CN112194125A - Normal pressure low temperature expansion method for natural flake graphite - Google Patents
Normal pressure low temperature expansion method for natural flake graphite Download PDFInfo
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- CN112194125A CN112194125A CN202011130167.1A CN202011130167A CN112194125A CN 112194125 A CN112194125 A CN 112194125A CN 202011130167 A CN202011130167 A CN 202011130167A CN 112194125 A CN112194125 A CN 112194125A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
Abstract
The invention provides a natural crystalline flake graphite expansion method with simple and convenient process and low energy consumption, which directly obtains expanded graphite with the expansion volume of not less than 300mL/g at normal pressure and low temperature (less than 100 ℃), and belongs to the technical field of inorganic nonmetallic materials. The method comprises the following specific steps: 1) placing natural crystalline flake graphite of 50-325 meshes in a beaker, adding an intercalation agent and an auxiliary agent, and uniformly stirring by using a glass rod; 2) dropwise adding an oxidant solution, standing, heating to 55-95 ℃, preserving heat for 0.5-3 h, cooling, and washing until filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g. The method has the advantages of less chemical reagent consumption, easy treatment of waste liquid, low energy consumption and capability of realizing continuous large-scale production.
Description
Technical Field
The invention provides a natural crystalline flake graphite expansion method with simple and convenient process and low energy consumption, which directly obtains expanded graphite with the expansion volume of not less than 300mL/g at normal pressure and low temperature (less than 100 ℃), and belongs to the technical field of inorganic nonmetallic materials.
Background
The graphite is a hexagonal plane layered structure formed by carbon elements in a three-dimensional space, and carbon atoms in the layer are combined in a covalent bond mode, so that the binding force is strong; the layers are bonded by van der waals force, and the spacing is large and the bonding force is weak. Under certain conditions, small molecule chemical substances (acids, alkali metals, salts, etc.) can enter Graphite interlayers to combine with carbon atoms to form Graphite Interlayer Compounds (GIC). When the interlayer compound is heated to a certain temperature, the interlayer compound can be instantaneously decomposed to generate a large amount of gas, so that Graphite interlayers are Expanded into a new substance, namely Expanded Graphite (EG). Compared with natural graphite, the expanded graphite has the characteristics of loose structure, porosity, reduced density, large volume and surface area, high surface energy and the like, thereby showing a plurality of excellent performances such as high and low temperature resistance, corrosion resistance, self lubrication, high adsorption capacity, compression resilience, sealing property and the like, being one of the products with the most acknowledged research values and application prospects in carbon materials, being widely applied in the fields of environment, energy, catalysis, medicine, machinery, military and the like, and being capable of being prepared into heat-insulating materials, sound-insulating materials, heat-radiating materials, flame-retardant fireproof materials and the like.
The traditional preparation method of expanded graphite takes natural crystalline flake graphite as a raw material, and the natural crystalline flake graphite is firstly oxidized to prepare the expandable graphite and then the expandable graphite is obtained through expansion treatment. The preparation method can be divided into a chemical oxidation method, an electrochemical method, a gas phase diffusion method, a melting method and the like according to the intercalation mode. The preparation method can be divided into a high-temperature electric furnace method, a microwave method, an explosion method and the like according to different puffing modes. The chemical oxidation method is the most widely and mature expanded graphite preparation method at present due to the advantages of low equipment requirement, simple operation and the like. Chemical treatment and high temperature heating are the main causes of volume expansion of graphite. After the graphite is chemically treated, a new compound is formed between graphite layers to realize the first expansion. When the interlayer compound is heated at high temperature, the expansion force generated by the vaporization of the interlayer compound is larger than the molecular force of interlayer combination, so that the interlayer distance is further enlarged, and the second expansion is realized. High temperature expansion is a traditional method for preparing expanded graphite, and is characterized in that a reaction vessel is preheated at high temperature and taken out, a certain amount of graphite intercalation compound is added into the reaction vessel, and then the reaction vessel is rapidly heated at high temperature, so that the graphite intercalation compound is expanded in a short time due to the sharp high temperature. In addition, as the graphite has good conductivity, strong eddy current is generated in the graphite under microwave irradiation, so that the graphite is rapidly heated, and the microwave heating is more uniform, so that the graphite can be uniformly expanded, and the method is more convenient and efficient in the aspects of equipment, operation and the like compared with a high-temperature expansion method.
However, the above methods have the disadvantages of high energy consumption, small expansion volume, large environmental pollution and the like, and cause serious waste of resources and energy. In order to respond to the actual requirements of low energy consumption and environmental protection, the development and application of expanded graphite products are expanded, and the search for a graphite expansion method at normal pressure and low temperature becomes the aim of the broad researchers.
Graphite is a mineral resource with strategic advantages in China, the reserves of the graphite resource are abundant in China, the geological causes of the graphite are comprehensive, and the types of graphite ores are prepared. The China is the export country with the largest graphite in the world and is also a great import country of graphite products. The total annual graphite yield in the world in 2018 is 93 ten thousand tons, wherein the yield in China is 63 ten thousand tons, which accounts for 67.8 percent, and is much higher than the yield of the second Brazil, which is 9.5 ten thousand tons. Different from other inorganic non-metal resource industries, the downstream industrial chain of graphite is very rich, the requirements of hundreds of products on the properties of graphite raw materials are thousands of different, and the demand on graphite is very large. Aiming at the downstream differentiated graphite industry requirements, a new graphite raw material quality grading system and the corresponding relation between different graphite ore types and different deep-processed products are established, and the high-value utilization of graphite resources is guided. Because high-added-value products of graphite are generally subjected to high-purity and expansion treatment, development of a new natural graphite expansion technology with simple process, convenience in operation and low energy consumption is imperative. The implementation of the method has important theoretical and practical significance for promoting the high added value application of the graphite resource. Meanwhile, the structure adjustment of the traditional graphite industry can be promoted, the application research and development of the expanded graphite can be enhanced and deepened, and the resource advantages and characteristics of China can be fully exerted.
Disclosure of Invention
The invention combines the structural characteristics and the expansion mechanism of graphite layers, selects the intercalation agent, the auxiliary agent and the oxidant, realizes the high volume multiplying power expansion of the natural crystalline flake graphite under normal pressure and low temperature, synchronously completes the chemical treatment and the expansion, simplifies the process flow and avoids the high consumption of energy by high temperature expansion.
The invention provides a normal-pressure low-temperature expansion method of natural crystalline flake graphite, which basically considers that an intercalation compound which can be rapidly decomposed under normal pressure and low temperature is formed by combining the interlaminar structure characteristics and the expansion mechanism of the graphite and preferably selecting an intercalation agent and an auxiliary agent. Thereby realizing the high volume multiplying power expansion of the natural crystalline flake graphite under normal pressure and low temperature.
The invention provides a normal-pressure low-temperature expansion method of natural crystalline flake graphite, which adopts the following main technical scheme:
1) placing natural crystalline flake graphite of 50-325 meshes in a beaker, adding an intercalation agent and an auxiliary agent, and uniformly stirring by using a glass rod;
2) dropwise adding an oxidant solution, standing, heating to 55-95 ℃, preserving heat for 0.5-3 h, cooling, and washing until filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
In the technical scheme of the invention, the intercalation agent used in the step 1) is one or a combination of more of concentrated sulfuric acid, concentrated phosphoric acid, concentrated nitric acid, perchloric acid, perbromic acid, acetic acid, citric acid and oxalic acid, and the ratio of the volume of the intercalation agent to the mass of the flake graphite is (10-70) (mL):1 (g); the assistant is one or a combination of more of sulfate, persulfate, phosphate, pyrophosphate, polyphosphate, nitrate, nitrite, perchlorate, perbromate, acetate, citrate and oxalate, and the mass ratio of the assistant to the scale graphite is (1-10) (g):1 (g).
In the technical scheme of the invention, the oxidant used in the step 2) is one or a combination of more of hydrogen peroxide, concentrated hydrochloric acid, concentrated nitric acid, nitrate, permanganate, chlorate, perchlorate, ferrate, perchlorate, dibenzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, peracetic acid, dicumyl peroxide and di-tert-butyl peroxide, the ratio of the volume of the oxidant to the mass of the crystalline flake graphite is (1-7) (mL):1(g), and the concentration of the oxidant is 5-10 mol/L.
In the technical scheme of the invention, the purity of the used chemical reagent is not lower than that of analytical purity.
The expansion volume of the expanded graphite obtained by the normal-pressure low-temperature expansion method of the natural crystalline flake graphite is not less than 300 mL/g. The method provided by the invention has the advantages of simple process, convenient operation, less chemical reagent consumption, easy treatment of waste liquid and less energy consumption, and can realize continuous large-scale production.
Drawings
FIG. 1 is a Raman spectrum of natural graphite and expanded graphite;
fig. 2 is an SEM photograph of expanded graphite at different magnifications.
Detailed Description
Example 1
1) Weighing 0.3g of natural crystalline flake graphite with the particle size of 50 meshes, placing the natural crystalline flake graphite in a beaker, adding 15mL of acetic acid and 1.5g of sodium nitrate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 1.5mL of 10mol/L nitric acid solution, standing, heating to 55 ℃, preserving heat for 3h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expanded volume not less than 300 mL/g.
Example 2
1) Weighing 0.3g of natural crystalline flake graphite with the particle size of 200 meshes, placing the natural crystalline flake graphite in a beaker, adding 20mL of concentrated sulfuric acid and 1.5g of sodium persulfate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 1mL of 9.8mol/L hydrogen peroxide solution, standing, heating to 75 ℃, preserving heat for 0.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 3
1) Weighing 0.3g of natural crystalline flake graphite with the size of 300 meshes, placing the natural crystalline flake graphite in a beaker, adding 10mL of concentrated sulfuric acid, 10mL of concentrated phosphoric acid and 2g of ammonium polyphosphate, and uniformly stirring by using a glass rod; 2) dropwise adding 1mL of 5mol/L potassium permanganate and potassium perbromite solution respectively, standing, heating to 65 ℃, preserving heat for 1h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 4
1) Weighing 0.3g of 250-mesh natural crystalline flake graphite, placing the natural crystalline flake graphite in a beaker, adding 12mL of citric acid and 2.5g of sodium nitrate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 0.5mL of 7.5mol/L dicumyl peroxide solution and di-tert-butyl peroxide solution respectively, standing, heating to 95 ℃, preserving heat for 1.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expanded volume not less than 300 mL/g.
Example 5
1) Weighing 0.3g of 325-mesh natural crystalline flake graphite, placing the natural crystalline flake graphite in a beaker, adding 18mL of perchloric acid and 1g of sodium perchlorate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 2mL of 7mol/L peracetic acid solution, standing, heating to 65 ℃, preserving heat for 2.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 6
1) Weighing 0.3g of natural crystalline flake graphite with 150 meshes, placing the natural crystalline flake graphite in a beaker, adding 15mL of high bromic acid and 1g of sodium nitrite, and uniformly stirring by using a glass rod; 2) dropwise adding 1mL of 9.8mol/L hydrogen peroxide solution, standing, heating to 85 ℃, preserving heat for 3h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 7
1) Weighing 0.3g of natural crystalline flake graphite with a particle size of 50 meshes, placing the natural crystalline flake graphite in a beaker, adding 21mL of oxalic acid and 3g of ammonium pyrophosphate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 1mL of 5mol/L sodium perchlorate and sodium dichromate solution respectively, standing, heating to 65 ℃, preserving heat for 2h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 8
1) Weighing 0.3g of natural crystalline flake graphite with the particle size of 200 meshes, placing the natural crystalline flake graphite in a beaker, adding 20mL of concentrated phosphoric acid and 2g of ammonium polyphosphate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 1mL of 9.8mol/L hydrogen peroxide solution, standing, heating to 95 ℃, preserving heat for 2.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 9
1) Weighing 0.3g of 325-mesh natural crystalline flake graphite, placing the natural crystalline flake graphite in a beaker, adding 21mL of concentrated sulfuric acid and 3g of sodium sulfate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 2mL of 10mol/L potassium ferrate solution, standing, heating to 75 ℃, preserving heat for 1.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expanded volume not less than 300 mL/g.
Example 10
1) Weighing 0.3g of 250-mesh natural crystalline flake graphite, placing the natural crystalline flake graphite in a beaker, adding 5mL of acetic acid, 5mL of citric acid and 1.5g of sodium citrate, and uniformly stirring the mixture by using a glass rod; 2) dropwise adding 1.5mL of 7mol/L dicumyl peroxide solution, standing, heating to 65 ℃, preserving heat for 0.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 11
1) Weighing 0.3g of natural crystalline flake graphite with 150 meshes, placing the natural crystalline flake graphite in a beaker, adding 10mL of concentrated phosphoric acid, 8mL of perbromic acid and 1.8g of ammonium oxalate, and stirring uniformly by using a glass rod; 2) dropwise adding 2mL of 10mol/L nitric acid solution, standing, heating to 95 ℃, preserving heat for 0.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Example 12
1) Weighing 0.3g of 325-mesh natural crystalline flake graphite, placing the natural crystalline flake graphite in a beaker, adding 20mL of concentrated nitric acid and 3g of sodium nitrite, and uniformly stirring by using a glass rod; 2) dropwise adding 2mL of 8mol/L dibenzoyl peroxide solution, standing, heating to 75 ℃, preserving heat for 2.5h, cooling, and washing until the filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
Claims (3)
1. The invention aims to develop a natural crystalline flake graphite expansion method with simple and convenient process, low energy consumption and high expansion volume, and the method can obtain expanded graphite with the expansion volume not less than 300mL/g under normal pressure and low temperature (<100 ℃), and is characterized by comprising the following process steps:
1) placing natural crystalline flake graphite of 50-325 meshes in a beaker, adding an intercalation agent and an auxiliary agent, and uniformly stirring by using a glass rod;
2) dropwise adding an oxidant solution, standing, heating to 55-95 ℃, preserving heat for 0.5-3 h, cooling, and washing until filtrate is neutral to obtain the expanded graphite with the expansion volume not less than 300 mL/g.
2. The normal-pressure low-temperature expansion method of natural crystalline flake graphite according to claim 1, characterized in that the intercalation agent used in step 1) is one or a combination of more of concentrated sulfuric acid, concentrated phosphoric acid, concentrated nitric acid, perchloric acid, perbromic acid, acetic acid, citric acid and oxalic acid, and the ratio of the volume of the intercalation agent to the mass of the crystalline flake graphite is (10-70) (mL):1 (g); the assistant is one or a combination of more of sulfate, persulfate, phosphate, pyrophosphate, polyphosphate, nitrate, nitrite, perchlorate, perbromate, acetate, citrate and oxalate, and the mass ratio of the assistant to the scale graphite is (1-10) (g):1 (g).
3. The normal-pressure low-temperature expansion method of natural crystalline flake graphite according to claim 1, wherein an oxidant used in the step 2) is one or a combination of more of hydrogen peroxide, concentrated hydrochloric acid, concentrated nitric acid, nitrate, permanganate, chlorate, perchlorate, ferrate, perchlorate, dibenzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, peracetic acid, dicumyl peroxide and di-tert-butyl peroxide, the ratio of the volume of the oxidant to the mass of the crystalline flake graphite is (1-7) (mL):1(g), and the concentration of the oxidant is 5-10 mol/L.
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Cited By (5)
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| CN113502146A (en) * | 2021-07-09 | 2021-10-15 | 西南石油大学 | Preparation and application of expansion type plugging material |
| CN113735111A (en) * | 2021-10-08 | 2021-12-03 | 黑龙江哈工石墨科技有限公司 | Preparation process method of low-sulfur expandable graphite |
| CN113753886A (en) * | 2021-08-19 | 2021-12-07 | 华南理工大学 | Expanded graphite and preparation method and application thereof |
| CN115028388A (en) * | 2022-04-27 | 2022-09-09 | 佛山科学技术学院 | Method for preparing high polymer material/expanded graphite composite material by non-covalent modification of expanded graphite by using ionic surfactant |
| CN115676819A (en) * | 2021-07-21 | 2023-02-03 | 比亚迪股份有限公司 | Graphite material preparation method, graphite material and power battery |
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