CN101760632B - Method for recovering zinc from zinc sulfate solution - Google Patents
Method for recovering zinc from zinc sulfate solution Download PDFInfo
- Publication number
- CN101760632B CN101760632B CN2008102388410A CN200810238841A CN101760632B CN 101760632 B CN101760632 B CN 101760632B CN 2008102388410 A CN2008102388410 A CN 2008102388410A CN 200810238841 A CN200810238841 A CN 200810238841A CN 101760632 B CN101760632 B CN 101760632B
- Authority
- CN
- China
- Prior art keywords
- zinc
- calcium
- sulfate
- solution
- hydroxide
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- NWONKYPBYAMBJT-UHFFFAOYSA-L Zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 229910000368 zinc sulfate Inorganic materials 0.000 title claims abstract description 56
- 229960001763 zinc sulfate Drugs 0.000 title claims abstract description 56
- 239000011701 zinc Substances 0.000 title claims abstract description 40
- 229940091251 Zinc Supplements Drugs 0.000 title claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 38
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 168
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000292 calcium oxide Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 235000011132 calcium sulphate Nutrition 0.000 claims description 79
- UGZADUVQMDAIAO-UHFFFAOYSA-L Zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 39
- 229940007718 zinc hydroxide Drugs 0.000 claims description 39
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 39
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 36
- 239000000920 calcium hydroxide Substances 0.000 claims description 36
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000001175 calcium sulphate Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L Calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 abstract 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 abstract 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 2
- ONIOAEVPMYCHKX-UHFFFAOYSA-M hydrogen carbonate;zinc Chemical compound [Zn].OC([O-])=O ONIOAEVPMYCHKX-UHFFFAOYSA-M 0.000 abstract 2
- 239000011505 plaster Substances 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 32
- 235000012255 calcium oxide Nutrition 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 hydrogen zinc oxide Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000015450 Tilia cordata Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 229940024464 emollients and protectives Zinc products Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000002035 prolonged Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- CKDIPCVMFITSCH-UHFFFAOYSA-N [H]O[O]([Zn])O[H] Chemical compound [H]O[O]([Zn])O[H] CKDIPCVMFITSCH-UHFFFAOYSA-N 0.000 description 1
- 230000003190 augmentative Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003203 everyday Effects 0.000 description 1
- 230000003311 flocculating Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for recovering zinc from a zinc sulfate solution, comprising the following steps of: (A) mixing calcium oxide and/or calcium hydrogen carbonate with calcium sulfate used as a seed crystal; (B) mixing the mixture of the calcium oxide and/or the calcium hydrogen carbonate and the calcium sulfate with the zinc sulfate solution to generate a calcium sulfate sediment and a zinc hydrogen carbonate sediment; and (C) separating the calcium sulfate and zinc hydrogen carbonate. The method for recovering the zinc from the zinc sulfate solution can recover the zinc from the zinc sulfate solution in the mode of low cost and pollution to recycle resources and also can produce the calcium sulfate (plaster), thereby reducing the production cost and relieving the environmental pollution.
Description
Technical field
The present invention relates to reclaim the method for zinc, relate in particular to the method that from solution of zinc sulfate, reclaims zinc.
Background technology
At present, in many industrial circles, often generation contains the zinc waste liquid in a large number.For example, in hydrometallurgy process zinc-containing ores or material containing zinc being carried out acidleach goes out to produce the solution that contains zinc sulfate in a large number.Traditional treatment process is to use chemical agent such as sodium hydroxide, yellow soda ash or vulcanizing agent depositing zinc oxyhydroxide or sulfide from the solution that contains zinc, but the price of reagent is higher or toxic.
Traditional method uses hydrogen sulfide and other vulcanizing agents to precipitate zinc sulphide from the solution that contains zinc.Though this technology can obtain high-quality product, operation is carried out in the toxicity environment, has unsafe factor, the production cost height.Use other vulcanizing agents for example sodium sulphite then product purity is low, the production cost height, production environment is bad.
Summary of the invention
Purpose of the present invention is intended to one of solve the aforementioned problems in the prior at least.
For this reason, one object of the present invention be to propose a kind of can the low-cost method that from solution of zinc sulfate, reclaims zinc.
The method that reclaims zinc from solution of zinc sulfate according to the embodiment of the invention may further comprise the steps: A) calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed; B) mixture with calcium oxide and/or calcium hydroxide and calcium sulfate mixes with solution of zinc sulfate, to generate calcium sulfate precipitation and zinc hydroxide precipitation; And C) separating calcium sulphate and zinc hydroxide.
The method that from solution of zinc sulfate, reclaims zinc according to the embodiment of the invention, owing in the reaction system of zinc sulfate and calcium oxide and/or calcium hydroxide, there is calcium sulfate as crystal seed, the granularity of the calcium sulfate that generates in can the augmenting response process, thereby can utilize the granularity of calcium sulfate precipitation and the difference of zinc hydroxide granularity, follow-up separating calcium sulphate at an easy rate and zinc hydroxide precipitation, and can improve the sedimentary rate of recovery of zinc hydroxide and purity.Therefore, the present invention can reclaim zinc with low-cost, oligosaprobic mode from solution of zinc sulfate, reach the recycling of resource, and attached product calcium sulfate (gypsum), and reducing production costs alleviates environmental pollution.
In one embodiment of the invention, the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate is mixed with solution of zinc sulfate comprise solution of zinc sulfate is added in take part in Taoism calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed.The present inventor finds, by solution of zinc sulfate being joined in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed, for example splash into wherein, can further improve the granularity of the calcium sulfate precipitation of reaction efficiency and generation, thus more separate easily calcium sulfate and zinc hydroxide.
Described solution of zinc sulfate is the leach liquor that contains zinc and the leaching of metal concentrate sulfuric acid.Owing in containing the leaching of zinc ore concentrate sulfuric acid, can produce the solution of a large amount of sulfur acid zinc, the effect of therefore low-cost recovery zinc technology in the industrial application that concentrate sulfuric acid leaches is better.In the further embodiment of the present invention, described solution of zinc sulfate is the solution of leach liquor through obtaining after purifying, and has so not only obtained the metal ingredient in the ore effectively, and can reclaim the zinc in the waste liquid that leaches as sulfuric acid.Purification comprises at least a metal of removing in the leach liquor, and for example iron, copper, nickel, chromium thus, not only can reclaim compositions such as iron, copper, nickel, chromium, and reclaim the zinc in the ore, have both reduced pollution, again recycle resource.
In one embodiment of the invention, calcium sulfate as crystal seed prepares by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction, the resulting like this calcium sulfate as crystal seed can make easier being attached on it of calcium sulfate in the solution of zinc sulfate, generate the precipitation of larger particle, thereby separate easilier with the precipitation zinc hydroxide.In further embodiment, described alkali-metal vitriol is sodium sulfate, can save cost like this.
In one embodiment of the invention, as the calcium sulfate of crystal seed by solution of zinc sulfate and calcium oxide and/or calcium hydroxide reaction obtain calcium sulfate and zinc hydroxide, separating calcium sulphate and zinc hydroxide, and isolating calcium sulfate washed after obtain, can save alkali-metal vitriol like this, save cost.
In one embodiment of the invention, further comprise isolated zinc hydroxide is washed and/or drying, can improve the purity of institute's separation of hydrogen zinc oxide like this, and be convenient to prolonged preservation.
In one embodiment of the invention, further comprise with separating the zinc hydroxide that obtains and produce zinc products, can utilize further zinc hydroxide like this, improve the economic value added that reclaims zinc hydroxide.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Fig. 1 is the schema of the method for zinc that reclaims from solution of zinc sulfate of first embodiment of the invention;
Fig. 2 is the schema of the method for zinc that reclaims from solution of zinc sulfate of second embodiment of the invention;
Fig. 3 is the schema of the method for zinc that reclaims from solution of zinc sulfate of third embodiment of the invention;
Fig. 4 is the schema of the method for zinc that reclaims from solution of zinc sulfate of fourth embodiment of the invention;
Fig. 5 is the schema of the method for zinc that reclaims from solution of zinc sulfate of fifth embodiment of the invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, is exemplary below by the embodiment that is described with reference to the drawings, and only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Need to prove that term " calcium oxide and/or calcium hydroxide " is meant and can uses calcium oxide (unslaked lime) also can use calcium hydroxide (white lime) in the present invention, also can add the mixture of the two.In actually operating, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2, the mixture of milk of lime as calcium oxide and calcium hydroxide used.
Fig. 1 shows the schema according to the method for zinc that reclaims of first embodiment of the invention from solution of zinc sulfate.According to shown in Figure 1, at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed.Then add solution of zinc sulfate in resulting mixture, to generate calcium sulfate precipitation and zinc hydroxide precipitation, its reaction that mainly takes place is:
ZnSO
4+Ca(OH)
2＝CaSO
4+Zn(OH)
2，
Last separating calcium sulphate and zinc hydroxide.
As mentioned above, zinc sulfate in the solution of zinc sulfate and calcium hydroxide reaction generate calcium sulfate precipitation and zinc hydroxide precipitation.Yet the sedimentary particle of calcium sulfate precipitation and zinc hydroxide is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and zinc hydroxide is a gel, and zinc hydroxide is coated on the calcium sulfate, so the two is difficult to separate.In addition, when zinc sulfate and calcium hydroxide reacted, the sedimentary formation of zinc hydroxide had limited the further increase of calcium sulfate granularity, thereby has further increased separating difficulty.
According to embodiments of the invention, in the reaction system that zinc sulfate and calcium hydroxide react, contain calcium sulfate as crystal seed, therefore, when zinc sulfate and calcium hydroxide react, formed calcium sulfate precipitation can be formed on the crystal seed, thereby the granularity of calcium sulfate precipitation can further increase, and promptly forms the calcium sulfate precipitation of volume particle size, separating between being convenient to follow-up calcium sulfate thus and zinc hydroxide precipitating.
The source of the employed in the present invention calcium sulfate as crystal seed is not restricted, both can be the ready-made calcium sulfate of buying from the market, also can be the calcium sulfate that obtains by independent chemical reaction, the product calcium sulfate that also can be in this technology to be generated.
In addition, in actually operating, at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate slurry as crystal seed, solution of zinc sulfate is added for example splash in the described mixture then, can further improve the granularity of the calcium sulfate precipitation of the efficient of reaction and generation like this.
With reference to figure 2, in one embodiment of the invention, be to use calcium sulfate precipitation that alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction generated in that to separate the back resulting as the calcium sulfate of crystal seed.The contriver finds that the calcium sulfate that uses this method to obtain can obviously increase the granularity of the calcium sulfate precipitation of generation as crystal seed.In addition, in a further embodiment, employed alkali-metal vitriol is sodium sulfate, because the cost of sodium sulfate is low, the sodium hydroxide that is generated is solvable and can reuse, and therefore when can being convenient to separation of hydrogen sodium oxide and calcium sulfate, has also reduced cost.
With reference to figure 4, in one embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate with zinc hydroxide, separating calcium sulphate and zinc hydroxide, then the calcium sulfate after separating is carried out obtaining after the classification washing by solution of zinc sulfate and calcium oxide and/or calcium hydroxide reaction, do not need extra independent preparation calcium sulfate crystal seed like this and saved alkali-metal vitriol, therefore further saved to produce and produced this.For example, can in the part of sulfuric acid zinc solution, add a certain amount of calcium oxide and/or calcium hydroxide earlier, obtain calcium sulfate and zinc hydroxide precipitation, from this reaction system, isolate calcium sulfate and zinc hydroxide then, the calcium sulfate precipitation that obtains is washed the calcium sulfate that obtains as crystal seed.
In addition, as mentioned above, at the beginning of technological process, also can be earlier in solution of zinc sulfate, add the calcium sulfate buied from market as crystal seed, then by reaction, separate the calcium sulfate that obtains and just can be used as after the crystal seed of use.
In an embodiment of the present invention, calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, both can use calcium oxide (unslaked lime), also can use calcium hydroxide (white lime), also can use the mixture of the two.Concrete, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H
2O=Ca (OH)
2More specifically, unslaked lime adds less water to be made its heating, aquation, is paste, and after thermopositive reaction finished substantially, thin up was sized mixing, and can prolong digestion time under the situation of time permission.When using commercial lime, except that prolonging digestion time, also need to sieve, to remove unreacted residue.It will be appreciated by those skilled in the art that, calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, both milk of lime can have been joined in the calcium sulfate solution of zinc sulfate as crystal seed, also the calcium sulfate solution of zinc sulfate as crystal seed can have been joined in the milk of lime.In one embodiment of the invention, be that milk of lime is joined in the calcium sulfate solution of zinc sulfate as crystal seed, the contriver finds to adopt this method can improve efficient at follow-up zinc sulfate and calcium hydroxide reaction, further facilitates later separation zinc hydroxide and calcium sulfate.
Milk of lime is mixed with solution of zinc sulfate, and stir, thereby zinc sulfate and milk of lime react, and have generated throw out calcium sulfate and zinc hydroxide, principal reaction is ZnSO
4+ Ca (OH)
2=Zn (OH)
2↓+CaSO
4↓.
Calcium sulfate can be with CaSO
4XH
2The crystallized form of O (x is about 2/3) is precipitated out, because the granularity of the size ratio zinc hydroxide of calcium sulfate wants big, and owing to added the calcium sulfate crystal seed, compares with not adding crystal seed, the granulometric facies of calcium sulfate can further increase for the granularity of zinc hydroxide.Therefore can easily calcium sulfate be separated with zinc hydroxide according to two kinds of sedimentary granular size differences.
In addition, in one embodiment of the invention, in order to obtain the higher zinc hydroxide of purity, and prolonged preservation, isolated zinc hydroxide is washed and/or dry.Washings can adopt deionized water, can prevent that like this zinc hydroxide suspension from flocculating.
With reference to figure 5, in one embodiment of the invention, separate the zinc hydroxide that obtains and to be used to prepare zinc products.
With reference to figure 4, in one embodiment of the invention, as previously mentioned, the calcium sulfate that separation is obtained can be used as crystal seed and turns back in the reaction system after removing the impurity (as zinc hydroxide) on surface through washing.In addition, resulting calcium sulfate can also be used to prepare sulfuric acid and cement.
The source of solution of zinc sulfate is not subjected to any restriction in the present invention, as long as contain zinc sulfate in its solution.With reference to figure 3, in one embodiment of the invention, solution of zinc sulfate is the leach liquor that zinc-containing ores or material containing zinc sulfuric acid leach.Using at present sulfuric acid that ore is carried out that acidleach goes out is that development is very fast at present, uses very wide wet process smelting technique, and still the sulfate waste liquid that is produced also becomes the factor that environment is made a very bad impression.Traditionally, the solution that contains zinc sulfate not only is untreated as waste liquid, and zinc wherein abandons as waste liquid.Consider that mining industry can produce the waste liquid of several tons even tens of tons every day, therefore use treatment process of the present invention can obtain extraordinary economic benefit, greatly reduce production cost.
In further embodiment of the present invention, employed solution of zinc sulfate is a sulphuric leachate through the solution that obtains after purifying, and promptly reclaims other compositions in (removals) leach liquor earlier, and then reclaims the interior zinc that exists with the zinc sulfate form of waste liquid.For example, " purification " can be at least a metal of removing in the sulphuric leachate, for example iron, copper, nickel and chromium, but the present invention is not limited to remove mentioned component.Because the purification in the sulfuric acid leaching process is known for those of ordinary skill in the art, gives unnecessary details no longer in detail here.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification that scope of the present invention is by claims and be equal to and limit to these embodiment.
Claims (6)
1. method that reclaims zinc from solution of zinc sulfate may further comprise the steps:
A) calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed;
B) solution of zinc sulfate is joined in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and zinc hydroxide precipitation, wherein said solution of zinc sulfate is the solution of leach liquor through obtaining after purifying that contains zinc ore concentrate or the leaching of material containing zinc sulfuric acid; And
C) separating calcium sulphate and zinc hydroxide.
2. the method that reclaims zinc from solution of zinc sulfate according to claim 1 is characterized in that described purification comprises at least a metal of removing in the leach liquor.
3. the method that reclaims zinc from solution of zinc sulfate according to claim 1 is characterized in that, prepares by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction as the calcium sulfate of crystal seed.
4. the method that reclaims zinc from solution of zinc sulfate according to claim 3 is characterized in that described alkali-metal vitriol is sodium sulfate.
5. the method that from solution of zinc sulfate, reclaims zinc according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed by solution of zinc sulfate and calcium oxide and/or calcium hydroxide reaction obtain calcium sulfate and zinc hydroxide, separating calcium sulphate and zinc hydroxide, and isolating calcium sulfate washed after obtain.
6. the method that reclaims zinc from solution of zinc sulfate according to claim 1 is characterized in that, further comprises isolated zinc hydroxide is washed and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102388410A CN101760632B (en) | 2008-12-02 | 2008-12-02 | Method for recovering zinc from zinc sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102388410A CN101760632B (en) | 2008-12-02 | 2008-12-02 | Method for recovering zinc from zinc sulfate solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101760632A CN101760632A (en) | 2010-06-30 |
| CN101760632B true CN101760632B (en) | 2011-08-10 |
Family
ID=42492011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102388410A Active CN101760632B (en) | 2008-12-02 | 2008-12-02 | Method for recovering zinc from zinc sulfate solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101760632B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649580A (en) * | 2011-02-26 | 2012-08-29 | 吉木青 | Recovering method for zincky waste liquor |
| CN102828033B (en) * | 2012-09-25 | 2014-06-18 | 四川锌鸿科技有限公司 | Method for recycling electrolytic zinc acid leaching slag |
| CN103011229A (en) * | 2012-12-13 | 2013-04-03 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing transition element hydroxide by using calcium hydroxide |
| CN105112660B (en) * | 2015-10-16 | 2017-03-22 | 江西理工大学 | Method for removing fluorine and chlorine in zinc sulfate solution |
| CN105366708B (en) * | 2015-12-15 | 2017-09-19 | 清远先导材料有限公司 | Method for producing aluminum zinc oxide by using zinc-containing waste liquid |
| CN105600817B (en) * | 2016-01-22 | 2018-08-21 | 广州英赛特生物技术有限公司 | A kind of zinc sulfate calcium complexes and its application in preparing feed addictive |
| CN107419100A (en) * | 2016-05-23 | 2017-12-01 | 西部矿业股份有限公司 | A kind of method of the Cobalt Purification from high-cobalt zinc sulfate solution |
| CN107893161A (en) * | 2017-11-21 | 2018-04-10 | 四环锌锗科技股份有限公司 | A kind of method that zinc ion is precipitated in silver-colored floatation system |
| CN111362482A (en) * | 2020-03-06 | 2020-07-03 | 山东默锐环境产业股份有限公司 | Method for recovering zinc chloride in zinc chloride wastewater and zero-discharge treatment of wastewater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107153A (en) * | 1985-09-20 | 1987-04-01 | 贵州工学院 | Zinc ore concentrate or the direct leaching method of zinc vulcanizing mine normal pressure |
| US5484579A (en) * | 1993-01-27 | 1996-01-16 | R & O Mining Processing Ltd. | Hydrometallurical recovery of copper and zinc from complex sulfide ores |
| CN1162340A (en) * | 1994-11-08 | 1997-10-15 | 谢里特公司 | Recovery of zinc from sulphidic concentrates |
| CN1530452A (en) * | 2003-03-14 | 2004-09-22 | 中国有色工程设计研究总院 | Method and apparatus for removing copper, cadmium and cobalt from zinc sulfate solution |
-
2008
- 2008-12-02 CN CN2008102388410A patent/CN101760632B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107153A (en) * | 1985-09-20 | 1987-04-01 | 贵州工学院 | Zinc ore concentrate or the direct leaching method of zinc vulcanizing mine normal pressure |
| US5484579A (en) * | 1993-01-27 | 1996-01-16 | R & O Mining Processing Ltd. | Hydrometallurical recovery of copper and zinc from complex sulfide ores |
| CN1162340A (en) * | 1994-11-08 | 1997-10-15 | 谢里特公司 | Recovery of zinc from sulphidic concentrates |
| CN1530452A (en) * | 2003-03-14 | 2004-09-22 | 中国有色工程设计研究总院 | Method and apparatus for removing copper, cadmium and cobalt from zinc sulfate solution |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-64736A 2001.03.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101760632A (en) | 2010-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101760632B (en) | Method for recovering zinc from zinc sulfate solution | |
| CN101760613B (en) | Method for leaching zinc-containing ores | |
| CN101845562B (en) | Improved device and method for producing electrolytic manganese metal by two-ore method | |
| CN109290060A (en) | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings | |
| CN105567976B (en) | A kind of vanadium extraction industrial acidic wastewater processing and the method for valuable metal synthetical recovery | |
| CN103757260B (en) | Treatment method of nickel-containing eluvial ores | |
| CN101759233B (en) | Method for recovering cobalt from cobalt sulfate solution | |
| CN101760614B (en) | Leaching method of nickel-containing ore | |
| CN107056388A (en) | The preparation method of chemical polishing waste phosphoric acid processing method and fertilizer | |
| CN101723431B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN101760635A (en) | Method for recovering nickel from nickel sulfate solution | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN106629806A (en) | Method for producing dihydrate gypsum from waste liquid in laterite nickel ore wet process | |
| CN101760630A (en) | Method for recovering copper from copper sulfate solution | |
| CN108622927A (en) | A method of producing nano zine oxide using containing zinc ore crude | |
| CN108950239A (en) | A method of it produces using containing zinc ore crude containing zinc complexes | |
| CN108977672A (en) | A method of using molybdenum removal slag as waste iron molybdate | |
| CN101898770B (en) | Method for recycling sodium hydroxide | |
| JP2003137545A (en) | Method for manufacturing waste acid gypsum | |
| CN1313379C (en) | Prepn process of iron red with salfated roasted dreg of sulfur containing aurin ore | |
| CN101760616B (en) | Leaching method of cobalt-containing ore | |
| CN101760615A (en) | Leaching method of copper-containing ore | |
| CN110817935A (en) | Method for preparing high-purity zinc oxide by utilizing zinc renewable resources | |
| CN104726700A (en) | Method for using copper-containing sludge to produce copper concentrate | |
| CN101724748A (en) | Method for leaching magnesium-containing ores |
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 |