CN104495803A - Purification method of natural microcrystalline graphite - Google Patents
Purification method of natural microcrystalline graphite Download PDFInfo
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- CN104495803A CN104495803A CN201410705623.9A CN201410705623A CN104495803A CN 104495803 A CN104495803 A CN 104495803A CN 201410705623 A CN201410705623 A CN 201410705623A CN 104495803 A CN104495803 A CN 104495803A
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Abstract
The invention provides a purification method of natural microcrystalline graphite. The method comprises the following steps: with natural microcrystalline graphite as a raw material, mixing the raw material with 20-50% caustic soda solution by mass, grinding and roasting at 350-700 DEG C while sufficiently stirring the solution for reaction; pulverizing, adding water and grinding into fine slurry; separating the solution and graphite, washing and precipitating, and finally filtering and drying to obtain alkali-washed graphite; adding the alkali-washed graphite, soluble villiaumite and nitric acid into a reaction container and heating while stirring and dipping for reaction; then separating the solution and graphite to obtain acid-containing graphite; washing the acid-containing graphite and precipitating; and finally, filtering and drying to obtain graphite with over 99.90% of carbon. The purification method causes little environmental pollution, and the purification efficiency is high.
Description
Technical field
The present invention relates to natural graphite method of purification, is especially that raw material is purified and the little method of environmental pollution to natural micro crystal graphite.
Background technology
Micro crystal graphite is starting material important in many industrial production and additive, is also widely regarded as industrial monosodium glutamate.Micro crystal graphite in Asia, there is storage America, some countries and regions such as Europe, and China is Asia and even the world has now verified maximum micro crystal graphite storage site, and the reserves through repeatedly exploring are greater than 34,000,000 tons.In recent years, along with the develop rapidly of electronic information industry, nuclear industry, national defense industry and automotive industry, graphite market also there occurs great variety.First, market is strengthened the demand of " amount ", is secondly to improve the requirement of graphite " matter ", and it is skyrocketing that the market requirement has promoted graphite price.Graphite is important strategic resource, occupies very consequence in socio-economic development.Along with the development of high-end technology, the deep development application requiring of graphite is to high purity, the development of high fineness, and this has become graphite industry common recognition out of question.
Early stage mainly concentrates on natural flake graphite to graphite purification, relatively less to the purification research of micro crystal graphite, the purification techniques difficulty of micro crystal graphite is larger simultaneously, also be the one of the main reasons of its range of application of restriction, the technology of natural flake graphite is much still used for reference in the purification of current micro crystal graphite, and common method of purification comprises (1) flotation process; (2) alkali acid two-step approach; (3) hydrogen fluoride; (4) hydrofluoric acid-salt (sulphur) acid system etc.Wherein, flotation process cost is minimum, energy consumption and reagent consumes least, but the graphite that will obtain carbon content more than 95% is difficult to; The dust removal rate of hydrogen fluoride and hydrofluoric acid-salt (sulphur) acid system is high, and energy consumption is also lower, but because the toxicity of hydrofluoric acid is large and severe corrosive makes the range of application of this method be restricted to environment.The carbon content of the graphite of the alkali acid two-step approach purification of existing report is difficult to reach more than 99.90%, even if melt temperature is increased to 800 degree, carbon content at most also can only bring up to 99.80%.
Summary of the invention
The object of the invention is the defect existed for existing alkali acid system purification graphite technology, provide a kind of environmental pollution little, and the method for purification of the high natural micro crystal graphite of purification efficiency.
Technical scheme of the present invention is achieved in that
A method of purification for natural micro crystal graphite, comprises the following steps:
1) with natural micro crystal graphite for raw material, mass concentration is roasting at 350 ~ 700 DEG C after 20% ~ 50% caustic soda soln mixed grinding, fully stirred solution reaction simultaneously, crushing and water-adding wears into screened stock, then solution is separated with graphite, washing postprecipitation, finally by filtration, dries, obtained alkali cleaning graphite;
2) again alkali cleaning graphite, solubility villiaumite are added in reaction vessel together with nitric acid, heating, carry out stirring simultaneously, impregnation, then solution is separated with graphite, obtainedly contains sour graphite;
3) containing sour graphite washing, precipitation, finally by filtration, will dry, obtained finished product graphite.
Further, the fixed carbon content as the natural micro crystal graphite of raw material is 80% ~ 85%, and particle diameter is 0.044mm ~ 0.150mm.
Further, be 100:6 ~ 10 as the natural micro crystal graphite of raw material, the mass ratio of caustic soda soln.
Further, step 1) in the mass concentration of caustic soda soln be 25 ~ 35%, maturing temperature is 400 ~ 500 DEG C.
Further, described solubility villiaumite is Sodium Fluoride, ammonium fluoride or difluoro hydrogen ammonia.
Further, step 2) nitric acid mass concentration be 55 ~ 65%.
Further, step 2) when being heated to 60 ~ 90 DEG C, carry out stirring simultaneously, impregnation 2 ~ 6 hours, then solution is separated with graphite, obtained containing sour graphite; Step 3) be washed with water to washings pH value 6 ~ 7 time containing sour graphite, precipitate, finally by filtration, dry, obtained finished product graphite.
The present invention, in acid cleaning process, adopts solubility villiaumite and nitric acid and alkali cleaning graphite one to react, and can eliminate and generally adopt hydrochloric acid, sulfuric acid or hydrochloric acid-nitric acid to be difficult to the impurity removed, the graphite carbon content that making purifies obtains reaches more than 99.90%.Further, the inorganic salt that the optional Sodium Fluoride of solubility villiaumite, ammonium fluoride or difluoro hydrogen ammonia etc. are fluorine-containing, can reduce the pollution level to environment like this.
Embodiment
Embodiment 1
Be the micro crystal graphite of 0.044mm by 100g fixed carbon content 80%, particle diameter, 10g mass concentration is after 25% caustic soda soln mixed grinding, roasting at 400 DEG C, then pulverize and add the water mill that alkali melts material 2 times of weight and become screened stock, then solution is separated with graphite, precipitation when washing sample to washing soln pH value is 8; Filter, be put in constant temperature blast drying oven subsequently and dry 2 hours.Take 20g after being dried by molten for alkali sample, 40ml 65% nitric acid adds reaction vessel together with 15g ammonium fluoride, and be 90 DEG C of reactions 2 hours in temperature, after reaction, solution is separated with graphite, precipitation when washing graphite to washing soln pH value is 7; Filter, be put in again in loft drier and dry 2 hours, obtain the Graphite Powder 99 of carbon content 99.93%.
Embodiment 2
Be the micro crystal graphite of 0.150mm by 100g fixed carbon content 80%, particle diameter, 6g mass concentration is after 20% caustic soda soln mixed grinding, roasting at 350 DEG C, then pulverize and add the water mill that alkali melts material 2.5 times of weight and become screened stock, then solution is separated with graphite, precipitation when washing sample to washing soln pH value is 7; Filter, be put in constant temperature blast drying oven subsequently and dry 2 hours.Take 20g after being dried by molten for alkali sample, 45ml 60% nitric acid adds reaction vessel together with 20g Sodium Fluoride, and be 70 DEG C of reactions 3 hours in temperature, after reaction, solution is separated with graphite, precipitation when washing graphite to washing soln pH value is 7; Filter, be put in again in loft drier and dry 2 hours, obtain the Graphite Powder 99 of carbon content 99.91%.
Embodiment 3
Be the micro crystal graphite of 0.120mm by 100g fixed carbon content 85%, particle diameter, 8g mass concentration is after 35% caustic soda soln mixed grinding, roasting at 700 DEG C, then pulverize and add the water mill that alkali melts material 2.5 times of weight and become screened stock, then solution is separated with graphite, precipitation when washing sample to washing soln pH value is 8; Filter, be put in constant temperature blast drying oven subsequently and dry 2 hours.Take 20g after being dried by molten for alkali sample, 50ml 60% nitric acid adds reaction vessel together with 16g difluoro hydrogen ammonia, and be 80 DEG C of reactions 4 hours in temperature, after reaction, solution is separated with graphite, precipitation when washing graphite to washing soln pH value is 7; Filter, be put in again in loft drier and dry 2 hours, obtain the Graphite Powder 99 of carbon content 99.94%.
Embodiment 4
Be the micro crystal graphite of 0.066mm by 100g fixed carbon content 85%, particle diameter, 8g mass concentration is after 50% caustic soda soln mixed grinding, roasting at 500 DEG C, then pulverize and add the water mill that alkali melts material 2.5 times of weight and become screened stock, then solution is separated with graphite, precipitation when washing sample to washing soln pH value is 8; Filter, be put in constant temperature blast drying oven subsequently and dry 2 hours.Take 20g after being dried by molten for alkali sample, 50ml 55% nitric acid adds reaction vessel together with 20g Sodium Fluoride, and be 60 DEG C of reactions 6 hours in temperature, after reaction, solution is separated with graphite, precipitation when washing graphite to washing soln pH value is 6; Filter, be put in again in loft drier and dry 2 hours, obtain the Graphite Powder 99 of carbon content 99.92%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a method of purification for natural micro crystal graphite, is characterized in that, comprises the following steps:
1) with natural micro crystal graphite for raw material, mass concentration is roasting at 350 ~ 700 DEG C after 20% ~ 50% caustic soda soln mixed grinding, fully stirred solution reaction simultaneously, crushing and water-adding wears into screened stock, then solution is separated with graphite, washing postprecipitation, finally by filtration, dries, obtained alkali cleaning graphite;
2) again alkali cleaning graphite, solubility villiaumite are added in reaction vessel together with nitric acid, heating, carry out stirring simultaneously, impregnation, then solution is separated with graphite, obtainedly contains sour graphite;
3) containing sour graphite washing, precipitation, finally by filtration, will dry, obtained finished product graphite.
2. the method for purification of natural micro crystal graphite according to claim 1, is characterized in that, the fixed carbon content as the natural micro crystal graphite of raw material is 80% ~ 85%, and particle diameter is 0.044mm ~ 0.150mm.
3. the method for purification of natural micro crystal graphite according to claim 1, is characterized in that, is 100:6 ~ 10 as the natural micro crystal graphite of raw material, the mass ratio of caustic soda soln.
4. the method for purification of natural micro crystal graphite according to claim 1, is characterized in that, step 1) in the mass concentration of caustic soda soln be 25 ~ 35%, maturing temperature is 400 ~ 500 DEG C.
5. the method for purification of natural micro crystal graphite according to claim 1, is characterized in that, described solubility villiaumite is Sodium Fluoride, ammonium fluoride or difluoro hydrogen ammonia.
6. the method for purification of natural micro crystal graphite according to claim 1, is characterized in that, step 2) nitric acid mass concentration be 55 ~ 65%.
7. the method for purification of natural micro crystal graphite according to claim 1 or 5, is characterized in that, step 2) when being heated to 60 ~ 90 DEG C, carry out stirring simultaneously, impregnation 2 ~ 6 hours, then solution is separated with graphite, obtained containing sour graphite; Step 3) be washed with water to washings pH value 6 ~ 7 time containing sour graphite, precipitate, finally by filtration, dry, obtained finished product graphite.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN107601493A (en) * | 2017-11-01 | 2018-01-19 | 河海大学 | A kind of method that secondary pickling combination thermal activation prepares high purity graphite |
| CN109231253A (en) * | 2018-11-09 | 2019-01-18 | 长沙万荣粉体设备科技有限公司 | A kind of native sulfate of barium method of purification and equipment |
| CN116496086A (en) * | 2023-04-10 | 2023-07-28 | 广西强强碳素股份有限公司 | Preparation method of pollution-free prebaked anode |
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| CN1060275A (en) * | 1991-07-19 | 1992-04-15 | 湖南郴州白山石墨制品研制所 | Phanerocrystalline-adiagnostic earthy (amorphous) graphite production method for comprehensively purifying |
| JP2003002623A (en) * | 2001-06-12 | 2003-01-08 | Korea Inst Of Mach & Materials | Method for manufacturing expansive graphite |
| CN101973545A (en) * | 2010-11-08 | 2011-02-16 | 昆明冶金研究院 | Method for purifying high-purity graphite |
| CN102583342A (en) * | 2012-02-05 | 2012-07-18 | 加拿大环球石墨有限公司 | Purification method of microcrystal graphite |
-
2014
- 2014-11-27 CN CN201410705623.9A patent/CN104495803A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060275A (en) * | 1991-07-19 | 1992-04-15 | 湖南郴州白山石墨制品研制所 | Phanerocrystalline-adiagnostic earthy (amorphous) graphite production method for comprehensively purifying |
| JP2003002623A (en) * | 2001-06-12 | 2003-01-08 | Korea Inst Of Mach & Materials | Method for manufacturing expansive graphite |
| CN101973545A (en) * | 2010-11-08 | 2011-02-16 | 昆明冶金研究院 | Method for purifying high-purity graphite |
| CN102583342A (en) * | 2012-02-05 | 2012-07-18 | 加拿大环球石墨有限公司 | Purification method of microcrystal graphite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN107601493A (en) * | 2017-11-01 | 2018-01-19 | 河海大学 | A kind of method that secondary pickling combination thermal activation prepares high purity graphite |
| CN109231253A (en) * | 2018-11-09 | 2019-01-18 | 长沙万荣粉体设备科技有限公司 | A kind of native sulfate of barium method of purification and equipment |
| CN116496086A (en) * | 2023-04-10 | 2023-07-28 | 广西强强碳素股份有限公司 | Preparation method of pollution-free prebaked anode |
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Application publication date: 20150408 |