CN105734298B - The method that valuable metal is reclaimed from colored solid waste residue with shunting common extraction technique - Google Patents
The method that valuable metal is reclaimed from colored solid waste residue with shunting common extraction technique Download PDFInfo
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- CN105734298B CN105734298B CN201610265344.4A CN201610265344A CN105734298B CN 105734298 B CN105734298 B CN 105734298B CN 201610265344 A CN201610265344 A CN 201610265344A CN 105734298 B CN105734298 B CN 105734298B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
- C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- 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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- 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
Abstract
The invention discloses a kind of method that valuable metal is reclaimed from colored solid waste residue with shunting common extraction technique.At present while to valuable metal recovery, the slag and industrial wastewater of secondary pollution can be produced, it is necessary to further be reprocessed to these pollutants.The present invention includes one section of pressure leaching and two sections of normal pressure counterflow leaching processes, cadmium manganese cleaning procedure, indium zinc-irons shunt common extraction process, regeneration of hydrochloric acid process and without MnZn electrodeposition process, and three kinds of load organic phases are formed after shunting common extraction process through indium zinc-iron and indium iron common extraction extraction raffinate, indium zinc common extraction extraction raffinate and extraction zinc extraction raffinate is produced respectively；Three kinds of described load organic phases are flowed at one, are sequentially passed through washing section, pickling section, anti-zinc section, anti-indium section, two sections of anti-iron, one section of anti-iron and are washed chlorine section.The present invention not only realizes zero cost and extracts indium, and no industry removes the generation of iron waste residue, and realizes zero discharge of industrial waste water truly.
Description
Technical field
The present invention relates to non-ferrous metal solid slag process field, it is specifically a kind of with shunting common extraction technique from coloured
The method of the valuable metal such as recovery indium zinc-iron in metal solid waste residue.
Background technology
Valuable metal composition in non-ferrous metal solid slag is complex, according to the difference of its composition, the recovery of use
Method is also not quite similar, but relatively simple to the recovery method of indium zinc-iron in colored solid waste residue both at home and abroad at present, mainly have with
Lower two kinds：
(1) acidleach impurity removal method：This method, as leaching agent, is leached indium, zinc, ferrous metal under peracid using sulfuric acid, then
With iron powder as reducing agent, by the ferric ion Restore All in solution into ferrous ion, after being extracted by P204, by indium
Proposed from solution, the zinc dust precipitation of liquid containing indium becomes and rises into by sponge indium, it is smelting after be changed into thick indium sale；And liquid after P204 extractions
Then neutralized with zinc oxide, zinc concentration brought up into 120~150g/L, using yellow modumite method remove iron, then respectively remove copper,
The impurity such as cadmium, nickel, cobalt, again must remove them respectively, what is obtained is pure if fluoride ion, chlorine ion concentration are too high in solution
Net solution of zinc sulfate can produce zinc metal with the method production white vitriol product or Direct Electrolysis of evaporative crystallization.It is this
Method, one be high energy consumption, produce industrial residue species it is more, such as：Scum, copper-cadmium slag, nickel cobalt slag etc.；Two be industrial wastewater row
It is high-volume big, such as：The waste water that fluorine removal, chlorine are produced；Three be that yield is relatively low, in process of the iron powder as reducing agent, can lose substantial amounts of
Indium metal is into slag；Four be that environmental issue is serious, is not suitable for the clean metallurgical direction of the following environmental protection development of China.
(2) synthesis recovery indium gallium germanium：Using rich in indium, gallium, germanium zinc leaching residue as raw material, it is heavy by leaching, with tannin
Shallow lake germanium and the process that indium, gallium, germanium are extracted with solvent extraction, it is main to include pretreatment, extract indium and extract the operations such as gallium, the method in
1975 in Chinese research success.In the zinc leaching residue for pre-processing zinc hydrometallurgy factory output, there are part zinc and iron formation zinc ferrite
(nZnO·mFe2O3), and 95% or so indium, germanium, gallium are present in zinc ferrite with isomorph.Leached and contained with zinc electrolysis lean solution
When indium, germanium, the zinc leaching residue of gallium, indium, germanium, gallium are transferred to leachate.Filtrate zincification powder substitution obtained by filtering, indium, germanium, gallium are set to
Change metal into, obtain and be rich in indium, germanium, gallium replacement slag.Replacement slag sulfuric acid counterflow leaching, the final acidity of control leachate is (containing trip
From sour 0.6mol/L or so), 96~100% indium, germanium, gallium in replacement slag just can be made to be transferred to solution.Born with hydrochloric acid back extraction indium
Organic phase is carried, the strip liquor of 67~84g/L containing indium is obtained, strip liquor zincification powder substitution obtains sponge indium, and sponge indium is through briquetting and alkali fusion
Power transmission solution after casting, obtains the indium of purity 99.99%, the rate of recovery of indium is more than 90%.And the rear liquid of zinc dust precipitation, then it is changed into soda
Solution is then discharged into sewage disposal system after the precipitation of zinc carbonate or zinc hydroxide, precipitation.This method to the pollution of water compared with
To be serious, with the implementation of increasingly severe environmental law, the synthetical recovery to metals such as indium gallium germanium has been no longer appropriate for.
Above-mentioned two methods, while to valuable metal recovery, can produce the slag and industrial wastewater of secondary pollution, need
These pollutants are further reprocessed.
The content of the invention
The technical problems to be solved by the invention are that the defect for overcoming above-mentioned prior art to exist is shunted altogether there is provided one kind
Extract the method for technique valuable metal such as recovery indium zinc-iron from colored solid waste residue, it is using metal ion in solvent extraction
Feature, the acid for constantly being consumed leaching metal ion is regenerated；By controlling solution acidity, to containing different metal from
The solution of son is shunted, and forms the closed cycle of a solution.
Therefore, the present invention is adopted the following technical scheme that：Reclaim valuable from colored solid waste residue with shunting common extraction technique
The method of metal, including the one section of pressure leaching and two sections of normal pressure counterflow leaching processes, cadmium manganese cleaning procedure, indium zinc carried out successively
Iron shunts common extraction process, regeneration of hydrochloric acid process and without MnZn electrodeposition process, it is characterised in that：
1) two sections of normal pressure counterflow leaching processes described in include zinc and soak two sections and one section of zinc leaching, soak in two sections, come from zinc
The extraction raffinate of the common extraction containing acid, colored solid waste residue and the air+SO of common extraction process are shunted in indium zinc-iron2Mixed gas carry out fully mix
Close and leach, pH controls are in 3-3.5, and T=45-55 DEG C, in addition to zinc, iron is suppressed with other metals and leached, and by iron with FeOOH
Form be present in zinc and soak in two sections of underflows, zinc soaks two sections of supernatants and enters cadmium manganese cleaning procedure, and zinc soaks two sections of underflows and enters zinc
In one section of leaching leaching is sufficiently mixed with the extraction zinc extraction raffinate containing acid；Soaked in zinc in one section, pH is controlled at 1~2.5, T=45-55 DEG C,
Zinc, iron and indium metal are leached, and zinc soaks zinc concentration in one section of underflow and controlled in 15~50g/L, and zinc soaks one section of underflow and enters one
Section pressure leaching process；
In one section of pressure leaching process, the process control condition of pressure leaching is：Under aerobic conditions, T=150-200
DEG C, P=1.2~1.8Mpa, H2SO4Concentration be 100~180g/L, zinc soaks one section of underflow and shunts common extraction process with indium zinc-iron
Leaching is sufficiently mixed containing sour common extraction extraction raffinate；Utilize this condition Selectively leaching In3+、Zn2+Ion, except Cd2+、Mn2+Outside ion, its
Its impurity is suppressed, and obtained pressurization supernatant and zinc soaks one section of supernatant and go indium zinc-iron to shunt common extraction process；
2) in the cadmium manganese cleaning procedure described in, zinc soaks two sections of supernatants and carries out two sections of displacement reactions with zinc powder, except cadmium underflow
Spongy Cadmium is obtained after filtration washing, except cadmium supernatant and air+SO2Mixed gas be sufficiently mixed demanganization, demanganization supernatant
Indium zinc-iron is gone to shunt common extraction process, demanganization underflow obtains manganese product after filtration washing；
3) in the indium zinc-iron shunting common extraction process described in, pressurization supernatant, zinc soak one section of supernatant and demanganization underflow difference
Into indium iron common extraction section, indium zinc common extraction section and zinc extraction section, three kinds of load organic phases are formed after extraction and generation indium iron is total to respectively
Raffinate, indium zinc common extraction extraction raffinate and extraction zinc extraction raffinate, indium iron common extraction extraction raffinate largely return to one section of pressure leaching and are circulated, small portion
Divide and enter two sections of zinc leaching, indium zinc common extraction extraction raffinate is all returned to zinc and soaks two sections, and extraction zinc extraction raffinate is all returned to one section of zinc leaching；
Three kinds of described load organic phases sequentially pass through washing section, pickling section, stripping section, anti-indium section, two sections of anti-iron, anti-iron
One section and wash chlorine section, load organic phases first pass through washing section and wash away the chlorine of mechanical entrapment, fluorine ion in load organic phases, then pass through
Pickling section wash in lower extraction copper, manganese ion.
The present invention is using one section of pressurization and two sections of normal pressure counterflow leachings and indium zinc-iron shunting common extraction new technology, with reference to wet without sodium
Method metallurgy system, realizes the circular regeneration of acid and industrial wastewater in system.The indium of original creation, zinc, iron segmentation are leached and extracted with segmentation
Technology is taken to be combined so that the acid produced during extraction of indium zinc-iron can be recycled completely, be run into than traditional handicraft saving
This more than 70%.The indium zinc-iron shunting abstraction technique of original creation, has accomplished that segmentation is leached and has been organically combined with stage extraction technology, optimization
With having innovated indium zinc-iron shunting common extraction technique.One section of pressurization of original creation and two sections of normal pressure reverse flow techniques realize indium zinc-iron selectivity
Leaching, pressure leaching improves the leaching rate of indium zinc, reached more than 95%.Unique extraction removes iron and Air+SO2Mixing
Iron removal by oxidation manganese technology is combined, and is solved the problems, such as that traditional handicraft is insoluble and is removed iron waste residue.Regeneration of hydrochloric acid technology is solved
The FeCl that extraction process is produced3Acid pickle problem, meanwhile, also by InCl3It has been directly changed high-purity In2O3；Regeneration of hydrochloric acid technology
Solve anti-indium rich solution and extract the ZnCl remained after indium2Acid pickle problem.Employ uniqueness without manganese electrodeposition technology, zinc electrolysis bath
Inside precipitated again without the earth of positive pole, improve the operating rate of electrowinning process and the quality of product.
The present invention is integrated with being carried from coloured solid waste slag for original creation by various original creation and unique technical combinations
The hydrometallurgy system of the valuable metals such as indium zinc-iron is taken, compared with traditional technology, zero cost is not only realized and extracts indium, no industry
Except the generation of iron waste residue, and realize zero discharge of industrial waste water truly.
In one section of pressurization and two sections of normal pressure counterflow leaching processes, Air+SO2Mixed oxidization removing of iron and manganese technology will be in normal pressure
Under conditions of, suppress the leaching of iron in coloured solid waste slag, and iron is fixed in normal pressure leaching slag with FeOOH form；Air+
SO2Into after aqueous solution state, a kind of FeSO can be formed immediately5Material, this material has extremely strong oxidisability, can will be molten
Fe in liquid2+Ion rapid oxidation is into Fe3+Ion, chemical equation is as follows：
FeSO5+Fe2++2H+=2Fe3++SO4 2-+H2O ⑴
And ferric ion now can be with occurring hydrolysis instead in coloured solid waste slag containing basic anhydride such as calcium, magnesium
Should, in the state of control pH is maintained at 3-3.5, chemical equation is as follows：
Fe3++OH-+H2O=FeOOH+2H+ ⑵
By two sections of normal pressure counterflow leachings, the leaching rate of zinc can reach more than 85%, and the leaching rate of indium is left~30%
The right side, and iron-based is originally suppressed in normal pressure leaching slag.Various valuable metals in normal pressure leaching slag will lead to the bar of oxygen in pressurization
Leached under part by substantial amounts of, during pressure leaching, temperature control at 150~200 DEG C, Stress control 1.2~
1.8Mpa, controlling pH is passed through oxygen in 100~180g/L, now, and total leaching rate of zinc reaches more than 95%, total leaching of indium
Extracting rate reaches more than 92%, in addition to goethite has been formed, and other iron rules are with bloodstone (Fe2O3) form be present in
There is the Fe no more than 5g/L in slag, but in pressureleaching solution3+Ion, chemical equation is as follows：
Using Air+SO2Mixed oxidization removing of iron and manganese technology, by controlling the terminal pH value of wherein one section normal pressure leaching 3.0
~3.5, it can effectively suppress the leaching of indium and iron, while can also be by containing a small amount of metal sulfide in coloured solid waste slag
Oxidation Leaching；Using high pressure peracid oxygen soak can selectivity reinforcing In3+、Zn2+The leaching of plasma, suppresses Sn2+、As2+Deng from
The leaching of son, makes 90% Fe3+Ion is with Fe2O3Form precipitates (other 5% Fe3+Ion is precipitated with FeOOH forms)；And lead to
The terminal pH value 1-2.5 for controlling another section of normal pressure leaching is crossed, then can allow In3+、Zn2+Plasma is leached jointly.
Arsenic then exists in the form of arsenate, and arsenate is easily precipitated with other metal ions formation arsenate, chemistry side
Formula is as follows：
2As2-+5O2=2AsO5 3+ ⑷
3Men++nAsO5 3+=Me3(AsO5)n ⑸
In cadmium manganese cleaning procedure, due to Cd2+、Mn2+Ion is pressurizeed by one section after two sections of normal pressure counterflow leachings, is leached
Rate is up to more than 95%, such as removes not in time, then can circulation collection in the solution, finally have influence on the normal of shunting common extraction process
Operation.The method that cadmium is removed using zinc powder, is also the process to the purification of a step to the greatest extent of other ions in solution, its chemical equation
It is as follows：
CdSO4+ Zn=Cd+ZnSO4 ⑹
MeSO4+ Zn=Me+ZnSO4 ⑺
Using Air+SO2Mixed oxidization removing of iron and manganese technology is in this process by Mn2+Ion is with MnO2Or Mn2O3Form remove
Go, to eliminate its enrichment in whole system, its chemical equation is as follows：
As pH ＜ 4, Mn2++SO2+O2+2H2O=MnO2+4H++SO4 2- ⑻
As pH=5~7,2Mn2++SO2+O2+3H2O=Mn2O3+6H++SO4 2- ⑼。
In indium zinc-iron shunting common extraction process, come from the indium in pressureleaching solution (pressurize supernatant) with iron in peracid
Direct common extraction under degree, the acidity of extraction is in 100~180g/L, under this acidity, In3+Preferentially occur with P204 extractants anti-
Should, next is only Fe3+Reacted with P204 extractants, chemical equation is as follows：
In3++ 3HR (org)=InR3(org)+3H+ ⑽
Fe3++ 3HR (org)=FeR3(org)+3H+ ⑾
Come from indium in normal pressure leaching liquid (i.e. one section supernatant) and the zinc direct common extraction in pH=1~3.5, chemistry is anti-
Answer equation as follows：
Zn2++ 2HR (org)=ZnR2(org)+2H+ ⑿
Anti- zinc section, then it is as back washing agent that zinc is anti-in 160~220g/L electric zinc lean solution (liquid before i.e. anti-zinc) with acidity
Under, become zinc-rich liquid, Zinc electrolysis is used for after oil removing, chemical equation is as follows：
ZnR2(org)+H2SO4=ZnSO4+2HR(org) ⒀
In anti-indium section, then with the HCl and 1~2NZnCl that acidity is 2~4N2As back washing agent by indium it is anti-under, become rich indium
Liquid, during this, also having fraction of ferric iron can be by under anti-, therefore after carrying indium through resin purification, is changed into pure height
Containing solution of indium, indium content is not less than 100g/L, and chemical equation is as follows：
InR3(org)+3HCl=InCl3+3HR(org) ⒁
In anti-iron section, then with 5~7N HCl as back washing agent using two sections of back extraction iron technique by iron it is anti-under, become richness
Fe in iron liquid, rich iron liquid3+Content is not less than 70g/L, and chemical equation is as follows：
FeR3(org)+3HCl=FeCl3+3HR(org) ⒂
In regeneration of hydrochloric acid process, pure InCl3Rich solution of indium can directly be reacted using regeneration of hydrochloric acid technology with water
Generate high-purity In2O3And hydrochloric acid is regenerated, its chemical equation is as follows：
2InCl3+3H2O=In2O3+6HCl ⒃
Pure FeCl3Rich ferrous solution directly can generate high-purity Fe using regeneration of hydrochloric acid technology with water reaction2O3And regenerate
Hydrochloric acid, its chemical equation is as follows：
2FeCl3+3H2O=Fe2O3+6HCl ⒄
The rich indium liquid for coming from anti-indium section extracts In with resin respectively3+And Fe3+It is pure to contain ZnCl after plasma2's
Solution, this solution is after anti-indium section is recycled, ZnCl2Content can produce enrichment, keep anti-indium need to 1~2N concentration
ZnCl2After content, unnecessary ZnCl2Then using regeneration of hydrochloric acid technology generation ZnSO4·7H2O and recovery hydrochloric acid, chemical reaction
Equation is as follows：
ZnCl2+H2SO4+7H2O=ZnSO4·7H2O+2HCl ⒅
In without MnZn electrodeposition process, the zinc-rich liquid that anti-zinc section is produced, respectively through one section of resin oil removing, two sections of activated carbon
Oil removing, by soluble oil control in solution in below 1ppm, carries out electrodeposition and carries zinc, its chemical equation is as follows：
Cathode reaction：Zn2++ 2e=Zn, anode reaction：2OH-- 2e=1/2O2+H2O ⒆
The anti-zinc section that the electric zinc lean solution produced after Zinc electrolysis returns to shunting common extraction process again is used as back washing agent.
Using Air+SO2Mixed oxidization removing of iron and manganese technology, by controlling the endpoint pH of wherein one section normal pressure leaching 3.0
~3.5, it can effectively suppress the leaching of indium and iron, while can also be by containing a small amount of metal sulfide in coloured solid waste slag
Oxidation Leaching；Using high pressure peracid oxygen soak can selectivity reinforcing In3+、Zn2+The leaching of plasma, suppresses Sn2+、As2+Deng from
The leaching of son, makes 90% Fe3+Ion is with Fe2O3Form precipitates (other 5% Fe3+Ion is precipitated with FeOOH forms)；And lead to
Endpoint pH~2 for controlling another section of normal pressure leaching are crossed, then can allow In3+、Zn2+Plasma is leached jointly.
In cadmium manganese cleaning procedure, the Cd in solution can be removed using zinc powder cadmium removing process for use first2+Ion, meanwhile, also enter
One step is by Cu2+、Ni2+、Co2+、Bi2+、Sn2+Purification is precipitated Deng many kinds of metal ions；Next uses Air+SO2Mixed oxidization removes iron
Manganese technology can be by the circulation Mn in solution2+Ion removes 70%；The important function of this process is by Cd2+、Mn2+Etc. be easy to leach
But the metal ion for being difficult to eliminate is removed respectively from solution, reaches that solution can be recycled constantly, and harmful metal ion
But the effect being no longer enriched with.
In indium zinc-iron shunting common extraction process, first, In3+And Fe3+The condition of two kinds of ion common extractions must control solution
Acidity [H2SO4] between 0~180g/L；In3+And Zn2+Two kinds of ions or In3+、Fe3+And Zn2+The bar of three kinds of ion common extractions
Part must be the pH value for controlling solution between 0.5~2.5；Secondly, above-mentioned common extraction condition is also that different solutions are shunted
Condition, different shunting solution have respectively entered extracting system by the requirement of common extraction；3rd, shunting common extraction is by indium iron common extraction
Section, indium zinc-iron common extraction section, washing section, pickling section, anti-zinc section, anti-indium section, anti-iron section, wash chlorine section etc. composition；4th, various sections
The composition of series different metal ions according to contained by solution of extraction, back extraction or washing, is selected between 3~8 grades respectively；The
Five, anti-iron section employs two sections of circulations and returns iron, can be by Fe3+Ion concentration is enriched to more than 70g/L.
In regeneration of hydrochloric acid process, InCl3、FeCl3After using regeneration of hydrochloric acid technology, In is generated respectively2O3、Fe2O3Two
Plant high pure oxide and regeneration hydrochloric acid；ZnCl2After using regeneration of hydrochloric acid technology, ZnSO is generated4·7H2O and regeneration hydrochloric acid.
Regeneration of hydrochloric acid process solves the problem of the wastewater zero discharge containing metal chloride in the anti-indium section of shunting common extraction；Extraction removes iron and salt
Acid regeneration technology realizes slitless connection, and the acid for leaching iron consumption is regenerated circulation by indium iron common extraction section, and iron is also passed through
Regeneration of hydrochloric acid technology becomes added value very high Fe2O3Product, solves the industrialization that scum pollutant is formed in hydrometallurgy
Problem.
Without the anti-zinc rich solution in MnZn electrodeposition process, coming from shunting the anti-zinc section of common extraction process first, in addition to zinc
All kinds of metals content impurities are respectively less than below 1ppm；Next to that electric zinc lean solution is as back washing agent, constantly with shunting common extraction process
Anti- zinc section is circulated back extraction, and producing high-purity anti-zinc rich solution is used for Zinc electrolysis process；3rd is to shunt common extraction process and without manganese
The solution circulating system of a closing is formd between Zinc electrolysis process, by this system, Zn2+Ion is then by shunting common extraction
Process enters, and is separated out further through without MnZn electrodeposition process in the form of zinc metal；4th be have the electric zinc lean solution of small part open a way to
Common extraction process pickling section is shunted, common extraction process is shunted and molten without this closing formed between MnZn electrodeposition process to maintain
Impurity metal content in liquid circulating system is controlled in below 1ppm.
Any one process in the present invention, is added without soda or sodium salt.
Further, in one section of pressure leaching and two sections of normal pressure counterflow leaching processes, using solid material and liquid charging stock
Countercurrently opposite segmentation Leaching way.The advantage that adverse current segmentation is leached is that the acid produced during shunting common extraction can be fully utilized,
Using these acid as leaching agent, the leaching rate of the valuable metal in coloured solid waste slag is substantially realized step by step.
Further, described load organic phases run to anti-zinc section, will be loaded by liquid before anti-zinc or electrodeposition lean solution organic
Zinc in phase is all stripped, and liquid goes no MnZn electrodeposition process after obtained anti-zinc；It is described in without MnZn electrodeposition process
Liquid controls dissolved organic matter within 10ppm by one section of resin oil removing after anti-zinc, then can through two sections of activated carbon oil removings
Soluble organism is controlled within 1ppm.
Further, the electric zinc lean solution through being obtained without MnZn electrodeposition process returns to the shunting of indium zinc-iron altogether as liquid before anti-zinc
In the anti-zinc section for extracting process.
Further, described load organic phases run to anti-indium section, by liquid before anti-indium that the indium in load organic phases is complete
Portion is stripped, and liquid goes regeneration of hydrochloric acid process after obtained anti-indium.
Further, in regeneration of hydrochloric acid process, liquid carries indium by resin and adsorbs indium ion after anti-indium, and indium will be adsorbed with hydrochloric acid
The resin backwash and regeneration of ion, indium ion enters after rich indium in liquid, and liquid carries out regeneration of hydrochloric acid, output In after rich indium2O3Product, and
Regenerate hydrochloric acid, the hydrochloric acid of regeneration removes before anti-indium liquid and for resin backwash and regeneration.
Further, put forward indium extraction raffinate by what resin carried that indium obtains and then carry out resin and carry iron, iron ion will be adsorbed with hydrochloric acid
Resin backwash and regeneration, iron ion enters after rich iron in liquid, and liquid carries out regeneration of hydrochloric acid after rich iron, output iron oxide product, and again
Raw hydrochloric acid, the hydrochloric acid of regeneration removes after anti-one section of iron liquid and washes liquid after chlorine.
Further, the liquid after iron that carries that iron obtains is carried by resin and adds sulfuric acid, carry out regeneration of hydrochloric acid, output is high-purity
ZnSO4·7H2O products, and regenerate hydrochloric acid, the hydrochloric acid of regeneration removes before anti-indium liquid and for resin backwash and regeneration；The crystallization of concentration is female
Liquid is largely recycled, and fraction returns to liquid before anti-indium and recycled.
Further, described load organic phases run to two sections of anti-iron and anti-one section of iron, will be loaded with by liquid before anti-iron
Iron in machine phase is all stripped, and liquid carries out regeneration of hydrochloric acid, output iron oxide product, and regenerant salt after two sections of obtained anti-iron
Acid, the hydrochloric acid of regeneration removes after anti-one section of iron liquid and washes liquid after chlorine.
Further, described load organic phases, which are run to, washes chlorine section, wash before chlorine liquid by the chlorine carried secretly in load organic phases from
Sub to be all stripped, obtained liquid after chlorine of washing is used as liquid before anti-one section of iron, and liquid is obtained after anti-one section of iron before anti-one section of iron
To one section of anti-iron after liquid act on liquid before anti-two sections of iron and use.
The device have the advantages that：(1) industrial water zero discharge, complete closed cycle are realized；(2) do not cause
The industrial scum of pollution (with the iron slag phase ratio for largely having pollution produced by traditional hydrometallurgy)；(3) zero cost is carried
Take indium metal；(4) sour circular regeneration and utilization；(5) relative to traditional hydrometallurgy mode of production have supplementary product onsumption it is low,
The advantages such as energy consumption is low, operating cost is low, metal yield height.
Brief description of the drawings
With reference to specification drawings and specific embodiments, the invention will be further described.
One section pressurizations and two section normal pressure counterflow leaching process flow charts of the Fig. 1 for the present invention.
Fig. 2 is cadmium manganese cleaning procedure flow chart of the invention.
Fig. 3 shunts common extraction process flow chart for the indium zinc-iron of the present invention.
Fig. 4 is regeneration of hydrochloric acid process flow chart of the invention.
Fig. 5 is the present invention without MnZn electrodeposition process flow chart.
Embodiment
One section of pressurization of the present invention and two sections of normal pressure counterflow leaching process flows are as shown in Figure 1：Two sections are soaked in zinc, is come from
The common extraction extraction raffinate containing acid and colored solid waste residue, Air+SO of indium zinc-iron shunting common extraction process2Mixed gas is carried out in reactor
It is sufficiently mixed, control ph 3~3.5, T=45~55 DEG C, after normal pressure leaching, ore pulp is carried out in zinc soaks two sections of thickening equipments
Solid-liquor separation, the zinc separated soaks two sections of supernatants and removes cadmium manganese cleaning procedure；And zinc soaks two sections of underflows and then enters one section of zinc leaching
It is sufficiently mixed with the extraction zinc extraction raffinate containing acid in reactor after leaching, control ph 1~2.5, T=45~55 DEG C, normal pressure leaching,
Ore pulp is subjected to solid-liquor separation in zinc soaks one section of thickening equipment, the zinc separated soaks one section of supernatant and carries out refined filtration, it is desirable to
ss≤1ppm；And zinc soaks one section of underflow and then enters one section of pressure leaching, T=150~200 DEG C are controlled, P=1.2~1.8Mpa,
[H2SO4]=100~180g/L, is passed through oxygen, and zinc is soaked more than the common extraction containing acid of one section of underflow and indium zinc-iron shunting common extraction process
Liquid is sufficiently mixed, and keeps suitable extraction time, the ore pulp after pressure leaching is then carried out into solid-liquor separation in thickening equipment,
The solid isolated becomes vendible lead product after filtration washing；And the pressurization supernatant isolated carries out refined filtration, it is desirable to
ss≤1ppm；The indium zinc that one section of supernatant of zinc leaching and pressurization supernatant after refined filtration respectively enter indium zinc-iron shunting common extraction process is total to
Extract section section and indium iron common extraction.
In one section of pressurization and two sections of normal pressure counterflow leaching processes, (1) utilizes the metal oxide in colored solid waste residue
Composition serves the adjustment effect of acidity；With Air+SO2During mixed gas normal pressure leaching, pH is controlled 3~3.5,
In addition to zinc, iron is suppressed and leached herein with other metals, in the common extraction extraction raffinate for coming from indium zinc-iron shunting common extraction process
Acid has obtained good utilization, but Cd2+、Mn2+Plasma opens a way out, it is necessary to remove in cadmium manganese cleaning procedure；And at another
During normal pressure leaching, pH is controlled 1~2.5, and the metal such as zinc, iron, indium is leached, and comes from indium zinc-iron shunting common extraction process
Common extraction extraction raffinate in acid obtained good utilization again；(2) holding for key is played in the control of zinc concentration in circulating leaching liquid
On open under effect, the concentration of P204 extractants determines zinc concentration control in circulating leaching liquid in the migration amount of zinc, the present invention
System is in 15~50g/L；(3) process control condition of pressure leaching is：Under aerobic conditions, T=150~200 DEG C, P=1.2~
1.8Mpa, [H2SO4]=100~180g/L；This condition is Selectively leaching In3+、Zn2+The key condition of ion, except Cd2+、
Mn2+Outside plasma, other impurity almost are suppressed.
The cadmium manganese cleaning procedure flow of the present invention is as shown in Figure 2：Zinc soaks two sections of supernatants and carries out two sections of displacements instead with zinc powder
Cadmium should be removed, the metal ions such as cadmium are precipitated from solution；Ore pulp passes through except cadmium thickening equipment carries out solid-liquor separation, after separation
Except cadmium underflow after filtration washing turn into vendible thick cadmium product；And remove cadmium supernatant and Air+SO after separating2Mixing
Gas is sufficiently mixed oxidation demanganization in reactor, and control ph is ＜ 4 or 5~7, T=~50 DEG C, after reaction a period of time,
Ore pulp after demanganization is subjected to solid-liquor separation in demanganization thickening equipment, the demanganization underflow after separation turns into after filtration washing can
The manganese product of sale；And the demanganization supernatant after separating carries out refined filtration, the demanganization supernatant after ss≤1ppm, refined filtration is asked to enter indium
The extraction zinc section of zinc-iron shunting common extraction process.
In cadmium manganese cleaning procedure, (1) substantial amounts of industrial test is it has been proved that Cd2+、Mn2+No matter plasma is in sulfuric acid
Salt or chlorination salt system have good leaching rate, therefore, Cd2+、Mn2+Circulation collection is influence point to plasma in the solution
The key factor that stream common extraction technology is used；(2)Cd2+It is to industrialize the method generally used that ion is removed using zinc powder, but
Mn2+Ion is extremely difficult as the removal of impurity in the solution, solution ph is controlled, using Air+SO2Mixed gas oxygen
It is unique method in the present invention, Mn to eliminate manganese2+Ion can be removed~70%, main technique control condition in this process
It is as follows：T=30~50 DEG C, pH ＜ 4 or pH=5~7；(3) this process, Cd are passed through2+、Mn2+Plasma can be followed repeatedly in the solution
Ring but not enrichment.
The indium zinc-iron shunting common extraction process flow of the present invention is as shown in Figure 3：It is respectively from one section of pressurization and two sections of normal pressures
Three kinds of solution of counterflow leaching process：Liquid after pressurization supernatant, latter section of supernatant of refined filtration and demanganization refined filtration after refined filtration, according to this
The different acidity of three kinds of solution, then respectively enter successively the indium iron common extraction section of indium zinc-iron shunting common extraction process, indium zinc common extraction section and
Extract zinc section, In3+、Zn2+、Fe3+Plasma enters in organic phase, and indium iron common extraction extraction raffinate, indium zinc common extraction extraction raffinate and extraction are generated respectively
Zinc extraction raffinate.Indium iron common extraction extraction raffinate largely returns to pressure leaching and is circulated, and seldom part enters zinc and soaks what two sections of open circuits were enriched with
The metal ions such as cadmium, manganese；Indium zinc common extraction extraction raffinate is then all returned to zinc and soaks two sections；Extraction zinc extraction raffinate is then all returned to zinc leaching one
Section.
Three kinds of load organic phases are flowed to together, and load organic phases first pass through washing section and wash away mechanical entrapment in organic phase
Chlorine, fluorine plasma, then through metal ions such as overpickling section copper, the manganese washed in lower extraction；Load organic phases run to anti-zinc section, electrolysis
Zinc in organic phase is all stripped by lean solution, and the requirement of electrodeposition can be carried out by meeting zinc concentration；Load organic phases are run
To anti-indium section, the indium in organic phase all be stripped by liquid before anti-indium, and the concentration for being enriched with indium ion reaches more than 100g/L；It is negative
Load organic phase runs to liquid before anti-iron section, anti-iron and is all stripped the iron in organic phase, by two sections of anti-iron of circulation, makes iron
The concentration of ion reaches more than 70g/L；Load organic phases, which are run to, washes chlorine section, washes before chlorine liquid by the chlorion carried secretly in organic phase
All wash, chlorine root will not be brought into solution circulating system when extraction section is mixed with shunting feed liquid.
In indium zinc-iron shunting common extraction process, the process conditions of (1) indium iron common extraction are as follows：Fe3+＜ 40g/L, In3+~5g/
L, [H2SO4]=100~180g/L；Under this condition, Fe3+、In3+Ion enters organic phase by extraction simultaneously；(2) indium zinc is total to
The process conditions of extraction are as follows：Zn2+=15~50g/L, In3+~5g/L, pH=1~3.5；Under this condition, Zn2+、In3+From
Son enters organic phase by extraction simultaneously；(3) process conditions of anti-zinc are as follows：Zn2+30~90g/L, [H2SO4]=160~220g/
L；(4) process conditions of anti-indium are as follows：ZnCl2=1~2N, [HCl]=2~4N；(5) process conditions of anti-iron are as follows：[HCl]
=5~7N；(6) different extraction sections are devised according to different extraction feed liquid situations, this is shunt common extraction new technology one
Core concept；(7) organic phase shared washing section, pickling section, anti-zinc section, anti-indium section, anti-iron section, wash chlorine section；(8) extraction section
(indium iron common extraction section, indium zinc common extraction section, zinc extraction section etc.), washing section, pickling section, anti-zinc section, anti-indium section, anti-iron section, wash chlorine section
It is a not reversible order successively, realizes shunting common extraction new technology, it is indispensable；(9) use two sections of anti-iron section are anti-
Iron combination regeneration of hydrochloric acid technology, the purpose is to utilize the method that circulation is stripped by Fe3+Concentration enrichment more than more than 70g/L.
The regeneration of hydrochloric acid process flow of the present invention is as shown in Figure 4：Contain In in liquid after anti-indium3+、Fe3+、Zn2+Deng metal from
Son, solution is after resin by In3+After absorption, carry and be left Fe in indium extraction raffinate3+、Zn2+Deng metal ion；In will be adsorbed with HCl3+
After the resin backwash and regeneration of ion, resin can continue on for the processing of liquid after anti-indium, and In3+Ion is all introduced into liquid after rich indium
In, liquid is after regeneration of hydrochloric acid technical finesse after rich indium, the high-purity In of output2O3Product, and regenerate hydrochloric acid.
Indium extraction raffinate is put forward to cross Fe after resin3+After absorption, carry and be only left Zn after iron in liquid2+Ion；Fe will be adsorbed with HCl3+From
After the resin backwash and regeneration of son, resin can continue on for proposing the processing of indium extraction raffinate, and Fe3+Ion is all introduced into liquid after rich iron
In, after liquid is mixed with liquid after anti-two sections of iron after rich iron after regeneration of hydrochloric acid technical finesse, the high-purity Fe of output2O3Product, and regenerant salt
Acid.
Sulfuric acid is added in liquid after carrying iron, and controls temperature, after regeneration of hydrochloric acid technical finesse, output is high-purity
ZnSO4·7H2O products, and regenerate hydrochloric acid, the crystalline mother solution (ZnCl of concentration2) it is largely returned to SSC regeneration of hydrochloric acid technologies system
System is recycled, and fraction returns to liquid before anti-indium and recycled.
The hydrochloric acid of regeneration then returns to before resin regeneration, the anti-indium of anti-indium section liquid and anti-iron section after liquid, one section of anti-iron respectively
Wash after chlorine in liquid and recycle.
In regeneration of hydrochloric acid process, the FeCl that (1) is formed3Acid pickle can be generated for making by regeneration of hydrochloric acid technology
High-purity Fe of soft magnetic materials2O3Product, and the anti-iron section recycling that hydrochloric acid may return to shunting common extraction process is regenerated, this
Any one current extraction process can not all be accomplished；(2) traditional high-purity In2O3Product is passed through using 4N smart indium
It is electrolysed, is evaporated in vacuo, is electrolysed again after the indium metal for reaching 6N, then dissolved with acid, and is dried with indium hydroxide is become after alkali precipitation
Dry calcining is formed, and the rich solution of indium (InCl after indium is carried using resin in the present invention3Solution) can be straight by regeneration of hydrochloric acid technology
Deliver a child into high-purity In2O3, production cost is greatly lowered；(3) acid pickle for carrying the Containing Zinc Chloride after indium uses regeneration of hydrochloric acid skill
Art, generates high-purity white vitriol product, and the hydrochloric acid of regeneration can return to before anti-indium again to be used in liquid.
The present invention's is as shown in Figure 5 without MnZn electrodeposition process flow：Liquid passes through one section of resin oil removing by solubility after anti-zinc
Organic matter is controlled within 10ppm, then is controlled dissolved organic matter within 1ppm through two sections of activated carbon oil removings, now molten
Liquid can enter to be electrolysed in electrolytic cell, the suitable tank voltage of control, current density and electric current, can with output 0# zinc products,
The anti-zinc section that electric zinc lean solution then returns to indium zinc-iron shunting common extraction process is recycled.
In without MnZn electrodeposition process, Mn in (1) zinc electrolyte2+Ion concentration is less than 1ppm, has thoroughly overturned traditional zinc
Mn is relied in electrolysis2+Ion protects the technological thought of lead anode；(2) the electric zinc lean solution produced by Zinc electrolysis returns to shunting altogether
The anti-zinc section for extracting process is recycled；(3) impurity content in zinc electrolyte is respectively less than below 1ppm；(4) electric zinc lean solution has few
Perhaps part can return to shunting common extraction process pickling section, with ensure the impurity content in zinc electrolysis circulation fluid be respectively less than 1ppm with
Under；(5) it by the way of one section of resin, two sections of activated carbon oil removings, have to be lower than the dissolved organic matter in zinc electrolyte
1ppm, to prevent from burning plate during electrolysis.
Claims (10)
1. the method that valuable metal is reclaimed from colored solid waste residue with shunting common extraction technique, including one section of pressure leaching and two sections
Normal pressure counterflow leaching process, cadmium manganese cleaning procedure, indium zinc-iron shunt common extraction process, regeneration of hydrochloric acid process and without MnZn electrodeposition work
Sequence, it is characterised in that
1) two sections of normal pressure counterflow leaching processes described in include zinc and soak two sections and one section of zinc leaching, are soaked in zinc in two sections, come from indium
Zinc-iron shunts common extraction extraction raffinate, colored solid waste residue and the air+SO of common extraction process2Mixed gas carry out be sufficiently mixed leaching,
PH controls are in 3-3.5, and T=45-55 DEG C, in addition to zinc, iron is suppressed with other metals and leached, and by iron with FeOOH form
It is present in zinc to soak in two sections of underflows, zinc soaks two sections of supernatants and enters cadmium manganese cleaning procedure, and zinc soaks two sections of underflows and soaks one section into zinc
In with extraction zinc extraction raffinate be sufficiently mixed leaching；Soaked in zinc in one section, pH is controlled in 1~2.5, T=45-55 DEG C, zinc, iron and indium metal
It is leached, zinc soaks zinc concentration in one section of underflow and controlled in 15~50g/L, and zinc soaks one section of underflow and enters one section of pressure leaching work
Sequence；
In one section of pressure leaching process, the process control condition of pressure leaching is：Under aerobic conditions, T=150-200 DEG C, P=
1.2~1.8MPa, H2SO4Concentration be 100~180g/L, zinc soaks one section of underflow and indium zinc-iron and shunted more than the common extraction of common extraction process
Liquid is sufficiently mixed leaching；Utilize this condition Selectively leaching In3+、Zn2+Ion, except Cd2+、Mn2+Outside ion, other impurity are pressed down
System, obtained pressurization supernatant and zinc soaks one section of supernatant and goes indium zinc-iron to shunt common extraction process；
2) in the cadmium manganese cleaning procedure described in, zinc soaks the two sections of displacement reactions of two sections of supernatants and zinc powder progress and removes cadmium, except cadmium underflow
Spongy Cadmium is obtained after filtration washing, except cadmium supernatant and air+SO2Mixed gas be sufficiently mixed demanganization, demanganization supernatant
It is liquid after demanganization refined filtration after refined filtration, goes indium zinc-iron to shunt common extraction process, demanganization underflow obtains manganese product after filtration washing；
3) in the indium zinc-iron shunting common extraction process described in, pressurization supernatant, zinc soak liquid after one section of supernatant and demanganization refined filtration and distinguished
Into indium iron common extraction section, indium zinc common extraction section and zinc extraction section, three kinds of load organic phases are formed after extraction and generation indium iron is total to respectively
Raffinate, indium zinc common extraction extraction raffinate and extraction zinc extraction raffinate, indium iron common extraction extraction raffinate largely return to one section of pressure leaching and are circulated, small portion
Divide and enter two sections of zinc leaching, indium zinc common extraction extraction raffinate is all returned to zinc and soaks two sections, and extraction zinc extraction raffinate is all returned to one section of zinc leaching；
Three kinds of described load organic phases are flowed at one, sequentially pass through washing section, pickling section, anti-zinc section, anti-indium section, anti-iron two
Section, one section of anti-iron and wash chlorine section, load organic phases first pass through washing section wash away in load organic phases the chlorine of mechanical entrapment, fluorine from
Son, then through overpickling section wash in lower extraction copper, manganese ion.
2. according to the method described in claim 1, it is characterised in that in one section of pressure leaching and two sections of normal pressure counterflow leaching processes
In, using solid material and the opposite segmentation Leaching way of liquid charging stock adverse current.
3. according to the method described in claim 1, it is characterised in that described load organic phases run to anti-zinc section, by anti-
The zinc in load organic phases is all stripped by liquid or electrodeposition lean solution before zinc, and liquid goes no MnZn electrodeposition work after obtained anti-zinc
Sequence；In without MnZn electrodeposition process, liquid controls dissolved organic matter in 10ppm by one section of resin oil removing after described anti-zinc
Within, then through two sections of activated carbon oil removings by dissolved organic matter control within 1ppm.
4. method according to claim 3, it is characterised in that the electric zinc lean solution through being obtained without MnZn electrodeposition process is as anti-
In liquid before zinc, the anti-zinc section for returning to indium zinc-iron shunting common extraction process.
5. according to the method described in claim 1, it is characterised in that described load organic phases run to anti-indium section, by anti-
The indium in load organic phases is all stripped by liquid before indium, and liquid goes regeneration of hydrochloric acid process after obtained anti-indium.
6. method according to claim 5, it is characterised in that in regeneration of hydrochloric acid process, liquid is carried by resin after anti-indium
Indium adsorbs indium ion, and the resin backwash and regeneration of indium ion will be adsorbed with hydrochloric acid, and indium ion enters after rich indium in liquid, and liquid enters after rich indium
Row regeneration of hydrochloric acid, output In2O3Product, and regenerate hydrochloric acid, the hydrochloric acid of regeneration removes before anti-indium liquid and for resin backwash and regeneration.
7. method according to claim 6, it is characterised in that put forward indium extraction raffinate by what resin carried that indium obtains and then set
Fat carries iron, and the resin backwash and regeneration of iron ion will be adsorbed with hydrochloric acid, and iron ion enters after rich iron in liquid, and liquid carries out hydrochloric acid after rich iron
Regeneration, output iron oxide product, and regenerate hydrochloric acid, the hydrochloric acid of regeneration removes after anti-one section of iron liquid and washes liquid after chlorine.
8. method according to claim 7, it is characterised in that carry the liquid after iron that carries that iron obtains by resin and add sulfuric acid,
Carry out regeneration of hydrochloric acid, the high-purity ZnSO of output4·7H2O products, and regenerate hydrochloric acid, the hydrochloric acid of regeneration removes before anti-indium liquid and for resin
Backwash and regeneration；The crystalline mother solution of concentration is largely recycled, and fraction returns to liquid before anti-indium and recycled.
9. according to the method described in claim 1, it is characterised in that described load organic phases run to two sections of anti-iron and anti-iron
One section, the iron in load organic phases is all stripped by liquid before anti-iron, liquid carries out hydrochloric acid again after two sections of obtained anti-iron
Raw, output iron oxide product, and regenerate hydrochloric acid, the hydrochloric acid of regeneration removes after anti-one section of iron liquid and washes liquid after chlorine.
10. method according to claim 9, it is characterised in that described load organic phases, which are run to, washes chlorine section, washes before chlorine
The chlorion carried secretly in load organic phases is all stripped by liquid, and obtained liquid after chlorine of washing is used as liquid before anti-one section of iron,
Liquid is used as liquid before anti-two sections of iron after one section of the anti-iron that liquid is obtained after anti-one section of iron before anti-one section of iron.
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