CN108516544A - It is electrolysed HF and KHF2Generate the method and system of fluorine gas purification graphite - Google Patents
It is electrolysed HF and KHF2Generate the method and system of fluorine gas purification graphite Download PDFInfo
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- CN108516544A CN108516544A CN201810555993.7A CN201810555993A CN108516544A CN 108516544 A CN108516544 A CN 108516544A CN 201810555993 A CN201810555993 A CN 201810555993A CN 108516544 A CN108516544 A CN 108516544A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 100
- 239000011737 fluorine Substances 0.000 title claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010439 graphite Substances 0.000 title claims abstract description 54
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 54
- 238000000746 purification Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 152
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 58
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000460 chlorine Substances 0.000 claims abstract description 25
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000010792 warming Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000012774 insulation material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 238000005087 graphitization Methods 0.000 claims description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 238000010926 purge Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 230000006872 improvement Effects 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000036647 reaction Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006052 feed supplement Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- -1 electrolysis cells I Chemical compound 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
-
- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/245—Fluorine; Compounds thereof
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to electrolysis HF and KHF2 to generate the method that fluorine gas purifies graphite, including following production stage:First by HF and KHF2It is mixed, is put into electrolytic cell in proportion；Electrolytic cell is heated, HF and KHF are made2Reach molten condition；Graphite product, resistance material and insulation material are added in graphitizing furnace after setting stove spacing；It is heated up with the speed of 10~250 DEG C/min, furnace core temperature reaches logical nitrogen purge gas at 1800~1900 DEG C；1900~2000 DEG C are warming up to, stops logical nitrogen and changes logical chlorine；2300~2500 DEG C are warming up to, logical chlorine simultaneously opens power supply electrolysis mixed liquor, and electrolysis generates fluorine gas and is passed through in graphitizing furnace；Fluorine gas generates fluoride with high-boiling-point impurity chemical combination and is discharged with gas.The present invention also provides a kind of devices for realizing the technique.The present invention generates fluorine gas by increasing electrolysis section, using electrolysis and is passed through the step of freon is purified instead of prior art, ensures to substantially reduce again while high-boiling-point impurity is removed in purification process and to be adversely affected caused by environment.
Description
Technical field：
The present invention relates to graphite preparing technical fields, are more particularly to electrolysed HF and KHF2It generates fluorine gas and purifies stone
The method and system of ink.
Background technology：
Existing technology status：Existing purification graphite is purified into promoting the circulation of qi heat in graphitization, most metals halogenation
The fusing point and boiling point of object are all relatively low, and especially some high-boiling-point impurities such as boron, vanadium, molybdenum, silicon etc. must pass through fluorination or chlorination
It can remove.When being graphitized purifying, generally reaches a timing in furnace core temperature and start to be passed through nitrogen, exclude the air in furnace core, so
After be passed through chlorine, freon and chlorine are passed through when reaching certain temperature to furnace core temperature again and is blown altogether, and then makes high-boiling-point impurity shape
It is discharged with gas at boiling point is reduced after compound.
But the freon that uses of the prior art can destroy ozone layer and lead to disruption of ecological balance, and need government using unit
Examine quota.
Invention content：
An object of the present invention is in view of the deficiencies of the prior art, to provide electrolysis HF and KHF2Generate fluorine gas purification
The method of graphite generates fluorine gas using electrolysis section and replaces prior art by increasing electrolysis section in graphite purification technique
In reach a timing in in-furnace temperature and need to be passed through the step of freon is purified, while ensureing that high-boiling-point impurity is removed
It can substantially reduce in purification process and be adversely affected caused by environment again.
The technology solution of the present invention is as follows：
It is electrolysed HF and KHF2The method for generating fluorine gas purification graphite, which is characterized in that including following production stage：
One, electrolysis section：By HF and KHF2In molar ratio 1:2~4 carry out being mixed to form electrolyte, are put into electrolytic cell,
Electrolytic cell is heated, the HF and KHF of electrolyte bath are made2Reach molten condition, opens power supply and electrolyte is electrolysed
Generate fluorine gas；
Two, graphitization/purification part：The spacing of multigroup graphite product as requested is arranged in graphitizing furnace, successively
Insulation material and resistance material are inserted, after shove charge, heating graphitizing furnace to furnace core temperature is passed through nitrogen when being 1800~1900 DEG C
The air in furnace core is excluded, heating rate is 10~30 DEG C/min；Continue to heat graphitizing furnace when being warming up to 1900~2000 DEG C,
Stopping is passed through chlorine, switchs to be passed through chlorine；Continue to heat graphitizing furnace when being warming up to 2300~2500 DEG C, will be electrolysed in step 1
The fluorine gas of generation is passed through in graphitizing furnace, and fluorine gas forms fluoride with the impurity chemical combination in graphite product, reduces its boiling point.
The power supply pair in step 1 is opened when as an improvement, graphitizing furnace being warming up to 2300~2500 DEG C in the step 2
Electrolyte electrolysis generates fluorine gas, is passed through the fluorine gas of electrolysis generation in graphitizing furnace in electrolysis.
As an improvement, HF and KHF in the step 12In molar ratio 1:2~3 are mixed, and are put into electrolytic cell, preferably
Ratio is 1:3, the wherein concentration of HF is maintained at 38%~40%, fluorine gas electrolytic cell all by the Hastelloy of heat-and corrosion-resistant or
Similar material is made, and electrolysis electrode is installed on electrolytic cell both sides respectively, and anode is nickel plate, and cathode is stainless steel plate；In electrolytic process
Reaction equation it is as follows：
Anode：2F--2e-→F2↑
Cathode：2HF2 -+2e-→H2↑+4F-。
HF and KHF is used in the present invention2Mixture is to have considered material cost and generation fluorine gas as electrolyte
The factors such as efficiency, naturally it is also possible to be used as electrolyte such as KF using others, preferably use HF and KHF herein2Mixture.
As an improvement, keeping micro-vacuum state, chlorine during being passed through fluorine gas and being purified in the graphitizing furnace
It is diffused in product by graphitizing furnace bottom with fluorine gas, wherein chlorine supplies gas unit consumption as 20~25kg/m3, fluorine gas unit consumption of supplying gas is
15-20kg/m3；Wherein fluorine gas generates fluoride with the impurity element chemical combination in sample reduces its boiling point；By taking boron as an example, boiling point
It more than 3500 DEG C, is reacted with fluorine gas, 2B+3F2→2BF2, -127.1 DEG C of the boron fluoride boiling point of generation.
As an improvement, heated to electrolytic cell by water-bath heater in the step 1, heating temperature 70 DEG C~
100 DEG C, preferably 80 DEG C~95 DEG C.
As an improvement, further including vent gas treatment part, the mixed gas generated in step 2 is passed into tail gas absorbing system
It is discharged after the middle removal by fluorine gas therein；Further include hydrogen purification part, the hydrogen of generation is electrolysed in step 1, and to enter hydrogen net
It is discharged after changing the hydrogen fluoride that device removal is wherein carried secretly, wherein tail gas absorbing system is by several sodium hydroxide solution absorber groups
At fluorine gas reacts removal, equation 2F with sodium hydroxide2+4NaOH→NaF+2H2O+O2, the molten people of fluoride of gasification is water-soluble
In liquid, after absorption system, after tail gas reaches discharge standard, it is discharged into air.
As an improvement, further including feed supplement part, in step 1 during electrolysis, pass through the monitoring electrolysis of online acidometer
Hydrofluoric acid concentration in slot when concentration is too low, injects hydrofluoric acid by hydrofluoric acid storage tank in electrolytic cell.
It is passed through molecular weight and boiling point parameter that chlorine and fluorine gas carry out pure treated the nuclear graphite materials metal chloride of core
It see the table below 1.
Table 1：The molecular weight and boiling point of typical metal chloride
Bibliography：
CRC Handbook of Chemistry and Physics, 75th ed., 1994
PlenumPress Handbook
Table 2：The molecular weight and boiling point of typical metal fluoride
Bibliography：
Merck Index, 11thEdition, 1989
CRC Handbook of Chemistry and Physics, 75th ed., 1994
By Tables 1 and 2 it is found that the present invention is under graphitization processing high temperature, it is passed through after chlorine and fluorine gas in nuclear graphite materials
Metal chloride and metal fluoride boiling point far below the high boron element in graphitization temperature, especially neutron absorption cross-section and
The fluoride boiling point of class boron element substantially reduces, and then can targetedly control the boron equivalent in nuclear graphite materials.
It is a further object of the present invention to provide electrolysis HF and KHF2The system for generating fluorine gas purification graphite, by furnace body
Electrolytic cell is arranged in side, and the fluorine gas generated using electrolytic cell Inner electrolysis, which is passed into furnace body, purifies graphite, and then solves
The problem of high-boiling-point impurity element is difficult to remove and cause the destruction to environment when being purified using freon in graphite.
It is electrolysed HF and KHF2The system that fluorine gas purifies graphite is generated, including electrolysis cells I, the electrolysis cells I include：
Electrolytic cell, the electrolyte bath add HF and KHF2Mixture, it is intermediate to completely cut off gas intercommunication, the electricity with diaphragm
The outside of solution slot is provided with water-bath heater；
Furnace body unit II, the furnace body unit II include：
The bottom of furnace body, the furnace body is disposed with furnace burdening, and graphite products are positioned at furnace core, the surrounding cloth of graphite products
It is equipped with resistance material, insulation material is disposed on the outside of resistance material, the side of the furnace body is provided with for respectively by nitrogen and chlorine
It is passed through the air inlet pipe a and air inlet pipe b of furnace core, the fluorine gas of generation is passed through the bottom of furnace core by link road a by the electrolytic cell.
As an improvement, online acidometer and hydrofluoric acid storage tank are provided at the top of the electrolytic cell, the online acidity
Hydrofluoric acid concentration in meter monitoring electrolytic cell, when concentration is too low, injects HF into electrolytic cell by hydrofluoric acid storage tank.
As another improvement, the side of the electrolytic cell is provided with hydrogen gas cleaner, and the hydrogen gas cleaner is for removing
The hydrogen fluoride carried secretly in the hydrogen that electrolytic cell emits；The side of the furnace body is provided with tail gas absorbing system, the tail gas
Absorption system is made of several sodium hydroxide solution absorbers, is used to remove the fluorine gas in the tail gas that graphitizing furnace discharges,
The tail gas absorbing system is provided on connecting tube b by being connected at the top of connecting tube b and furnace core for pumping gas in furnace core
To the air pump of tail gas absorbing system.
It should be noted that electrolytic cell is passed through the fluorine gas of furnace body, it is passed through the hydrogen and hydrofluoric acid storage tank of hydrogen gas cleaner
HF is injected into electrolytic cell, and uninterrupted is controlled by control valve.
In addition, the reaction equation in the present invention in electrolytic process is as follows：
Anode：2F--2e-→F2↑
Cathode：2HF2 -+2e-→H2↑+4F-。
It should be noted that being purified instead of freon using the fluorine gas generated in the present invention, for ability
Field technique personnel using air accumulator fluorine gas storage, then by the fluorine gas of air accumulator it is contemplated that be passed into graphitizing furnace, but be somebody's turn to do
Kind of mode firstly there are the problem of to be that fluorine gas vivaciously stores very much more difficult, can be very high overcoming the cost of its storage,
Even if the problem of overcoming cost again, the fluorine gas in air accumulator is with using, and the pressure in tank can slowly decline, with pressure
Decline, the rate of gas supply can also decline, and be similar to the same using gas tank in life, use and will appear below for unsaturated vapor fire
The case where can burning, in the case that negative pressure state is certain in air pump holding graphitizing furnace, gassing rate deficiency is just difficult to ensure
The fluorine gas feed rate that graphite purification needs；
Assuming that the rate that cell reaction generates fluorine gas is V1, the rate that graphitizing furnace is passed through fluorine gas needs is V2, herein may be used
To ensure that V1 is consistently greater than V2 by artificially controlling the process of cell reaction, negative pressure state one in graphitizing furnace is kept in air pump
In the case of fixed and V1 ＞ V2, V1 suitably can be reduced by adjusting the valve on link road a, to ensure in purification process
The rate stabilization that fluorine gas is passed through.
The beneficial effects of the present invention are：
(1) in the present invention HF in electrolysis cell and KHF is utilized by the way that electrolytic cell is arranged2The mode of mixture generates fluorine
Gas replaces the freon used during graphite purification in the prior art, is passed into graphitizing furnace, makes the height boiling in graphite
Point impurity element chemical combination generate low boiling point fluoride and be discharged with gas, which obviate in graphite production process freon it is a large amount of
It uses, reduces the destruction to environment.
(2) rate of cell reaction generation fluorine gas is assumed to be V1 in the present invention, and graphitizing furnace is passed through the rate of fluorine gas needs
For V2, it can ensure that V1 is consistently greater than V2 by artificially controlling the process of cell reaction herein, to ensure in purification process
The rate holds steady that fluorine gas is passed through.
(3) HF and KHF used in the present invention in addition2Relative to freon, it is easier to obtain, and needs use fast
HF and KHF is added in speed2It carries out electrolysis and generates fluorine gas, overcome interim in use, freon needs to examine then transport turnover, shadow
The problem of ringing production efficiency；And cell reaction is easy to control, needs to be powered when generating fluorine gas, can stop energization horse when not needing
Upper stopping fluorine gas supply, it is more convenient.
(4) and in the present invention product for being electrolysed generation is relatively stable, will not be polluted to graphite, stability in use
Good, the graphite quality produced is high.
In conclusion the present invention has process optimization, device structure is simple, and graphite macromolecule impurity removal effect is good, ring
The advantages that guarantor, is particularly suitable in isostatic pressing formed graphite purifying process technology.
Description of the drawings：
Following further describes the present invention with reference to the drawings：
Fig. 1 is electrolysis HF and KHF2Generate the process flow chart of the method for fluorine gas purification graphite；
Fig. 2 is electrolysis HF and KHF2Generate the system schematic of fluorine gas purification graphite.
Specific implementation mode：
As described below is only presently preferred embodiments of the present invention, is not defined to the scope of the present invention.
Embodiment one
As shown in Figure 1, electrolysis HF and KHF2The method for generating fluorine gas purification graphite, including following production stage：
One, electrolysis section：By HF and KHF2In molar ratio 1:3 carry out being mixed to form electrolyte, are put into electrolytic cell, wherein
The concentration of HF is maintained at 38%~40%, and fluorine gas electrolytic cell is all made of the Hastelloy of heat-and corrosion-resistant or similar material,
Electrolysis electrode is installed on electrolytic cell both sides respectively, and anode is nickel plate, and cathode is stainless steel plate；By water-bath heater to electrolytic cell into
Row heating, heating temperature make the HF and KHF of electrolyte bath at 80 DEG C~95 DEG C2Reach molten condition, opens power supply to electrolysis
Liquid carries out electrolysis and generates fluorine gas；
Reaction equation in electrolytic process is as follows：
Anode：2F--2e-→F2↑
Cathode：2HF2 -+2e-→H2↑+4F-；
Two, graphitization/purification part：The spacing of multigroup graphite product as requested is arranged in graphitizing furnace, successively
Insulation material and resistance material are inserted, after shove charge, heating graphitizing furnace to furnace core temperature is passed through nitrogen when being 1800~1900 DEG C
The air in furnace core is excluded, heating rate is 10~30 DEG C/min；Continue to heat graphitizing furnace when being warming up to 1900~2000 DEG C,
Stopping is passed through chlorine, switchs to be passed through chlorine；Continue to heat graphitizing furnace when being warming up to 2300~2500 DEG C, will be electrolysed in step 1
The fluorine gas of generation is passed through in graphitizing furnace, and micro-vacuum state is kept during being passed through fluorine gas and being purified in graphitizing furnace,
Chlorine and fluorine gas are diffused to by graphitizing furnace bottom in product, and wherein chlorine supplies gas unit consumption as 20~25kg/m3, fluorine gas supplies gas list
Consumption is 15-20kg/m3；Wherein fluorine gas generates fluoride with the impurity element chemical combination in sample reduces its boiling point；By taking boron as an example,
Boiling point is more than 3500 DEG C, is reacted with fluorine gas, 2B+3F2→2BF3, -127.1 DEG C of the boron fluoride boiling point of generation.
Further, further include vent gas treatment part, the mixed gas generated in step 2 is passed into tail gas absorbing system
It is discharged after the middle removal by fluorine gas therein；Further include hydrogen purification part, the hydrogen of generation is electrolysed in step 1, and to enter hydrogen net
It is discharged after changing the hydrogen fluoride that device removal is wherein carried secretly, wherein tail gas absorbing system is by several sodium hydroxide solution absorber groups
At fluorine gas reacts removal, equation 2F with sodium hydroxide2+4NaOH→NaF+2H2O+O2, the molten people of fluoride of gasification is water-soluble
In liquid, after absorption system, after tail gas reaches discharge standard, it is discharged into air.
Further, further include feed supplement part, in step 1 during electrolysis, pass through the monitoring electrolysis of online acidometer
Hydrofluoric acid concentration in slot when concentration is too low, injects hydrofluoric acid by hydrofluoric acid storage tank in electrolytic cell.
It is noted that in the present embodiment, by the way that electrolytic cell is arranged, HF in electrolysis cell and KHF is utilized2Mixture
Mode generate fluorine gas to replace the freon used during graphite purification in the prior art, be passed into graphitizing furnace, make
High-boiling-point impurity element compounds in graphite generate low boiling point fluoride and are discharged with gas, and which obviate in graphite production process
A large amount of uses of freon, reduce the destruction to environment；
In addition, the HF and KHF that are used in the present embodiment2Relative to freon, it is easier to obtain, and needs use fast
HF and KHF is added in speed2It carries out electrolysis and generates fluorine gas, overcome interim in use, freon needs to examine then transport turnover, shadow
The problem of ringing production efficiency；And cell reaction is easy to control, needs to be powered when generating fluorine gas, can stop energization horse when not needing
Upper stopping fluorine gas supply, it is more convenient；
And the product that generation is electrolysed in the present embodiment is relatively stable, will not be polluted to graphite, and stability in use is good,
The graphite quality produced is high.
Embodiment two
It is electrolysed the method that HF and KHF2 generates fluorine gas purification graphite, including following production stage：
One, electrolysis section：By HF and KHF2In molar ratio 1:3 carry out being mixed to form electrolyte, are put into electrolytic cell, wherein
The concentration of HF is maintained at 38%~40%, and fluorine gas electrolytic cell is all made of the Hastelloy of heat-and corrosion-resistant or similar material,
Electrolysis electrode is installed on electrolytic cell both sides respectively, and anode is nickel plate, and cathode is stainless steel plate；
Two, graphitization/purification part：The spacing of multigroup graphite product as requested is arranged in graphitizing furnace, successively
Insulation material and resistance material are inserted, after shove charge, heating graphitizing furnace to furnace core temperature is passed through nitrogen when being 1800~1900 DEG C
The air in furnace core is excluded, heating rate is 10~30 DEG C/min；Continue to heat graphitizing furnace when being warming up to 1900~2000 DEG C,
Stopping is passed through chlorine, switchs to be passed through chlorine；Continue to heat graphitizing furnace when being warming up to 2300~2500 DEG C, the electrolysis to step 1
Slot is heated by water-bath heater, and heating temperature makes the HF and KHF of electrolyte bath at 80 DEG C~95 DEG C2Reach melting
State opens power supply and carries out electrolysis generation fluorine gas to electrolyte；
Reaction equation in electrolytic process is as follows：
Anode：2F--2e-→F2↑
Cathode：2HF2 -+2e-→H2↑+4F-；,
The fluorine gas of generation is passed through in graphitizing furnace, keeps micro- negative in graphitizing furnace during being passed through fluorine gas and being purified
Pressure condition, chlorine and fluorine gas are diffused to by graphitizing furnace bottom in product, and wherein chlorine supplies gas unit consumption as 20~25kg/m3, fluorine
Pneumatic transmission gas unit consumption is 15-20kg/m3；Wherein fluorine gas generates fluoride with the impurity element chemical combination in sample reduces its boiling point；With
For boron, boiling point is more than 3500 DEG C, is reacted with fluorine gas, 2B+3F2→2BF2, -127.1 DEG C of the boron fluoride boiling point of generation.
Further, further include vent gas treatment part, the mixed gas generated in step 2 is passed into tail gas absorbing system
It is discharged after the middle removal by fluorine gas therein；Further include hydrogen purification part, the hydrogen of generation is electrolysed in step 1, and to enter hydrogen net
It is discharged after changing the hydrogen fluoride that device removal is wherein carried secretly, wherein tail gas absorbing system is by several sodium hydroxide solution absorber groups
At fluorine gas reacts removal, equation 2F with sodium hydroxide2+4NaOH→NaF+2H2O+O2, the molten people of fluoride of gasification is water-soluble
In liquid, after absorption system, after tail gas reaches discharge standard, it is discharged into air.
Further, further include feed supplement part, in step 1 during electrolysis, pass through the monitoring electrolysis of online acidometer
Hydrofluoric acid concentration in slot when concentration is too low, injects hydrofluoric acid by hydrofluoric acid storage tank in electrolytic cell.
Embodiment three
As shown in Fig. 2, electrolysis HF and KHF2The system for generating fluorine gas purification graphite, including electrolysis cells I, the electrolysis are single
First I includes：
HF and KHF is added in electrolytic cell 1,1 inside of the electrolytic cell2Mixture, centre completely cut off gas intercommunication, institute with diaphragm 2
The outside for stating electrolytic cell 1 is provided with water-bath heater 3；
Furnace body unit II, the furnace body unit II include：
The bottom of furnace body 4, the furnace body 4 is disposed with furnace burdening 41, and graphite products are positioned at furnace core 42, graphite products
Surrounding is disposed with resistance material 43, and the outside of resistance material 43 is disposed with insulation material 44, and the side of the furnace body 4 is provided with for distinguishing
Nitrogen and chlorine is passed through to the air inlet pipe a5 and air inlet pipe b6 of furnace core 42, the electrolytic cell 1 is by link road a7 by the fluorine of generation
Gas is passed through the bottom of furnace core 42.
Further, the top of the electrolytic cell 1 is provided with online acidometer 8 and hydrofluoric acid storage tank 9, the online acid
Hydrofluoric acid concentration in 8 monitoring electrolytic cell 1 of degree meter, when concentration is too low, injects HF by hydrofluoric acid storage tank 9 into electrolytic cell 1.
Further, the side of the electrolytic cell 1 is provided with hydrogen gas cleaner 10, and the hydrogen gas cleaner 10 is for clear
The hydrogen fluoride carried secretly in the hydrogen emitted except electrolytic cell 1；The side of the furnace body 4 is provided with tail gas absorbing system 11, institute
It states tail gas absorbing system 11 to be made of several sodium hydroxide solution absorbers, in the tail gas for being used to remove graphitizing furnace discharge
Fluorine gas, the tail gas absorbing system 11 is connected to by connecting tube b12 and the top of furnace core 42, is provided with and is used on connecting tube b12
Gas in furnace core 42 is pumped to the air pump 13 of tail gas absorbing system 11.
Above in association with described in attached drawing being only the preferred embodiment of the present invention, but the present invention is not limited to above-mentioned embodiment party
Formula, it is noted that for those skilled in the art, without departing from the structure of the invention, can also make various
Modification and improvement, these should also be considered as protection scope of the present invention, all not interfere with effect and practicability that the present invention is implemented.
Claims (10)
1. being electrolysed HF and KHF2The method for generating fluorine gas purification graphite, which is characterized in that including following production stage：
One, electrolysis section：By HF and KHF2In molar ratio 1:2~4 carry out being mixed to form electrolyte, are put into electrolytic cell, to electrolysis
Slot is heated, and the HF and KHF of electrolyte bath are made2Reach molten condition, opens power supply and electrolysis generation fluorine is carried out to electrolyte
Gas；
Two, graphitization/purification part：The spacing of multigroup graphite product as requested is arranged in graphitizing furnace, is successively filled
Insulation material and resistance material, after shove charge, heating graphitizing furnace to furnace core temperature is passed through nitrogen and excludes when being 1800~1900 DEG C
Air in furnace core, heating rate are 10~30 DEG C/min；Continue to heat graphitizing furnace when being warming up to 1900~2000 DEG C, stops
It is passed through chlorine, switchs to be passed through chlorine；Continue to heat graphitizing furnace when being warming up to 2300~2500 DEG C, will be electrolysed and generate in step 1
Fluorine gas be passed through in graphitizing furnace, the impurity chemical combination in fluorine gas and graphite product forms fluoride, reduces its boiling point.
2. electrolysis HF and KHF as described in claim 12The method for generating fluorine gas purification graphite, it is characterised in that：The step
The power supply opened when graphitizing furnace is warming up to 2300~2500 DEG C in two in step 1 is electrolysed generation fluorine gas, side electrolysis to electrolyte
While being passed through the fluorine gas that electrolysis generates in graphitizing furnace.
3. the method that electrolysis HF and KHF2 generates fluorine gas purification graphite as described in claim 1, it is characterised in that：The step
HF and KHF in one2In molar ratio 1:2~3 are mixed, and are put into electrolytic cell, are preferably in a proportion of 1:The concentration of 3, wherein HF are protected
The reaction equation held in 38%~40%, electrolytic process is as follows：
Anode：2F--2e-→F2↑
Cathode：2HF2 -+2e-→H2↑+4F-。
4. electrolysis HF and KHF as described in claim 12The method for generating fluorine gas purification graphite, it is characterised in that：The step
Electrolytic cell is heated by water-bath heater in one, heating temperature is at 70 DEG C~100 DEG C.
5. the method that electrolysis HF and KHF2 generates fluorine gas purification graphite as described in claim 1, it is characterised in that：The graphite
Change in stove keeps micro-vacuum state, chlorine and fluorine gas to be diffused to by graphitizing furnace bottom during being passed through fluorine gas and being purified
In product, wherein chlorine supplies gas unit consumption as 20~25kg/m3, fluorine gas supply gas unit consumption be 15-20kg/m3。
6. electrolysis HF and KHF as described in claim 12The method for generating fluorine gas purification graphite, it is characterised in that：It further include tail
Gas disposal part, the mixed gas generated in step 2, which will be passed into tail gas absorbing system, to be discharged after fluorine gas therein removal；
Further include hydrogen purification part, be electrolysed in step 1 generation hydrogen enter the hydrogen fluoride that hydrogen gas cleaner removal is wherein carried secretly after
Discharge.
7. electrolysis HF and KHF as described in claim 12The method for generating fluorine gas purification graphite, it is characterised in that：Further include mending
Expect part, in step 1 during electrolysis, hydrofluoric acid concentration in electrolytic cell is monitored by online acidometer, concentration is too low
When, hydrofluoric acid is injected in electrolytic cell by hydrofluoric acid storage tank.
8. being electrolysed HF and KHF2The system for generating fluorine gas purification graphite, it is characterised in that：Including electrolysis cells I, the electrolysis cells
I includes：
Electrolytic cell (1), the electrolytic cell (1) is internal to add HF and KHF2Mixture, intermediate diaphragm (2) completely cut off gas intercommunication, institute
The outside for stating electrolytic cell (1) is provided with water-bath heater (3)；
Furnace body unit II, the furnace body unit II include：
The bottom of furnace body (4), the furnace body (4) is disposed with furnace burdening (41), and graphite products are positioned at furnace core (42), graphite production
The surrounding of product is disposed with resistance material (43), and insulation material (44) is disposed on the outside of resistance material (43), and the side of the furnace body (4) is set
It is equipped with the air inlet pipe a (5) and air inlet pipe b (6) for nitrogen and chlorine to be passed through to furnace core (42) respectively, the electrolytic cell (1) is logical
Cross the bottom that the fluorine gas of generation is passed through furnace core (42) by link road a (7).
9. the system that electrolysis HF and KHF2 generates fluorine gas purification graphite as claimed in claim 8, it is characterised in that：The electrolysis
Online acidometer (8) and hydrofluoric acid storage tank (9) are provided at the top of slot (1), the online acidometer (8) monitors electrolytic cell
(1) interior hydrofluoric acid concentration when concentration is too low, injects HF into electrolytic cell (1) by hydrofluoric acid storage tank (9).
10. the system that electrolysis HF and KHF2 generates fluorine gas purification graphite as claimed in claim 8, it is characterised in that：The electricity
The side of solution slot (1) is provided with hydrogen gas cleaner (10), and the hydrogen gas cleaner (10) emits for removing electrolytic cell (1)
Hydrogen in the hydrogen fluoride carried secretly；The side of the furnace body (4) is provided with tail gas absorbing system (11), the tail gas absorbing system
(11) it is made of several sodium hydroxide solution absorbers, is used to remove the fluorine gas in the tail gas that graphitizing furnace discharges, it is described
Tail gas absorbing system (11) is provided with for by stove on connecting tube b (12) by being connected at the top of connecting tube b (12) and furnace core (42)
Core (42) interior gas pumps to the air pump (13) of tail gas absorbing system (11).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160511A (en) * | 2018-09-17 | 2019-01-08 | 厦门大学 | A kind of device and method of graphite purification |
| CN115747833A (en) * | 2022-11-01 | 2023-03-07 | 福建德尔科技股份有限公司 | Highly integrated high purity fluorine gas supply system |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH180682A (en) * | 1932-10-31 | 1935-11-15 | Du Pont | Process and device for the electrolytic production of fluorine. |
| FR1205756A (en) * | 1957-10-25 | 1960-02-04 | Siemens Planiawerke Ag | Process for preparing high purity graphite |
| JPH11236205A (en) * | 1998-02-20 | 1999-08-31 | Akechi Ceramics Kk | Purifying method of graphite |
| CN102126721A (en) * | 2011-04-27 | 2011-07-20 | 深圳市贝特瑞新能源材料股份有限公司 | Purification and graphitization method of graphite material |
| CN105271216A (en) * | 2015-12-07 | 2016-01-27 | 湖南顶立科技有限公司 | Preparation method of high-purity graphite |
| CN106698352A (en) * | 2017-01-03 | 2017-05-24 | 多氟多化工股份有限公司 | Method and device for preparing high-purity fluorine gas or high-purity fluorine-containing mixed gas |
| US20180050923A1 (en) * | 2016-08-19 | 2018-02-22 | General Electric Company | Purified potassium hexafluoromanganate and methods for purifying potassium hexafluoromanganate |
| CN208378429U (en) * | 2018-06-01 | 2019-01-15 | 中钢集团新型材料（浙江）有限公司 | It is electrolysed HF and KHF2The system for generating fluorine gas purification graphite |
-
2018
- 2018-06-01 CN CN201810555993.7A patent/CN108516544A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH180682A (en) * | 1932-10-31 | 1935-11-15 | Du Pont | Process and device for the electrolytic production of fluorine. |
| FR1205756A (en) * | 1957-10-25 | 1960-02-04 | Siemens Planiawerke Ag | Process for preparing high purity graphite |
| GB880547A (en) * | 1957-10-25 | 1961-10-25 | Siemens Planiawerke Ag | Improvements in or relating to processes for the production of graphite of sufficient purity for use as a reactor material |
| JPH11236205A (en) * | 1998-02-20 | 1999-08-31 | Akechi Ceramics Kk | Purifying method of graphite |
| CN102126721A (en) * | 2011-04-27 | 2011-07-20 | 深圳市贝特瑞新能源材料股份有限公司 | Purification and graphitization method of graphite material |
| CN105271216A (en) * | 2015-12-07 | 2016-01-27 | 湖南顶立科技有限公司 | Preparation method of high-purity graphite |
| US20180050923A1 (en) * | 2016-08-19 | 2018-02-22 | General Electric Company | Purified potassium hexafluoromanganate and methods for purifying potassium hexafluoromanganate |
| CN106698352A (en) * | 2017-01-03 | 2017-05-24 | 多氟多化工股份有限公司 | Method and device for preparing high-purity fluorine gas or high-purity fluorine-containing mixed gas |
| CN208378429U (en) * | 2018-06-01 | 2019-01-15 | 中钢集团新型材料（浙江）有限公司 | It is electrolysed HF and KHF2The system for generating fluorine gas purification graphite |
Non-Patent Citations (2)
| Title |
|---|
| 姜文军,吴国颖,马圭,高峰莲: "氟气制备及其下游产品与应用" * |
| 谢刚;李晓阳;臧健;阎江峰;杨大锦;俞小花;于站良;: "高纯石墨制备现状及进展" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160511A (en) * | 2018-09-17 | 2019-01-08 | 厦门大学 | A kind of device and method of graphite purification |
| CN115747833A (en) * | 2022-11-01 | 2023-03-07 | 福建德尔科技股份有限公司 | Highly integrated high purity fluorine gas supply system |
| CN115747833B (en) * | 2022-11-01 | 2023-09-22 | 福建德尔科技股份有限公司 | High-integration-level high-purity fluorine gas supply system |
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Application publication date: 20180911 |