution for reaction, and filtering to obtain the crystalline ethylenediamine tetraacetate catalyst.
Example 2
The example provides a preparation process and measurement of rice hull-based porous graphene, firstly, 1.8g of ferric ethylenediamine tetraacetate and 1.0g of rice hull carbon powder (100 meshes) are put into a 50ml PTFE tank, and ball-milled in a ball mill. The grinding time is set to be 1.0h, and the mass ratio of agate balls to rice hull carbon powder is 4:1. the ball-milled product was placed in an atmosphere furnace in a closed nitrogen atmosphere. Heating from 25 ℃ to 600 ℃ at a rate of 10 ℃/min, then heating to 750 ℃ at a heating rate of 2 ℃/min, and maintaining at that temperature for 3.0h. Cooling the product to room temperature, and under the action of ultrasound, removing the stoneThe graphene product was reacted with 1.0M ethylenediamine tetraacetic acid (10 ml) at 60℃for 2.0h, then allowed to stand at room temperature overnight, then washed with 20wt% aqueous ethanol. Finally drying for 12h at 80 ℃ to obtain rice husk-based graphene (ID/IG approximately equal to 0.38), and measuring the specific surface area of the rice husk-based graphene to be 258.5m 2 g -1 The yield thereof was found to be 46%.
Example 3
The example provides a preparation process and measurement of rice hull-based porous graphene, 2.2g of manganese ethylenediamine tetraacetate and 1.0g of rice hull carbon powder (100 meshes) are placed in a 50ml PTFE tank, and ball-milled in a ball mill. The grinding time is set to 2.0h, and the mass ratio of agate balls to rice hull carbon powder is 3:1. the ball-milled product was placed in an atmosphere furnace in a closed nitrogen atmosphere. Heating from 25 ℃ to 400 ℃ at a rate of 10 ℃/min, then heating to 950 ℃ at a heating rate of 2 ℃/min, and maintaining at that temperature for 1.0h. After cooling the product to room temperature, the graphene product was reacted with 1.0M ethylenediamine tetraacetic acid (10 ml) at 60 ℃ for 2.0h under the action of ultrasound, then allowed to stand at room temperature overnight, and then washed with 20wt% aqueous ethanol. Finally, the graphene (ID/IG. Apprxeq. 0.35) was obtained by drying at 80℃for 12 hours, with a specific surface area of 640.8m2g-1 and a yield of 44%.
Example 4
The present example provides a preparation process and measurement of rice hull-based porous graphene, 1.5g of cobalt ethylenediamine tetraacetate and 1.0g of rice hull carbon powder (100 mesh) were put into a 50ml PTFE tank, and ball-milled in a ball mill. The grinding time is set to be 4.0h, and the mass ratio of agate balls to rice hull carbon powder is 4:1. the ball-milled product was placed in an atmosphere furnace in a closed nitrogen atmosphere. Heating from 25 ℃ to 400 ℃ at a rate of 8 ℃/min, then heating to 850 ℃ at a heating rate of 2 ℃/min, and maintaining at that temperature for 1.0h. After cooling the product to room temperature, the graphene product was reacted with 1.0M ethylenediamine tetraacetic acid (10 ml) at 60 ℃ for 2.0h under the action of ultrasound, then allowed to stand at room temperature overnight, and then washed with 20wt% aqueous ethanol. Finally drying at 80deg.C for 12 hr to obtain graphene (ID/IG about 0.45) 0.48g with specific surface area of 734.5m 2 g -1 The yield thereof was found to be 48%.
Example 5
The present example provides a preparation process and measurement of rice hull-based porous graphene, 2.5g of nickel ethylenediamine tetraacetate and 1.0g of rice hull carbon powder (100 mesh) were put into a 50ml PTFE tank, and ball-milled in a ball mill. The grinding time is set to be 4.0h, and the mass ratio of agate balls to rice hull carbon powder is 4:1. the ball-milled product was placed in an atmosphere furnace in a closed nitrogen atmosphere. Heating from 25 ℃ to 500 ℃ at a rate of 10 ℃/min, then heating to 1000 ℃ at a heating rate of 2 ℃/min, and maintaining at that temperature for 1.0h. After cooling the product to room temperature, the graphene product was reacted with 1.0M ethylenediamine tetraacetic acid (10 ml) at 60 ℃ for 2.0h under the action of ultrasound, then allowed to stand at room temperature overnight, and then washed with 20wt% aqueous ethanol. Finally, the graphene (ID/IG. Apprxeq. 0.28) is obtained by drying at 80 ℃ for 12 hours, wherein the specific surface area is 1187.2m2g-1, and the yield is 45%.
Determining the performance index of the products of the examples 2-5 to be moisture content less than or equal to 1.50 according to a graphene chemical analysis method; volatile component less than 0.50-1.00; ash% <2.0; sulfur% <0.50; acid soluble iron% <1.00, specific data are given in Table 1 below
Table 1 BET-related data tables for graphene products of examples 2-5
The method for measuring the technical parameters and product indexes in the above examples 2 to 5 is as follows:
the structural confirmation of the graphene product was detected by Raman spectroscopy.
Graphene product yield = obtained graphene product mass/carbonaceous feedstock mass x 100%;
the grapheme carbon content is detected according to the method provided by the graphite chemical analysis method.
The Raman spectra of the graphene products of examples 2-5 are shown in figure 2 of the accompanying specification, and the XRD pattern of the graphene product of example 5 is shown in figure 3 of the accompanying specification.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the rice hull-based porous graphene is characterized by comprising the following steps of:
firstly, preprocessing rice hulls, namely cleaning surface soil by using clean water, drying the rice hulls by using collected waste rice hulls as biomass raw materials, crushing the rice hulls by using a crusher, and sieving and preserving the crushed rice hulls to obtain rice hull powder;
step two, mixing materials, namely adding rice hull powder and a catalyst into a ball mill for ball milling and mixing to obtain mixed powder;
step three, carrying out graphene treatment, namely placing the obtained mixed powder in an atmosphere furnace, and carrying out catalytic pyrolysis under the condition of introducing inert gas to protect the atmosphere to obtain a graphene-containing product;
step four, acid washing treatment, namely sequentially treating graphene-containing products obtained by catalytic pyrolysis by adopting oxalic acid tetraacetic acid and deionized water until the pH value is neutral, and drying to obtain rice hull-based porous graphene;
and fifthly, recovering, namely adjusting the pH value of the ethylenediamine tetraacetate solution obtained after the acid washing reaction in the step four to 6-8, then carrying out distillation concentration, adding an ethanol solution into the concentrated solution, and filtering to obtain the crystalline ethylenediamine tetraacetate catalyst.
2. The method for preparing rice hull-based porous graphene according to claim 1, wherein the method comprises the following steps: and in the first step, drying overnight at 80-120 ℃ for 12 hours to ensure that the water content of the raw materials is less than 5%, sieving by using a 200-mesh sieve when sieving after drying, and continuously returning unqualified rice hull powder to a pulverizer for repeatedly pulverizing and sieving.
3. The method for preparing rice hull-based porous graphene according to claim 1, wherein the method comprises the following steps: the catalyst in the second step is one or a mixture of more than one of ferric ethylenediamine tetraacetate, cobalt ethylenediamine tetraacetate, nickel ethylenediamine tetraacetate and manganese ethylenediamine tetraacetate, and the mixing mass ratio of the rice hull powder to the catalyst is 0.25-3:1.
4. The method for preparing rice hull-based porous graphene according to claim 1, wherein the method comprises the following steps: ball-milling in the second step, wherein the ball-material ratio is 8:1-2:1, and the ball-milling mixing time is 0.5-8.0 h.
5. The method for preparing rice hull-based porous graphene according to claim 1, wherein the method comprises the following steps: the temperature of the catalytic graphitization process in the step three is 700-1000 ℃, the heating speed is controlled to be 1-15 ℃/min, the heat preservation time is 0.5-3 h, and nitrogen is introduced as protective gas in the process.
6. The method for preparing rice hull-based porous graphene according to claim 1, wherein the method comprises the following steps: the carbon content of the rice hull-based porous graphene prepared in the fourth step is 96% -98%; the concentration of the ethanol solution added in the step five is 95-99%.
7. The method for preparing rice hull-based porous graphene according to claim 1, wherein the obtained rice hull-based porous graphene is applied to the production of conductive agents, heat conductive agents, material reinforcing auxiliary products and materials.
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| CN113149000A (en) * | 2021-05-12 | 2021-07-23 | 长春工业大学 | Preparation method of rice husk carbon-based graphitized carbon material |
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