CN108033589A - The method that a kind of waste acid removal of impurities in acid making system recycles - Google Patents
The method that a kind of waste acid removal of impurities in acid making system recycles Download PDFInfo
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- CN108033589A CN108033589A CN201711030889.8A CN201711030889A CN108033589A CN 108033589 A CN108033589 A CN 108033589A CN 201711030889 A CN201711030889 A CN 201711030889A CN 108033589 A CN108033589 A CN 108033589A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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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
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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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
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- 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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Abstract
The method that a kind of waste acid removal of impurities in acid making system recycles, comprises the following steps：A. extract, F, Cl in water phase is largely transferred to organic phase；B. wash, the valuable element such as zinc, lead, copper and cadmium for making to carry secretly in organic phase is transferred to cleaning solution；C. blank, further separates valuable element and the water phases such as zinc, lead, copper and the cadmium carried secretly in organic phase；D. it is stripped, F, Cl in organic phase is transferred in water phase；E. regenerate, lean organic phase is mixed with regenerative agent in mixing channel to be regenerated and be acidified.This invention ensures that the raffinate for returning Zn system meets the process specifications of zinc electrolysis, while the heavy metal in waste acid is recycled.
Description
Technical field
The present invention relates to a kind of processing reuse method of waste acid, cleans again more particularly to a kind of waste acid in acid producing system
The method utilized.
Background technology
Substantial amounts of flue gas can be produced in the pyrometallurgical smelting such as copper, lead, zinc process, includes substantial amounts of SO2And some harmful gold
Belong to component, through double conversion double absorption acid making system, realize fume recovery and SO2Flue gas acid preparing, what is produced in the process is a large amount of containing weight
The strongly acid wastewater of metal, abbreviation waste acid, containing volume fraction in the zinc of below 0.5g/L, lead, copper, cadmium, mercury, arsenic etc. in waste acid
Heavy metal ion, content are higher than common industrial wastewater, while are respectively 10-20g/L, 0.8- containing volume fraction in waste acid
The H of 2.0g/L and 1.0-3.5g/L2SO4, Cl and F, it is big to environmental hazard.The processing of waste acid at present more using lime under agitation neutralize,
Molysite aerating oxidation, concentrator and settling tank precipitation, the traditional handicraft of filter press separation of solid and liquid.There are technique for this treatment process
Long flow path, operating cost are high, separation of solid and liquid is not thorough, outer draining control is unstable, take up a large area, system operatio poor flexibility
The defects of.At present, conventional waste acid process flow includes waste acid adjusting, lime neutralization, dosing, precipitation, press filtration, filtering, outer row
Etc. process, device therefor is relatively bulky in process flow, need to build two to three-storey building, so not only investment cost is high, Er Qiecun
The CaSO produced in the reaction4Block the defects of serious and filter life is short.Also need to put into substantial amounts of manpower, electricity in operation
Force-summing device maintenance cost；In addition, the dilute sulfuric acid in waste acid is wasted, it is harmful useless containing heavy metals such as lead, arsenic, cadmiums
Slag is difficult to store, and easily causes secondary pollution, if waste residue reuse will be enriched with poisonous metal, influences to produce.In recent years, with
Country and local government's environmental pollution pay attention to day by day, and energy-saving and emission-reduction work carry out in a deep going way, sewage arrange
Putting aspect has tightened up requirement.Thus, sewage discharge is reduced as far as possible, avoids producing environment pollution, strives for realizing zero-emission
Put, be an extremely urgent serious problems so as to achieve the purpose that cleanly production and water-saving, energy saving, synergy, pollution treatment.Close
Also there are relevant patent literature, such as 1, application number 200910065664. 5 in terms of waste acid processing, it is entitled
" waste acid sewage-treatment plant and treatment process ", the patent of invention be related to a kind of sour water to acid making system cleaning procedure into
Waste acid is pumped into first segment level-one neutralization reaction groove, added by the waste acid sewage-treatment plant of row processing and treatment process, the invention
Carbide slag cream adjusts pH value in 1-6, liquid flooding to first segment two level neutralization reaction groove, and it is 5- to add carbide slag cream adjustment pH value
6, enter cesspool after liquid is carried out separation of solid and liquid；Liquid in cesspool is pumped into second segment level-one neutralization reaction groove,
For feeding lime breast adjustment pH value between 6-7, liquid self-flowing enters second segment two level neutralization reaction groove, feeding lime breast adjustment pH value
Between 7-8, liquid self-flowing enters vulcanization, flocculation reaction groove, and it is 7% that percentage by weight is added into vulcanization, flocculation reaction groove
Vulcanized sodium and 15% ferrous sulfate, liquid carry out fine particle separation of solid and liquid by filter press, film filter, are arranged outside liquid, very
The continuous qualified discharge of outer draining easy to implement, the invention there are the substantial amounts of slag that neutralizes as conventional method and produce, and neutralize slag
Environment is polluted in stacking process, while production cost is high, the problems such as row outside liquid.2nd, application number 200710193018. 8, invention
Entitled " recoverying and utilizing method of Waste Sulfuric Acid in wet smelting acid making system ", which is to wet smelting acid making system
In purification section produce Waste Sulfuric Acid carry out concentrate, sulfur waste acid concentration is brought up into 10-18%, the Waste Sulfuric Acid after concentrate is added
In the surge tank for entering to fill ground phosphate rock, stir and size mixing to ground phosphate rock, raw material utilization is re-used as after sizing mixing, this method exists
Problem is F, Cl containing higher concentration in Waste Sulfuric Acid, seriously affects the quality of product, as added during production calcium monohydrogen phosphate
De- F processes, cause that the production cost increases, while, it is necessary to which substantial amounts of thermal energy, concentrated cost is excessively high to ask in Waste Sulfuric Acid concentration process
Topic.3rd, application number：201010608190.7, entitled " processing method of waste acid in acid producing system ", patent of invention head
The waste acid that first acid making system is produced is sent into PM film filters and is filtered, and is removed after the filtering of PM film filters in decontaminated acid
Most of dirt and beavy metal impurity ion arsenic, copper, cadmium, lead and iron, obtain filtrate and acid sludge；Then will be through PM film filters
Filtrate after filtering, which is further imported in PL film filters, is filtered, and filtrate and acidity are obtained after the filtering of PL film filters
Sludge, gained filtrate enter dry desorption system and replace moisturizing or enter cleaning system reuse again；Will be through PM films, PL film filter mistakes
The acid sludge obtained after filter imports in filter press and carries out press filtration, and gained filtrate returns to PM film filters and re-started after press filtration
Filter, gained filter residue are transported to stock ground reuse.It can be completely free of in traditional waste acid treatment process and deposited using processing method of the present invention
Highly energy-consuming problem, achieveed the purpose that energy-saving and emission-reduction, synergy pollution treatment, but this method use PM and PL membrane filtrations, therefore deposit
The cost of investment and actual motion of high cost the problem of, contain the metals such as arsenic, copper, cadmium, lead and iron with caused acid sludge,
And content is not high, it is difficult to recycles, there is secondary pollution problems.
Containing volume fraction in the heavy metal ion such as the zinc of below 0.5g/L, lead, copper, cadmium, mercury, arsenic and volume integral in waste acid
Number is respectively the H of 10-20g/L, 0.8-2.0g/L and 1.0-3.5g/L2SO4, Cl and F, it is valuable during conventional wet lay zinc metallurgy
Metallic zinc, lead, copper, cadmium and sulfuric acid are all utilized and recycle in leaching and purification process, and arsenic, mercury are in neutral leaching process
Removed into leached mud, but in the electrolysis production of zinc hydrometallurgy, chlorion can corrode alloy lead anode, make lead with two
Lead chloride form enters electrolyte and is separated out in cathode zinc, so that the leaded height of cathode zinc, when serious, can cause the lead anode longevity
Order short, cathode zinc quality is unqualified, also stainless steel agitating paddle and heater can be caused to corrode in addition, chloride ion content is excessive；
Fluorine ion causes stripping zinc difficult outer except corroding aluminium minus plate, with chlorion collective effect during its too high levels, accelerates lead anode
Corrosion, while can also damage the ceramic tile erosion resistant coating of batch extractor.The also constantly enrichment in solution is produced of fluorine chlorion, is not easy to remove
Go, effectively cause electrolytic zinc production harm, therefore zinc wet method smelting process requires F, Cl volume fraction content respectively in 100mg/L
Within 600mg/L.
The relevant patent literature in terms of F, Cl processing, 1,《Non-ferrous metal (Smelting Part)》Magazine, 1977
02nd phase,《The chlorion in zinc solution is removed with extraction》, page 52.Disclose and use N235 from 158g/L containing zinc, chlorion
4.43g/L, sulfuric acid 13g/L solution in extract dechlorination, the sodium carbonate liquor for being 2%-3% with mass fraction is stripped, then anti-from alkali
Extract in liquid with the laboratory research of basic zinc carbonate depositing zinc.Although this method achieves preferable dechlorination effect, but exist such as
Lower problem is not directed to defluorinate problem, and N235 is a kind of anion extractant, and fluorine ion is mainly with H in an acidic solution2F+Cation
In the presence of, and N235 cannot extract fluorine ion in the case；Industrial production successively carries out, organic extractant phase zinc and its
Mechanical entrapment zinc, which constantly enters in strip liquor, to be accumulated, and makes strip liquor high containing zinc, mass fraction be only 2%-3% sodium carbonate liquor by
It is inadequate in basicity, it is impossible to the zinc of the high-content in strip liquor is converted to solvable sodium zincate, and substantial amounts of zinc is with hydroxide
Zinc hydrolyzed state exists, so as to bring the emulsification problem of organic phase, makes back extraction process be difficult to be normally carried out；Alkali back extraction without
It is recycled for multiple times, causes back extraction liquid measure big, chloride low, be unfavorable for wastewater treatment and synthetical recovery sodium chloride.2nd, it is " a kind of from sulphur
The method that chlorine is removed in sour zinc solution ", is disclosed in September, the 2010 CN101818262A patent documents of I days.Disclose use
Tri-n-butylamine does extractant, kerosene or sec-octyl alcohol and does diluent extraction chlorion, makees back washing agent with ammonium hydroxide or sodium hydroxide solution
It is stripped, removes the chlorion in solution of zinc sulfate with the method for sodium hydroxide solution regeneration organic phase, the patent application
Document only proposes the extraction to the chloride solution of zinc sulfate of PH=5, is equally not directed to defluorinate problem；And to impurity effect, it is special
It is not Fe3+、SiO2Content without reference to one of impurity most feared when amine extractant is extracted is SiO2, its
More than 300mg/L will cause extractant to emulsify, and extraction is prevented when serious from carrying out；Another impurity F e3+, it should reduce as far as possible,
Because amine extractant will preferentially extract Fe3+, and the extraction to chlorine is reduced, it will not extract chlorine when serious and only extract Fe3+.3rd, it is " a kind of
Effectively removing neutrality or the method for Cl ~-In Acidic Solution ", is disclosed in the CN1920070A patents text of on 2 28th, 2007
Offer.Disclose using kerosene do diluent prepare ertiary amine solution make extractant extraction chlorion, with ammonium hydroxide or aqueous sodium carbonate
The method being stripped as back washing agent removes the chlorion in neutral or acid solution, and dechlorination rate is more than 80%, this method
The problem of being equally not directed to removing fluorine and impurity effect extraction.4th, Application No. CN201210159097.1's is entitled
" a kind of extraction removing fluorine, the wet zinc smelting method of chlorine ", which disclose extractant is N235, and diluent is kerosene, makes extraction
Organic phase is taken after dilute sulfuric acid is acidified, fluorine, chlorine, water phase and organic phase are extracted at the same time from the fluorine-containing of PH5. 2-5. 4, chlorine zinc liquid
Velocity ratio be 3-5, fluorine-containing, solutions of chlorine before extraction, by neutralizing iron removal by oxidation and/or zinc powder purification except metal impurities are located in advance
Manage, the Fe in fluorine-containing after processing, solutions of chlorine3+Control is in below 30mg/L, SiO2Control is in below 300mg/L, although this method
It is related to and removes F, but requires as zinc liquid, 5. 2-5. 4 and Fe of PH3+ SiO2Control respectively in the tight of 30mg/L and below 300mg/L
Lattice requirement, adds production cost.
Therefore, how to find it is a kind of effectively and produced without " three wastes " while recycle the valuable metal lead in waste acid, zinc, copper and
The method of cadmium and sulfuric acid, is the problem for needing further to be explored.
The content of the invention
It is an object of the invention to provide the method that the waste acid removal of impurities in a kind of acid making system recycles.It can make relieving haperacidity system
Waste acid in system realizes the removing of F, Cl by extraction, reduces the raw and auxiliary material consumption in other waste acid processing methods；Realize dirty
The recycling of harmful element zinc in acid, lead, copper, cadmium, fluorine, chlorine and sulfuric acid；Water consumption in Zn system is supplemented, is reached in Zn system
Volumetric balance；Realize that organic phase recycles.The present invention leads to harmful element zinc, lead, copper, cadmium, fluorine, chlorine and sulfuric acid in waste acid
The hydrometallurgy for crossing zinc is obtained for recycling, is produced without " three wastes ", and with process, operating cost is low and quantity-produced
Advantage.
The technical scheme is that：
The method that a kind of waste acid removal of impurities in acid making system recycles, comprises the following steps：
Step A：Extraction, extractant be three pungent decyl tertiary amines, abbreviation P235, and diluent is that 200# solvents kerosene is (or sulfonated
Common kerosene), synergic reagent is tributyl phosphate, and abbreviation TBP, extractant, diluent and synergic reagent are mixed to prepare extraction has
Machine phase, the waste acid in acid making system is mixed with organic phase in mixing channel and is extracted, and F, Cl in water phase is transferred to organic phase
In, and in defecator split-phase, separate rich organic phase and raffinate；
Step B：Washing, the dilution for the waste electrolyte that detergent produces for zinc electrolysis, by the rich organic phase obtained by step A with giving up
Electrolyte is transferred to cleaning solution in mixing channel mixing, the heavy metal such as washing, the copper, lead, zinc for making to carry secretly in organic phase, and in defecator
Split-phase, organic phase is separated with cleaning solution after making washing.
Step C：Blank, defecator clarification split-phase is flow to by the washing organic phase obtained by step B in blank level through mixing channel,
The heavy metals such as water phase and copper, lead, the zinc that extraction F, Cl organic phase is carried secretly are made further to be separated with organic phase；
Step D：Back extraction, back washing agent is sodium carbonate and sodium hydroxide mixed liquor, by extraction F, the Cl organic phase obtained by step C and configuration
Good sodium carbonate and sodium hydroxide mixed liquor mixes in level is stripped to be stripped, and F, Cl in organic phase is transferred to strip liquor
In, and in defecator split-phase, lean organic phase is separated with strip liquor；
Step E：Regeneration, the dilution for the waste electrolyte that regenerative agent produces for zinc electrolysis, by the lean organic phase obtained by step D and again
Raw agent is regenerated in mixing channel mixing, and in defecator split-phase, organic phase is separated with regenerated liquid after making regeneration, and organic phase obtains
Regeneration and acidifying；
As a further refinement of the present invention, the step extraction is 3~5 grades of extractions, extraction organic phase is volume fraction 15
~37% P204, the 200# kerosene (or sulfonated common kerosene) of volume fraction 60~80% and volume fraction 3~5%
The mixed liquor of TBP compositions；It in organic phase and water phase volume ratio is 1 that the extraction of the step A, which is,:4~1:8, extraction time for 4~
8 minutes, temperature was room temperature, and settling time carries out under conditions of being more than 7 minutes, raffinate enter Zn system recycle zinc therein,
Lead, copper, cadmium and sulfuric acid.
As a further refinement of the present invention, the step washing is 2 grades of washings, detergent is the quality percentage of sulfuric acid
The dilution of the zinc waste electrolyte of 30~50g/L of concentration；Organic phase washing is in organic phase and water phase after the extraction of the step B
Volume ratio is 20:1~10:1, wash time is 4~8 minutes, and settling time carries out under conditions of being more than 7 minutes.
As a further refinement of the present invention, the blank of the step C is 1 grade of blank, settling time is more than 7 minutes
Under the conditions of carry out.
As a further refinement of the present invention, the step back extraction is 4~6 grades of back extraction, back washing agent is dense for quality percentage
Degree is respectively the mixed liquor of 50~100g/L sodium carbonate liquors and 40~80g/L sodium hydroxide solutions；The back extraction of the step D is
It is 6 in organic phase and water phase volume ratio:1~3:1, Stripping times be 4~8 minutes, settling time be more than 7 minutes under conditions of into
OK.
As a further refinement of the present invention, the separated water of step D mutually recycles, when chlorine is enriched with back washing agent
During to 35~48g/L, with recrystallization recycling NaCl after lime defluorinate；When the quality hundred of the sodium carbonate in back washing agent or sodium hydroxide
When dividing concentration relatively low, corresponding material should be suitably supplemented.
As a further refinement of the present invention, the step is regenerated as 1~3 grade of regeneration, regenerative agent is the quality of sulfuric acid
The dilution of the zinc waste electrolyte of 50~100g/L of percentage concentration；Organic phase regeneration is in organic phase after the back extraction of the step E
It is 1 with water phase volume ratio:1~3:1, wash time is 4~8 minutes, and settling time carries out under conditions of being more than 7 minutes.
The beneficial effects of the present invention are：
Waste acid removal of impurities recycling in acid making system of the present invention is designed using zinc wet method smelting process, overcomes waste acid completely
Traditional treatment method, whole process produces without " three wastes ", and raffinate, cleaning solution, blank solution and regenerated liquid can all return Zn system,
Both recyclable valuable metal therein and sulfuric acid, while the water in Zn system can be supplemented, reach system bulk balance, save zinc
The production cost of smelting；The slags such as sodium chloride can do product take-away, reduce production cost, and whole impurity removal process connects in extraction box
Continuous to carry out, mass percentage concentration of the raffinate containing F, Cl is respectively smaller than 100mg/L and 300mg/L, ensure that the extraction for returning Zn system
F, Cl content in extraction raffinate meets process specifications of the zinc electrolysis to F, Cl in electrolyte, while heavy metal zinc in waste acid,
Lead, copper and cadmium and sulfuric acid are recycled by zinc hydrometallurgy；The addition of synergic reagent TBP, eliminates in waste acid in organic phase
The influence that silicon, iron emulsify organic phase, and solve the efficient extraction of F, the extraction yield of F is more than 92%.The present invention makes to have in waste acid
Evil element zinc, lead, copper, cadmium, fluorine, chlorine and sulfuric acid are obtained for recycling, are produced without " three wastes ", and with process, run into
The advantages of this low and continuous production.
Brief description of the drawings
Fig. 1 is the process flow chart of the present invention.
Embodiment
Embodiment 1
Waste acid composition in the acid making system that the present invention uses is following mass concentration (unit mg/L)： As 58.5、Fe
12.4、Cu 9.5、Cd 137.3、Pb 115.7、Zn 62.8、Hg 21.6、SiO2 481.2、H2SO4 18.53、F 2167、Cl
1845.Carry out according to the following steps：
Step A：It is P204, the 200# kerosene of volume fraction 80% of volume fraction 15% to extract as 3 grades of extractions, extraction organic phase
The mixing organic phase formed with the TBP of volume fraction 5%；Organic phase is 1 with water phase volume ratio:4, extraction time is 8 minutes, temperature
Spend for room temperature, settling time 7 minutes, F, Cl content are respectively 86.5mg/L and 251.8mg/L in raffinate.
Step B：It is the dilution of the zinc waste electrolyte of the mass percentage concentration 30g/L of sulfuric acid to wash as 2 grades of washings, detergent
Liquid；Organic phase is 10 with water phase volume ratio:1, wash time is 8 minutes, settling time 7 minutes.
Step C：Blank is 1 grade of blank, settling time 7 minutes.
Step D：It is respectively 100g/L sodium carbonate liquors and 40g/L for mass percentage concentration to be stripped as 4 grades of back extraction, back washing agent
The mixed liquor of sodium hydroxide solution, organic phase are 6 with water phase volume ratio:1, Stripping times are 8 minutes, settling time 7 minutes, instead
Extract As 0.045mg/L in liquid, Fe 0.072 mg/L, Cu 0.061 mg/L, Cd 0.038 mg/L, Pb 0.027 mg/L, Zn
0.034mg/L、Hg 0.014 mg/L、SiO215.2 mg/L、F 49.17 g/L、Cl 42.81 g/L；Back washing agent lime
Defluorinate, crystallization obtain the industrial NaCl products of qualification.
Step E：3 grades of regeneration are regenerated as, regenerative agent is the dilution of the zinc waste electrolyte of the mass percentage concentration 50g/L of sulfuric acid
Liquid, organic phase are 1 with water phase volume ratio:1, wash time is 8 minutes, settling time 7 minutes.
Waste acid in acid making system is through extracting, washing, blank, back extraction, regeneration treatment, the removal efficiency of F, Cl reaches respectively
96.01% and 86.35%, F, Cl content reach the process specifications of zinc electrolysis in raffinate, arsenic in strip liquor, iron, copper, cadmium,
Lead, zinc, the content of mercury obtain the industrial chlorinations sodium product of qualification in below 0.1mg/L, meanwhile, organic phase realizes circulation
Use.
Embodiment 2
Waste acid composition in the acid making system that the present invention uses is following mass concentration (unit mg/L)： As 58.5、Fe
12.4、Cu 9.5、Cd 137.3、Pb 115.7、Zn 62.8、Hg 21.6、SiO2 481.2、H2SO4 18.53、F 2167、Cl
1845.Carry out according to the following steps：
Step A：It is P204, the 200# kerosene of volume fraction 60% of volume fraction 37% to extract as 5 grades of extractions, extraction organic phase
The mixing organic phase formed with the TBP of volume fraction 3%；Organic phase is 1 with water phase volume ratio:8, extraction time is 4 minutes, temperature
Spend for room temperature, settling time 10 minutes, F, Cl content are respectively 95.8mg/L and 341.6mg/L in raffinate.
Step B：It is the dilution of the zinc waste electrolyte of the mass percentage concentration 50g/L of sulfuric acid to wash as 2 grades of washings, detergent
Liquid；Organic phase is 20 with water phase volume ratio:1, wash time is 4 minutes, settling time 10 minutes.
Step C：Blank is 1 grade of blank, settling time 10 minutes.
Step D：It is respectively 50g/L sodium carbonate liquors and 80g/L for mass percentage concentration to be stripped as 6 grades of back extraction, back washing agent
The mixed liquor of sodium hydroxide solution, organic phase are 3 with water phase volume ratio:1, Stripping times are 4 minutes, settling time 10 minutes,
As 0.028mg/L in strip liquor, the mg/L of Fe 0.051 mg/L, Cu 0.047, Cd 0.023mg/L, 0.024 mg/L of Pb,
Zn 0.029mg/L、Hg 0.011mg/L、SiO230.48 mg/L、F 50.24 g/L、Cl 43.08 g/L；Back washing agent stone
Grey defluorinate, crystallization obtain the industrial NaCl products of qualification.
Step E：1 grade of regeneration is regenerated as, regenerative agent is dilute for the zinc waste electrolyte of the mass percentage concentration 100g/L of sulfuric acid
Liquid is released, organic phase is 3 with water phase volume ratio:1, wash time is 4 minutes, settling time 10 minutes.
Waste acid in acid making system is through extracting, washing, blank, back extraction, regeneration treatment, the removal efficiency of F, Cl reaches respectively
95.58% and 81.48%, F, Cl content reach the process specifications of zinc electrolysis in raffinate, arsenic in strip liquor, iron, copper, cadmium,
Lead, zinc, the content of mercury obtain the industrial chlorinations sodium product of qualification in below 0.1mg/L, meanwhile, organic phase realizes circulation
Use.
Embodiment 3
Waste acid composition in the acid making system that the present invention uses is following mass concentration (unit mg/L)： As 58.5、Fe
12.4、Cu 9.5、Cd 137.3、Pb 115.7、Zn 62.8、Hg 21.6、SiO2 481.2、H2SO4 18.53、F 2167、Cl
1845.Carry out according to the following steps：
Step A：It is P204, the 200# kerosene of volume fraction 66% of volume fraction 30% to extract as 4 grades of extractions, extraction organic phase
The mixing organic phase formed with the TBP of volume fraction 4%；Organic phase is 1 with water phase volume ratio:6, extraction time is 6 minutes, temperature
Spend for room temperature, settling time 15 minutes, F, Cl content are respectively 87.26mg/L and 282.17mg/L in raffinate.
Step B：It is the dilution of the zinc waste electrolyte of the mass percentage concentration 40g/L of sulfuric acid to wash as 2 grades of washings, detergent
Liquid；Organic phase is 15 with water phase volume ratio:1, wash time is 6 minutes, settling time 15 minutes.
Step C：Blank is 1 grade of blank, settling time 15 minutes.
Step D：It is respectively 80g/L sodium carbonate liquors and 60g/L for mass percentage concentration to be stripped as 5 grades of back extraction, back washing agent
The mixed liquor of sodium hydroxide solution, organic phase are 4 with water phase volume ratio:1, Stripping times are 6 minutes, settling time 15 minutes,
As 0.067mg/L in strip liquor, Fe 0.081mg/L, 0.066 0.035 0.031 mg/L of mg/L, Pb of mg/L, Cd of Cu,
Zn 0.040mg/L、Hg 0.018 mg/L、SiO231.57 mg/L、F 50.54 g/L、Cl 42.47 g/L；Back washing agent is used
Lime defluorinate, crystallization obtain the industrial NaCl products of qualification.
Step E：2 grades of regeneration are regenerated as, regenerative agent is the dilution of the zinc waste electrolyte of the mass percentage concentration 80g/L of sulfuric acid
Liquid, organic phase are 2 with water phase volume ratio:1, wash time is 6 minutes, settling time 15 minutes.
Waste acid in acid making system is through extracting, washing, blank, back extraction, regeneration treatment, the removal efficiency of F, Cl reaches respectively
95.97% and 84.71%, F, Cl content reach the process specifications of zinc electrolysis in raffinate, arsenic in strip liquor, iron, copper, cadmium,
Lead, zinc, the content of mercury obtain the industrial chlorinations sodium product of qualification in below 0.1mg/L, meanwhile, organic phase realizes circulation
Use.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (7)
1. the method that the waste acid removal of impurities in a kind of acid making system recycles, it is characterised in that comprise the following steps：
A, extract：Extractant is three pungent decyl tertiary amines, abbreviation P235, and diluent is (or sulfonated general for 200# solvents kerosene
Logical kerosene), synergic reagent is tributyl phosphate, and abbreviation TBP, extraction organic phase is mixed to prepare by extractant, diluent and synergic reagent,
Waste acid in acid making system is mixed with organic phase in mixing channel and is extracted, F, Cl in water phase is transferred in organic phase, and
In defecator split-phase, separate rich organic phase and raffinate；
B, wash：The dilution for the waste electrolyte that detergent produces for zinc electrolysis, by the rich organic phase obtained by step A and useless electrolysis
Liquid is transferred to cleaning solution in mixing channel mixing, the heavy metal such as washing, the copper, lead, zinc for making to carry secretly in organic phase, and in defecator point
Phase, organic phase is separated with cleaning solution after making washing.
2.C, blank：By the washing organic phase obtained by step B blank level through mixing channel flow to defecator clarification split-phase, make extraction F,
The heavy metal such as the water phase of Cl organic phases entrainment and copper, lead, zinc is further separated with organic phase；
D, it is stripped：Back washing agent is sodium carbonate and sodium hydroxide mixed liquor, by extraction F, Cl organic phase obtained by step C and has been configured
Sodium carbonate and sodium hydroxide mixed liquor mix in level is stripped to be stripped, and F, Cl in organic phase is transferred in strip liquor, and
In defecator split-phase, lean organic phase is set to be separated with strip liquor；
E, regenerate：The dilution for the waste electrolyte that regenerative agent produces for zinc electrolysis, by the lean organic phase and regenerative agent obtained by step D
Regenerated in mixing channel mixing, and in defecator split-phase, organic phase is separated with regenerated liquid after making regeneration, and organic phase has obtained again
Raw and acidifying；
The method that waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：Described
It is P204, the 200# coals of volume fraction 60~80% of volume fraction 15~37% to extract as 3~5 grades of extractions, extraction organic phase
The mixed liquor of oily (or sulfonated common kerosene) and the TBP of volume fraction 3~5% compositions；The extraction of the step A is that having
Machine phase is 1 with water phase volume ratio:4~1:8, extraction time is 4~8 minutes, and temperature is room temperature, and settling time is more than 7 minutes
Under the conditions of carry out, raffinate enters Zn system and recycles zinc, lead, copper, cadmium and sulfuric acid therein.
3. the method that the waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：It is described
Washing for 2 grades washing, detergent for sulfuric acid 30~50g/L of mass percentage concentration zinc waste electrolyte dilution；It is described
It in organic phase and water phase volume ratio is 20 that organic phase washing, which is, after the extraction of step B:1~10:1, wash time is 4~8 minutes,
Settling time carries out under conditions of being more than 7 minutes.
4. the method that the waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：It is described
The blank of step C is 1 grade of blank, and settling time carries out under conditions of being more than 7 minutes.
5. the method that the waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：It is described
Back extraction for 4~6 grades back extraction, back washing agent for mass percentage concentration be respectively 50~100g/L sodium carbonate liquors and 40~80g/L
The mixed liquor of sodium hydroxide solution；It in organic phase and water phase volume ratio is 6 that the back extraction of the step D, which is,:1~3:1, Stripping times
For 4~8 minutes, settling time carried out under conditions of being more than 7 minutes.
6. the method that the waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：When anti-
When chlorine is enriched to 35~48g/L in extraction agent, with recrystallization recycling NaCl after lime defluorinate.
7. the method that the waste acid removal of impurities in a kind of acid making system according to claim 1 recycles, it is characterised in that：It is described
Be regenerated as 1~3 grade regeneration, regenerative agent for sulfuric acid 50~100g/L of mass percentage concentration zinc waste electrolyte dilution；
It in organic phase and water phase volume ratio is 1 that organic phase regeneration, which is, after the back extraction of the step E:1~3:1, wash time is 4~8 points
Clock, settling time carry out under conditions of being more than 7 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112499820A (en) * | 2020-11-30 | 2021-03-16 | 安道麦安邦(江苏)有限公司 | Method for recycling zinc-containing wastewater of buprofezin |
| CN116395779A (en) * | 2023-06-07 | 2023-07-07 | 赛恩斯环保股份有限公司 | Method for inhibiting cadmium and extracting fluorine from waste acid vulcanized liquid |
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| CN102399984A (en) * | 2011-12-16 | 2012-04-04 | 东北大学 | Method for extracting and recovering zinc from zinc-containing waste water |
| CN102978421A (en) * | 2012-12-31 | 2013-03-20 | 株洲冶炼集团股份有限公司 | Indium extraction method of ferrous iron-rich zinc oxide acid supernatant |
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| CN112499820A (en) * | 2020-11-30 | 2021-03-16 | 安道麦安邦(江苏)有限公司 | Method for recycling zinc-containing wastewater of buprofezin |
| CN112499820B (en) * | 2020-11-30 | 2022-07-01 | 安道麦安邦(江苏)有限公司 | Method for recycling zinc-containing wastewater of buprofezin |
| CN116395779A (en) * | 2023-06-07 | 2023-07-07 | 赛恩斯环保股份有限公司 | Method for inhibiting cadmium and extracting fluorine from waste acid vulcanized liquid |
| CN116395779B (en) * | 2023-06-07 | 2023-09-26 | 赛恩斯环保股份有限公司 | Method for inhibiting cadmium and extracting fluorine from waste acid vulcanized liquid |
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