CN104909354A - Graphite purification method - Google Patents
Graphite purification method Download PDFInfo
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- CN104909354A CN104909354A CN201410757367.8A CN201410757367A CN104909354A CN 104909354 A CN104909354 A CN 104909354A CN 201410757367 A CN201410757367 A CN 201410757367A CN 104909354 A CN104909354 A CN 104909354A
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Abstract
The invention relates to a graphite purification process, in particular to a method for purification of natural graphite by ion exchange resin under the assistance of an external direct-current electric field. The preparation process includes: mixing graphite serving as the raw material with a sodium hydroxide solution evenly, raising the temperature from room temperature to 450-650DEG C, and maintaining the temperature for 60-90min; conducting cooling and washing to neutral; mixing the product with hydrochloric acid, performing stirring at 70DEG C for 4h; conducting washing to neutral; placing the graphite sample and high purity water at both poles of a direct current power supply to form a closed loop system, the direct current power supply positive pole and negative pole of which are respectively fixed with water treatment anion exchange resin and water treatment cation exchange resin that are coated with fine gauze or semi-transparent film; applying a constant voltage and letting the voltage act for 30-60min, and carrying out filtering and drying. The method provided by the invention has the advantages of simple technological operation, small energy consumption, short time, small pollution and low production cost, and is in accordance with industrial development requirements of fluorine-free production, and the purified graphite has fixed carbon content up to 99.9%-99.99%.
Description
Technical field
The present invention relates to a kind of graphite purification method, especially a kind of method of answering spent ion exchange resin purification natural graphite under applying direct current electric field is assisted.
Background technology
Graphite has been widely used in the departments such as metallurgy, chemical industry, oil refining, machinery, light industry, electronics, space flight and nuclear industry as a kind of important non-metallic material.Needed for these industries, the carbon content of graphite is up to more than 99.9%, and natural graphite carbon content only can reach about 95%, can not meet high-purity requirement far away, therefore graphite industry will develop in wider, darker field, just must solve the high-purity key problem of graphite raw material.
The main method of purification of current natural graphite has flotation process, pyroprocess and chemical method, and wherein chemical method application is more.The method (201110145009) utilizing chemical liquid phase reaction to prepare high purity graphite discloses a kind of preparation method of high purity graphite.Be characterized in: 1. in powdered graphite, add sodium hydroxide, fully stir post-drying, be incubated under high temperature, be cooled to room temperature; 2. use process water cleaning and filtering; 3. use hydrochloric acid acidleach, then clean with distilled water; 4. add in HF solution, be heated to unnecessary HF volatilization, then filter post-drying; Namely high purity graphite is obtained.Weak point is to heat and makes unnecessary HF volatilization comparatively serious to the pollution of environment.In addition, the method (application number: CN201310388752) also having a kind of alkali acid-complexometry purification high-carbon natural flake graphite to prepare high purity graphite is characterized in: 1. high-temperature alkali process; 2. chloroazotic acid process; 3. second time alkaline purification; 4. collaborative complexing process.Graphite purity prepared by the method is high, but through the acid-alkali treatment of multi-step, will especially use the acid of chloroazotic acid highly corrosive, serious for equipment corrosion, causes production cost to increase.The present invention proposes a kind of energy consumption little, pollute little, technique is simple and lower-cost graphite purification novel process, this technique obtains promotion and application more widely in actual production.
Summary of the invention
The object of the invention is to overcome large, the consuming time length of existing graphite purfying process energy consumption, with serious pollution technical problem, propose a kind of method utilizing ion exchange resin purification graphite under applying direct current electric field is assisted, the Zeo-karb such as the method employing 732, D001, D113, the anionresin trees such as 210 × 4,210 × 7, under 20 ~ 80V DC electric field, effect 30 ~ 60min, under electric field action graphite can automatic absorbing on ion exchange resin surface, to make in graphite H in hetero-ion and ion exchange resin
+or OH
-exchange, removing electric field action, the automatic desorption of graphite, namely obtains high purity graphite after directly collecting drying.This method technological operation is simple, energy consumption is little, consuming time short, pollute little, production cost is low, meet the requirement of floride-free industrialized development of producing, and after purifying, graphite fixed carbon content can reach 99.9%-99.99%.
The present invention realizes by the following technical solutions, a kind of graphite purification method, and the method comprises the following steps:
(1) with carbon content 85% ~ 95% natural graphite for raw material, by its with 30% ~ 38% sodium hydroxide solution in mass ratio 1:1 mix, rise to 450 ~ 650 DEG C with the speed of 3 ~ 5min/s by room temperature, this temperature keep 60 ~ 90min; Be cooled to room temperature after reaction, with high purity water, obtained sample be washed till neutrality; According to sample and 8% ~ 10% hydrochloric acid in mass ratio 1:3.84 mix, stir 4 hours at 70 DEG C; Elimination solution after reaction, and with high purity water washing sample to neutral, and AgNO
3detect in filtrate without Cl
-;
(2) above-mentioned graphite sample and high purity water to be placed in the containers such as beaker and with formation loop line, direct supply the two poles of the earth, these direct supply positive and negative polarities are fixed with crocus cloth or the coated water treatment anionite-exchange resin of semi-permeable membranes and water treatment Zeo-karb respectively;
(3) apply the constant voltage of 20 ~ 80V to system, and act on 30 ~ 60min, under DC Electric Field, graphite automatic absorbing is at the two poles of the earth, hetero-ion wherein and the H of ion exchange resin
+or OH
-carry out ion-exchange, remove the automatic desorption of electric field graphite, graphite is filtered, be less than 0.1% 110 DEG C of oven dry to water content.
The present invention purifies to graphite stage by stage, wherein the object of alkali fusion is that the impurity in graphite such as the compositions such as silicate, silico-aluminate, quartz and sodium hydroxide are reacted, generate the water glass of solubility or acid soluble sodium silicoaluminate, reach the object of desiliconization by washing removing; Another part impurity, as metal oxide etc., is still present in graphite after alkali fusion, is converted into metal ion or other solvends enter liquid phase by ensuing acidleach process, by washing removing.But experiment proves because graphite specific surface area is larger, some hetero-ions are easily adsorbed on its surface, and make its extremely difficult removing in follow-up water treatment procedure, therefore the graphite purity obtained through alkali acidic process does not reach the requirement of 99.9%, so must process to obtain high purity graphite further it.As everyone knows, under electric field action, electric field can and ion between form electrical forces, can depart from graphite surface at the ion of graphite surface and enter solution by induced adsorption under the effect of this electrical forces, and ion exchange resin is the macromolecular material that a class has ion exchanging function.Jack per line ion in the ion of itself and solution can exchange by it in the solution.Zeo-karb mostly contains the acidic-groups such as sulfonic group, carboxyl or phenylol, H wherein
+can exchange with the metal ion in solution or other positively charged ions.Anionite-exchange resin contains the basic groups such as quaternary amine base, amido or imido grpup, and it can generate OH in water
-ion, can play exchange interaction with various negatively charged ion.And ion exchange is reversible, the ion exchange resin therefore used generally washs with the mineral acid of proper concn or alkali, can return to raw state and reuse, can greatly reduce costs.The present invention utilizes these features of anion-cation exchange resin just, utilizes extra electric field to induce foreign ion desorption remaining in graphite after alkali acid treatment, and then carries out ion-exchange with ion exchange resin, reach further purification graphite to high-purity object.Graphite has good electroconductibility in addition, extra electric field auxiliary under, what can realize graphite on the one hand makes experiment easily control from adsorption and desorption, and graphite is easy to collect.Under electric field action, also accelerate the transmission speed of ion on the other hand, speeding-up ion permutoid reaction, thus the saving reaction times reduce further production cost.
The invention has the beneficial effects as follows: first, this method of purification adopts auxiliary direct current field ion exchange process, purifies further to alkali fusion acid wash purification gained graphite, purification after product need not other process, namely convection drying obtains high purity graphite, pollution-free, can repeatedly repetitive operation.Secondly, this method by electric field action realize graphite from adsorption and desorption, be convenient to control and collect.Again, this method has the advantage that process treatment time is short, operating procedure simple, equipment investment cost is low.
Embodiment
embodiment 1
With carbon content 85% ~ 95% natural graphite for raw material, by its with 30% ~ 38% sodium hydroxide solution in mass ratio 1:1 mix, rise to 450 ~ 650 DEG C with the speed of 3 ~ 5min/s by room temperature, this temperature keep 60 ~ 90min; Be cooled to room temperature after reaction, sample wash will be obtained to neutral with high purity water; According to sample and 8% ~ 10% hydrochloric acid in mass ratio 1:3.84 mix, stir 4 hours at 70 DEG C; Elimination solution after reaction, and with extremely neutral in high purity water washing sample, and AgNO
3detect in filtrate without Cl
-; Above-mentioned graphite sample and high purity water are placed in beaker and with formation loop line, direct supply the two poles of the earth, direct supply positive and negative polarities are fixed with by crocus cloth or the coated water treatment anion and cation exchange resin of semi-permeable membranes respectively; Apply the constant voltage of 20 ~ 80V, and act on 30 ~ 60min, under DC Electric Field, graphite automatic absorbing is at the two poles of the earth, wherein the H of hetero-ion and ion exchange resin
+or OH
-carry out ion-exchange, remove the automatic desorption of electric field graphite, graphite is filtered, be less than 0.1% 110 DEG C of oven dry to water content.After being purified by aforesaid method, in graphite, fixed carbon content is 99.9-99.99%.
embodiment 2
The difference of the present embodiment and embodiment 1 is: with carbon content 90% natural graphite for raw material, by its with 30% sodium hydroxide solution in mass ratio 1:1 mix, rise to 450 DEG C with the speed of 5min/s by room temperature, this temperature keep 60min.The present embodiment shortens time that sodium hydroxide and graphite reacts and reduces temperature of reaction, can reduce the extent of corrosion to equipment, still can reach corresponding technique effect.After being purified by aforesaid method, in graphite, fixed carbon content is 99.9%.The alkali leaching of graphite is removed impurity and is had vital role for whole purification process, but usually needs higher temperature and longer reaction times.Purify owing to answering spent ion exchange resin under applying direct current electric field is auxiliary and there is good refining effect, therefore can Reaction time shorten and temperature, still can prepare high purity graphite.
embodiment 3
The difference of the present embodiment and embodiment 1 is: the water treatment anionite-exchange resin described in embodiment 1 be 210 × 4 or 210 × 7 or D201 or D202 in one.
embodiment 4
The difference of the present embodiment and embodiment 3 is: the water treatment Zeo-karb described in embodiment 3 be 732 or D001 or D113 in one.
embodiment 5
The present embodiment is with the difference of embodiment 4: 10% hydrochloric acid in mass ratio 1:3.84 mixes.The hydrochloric acid of higher concentration is adopted to be conducive to the removal of impurity.
embodiment 6
The difference of the present embodiment and embodiment 5 is: apply 80V direct current constant voltage to system, and act on 60min.
embodiment 7
The difference of the present embodiment and embodiment 6 is: carbon amounts is raw material at the natural graphite of 90%, by its with 38% sodium hydroxide solution in mass ratio 1:1 mix, rise to 650 DEG C with the speed of 5 DEG C/min by room temperature, this temperature keep 90min.After being purified by aforesaid method, in graphite, fixed carbon content is 99.95%.
embodiment 8
The difference of the present embodiment and embodiment 7 is: carbon amounts is raw material at the natural graphite of 92%, rises to 600 DEG C with the speed of 5 DEG C/min by room temperature, keeps 60min in this temperature.After being purified by aforesaid method, in graphite, fixed carbon content is 99.97%.
embodiment 9
The difference of the present embodiment and embodiment 8 is: carbon amounts is raw material at the natural graphite of 95%, rises to 600 DEG C with the speed of 5 DEG C/min by room temperature, keeps 90min in this temperature.After being purified by aforesaid method, in graphite, fixed carbon content is 99.99%.
embodiment 10
The difference of the present embodiment and embodiment 7 is: carbon amounts is raw material at the natural graphite of 88%.After being purified by aforesaid method, in graphite, fixed carbon content is 99.95%.
embodiment 11
The difference of the present embodiment and embodiment 7 is: apply 20V direct current constant voltage to system, and act on 30min.After being purified by aforesaid method, in graphite, fixed carbon content is 99.91%.
embodiment 12
The difference of the present embodiment and embodiment 8 is: apply 40V direct current constant voltage to system, and act on 60min.After being purified by aforesaid method, in graphite, fixed carbon content is 99.95%.
embodiment 13
The difference of the present embodiment and embodiment 8 is: rise to 650 DEG C with the speed of 3 DEG C/min by room temperature, keeps 60min in this temperature.After being purified by aforesaid method, in graphite, fixed carbon content is 99.99%.
embodiment 14
The difference of the present embodiment and embodiment 12 is: rise to 650 DEG C with the speed of 3 DEG C/min by room temperature, keeps 45min in this temperature.After being purified by aforesaid method, in graphite, fixed carbon content is 99.95%.
Claims (10)
1. the method for a graphite purification, its preparation process is: with carbon content 85% ~ 95% natural graphite for raw material, by its with 30% ~ 38% sodium hydroxide solution in mass ratio 1:1 mix, rise to 450 ~ 650 DEG C with the speed of 3 ~ 5min/s by room temperature, this temperature keep 60 ~ 90min; Be cooled to room temperature after reaction, sample wash will be obtained to neutral with high purity water; According to sample and 8% ~ 10% hydrochloric acid in mass ratio 1:3.84 mix, stir 4 hours at 70 DEG C; Elimination solution after reaction, and with high purity water washing sample to neutral, and AgNO
3detect in filtrate without Cl
-; Above-mentioned graphite sample and high purity water are placed in beaker and with formation loop line, direct supply the two poles of the earth, direct supply positive and negative polarities are fixed with by crocus cloth or the coated water treatment anion and cation exchange resin of semi-permeable membranes respectively; Apply the constant voltage of 20 ~ 80V, and act on 30 ~ 60min, under DC Electric Field, graphite automatic absorbing is at the two poles of the earth, wherein the H of hetero-ion and ion exchange resin
+or OH
-carry out ion-exchange, remove the automatic desorption of electric field graphite, graphite is filtered, be less than 0.1% 110 DEG C of oven dry to water content.
2. the method for a kind of graphite purification according to claim 1, it is characterized in that with carbon content 90% natural graphite for raw material, by its with 30% sodium hydroxide solution in mass ratio 1:1 mix, rise to 450 DEG C with the speed of 5min/s by room temperature, this temperature keep 60min.
3. the method for a kind of graphite purification according to claim 2, it is characterized in that described water treatment anionite-exchange resin be 210 × 4 or 210 × 7 or D201 or D202 in one.
4. the method for a kind of graphite purification according to claim 3, it is characterized in that described water treatment Zeo-karb be 732 or D001 or D113 in one.
5. the method for a kind of graphite purification according to claim 4, it is characterized in that graphite and 10% hydrochloric acid in mass ratio 1:3.84 mix.
6. the method for a kind of graphite purification according to claim 5, is characterized in that applying 80V direct current constant voltage to system, and acts on 60min.
7. the method for a kind of graphite purification according to claim 6, it is characterized in that carbon content 90% natural graphite be raw material, by its with 38% sodium hydroxide solution in mass ratio 1:1 mix, rise to 650 DEG C with the speed of 5 DEG C/min by room temperature, this temperature keep 90min.
8. the method for a kind of graphite purification according to claim 7, is characterized in that carbon amounts is that the natural graphite of 92% is raw material, rises to 600 DEG C with the speed of 5 DEG C/min by room temperature, keeps 60min in this temperature.
9. the method for a kind of graphite purification according to claim 8, it is characterized in that carbon content 95% natural graphite be raw material, rise to 600 DEG C with the speed of 5 DEG C/min by room temperature, this temperature keep 90min.
10. the method for a kind of graphite purification according to claim 7, is characterized in that carbon content is to rise to 650 DEG C with the speed of 3 DEG C/min by room temperature, keeps 60min in this temperature.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587011A (en) * | 2016-12-09 | 2017-04-26 | 苏州工业园区恒量咨询有限公司 | Purification device and method for purifying carbon nano tube |
| CN108751188A (en) * | 2018-08-08 | 2018-11-06 | 青岛领军节能与新材料研究院 | A kind of graphite purification method |
| CN110526240A (en) * | 2019-09-09 | 2019-12-03 | 北京化工大学 | A kind of method of purification of natural micro crystal graphite |
| CN117049533A (en) * | 2023-09-26 | 2023-11-14 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
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| CN101258332A (en) * | 2005-09-20 | 2008-09-03 | 电力产品Ⅲ有限公司 | Carrier strip system and method for different diameter fasteners |
| 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 |
| KR20140104783A (en) * | 2013-02-21 | 2014-08-29 | 오원춘 | Method for purifying graphite |
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2014
- 2014-12-12 CN CN201410757367.8A patent/CN104909354B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258332A (en) * | 2005-09-20 | 2008-09-03 | 电力产品Ⅲ有限公司 | Carrier strip system and method for different diameter fasteners |
| 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 |
| KR20140104783A (en) * | 2013-02-21 | 2014-08-29 | 오원춘 | Method for purifying graphite |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587011A (en) * | 2016-12-09 | 2017-04-26 | 苏州工业园区恒量咨询有限公司 | Purification device and method for purifying carbon nano tube |
| CN106587011B (en) * | 2016-12-09 | 2019-04-02 | 苏州工业园区恒量咨询有限公司 | Purification devices and its method for Purification of Carbon Nanotubes |
| CN108751188A (en) * | 2018-08-08 | 2018-11-06 | 青岛领军节能与新材料研究院 | A kind of graphite purification method |
| CN110526240A (en) * | 2019-09-09 | 2019-12-03 | 北京化工大学 | A kind of method of purification of natural micro crystal graphite |
| CN117049533A (en) * | 2023-09-26 | 2023-11-14 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
| CN117049533B (en) * | 2023-09-26 | 2024-04-30 | 黑龙江工业学院 | Method for purifying graphite by electric field induced graphite acid method and application |
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