CN104556023A - Automatic purifying method for spherical graphite - Google Patents
Automatic purifying method for spherical graphite Download PDFInfo
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- CN104556023A CN104556023A CN201510063335.2A CN201510063335A CN104556023A CN 104556023 A CN104556023 A CN 104556023A CN 201510063335 A CN201510063335 A CN 201510063335A CN 104556023 A CN104556023 A CN 104556023A
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Abstract
The invention discloses a purifying method for spherical graphite. The automatic purifying method for the spherical graphite comprises the following steps: adding the spherical graphite, fluoride, a complexing agent and water into a primary reaction tank, uniformly stirring, introducing steam, heating for 3h, and carrying out reaction for 8-12h at the temperature of 80-120 DEG C; after reaction, pumping a material into a primary filter press through a pipeline at the bottom by virtue of a material conveying pump, carrying out filtration and deacidification, collecting waste acid liquid into an acid storage tank for secondary reserve, introducing soft water, and cleaning the material to be neutral; sending the material discharged by the primary filter press into a middle pulping tank by virtue of a spiral material conveying device; adding aqua regia and water into the middle pulping tank according to a certain ratio, and stirring until the material is in a gruel shape, and pumping the material into a secondary reaction tank by virtue of the material conveying pump; introducing the steam, heating, and carrying out reaction for 4-8h at the temperature of 80-120 DEG C; after reaction, discharging the material, enabling the material to enter a secondary filter press by virtue of the material conveying pump, carrying out filtration and deacidification, collecting concentrated acid liquid into an acid storage tank, introducing deionized water, cleaning the material to be neutral, and drying the discharged material to obtain the high-purity spherical graphite, wherein the purity of the spherical graphite can achieve 99.99-99.995 percent.
Description
Technical field
The present invention relates to graphite production unit, particularly relate to a kind of purification techniques of spherical graphite.
Background technology
Along with the popularization and application on a large scale of lithium-ion secondary cell, natural flake graphite is made the technology that spherical graphite is applied to lithium-ion secondary cell and is reached its maturity, and its specific storage is high, and having extended cycle life is that other many material is unrivaled; But spherical graphite in process of production will through two processes, and one is pulverize ball process processed, i.e. physical process; Two is improve pure process, is a chemical process.Wherein chemical process is the most complicated, use multiple acid, remove various impurity, also repeatedly will carry out chemical reaction, method of purification present in industry is different, but all there is technological process and exist incomplete, unreasonable, flash, leaks the phenomenon such as material, and the situation of acid liquor leakage and the personnel that burn happens occasionally.In addition, the waste of existing purification means is comparatively large, and acid solution ratio is excessive, causes that cost is high, yield is low; And processing parameter instability causes unstable product quality, easily there is phenomenon of doing over again, affect output and cost is improved.
Ma Yongming, Han Yuying propose to remove graphite mineral with diluted acid and fluorochemical two-step pretreatment, and they process with diluted acid and fluoride aqueous solution, investigate the effect of their demineralization.At 100 DEG C, with dilute acid pretreatment 2 hours, then with fluoride aqueous solution about 70 DEG C process 2.5 hours, graphite purity brings up to 99.8-99.93%, but fluoride aqueous solution easily gives birth to normal hydrofluoric acid, very big to equipment corrosion.
Summary of the invention
The present invention is intended to the defect overcoming graphite purification method and equipment for purifying, provides a kind of method of purification and equipment for purifying of spherical graphite.The present invention proposes rational operational path and Equipments Setting, improve the convenience of operation, level of automation, reduce cost, improve production efficiency, make product have more the market competitiveness.
The method of purification of a kind of spherical graphite of the present invention, it comprises:
Step one, spherical graphite, fluorochemical, complexing agent, water add primary first-order equation tank by a certain percentage, stir, and pass into steam heating 3 hours, and constant temperature reacts 8-12 hour under 80-120 degree condition;
Step 2, has reacted material and has squeezed into a Filter Press depickling by bottom pipe through dehvery pump, and it is for subsequent use that spent acid solution is collected into the sour tank secondary of storage, then passes into softening water to material cleaning to neutral;
Step 3, the material that pressure filter unloads sent into by spiral conveyer in the middle of pulping tank;
Step 4, adds middle pulping tank by a certain percentage by chloroazotic acid, water, and being stirred to material is gruel shape, squeezes into secondary reaction tank by dehvery pump;
Step 5, passes into steam heating, under temperature is 80-100 degree condition, react 4-8 hour;
Step 6, reacts complete blowing, and material enters the depickling of secondary Filter Press by carrier pipe through dehvery pump, concentrated acid liquid is collected into the sour tank of storage, pass into washed with de-ionized water material to neutral, discharging drying obtains high purity spherical graphite, and its purity can reach 99.99% ~ 99.995%.
The method of purification of described spherical graphite, washing lotion after washed with de-ionized water in described step 6 enters secondary filtration in centrifuge and cleans, collect the subparticle material run off in secondary filtration, cleaning is to neutral, high speed dewatering, discharging obtains minute spherical graphite, obtains material enter baking operation in the lump after qualified after testing with secondary press filtration.
The method of purification of described spherical graphite, the steam in described step one and step 5 is superheated vapour.
The method of purification of described spherical graphite, the fluorochemical in described step one comprises one or more in Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride, Potassium monofluoride; Complexing agent mainly comprises one or more in EDTA, trolamine, EGTA, ethylenediamine tetrapropionic acid(EDTP); The weight ratio of the spherical graphite added, fluorochemical, complexing agent and water is 1:0.4 ~ 2:0.1 ~ 0.4:0.4 ~ 0.8.
The method of purification of described spherical graphite, in the softening water in described step 2, Ca2+Mg2+ ion content is less than 50ppm.
The method of purification of described spherical graphite, the chloroazotic acid in the middle of described step 4 is 3+1 chloroazotic acid, and material, chloroazotic acid, softening water additional proportion are: 1:0.2 ~ 0.6:0.1 ~ 0.4.
The method of purification of described spherical graphite, the deionization electrical conductivity of water in described step 6 is less than 10 μ s/cm.
The method of purification of described spherical graphite, described cleaning refers to pH value 4-8 to neutrality.
The method of purification of described spherical graphite, described centrifugal filter filter cloth used is selected according to material specification, and material specification is less, then corresponding filter cloth order number is higher, and its material is high temperature resistant, that acid and alkali-resistance is rotten terylene macrofiber twill filter cloth.
The reaction principle of method of purification of the present invention: the impurity major ingredient in spherical graphite is silicon-dioxide, ferric oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, cupric oxide etc., primary first-order equation mainly silicon-dioxide and fluorochemical is reacted, produce silicon tetrafluoride and water, silicon tetrafluoride is gas evolution, metal ion in impurity cements out by complex compound, accelerate dissolution and chemical reaction, play katalysis.Primary first-order equation material carbon content can be increased to more than 99.9% by 95%.Secondary reaction mainly adopt micro-soluble material in chloroazotic acid and material or insolubles as: ironic hydroxide, magnesium hydroxide, the reactions such as calcium hydroxide, generate completely water-soluble nitrate through cleaning removing.Secondary reaction material carbon content by 99.9% being increased to more than 99.99%, Qi Zhongtie, calcium, aluminium, plasma content is all less than 30ppm.
The present invention adopts pressed powder fluorochemical and graphite, complex compound to react, and replace original hydrofluoric acid, advantage: convenient transportation, environmental protection harm is little, and easy to operate in factory, complex compound makes speed of response accelerate, and chemical reaction is more thorough.In addition, equipment for purifying of the present invention taken into full account system stopping property, utilize modern Controlling System, substantially increase the level of automation of graphite purification equipment, improve production efficiency, reduce production cost.
Embodiment
The invention provides a kind of automatization method of purification of spherical graphite, comprise the following steps:
1. spherical graphite, fluorochemical, complexing agent, water add primary first-order equation tank by a certain percentage, stir, and pass into steam heating 3 hours, and constant temperature reacts 8-12 hour under 80-120 degree condition;
2. reacted material and squeezed into a Filter Press depickling by bottom pipe through dehvery pump, it is for subsequent use that spent acid solution is collected into the sour tank secondary of storage, then pass into softening water to material cleaning to neutral;
3. filter discharging sends into middle pulping tank by spiral conveyer.
4. chloroazotic acid, water are added middle pulping tank by a certain percentage, being stirred to material is gruel shape, squeezes into secondary reaction tank by dehvery pump;
5. pass into steam heating, under temperature is 80-100 degree condition, reacts 4-8 hour;
6. react complete blowing, material enters the depickling of secondary Filter Press by carrier pipe through dehvery pump, and concentrated acid liquid is collected into the sour tank of storage, passes into washed with de-ionized water material to neutral, discharging drying obtains high purity spherical graphite, and its purity can reach 99.99% ~ 99.995%.Washing lotion enters in centrifuge again filters and cleans, the subparticle material run off in secondary filtration is collected in centrifuge effect, and cleaning is extremely neutral, high speed dewatering, discharging obtains minute spherical graphite, can obtain material enter baking operation in the lump after qualified after testing with secondary press filtration.
Example one:
The material 4 tons that spherical graphite specification is SG17 is dropped in primary first-order equation tank, add softening water 2 tons, add Neutral ammonium fluoride 800 kilograms, add EDTA200 kilogram, open and stir and pass into steam heating two hours, treat that temperature of charge reaches more than 80 degree, stop heating, close tank mouth, stop stirring, standing and reacting, temperature must keep more than 80 degree, 12 hours reaction times; Reaction terminates to open bottom discharge valve, opens pump for mortar transmission, material is squeezed into first press filtration in a pressure filter, open High-pressure air valve, acid solution is purified, then closes gas check valve, open softening water valve, material is cleaned, be greater than 4 to pH value, close softening water valve, open High-pressure air valve, material dewatering is less than 30% to water content, closes gas check valve, open filter press filter board, unload material and send into pulping tank by spiral conveyer.Add softening water 1000 kilograms, add chloroazotic acid 1200 kilograms, stir.Open bottom valve, send in secondary reaction tank by dehvery pump, open stirring heating sealed reaction 8 hours, open baiting valve, by dehvery pump, slip is squeezed into depickling in secondary pressure filter, then pass into washed with de-ionized water and be greater than 4 to material pH value, material after dehydration, material enters baking operation drying and obtains high purity spherical graphite, and its purity is 99.9915%.Rinse water is out entered in centrifugal filter by secondary filtration machine, through cleaning and dewatering, obtains the fine granular materials that purity is 99.991%, and the material that its particle fineness is D50=12.373 μm and secondary press filtration are gone out together with material dries.Be weighed as 3756 kilograms through weighing, yield is 93.9% higher than the mean value 93% of other producer in of the same trade.
Example two:
The material 6 tons that spherical graphite specification is SG22 is dropped in primary first-order equation tank, add softening water 3 tons, add ammonium bifluoride 1600 kilograms, add EDTG400 kilogram, open and stir and pass into steam heating two hours, treat that temperature of charge reaches more than 80 degree, stop heating, stop stirring, airtight standing and reacting, temperature must keep more than 80 degree, 12 hours reaction times; Reaction terminates to open bottom discharge valve, opens pump for mortar transmission, material is squeezed into first press filtration in a pressure filter, open High-pressure air valve, depickling, then close gas check valve, open softening water valve, material is cleaned, be greater than 4 to pH value, close softening water valve, open High-pressure air valve, material dewatering is less than 30% to water content, stops air feed, open filter press filter board, unload material and send into pulping tank by spiral conveyer.Add softening water 1800 kilograms, add chloroazotic acid 2000 kilograms, stir.Open bottom valve, send in secondary reaction tank by dehvery pump, open stirring heating sealed reaction 4 hours, open baiting valve, by dehvery pump, slip is squeezed into depickling in secondary pressure filter, then pass into washed with de-ionized water and be greater than 4 to material pH value, discharging after dehydration, material enters baking operation drying and obtains high purity spherical graphite, and its purity is 99.9936%.Rinse water is out entered in centrifugal filter by secondary filtration machine, through cleaning and dewatering, obtains the fine granular materials that purity is 99.9920%, and the material that its particle fineness is D50=14.242 μm and secondary press filtration are gone out together with material dries.Be weighed as 5630 kilograms through weighing, yield is 93.83% higher than the mean value 93.5% of other producer in of the same trade.
Claims (9)
1. an automatization method of purification for spherical graphite, it is characterized in that, it comprises:
Step one, spherical graphite, fluorochemical, complexing agent, water add primary first-order equation tank by a certain percentage, stir, and pass into steam heating 3 hours, and constant temperature reacts 8-12 hour under 80-120 degree condition;
Step 2, has reacted material and has squeezed into a Filter Press depickling by bottom pipe through dehvery pump, and it is for subsequent use that spent acid solution is collected into the sour tank secondary of storage, then passes into softening water to material cleaning to neutral;
Step 3, the material that pressure filter unloads sent into by spiral conveyer in the middle of pulping tank;
Step 4, adds middle pulping tank by a certain percentage by chloroazotic acid, water, and being stirred to material is gruel shape, squeezes into secondary reaction tank by dehvery pump;
Step 5, passes into steam heating, under temperature is 80-100 degree condition, react 4-8 hour;
Step 6, reacts complete blowing, and material enters the depickling of secondary Filter Press by carrier pipe through dehvery pump, concentrated acid liquid is collected into the sour tank of storage, pass into washed with de-ionized water material to neutral, discharging drying obtains high purity spherical graphite, and its purity can reach 99.99% ~ 99.995%.
2. the automatization method of purification of a kind of spherical graphite according to claim 1, it is characterized in that, washing lotion after washed with de-ionized water in described step 6 enters secondary filtration in centrifuge and cleans, collect the subparticle material run off in secondary filtration, cleaning is to neutral, high speed dewatering, discharging obtains minute spherical graphite, obtains material enter baking operation in the lump after qualified after testing with secondary press filtration.
3. the automatization method of purification of a kind of spherical graphite according to claim 1, is characterized in that, the steam in described step one and step 5 is superheated vapour.
4. the automatization method of purification of a kind of spherical graphite according to claim 1, is characterized in that, the fluorochemical in described step one comprises one or more in Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride, Potassium monofluoride; Complexing agent mainly comprises one or more in EDTA, trolamine, EGTA, ethylenediamine tetrapropionic acid(EDTP); The weight ratio of the spherical graphite added, fluorochemical, complexing agent and water is 1:0.4 ~ 2:0.1 ~ 0.4:0.4 ~ 0.8.
5. the automatization method of purification of a kind of spherical graphite according to claim 1, is characterized in that, Ca in the softening water in described step 2
2+mg
2+ion content is less than 50ppm.
6. the automatization method of purification of a kind of spherical graphite according to claim 1, is characterized in that, the chloroazotic acid in the middle of described step 4 is 3+1 chloroazotic acid, and material, chloroazotic acid, softening water additional proportion are: 1:0.2 ~ 0.6:0.1 ~ 0.4.
7. the automatization method of purification of a kind of spherical graphite according to claim 1, is characterized in that, the deionization electrical conductivity of water in described step 6 is less than 10 μ s/cm.
8. the automatization method of purification of a kind of spherical graphite according to claim 1 and 2, is characterized in that, described cleaning refers to pH value 4-8 to neutrality.
9. the automatization method of purification of a kind of spherical graphite according to claim 1, it is characterized in that, described centrifugal filter filter cloth used is selected according to material specification, material specification is less, then corresponding filter cloth order number is higher, and its material is high temperature resistant, that acid and alkali-resistance is rotten terylene macrofiber twill filter cloth.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776191A (en) * | 2016-02-19 | 2016-07-20 | 青岛田庄恒源石墨有限公司 | Spherical graphite production process |
| CN108455594A (en) * | 2018-06-08 | 2018-08-28 | 黑龙江工业学院 | A kind of method of purification of high-carbon graphite |
| CN110723731A (en) * | 2019-11-27 | 2020-01-24 | 曹勇 | Automatic device and method for chemically purifying graphite |
| CN115849369A (en) * | 2023-02-24 | 2023-03-28 | 潍坊新翰泽能源科技有限公司 | Energy-saving environment-friendly high-purity graphite deep processing production line and control method |
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| CN101983917A (en) * | 2010-11-02 | 2011-03-09 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Preparation method of high purity graphite |
| CN102001649A (en) * | 2010-11-25 | 2011-04-06 | 洛阳市冠奇工贸有限责任公司 | Purification method for high-purity natural graphite |
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- 2015-02-06 CN CN201510063335.2A patent/CN104556023A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983917A (en) * | 2010-11-02 | 2011-03-09 | 黑龙江省牡丹江农垦奥宇石墨深加工有限公司 | Preparation method of high purity graphite |
| CN102001649A (en) * | 2010-11-25 | 2011-04-06 | 洛阳市冠奇工贸有限责任公司 | Purification method for high-purity natural graphite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776191A (en) * | 2016-02-19 | 2016-07-20 | 青岛田庄恒源石墨有限公司 | Spherical graphite production process |
| CN105776191B (en) * | 2016-02-19 | 2017-12-01 | 青岛田庄恒源石墨有限公司 | A kind of production technology of spherical graphite |
| CN108455594A (en) * | 2018-06-08 | 2018-08-28 | 黑龙江工业学院 | A kind of method of purification of high-carbon graphite |
| CN108455594B (en) * | 2018-06-08 | 2021-08-03 | 黑龙江工业学院 | Purification method of high-carbon graphite |
| CN110723731A (en) * | 2019-11-27 | 2020-01-24 | 曹勇 | Automatic device and method for chemically purifying graphite |
| CN115849369A (en) * | 2023-02-24 | 2023-03-28 | 潍坊新翰泽能源科技有限公司 | Energy-saving environment-friendly high-purity graphite deep processing production line and control method |
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