CN109881011A - A method of recycling zinc - Google Patents
A method of recycling zinc Download PDFInfo
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- CN109881011A CN109881011A CN201910214864.6A CN201910214864A CN109881011A CN 109881011 A CN109881011 A CN 109881011A CN 201910214864 A CN201910214864 A CN 201910214864A CN 109881011 A CN109881011 A CN 109881011A
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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
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Abstract
The invention discloses a kind of methods for recycling zinc, are related to technical field of sewage, and method includes that will contain the dissolution of zinc abraum salt to obtain solid-liquid mixed solution；Solid-liquid mixed solution is separated by solid-liquid separation, insoluble solid and the solution of abraum salt containing zinc are obtained；Zinc abraum salt solution will be contained to be added in NaOH solution, so that non-zinc metal hydroxides and a small amount of zinc hydroxide precipitation is got off, obtain filtrate containing zinc；NaOH solution is added in filtrate containing zinc, the zinc in filtrate containing zinc is made to precipitate in the form of zinc hydroxide, obtains the first zinc hydroxide filter residue and the first filtrate；NaOH solution is continuously added at least partly the first filtrate, makes a small amount of zinc in the first filtrate continue to precipitate in the form of zinc hydroxide, obtains the second zinc hydroxide filter residue；It will be electrolysed after first, second zinc hydroxide filter residue dissolving with hydrochloric acid, be electrodeposited in zinc on cathode；It will at least partly raffinate recycle.The present invention has the advantages that zinc recovery is high, realizes being effectively treated for the recycling of abraum salt containing zinc.
Description
Technical field
The present invention relates to technical field of sewage, and in particular to a method of recycling zinc.
Background technique
With the development of economy with the deterioration of water environment, environmental protection administration formulated stringenter sewage drainage standard, and
Increase law enforcement dynamics.Except organic matter standard as strict as possible in addition to, increase waste water in salt discharge standard, such as " Beijing's water pollutant is comprehensive
Close discharge standard (DB11/307-2013) " in total dissolved solidss (TDS) discharge in A class standard be limited to 1000 mg/litres.
Currently, existing disposal technology are as follows:
1, using direct flame combustion method, i.e., abraum salt powder is sprayed into incinerator, wherein organic matter decomposes destruction at high temperature, so
And general inorganic salts fusing point melts at high operating temperatures all at 800 degrees Celsius or more, will cause incinerator and glues wall, resistance to material
The problems such as damage, equipment burn into flue blockage, it there are no the equipment of normal use at present.
2, in view of the high-temperature fusion of inorganic salts carries out process modification, thermal cracking carbonization technique is generally used, i.e., by abraum salt
Powder is continuously put into thermal cracking carbonization kiln, organic matter therein lower than inorganic salts melting temperature (be lower than 700 degrees Celsius) and
It decomposes gasification under the conditions of control oxygen atmosphere, but although the technique solves the problems, such as inorganic salts melting, but due to thermal cracking temperature
It spends low, organic matter is caused not to be destroyed thoroughly, or even is due to organism kinds in abraum salt and content uncertain, decomposition gas is dense
The safety problems such as explosion easily occur for degree variation.
3, the landfill stabilization of dangerous waste salt contains toxic harmful metal ion, organic pollutant etc. due to abraum salt high water solubility,
Fatal impact is caused to landfill yard sewerage, needs to dispose depth after specification carries out stable curing according to national dangerous waste and fills.
This method technical difficulty (antiseepage, waterproof, leakproof etc.) is big, land occupation is big, cost of investment is high, two caused by having because of factors such as geological disasters
The risk of secondary environment harm.
In conclusion being allowed to process resource there has been no the effective ways that one kind can be successfully processed industrial waste salt at present.
Summary of the invention
Therefore, technical problems to be solved of the embodiment of the present invention are that there has been no a kind of abraum salt recyclings in the prior art
Effective treating method, to provide a kind of method for recycling zinc.
For this purpose, a kind of method of recycling zinc of the embodiment of the present invention, comprising the following steps:
Zinc abraum salt addition warm water solution will be contained to be sufficiently mixed or dissolve, obtain solid-liquid mixed solution；
The solid-liquid mixed solution is separated by solid-liquid separation, insoluble solid and the solution of abraum salt containing zinc are obtained；
The solution of abraum salt containing zinc is added in the NaOH solution of 150-250g/L, adjusting pH value is 3.0-6.0, makes non-zinc gold
Belong to hydroxide and a small amount of zinc hydroxide precipitation gets off, be separated by solid-liquid separation, obtains non-zinc metal hydroxides and zinc hydroxide mixing
Filter residue and filtrate containing zinc are recycled to after mixed filter residue dissolving with hydrochloric acid in the solution of abraum salt containing zinc；
NaOH solution is added in the filtrate containing zinc, adjusting pH value is 7.0-8.0, makes the zinc in filtrate containing zinc with zinc hydroxide
Form precipitate, be separated by solid-liquid separation, obtain the first zinc hydroxide filter residue and the first filtrate；
NaOH solution is continuously added at least partly described first filtrate, adjusting pH value is 8.5-9.0, is made in the first filtrate
A small amount of zinc continuation is precipitated in the form of zinc hydroxide, is separated by solid-liquid separation, is obtained the second zinc hydroxide filter residue and the second filtrate, institute
The Zn content stated in the second filtrate has met emission request；
It will be electrolysed after the first zinc hydroxide filter residue and the second zinc hydroxide filter residue dissolving with hydrochloric acid, the electric current of electrolysis is close
Degree is 900-1100A/m2, temperature be 80-95 DEG C, voltage 3-5V, be electrodeposited in zinc on cathode and remaining raffinate；And
At least partly described raffinate is recycled in the solution of abraum salt containing zinc.
Preferably, the reaction temperature of the non-zinc metal hydroxides and a small amount of zinc hydroxide precipitation is 50~70 DEG C, when
Between be 30-50 minutes.
Preferably, electrolytic cell used in the electrolysis includes cathode chamber, anode chamber and the separation unit for allowing anion to pass through.
Preferably, the cathode of the cathode chamber is using one of titanium, titanium alloy, zirconium and zircaloy.
Preferably, the catholyte of the cathode chamber includes: that divalent zinc metal salt, the non-zinc metal salt of trivalent, divalent are non-
Zinc metal salt and hydrochloric acid solution.
Preferably, the anode of the anode chamber is using one of titanium, titanium alloy, zirconium and zircaloy.
Preferably, the anolyte of the anode chamber includes: hydrochloric acid and the non-zinc metal salt solution of divalent.
Preferably, the warm water solution is warm industrial water, warm dilute hydrochloric acid or pickle liquor.
Preferably, the recycling is to recycle the 80-98% of remaining raffinate.
Preferably, further comprising the steps of:
By the insoluble solid, drying to constant weight；
It is 1cm or less that solid after drying, which is crushed to average grain diameter,.
The technical solution of the embodiment of the present invention, has the advantages that
The method of recycling zinc provided in an embodiment of the present invention, will contain zinc abraum salt after completely dissolution by using warm water solution, can incite somebody to action
Zinc is completely dissolved in solution, so that the zinc in the raw material of abraum salt containing zinc sufficiently can be extracted recycling when being electrolysed.By first by non-zinc
Metal hydroxides is precipitated, and simple zinc hydroxide is re-precipitated, and improves purity, and by by non-zinc metal hydrogen-oxygen
It is recycled to the solution of abraum salt containing zinc after compound and zinc hydroxide mixed filter residue dissolving with hydrochloric acid, improves the rate of recovery of zinc.Pass through
It is gradually added NaOH solution according to different pH value, the first, second zinc hydroxide filter residue is respectively obtained, to be conducive to zinc hydroxide
It is settled out, zinc is made to be fully recycled, realize being effectively treated for the recycling of abraum salt containing zinc.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the specific embodiment of the invention, specific embodiment will be retouched below
Attached drawing needed in stating is briefly described, it should be apparent that, the accompanying drawings in the following description is some realities of the invention
Mode is applied, it for those of ordinary skill in the art, without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
Fig. 1 is the flow chart that a specific example of method for zinc is recycled in the embodiment of the present invention 1.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the term as used herein is only used for the mesh of description specific embodiment
, and it is not intended to limit the present invention.Unless clearly indicated by the context, otherwise singular " one " as used herein,
The intentions such as "one" and "the" also include plural form.When using terms such as " include " and or " include ", it is intended to illustrate exist
This feature, integer, step, operation, element and/or component, and it is not excluded for one or more other features, integer, step, behaviour
Work, element, component, and/or other presence or increase for combining.It for the ordinary skill in the art, can be specific
Situation understands the concrete meaning of above-mentioned term in the present invention.
As long as in addition, the non-structure each other of technical characteristic involved in invention described below different embodiments
It can be combined with each other at conflict.
Embodiment 1
The present embodiment provides a kind of method for recycling zinc, such as a kind of chemical industry abraum salt, main component is sodium salt, magnesium salts, calcium salt, aluminium
Salt etc..As shown in Figure 1, method includes the following steps:
S1, will contain zinc abraum salt be added warm water solution be sufficiently mixed or dissolve, obtain solid-liquid mixed solution.Warm water solution is temperature production
With water, warm dilute hydrochloric acid or pickle liquor.The duration of mixing is generally 10-30 minutes, and alkaline soluble materials are obtained sufficiently
Dissolution guarantees that zinc-containing metal salt is substantially dissolved in solution.
S2, solid-liquid mixed solution is separated by solid-liquid separation, obtains insoluble solid and the solution of abraum salt containing zinc.It is separated by solid-liquid separation
It is carried out by physical separation method, such as inclination, centrifugation, filtering etc..Zinc has not been contained in insoluble solid or zinc contains
Amount is considerably less, can satisfy discharge standard.By first separating insoluble solid, reduce produced by subsequent zinc recovering
Interference, improve recycling zinc purity.
S3, the solution of abraum salt containing zinc is added in the NaOH solution of 150-250g/L, adjusting pH value is 3.0-6.0, is made non-
Zinc metal hydroxides and a small amount of zinc hydroxide precipitation get off, and are separated by solid-liquid separation, obtain non-zinc metal hydroxides and zinc hydroxide
Mixed filter residue and filtrate containing zinc are recycled in the solution of abraum salt containing zinc after mixed filter residue dissolving with hydrochloric acid.Non- zinc metal hydroxide
The reaction temperature of object and a small amount of zinc hydroxide precipitation is 50~70 DEG C, and the time is 30-50 minutes.
S4, NaOH solution is added in filtrate containing zinc, adjusting pH value is 7.0-8.0, makes the zinc in filtrate containing zinc with hydrogen-oxygen
The form for changing zinc precipitates, and is separated by solid-liquid separation, obtains the first zinc hydroxide filter residue and the first filtrate.
S5, it is continuously added at least partly the first filtrate and continues to add in NaOH solution, such as the first filtrate of 30-40%
Enter NaOH solution, the first filtrate of 60-70% continues to use as recycle-water, and adjusting pH value is 8.5-9.0, makes in the first filtrate
A small amount of zinc continuation precipitated in the form of zinc hydroxide, be separated by solid-liquid separation, obtain the second zinc hydroxide filter residue and the second filtrate,
Zn content in second filtrate has met emission request, so that a small amount of precipitation process of zinc hydroxide is realized, by adjusting pH value
To adapt to current environment, zinc precipitate recovery rate is improved.
S6, it will be electrolysed after the first zinc hydroxide filter residue and the second zinc hydroxide filter residue dissolving with hydrochloric acid, the electricity of electrolysis
Current density is 900-1100A/m2, temperature be 80-95 DEG C, voltage 3-5V, be electrodeposited in zinc on cathode and remaining raffinate.It is surplus
Lower raffinate has reached zinc discharge standard.Electrolysis usually carries out under constant current controlling.The zinc of electro-deposition is recycled later.Pass through physics
Stripping means recycles the zinc for being electrodeposited in cathode.
The electrolytic cell of electrolysis includes cathode chamber, anode chamber and the separation unit for allowing anion to pass through.The solution of abraum salt containing zinc
It is placed in cathode chamber, can be used as catholyte.Separated between cathode chamber and anode chamber by separation unit, separation unit is for example
It can be amberplex.The cathode of cathode chamber is using one of titanium, titanium alloy, zirconium and zircaloy.The anode of anode chamber is adopted
With one of titanium, titanium alloy, zirconium and zircaloy.
The catholyte of cathode chamber includes: divalent zinc metal salt, the non-zinc metal salt of trivalent, the non-zinc metal salt of divalent and salt
Acid solution.E.g., including the MgCl of the zinc chloride of 40-60 weight %, 15-30 weight %2Or CaCl2Or mixtures thereof, 10-30 weight
Measure the AlCl of %3And the HCl of 0-35 weight %.
The anolyte of anode chamber includes: hydrochloric acid and the non-zinc metal salt solution of divalent.E.g., including 30-50 weight %'s
The MgCl of HCl, 50-70 weight %2、CaCl2, it is one or more kinds of in LiCl, KCl or NaCl.
It further include by the pretreated step of cathode before carrying out electrolysis step.Include by cathode immersion: 75 volume % are dense
Spend HNO3, 10 volume % concentration HF and 15 volume % H2Carried out pickling 5-20 minutes in the pickling solution of O, then spend from
Sub- water cleaning down is to remove remained on surface acid solution.
S7, it will at least partly raffinate be recycled in the solution of abraum salt containing zinc.The recycling is by the 80-98% of remaining raffinate
It is recycled, such as the 80% of remaining raffinate is recycled, be passed through in the solution of abraum salt containing zinc.
Preferably, the method for recycling zinc is further comprising the steps of:
S8, by insoluble solid, drying to constant weight.Drying temperature is 110-120 DEG C.
S9, the solid after drying is crushed to average grain diameter for 1cm or less powder.Smashed powder centralized processing is used for
Harmless treatment, such as fill etc..
The method of above-mentioned recycling zinc will contain zinc abraum salt after completely dissolution by using warm water solution, can be completely dissolved zinc
Into solution, so that the zinc in the raw material of abraum salt containing zinc sufficiently can be extracted recycling when being electrolysed.By first by non-zinc metal hydroxide
Object is precipitated, and simple zinc hydroxide is re-precipitated, and improves purity, and by by non-zinc metal hydroxides and hydrogen-oxygen
It is recycled to the solution of abraum salt containing zinc after changing zinc mixed filter residue dissolving with hydrochloric acid, improves the rate of recovery of zinc.By according to different pH
Value is gradually added NaOH solution, respectively obtains the first, second zinc hydroxide filter residue, goes out to be conducive to zinc hydroxide precipitation, make
Zinc is fully recycled, and realizes being effectively treated for the recycling of abraum salt containing zinc.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of method for recycling zinc, which comprises the following steps:
Zinc abraum salt addition warm water solution will be contained to be sufficiently mixed or dissolve, obtain solid-liquid mixed solution；
The solid-liquid mixed solution is separated by solid-liquid separation, insoluble solid and the solution of abraum salt containing zinc are obtained；
The solution of abraum salt containing zinc is added in the NaOH solution of 150-250g/L, adjusting pH value is 3.0-6.0, makes non-zinc gold
Belong to hydroxide and a small amount of zinc hydroxide precipitation gets off, be separated by solid-liquid separation, obtains non-zinc metal hydroxides and zinc hydroxide mixing
Filter residue and filtrate containing zinc are recycled to after mixed filter residue dissolving with hydrochloric acid in the solution of abraum salt containing zinc；
NaOH solution is added in the filtrate containing zinc, adjusting pH value is 7.0-8.0, makes the zinc in filtrate containing zinc with zinc hydroxide
Form precipitate, be separated by solid-liquid separation, obtain the first zinc hydroxide filter residue and the first filtrate；
NaOH solution is continuously added at least partly described first filtrate, adjusting pH value is 8.5-9.0, is made in the first filtrate
A small amount of zinc continuation is precipitated in the form of zinc hydroxide, is separated by solid-liquid separation, is obtained the second zinc hydroxide filter residue and the second filtrate, institute
The Zn content stated in the second filtrate has met emission request；
It will be electrolysed after the first zinc hydroxide filter residue and the second zinc hydroxide filter residue dissolving with hydrochloric acid, the electric current of electrolysis is close
Degree is 900-1100A/m2, temperature be 80-95 DEG C, voltage 3-5V, be electrodeposited in zinc on cathode and remaining raffinate；And
At least partly described raffinate is recycled in the solution of abraum salt containing zinc.
2. the method for recycling zinc according to claim 1, which is characterized in that the non-zinc metal hydroxides and a small amount of hydrogen
The reaction temperature of zinc oxide precipitate is 50~70 DEG C, and the time is 30-50 minutes.
3. the method for recycling zinc according to claim 1 or 2, which is characterized in that electrolytic cell used in the electrolysis includes yin
Pole room, anode chamber and the separation unit for allowing anion to pass through.
4. the method for recycling zinc according to claim 3, which is characterized in that the cathode of the cathode chamber is closed using titanium, titanium
One of gold, zirconium and zircaloy.
5. the method for recycling zinc according to claim 3 or 4, which is characterized in that the catholyte packet of the cathode chamber
It includes: the non-zinc metal salt of divalent zinc metal salt, trivalent, the non-zinc metal salt of divalent and hydrochloric acid solution.
6. according to the method for the described in any item recycling zinc of claim 3-5, which is characterized in that the anode of the anode chamber uses
One of titanium, titanium alloy, zirconium and zircaloy.
7. according to the method for the described in any item recycling zinc of claim 3-6, which is characterized in that the anode electrolysis of the anode chamber
Liquid includes: hydrochloric acid and the non-zinc metal salt solution of divalent.
8. the method for recycling zinc according to claim 1-7, which is characterized in that the warm water solution is temperature production
With water, warm dilute hydrochloric acid or pickle liquor.
9. it is according to claim 1-8 recycling zinc method, which is characterized in that it is described recycling be will be left it is residual
The 80-98% of liquid is recycled.
10. the method for -9 described in any item recycling zinc according to claim 1, which is characterized in that further comprising the steps of:
By the insoluble solid, drying to constant weight；
It is 1cm or less that solid after drying, which is crushed to average grain diameter,.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910214864.6A CN109881011A (en) | 2019-03-20 | 2019-03-20 | A method of recycling zinc |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910214864.6A CN109881011A (en) | 2019-03-20 | 2019-03-20 | A method of recycling zinc |
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| CN109881011A true CN109881011A (en) | 2019-06-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116022943A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | A kind of step-by-step treatment method of waste water containing ruthenium and zinc |
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| CN102037160A (en) * | 2008-03-20 | 2011-04-27 | 魁北克钛铁公司 | Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes |
| CN104099479A (en) * | 2014-07-31 | 2014-10-15 | 邱政 | Process for producing zinc compound by acid and alkali combination method |
| CN105696010A (en) * | 2016-01-12 | 2016-06-22 | 惠州市斯瑞尔环境化工有限公司 | Method for recycling iron and zinc containing waste hydrochloric acid solution |
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2019
- 2019-03-20 CN CN201910214864.6A patent/CN109881011A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037160A (en) * | 2008-03-20 | 2011-04-27 | 魁北克钛铁公司 | Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes |
| CN104099479A (en) * | 2014-07-31 | 2014-10-15 | 邱政 | Process for producing zinc compound by acid and alkali combination method |
| CN105696010A (en) * | 2016-01-12 | 2016-06-22 | 惠州市斯瑞尔环境化工有限公司 | Method for recycling iron and zinc containing waste hydrochloric acid solution |
Non-Patent Citations (1)
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| 戴祖源 等: "自氯化锌溶液中电积锌", 《有色金属(冶炼部分)》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116022943A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | A kind of step-by-step treatment method of waste water containing ruthenium and zinc |
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Application publication date: 20190614 |