CN100450942C - Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution - Google Patents

Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution Download PDF

Info

Publication number
CN100450942C
CN100450942C CNB2006100487357A CN200610048735A CN100450942C CN 100450942 C CN100450942 C CN 100450942C CN B2006100487357 A CNB2006100487357 A CN B2006100487357A CN 200610048735 A CN200610048735 A CN 200610048735A CN 100450942 C CN100450942 C CN 100450942C
Authority
CN
China
Prior art keywords
zinc
acid
waste solution
electrolysis waste
impurities
Prior art date
Application number
CNB2006100487357A
Other languages
Chinese (zh)
Other versions
CN1935705A (en
Inventor
邹平
雷霆
张玉林
李云昌
王振东
Original Assignee
云南冶金集团总公司技术中心
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 云南冶金集团总公司技术中心 filed Critical 云南冶金集团总公司技术中心
Priority to CNB2006100487357A priority Critical patent/CN100450942C/en
Publication of CN1935705A publication Critical patent/CN1935705A/en
Application granted granted Critical
Publication of CN100450942C publication Critical patent/CN100450942C/en

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a method for removing Mg and other impurities from Zn electrolysis waste liquid and recovering vitriol and Zn, comprising: when Mg and other impurities exceed allowable contents in Zinc eletrolysis system, taking a fixed quantity of electrolysis waste water, and filtering; filling filtrate and tap water into the respective gravity tanks; making zinc electrolysis waste water and tap water enter through corresponding inlets into homogeneous negative membrane dialyzer from the top down at given speeds; proudcing regenerated acid and residual solution after cations and anions of the waste liquid and water make membrane exchange; making the regenerated acid and residual solution flow out of the dialyzer through the respective outlets, where the regenerated acid mainly contains anions, vitriol above 80% of that in the waste liquid, F- anions about 50% and Cl- anions about 60%, and very low cation contents; and the residual solution mainly contains cations above 90% of that in the waste liquid, F- anions about 50%, Cl-anions about 40% and vitriol below 20%.

Description

A kind of method from zinc electrolysis waste solution removing impurities suchas magnesium and reclaim(ed) sulfuric acid and zinc
Technical field:
The present invention relates to a kind of method from zinc electrolysis waste solution removing impurities suchas magnesium and reclaim(ed) sulfuric acid and zinc.Belong to the hydrometallurgy field.
Background technology:
Along with the exploitation year by year of zinc sulfide ore, its stock number constantly reduces.In order to remedy the deficiency of zinc sulfide ore, zinc oxide ore is utilized gradually by a lot of electric zinc factory, but also occurred some new problems thereupon, as in the zinc electrolytic system, having introduced electrolytic impurity of a large amount of influences such as magnesium, fluorine, chlorine, manganese etc., thereby limited the widespread use of zinc oxide ore.
Domestic many electric zinc factories are because the application zinc electrolytic system Mg of zinc oxide ore 2+Content is higher, and MgO content is up to more than the 40g/L sometimes.Following point mainly occurs: the sal epsom crystallization deposits in producing pipeline and chute, causes structure deteriorate and line clogging; Mg 2+Remain in a standstill in zinc electrolyte, electrolytic solution viscosity is increased, increase the resistance of electric effusion, cause power consumption to raise, reduce the current efficiency of zinc electrodeposition.Demagging way commonly used: (1) purifies slag for one, two, three section with the electrolysis waste solution dissolving, again with promptly removing the magnesium that electrolysis waste solution is taken with heavy zinc demagging in the milk of lime; (2) cooling demagging method.But aforesaid method demagging rate is all very low, about 30~40%.In order to improve the economical efficiency of electric zinc factory, must improve the demagging rate.Present electric zinc factory does not have the more efficient methods demagging.
Membrane separation technique is one of modern hydrometallurgy new technology.Have energy-conservation, low consumption, pollution-free, equipment is simple, easy to operate, restored acid can be recycled and separate acid after characteristics such as the recyclable useful metal of raffinate.As a kind of new separation technology, in handling, industrial effluent obtained using widely and having shown vast potential for future development, will become the important topic of 21 century hydrometallurgical technology innovation.Membrane separation technique mainly comprises diffusion dialysis, electrodialysis, film electrolysis, reverse osmosis, nanofiltration etc., and the impellent of membrane sepn process mainly is concentration gradient, potential gradient and pressure gradient.
The homogeneous membrane diffusion dialysis is a kind of of membrane separation technique.The dependence concentration difference is an impellent, utilize the selection perviousness of film to separate, and do not need applying direct current, so energy consumption is very low.For the industrial acid waste liquid that contains, utilize diffusion dialysis to reclaim and caused people's keen interest.From the waste pickle liquor of iron and steel and the processing of Non-ferrous Metals Processing Factory's metal material surface, successfully reclaimed acid with diffusion dialysis in existing more than the 50 tame factories of Japan.A.D.Daniel Boateng will contain Zn 2+, Cd 2+, Ca 2+Rare spent acid solution feeding dialyzer Deng metal ion has successfully reclaimed acid.Yoshiharu Aoki etc. to the method and apparatus application of recovered acid from acid-bearing wastewater patent.
In China, diffusion dialysis in recent years has been widely used for the field of various discharging spent acid: as Iron And Steel Industry, wet type copper smelting industry, titanium material processing industry, plating industry and some other non-ferrous metal metallurgies industries etc.The kind of recovered acid comprises H 2SO 4, HCl, HF, HNO 3, CH 3COOH etc.
Summary of the invention:
The objective of the invention is to propose a kind of, solved electrolytic system Mg in the electric zinc industry in modern advanced membrane separation technique and the traditional milk of lime and the combine way of impurity such as magnesium in the removal zinc electrolytic system of heavy zinc technology for removal of magnesium from phosphorous 2+Deng the higher common problem that influences the zinc electrodeposition of foreign matter content.
The present invention is from the method feature of zinc electrolysis waste solution removing impurities suchas magnesium and reclaim(ed) sulfuric acid and zinc: the zinc electrolysis waste solution is in the process of the heavy zinc removing impurities suchas magnesium of neutralization of the generative process of the diffusion dialysis of homogeneous phase cavity block and regenerating acid and raffinate, raffinate, the sour molten process of heavy cadmia, concrete processing step is:
(a) filtering zinc electrolysis waste solution, water are contained separately into header tank, entered homogeneous phase cavity block dialyzer from corresponding inlet with setting speed respectively.The zwitterion of zinc electrolysis waste solution and water generate regenerating acid and raffinate after the film exchange, regenerating acid and raffinate flow out from the corresponding outlet of homogeneous phase cavity block dialyzer respectively.
(b) regenerating acid returns and leaches the use of zinc flow process.
(c) in the residual liquid milk of lime and heavy zinc removing impurities suchas magnesium.Zinc is with basic zinc sulfate form precipitation, and magnesium exists in solution with the sal epsom form.Question response arrives 0.5~1.0 hour stopped reaction of terminal point of PH 6~10.Filter, the heavy cadmia of washing, most F, Cl, As in the raffinate are discharged in the filtrate discharge demagging simultaneously, most of Sb, Cu and a small amount of Mn, Co.
(d) after heavy cadmia soaks two sections acid leachings in one section, filter.Filtrate Zn 2+Concentration is 41g/L, is used with high zinc liquid, and 98.6% zinc enters electric zinc and produces main flow.Filter residue is stored up.
In above-mentioned (a) step, the speed that zinc electrolysis waste solution and tap water enter homogeneous phase cavity block dialyzer is respectively 6~12ml/min and 10~20ml/min.
In above-mentioned (c) step, 50~90 ℃ of the heavy zinc removing impurities suchas magnesium temperature of reaction of control, the liquid-solid ratio of milk of lime 2: 1~7: 1, terminal point PH6~10, stirring velocity 120~150rpm.
In above-mentioned (d) step, one section neutral leaching, two sections acid extraction temperatures are 50~90 ℃, stirring velocity 120~150rpm, and leaching medium is sulfuric acid or regenerating acid.One section neutral 4.8~5.5, two sections acid terminal point PH 1.0~2.5 that leach of terminal point PH that leach
Inventive principle: the diffusion dialysis of homogeneous phase cavity block is reclaimed spent acid and is adopted the dialysis principle, do impellent with concentration difference, whole device is made of the structural unit of different quantities the film of some amount, wherein each unit comprises dialysing compartment (A) and diffuser casing (B), when feeding zinc electrolysis waste solution and acceptable solution (water) respectively in the both sides of negatively charged ion homogeneous membrane, the acid of zinc electrolysis waste solution side and the concentration of salt thereof are far above a side of water, therefore because the existence of concentration gradient, the trend of the oriented B of the acid of zinc electrolysis waste solution and its esters chamber infiltration, but cavity block has the selection perviousness, can not allow every kind of ion pass through with equal opportunity.At first anionic membrane skeleton itself is positively charged, in solution, has the characteristic that attracts electronegative ion hydration and repel positively charged ion hydration, so under the effect of concentration difference, the negatively charged ion of zinc electrolysis waste solution side is attracted and successfully sees through the side that the fenestra road enters water.According to the electric neutrality requirement, also can carry the ion of positive charge secretly simultaneously, because H +Hydrated radius smaller, electric charge is less; And the ion hydration radius of metal-salt is bigger, is again at high price, so H +Can be preferential by film, the acid in the waste liquid will be separated like this.This method all can reach more than 80% the rate of recovery of acid, and the leakage rate of salt is less than 10%.
The diffusion dialysis of homogeneous phase cavity block is mainly used in acid and the separating, purify of metallic salt mixed solution, and is the good selection of waste acid recycling and removal of impurities.
As can be seen from Figure 1, Zn 2+Have precedence over Mg 2+Precipitation.From data, check in Zn (OH) 2Solubility product be 5 * 10 -17, Mg (OH) 2Solubility product be 6.8 * 10 -12
When pH=6:
lg[Zn 2+]=14n+lgK sp-npH=14×2+lg5×10 -17-2×6=4.1
[Zn 2+]=10 4.1=12589.25mol/l
lg[Mg 2+]=14n+lgK sp-npH=14×2+lg6.8×10 -12-2×6=6
[Mg 2+]=10 6=1000000mol/l
[Mg 2+]/[Zn 2+]=1000000/12589.25=79.43
When pH=10:
lg[Zn 2+]=14n+lgK sp-npH==14×2+lg5×10 -17-2×10=-3.99
[Zn 2+]=10 -3.99=1.02×10 -4
lg[Mg 2+]=14n+lgK sp-npH==14×2+lg?6.8×10 -12-2×10=-1.99
[Mg 2+]=10 -1.99=1.02×10 -2
[Mg 2+]/[Zn 2+]=1.02×10 -2/1.02×10 -4=100
From calculation result as can be seen, in pH 6.0~10.0 scopes, the separation factor between Zn and the Mg is very big, all differs 80~100 times.Here it is, and pH values of pulp 6.0~10.0, Zn are controlled in the heavy zinc demagging test of raffinate 2+Be precipitated out, and Mg 2+Still stay the reason in the liquid.This has obtained checking in follow-up test.
Basic zinc sulfate forms chemical equation:
50~90 ℃ of heavy zinc reactions, pH 6.0~10.0 o'clock, basic zinc sulfate press following formula formation:
4ZnSO 4+3Ca(OH) 2+10H 2O=ZnSO 4·3Zn(OH) 2·4H 2O+3CaSO 4·2H 2O
The molten chemical equation of zincic acid in the heavy cadmia:
ZnSO 4·3Zn(OH) 2·4H 2O+3H 2SO 4=4ZnSO 4+10H 2O
At the characteristics of impurity content exceeding indexs such as zinc electrolysis waste solution magnesium, the present invention adopts the way of homogeneous phase cavity block diffusion dialysis to handle the zinc electrolysis waste solution, and wherein most of zwitterions are separated.Negatively charged ion mainly is present in the regenerating acid, positively charged ion (H +Except) mainly be present in the raffinate.Control reaction end pH at a certain temperature, utilize milk of lime in the raffinate and heavy zinc removing impurities suchas magnesium.About zinc more than 99.9% generates the basic zinc sulfate precipitation, and the magnesium more than 90% exists in solution with the form of sal epsom, and filtration can separate impurity such as zinc and magnesium.
The present invention is from the method for zinc electrolysis waste solution removing impurities suchas magnesium and reclaim(ed) sulfuric acid and zinc.Following advantage:
(1) the film diffusion dialysis is reclaimed spent acid and is adopted the dialysis principle, do impellent with concentration difference, so the film dialyzer does not need power consumption.Floor space is little, easy and simple to handle, can realize full-automatic process, and device structure is simple, easy to maintenance.Looking treatment scale can recoup capital outlay in about 1.0~2.0 years.
(2) demagging rate is higher, can improve the not high situation of present enterprise's demagging degree, increases the current efficiency of electrolytic system, improves situations such as line clogging and structure deteriorate.
(3) directly remove magnesium in the electrolytic system, can solve the too high problem of magnesium in the electrolytic solution effective and rapidly, the magnesium of removal no longer enters electrolytic system.
(4) zinc recovery height loses for a short time, can reach 99.96%.
(5) the film dialyzer is with the most of sulfuric acid reclaiming in the electrolysis waste solution, and this sulfuric acid Returning process uses on the one hand, reduces the consumption of eo-acid; Reduce the acid concentration of raffinate on the other hand, reduced the consumption and the quantity of slag of lime, helped follow-up removal of impurities process.
Description of drawings:
Be described further below in conjunction with the accompanying drawing illustrated embodiment, but protection domain of the present invention is not limited thereto embodiment.
Fig. 1 is the relation of metal ion of the present invention and pH value.
Fig. 2 handles each steps flow chart synoptic diagram of zinc electrolysis waste solution for diffusive dialysis method of the present invention
Fig. 3 is the process flow sheet of zinc electrolysis waste solution removing impurities suchas magnesium of the present invention and reclaim(ed) sulfuric acid and zinc.
Among Fig. 2: 1-electrolysis waste solution header tank; 2-water header tank; The 3-pressure stabilizing tank; The 4-under meter; The 5-raffinate; 6-water; The 7-electrolysis waste solution; The 8-regenerating acid; 9-homogeneous phase cavity block; 10-homogeneous phase cavity block diffusion dialysis device.
Embodiment:
Embodiment 1:
Get representational zinc electrolysis waste solution sample, its chemical composition analysis sees Table 1.
Table 1 zinc electrolysis waste solution main chemical compositions is analyzed (mg/L)
Element ??Zn ??g/L ??H +??mol/L ??Mg ??g/L ??Mn ??g/L ??Cd ??Cu ??Co ??Ni ??Fe ??F ??Cl
Content ??40.70 ??2.6~2.8 ??9.62 ??18.75 ??1.99 ??0.71 ??3.5 ??0.67 ??15.0 ??20.0 ??390.6
The Mn of zinc electrolysis waste solution, Mg content are higher, and except that Ni, Fe, F, other impurity has all surpassed the new liquid impurity of electrolysis permissible level.The content of each zwitterion is with the difference of sample presentation batch and slightly variant in this electrolysis waste solution.As Zn 2+Content in following scope, fluctuate: 40~55g/L.
With electrolysis waste solution (7) vacuum filtration, filtrate, tap water pour all separately that header tank (1,2), zinc electrolysis waste solution (7) enter homogeneous phase cavity block diffusion dialysis device (10) with setting speed 10ml/min into, and tap water (6) enters homogeneous phase cavity block diffusion dialysis device (10) with setting speed 15ml/min.The zwitterion of electrolysis waste solution and tap water generate regenerating acid (8) and raffinate (5) after the film exchange, respectively from corresponding outlet outflow separately.
Get 1000ml raffinate (5) in suitable beaker, be put in slowly heating in the water-bath, treat that temperature rises to 60 ℃ after, slowly add 3: 1 milk of lime of liquid-solid ratio, question response PH arrives 7.0~8.0 terminal point stopped reaction after 0.8 hour.Filter washing.Filtrate is discharged, and filter residue (heavy cadmia) is standby.
One section neutral leaching: measure quantitative regenerating acid of concentration known or sulfuric acid, be heated to 70 ℃, slowly add the heavy cadmia of known zinc content and weight.When question response is reached home PH 5.3, stop to add cadmia immediately.Filter.Filtrate, filter residue are standby.
Two sections low acidleach go out: measure the quantitative regenerating acid or the sulfuric acid of concentration known, be heated to 70 ℃, slowly add in known zinc content and weight one section and soak slag.When question response is reached home PH 1.5, soak slag in stopping immediately adding.Filter.Filter residue is stored up, filtrate for later use
Above-mentioned to contain the most of vitriolic regenerating acid of zinc electrolysis waste solution (8) colourless, is fit to return leach the zinc flow process and use.Adopt in the milk of lime with the way of heavy zinc removing impurities suchas magnesium impurity such as zinc in the raffinate and magnesium are separated.The heavy zinc removal of impurities reaction end pH of control is 7.0~8.0,60 ℃ of temperature, and the liquid-solid ratio of milk of lime 3: 1, stirring velocity 140rpm, question response pH reach 0.5~1.0 hour stopped reaction of terminal point.Filter washing.Zinc is present in the filter residue with the basic zinc sulfate precipitation forms, and heavy zinc rate is more than 99.9%.Heavy cadmia easily acid is molten, soaks two sections low acidleach in one section and goes out the total leaching yield 98.6% of zinc, and the molten back of acid zinc enters main flow.Magnesium is present in the filtrate with the sal epsom form.Zinc content in removal of impurities filtrate is very low, is 2~15mg/L, thereby the magnesium filtrate discharge that contains after the removal of impurities is removed removing impurities suchas magnesium.The demagging rate is more than 90%, secondly fluoride removing rate about 50%; Dechlorination rate about 40%; Demanganization rate 21.7%; Other content of zinc electrolysis waste solution low impurity A s, Sb, Co, Cu also there are removal effect in various degree, are respectively except that As and lead 65%, remove Sb and lead 54.7%, remove Co and lead 16.8%, remove Cu and lead 60.3%.Sulfuric acid content is low in the raffinate, is about 10~30g/L, and milk of lime consumes less, the about 260g/L of slag rate (lime is in commercially available CaO content 70%).
The zinc electrolysis waste solution after diffusion dialysis, each zwitterion content of the regenerating acid of generation and electrolysis waste solution more as shown in table 2.
The comparison (mg/L) of table 2 regenerating acid zwitterion content and zinc electrolysis waste solution
Numbering ??Zn ??(g/L) ??Mn ??(g/L) ??Mg ??(g/L) ??Cd ??Cu ??Co ??Ni ??Fe ??F ??Cl
Waste electrolyte ??40.70 ??18.75 ??9.62 ??1.99 ??0.71 ??3.5 ??0.67 ??15.0 ??20.0 ??390.6
Regenerating acid ??3.38 ??1.72 ??0.95 ??0.28 ??<0.001 ??0.5 ??0.45 ??2.0 ??9.30 ??273.4
Rejection (%) ??91.7 ??90.83 ??90.12 ??85.93 ??99.86 ??85.71 ??32.84 ??86.67 ??53.5 ??40.2
As known from Table 2: the zinc electrolysis waste solution is after the film diffusion dialysis, and cation concn is much lower than waste electrolyte in the regenerating acid.Show that diffusion dialysis really can be trapped in the most of positively charged ion of electrolysis waste solution in the raffinate, most of sulfuric acid exchanges to and obtains in the regenerating acid reclaiming, but F -And Cl -Only there is part can enter regenerating acid.
In table 3 milk of lime and heavy zinc removing impurities suchas magnesium test conditions and result
As known from Table 3; Heavy zinc removal of impurities reaction end 7.0~8.0 o'clock, zinc recovery is higher to be 99.91%, and liquid zinc content is below the 15mg/L after the demagging, and the demagging rate is higher, is 95.0%.Several in addition removal effects to the bigger fluorine of electrolysis effectiveness influence, chlorine, manganese are also better, and in electrolysis waste solution, fluoride removing rate is 50.0%, and the dechlorination rate is 40.0%, and the demanganization rate is 21.7%.Impurity such as As, Sb, Co, Cu also there is in various degree removal effect, is respectively except that As and leads 65%, remove Sb and lead 54.7%, remove Co and lead 16.8%, remove Cu and lead 60.3%.This technology has multiple impurity-eliminating effect, and the demagging effect is best, secondly is fluorine, chlorine, arsenic, antimony, steel, secondly is manganese, cobalt again.
The cadmia that will quantitatively sink dissolves with an amount of regenerating acid, and test conditions and result are shown in table 4 and table 5.
Soak test conditions and result in one section of the heavy cadmia of table 4
Group Heavy cadmia heavy (g) Zinc content (%) Regenerating acid volume (ml) Terminal point (pH) Processing temperature (℃) In soak slag heavy (g) Zn content (%) Zn leaching yield (%)
Soak in one section ??537.5 ??13.33 ??1700 ??5.3 ??70 ??346.89 ??2.3 ??86.14
As known from Table 4: with the cadmia that soaks in one section of the regenerating acid, leaching yield is more than 86.14%.Show that heavy cadmia is easily molten by acid.
Immersion liquid and two sections low pickling liquor chemical ingredientss (mg/L) in one section in the table 5
Leach liquor ??H 2SO 4??(g/L ??) ??Zn ??(g/L) ??Mg ??(g/L) ??Mn ??(g/L) ??Sb ??Co ??Cd ??Cu ??Ge ??F ??Cl ??As
New liquid ??150 ??125~ ??135 ??18.0 ??2.0~ ??5.0 ??0.25 ??2.3 ??1.8 ??0.3 ??0.04 ??<50 ??<200 ??<0.24
The comprehensive sample of regenerating acid ??72.54 ??3.60 ??6.0 ??1.94 ??0.072 ??0.35 ??1.20 ??0.33 ??0.018 ??5.98 ??273.42 ??0.03
Immersion liquid in one section Trace ??40.22 ??4.71 ??8.17 ??0.18 ??2.06 ??1.79 ??0.24 ??0.009 ??7.32 ??333.1 ??0.044
Two sections low immersion liquid ??30.55 ??9.47 ??1.6 ??5.19 ??0.63 ??1.32 ??2.44 ??3.11 ??0.031 ??12.09 ??442.57 ??0.26
As known from Table 5: the immersion liquid foreign matter content has reached the requirement of the new liquid of electrolysis to impurity in one section, but the content of zinc is lower, is 40.22g/L, does not reach the requirement of new liquid, can be used with other high zinc solution.
Two sections low acidleach of table 6 go out test conditions and result
Group In soak slag heavy (g) Zinc content (%) Regenerating acid volume (ml) Terminal point H 2SO 4??(g/L) Processing temperature (℃) Low acid leaching residue heavy (g) Zinc content (%) Slag meter leaching yield (%)
Two sections low are soaked ??593.8 ??2.3 ??1200 ??30.75 ??70 ??537.5 ??0.28 ??98.55
As known from Table 6: after going out through two sections low acidleach, zinc leaching rate rises to 98.55% by 86.14%, and zinc leaching rate has a net increase of 12.41%.But as known from Table 5: all than immersion liquid height in a section, wherein Sb, Cd and Cu are all above the requirement of the new liquid of electrolysis to foreign matter content for foreign matter contents such as Sb, Cd, Cu, Ge, F, Cl and As.Therefore low acidleach goes out when leaching sour molten slag zinc, and therefore a large amount of strippings of impurity that also will be wherein should should be handled in removal of impurities in low pickling liquor.
Soak with in one section of the regenerating acid, the two sections low cadmias that soak, total zinc leaching rate 98.55%, heavy cadmia is easily molten.The immersion liquid foreign matter content does not surpass the standard of new liquid in one section, but two sections low immersion liquid have more impurity to exceed standard, and needs purifying treatment.The zinc content of immersion liquid and two sections low immersion liquid all is lower than the requirement of new liquid in one section, need be used with high zinc liquid in the main flow.
Embodiment 2:
Get the filtering zinc electrolysis waste solution identical and carry out homogeneous membrane diffusion dialysis in continuous 10 days test with embodiment 1.Homogeneous membrane diffusion dialysis test concrete operations are identical with embodiment 1.Zinc electrolysis waste solution (7) enters homogeneous phase cavity block diffusion dialysis device (10) with setting speed 6ml/min, and tap water (6) enters homogeneous phase cavity block diffusion dialysis device (10) with setting speed 10ml/min.
Get the 100L raffinate in reactor, slowly heating, treat that the raffinate temperature rises to 50 ℃ after, slowly add about 2: 1 milk of lime 53kg of liquid-solid ratio, stirring velocity 300rpm, question response pH arrive 6.0 terminal points stopped reaction after 0.5 hour.Filter washing.Filtrate is discharged, and heavy cadmia is standby.
One section neutral leaching: measure concentration known regenerating acid 50L, be heated to 50 ℃, slowly add the heavy cadmia of known zinc content and weight.When question response is reached home pH4.8, stop to add cadmia immediately.Filter.Filtrate, filter residue are standby.
Two sections low acidleach go out: measure the quantitative regenerating acid 30L of concentration known, be heated to 50 ℃, slowly add in known zinc content and weight one section and soak slag.When question response is reached home pH1.0, soak slag in stopping immediately adding.Filter.Filter residue is stored up, filtrate for later use.
The comparison of homogeneous membrane diffusion dialysis test regenerating acid zwitterion content and zinc electrolysis waste solution is referring to table 2 continuously; In the milk of lime and heavy zinc removing impurities suchas magnesium expanding test condition and result referring to table 3; Soak expanding test condition and result in one section of the heavy cadmia referring to table 4; Immersion liquid and two sections low pickling liquor chemical ingredientss (mg/L) are referring to table 5 in one section; Two sections low acidleach go out expanding test condition and result referring to table 6.
Embodiment 3:
Get the filtering zinc electrolysis waste solution identical and carry out homogeneous membrane diffusion dialysis in continuous 10 days test with embodiment 1.Homogeneous membrane diffusion dialysis test concrete operations are identical with embodiment 1.Zinc electrolysis waste solution (7) enters homogeneous phase cavity block diffusion dialysis device (10) with setting speed 12ml/min, and tap water (6) enters homogeneous phase cavity block diffusion dialysis device (10) with setting speed 20ml/min.
Get the 100L raffinate in reactor, slowly heating, treat that the raffinate temperature rises to 90 ℃ after, slowly add about 7: 1 milk of lime 93kg of liquid-solid ratio, stirring velocity 400rpm, question response pH arrive 10.0 terminal points stopped reaction after 1.0 hours.Filter washing.Filtrate is discharged, and heavy cadmia is standby.
One section neutral leaching: measure concentration known regenerating acid 50L, be heated to 90 ℃, slowly add the heavy cadmia of known zinc content and weight.When question response is reached home pH5.5, stop to add cadmia immediately.Filter.Filtrate, filter residue are standby.
Two sections low acidleach go out: measure the quantitative regenerating acid 30L of concentration known, be heated to 90 ℃, slowly add in known zinc content and weight one section and soak slag.When question response is reached home pH 2.5, soak slag in stopping immediately adding.Filter.Filter residue is stored up, filtrate for later use.
The comparison of homogeneous membrane diffusion dialysis test regenerating acid zwitterion content and zinc electrolysis waste solution is referring to table 2 continuously; In the milk of lime and heavy zinc removing impurities suchas magnesium expanding test condition and result referring to table 3; Soak expanding test condition and result in one section of the heavy cadmia referring to table 4; Immersion liquid and two sections low pickling liquor chemical ingredientss (mg/L) are referring to table 5 in one section; Two sections low acidleach go out expanding test condition and result referring to table 6.
1-electrolysis waste solution head tank; 2-water head tank; The 3-pressure stabilizing tank; The 4-flowmeter; The 5-raffinate; 6-water; The 7-electrolysis waste solution; The 8-regenerated acid; 9-homogeneous phase cavity block; 10-homogeneous phase cavity block diffusion dialysis device.

Claims (4)

1, a kind of method from zinc electrolysis waste solution removing impurities suchas magnesium and reclaim(ed) sulfuric acid and zinc, it is characterized in that zinc electrolysis waste solution and water are in the generative process of the diffusion dialysis of homogeneous phase cavity block dialyzer and regenerating acid and raffinate, the milk of lime process to the heavy zinc removing impurities suchas magnesium of neutralization of raffinate, the sour molten process of heavy cadmia, concrete processing step is:
(a) filtering zinc electrolysis waste solution and tap water are contained separately into header tank (1,2), enter into homogeneous phase cavity block dialyzer (10) from zinc electrolysis waste solution header tank (1) and the corresponding outlet of water header tank (2) with setting speed respectively, the zwitterion of zinc electrolysis waste solution and water are after homogeneous phase cavity block (9) exchange, generate regenerating acid (8) and raffinate (5), regenerating acid (8) and raffinate (5) flow out from the corresponding outlet of homogeneous phase cavity block dialyzer (10) respectively;
(b) regenerating acid (8) returns and leaches the use of zinc flow process;
(c) raffinate (5) utilizes in the milk of lime and heavy zinc removing impurities suchas magnesium, zinc precipitates with the basic zinc sulfate form, magnesium exists in solution with the sal epsom form, question response arrives 0.5~1.0 hour stopped reaction of terminal point of PH 6~10, filter the heavy cadmia of washing, filtrate discharge demagging, discharge most F, Cl, As in the raffinate simultaneously, most of Sb, Cu and a small amount of Mn, Co;
(d) heavy cadmia filters filtrate Zn after one section neutral leaching, two sections acidity leach 2+Concentration is about 40g/L, is used with high zinc liquid, and 98.6% zinc enters electric zinc and produces main flow, and filter residue is stored up.
2, a kind of method according to claim 1 from zinc electrolysis waste solution removing impurities suchas magnesium and recovered acid and zinc, its feature is in (a) step, the flow that zinc electrolysis waste solution and tap water enter homogeneous phase cavity block dialyzer (10) is respectively 6~12ml/min and 10~20ml/min, between zinc electrolysis waste solution header tank (1) and tap water header tank (2) and homogeneous phase cavity block dialyzer (10), respectively be connected to a pressure stabilizing tank (3) and under meter (4).
3, a kind of method according to claim 1 from zinc electrolysis waste solution removing impurities suchas magnesium and recovered acid and zinc, its feature is controlled 50~90 ℃ of heavy zinc removal of impurities temperature of reaction, the liquid-solid ratio of milk of lime 2: 1~7: 1 in (c) step, terminal point pH6~10, stirring velocity 120~150rpm.
4, a kind of method according to claim 1 from zinc electrolysis waste solution removing impurities suchas magnesium and recovered acid and zinc, its feature is in (d) step, one section neutral leaching, two sections acid extraction temperatures are 50~90 ℃, stirring velocity 120~150rpm, leaching medium is sulfuric acid or regenerating acid, one section neutral 4.8~5.5, two sections acid terminal point PH1.0~2.5 of leaching of terminal point PH of leaching.
CNB2006100487357A 2006-10-20 2006-10-20 Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution CN100450942C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100487357A CN100450942C (en) 2006-10-20 2006-10-20 Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100487357A CN100450942C (en) 2006-10-20 2006-10-20 Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution

Publications (2)

Publication Number Publication Date
CN1935705A CN1935705A (en) 2007-03-28
CN100450942C true CN100450942C (en) 2009-01-14

Family

ID=37953479

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100487357A CN100450942C (en) 2006-10-20 2006-10-20 Method for removing impurities suchas magnesium and recovering sulfuricacid and zinc from zinc electrolytic waste solution

Country Status (1)

Country Link
CN (1) CN100450942C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106868544A (en) * 2017-03-06 2017-06-20 温州大学 A kind of method of selective removal univalent anion impurity in electrolyte from sulfuric acid system

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101654293B (en) * 2008-08-18 2012-11-07 上海轻工业研究所有限公司 Reclamation method for hot galvanizing acid waste liquid
CN101659487B (en) * 2009-01-23 2011-07-27 云南祥云飞龙有色金属股份有限公司 Zero emission method of wastewater in lead-zinc metallurgical refinery
CN102992526A (en) * 2012-12-07 2013-03-27 来宾华锡冶炼有限公司 Method for removing zinc and acid from zinc electrolyzing waste water
CN103014782B (en) * 2012-12-27 2015-09-02 云南云铜锌业股份有限公司 Row's magnesium method in a kind of process in zinc electrolyzing
CN103553248B (en) * 2013-10-23 2015-04-08 中南大学 Heavy metal waste acid and wastewater resource recycling method and device
CN103695971A (en) * 2013-12-13 2014-04-02 武汉钢铁(集团)公司 Method for reducing total iron concentration in zinc sulfate electroplating liquid
CN104372377B (en) * 2014-10-23 2017-04-05 云南煜锜环保科技有限公司 A kind of circulating and evaporating Crystallization Separation method of zinc-magnesium in zinc electrolyte
CN105603190B (en) * 2015-12-28 2017-10-20 中南大学 A kind of method that cleaning copper electrolyte reclaims valuable metal
CN106435214B (en) * 2016-11-14 2019-03-15 云南驰宏锌锗股份有限公司 The method of demagging is gone in a kind of zinc abstraction system
CN107904414A (en) * 2017-11-21 2018-04-13 四环锌锗科技股份有限公司 A kind of method that magnesium is arranged in solution of zinc sulfate
CN108396155B (en) * 2018-03-05 2020-06-30 云南驰宏锌锗股份有限公司 Process method for producing high-quality zinc by purifying zinc electrodeposition electrolysis waste liquid
CN110923470B (en) * 2019-12-16 2020-10-02 长沙华时捷环保科技发展股份有限公司 Comprehensive recovery process of zinc electrolysis waste liquid
CN110964914A (en) * 2019-12-30 2020-04-07 南丹县南方有色金属有限责任公司 Method for removing calcium and magnesium in zinc hydrometallurgy process
CN111394750A (en) * 2020-04-23 2020-07-10 白银原点科技有限公司 Device for preparing zinc by directly electrolyzing and dechlorinating zinc sulfate solution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5393180A (en) * 1977-01-26 1978-08-15 Asahi Glass Co Ltd Diffusing and dialyzing for solution containing base
US20040149658A1 (en) * 2001-08-03 2004-08-05 Dukhin Andrei S. Method for the removal of heavy metals from aqueous solution by means of silica as an adsorbent in counter-flow selective dialysis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5393180A (en) * 1977-01-26 1978-08-15 Asahi Glass Co Ltd Diffusing and dialyzing for solution containing base
US20040149658A1 (en) * 2001-08-03 2004-08-05 Dukhin Andrei S. Method for the removal of heavy metals from aqueous solution by means of silica as an adsorbent in counter-flow selective dialysis

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106868544A (en) * 2017-03-06 2017-06-20 温州大学 A kind of method of selective removal univalent anion impurity in electrolyte from sulfuric acid system
CN106868544B (en) * 2017-03-06 2019-07-19 温州大学 A method of the selective removal univalent anion impurity from sulfuric acid system electrolyte

Also Published As

Publication number Publication date
CN1935705A (en) 2007-03-28

Similar Documents

Publication Publication Date Title
US8894865B2 (en) Process for depleting calcium and/or iron from geothermal brines
CN104060097B (en) Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge
Peters et al. Evaluation of recent treatment techniques for removal of heavy metals from industrial wastewaters
US3800024A (en) Process for neutralization and regeneration of aqueous solutions of acids and dissolved metals
CN103773961B (en) The method of cobalt and nickel is extracted in a kind of manganese cobalt nickel waste residue
CN102355933B (en) System and method for wastewater treatment
JP2020033644A (en) Improved devices and method for smelterless recycling of lead acid batteries
CN102220490B (en) Production method for electrolytic manganese dioxide
CN101921032B (en) Electrolytic deposition-membrane separation combined treatment device for electrolytic zinc rinse wastewater
US4655928A (en) Membrane processes for metal recovery and pollution control in metal process industries
CN102851693B (en) Technology for recovering production of electrolytic copper and zinc from smelting ash
CN104805291B (en) The process of a kind of stainless steel acid-washing waste liquid and iron, chromium, the recovery method of nickel
CN102766765B (en) Zinc oxide powder recycling method
CN101323908B (en) Method for reclaiming cobalt from manganese cobalt slag
CN104628217B (en) A kind of processing method recycling waste lithium cell electrolyte and electrolyte waste water
CN103290224B (en) Recovery process for valuable metals in tungsten residues
CN103194615B (en) Lead hydrometallurgical technology through utilizing lead sulfate
CN102286759B (en) Method for preparing electrodeposited zinc from high-fluorine high-chlorine secondary zinc oxide powder
CN104659438B (en) A kind of method that utilization refuse battery prepares ternary anode material precursor
CN102676853A (en) Rare earth separation method with material linkage cyclic utilization function
CN102603097B (en) Advanced treatment and recycling process for wastewater containing heavy metal ions
CN103290222B (en) A kind of method that reclaims copper and mickel from electroplating sludge
CN101671777B (en) Multi-metal recovery processing technique of waste liquid generated in germanium producing process
CN104129831B (en) Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin
CN102002594B (en) Method for recycling tin

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EXPY Termination of patent right or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090114

Termination date: 20141020