CN112520733A - Chemical purification method for graphite - Google Patents
Chemical purification method for graphite Download PDFInfo
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- CN112520733A CN112520733A CN202011387435.8A CN202011387435A CN112520733A CN 112520733 A CN112520733 A CN 112520733A CN 202011387435 A CN202011387435 A CN 202011387435A CN 112520733 A CN112520733 A CN 112520733A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010439 graphite Substances 0.000 title claims abstract description 88
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000746 purification Methods 0.000 title claims abstract description 22
- 239000000126 substance Substances 0.000 title claims abstract description 19
- 238000005188 flotation Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000678 plasma activation Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005189 flocculation Methods 0.000 claims abstract description 7
- 230000016615 flocculation Effects 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000006260 foam Substances 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000008213 purified water Substances 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008396 flotation agent Substances 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 229910021489 α-quartz Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000003921 oil Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005120 petroleum cracking Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 terpene alcohols Chemical class 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a chemical purification method of graphite, which specifically comprises the following steps: crushing graphite raw ore, deeply grinding the graphite raw ore, adding the graphite raw ore into a plasma activation reactor for reaction, adding the graphite raw ore into a mixed acid dissolution tank for reaction, finally adopting a high-shear selective flocculation size-mixing flotation method, stirring and carrying out flotation for multiple times until the material is nearly neutral, and sending the material into a vacuum filter for vacuum filtration to obtain the high-purity graphite. The invention provides a graphite chemical purification method, which comprises the steps of firstly adopting deep ore grinding, a plasma activation reactor, mixed acid and high-shear selective flocculation size mixing flotation treatment to finally obtain high-purity and high-yield graphite, wherein the yield of the graphite is 92-96%, and the purity is 99.991-99.995%.
Description
Technical Field
The invention relates to the technical field of graphite processing, in particular to a chemical purification method of graphite.
Background
Graphite is a carbonaceous element crystalline mineral and has good electrical conductivity, thermal conductivity, corrosion resistance and high temperature resistance, and graphite and products thereof are indispensable conductive, fireproof, lubricating, sealing, acid-resistant and alkali-resistant materials and structural materials in the industries of developing metallurgy, machinery, petroleum, chemical engineering, nuclear industry, agriculture, national defense advanced technology, yarn weaving, pencil manufacturing, electricity, television, glass manufacturing, cast iron welding rods and the like. The fixed carbon content of the graphite required by the industries is up to more than 99.9 percent, while the carbon content of the natural graphite after mineral processing can only reach about 95 percent at most, and the requirement of the application field of the high-purity graphite can not be met, so that the preparation of the high-purity graphite is very critical to the application of the graphite.
Although the existing purification technologies have certain advantages, the existing purification technologies have certain defects, such as poor graphite treatment effect by a physical ore dressing method, low concentrate grade which is generally about 79-90%, and low graphite recovery rate; the acid-base method for producing the high-carbon graphite has the problems of high production cost, complex process flow, low recovery rate, serious wastewater pollution and the like; the hydrofluoric acid method has the defects of high toxicity, serious corrosivity, serious three-waste pollution and the like; the purification process of the chlorination roasting method has the defects of difficult treatment of tail gas, serious pollution, serious corrosion to equipment, higher chlorine cost and the like.
Therefore, how to provide a new high-purity and high-yield graphite is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a chemical purification method of graphite, which comprises the steps of firstly, deeply grinding the graphite ore to fully expose the metal in the raw graphite ore, and then activating the impurities in the graphite through a plasma activation reactor, so that the dispersibility is enhanced, the surface charge and the potential are changed, and the impurities are easy to disperse; removing the graphite by mixed acid treatmentSiO2、Al2O3、MgO、CaO、P2O5CuO, and the like; and performing high-shear selective flocculation size mixing flotation, improving the flotation effect, ensuring the yield of the high-purity graphite, and finally obtaining the high-purity and high-yield graphite.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chemical purification method of graphite specifically comprises the following steps:
s1, preprocessing: crushing graphite raw ore with the fixed carbon content of 60-70%, and then carrying out deep grinding on the graphite raw ore to obtain the graphite raw ore with the grinding fineness of less than 0.074mm and the material content of more than 95%;
s2, adding the graphite raw ore processed in the step S1 into a plasma activation reactor, filling inert gas, adding 10-20% of water, reacting for 1-3h, stopping heating, and continuously filling the inert gas;
s3, adding the material processed in the step S2 into a mixed acid dissolving tank, and stirring to uniformly mix the materials for reaction;
and S4, performing high-shear selective flocculation size mixing flotation on the material processed in the step S3 by stirring and performing flotation for multiple times until the material is nearly neutral, and feeding the material into a vacuum filter to perform vacuum filtration to obtain the high-purity graphite.
Preferably, in step S1, the deep grinding time is 15-20 min.
The technical effect of adopting the technical scheme is as follows: and (3) further dissociating the crushed graphite raw ore to obtain a completely dissociated ore, so that the metal is exposed, and preparing for fully collecting the collecting agent in subsequent mixed acid treatment and flotation.
Preferably, in step S2, the temperature of the plasma activation reactor is 300-500 ℃, and the inert gas flow rate is 0.5-1.5L/min.
Preferably, the plasma activation reactor is in a plate-plate or wire-cylinder dielectric barrier discharge form, the discharge gap is 3-6cm, the discharge voltage is 5-10kV, and the barrier dielectric is alpha-Al2O3Or alpha-quartz.
The technical effect of adopting the technical scheme is as follows: through plasma heating activation, under the action of active particles such as free radical molecules, ions, electrons and the like, impurities in the graphite are activated, the dispersibility is enhanced, surface charges and potentials are changed, the impurities are easy to disperse, and meanwhile, under the action of heating and plasma, molecular bonds and hydrogen bonds between kaolinite layers of the impurities are opened, so that impurity molecules such as Si, Al and the like serve as a basis for the next full acid reaction.
Preferably, in step S3, the mixed acid is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and the volume ratio is: (3-6): (1-2): (1-2): (0.5-1).
The technical effect of adopting the technical scheme is as follows: can carry out sufficient chemical reaction on the added graphite raw material to remove SiO contained in the graphite2、Al2O3、MgO、CaO、P2O5And CuO and the like, thereby achieving the best effect of removing impurities. Compared with the prior art, the method reduces the dosage of chemical reagents and reduces the production cost.
Preferably, in step S3, the stirring rate is 100-300rpm, the reaction time is 15-20 hours, and the reaction temperature is 100-250 ℃.
Preferably, the materials are added into a flotation machine, the pulp mixing rotating speed is 10000-.
The technical effect of adopting the technical scheme is as follows: and high-shear selective flocculation size mixing flotation is adopted, so that the flotation effect is obviously improved, and the yield of high-purity graphite is improved.
Preferably, in step S4, adding a flotation reagent and clean water into the flotation machine, introducing high-pressure gas to generate a large amount of bubbles in the tank, stirring the bubbles to form foam by collecting the reagent, and feeding the foam slurry to the next flotation process by the scraper of the flotation machine; repeating the steps eight times, washing by filtered purified water each time, collecting by high diesel oil and entering the next flotation procedure; the last time of flotation is performed by using deionized water; finally, the pH value of the floated foam slurry is 7.0-7.2.
Preferably, in step S4, the flotation reagent comprises a mixture of a collector, a foaming agent and a modifier, the dosage of the collector is 40-60kg/t, the dosage of the foaming agent is 1-2kg/t, and the dosage of the modifier is 2-3 kg/t;
the deionized water is purified water produced by filtering and ion exchange through a reverse osmosis membrane, and the conductivity of the deionized water is less than or equal to 10 mu S/cm.
Preferably, the collector is petroleum cracking product C5-C9High diesel or a3 oil; the foaming agent is 2#Oil, sec-octanol, terpene alcohol, butyl ether alcohol, or methyl isobutyl carbinol; the finishing agent is sodium carbonate or lime powder.
The invention also provides high-purity graphite prepared by the preparation method; the purity of the high-purity graphite is 99.991-99.995%, and the high-purity graphite is applied to the preparation of a negative electrode material of a lithium power battery.
According to the technical scheme, compared with the prior art, the chemical purification method for graphite disclosed by the invention has the following beneficial effects:
(2) the chemical purification process of graphite provided by the invention comprises the steps of firstly, deeply grinding to fully expose metal in raw graphite ore, and then activating impurities in the graphite through a plasma activation reactor, so that the dispersibility is enhanced, and the surface charge and the potential are changed to ensure that the impurities are easy to disperse; removing SiO contained in the graphite by mixed acid treatment2、Al2O3、MgO、CaO、P2O5CuO, and the like; and the flotation effect is improved and the yield of high-purity graphite is ensured by high-shear selective flocculation size-mixing flotation.
(3) The yield of the high-purity graphite prepared by the method is 92-96%, and the purity of the high-purity graphite is 99.991-99.995%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Feedstock used in the examples of the present invention, such as Petroleum cracking product C5-C9High diesel oil, A3 oil, 2#Oils, sec-octanols, terpene alcohols, butyl ether alcohols, methyl isobutyl carbinol, sodium carbonate, lime powder, etc., are purchased from conventional sources by those skilled in the art and will not be discussed further herein.
Example 1
The embodiment provides a chemical purification method of graphite, which specifically comprises the following steps:
s1, preprocessing: crushing graphite raw ore with the fixed carbon content of 60%, and then carrying out deep grinding on the graphite raw ore for 15min to obtain the graphite raw ore with the grinding fineness of less than 0.074mm and the material content of 95%;
s2, adding the graphite raw ore processed in the step S1 into a plasma activation reactor, wherein the plasma activation reactor is in a plate-plate or wire-cylinder dielectric barrier discharge mode, the discharge gap is 6cm, the discharge voltage is 5kV, and the barrier dielectric is alpha-Al2O3The temperature of the plasma activation reactor is 500 ℃, inert gas is filled, wherein the flow rate of the inert gas is 1.5L/min, 10 percent of water is added, after the reaction is carried out for 3 hours, the heating is stopped, and the inert gas is continuously filled;
s3, adding the material processed in the step S2 into a mixed acid dissolving tank, wherein the mixed acid is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and the volume ratio is as follows: 3: 1: 1: 0.5, the solid-to-solid ratio of the mixed acid to the graphite solution is 3.5:1, and then the reaction is carried out for 15 hours at the stirring speed of 100rpm and the reaction temperature of 100 ℃;
s4, adding the material processed in the step S3 into a flotation machine, adjusting the pulp rotation speed to 28000rpm, adjusting the pulp time to 10min, adding a flotation reagent and clean water into the flotation machine, introducing high-pressure gas to generate a large amount of bubbles in a tank, stirring the bubbles to form foams by collecting the reagents, and sending the foams to the next flotation process by a scraper of the flotation machine; repeating eight times, each time by passingWashing the filtered purified water with high-grade diesel oil and collecting the filtered purified water and then entering the next flotation process; the last time of flotation is performed by using deionized water; finally, the pH value of the floated foam slurry is 7.0-7.2; the flotation agent comprises a mixture of a collecting agent, a foaming agent and a regulator, wherein the collecting agent is high-grade diesel oil, the dosage of the collecting agent is 60kg/t, and the foaming agent is 2#2kg/t of oil, 3kg/t of sodium carbonate as a regulator; the deionized water is purified water produced by filtering and passing through a reverse osmosis membrane through ion exchange, and the conductivity of the deionized water is less than or equal to 10 mu S/cm.
And performing flotation for multiple times until the material is nearly neutral, feeding the material into a vacuum filter, performing vacuum filtration, and drying at the temperature of 150 ℃ for 2 hours to obtain graphite with the purity of 99.992% and the yield of 99.92%.
Example 2
The embodiment provides a chemical purification method of graphite, which specifically comprises the following steps:
s1, preprocessing: crushing graphite raw ore with the fixed carbon content of 70%, and then carrying out deep grinding on the graphite raw ore for 20min to obtain the graphite raw ore with the grinding fineness of less than 0.074mm and the material content of 96%;
s2, adding the graphite raw ore processed in the step S1 into a plasma activation reactor, wherein the plasma activation reactor is in a plate-plate or line-cylinder dielectric barrier discharge mode, the discharge gap is 3cm, the discharge voltage is 10kV, the barrier dielectric is alpha-quartz, the temperature of the plasma activation reactor is 300 ℃, and inert gas is filled, wherein the inert gas flow rate is 0.5L/min, 20% of water is added, after the reaction is carried out for 1h, the heating is stopped, and the inert gas is continuously filled;
s3, adding the material processed in the step S2 into a mixed acid dissolving tank, wherein the mixed acid is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and the volume ratio is as follows: 6: 2: 2: 1, the solid-to-solid ratio of the mixed acid to the graphite liquid is 4.5:1, and then the mixed acid and the graphite liquid are stirred at the speed of 300rpm, the reaction temperature is 250 ℃, and the reaction time is 20 hours;
s4, adding the material processed in the step S3 into a flotation machine, adjusting the pulp rotating speed to 10000rpm, adjusting the pulp time to 30min, and performing flotationAdding a flotation reagent and clean water into the flotation machine, introducing high-pressure gas to generate a large amount of bubbles in the tank, stirring, collecting the reagent to form foam, and sending the foam slurry to the next flotation process by a scraper of the flotation machine; repeating the steps eight times, washing by filtered purified water each time, collecting by high diesel oil and entering the next flotation procedure; the last time of flotation is performed by using deionized water; finally, the pH value of the floated foam slurry is 7.0-7.2; the flotation agent comprises a mixture of a collector, a foaming agent and a regulator, wherein the collector is a petroleum cracking product C5-C940kg/t of foaming agent, 1kg/t of secondary octanol and 2kg/t of lime powder as regulator; the deionized water is purified water produced by filtering and passing through a reverse osmosis membrane through ion exchange, and the conductivity of the deionized water is less than or equal to 10 mu S/cm.
After multiple times of flotation, the material is nearly neutral, and the material is sent into a vacuum filter to be filtered in vacuum, and is dried for 3 hours at the temperature of 80 ℃ to obtain the graphite, the purity is 99.994%, and the yield is 99.93%.
Example 3
The embodiment provides a chemical purification method of graphite, which specifically comprises the following steps:
s1, preprocessing: crushing graphite raw ore with the fixed carbon content of 65%, and then carrying out deep grinding on the graphite raw ore for 18min to obtain the graphite raw ore with the grinding fineness of less than 0.074mm and the material content of 96%;
s2, adding the graphite raw ore processed in the step S1 into a plasma activation reactor, wherein the plasma activation reactor is in a plate-plate or wire-cylinder dielectric barrier discharge mode, the discharge gap is 5cm, the discharge voltage is 8kV, and the barrier dielectric is alpha-Al2O3The temperature of the plasma activation reactor is 400 ℃, inert gas is filled, wherein the flow rate of the inert gas is 1.0L/min, 15% of water is added, after the reaction is carried out for 2 hours, the heating is stopped, and the inert gas is continuously filled;
s3, adding the material processed in the step S2 into a mixed acid dissolving tank, wherein the mixed acid is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and the volume ratio is as follows: 5: 1.5: 1.5: 0.8, the solid-to-solid ratio of the mixed acid to the graphite solution is 4.0:1, and then the reaction is carried out for 18 hours at the stirring speed of 200rpm and the reaction temperature of 200 ℃;
s4, adding the material processed in the step S3 into a flotation machine, adjusting the pulp rotation speed to 24000rpm, adjusting the pulp time to 15min, adding a flotation reagent and clean water into the flotation machine, introducing high-pressure gas to generate a large amount of bubbles in a tank, stirring the bubbles to form foams by collecting the reagents, and sending the foams to the next flotation process by a scraper of the flotation machine; repeating the steps eight times, washing by filtered purified water each time, collecting by high diesel oil and entering the next flotation procedure; the last time of flotation is performed by using deionized water; finally, the pH value of the floated foam slurry is 7.0-7.2; the flotation reagent comprises a mixture of a collecting agent, a foaming agent and a regulator, wherein the collecting agent is A3 oil, the using amount of the collecting agent is 50kg/t, the foaming agent is methyl isobutyl carbinol, the using amount of the foaming agent is 1.5kg/t, the regulator is sodium carbonate, the using amount of the regulating agent is 2.5kg/t, deionized water is purified water generated by a reverse osmosis membrane through filtration and ion exchange, and the conductivity of the purified water is less than or equal to 10 mu S/cm.
Performing multiple flotation until the material is nearly neutral, vacuum filtering the material in a vacuum filter, and drying at 120 deg.C for 2.5 hr to obtain graphite with purity of 99.995% and yield of 99.96%
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A chemical purification method of graphite is characterized by comprising the following steps:
s1, preprocessing: crushing graphite raw ore with the fixed carbon content of 60-70%, and then carrying out deep grinding on the graphite raw ore to obtain the graphite raw ore with the grinding fineness of less than 0.074mm and the material content of more than 95%;
s2, adding the graphite raw ore processed in the step S1 into a plasma activation reactor, filling inert gas, adding 10-20% of water, reacting for 1-3h, stopping heating, and continuously filling the inert gas;
s3, adding the material processed in the step S2 into a mixed acid dissolving tank, and stirring to uniformly mix the materials for reaction;
and S4, performing high-shear selective flocculation size mixing flotation on the material processed in the step S3 by stirring and performing flotation for multiple times until the material is nearly neutral, and performing vacuum filtration to obtain the high-purity graphite.
2. The chemical purification method of graphite according to claim 1, wherein in step S1, the deep grinding time is 15-20 min.
3. The method of claim 1, wherein in step S2, the temperature of the plasma activation reactor is 300-500 ℃, and the inert gas flow rate is 0.5-1.5L/min.
4. A chemical purification method of graphite according to claim 3, wherein the plasma activation reactor is in the form of plate-plate or wire-cylinder dielectric barrier discharge with a discharge gap of 3-6cm, a discharge voltage of 5-10kV, and a barrier dielectric of α -Al2O3Or alpha-quartz.
5. The method for chemical purification of graphite according to claim 1, wherein in step S3, the mixed acid is a mixture of hydrofluoric acid, hydrochloric acid, sulfuric acid and nitric acid, and the volume ratio is: (3-6): (1-2): (1-2): (0.5-1).
6. The method for chemical purification of graphite as claimed in claim 1, wherein in step S3, the stirring rate is 100-.
7. The method as claimed in claim 1, wherein in step S4, the material is added into the flotation machine, the slurry mixing speed is 10000-.
8. A chemical purification method of graphite according to claim 7, wherein in step S4, a flotation reagent and clean water are added into the flotation machine, high pressure gas is introduced to generate a large amount of bubbles in the cell, the agent is stirred and collected to form foam, and the foam slurry is sent to the next flotation process by the scraper of the flotation machine; repeating the steps eight times, washing by filtered purified water each time, collecting by high diesel oil and entering the next flotation procedure; the last time of flotation is performed by using deionized water; finally, the pH value of the floated foam slurry is 7.0-7.2.
9. The method for chemical purification of graphite according to claim 8, wherein in step S4, the flotation agent comprises a mixture of a collector, a foaming agent and a modifier;
the deionized water is purified water produced by filtering and ion exchange through a reverse osmosis membrane, and the conductivity of the deionized water is less than or equal to 10 mu S/cm.
10. A high purity graphite produced by the production method according to any one of claims 1 to 8; the purity of the high-purity graphite is 99.991-99.995%.
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