CN118145638A - Electrochemical preparation method of expanded graphite - Google Patents
Electrochemical preparation method of expanded graphite Download PDFInfo
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- CN118145638A CN118145638A CN202410218731.7A CN202410218731A CN118145638A CN 118145638 A CN118145638 A CN 118145638A CN 202410218731 A CN202410218731 A CN 202410218731A CN 118145638 A CN118145638 A CN 118145638A
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- solution
- graphite
- electrolyte
- ammonium bifluoride
- expanded graphite
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 74
- 239000010439 graphite Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 239000007790 solid phase Substances 0.000 claims abstract description 25
- -1 polypropylene Polymers 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000004743 Polypropylene Substances 0.000 claims abstract description 20
- 229920001155 polypropylene Polymers 0.000 claims abstract description 20
- 239000004744 fabric Substances 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 13
- 229910021382 natural graphite Inorganic materials 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 57
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 11
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000005188 flotation Methods 0.000 description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000607734 Yersinia <bacteria> Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001007 puffing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940009662 edetate Drugs 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000001052 yellow pigment Substances 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
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/135—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an electrochemical preparation method of expanded graphite, which comprises the following steps: s1: preparing electrolyte, and uniformly coating a mixture of graphite powder and the electrolyte on the surface of an anode of an electrochemical reactor; s2: a porous membrane is paved on the mixture layer of the graphite powder and the electrolyte; s3: pressing a cathode on the polypropylene cloth layer for electrolysis; s4: separating the solid phase from the solution after the electrolysis process is finished, and then adding ammonia water into the solid phase until the solution is in alkaline reaction; s5: adding disodium ethylenediamine tetraacetate solution, heating the prepared mixture to 50-100 ℃ for 1-2 hours, filtering the solution, washing filter residues with deionized water, adding ammonium bifluoride-hydrochloric acid solution, preserving the temperature for 5-10 hours at 55-75 ℃, and washing with deionized water until no chloride ions exist; s6: separating the residue from the solution, drying and heat treating at 800-1200deg.C. Can effectively improve the purity of the expanded graphite and produce better economic benefit.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to an electrochemical preparation method of expanded graphite.
Background
The expanded graphite is used as an intermediate product for manufacturing flexible graphite, and is a loose porous vermiform substance obtained by oxidizing, acidifying, intercalating, washing with water, drying and puffing at high temperature natural crystalline flake graphite. The expanded graphite not only has the excellent characteristics of heat resistance, corrosion resistance, electric conduction, heat conduction, self lubrication and the like of the natural graphite, but also has the performances of light weight, softness, compressibility, resilience and the like which are not possessed by the natural graphite, and the expanded graphite is widely used in industries such as petroleum, chemical industry, electric power, metallurgy, machinery, aerospace, nuclear industry and the like at present.
The prior art discloses a method for preparing expanded graphite, which comprises the steps of pre-mixing 100-200 g of dispersed graphite with 50-57% sulfuric acid aqueous solution according to the proportion of 750-850 cubic centimeters sulfuric acid aqueous solution per 1 kg of graphite, loading the obtained mixture into a reaction container, trowelling, and placing a separator and a cathode with a cover on the top of the mixture. After the separator was immersed in the electrolyte, the current was applied and the treatment was performed in constant current mode. After 80Ah/kg of anodic treatment, the graphite mixture was extruded into a filter, sulfuric acid and ammonium difluoride were added in a ratio of 10g of ammonium difluoride per 100g of graphite. The reaction temperature is 20-70 ℃ and the reaction time is 2-12 hours. The solid is pickled and dried, and is put into a quartz reactor of a shaft furnace to be heated at the temperature of 1000 ℃. The purity of the obtained expanded graphite is 98.5-99.3%. The preparation method mainly comprises the steps of adding sulfuric acid solution into natural dispersed graphite, carrying out electrochemical treatment, removing liquid phase, washing with water, carrying out acid solution treatment by ammonium bifluoride, removing liquid phase, drying and carrying out heat treatment. However, this method has the following general problems: the purity of the obtained expanded graphite is lower.
Disclosure of Invention
In order to solve the above technical problems, the inventors have developed an electrochemical preparation method of expanded graphite according to their experience accumulated in the art.
The invention adopts the technical scheme that:
An electrochemical preparation method of expanded graphite comprises the following steps: s1: preparing sulfuric acid with the concentration of 30-94% as electrolyte, and uniformly coating a mixture of graphite powder with the thickness of 4-10 mm and the electrolyte on the surface of an anode of an electrochemical reactor;
s2: a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte;
S3: pressing a cathode on the polypropylene cloth layer to ensure electrical contact with graphite powder, then switching on direct current to electrolyze the graphite, wherein the current density is 0.5-55mA/cm 2, and the power consumption is 90-120 A.h/kg;
s4: separating the solid phase from the solution after the electrolysis process is finished, and then adding ammonia water into the solid phase until the solution is in alkaline reaction;
S5: adding disodium ethylenediamine tetraacetate solution, heating the prepared mixture to 50-100 ℃ for 1-2 hours, filtering the solution, washing filter residues with deionized water, adding ammonium bifluoride-hydrochloric acid solution, preserving the temperature for 5-10 hours at 55-75 ℃, and washing with deionized water until no chloride ions exist;
s6: separating the residue from the solution, drying and heat treating at 800-1200deg.C.
Further, in the step S5, disodium ethylenediamine tetraacetate solution is added in a proportion of 5-40 g disodium ethylenediamine tetraacetate per 100 g graphite.
Further, in the step S5, the addition amount of the ammonium bifluoride-hydrochloric acid solution is 10-20 g of ammonium bifluoride per 100 g of natural graphite.
Further, the content of ammonium bifluoride in the ammonium bifluoride-hydrochloric acid solution is 2-4wt%.
The preparation method of the invention uses the following materials:
Flotation enriched graphite produced by Chinese Xiangyang company contains 94% of carbon;
GT-2 grade flotation of Zawamori graphite joint factory (Zavalyevskiy Graphite) GOST 17022-81 enriches graphite with carbon content of 96.4%;
flotation enriched graphite produced by Qingdao China company has 94.7 percent of carbon content;
Flotation enriched graphite produced in india TITAN METALS AND MINERALS LIMITED, carbon content 97%;
Sulfuric acid, DSTU GOST 2184:2018 industrial sulfuric acid; among them, concentrated sulfuric acid, anhydrous sulfuric acid, fuming sulfuric acid, and the like can be used as the sulfuric acid. The sulfuric acid concentration is usually 95% or more, preferably 98% or more. The content of sulfuric acid in the treatment solution is in the range of 90% or more, preferably 95% or more, and particularly preferably 97% or more. If the reaction rate is less than 90%, the reaction rate may be significantly reduced. In addition, as described above, since moisture acts to lower the thermal expansion start temperature of the thermally expandable graphite, it is preferable to reduce the moisture concentration as much as possible in the treatment liquid.
Ammonium bifluoride GOST 4518-75; the molecular formula is NH4HF2, the relative molecular weight is 57.05, and the crystal is white or colorless transparent orthorhombic crystal, the relative density is 1.52 (25 ℃), the melting point is 125.6 ℃ and the boiling point is 239.℃. Ammonium bifluoride can be used as glass etchant, preservative, solvent for beryllium oxide to prepare metallic beryllium, chemical reagent, cleaning agent for boiler water supply system and steam generation system, fermentation industrial disinfectant and surface treating agent for siliceous steel plate, oxidizing agent for producing ceramics and aluminium-magnesium alloy, organic synthesis fluorinating agent, electroplating solution, solvent for extracting rare elements, surface treating agent for siliceous steel plate and corrosive agent for surface treatment of aluminium profile, acidifying treating agent for oilfield sand and the like.
Potassium dichromate GOST 4220-75; the molecular formula is K2Cr2O7, which is an important chromium chemical product. The method is mainly used for preparing chromium salt products such as chromium trioxide, potassium chromium sulfate, chrome yellow pigment and the like, and also used for manufacturing matches, explosives, electroplating additives, mordant, tanning agents, medicines, oxidizing agents, synthetic fragrances, enamel glaze powder, metal passivating agents, printing ink, welding electrodes and the like.
Ammonia water solution, purchased commercially; ammonia water is also called Ammonia water, the main component of which is NH3.H2O, is an aqueous solution of ammonia, is colorless and transparent, and has pungent smell. Ammonia has a melting point of-77.773 ℃, a boiling point of-33.34 ℃ and a density of 0.91g/cm 3. Ammonia is easily dissolved in water and ethanol. Is volatile, has partial alkali permeability, and is prepared by introducing ammonia into water. Ammonia is toxic, has irritation and corrosiveness to eyes, nose and skin, can suffocate people, and has the maximum allowable concentration of 30mg/m in air. The fertilizer is mainly used as a chemical fertilizer.
Industrial ammonia water is an aqueous solution containing 25% -28% ammonia, and only a small part of ammonia molecules in the ammonia water react with water to form ammonia monohydrate, which is a weak base only existing in the ammonia water. The freezing point of ammonia is related to the concentration of ammonia, and the usual (wt) 20% concentration freezing point is about-35 ℃. Heat is generated by the neutralization reaction with an acid. There is a risk of combustion explosion. Specific heat capacity of 4.3X10 3 J/kg (10% ammonia water)
Disodium Edetate (EDTA) GOST 10652-73 tetrasodium edetate, ethylenediamine-N, N, N ', N' -tetraacetic acid, 2-water (TrilonB); is an important complexing agent. The EDTA-Na can be used for electroless copper plating, gold plating, lead-tin alloy plating, electrochemical polishing of steel and iron pieces and solution before silver plating of the copper pieces. It is also used in detergent, liquid soap, shampoo, agrochemical spray, color photosensitive material washing, bleaching and fixing liquid, water purifying agent, pH regulator, coagulant inhibitor, etc. In the reduction initiation system for styrene-butadiene rubber polymerization, EDTA disodium is used as a component part of an active agent and is mainly used for complexing ferrous ions to control the polymerization reaction speed.
Deionized water, quality standard MOL-LUB 09619;
Deionized water refers to pure water from which impurities in ionic form have been removed. "deionization" defined by International organization for standardization ISO/TC 147 is defined as: "deionized water completely or incompletely removes ionic substances" refers primarily to the treatment with ion exchange resins. The present technology is mainly prepared by adopting an RO reverse osmosis method. Ion exchange resin is used for removing anions and cations in water, but soluble organic matters still exist in the water, so that the ion exchange column can be polluted to reduce the efficacy of the ion exchange column, and bacteria are easy to multiply after deionized water is stored.
Films made of polypropylene cloth.
The polypropylene cloth is a crystalline polymer with regular structure, is white granular or powder, is odorless, nontoxic and light thermoplastic resin, has the advantages of easy processing, good impact strength, flexibility, good electrical insulation and the like, and has wide application in the aspects of automobile industry, household appliances, electronics, packaging, building materials, furniture and the like, wherein the longitudinal tensile modulus of the polypropylene film used by the invention can reach more than 3.49GPa, the transverse tensile modulus can reach more than 5.32GPa, the longitudinal breaking strength can reach more than 72MPa, and the transverse breaking strength can reach more than 105 MPa.
Compared with the prior art, the invention has the following beneficial effects:
The invention can better solve the problem of lower purity through the steps of electrochemical treatment, liquid-solid phase separation, washing, drying, puffing and the like, effectively improves the purity of the expanded graphite, meets the existing demands of the market, and generates better economic benefit.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
An electrochemical preparation method of expanded graphite comprises the following steps: 800 g of natural flotation enriched graphite produced by Xianyang China company is selected, and the natural flotation enriched graphite is mixed with 30% sulfuric acid solution according to the proportion of taking 100 cubic centimeters of electrolyte per 100 g of graphite. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 10mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the membrane is a good membrane, has small ion movement resistance and has enough thickness. A cathode is pressed on the polypropylene cloth layer to ensure electrical contact with graphite powder, and then the graphite is connected with direct current, the current density is 0.5mA/cm 2, and the power consumption is 90 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an ethylene diamine tetraacetic acid disodium solution was added in a proportion of 40 g of ethylene diamine tetraacetic acid disodium per 100 g of graphite, the prepared mixture was heated to 100 ℃ for 1 hour, then the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (content of ammonium bifluoride was 4 wt%) was added in an amount of 20 g of ammonium bifluoride per 100 g of natural graphite, heat was preserved at 75 ℃ for 5 hours, the solid phase was separated from the solution by washing with deionized water until no chloride ions, and dried and heat treated at 800 ℃. The purity of the obtained expanded graphite was 99.93%.
Example 2
An electrochemical preparation method of expanded graphite comprises the following steps: 1000 g of GT-2 grade flotation enriched graphite of GOST 17022-81 of Zawamori Yersinia graphite joint factory (Zavalyevskiy Graphite) is selected, the carbon content is 96.4%, and the graphite is mixed with 50% sulfuric acid solution according to the proportion of 80 cubic centimeters of electrolyte per 100 g of graphite. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 6 mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the membrane is a good membrane, has small ion movement resistance and has enough thickness. A cathode is pressed on the polypropylene cloth layer to ensure the electrical contact with graphite powder, and then the graphite is connected with direct current, the current density is 10mA/cm 2, and the power consumption is 95 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an ethylene diamine tetraacetic acid disodium solution was added in a proportion of 30 g of ethylene diamine tetraacetic acid disodium per 100 g of graphite, the prepared mixture was heated to 80 ℃ for 2 hours, then the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (ammonium bifluoride content was 4 wt%) was added in an amount of 15 g of ammonium bifluoride per 100 g of natural graphite, heat was preserved for 6 hours at 70 ℃, the solid phase was separated from the solution by washing with deionized water until no chloride ions, and dried and heat-treated at 1100 ℃. The purity of the obtained expanded graphite was 99.91%.
Example 3
An electrochemical preparation method of expanded graphite comprises the following steps: 1200 g of natural graphite produced by Qingdao China with 94.7% carbon content is selected and mixed with 40% sulfuric acid solution in a proportion of 90 cubic centimeters of electrolyte per 100 g of graphite. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 4 mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the membrane is a good membrane, has small ion movement resistance and has enough thickness. A cathode is pressed on the polypropylene cloth layer to ensure the electrical contact with graphite powder, and then the graphite is connected with direct current, the current density is 30mA/cm 2, and the power consumption is 100 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an ethylene diamine tetraacetic acid disodium solution was added in a proportion of 35g of ethylene diamine tetraacetic acid disodium per 100 g of graphite, the prepared mixture was heated to 90 ℃ for 1 hour, then the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (content of ammonium bifluoride was 4 wt%) was added in an amount of 20g of ammonium bifluoride per 100 g of natural graphite, heat was preserved at 55 ℃ for 10 hours, the solid phase was separated from the solution by washing with deionized water until no chloride ions, and dried and heat treated at 1000 ℃. The purity of the obtained expanded graphite was 99.95%.
Example 4
An electrochemical preparation method of expanded graphite comprises the following steps: flotation concentrate from indian TITAN METALS AND MINERALS LIMITED was selected, 1500 grams of carbon content 97.0%, and mixed with 94% sulfuric acid solution in a ratio of 50 cubic centimeters of electrolyte per 100 grams of graphite. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 8 mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the membrane is a good membrane, has small ion movement resistance and has enough thickness. And (3) pressing a cathode on the polypropylene cloth layer to ensure electrical contact with graphite powder, and then switching on direct current with current density of 55mA/cm 2 and power consumption of 120 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an disodium ethylenediamine tetraacetate solution was added in a proportion of 5 g disodium ethylenediamine tetraacetate per 100 g graphite, the prepared mixture was heated to 50 ℃ for 2 hours, then the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (the content of ammonium bifluoride was 4 wt%) was added in an amount of 10g ammonium bifluoride per 100 g natural graphite, heat was preserved for 7 hours at 60 ℃, the solid phase was separated from the solution by washing with deionized water until no chloride ions, and dried and heat treated at a temperature of 1200 ℃. The purity of the obtained expanded graphite was 99.96%.
Example 5
An electrochemical preparation method of expanded graphite comprises the following steps: the process comprises selecting 1200 g of GT-2 grade flotation enriched graphite of GOST 17022-81 of Zawamori Yersinia graphite joint factory (Zavalyevskiy Graphite), mixing with 50% sulfuric acid solution at a ratio of 80 cubic centimeters of electrolyte per 100 g of graphite, wherein the carbon content is 97.9%. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 7 mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the electrochemical reactor is a good diaphragm, has small ion movement resistance and has enough thickness. A cathode is pressed on the polypropylene cloth layer to ensure the electrical contact with graphite powder, and then the graphite is connected with direct current, the current density is 10mA/cm 2, and the power consumption is 95 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an ethylene diamine tetraacetic acid disodium solution was added in a proportion of 30g of ethylene diamine tetraacetic acid disodium per 100 g of graphite, the prepared mixture was heated to 100 ℃ for 3 hours, then the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (content of ammonium bifluoride was 4 wt%) was added in an amount of 18 g of ammonium bifluoride per 100 g of natural graphite, heat was preserved at 80 ℃ for 6 hours, the solid phase was separated from the solution by washing with deionized water until no chloride ions, and dried and heat treated at 1100 ℃. The purity of the obtained expanded graphite was 99.80%.
Example 6
An electrochemical preparation method of expanded graphite comprises the following steps: 1000 g of natural graphite produced by Qingdao China with the carbon content of 95.5 percent is selected and mixed with 40 percent sulfuric acid solution according to the proportion of 90 cubic centimeters of electrolyte per 100 g of graphite. The anode surface of the electrochemical reactor is uniformly coated with a mixture of graphite powder and electrolyte with the thickness of 4mm, and a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte, so that the membrane is a good membrane, has small ion movement resistance and has enough thickness. A cathode is pressed on the polypropylene cloth layer to ensure the electrical contact with graphite powder, and then the graphite is connected with direct current, the current density is 30mA/cm 2, and the power consumption is 100 A.h/kg. After the electrolysis process was completed, the solid phase was separated from the solution, then ammonia water was added to the solid phase until the solution was alkaline, and an ethylene diamine tetraacetic acid disodium solution was added in an amount of 38 g of ethylene diamine tetraacetic acid disodium per 100 g of graphite, the prepared mixture was heated to 100 ℃ for 1.5 hours, the solution was filtered off, the filter residue was washed with deionized water, ammonium bifluoride-hydrochloric acid solution (ammonium bifluoride content was 4 wt%) was added in an amount of 18 g of ammonium bifluoride per 100 g of natural graphite, heat was preserved for 11 hours at 68 ℃, the solid phase was separated from the solution by washing with deionized water until no chloride ion was present, and dried and heat treated at 1100 ℃. The purity of the obtained expanded graphite was 99.82%.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (4)
1. An electrochemical preparation method of expanded graphite is characterized in that: the method comprises the following steps:
s1: preparing sulfuric acid with the concentration of 30-94% as electrolyte, and uniformly coating a mixture of graphite powder with the thickness of 4-10 mm and the electrolyte on the surface of an anode of an electrochemical reactor;
s2: a porous membrane made of chemical corrosion resistant polypropylene cloth is paved on the mixture layer of the graphite powder and the electrolyte;
S3: pressing a cathode on the polypropylene cloth layer to ensure electrical contact with graphite powder, then switching on direct current to electrolyze the graphite, wherein the current density is 0.5-55mA/cm 2, and the power consumption is 90-120 A.h/kg;
s4: separating the solid phase from the solution after the electrolysis process is finished, and then adding ammonia water into the solid phase until the solution is in alkaline reaction;
S5: adding disodium ethylenediamine tetraacetate solution, heating the prepared mixture to 50-100 ℃ for 1-2 hours, filtering the solution, washing filter residues with deionized water, adding ammonium bifluoride-hydrochloric acid solution, preserving the temperature for 5-10 hours at 55-75 ℃, and washing with deionized water until no chloride ions exist;
s6: separating the residue from the solution, drying and heat treating at 800-1200deg.C.
2. The electrochemical preparation method of the expanded graphite according to claim 1, wherein: in the step S5, disodium ethylenediamine tetraacetate solution is added in a proportion of 5-40 g of disodium ethylenediamine tetraacetate per 100 g of graphite.
3. The electrochemical preparation method of the expanded graphite according to claim 1, wherein: in the step S5, the addition amount of the ammonium bifluoride-hydrochloric acid solution is 10-20 g of ammonium bifluoride per 100g of natural graphite.
4. The electrochemical preparation method of the expanded graphite according to claim 1, wherein: the content of ammonium bifluoride in the ammonium bifluoride-hydrochloric acid solution is 2-4wt%.
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