CN107385216B - The method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue - Google Patents

The method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue Download PDF

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CN107385216B
CN107385216B CN201710593278.8A CN201710593278A CN107385216B CN 107385216 B CN107385216 B CN 107385216B CN 201710593278 A CN201710593278 A CN 201710593278A CN 107385216 B CN107385216 B CN 107385216B
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zinc
filter residue
filtrate
sulfuric acid
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CN107385216A (en
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叶宏裕
杨庆辉
黄志远
肖国寅
马景荣
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Taishan Chemical Works Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/06—Sulfates
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses the methods that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, it is characterised in that comprises the following steps：(1) acidleach；(2) iron removal by oxidation；(3) extracting copper；(4) displacement is except cadmium；(5) condensing crystallizing.The method that the slave utilising zinc containing waste residue of the present invention prepares monohydrate zinc sulphate is low-carbon environment-friendly scheme, not only prepare low raw-material cost, refuse reclamation, solves the environmental problem that existing utilising zinc containing waste residue is difficult to recycle, and preparation process also energy conservation and environmental protection, no exhaust gas and waste water generate, without using to the unfavorable reagent of environment, it recycles the metals such as copper cadmium simultaneously and waste residue reuses.

Description

The method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue
Technical field
The present invention relates to the preparation fields of monohydrate zinc sulphate, and in particular to the side of monohydrate zinc sulphate is prepared from utilising zinc containing waste residue Method.
Background technology
Zinc sulfate is a kind of important raw material of industry, is widely used in feed addictive, fertilizer, chemical industry, pharmacy, national defence, rubber The industries such as glue, electronics, plating, water process are the raw materials for manufacturing zinc salt and lithopone.Electrolytic industry for cable it is zinc-plated and electrolysis Pure zinc is additionally operable to prevent fruit tree nursery disease, timber and leather preservative agent and man-made fibres industry, and food-grade also serves as nutrition increasing Tonic (zinc enhancer).The common preparation method of industry be with sulfuric acid with zinc oxide reaction or with zinc powder or zinc ingot metal directly and sulfuric acid reaction, Then filter, add zinc dust precipitation and remove impurity, it is filtered, increase potassium manganate or hydrogen peroxide oxidation, then through drying, separation, Concentration, filtering, twice replaced, press filtration, screening and etc., obtain monohydrate zinc sulphate.Although such preparation method preparation process Simple but required of high cost and energy consumption is big.
And zinc hydrometallurgy or electrolytic zinc can generate a large amount of utilising zinc containing waste residues, often contain in this utilising zinc containing waste residue zinc oxide and The metal impurities including heavy metal such as iron, copper, cadmium if directly thrown aside without being recycled, be easy to cause money The waste in source, and cause environmental pollution.
The content of the invention
It is an object of the invention to overcome shortcoming and deficiency of the prior art, provide from utilising zinc containing waste residue and prepare sulfuric acid monohydrate The method of zinc, makes the preparation low raw-material cost of monohydrate zinc sulphate, and refuse reclamation solves existing utilising zinc containing waste residue and is difficult to back Receive the environmental problem that utilizes, and preparation process also energy conservation and environmental protection, no exhaust gas and waste water generate, few using reagent, without using to ring The unfavorable reagent in border recycles the metals such as copper cadmium while monohydrate zinc sulphate is prepared and waste residue reuses every time, reachable To the comprehensive utilization of utilising zinc containing waste residue.
The present invention is achieved by the following technical solutions：
The method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, it is characterised in that comprise the following steps：
(1) acidleach：By sulfuric acid or Waste Sulfuric Acid that utilising zinc containing waste residue and weight percent content are 20~30% by weight 1:3 The first acidleach pond is added to, continuously stirs 2h, when reaction end controls pH, and press filtration carries out solid-liquor separation, obtains one for 4.8~5.0 Secondary filtrate and a filter residue；
(2) iron removal by oxidation：First-time filtrate is placed in iron-removing tank, be passed through air or oxygen and is stirred, detects ferric ion Concentration works as Fe3+During content≤5ppm, continue to be heated to 80~100 DEG C, reddish-brown precipitation occur until no longer generating, stand That is press filtration, obtains secondary filtrate and secondary filter residue, and the secondary filtrate enters next step；
(3) extracting copper：Secondary filtrate is obtained into cupric extract liquor and raffinate using copper extraction process；
(4) displacement is except cadmium：Zinc powder is added in raffinate, and is stirred, until Cd in raffinate2+Content≤5ppm is stood Filtering, obtains filtrate three times and three times filter residue, three times filter residue, that is, thick cadmium；
(5) condensing crystallizing：Filtrate crystallization kettle will be added in three times, controlled at 70~100 DEG C, condensing crystallizing, get Yi Shui Zinc sulfate, the Recycling Mother Solution after filtering, which is added in crystallization kettle, to be continued to crystallize.
Further, in the utilising zinc containing waste residue by weight percentage, containing zinc 40~60%, iron 2~4%, copper 3~5%, Cadmium 10~20%, silica 8~16%.
The present invention mainly separates each impurity by the realization of above 5 steps from utilising zinc containing waste residue, and prepares monohydrate zinc sulphate, The purpose of (1) step is that each metal oxide in utilising zinc containing waste residue and sulfuric acid reaction entered solution, a filter residue mainly into It is silica to divide, and available for brick-making raw material, this can be sent into system together when subsequent utilising zinc containing waste residue comprehensively utilizes with secondary filter residue Brick field, directly and sulfuric acid reaction, due to being exothermic reaction, reaction can be warming up to 85 DEG C or so to the utilising zinc containing waste residue of the step certainly, because This present invention does not heat, can be energy saving；The Waste Sulfuric Acid in chemical plant may be employed in sulfuric acid, and (wet method zinc can generate largely Waste Sulfuric Acid) it replaces, it is further cost-effective；Step (2) iron removal by oxidation is not using conventional strong oxidizer hydrogen peroxide or Gao Meng Sour potassium eliminates subsequent demanganization step and remaining reagent processing, air or oxygen is passed through and with certain in direct first-time filtrate Rate strong stirring, makes ferrous ion be oxidized to ferric ion, and first-time filtrate can be observed and be changed into rust red by colourless, Work as Fe3+During content≤5ppm, 80~100 DEG C are then again heated to, iron ion hydrolysis is made to generate ferric hydroxide precipitate, in the application Hydrolysis under the conditions of the pH of control, ferric ion complete hydrolysis precipitation, and zinc ion, copper ion and cadmium ion are substantially anhydrous Solution, the secondary filter residue this time generated can be sent to brickmaking factory together as brick-making raw material with a filter residue；Secondary filter in step (3) It is main also containing impurity copper ion and cadmium ion in liquid, copper cadmium is separated by extracting copper；Step (4) in raffinate by adding Enter zinc dust precipitation cadmium, three times filtrate, that is, solution of zinc sulfate, monohydrate zinc sulphate is obtained after step (5) concentration.
Preferably, secondary pickling step is further included after described (1) step, by a filter residue and 20~30% sulphur Acid or Waste Sulfuric Acid are by weight 1:4 are added to the second acidleach pond, are heated to 30~40 DEG C of temperature, continuously stir 2.5~3h, reaction It is 4.5~4.8 that pH is controlled during terminal, and press filtration carries out solid-liquor separation, and obtained filtrate is incorporated to first-time filtrate, and obtained filter residue is incorporated to Filter residue.This step further ensures that each metal in a filter residue is all entered by acidleach in solution.
Preferably, after the first-time filtrate of described (2) is placed in iron-removing tank, 70~75 DEG C are heated to, then is passed through air or oxygen Gas simultaneously stirs, and the gas flow rate of the air or oxygen is 6~8L/min, and mixing speed is 800~1000r/min.
Further, the copper extraction process uses organic extractant, and organic extractant is compared with secondary filtrate：2: 1~3:1.
Further, the organic extractant selects LIX984 models or LIX984N models, and using kerosene as solvent, has The weight percent concentration of solute is 10~30% in machine extractant.
Further, the method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue further includes step (6) cupric extract liquor Processing：Back extraction is mixed with the cupric extract liquor with sulfuric acid solution or Waste Sulfuric Acid, obtains strip liquor, i.e. copper-bath, the sulphur Acid solution or Waste Sulfuric Acid are 1 compared with cupric extract liquor:2~1:4, it is preferable that the step (6) is regenerated after back extraction Organic phase, that is, organic extractant input step (3) recycles.
Further, the method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue further includes step (7) displacement copper：Add Enter zinc powder and stir, until Cu in strip liquor2+Content≤5ppm stands filtering, obtains four filtrates and four filter residues, four filter residues That is four filtrates with filtrate are three times merged and add in progress step (5) in crystallization kettle by blister copper, four filtrate, that is, solution of zinc sulfate.
Further, the step (5) further includes：By monohydrate zinc sulphate crystal through centrifuge dripping, then dry, through examining Packed products after qualification.
Preferably, the comprehensive recovering process of utilising zinc containing waste residue, which is characterized in that prepare monohydrate zinc sulphate including above-mentioned, also wrap Include the processing of step (8) filter residue：Filter residue and secondary filter residue are sent into brickmaking factory as brick-making raw material, and filter residue is sent into cadmium and is refined three times Process.Further include the processing of step (8) filter residue：Filter residue and secondary filter residue are sent into brickmaking factory as brick-making raw material, three times filter residue It is sent into cadmium refining step.Monohydrate zinc sulphate is prepared from utilising zinc containing waste residue since the application can not only reach, remaining impurity also obtains To preferable separation, the filter residue generated every time can still be recycled, and further achieve the purpose that environmental protection and energy saving.
The method that slave utilising zinc containing waste residue prepared by the present invention prepares monohydrate zinc sulphate has the following advantages：
(1) the preparation low raw-material cost of monohydrate zinc sulphate, refuse reclamation solve existing utilising zinc containing waste residue and are difficult to back Receive the environmental problem utilized；
(2) whole preparation process energy conservation and environmental protection, no exhaust gas and waste water generate, and drug or reagent are few used in processing, without using The reagent unfavorable to environment, as far as possible using discarded object or the raw material that is easy to get at low cost, such as spent acid, air or oxygen etc., processing Only a few places, which heat, in the process can also be used hot waste water in chemical plant to reach using jacket type heating means；
(3) it is high to prepare the purity of monohydrate zinc sulphate, and the good separating effect of each impurity composition, sulfuric acid monohydrate is being prepared Metals, the waste residue such as also recyclable copper cadmium can be reused as brick-making raw material etc. while zinc；
(4) slave utilising zinc containing waste residue of the invention prepare the method for monohydrate zinc sulphate for China discard cadmia reuse with it is comprehensive The new technology approach that recycling provides a high efficiency, low power consuming, low cost, resource utilization height and non-secondary pollution is closed, it is real The organic unity of existing economic benefit, social benefit and environmental benefit, has good social value and economic value, is easy to push away Extensively.
Specific embodiment
Embodiment 1
Raw materials for production utilising zinc containing waste residue, by weight percentage, containing zinc 40~60%, iron 2~4%, copper 3~5%, cadmium 10~ 20%, silica 8~16%.
The method that the present embodiment prepares monohydrate zinc sulphate from utilising zinc containing waste residue, its preparation method are as follows：
(1) acidleach：By the sulfuric acid of utilising zinc containing waste residue and weight percent content 20~30% by weight 1:3 are added to first Acidleach pond, continuously stirs 2h, and when reaction end controls pH, and press filtration carries out solid-liquor separation, obtains first-time filtrate and one for 4.8~5.0 Secondary filter residue；
(2) iron removal by oxidation：First-time filtrate is placed in iron-removing tank, is heated to 70 DEG C, air or oxygen is passed through and stirs, filtrate Color is changed into rust red by colourless, detects ferric ion concentration, works as Fe3+During content≤5ppm, continue to be heated to 100 DEG C, Reddish-brown precipitation is generated until no longer generating, press filtration immediately obtains secondary filtrate and secondary filter residue, and the secondary filtrate enters Next step；
(3) extracting copper：Secondary filtrate is obtained into cupric extract liquor and raffinate using copper extraction process；
(4) displacement is except cadmium：Zinc powder is added in raffinate, and is stirred, until Cd in raffinate2+Content≤5ppm is stood Filtering, obtains filtrate three times and three times filter residue, three times filter residue, that is, thick cadmium；
(5) condensing crystallizing：Filtrate crystallization kettle will be added in three times, controlled at 70~100 DEG C, condensing crystallizing, get Yi Shui Zinc sulfate, the Recycling Mother Solution after filtering, which is added in crystallization kettle, to be continued to crystallize.
Each component content is as follows in the monohydrate zinc sulphate being prepared：
Embodiment 2
Raw materials for production utilising zinc containing waste residue, by weight percentage, containing zinc 40~60%, iron 2~4%, copper 3~5%, cadmium 10~ 20%, silica 8~16%.
The method that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, its preparation method are as follows：
(1) acidleach：By factory's Waste Sulfuric Acid of utilising zinc containing waste residue and weight percent content 20~30% by weight 1:3 add in To the first acidleach pond, 2h is continuously stirred, when reaction end controls pH, and press filtration carries out solid-liquor separation, obtains and once filters for 4.8~5.0 Liquid and a filter residue；Then secondary pickling step again, by a filter residue and 20~30% factory's Waste Sulfuric Acid by weight 1:4 add Entering to the second acidleach pond, be heated to 30~40 DEG C of temperature, connection 2.5~3h of stirring, it is 4.5~4.8 that when reaction end, which control pH, Press filtration carries out solid-liquor separation, and obtained filtrate is incorporated to first-time filtrate, and obtained filter residue is incorporated to a filter residue；
(2) iron removal by oxidation：First-time filtrate is placed in iron-removing tank, 75 DEG C is heated to using plant chimney stalk jacket type, is passed through sky Gas or oxygen simultaneously stir, mixing speed 1000r/min, and the gas flow rate of the air or oxygen is 6~8L/min, filtrate face Color is changed into rust red by colourless, detects ferric ion concentration, works as Fe3+During content≤5ppm, continue to be heated to 90 DEG C, generate Reddish-brown precipitation is until no longer generating, press filtration immediately, obtains secondary filtrate and secondary filter residue, and the secondary filtrate enters next Step；
(3) extracting copper：Secondary filtrate is obtained into cupric extract liquor and raffinate using copper extraction process, copper extraction process is adopted With organic extractant LIX984 models, and using kerosene as solvent, wherein the weight percent concentration of solute is in organic extractant 30%, organic extractant is compared with secondary filtrate：2:1；
(4) displacement is except cadmium：Zinc powder is added in raffinate, and is stirred, until Cd in raffinate2+Content≤5ppm is stood Filtering, obtains filtrate three times and three times filter residue, three times filter residue, that is, thick cadmium；
(5) condensing crystallizing：Filtrate crystallization kettle will be added in three times, be heated using plant chimney stalk jacket type, controlled at 70 ~100 DEG C, condensing crystallizing obtains monohydrate zinc sulphate, and the Recycling Mother Solution after filtering, which is added in crystallization kettle, to be continued to crystallize, by sulfuric acid monohydrate Then zinc crystal is dried, through centrifuge dripping through packed products after the assay was approved；
(6) cupric extract liquor is handled：Back extraction is mixed with the cupric extract liquor with sulfuric acid solution or Waste Sulfuric Acid, must be stripped Liquid, the sulfuric acid solution or Waste Sulfuric Acid are 1 compared with cupric extract liquor:2, regeneration organic phase input step is obtained after back extraction (3) recycle；
(7) copper is replaced：It adds in zinc powder and stirs, until Cu in strip liquor2+Content≤5ppm stands filtering, obtains four filters Four filtrates are merged addition by liquid and four filter residues, four filter residue, that is, blister coppers, four filtrate, that is, solution of zinc sulfate with filtrate three times Step (5) is carried out in crystallization kettle.
After the completion of the preparation of above-mentioned monohydrate zinc sulphate, then follow the steps below：(8) filter residue is handled：Filter residue and secondary Filter residue is sent into brickmaking factory as brick-making raw material, and filter residue is sent into cadmium refining step three times.
Each component content is as follows in the monohydrate zinc sulphate being prepared：
Embodiment 3
Raw materials for production utilising zinc containing waste residue, by weight percentage, containing zinc 40~60%, iron 2~4%, copper 3~5%, cadmium 10~ 20%, silica 8~16%.
The method that the present embodiment prepares monohydrate zinc sulphate from utilising zinc containing waste residue, its preparation method are as follows：
(1) acidleach：By the sulfuric acid of utilising zinc containing waste residue and weight percent content 20~30% by weight 1:3 are added to first Acidleach pond, continuously stirs 2h, and when reaction end controls pH, and press filtration carries out solid-liquor separation, obtains first-time filtrate and one for 4.8~5.0 Secondary filter residue；
(2) iron removal by oxidation：First-time filtrate is placed in iron-removing tank, is heated to 75 DEG C, air or oxygen is passed through and stirs, is stirred Speed is 800r/min, and the gas flow rate of the air or oxygen is 6~8L/min, and filtrate color is changed into iron rust by colourless It is red, ferric ion concentration is detected, works as Fe3+During content≤5ppm, continue to be heated to 100 DEG C, generate reddish-brown precipitation until not Until generating again, then press filtration obtains secondary filtrate and secondary filter residue, and the secondary filtrate enters next step；
(3) extracting copper：Secondary filtrate is obtained into cupric extract liquor and raffinate using copper extraction process, copper extraction process is adopted With organic extractant LIX984N models, and using kerosene as solvent, wherein solute weight percent concentration is in organic extractant 10%, organic extractant is compared with secondary filtrate：3:1；
(4) displacement is except cadmium：Zinc powder is added in raffinate, and is stirred, until Cd in raffinate2+Content≤5ppm is stood Filtering, obtains filtrate three times and three times filter residue, three times filter residue, that is, thick cadmium；
(5) condensing crystallizing：Filtrate crystallization kettle will be added in three times, controlled at 70~100 DEG C, condensing crystallizing, get Yi Shui Zinc sulfate, the Recycling Mother Solution after filtering, which is added in crystallization kettle, to be continued to crystallize, by monohydrate zinc sulphate crystal through centrifuge dripping, Ran Hougan It is dry, through packed products after the assay was approved；
(6) cupric extract liquor is handled：Back extraction is mixed with the cupric extract liquor with sulfuric acid solution, obtains strip liquor, the sulphur Acid solution or Waste Sulfuric Acid are 1 compared with cupric extract liquor:4, regeneration organic phase input step (3) is obtained after back extraction and cycles profit With；
(7) copper is replaced：It adds in zinc powder and stirs, until Cu in strip liquor2+Content≤5ppm stands filtering, obtains four filters Four filtrates are merged addition by liquid and four filter residues, four filter residue, that is, blister coppers, four filtrate, that is, solution of zinc sulfate with filtrate three times Step (5) is carried out in crystallization kettle.
After the completion of the preparation of above-mentioned monohydrate zinc sulphate, then follow the steps below：Filter residue processing：Filter residue and secondary filter residue Brickmaking factory is sent into as brick-making raw material, filter residue is sent into cadmium refining step three times.
Each component content is as follows in the monohydrate zinc sulphate being prepared：
The invention is not limited in the above embodiment, if the various changes or deformation to the present invention do not depart from the present invention Spirit and scope, if these changes and deformation belong within the scope of the claim and equivalent technologies of the present invention, then this hair It is bright to be also intended to comprising these changes and deformation.

Claims (4)

1. the method for monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, which is characterized in that in the utilising zinc containing waste residue by weight percentage, Containing zinc 40~60%, iron 2~4%, copper 3~5%, cadmium 10~20%, silica 8~16% comprises the following steps：
(1) acidleach：By sulfuric acid or Waste Sulfuric Acid that utilising zinc containing waste residue and weight percent content are 20~30% by weight 1:3 add in To the first acidleach pond, 2h is continuously stirred, when reaction end controls pH, and press filtration carries out solid-liquor separation, obtains and once filters for 4.8~5.0 Liquid and a filter residue；
(2) iron removal by oxidation：First-time filtrate is placed in iron-removing tank, is heated to 70~75 DEG C, air or oxygen is passed through and stirs, it is described The gas flow rate of air or oxygen is 6~8L/min, and mixing speed is 800~1000r/min, detects ferric ion concentration, Work as Fe3+During content≤5ppm, continue to be heated to 80~100 DEG C, reddish-brown precipitation occur until no longer generating, press immediately Filter, obtains secondary filtrate and secondary filter residue, the secondary filtrate enters next step；
(3) extracting copper：Secondary filtrate is obtained into cupric extract liquor and raffinate using copper extraction process, the copper extraction process is adopted With organic extractant, organic extractant is compared with secondary filtrate：2:1~3:1, the organic extractant selects LIX984 types Number or LIX984N models, and using kerosene as solvent, the weight percent concentration of solute is 10~30% in organic extractant；
(4) displacement is except cadmium：Zinc powder is added in raffinate, and is stirred, until Cd in raffinate2+Content≤5ppm stands filtering, Filtrate and three times filter residue three times are obtained, three times filter residue, that is, thick cadmium；
(5) condensing crystallizing：Filtrate crystallization kettle will be added in three times, controlled at 70~100 DEG C, condensing crystallizing obtains sulfuric acid monohydrate Zinc, the Recycling Mother Solution after filtering, which is added in crystallization kettle, to be continued to crystallize, the weight content of each component in gained sulfuric acid monohydrate zinc product It is：Monohydrate zinc sulphate >=96.5%, Zn content >=35.0%, iron≤0.0015%, cadmium≤0.0015%, copper≤0.0005%；
(6) cupric extract liquor is handled：Back extraction is mixed with the cupric extract liquor with sulfuric acid solution or Waste Sulfuric Acid, obtains strip liquor, institute It is 1 that sulfuric acid solution or Waste Sulfuric Acid, which are stated, compared with cupric extract liquor:2~1:4, regeneration organic phase input step is obtained after back extraction (3) recycle；
(7) copper is replaced：It adds in zinc powder and stirs, until Cu in strip liquor2+Content≤5ppm, stand filtering, obtain four filtrates and Four filtrates with filtrate are three times merged and add in progress step (5) in crystallization kettle by four filter residues, four filter residue, that is, blister coppers.
2. the method according to claim 1 that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, it is characterised in that：Described (1) Secondary pickling step is further included after step, by a filter residue and 20~30% sulfuric acid or Waste Sulfuric Acid by weight 1:4 add Entering to the second acidleach pond, be heated to 30~40 DEG C of temperature, continuously stir 2.5~3h, when reaction end, controls pH as 4.5~4.8, Press filtration carries out solid-liquor separation, and obtained filtrate is incorporated to first-time filtrate, and obtained filter residue is incorporated to a filter residue.
3. the method according to claim 1 that monohydrate zinc sulphate is prepared from utilising zinc containing waste residue, it is characterised in that：The step (5) further include：By monohydrate zinc sulphate crystal through centrifuge dripping, then dry, through packed products after the assay was approved.
4. the comprehensive recovering process of utilising zinc containing waste residue, which is characterized in that including according to any method system of claims 1 to 3 Standby monohydrate zinc sulphate further includes the processing of step (8) filter residue：Filter residue and secondary filter residue are sent into brickmaking factory as brick-making raw material, Filter residue is sent into cadmium refining step three times.
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