CN102275904A - Method of preparing high-purity graphite by using chemical liquid-phase method - Google Patents
Method of preparing high-purity graphite by using chemical liquid-phase method Download PDFInfo
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Abstract
The invention discloses a method of preparing high-purity graphite by using a chemical liquid-phase method, belonging to the field of preparation of high-purity graphite and aiming at providing a preparation method of the high-purity graphite. The method disclosed by the invention comprises the following steps of: 1. adding sodium hydroxide into powdered graphite, drying after fully stirring, carrying out heat preservation at a high temperature, and cooling to the room temperature; 2. washing by using industrial water, and filtering; 3. carrying out acid leaching by using diluted hydrochloric acid, and then washing by using distilled water; and 4. adding into a HF (hydrogen fluoride) solution, heating till spare HF (hydrogen fluoride) volatilizes, and then drying after filtering to obtain the high-purity graphite. The method has the advantages that the process flow is simple, the amount of water for treatment is greatly reduced, production conditions are good, hydrofluoric acid can be effectively recycled, the environmental pollution is avoided, and the carbon content of the graphite reaches production indexes of a hydrofluoric acid method; and compared with the traditional high-temperature purifying method and the chloridizing roasting method, the method in the invention has the advantages of fewer required equipment and investment, good production conditions, no pollution and good purification effect; and the purity of the prepared graphite can reach more than 99.93% theoretically.
Description
Technical field
The invention belongs to the high purity graphite preparation field.
Background technology
Graphite is a kind of high energy crystal carbon material, because of characteristics such as its particular structure and conduction, heat conduction, lubricated, high temperature resistant, stable chemical performance, make it in high performance material, have higher using value, be widely used in fields such as metallurgy, machinery, environmental protection, chemical industry, fire-resistant, electronics, medicine, military project and aerospace, become modern industry and height, the requisite non-metallic material of new, sharp technical development.
High purity graphite requires C 〉=99.9%, and purposes is very widely arranged in industry.
There are following several preparation methods in the production technique of high purity graphite at present: flotation, high temperature purification method and chemical purification are arranged.Flotation process is to utilize the natural hydrophobicity of graphite with flotability it to be separated with impurity, but the graphite grade of purifying is lower, generally the first step of purifying as graphite.High temperature purification is owned by France in the physical purification method, requires temperature to be controlled at 2300～3000 ℃, stoichiometric number hour under the condition of secluding air, and apparatus expensive, the electric heating heating technique is strict, and energy consumption is bigger.The chemical purification method comprises chlorinating roasting, alkali acid system and hydrofluoric acid method.Alkali acid system and hydrofluoric acid method of purification belong to wet purification, and chlorinating roasting belongs to dry purification.Chlorinating roasting is not high to temperature requirement, be lower than the high temperature purification method in facility investment, but chlorine is poisonous, and tail gas is difficult, and is seriously polluted, and refining effect is not as alkali acid system and hydrofluoric acid method.The hydrofluoric acid method can make the graphite carbon content reach more than 99.9%, have the minimum advantage of one-time investment, but HF is volatile, and severe toxicity and severe corrosive are arranged, and is unwell to suitability for industrialized production.The alkali acid system can make the graphite carbon content reach more than 98%, and it is low to have a production cost, and one-time investment is less, and it is reliable to improve index, the purifying technique characteristic of simple.
Summary of the invention
The method of utilizing chemical liquid phase reaction to prepare high purity graphite in order to provide is provided.
The method that the present invention utilizes chemical liquid phase reaction to prepare high purity graphite realizes by following step:
One, in powdered graphite, add sodium hydroxide, add water then, the mass ratio of powdered graphite and sodium hydroxide 1: 1～1.5, powdered graphite is 1: 2～3 with the quality ratio, dry the abundant back of stirring, and is incubated 12 hours down at 380～420 ℃ then, is cooled to room temperature;
Two, the powdered graphite after step 1 is handled is blunged with industry and was cleaned 1 hour, filters, and wherein, the process water consumption equals the total mass (graphite purity reaches 98%) of graphite and sodium hydroxide;
Three, the powdered graphite after step 2 is handled is with dilute hydrochloric acid acidleach 2～4h, and the described powdered graphite mass ratio of dilute hydrochloric acid and step 1 is that 0.8～1.5: 1 (the graphite volume is bigger, can carry out in batches; Contain sodium-chlor, silicic acid precipitation, aluminum chloride, iron(ic) chloride, calcium chloride, Repone K etc. in the solution this moment), clean (adopt distilled water to clean in order not introduce impurity, purity can reach more than 99%) 3～4 times with distilled water again;
Four, to add mass concentration be in 2%～5% the HF solution to the powdered graphite after step 3 is handled, the mass ratio of HF solution and the described powdered graphite of step 1 is 0.3～0.8: 1, be heated to 80 ℃, treat that the whole volatilizations of HF stop heating, filter the back then and dry under 400 ℃ of conditions; Promptly obtain high purity graphite.
Natural graphite is comparatively serious at oxidation weight loss more than 430 ℃; and the fusing point of caustic alkali is 318.4 ℃; even impurity rapid reactions such as heating abundant fusion of caustic alkali and graphite companion graphite silicon, aluminium under 380～420 ℃ of temperature; graphite degree of oxidation under this temperature is less; weightless less, do not need gas shield.
The inventive method adopts the process water stirring and washing, do not need to waste a large amount of service waters, help the recovery of sodium hydroxide, after industry is filtered, contain a certain amount of NaOH, water glass, sodium aluminate, ironic hydroxide, magnesium oxide, calcium oxide, sodium oxide, potassium oxide in the graphite, needn't clean to about PH=7, just in the aqueous solution of fixed amount, stir 1 hour.
The present invention adds the HF solution-treated after adopting existing dilute hydrochloric acid acidleach: the metal oxide of graphite companion graphite mineral is removed in the dilute hydrochloric acid acidleach, as magnesium oxide, ferric oxide, calcium oxide, sodium oxide etc.Add hydrofluoric acid, purpose is removed unnecessary silicon, aluminum oxide and sedimentary silicic acid, and this kind technology contrasts traditional hydrofluoric acid purification advantage and is that the hydrofluoric acid consumption is less, pollute lower, graphite resulting product purity is higher.The HF consumption is low, and the very low industry of consumption can be ignored the negative impact of HF; Graphite solution does not contain HF through the no remaining HF of heating in the waste water; Gaseous state HF handles and is easier to; This process water solution is not handled, and recycles, and step 4 is dried (iron(ic) chloride and aluminum chloride volatilization that purpose makes synusia) under 400 ℃ of conditions.
If adopt hydrofluoric acid and hydrochloric acid to handle jointly, hydrofluoric acid and above several oxide compound generate the fluorochemical that is refractory to water, and graphite and impurity are not easily separated.
Compare with traditional chemical alkali acid system, technical process is simple, and the water treatment amount greatly reduces; Compare with traditional chemical hydrofluoric acid method, working condition is good, and hydrofluoric acid can effectively be recycled, non-environmental-pollution, and make the graphite carbon content reach the productive capacity of hydrofluoric acid method; Compare with traditional high temperature purification method and chlorinating roasting, equipment requirements and less investment, working condition is good, and is pollution-free and refining effect good; The graphite purity of preparation can reach more than 99.93% in theory.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for utilizing chemical liquid phase reaction to prepare high purity graphite in the present embodiment realizes by following step:
One, in powdered graphite, adds sodium hydroxide, add water then, the mass ratio of powdered graphite and sodium hydroxide 1: 1～1.5, powdered graphite is 1: 2～3 with the quality ratio, dry the abundant back of stirring, and is incubated 12 hours down at 380～420 ℃ then, is cooled to the room temperature after-filtration;
Two, the powdered graphite after step 1 is handled is blunged with industry and was cleaned 1 hour, filters, and wherein, the process water consumption equals the total mass of graphite and sodium hydroxide;
Three, with the dilute hydrochloric acid acidleach 2～4h of the powdered graphite after the step 2 processing, the described powdered graphite mass ratio of dilute hydrochloric acid and step 1 is 0.8～1.5: 1, cleans 3～4 times with distilled water again;
Four, to add mass concentration be in 2%～5% the HF solution to the powdered graphite after step 3 is handled, the mass ratio of HF solution and the described powdered graphite of step 1 is 0.3～0.8: 1, be heated to 80 ℃, treat that the whole volatilizations of HF stop heating, filter the back then and dry under 400 ℃ of conditions; Promptly obtain high purity graphite.
Embodiment two: what present embodiment and embodiment one were different is: the mass ratio 1: 1.2～1.4 of described powdered graphite of step 1 and sodium hydroxide.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment and embodiment one were different is: the mass ratio of described powdered graphite of step 1 and sodium hydroxide 1: 1.3.Other step is identical with embodiment one with parameter.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the granularity of the described powdered graphite of step 1 is below 200 orders.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the described powdered graphite of step 1 is natural flake graphite breeze or nodularization graphite breeze.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: the described dilute hydrochloric acid mass concentration of step 3 is 10%～20%.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: the described powdered graphite mass ratio of described dilute hydrochloric acid of step 3 and step 1 is 1.0～1.4: 1.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment one to six is: the described powdered graphite mass ratio of described dilute hydrochloric acid of step 3 and step 1 is 1.2: 1.Other step is identical with one of embodiment one to six with parameter.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: the mass ratio of described HF solution of step 4 and the described powdered graphite of step 1 is 0.4～0.6: 1.Other step is identical with one of embodiment one to eight with parameter.
Embodiment ten: what present embodiment was different with one of embodiment one to eight is: the mass ratio of described HF solution of step 4 and the described powdered graphite of step 1 is 0.5: 1.Other step is identical with one of embodiment one to eight with parameter.
Embodiment 11: the method for utilizing chemical liquid phase reaction to prepare high purity graphite in the present embodiment realizes by following step:
One, adds 400g sodium hydroxide to 400g purity 82% (quality) natural flake graphite breeze, add 600g water then, be incubated 12 hours down at 400 ℃ then, be cooled to room temperature;
Two, the natural scale stone after the step 1 processing is used 800g process water stirring and washing 1 hour, filter (reclaim alkali 258.8g, consume alkali 141.2g);
Three, the natural scale stone mass concentration after step 2 is handled is 15% dilute hydrochloric acid acidleach 2h, again with distilled water cleaning 4 times;
Four, to add the 200g mass concentration be in 2% the HF solution, to be heated to 80 ℃ to the natural scale stone after step 3 is handled, treat HF all volatilization stop heating, filter the back then and under 400 ℃ of conditions, dry; Promptly obtain the 340.4g high purity graphite.
The purity that present embodiment makes high purity graphite is 99.93%, and the carbon rate of recovery is 93%.
Embodiment 11: the method for utilizing chemical liquid phase reaction to prepare high purity graphite in the present embodiment realizes by following step:
One, adds 450g sodium hydroxide to 400g purity 82% (quality) nodularization graphite breeze, add 900g water then, be incubated 12 hours down at 400 ℃ then, be cooled to room temperature;
Two, the nodularization graphite breeze after the step 1 processing is used 800g process water stirring and washing 1 hour, filter (reclaim alkali 338.5g, consume alkali 111.5g);
Three, the nodularization graphite breeze after step 2 is handled is 15% dilute hydrochloric acid acidleach 2h with the 600g mass concentration, again with distilled water cleaning 4 times;
Four, to add the 300g mass concentration be in 2% the HF solution, to be heated to 80 ℃ to the nodularization graphite breeze after step 3 is handled, treat HF all volatilization stop heating, filter the back then and under 400 ℃ of conditions, dry; Promptly obtain 360.2g 3 high purity graphites.
The purity 99.99% of the high purity graphite that present embodiment makes, the carbon rate of recovery are 96.3%.
Claims (10)
1. utilize chemical liquid phase reaction to prepare the method for high purity graphite, it is characterized in that the method for utilizing chemical liquid phase reaction to prepare high purity graphite realizes by following step:
One, in powdered graphite, add sodium hydroxide, add water then, the mass ratio of powdered graphite and sodium hydroxide 1: 1～1.5, powdered graphite is 1: 2～3 with the quality ratio, dry the abundant back of stirring, and is incubated 12 hours down at 380～420 ℃ then, is cooled to room temperature;
Two, the powdered graphite after step 1 is handled is blunged with industry and was cleaned 1 hour, filters, and wherein, the process water consumption equals the total mass of graphite and sodium hydroxide;
Three, with the dilute hydrochloric acid acidleach 2～4h of the powdered graphite after the step 2 processing, the described powdered graphite mass ratio of dilute hydrochloric acid and step 1 is 0.8～1.5: 1, cleans 3～4 times with distilled water again;
Four, to add mass concentration be in 2%～5% the HF solution to the powdered graphite after step 3 is handled, the mass ratio of HF solution and the described powdered graphite of step 1 is 0.3～0.8: 1, be heated to 80 ℃, treat that the whole volatilizations of HF stop heating, filter the back then and dry under 400 ℃ of conditions; Promptly obtain high purity graphite.
2. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 1 is characterized in that the mass ratio 1: 1.2～1.4 of described powdered graphite of step 1 and sodium hydroxide.
3. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 1 is characterized in that the mass ratio 1: 1.3 of described powdered graphite of step 1 and sodium hydroxide.
4. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 2, the granularity that it is characterized in that the described powdered graphite of step 1 is below 200 orders.
5. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 2 is characterized in that the described powdered graphite of step 1 is natural flake graphite breeze or nodularization graphite breeze.
6. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 4 is characterized in that the described dilute hydrochloric acid mass concentration of step 3 is 10%～20%.
7. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 6 is characterized in that the described powdered graphite mass ratio of described dilute hydrochloric acid of step 3 and step 1 is 1.0～1.4: 1.
8. the method for utilizing chemical liquid phase reaction to prepare high purity graphite according to claim 6 is characterized in that the described powdered graphite mass ratio of described dilute hydrochloric acid of step 3 and step 1 is 1.2: 1.
9. according to the described method of utilizing chemical liquid phase reaction to prepare high purity graphite of each claim among the claim 1-8, it is characterized in that the mass ratio of described HF solution of step 4 and the described powdered graphite of step 1 is 0.4～0.6: 1.
10. according to the described method of utilizing chemical liquid phase reaction to prepare high purity graphite of each claim among the claim 1-8, it is characterized in that the mass ratio of described HF solution of step 4 and the described powdered graphite of step 1 is 0.5: 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911374A (en) * | 2015-04-27 | 2015-09-16 | 安徽永杰铜业有限公司 | Copper smelting processing method |
| CN107462452A (en) * | 2017-09-25 | 2017-12-12 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method for determining crystalline flake graphite ore deposit particle size distribution characteristics |
| CN115159519A (en) * | 2022-06-08 | 2022-10-11 | 中国科学院过程工程研究所 | Method for purifying natural graphite by pressurization electrolysis |
| CN115215335A (en) * | 2022-08-31 | 2022-10-21 | 浙江碳一新能源有限责任公司 | Modified graphite and preparation method and application thereof |
| CN115321533A (en) * | 2022-08-31 | 2022-11-11 | 浙江碳一新能源有限责任公司 | Modified graphite negative electrode material and preparation method and application thereof |
| CN117374446A (en) * | 2023-12-04 | 2024-01-09 | 广州天赐高新材料股份有限公司 | Recycling method of graphite anode material of waste lithium ion battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911374A (en) * | 2015-04-27 | 2015-09-16 | 安徽永杰铜业有限公司 | Copper smelting processing method |
| CN107462452A (en) * | 2017-09-25 | 2017-12-12 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method for determining crystalline flake graphite ore deposit particle size distribution characteristics |
| CN107462452B (en) * | 2017-09-25 | 2020-07-07 | 苏州中材非金属矿工业设计研究院有限公司 | Method for measuring particle size distribution characteristics of flake graphite ore |
| CN115159519A (en) * | 2022-06-08 | 2022-10-11 | 中国科学院过程工程研究所 | Method for purifying natural graphite by pressurization electrolysis |
| CN115215335A (en) * | 2022-08-31 | 2022-10-21 | 浙江碳一新能源有限责任公司 | Modified graphite and preparation method and application thereof |
| CN115321533A (en) * | 2022-08-31 | 2022-11-11 | 浙江碳一新能源有限责任公司 | Modified graphite negative electrode material and preparation method and application thereof |
| CN115321533B (en) * | 2022-08-31 | 2024-09-10 | 碳一新能源集团有限责任公司 | Modified graphite negative electrode material and preparation method and application thereof |
| CN117374446A (en) * | 2023-12-04 | 2024-01-09 | 广州天赐高新材料股份有限公司 | Recycling method of graphite anode material of waste lithium ion battery |
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