CN1034593C - Process for preparing zinc oxide - Google Patents
Process for preparing zinc oxide Download PDFInfo
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- CN1034593C CN1034593C CN91111600A CN91111600A CN1034593C CN 1034593 C CN1034593 C CN 1034593C CN 91111600 A CN91111600 A CN 91111600A CN 91111600 A CN91111600 A CN 91111600A CN 1034593 C CN1034593 C CN 1034593C
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- zinc
- ammonia
- removing impurities
- zinc oxide
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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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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a new process for preparing zinc oxides, which is especially suitable for preparing zinc carbonate hydroxide or zinc oxide products by an ammonia-ammonium method. The existing method comprises the following steps: leaching with an ammonia-ammonium liquid; reducing, transposing and removing impurities for purification; heating for zinc precipitation; calcining; recovering ammonia. The present invention is characterized in that the present invention is added with a step of oxidizing for removing impurities in a process of removing impurities for purification, namely that air or oxygen is used as an oxidizer under a certain reaction condition, to remove ferrite ions, manganese ions, calcium ions and magnesium ions which can not be removed in the prior art. Thereby, the present invention enhances product purity, and the present invention has the advantages of simple manufacturing process, economic feasibility, no pollution and adaption to industrial production.
Description
The present invention relates to the inorganic chemical industry production technology, be specially adapted to ammonia azanium method and produce zinc subcarbonate or zinc oxide product.
The method of producing zinc subcarbonate and zinc oxide product at present is more, in the wet chemical production technology, ammonia ammonium method production technology is strong to adaptability to raw material, contain zinc applicable to low-grade zinc and other and pay product, and avoided the various disadvantages of acid system production technology, it is little to have equipment corrosion, and technology is simple, easy to operate, produce in ammonia and carbonic acid gas and recyclable the recycling of mother liquor and do not have advantages such as waste liquid, exhaust gas emission substantially.Example: put down in writing with ammonia azanium method among the CN90105488.7 " a kind of method of producing zinc oxide " and from Zn dust mud and low grade zinc breeze, produced zinc oxide; Routine again: as to have put down in writing among the CN88102610 with ammonia azanium method from smithsonite oxygenerating zinc, but existing ammonia azanium method is produced zinc oxide technology, also has weak point, mainly be poor to the detergent power of impurity, influenced the purity of zinc oxide product, thereby can influence the grade of product, also can and then having influence on of having uses this zinc oxide to make raw material and the quality of the product produced.Example: manganese is the aging agent of rubber item, thereby the content of manganese also can influence the quality of rubber in the zinc oxide product.In existing technology when containing the zinc raw material after ammonia-ammonium solution leaches, when Zn enters solution with ammonia complex, also have plumbous, copper, cadmium, cobalt, nickel, iron, manganese, calcium, impurity such as magnesium also enter solution with ammonia complex or hydrated ion respectively, in the described technology of CN90105488.7, leaching liquid is reduced displacement with zinc powder, make lead, copper, cadmium, cobalt, heavy metal ion such as nickel are converted into precipitation and remove, but iron, manganese, calcium, the magnesium plasma still remains in the solution, the purity and the colourity of product have been had a strong impact on, the content of its product ZnO has only 99.4-99.7%, and it is very big that this content is subjected to raw material to bring the influence of impurity level into.So unstable product quality.In CN88102610, leaching liquid is removed heavy metal with sulfide, this method has two defectives: (1) part zine ion easily generates ZnS precipitation and causes the loss of zinc.(2) because the sulfide solubility product of manganese, iron, cobalt, nickel is bigger than the solubility product of zinc sulphide, so these four kinds of ions are difficult to precipitated and separate.
The purpose of this invention is to provide a kind of novel process of producing zinc subcarbonate or zinc oxide with ammonia azanium method, this technology good impurity removing effect, technology is simple, viable economically, pollution-free, be suitable for suitability for industrialized production, and use the product of this explained hereafter, steady quality, recovery rate height.
The present invention seeks to realize like this: paying product zinc oxide, low oxidisability, zinc baking sand or smithsonite with the powdery that contains zinc oxide is raw material, with ammonia-sal volatile leaching, employing adds zinc powder reduction displacement impurity elimination and oxidation impurity elimination, leaching liquid after purifying through impurity elimination is added heat sink zinc make zinc subcarbonate, zinc oxide is produced in the zinc subcarbonate calcining.Ammonia, carbonic acid gas and mother liquor are provided with the recycling use device in technology.
Above-mentioned oxidation impurity elimination is performed such: will be through the solution after adding zinc powder reduction displacement impurity elimination, be heated to more than 95 ℃, bubbling air or oxygen, and the control equilibrium pressure is at 0.2-1.0Mpa, stirring reaction 20-40 minute, make low price iron, mn ion be oxidized to the high price ferromanganese ion and generate corresponding throw out, reaction formula is as follows:
Because the Fe (OH) that generates
3And MnO (OH)
2Have colloidal property, but other impurity of absorption part are coprecipitated in solution, play further cleaning action; In addition, under this temperature, impurity such as the calcium magnesium in the solution also further change into the carbonate deposition of indissoluble, and reaction formula is as follows:
Because in the above-mentioned technology, compared with prior art, impurity elimination has been adopted two step method in purifying, increased the heated oxide impurity removal process, made the heavy metal metal ion in addition in the solution, example: calcium, magnesium, iron, mn ion are also separated to be removed, thereby improved the purity of zinc oxide product, press national standard: GB3185-82 test item detected result, zinc oxide content can reach 99.87%, and the content of Mn can reduce to 0.00008%.The content of iron, calcium, magnesium ion wherein, though there is not specific requirement in standard, their existence is relevant with the overall performance of zinc oxide content, and in addition, iron ion content is also relevant with the colourity of product, and the present invention is because good iron removal effect, so look white.Because this removing impurities by oxidation technology is to adopt in certain temperature, and the method to solution blowing air or oxygen under the pressure condition realizes, so technology is simple, expense is reasonable, no new impurity is brought in scavenging process, and is also pollution-free, can be suitable for suitability for industrialized production again.
Be described further below in conjunction with process flow sheet and embodiment:
Embodiment 1: with Hunan Shuikoushan Mining Bureau pay produce zinc oxide (contain Zn56.2%, Pb9.5%) raw material 105kg, 175 microns of granularities are with containing NH
3The sal volatile of 12% degree of carbonisation 70% is made leaching agent, presses liquid: Gu (weight ratio)=6.5 batchings, in the leaching groove, about 60 ℃ of temperature of reaction, stirring reaction 1.5 hours makes and contains Zn (NH
3)
4 2+With the leaching liquid of other metal ions (being impurity), the filtrate that leaching liquid removes slag after filtration enters in the reduction displacement slot, adds zinc powder 1.2kg and makes reductive agent (zinc powder contains Zn90%).55 ℃ of control reaction temperature, stirring reaction 1.5 hours, sedimentation filter, elimination the filtrate of heavy metal precipitation thing enter in the 1000 liter stills for air blowing, be heated to 95 ℃, the control equilibrium pressure is 0.2Mpa, feeds after reducing pressure in the solution in the stills for air blowing with steel cylinder oxygen simultaneously, carries out oxidation impurity elimination reaction, stirring reaction 30 minutes, sedimentation is filtered, and again filtrate is carried out pyrolysis adding heat sink zinc groove internal heating under 80-100 ℃ of condition, and the zinc in the solution in the zinc ammonium complex ion changes into zinc subcarbonate (ZnCO
32Zn (OH)
2NH
2O) precipitation enters separation, and ammonia and carbonic acid gas volatilization are overflowed, and enter the absorption recovery process.Separating obtained zinc subcarbonate at calcining furnace internal heating to 900 ℃, was calcined 2 hours, made zinc oxide product 62.85kg, quality meets first grade standard among the GB3185-82, and recovery rate is 88%.
In addition, with identical raw material, identical processing condition, do a pair of than testing its result such as following table but deduct oxidation impurity elimination technology:
| Quality product | Through removing impurities by oxidation | The not oxidised removal of impurities |
| ZnO content | 99.84％ | 99.0％ |
| Manganese content (in Mn) | 0.00008％ | 0.005％ |
| Product colourity | White | Little Huang |
Embodiment 2: with zinc baking sand (contain zinc 31.4%, Pb6.1%) raw material 80kg, (through being crushed to 175 microns) is with containing NH
38%, the sal volatile of degree of carbonisation 80% is made leaching agent, by liquid: Gu leaching liquid is joined in (weight ratio)=5.6, add zinc powder 1kg and make reductive agent; Temperature is 120 ℃ in the stills for air blowing, and equilibrium pressure is 0.5Mpa, the bubbling air oxidation, stirring reaction 35 minutes, in last calcination process, calcining temperature is 500 ℃, 4.5 hour, all the other conditions make active oxidation zinc product 27.63kg with example 1, and containing ZnO is 99.71%, Mn%=0.0001%, look white, and all the other indexs also all meet first grade standard among the GB3185-82, recovery rate 85%.
Embodiment 3: (contain zinc 68.2%, Pb2.3%) raw material 100kg is with containing NH with Kaiyuan City, Yunnan low-grade zinc oxide
315%, the sal volatile of degree of carbonisation 60% is made leaching agent, presses liquid: Gu (weight ratio)=5.3 batching is produced leaching liquid, add zinc powder 1kg and make reductive agent; The oxidation temperature in the kettle is 140 ℃, equilibrium pressure is 1.0Mpa, adopt steel cylinder oxygen decompression back to feed, reacted 20 minutes, all the other conditions make product zinc oxide 79.3kg with embodiment 1, ZnO content is 99.9%, manganese content (in Mn) is 0.00007%, and look white, and all the other every indexs all reach GB3185-82 first grade standard.Recovery rate 92%.
Claims (1)
1. produce the technology of zinc oxide, with the zinc thing that contains after pulverizing is raw material, purify, add heat sink zinc, calcine the high pure zinc oxide of making through leaching, impurity elimination, the leaching agent that wherein leaches in the operation is ammonia-carbonic acid ammonia solution, and ammonia and carbonic acid gas are provided with recovery and Recycling Mother Solution operation; In impurity elimination purifies, adopt to add zinc powder reduction displacement impurity elimination and removing impurities by oxidation, it is characterized in that:
A. leaching is after filter and remove residue, and impurity elimination purifies again;
B. the removing impurities by oxidation operation is set at after the zincification displacement filtration impurity elimination, adopts the cleaner of air or oxygen as removing impurities by oxidation, and temperature is controlled to be 95 ℃-140 ℃ during removing impurities by oxidation, and pressure-controlling is 0.2Mpa-1Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111600A CN1034593C (en) | 1991-12-13 | 1991-12-13 | Process for preparing zinc oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111600A CN1034593C (en) | 1991-12-13 | 1991-12-13 | Process for preparing zinc oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062004A CN1062004A (en) | 1992-06-17 |
| CN1034593C true CN1034593C (en) | 1997-04-16 |
Family
ID=4910726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111600A Expired - Fee Related CN1034593C (en) | 1991-12-13 | 1991-12-13 | Process for preparing zinc oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1034593C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035870C (en) * | 1994-08-11 | 1997-09-17 | 重庆化肥矿山工业公司 | Process for producing high-dispersivity active zinc oxide |
| CN1102175C (en) * | 1998-12-30 | 2003-02-26 | 王犇 | Method for recovering copper and zinc oxide from copper-zinc waste catalyst |
| CN110790439B (en) * | 2019-11-29 | 2022-04-26 | 镇江市和云工业废水处置有限公司 | Treatment method of hot galvanizing pickling wastewater |
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1991
- 1991-12-13 CN CN91111600A patent/CN1034593C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1062004A (en) | 1992-06-17 |
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