CN106757147B - A kind of method of arsenic removal in nickel electrowinning mixed acid system - Google Patents
A kind of method of arsenic removal in nickel electrowinning mixed acid system Download PDFInfo
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- CN106757147B CN106757147B CN201611073292.7A CN201611073292A CN106757147B CN 106757147 B CN106757147 B CN 106757147B CN 201611073292 A CN201611073292 A CN 201611073292A CN 106757147 B CN106757147 B CN 106757147B
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 140
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 140
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- 239000002253 acid Substances 0.000 title claims abstract description 40
- 238000005363 electrowinning Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 132
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052742 iron Inorganic materials 0.000 claims abstract description 51
- 238000001914 filtration Methods 0.000 claims abstract description 48
- 239000010941 cobalt Substances 0.000 claims abstract description 47
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 47
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002893 slag Substances 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000003834 hydroxide co-precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- 238000003860 storage Methods 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 235000014413 iron hydroxide Nutrition 0.000 claims description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 6
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical group O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 5
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of methods of arsenic removal in nickel electrowinning mixed acid system, this method rationally controls the iron arsenic ratio of electrolytic anode liquid by mending iron, the temperature and pH value of iron removal step are controlled simultaneously, so that the arsenic in 80% or more iron removal step is deviate from the form of ferric arsenate or absorption, then the liquid pH value before except cobalt stage control except cobalt oxidation current potential, reaction time and its except cobalt will further be removed except the remaining arsenic in liquid after iron, arsenic filtering except cobalt section and cobalt hydroxide co-precipitation.In addition, slag filtered after being handled except nickel after purification generation is filtered except slag after iron, arsenic filtering and except cobalt, arsenic, liquid returns liquid making and is handled after filtering, can enter liquid making process with part arsenic, and dearsenification is induced by controlling solution copper ion and current density in liquid making process.The method of the present invention has well solved nickel electrowinning excessive problem containing arsenic, is electrolysed new liquid and is less than 0.0002g/l containing arsenic, electrolytic nickel is respectively less than 0.0005% containing arsenic, and total system solution arsenic extrusion rate reaches 98% or more.
Description
Technical field
The invention belongs to nickel electrowinning technical fields, and in particular to a kind of method of arsenic removal in nickel electrowinning mixed acid system.
Background technology
The nickel sulfide soluble anode diaphragm electrolysis technique that nickel electrowinning uses, electrowinning process make anode, nickel with high sulfonium anode plate
Starting sheet makees cathode, and the purified process output of nickle electrolysis anode solution is electrolysed new liquid pump to the cathode chamber of electrolytic cell, in direct current
Under effect, the nickel ion in catholyte is precipitated in cathode, obtains electrolytic nickel.During nickel electrowinning, since outsourcing nickel ore concentrate contains
Arsenic gradually rises and nickel electrowinning hydrometallurgy slag containing arsenic returns pyrogenic process, causes the high nickel matte of top blast stove containing arsenic by 2012
0.095% is increased to 0.107% in 2013, and nickle electrolysis anode solution is caused constantly to be increased containing arsenic, due in nickel electrowinning mixed acid system
In there is no a method of arsenic removal, anolyte arsenic enters after cleaning procedure is electrolysed new liquid so that be electrolysed new liquid is more than containing arsenic
0.0003g/L, so that electrolytic nickel is containing the Ni9996 national technical standards requirement that arsenic is more than 0.00085%, electric nickel impurity element
Flat when content is more than state's household electrical appliances nickel technical standard（Reduce price）Sale, influences electric nickel economic benefit.
Invention content
The purpose of the present invention is to solve technical problems of the existing technology, provide a kind of simple for process, technique step
The method of arsenic removal in rapid easily manipulation, the nickel electrowinning mixed acid system that cost is relatively low, effect of removing arsenic is good.
In order to achieve the above object, the present invention uses following technical scheme：The side of arsenic removal in a kind of nickel electrowinning mixed acid system
Method, this approach includes the following steps：
A, in liquid making process electrochemical deposition copper removal, arsenic, the low acid of liquid making after removal of impurities in nickel sulfide soluble anode electrolysis process
Go out in oral fluid storage tank and H is added2O2The low acid of liquid making is gone out trivalent arsenic in oral fluid and is oxidized to pentavalent arsenic by solution；
B, H is added2O2The low acid of liquid making go out oral fluid and return electrolytic anode liquid storage tank and mixed with electrolytic anode liquid；
C, ferric trichloride is filled into electrolytic anode liquid storage tank, the low acid of control liquid making goes out the mixing of oral fluid and electrolytic anode liquid
Anolyte iron arsenic ratio is 6~8:1, meanwhile, H is added in electrolytic anode liquid storage tank2O2Solution；
D, the mixing anolyte in electrolytic anode liquid storage tank is returned into purification arsenic removal, cleaning procedure include neutralizing hydrolysis except iron,
Boiling copper removal slot copper removal, chlorine oxidation hydrolysis remove cobalt, and iron is mainly with FeCl in mixed solution anolyte3Form exists, and adjusts mixed
The pH value for closing anolyte is 3.5~4.2, temperature is 65~70 DEG C, so that iron is hydrolyzed to iron hydroxide under this condition, utilizes hydrogen-oxygen
The precipitation for changing iron colloid removes most arsenic in mixing anolyte with arsenate form adsorption coprecipitation, reaction time control
System is in 1~1.5h；
E, liquid carries out chlorine oxidation hydrolysis except cobalt after removing iron, arsenic filtering, and control removes cobalt oxidation 1060~1090mv of current potential,
Reaction time control is in 1~1.5h, except liquid pH value is 4.5~5.0 before cobalt, will except the remaining arsenic in liquid after iron, arsenic filtering except
Cobalt section is removed with cobalt hydroxide co-precipitation；
F, it in order to effectively recycle except slag after iron, arsenic filtering and except the nickel in slag after cobalt, arsenic filtering, is removed what purification generated
After iron, arsenic filtering slag and except after cobalt, arsenic filtering slag handled after filter, paid outside slag after filtering, after filtering liquid return liquid making into
Row processing, these solution can enter liquid making process with part arsenic and carry out electrochemistry arsenic removal.
Further, in the step A in liquid making process electrochemical deposition induces arsenic removal process, anode is nickel anode
Plate, cathode are the copper sheet that size is 700 × 720mm, control liquid making process solution 8~10g/l of copper ion, current density 220A/
m2, arsenic is made to be removed in negative electrode electro-deposition in the form of copper arsenide.
Further, H in the step A2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:It is molten after 1 dilution
The amount of liquid, addition is that the low acid of liquid making goes out the 0.2% of oral fluid quality.
Further, H in the step C2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:It is molten after 1 dilution
Liquid, the amount of addition are mix anolyte quality 0.2%.
The present invention has the advantages that compared with the prior art：The method of arsenic removal in nickel electrowinning mixed acid system of the present invention is logical
It crosses benefit iron and rationally controls the iron arsenic ratio of electrolytic anode liquid, while controlling the temperature and pH value of iron removal step so that except ironworker
The arsenic of 80% or more sequence is deviate from the form of ferric arsenate or absorption, then except cobalt stage control is except cobalt oxidation current potential, reaction time
And its except liquid pH value before cobalt, will further be removed except cobalt section and cobalt hydroxide co-precipitation except the remaining arsenic in liquid after iron, arsenic filtering
It goes.In addition, slag filtered after being handled except nickel after purification generation is filtered except slag after iron, arsenic filtering and except cobalt, arsenic, filter
Liquid returns liquid making and is handled afterwards, can enter liquid making process with part arsenic, in liquid making process by controlling solution copper ion and electricity
Current density induces dearsenification, and H is added in liquid making process2O2Solution aoxidizes arsenic and improves arsenic removal efficiency.The method of the present invention is well
It solves nickel electrowinning excessive problem containing arsenic, is electrolysed new liquid and is less than 0.0002g/l containing arsenic, electrolytic nickel is respectively less than 0.0005% containing arsenic, whole
Body System Solution arsenic extrusion rate reaches 98% or more, stabilizes electric nickel chemical quality, can be widely applied to nickel hydrometallurgy and its
In the daily production process of his chemical industry.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
Nickel electrowinning mixed acid system contains chlorion 65g/l, iron content 0.2g/l, 0.06g/l containing arsenic, the nickel electrowinning nitration mixture body
The method of arsenic removal includes the following steps in system：
A, in liquid making process electrochemical deposition copper removal, arsenic, the low acid of liquid making after removal of impurities in nickel sulfide soluble anode electrolysis process
Go out in oral fluid storage tank and H is added2O2The low acid of liquid making is gone out trivalent arsenic in oral fluid and is oxidized to pentavalent arsenic, is conducive to the removing of arsenic by solution,
H2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:The amount of solution after 1 dilution, addition is that the low acid of liquid making goes out oral fluid
The 0.2% of quality；In liquid making process electrochemical deposition induces arsenic removal process, anode is Nickel Anode Plate, and cathode is that size is 700
The copper sheet of × 720mm, control liquid making process solution copper ion 8g/l, current density 220A/m2, make arsenic in the form of copper arsenide in the moon
Pole electro-deposition removing.
B, H is added2O2The low acid of liquid making of solution goes out oral fluid and returns electrolytic anode liquid storage tank to be mixed with electrolytic anode liquid.
C, ferric trichloride is filled into electrolytic anode liquid storage tank, the low acid of control liquid making goes out the mixing of oral fluid and electrolytic anode liquid
Anolyte iron arsenic ratio is 6:1, meanwhile, H is added in electrolytic anode liquid storage tank2O2Solution, H2O2Solution is that mass fraction is 30%
Industrial H2O2With water 1:Solution after 1 dilution, the amount of addition are mix anolyte quality 0.2%.
D, the mixing anolyte in electrolytic anode liquid storage tank is returned into purification arsenic removal, cleaning procedure include neutralizing hydrolysis except iron,
Boiling copper removal slot copper removal, chlorine oxidation hydrolysis remove cobalt, and iron is mainly with FeCl in mixed solution anolyte3Form exists, and adjusts mixed
The pH value for closing anolyte is 3.5, temperature is 65 DEG C, so that iron is hydrolyzed to iron hydroxide under this condition, utilizes ferric hydroxide colloid
Precipitation to mixing anolyte in 80% arsenic with arsenate form adsorption coprecipitation remove, the reaction time control in 1h.It removes
Liquid is less than 0.01g/L containing arsenic after iron, arsenic filtering.
E, liquid carries out chlorine oxidation hydrolysis except cobalt after removing iron, arsenic filtering, and control removes cobalt oxidation current potential 1060mv, reaction
Time control is in 1h, will be except the remaining arsenic in liquid after iron, arsenic filtering is except cobalt section and cobalt hydroxide except liquid pH value is 4.5 before cobalt
Co-precipitation removes.Except liquid is less than 0.0002 g/L containing arsenic after cobalt.
F, it in order to effectively recycle except slag after iron, arsenic filtering and except the nickel in slag after cobalt, arsenic filtering, is removed what purification generated
After iron, arsenic filtering slag and except after cobalt, arsenic filtering slag except being filtered after nickel processing, paid outside slag after filtering, liquid, which returns, after filtering makes
Liquid is handled, these solution can enter liquid making process with part arsenic.The present embodiment total system solution arsenic extrusion rate reaches
99.6% or more.
Embodiment 2
Nickel electrowinning mixed acid system contains chlorion 70g/l, iron content 0.3g/l, 0.03g/l containing arsenic, the nickel electrowinning nitration mixture body
The method of arsenic removal includes the following steps in system：
A, in liquid making process electrochemical deposition copper removal, arsenic, the low acid of liquid making after removal of impurities in nickel sulfide soluble anode electrolysis process
Go out in oral fluid storage tank and H is added2O2The low acid of liquid making is gone out trivalent arsenic in oral fluid and is oxidized to pentavalent arsenic, is conducive to the removing of arsenic by solution,
H2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:The amount of solution after 1 dilution, addition is that the low acid of liquid making goes out oral fluid
The 0.2% of quality；In liquid making process electrochemical deposition induces arsenic removal process, anode is Nickel Anode Plate, and cathode is that size is 700
The copper sheet of × 720mm, control liquid making process solution copper ion 10g/l, current density 220A/m2, make arsenic in the form of copper arsenide
Negative electrode electro-deposition removes.
B, H is added2O2The low acid of liquid making of solution goes out oral fluid and returns electrolytic anode liquid storage tank to be mixed with electrolytic anode liquid.
C, ferric trichloride is filled into electrolytic anode liquid storage tank, the low acid of control liquid making goes out the mixing of oral fluid and electrolytic anode liquid
Anolyte iron arsenic ratio is 8:1, meanwhile, H is added in electrolytic anode liquid storage tank2O2Solution, H2O2Solution is that mass fraction is 30%
Industrial H2O2With water 1:Solution after 1 dilution, the amount of addition are mix anolyte quality 0.2%.
D, the mixing anolyte in electrolytic anode liquid storage tank is returned into purification arsenic removal, cleaning procedure include neutralizing hydrolysis except iron,
Boiling copper removal slot copper removal, chlorine oxidation hydrolysis remove cobalt, and iron is mainly with FeCl in mixed solution anolyte3Form exists, and adjusts mixed
The pH value for closing anolyte is 4.2, temperature is 70 DEG C, so that iron is hydrolyzed to iron hydroxide under this condition, utilizes ferric hydroxide colloid
Precipitation to mixing anolyte in 80% arsenic with arsenate form adsorption coprecipitation remove, the reaction time control in 1.5h.
Except liquid is less than 0.008g/L containing arsenic after iron, arsenic filtering.
E, liquid carries out chlorine oxidation hydrolysis except cobalt after removing iron, arsenic filtering, and control removes cobalt oxidation current potential 1090mv, reaction
Time control is in 1.5h, will be except the remaining arsenic in liquid after iron, arsenic filtering is except cobalt section and hydroxide except liquid pH value is 5.0 before cobalt
Cobalt co-precipitation removes.Except liquid is less than 0.0002 g/L containing arsenic after cobalt.
F, it in order to effectively recycle except slag after iron, arsenic filtering and except the nickel in slag after cobalt, arsenic filtering, is removed what purification generated
After iron, arsenic filtering slag and except after cobalt, arsenic filtering slag except being filtered after nickel processing, paid outside slag after filtering, liquid, which returns, after filtering makes
Liquid is handled, these solution can enter liquid making process with part arsenic.The present embodiment total system solution arsenic extrusion rate reaches
99.3% or more.
Embodiment 3
Nickel electrowinning mixed acid system contains chlorion 68g/l, iron content 0.2g/l, 0.04g/l containing arsenic, the nickel electrowinning nitration mixture body
The method of arsenic removal includes the following steps in system：
A, in liquid making process electrochemical deposition copper removal, arsenic, the low acid of liquid making after removal of impurities in nickel sulfide soluble anode electrolysis process
Go out in oral fluid storage tank and H is added2O2The low acid of liquid making is gone out trivalent arsenic in oral fluid and is oxidized to pentavalent arsenic, is conducive to the removing of arsenic by solution,
H2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:The amount of solution after 1 dilution, addition is that the low acid of liquid making goes out oral fluid
The 0.2% of quality；In liquid making process electrochemical deposition induces arsenic removal process, anode is Nickel Anode Plate, and cathode is that size is 700
The copper sheet of × 720mm, control liquid making process solution copper ion 9g/l, current density 220A/m2, make arsenic in the form of copper arsenide in the moon
Pole electro-deposition removing.
B, H is added2O2The low acid of liquid making of solution goes out oral fluid and returns electrolytic anode liquid storage tank to be mixed with electrolytic anode liquid.
C, ferric trichloride is filled into electrolytic anode liquid storage tank, the low acid of control liquid making goes out the mixing of oral fluid and electrolytic anode liquid
Anolyte iron arsenic ratio is 7:1, meanwhile, H is added in electrolytic anode liquid storage tank2O2Solution, H2O2Solution is that mass fraction is 30%
Industrial H2O2With water 1:Solution after 1 dilution, the amount of addition are mix anolyte quality 0.2%.
D, the mixing anolyte in electrolytic anode liquid storage tank is returned into purification arsenic removal, cleaning procedure include neutralizing hydrolysis except iron,
Boiling copper removal slot copper removal, chlorine oxidation hydrolysis remove cobalt, and iron is mainly with FeCl in mixed solution anolyte3Form exists, and adjusts mixed
The pH value for closing anolyte is 4, temperature is 68 DEG C, so that iron is hydrolyzed to iron hydroxide under this condition, utilizes ferric hydroxide colloid
It precipitates to being removed with arsenate form adsorption coprecipitation to 80% arsenic in mixing anolyte, the reaction time controls in 1.5h.It removes
Liquid is less than 0.009g/L containing arsenic after iron, arsenic filtering.
E, liquid carries out chlorine oxidation hydrolysis except cobalt after removing iron, arsenic filtering, and control removes cobalt oxidation current potential 1080mv, reaction
Time control is in 1h, will be except the remaining arsenic in liquid after iron, arsenic filtering is except cobalt section and cobalt hydroxide except liquid pH value is 4.7 before cobalt
Co-precipitation removes.Except liquid is less than 0.0002 g/L containing arsenic after cobalt.
F, it in order to effectively recycle except slag after iron, arsenic filtering and except the nickel in slag after cobalt, arsenic filtering, is removed what purification generated
After iron, arsenic filtering slag and except after cobalt, arsenic filtering slag except being filtered after nickel processing, paid outside slag after filtering, liquid, which returns, after filtering makes
Liquid is handled, these solution can enter liquid making process with part arsenic.The present embodiment total system solution arsenic extrusion rate reaches
99.5% or more.
Claims (4)
1. a kind of method of arsenic removal in nickel electrowinning mixed acid system, it is characterised in that this approach includes the following steps：
A, in liquid making process electrochemical deposition copper removal, arsenic, the low acid outlet of liquid making after removal of impurities in nickel sulfide soluble anode electrolysis process
H is added in liquid storage tank2O2The low acid of liquid making is gone out trivalent arsenic in oral fluid and is oxidized to pentavalent arsenic by solution；
B, H is added2O2The low acid of liquid making go out oral fluid and return electrolytic anode liquid storage tank and mixed with electrolytic anode liquid；
C, ferric trichloride is filled into electrolytic anode liquid storage tank, the low acid of control liquid making goes out the mixing anode of oral fluid and electrolytic anode liquid
Liquid iron arsenic ratio is 6~8:1, meanwhile, H is added in electrolytic anode liquid storage tank2O2Solution；
D, the mixing anolyte in electrolytic anode liquid storage tank is returned into purification arsenic removal, cleaning procedure includes neutralizing hydrolysis except iron, boiling
Copper removal slot copper removal, chlorine oxidation hydrolysis remove cobalt, and iron is mainly with FeCl in mixed solution anolyte3Form exists, and adjusts mixing sun
The pH value of pole liquid is 3.5~4.2, temperature is 65~70 DEG C, so that iron is hydrolyzed to iron hydroxide under this condition, utilizes iron hydroxide
The precipitation of colloid removes most arsenic in mixing anolyte with arsenate form adsorption coprecipitation, and reaction time control exists
1~1.5h；
E, to remove iron, arsenic filtering after liquid carry out chlorine oxidation hydrolysis except cobalt when, control remove cobalt oxidation 1060~1090mv of current potential,
Reaction time control is in 1~1.5h, except liquid pH value is 4.5~5.0 before cobalt, will except the remaining arsenic in liquid after iron, arsenic filtering except
Cobalt section is removed with cobalt hydroxide co-precipitation；
F, in order to effectively recycle except slag after iron, arsenic filtering and except the nickel after cobalt, arsenic filtering in slag, by purification generate except iron,
After arsenic filtering slag and except after cobalt, arsenic filtering slag handled after filter, paid outside slag after filtering, liquid returns at liquid making after filtering
Reason, these solution can enter liquid making process with part arsenic and carry out electrochemistry arsenic removal.
2. the method for arsenic removal in a kind of nickel electrowinning mixed acid system according to claim 1, it is characterised in that：The step A
In liquid making process electrochemical deposition induce arsenic removal process in, anode is Nickel Anode Plate, and cathode is that size is 700 × 720mm's
Copper sheet, control liquid making process solution 8~10g/l of copper ion, current density 220A/m2, make arsenic in the form of copper arsenide in cathode electricity
Deposition removing.
3. the method for arsenic removal in a kind of nickel electrowinning mixed acid system according to claim 1, it is characterised in that：The step A
Middle H2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:The amount of solution after 1 dilution, addition is the low acid outlet of liquid making
The 0.2% of liquid quality.
4. the method for arsenic removal in a kind of nickel electrowinning mixed acid system according to claim 1, it is characterised in that：The step C
Middle H2O2Solution is the industrial H that mass fraction is 30%2O2With water 1:The amount of solution after 1 dilution, addition is mixing anolyte matter
The 0.2% of amount.
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| CN111663153B (en) * | 2020-05-20 | 2022-03-15 | 金川集团股份有限公司 | Method for inhibiting impurities of lead and zinc from being separated out at cathode in nickel electrolysis process |
| CN113979488B (en) * | 2021-09-18 | 2023-02-07 | 中南大学 | Method for synchronously removing iron and cobalt from nickel electrolysis anolyte through efficient oxidation and preparing magnetic material |
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| CN109781930A (en) * | 2019-03-20 | 2019-05-21 | 金川集团股份有限公司 | Ferrimetry test paper in a kind of nickel electrowinning system solution |
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Effective date of registration: 20240131 Address after: 737100 No. 2 Lanzhou Road, Beijing Road Street, Jinchuan District, Jinchang City, Gansu Province Patentee after: Jinchuan Group Nickel Cobalt Co.,Ltd. Country or region after: China Address before: 737103 No. 98, Jinchuan Road, Jinchang, Gansu Patentee before: JINCHUAN GROUP Co.,Ltd. Country or region before: China |