CN101973574A - Method for preparing sulfates from waste residues in lithopone production - Google Patents
Method for preparing sulfates from waste residues in lithopone production Download PDFInfo
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- CN101973574A CN101973574A CN 201010519173 CN201010519173A CN101973574A CN 101973574 A CN101973574 A CN 101973574A CN 201010519173 CN201010519173 CN 201010519173 CN 201010519173 A CN201010519173 A CN 201010519173A CN 101973574 A CN101973574 A CN 101973574A
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- zinc
- vitriol
- iron
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Abstract
The invention provides a method for preparing sulfates from waste residues in lithopone production, which comprises the following steps of: reacting the waste residues in the lithopone production with concentrated hydrochloric acid, so that metallic oxides in the waste residues are converted into metal chlorides; and reacting the metal chlorides with concentrated sulfuric acid to obtain various sulfates, distilling under reduced pressure, and separating products of zinc sulfate heptahydrate crystals, crystallized manganese sulfate and ferrous sulfate heptahydrate out sequentially according to different solubility of the sulfates. By the method, wastes are turned into wealth, the waste residues in the lithopone production are converted into the sulfates with high economic significance, the potential economic value is fully excavated and utilized, and a new way is provided for the comprehensive utilization and treatment of the waste residues in the lithopone production.
Description
Technical field
The present invention relates to produce the comprehensive regulation of zinc sulfide white gained waste residue and utilize technical field particularly a kind of method for preparing vitriol with zinc sulfide white gained waste residue.
Background technology
Zinc sulfide white is commonly called as lithopone, is the mixture of zinc sulphide and barium sulfate, and its main production raw material is a zinc oxide, is to be smelted by plumbous zinc ore to form.Contain a large amount of plumbous oxide impurity in this zinc oxide, plumbous oxide content is generally 60-80%.0.165 ton of the scrap lead slag that one ton of zinc sulfide white of every production produces ejects to produce 1.5 ten thousand tons of zinc sulfide white per year, 2480 tons of lead tolerance are just arranged the scrap lead slag that is 30-40%.The main chemical composition of its scrap lead slag is: lead tolerance is 34.63%, and zinc content is 10.50%, and manganese content is 2.32%, copper content is 0.23%, and cadmium content is 0.31%, and iron-holder is 3.15%, sulphur content is 5.01%, and magnesium content is 2.32%, and water content is 48.65%.
At present, resource is so not only wasted in the most air storage of this waste residue or be used to fill a vacancy, pave the way, and heavy metal is serious environment pollution also.People have carried out a large amount of research for this reason, study producing multiple product in 1973 01 phases " fine-chemical intermediate " with the zinc sulfide white waste residue, " Hunan chemical industry " 1992 the 22nd the 1st phase of volume has also been reported " research of producing lead sulfate from zinc sulfide white acidleach waste residue ", but all also just be in theoretical investigation in the literary composition, also actual without comparison processing and utilize method.
For this reason, be necessary to explore the comprehensive regulation and utilize production zinc sulfide white gained waste residue commercial run, produce of the pollution of zinc sulfide white gained waste residue environment to alleviate.
Summary of the invention
The objective of the invention is to, a kind of method for preparing vitriol with zinc sulfide white gained waste residue is provided.This method turns waste into wealth, and effectively will produce zinc sulfide white gained waste residue and be converted into the vitriol that has than the large economy meaning, fully excavates and utilized the potential economic worth, also provides new approach for the comprehensive utilization and the improvement of producing zinc sulfide white gained waste residue.
Technical scheme of the present invention is as follows: a kind ofly prepare the method for vitriol with producing zinc sulfide white gained waste residue, comprise following concrete steps:
Steps A: zinc sulfide white gained waste residue is produced in weighing, conversion zinc oxide wherein, the molar content sum of manganese oxide and iron protoxide, and it is worn into 80-120 purpose meal, with mass concentration is that the concentrated hydrochloric acid of 20-30% drops into corrosion-resistant reactor one (1) lining, make zinc oxide in the corrosion-resistant reactor, the molar content sum of manganese oxide and iron protoxide is 1 with the ratio of the molar content of hydrogenchloride: 1.5-2.5, issue biochemical reaction in the stirring that blows slowly, obtain containing zinc chloride, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride;
Step B: with the above-mentioned zinc chloride that contains, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride filters through filter (2), obtains clarifying muriate filtrate and filter cake;
Step C: is 1 with clarifying muriate filtrate and sulfuric acid according to the ratio of muriate and vitriolic molar weight: 0.5-1.5 drops into corrosion-resistant reactor two (3) linings, under stirring slowly, carry out chemical reaction, obtain sulfur acid zinc, the mixed sulfate liquid of manganous sulfate and ferrous sulfate;
Step D: the mixed sulfate liquid of above-mentioned gained is sent into underpressure distillation device (4) carry out underpressure distillation,, successively separate out Zinc Sulphate Heptahydrate crystal, crystalline sulfuric acid manganese, iron vitriol product successively according to the vitriol different solubility.
After various vitriol are separated out among the step D, be mainly hydrogenchloride in the residual solution, return steps A and reuse.
The method chemical equation for preparing zinc sulfate and manganous sulfate with production zinc sulfide white gained waste residue is as follows:
ZnO+2HCl＝＝＝＝ZnCl
2+H
2O
ZnCl
2+H
2SO
4+7H
2O＝＝＝＝ZnSO
4·7H
2O+2HCl
MnO+2HCl＝＝＝＝MnCl
2+H
2O
MnCl
2+H
2SO
4+H
2O＝＝＝＝MnSO
4·H
2O+2HCl
FeO+2HCl＝＝＝＝FeCl
2+H
2O
FeCl
2+H
2SO
4+7H
2O＝＝＝＝FeSO
4·7H
2O+2HCl
The invention has the beneficial effects as follows: the present invention prepares the method for vitriol with production zinc sulfide white gained waste residue, effectively produce zinc sulfide white gained waste residue and will be converted into the vitriol that has than the large economy meaning, fully excavate and utilized the potential economic worth, also for comprehensive utilization and improvement provide new approach.Simultaneously, this method is simple to operate, and the facility investment expense is low, and by product is few, is suitable for applying.
Description of drawings
Fig. 1 prepares the process flow sheet of the method for vitriol for of the present invention with production zinc sulfide white gained waste residue, among this figure, and (1) corrosion-resistant reactor one, (2) strainer, (3) corrosion-resistant reactor two, (4) underpressure distillation device, (5) vitriol.
Embodiment
Embodiment 1
With reference to Fig. 1, a kind of method for preparing vitriol with production zinc sulfide white gained waste residue, zinc sulfide white gained waste residue 500kg is produced in weighing, wherein zinc content is 10.50%, manganese content is 2.32%, iron-holder is 3.15%, conversion zinc oxide molar content wherein is 810 moles, the manganese oxide molar content is that 20 moles of molar content with iron protoxide are 28 moles, zinc then, manganese, iron molar content sum is 858 moles, and it is worn into 80-120 purpose meal, and be that the concentrated hydrochloric acid of 20-30% drops into corrosion-resistant reactor one (1) lining with mass concentration, make zinc oxide in the corrosion-resistant reactor, the molar content sum of manganese oxide and iron protoxide is 1: 1.5 with the ratio of the molar content of hydrogenchloride, issue biochemical reaction in the stirring that blows slowly, obtain containing zinc chloride, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride; With the above-mentioned zinc chloride that contains, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride filters through filter (2), obtains clarifying muriate filtrate and filter cake; Is to drop into corrosion-resistant reactor two (3) linings at 1: 0.5 with clarifying muriate filtrate and sulfuric acid according to the ratio of muriate and vitriolic molar weight, carries out chemical reaction under stirring slowly, obtains sulfur acid zinc, the mixed sulfate liquid of manganous sulfate and ferrous sulfate; The mixed sulfate liquid of gained is sent into underpressure distillation device (4) carry out underpressure distillation,, successively separate out Zinc Sulphate Heptahydrate crystal, crystalline sulfuric acid manganese, iron vitriol product successively according to the vitriol different solubility.After various vitriol are separated out, be mainly hydrogenchloride in the residual solution, return repeated use.Above-mentioned technology gained Zinc Sulphate Heptahydrate crystal is that 87.18kg, crystalline sulfuric acid manganese are that 11.89kg, iron vitriol are 29.19kg.
With reference to Fig. 1, a kind of method for preparing vitriol with production zinc sulfide white gained waste residue, zinc sulfide white gained waste residue 500kg is produced in weighing, wherein zinc content is 10.50%, manganese content is 2.32%, iron-holder is 3.15%, conversion zinc oxide molar content wherein is 810 moles, the manganese oxide molar content is that 20 moles of molar content with iron protoxide are 28 moles, zinc then, manganese, iron molar content sum is 858 moles, and it is worn into 80-120 purpose meal, and be that the concentrated hydrochloric acid of 20-30% drops into corrosion-resistant reactor one (1) lining with mass concentration, make zinc oxide in the corrosion-resistant reactor, the molar content sum of manganese oxide and iron protoxide is 1: 2 with the ratio of the molar content of hydrogenchloride, issue biochemical reaction in the stirring that blows slowly, obtain containing zinc chloride, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride; With the above-mentioned zinc chloride that contains, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride filters through filter (2), obtains clarifying muriate filtrate and filter cake; Is to drop into corrosion-resistant reactor two (3) linings at 1: 1 with clarifying muriate filtrate and sulfuric acid according to the ratio of muriate and vitriolic molar weight, carries out chemical reaction under stirring slowly, obtains sulfur acid zinc, the mixed sulfate liquid of manganous sulfate and ferrous sulfate; The mixed sulfate liquid of gained is sent into underpressure distillation device (4) carry out underpressure distillation,, successively separate out Zinc Sulphate Heptahydrate crystal, crystalline sulfuric acid manganese, iron vitriol product successively according to the vitriol different solubility.After various vitriol are separated out, be mainly hydrogenchloride in the residual solution, return repeated use.Above-mentioned technology gained Zinc Sulphate Heptahydrate crystal is that 232.47kg, crystalline sulfuric acid manganese are that 31.71kg, iron vitriol are 77.84kg.
Embodiment 3
With reference to Fig. 1, a kind of method for preparing vitriol with production zinc sulfide white gained waste residue, zinc sulfide white gained waste residue 500kg is produced in weighing, wherein zinc content is 10.50%, manganese content is 2.32%, iron-holder is 3.15%, conversion zinc oxide molar content wherein is 810 moles, the manganese oxide molar content is that 20 moles of molar content with iron protoxide are 28 moles, zinc then, manganese, iron molar content sum is 858 moles, and it is worn into 80-120 purpose meal, and be that the concentrated hydrochloric acid of 20-30% drops into corrosion-resistant reactor one (1) lining with mass concentration, make zinc oxide in the corrosion-resistant reactor, the molar content sum of manganese oxide and iron protoxide is 1: 2.5 with the ratio of the molar content of hydrogenchloride, issue biochemical reaction in the stirring that blows slowly, obtain containing zinc chloride, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride; With the above-mentioned zinc chloride that contains, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride filters through filter (2), obtains clarifying muriate filtrate and filter cake; Is to drop into corrosion-resistant reactor two (3) linings at 1: 1.5 with clarifying muriate filtrate and sulfuric acid according to the ratio of muriate and vitriolic molar weight, carries out chemical reaction under stirring slowly, obtains sulfur acid zinc, the mixed sulfate liquid of manganous sulfate and ferrous sulfate; The mixed sulfate liquid of gained is sent into underpressure distillation device (4) carry out underpressure distillation,, successively separate out Zinc Sulphate Heptahydrate crystal, crystalline sulfuric acid manganese, iron vitriol product successively according to the vitriol different solubility.After various vitriol are separated out, be mainly hydrogenchloride in the residual solution, return repeated use.Above-mentioned technology gained Zinc Sulphate Heptahydrate crystal is that 232.47kg, crystalline sulfuric acid manganese are that 31.71kg, iron vitriol are 77.84kg.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries method.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.
Claims (2)
1. one kind prepares the method for vitriol with producing zinc sulfide white gained waste residue, it is characterized in that, comprises following concrete steps:
Steps A: zinc sulfide white gained waste residue is produced in weighing, conversion zinc oxide wherein, the molar content sum of manganese oxide and iron protoxide, and it is worn into 80-120 purpose meal, with mass concentration is that the concentrated hydrochloric acid of 20-30% drops into corrosion-resistant reactor one (1) lining, make zinc oxide in the corrosion-resistant reactor, the molar content sum of manganese oxide and iron protoxide is 1 with the ratio of the molar content of hydrogenchloride: 1.5-2.5, issue biochemical reaction in the stirring that blows slowly, obtain containing zinc chloride, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride;
Step B: with the above-mentioned zinc chloride that contains, the mixing solutions of Manganous chloride tetrahydrate and iron protochloride filters through filter (2), obtains clarifying muriate filtrate and filter cake;
Step C: is 1 with clarifying muriate filtrate and sulfuric acid according to the ratio of muriate and vitriolic molar weight: 0.5-1.5 drops into corrosion-resistant reactor two (3) linings, under stirring slowly, carry out chemical reaction, obtain sulfur acid zinc, the mixed sulfate liquid of manganous sulfate and ferrous sulfate;
Step D: the mixed sulfate liquid of above-mentioned gained is sent into underpressure distillation device (4) carry out underpressure distillation,, successively separate out Zinc Sulphate Heptahydrate crystal, crystalline sulfuric acid manganese, iron vitriol product successively according to the vitriol different solubility.
2. as claimed in claim 1ly prepare the method for vitriol, it is characterized in that, after various vitriol are separated out among the step D, be mainly hydrogenchloride in the residual solution, return steps A and reuse with producing zinc sulfide white gained waste residue.
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| CN 201010519173 CN101973574A (en) | 2010-10-25 | 2010-10-25 | Method for preparing sulfates from waste residues in lithopone production |
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| CN 201010519173 CN101973574A (en) | 2010-10-25 | 2010-10-25 | Method for preparing sulfates from waste residues in lithopone production |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539302A (en) * | 2013-10-31 | 2014-01-29 | 惠州市斯瑞尔环境化工有限公司 | Treatment method of zinc-containing and iron-containing waste acid |
| CN115554647A (en) * | 2022-10-26 | 2023-01-03 | 中节能（攀枝花）清洁技术发展有限公司 | Method for cooperative treatment of dangerous chemicals |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090983A (en) * | 2004-10-21 | 2007-12-19 | 安格洛操作有限公司 | Leaching process in the presence of hydrochloric acid for the recovery of a value metal from an ore |
-
2010
- 2010-10-25 CN CN 201010519173 patent/CN101973574A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090983A (en) * | 2004-10-21 | 2007-12-19 | 安格洛操作有限公司 | Leaching process in the presence of hydrochloric acid for the recovery of a value metal from an ore |
Non-Patent Citations (2)
| Title |
|---|
| 《化工环保》 19931231 戴友芝等 立德粉生产废渣的回收利用 154-157 1-2 第13卷, 第3期 2 * |
| 《湖南化工》 19921231 李文郁等 从立德粉酸浸废渣制取硫酸铅的研究 32-34 1-2 , 第1期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539302A (en) * | 2013-10-31 | 2014-01-29 | 惠州市斯瑞尔环境化工有限公司 | Treatment method of zinc-containing and iron-containing waste acid |
| CN103539302B (en) * | 2013-10-31 | 2015-04-22 | 惠州市斯瑞尔环境化工有限公司 | Treatment method of zinc-containing and iron-containing waste acid |
| CN115554647A (en) * | 2022-10-26 | 2023-01-03 | 中节能（攀枝花）清洁技术发展有限公司 | Method for cooperative treatment of dangerous chemicals |
| CN115554647B (en) * | 2022-10-26 | 2023-09-01 | 中节能（攀枝花）清洁技术发展有限公司 | Method for cooperatively treating dangerous chemicals |
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Application publication date: 20110216 |