CN102115137B - Method for co-production of barium sulfate and zinc chloride from barium chloride waste - Google Patents
Method for co-production of barium sulfate and zinc chloride from barium chloride waste Download PDFInfo
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- CN102115137B CN102115137B CN2010106154537A CN201010615453A CN102115137B CN 102115137 B CN102115137 B CN 102115137B CN 2010106154537 A CN2010106154537 A CN 2010106154537A CN 201010615453 A CN201010615453 A CN 201010615453A CN 102115137 B CN102115137 B CN 102115137B
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- bariumchloride
- barium
- zinc chloride
- solution
- chloride
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Abstract
The invention provides a method for co-production of barium sulfate and zinc chloride from barium chloride waste. The barium chloride waste is generated during the preparation of thiourea from the reaction between hydrochloric acid and barium sulfide. The barium chloride waste is thoroughly dissolved with water and then mixes and reacts with hydrochloric acid to produce a liquid containing barium chloride; the liquid containing barium chloride mixes and reacts with zinc sulfate to produce barium sulfate and zinc chloride; the reaction product is filtered to produce a filter cake of barium sulfate and a liquid containing zinc chloride; the filter cake of barium sulfate is washed, pulverized and dried to obtain a barium sulfate product; and the liquid containing zinc chloride is distilled to produce a supersaturated solution of zinc chloride so that zinc chloride is crystallized to obtain a zinc chloride product. The method has the advantages that the operation is easy, the investment of equipment is reduced, effective components in the barium chloride waste are changed to be the industrially valuable materials, and the method is economical and applicable.
Description
Technical field
The present invention relates to the disposal of three wastes of inorganic chemical industry thiocarbamide manufacturing and utilize technical field; Especially the method for preparing barium sulfate and co-produced zinc chloride with the bariumchloride waste residue, the said waste residue
that uses the bariumchloride waste residue as hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained.
Background technology
The working method of thiocarbamide is a lot, and wherein traditional method is to utilize barium sulphide and hydrochloric acid reaction to generate hydrogen sulfide and bariumchloride deposition, and hydrogen sulfide makes the hydrogen sulfide calcium solution through the absorption of milk of lime negative pressure; Then react with calcium cyanamide, the mol ratio of calcium sulfhydrate and calcium cyanamide is 1: 5 again, under constantly stirring; Temperature of reaction is (80 ± 5) ℃, and the reaction times is 3h, through negative pressure filtration; Can generate thiocarbamide liquid; Through evaporation, filtration, cooling, crystallization, promptly get the crystal thiocarbamide again, centrifugal drying gets product.Reaction equation is following:
BaS+2HCl→BaC12+H2S↑
CaO+H2O→Ca(OH)2
2H
2S+Ca(OH)
2→Ca(SH)
2+2H
2O
2CaCN
2+Ca(SH
2)
2+6H
2O→2(NH
2)
2CS+3Ca(OH)
2
Aforesaid method is produced thiocarbamide, and its main industrial residue is exactly the bariumchloride waste residue, according to one's analysis, also contains a large amount of barium sulphides in the bariumchloride waste residue.
Summary of the invention
The waste residue of hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained is bariumchloride waste residue according to the invention, and its staple is a bariumchloride, also contains a large amount of barium sulphides, and the present invention provides the method for preparing common permanent white and zinc chloride with above-mentioned bariumchloride waste residue.This method is simple to operate, and facility investment is few, and the effective constituent in the bariumchloride waste residue is converted into upward utilizable material of industry, is an economic and practical method.
Technical scheme of the present invention is following: prepare the method for barium sulfate and co-produced zinc chloride with the bariumchloride waste residue, the said waste residue that uses the bariumchloride waste residue as hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained comprises following concrete steps:
Steps A: the bariumchloride waste residue fully is dissolved in water, is mainly contained the solution of bariumchloride and barium sulphide, convert the wherein molar content of barium sulphide;
Step B: with the steps A gained mainly contain bariumchloride and barium sulfide solution mixes with excessive hydrochloric acid; The molar content that makes barium sulphide is 1:1.6-2.4 with the ratio of the molar content of hydrogenchloride; Hydrochloric acid and barium sulphide reaction generate bariumchloride and hydrogen sulfide, after hydrogen sulfide is overflowed from solution, obtain containing the solution of bariumchloride; The effusion hydrogen sulfide feeds in the sodium hydroxide solution and absorbs, in order to avoid contaminate environment;
Step C: the solution that contains bariumchloride and small amount of hydrochloric acid of step B gained is mixed with zinc sulfate, and making the bariumchloride and the ratio of the molar content of the material of zinc sulfate is 1:0.8-1.2; Zinc sulfate and bariumchloride reaction generate permanent white and zinc chloride; Through filtering, obtain permanent white filter cake and the solution that contains zinc chloride;
Step D: after permanent white filter cake washing, pulverizing and drying, obtain barium sulfate product;
Step e: with the solution distillation that contains zinc chloride of step C gained is the zinc chloride supersaturated solution, and the zinc chloride crystallization is separated out, and obtains the zinc chloride product.
According to the inventionly prepare the method for barium sulfate and co-produced ammonia chloride with the bariumchloride waste residue, related chemical principle is:
BaS+2HCl=====BaCl
2+H
2S
BaCl
2+ZnSO
4=====BaSO
4↓+2?ZnCl2
Beneficial effect of the present invention is: the method for preparing barium sulfate and co-produced zinc chloride with the bariumchloride waste residue according to the invention; This method is simple to operate; Facility investment is few, and the effective constituent in the bariumchloride waste residue is converted into upward utilizable material of industry, is an economic and practical method.
Embodiment
Embodiment 1:
Prepare the method for barium sulfate and co-produced zinc chloride with the bariumchloride waste residue, the said waste residue that uses the bariumchloride waste residue as hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained comprises following concrete steps:
Steps A: 500kg bariumchloride waste residue fully is dissolved in water, is mainly contained the solution of bariumchloride and barium sulphide, convert the wherein molar content of barium sulphide;
Step B: the steps A gained mainly contained bariumchloride and barium sulfide solution and mixed in hydrochloric acid; The molar content that makes barium sulphide is 1:1.6 with the ratio of the molar content of hydrogenchloride; Hydrochloric acid and barium sulphide reaction generate bariumchloride and hydrogen sulfide, after hydrogen sulfide is overflowed from solution, obtain containing the solution of bariumchloride; The effusion hydrogen sulfide feeds in the sodium hydroxide solution and absorbs, in order to avoid contaminate environment;
Step C: the solution that contains bariumchloride and small amount of hydrochloric acid of step B gained is mixed with zinc sulfate, and making the bariumchloride and the ratio of the molar content of the material of zinc sulfate is 1:1.2; Zinc sulfate and bariumchloride reaction generate permanent white and zinc chloride; Through filtering, obtain permanent white filter cake and the solution that contains zinc chloride;
Step D: after permanent white filter cake washing, pulverizing and drying, obtain barium sulfate product;
Step e: with the solution distillation that contains zinc chloride of step C gained is the zinc chloride supersaturated solution, and the zinc chloride crystallization is separated out, and obtains the zinc chloride product.
Embodiment 2:
Prepare the method for barium sulfate and co-produced zinc chloride with the bariumchloride waste residue, the said waste residue that uses the bariumchloride waste residue as hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained comprises following concrete steps:
Steps A: 500kg bariumchloride waste residue fully is dissolved in water, is mainly contained the solution of bariumchloride and barium sulphide, convert the wherein molar content of barium sulphide;
Step B: the steps A gained mainly contained bariumchloride and barium sulfide solution and mixed in hydrochloric acid; The molar content that makes barium sulphide is 1:2 with the ratio of the molar content of hydrogenchloride; Hydrochloric acid and barium sulphide reaction generate bariumchloride and hydrogen sulfide, after hydrogen sulfide is overflowed from solution, obtain containing the solution of bariumchloride; The effusion hydrogen sulfide feeds in the sodium hydroxide solution and absorbs, in order to avoid contaminate environment;
Step C: the solution that contains bariumchloride and small amount of hydrochloric acid of step B gained is mixed with zinc sulfate, and making the bariumchloride and the ratio of the molar content of the material of zinc sulfate is 1:1; Zinc sulfate and bariumchloride reaction generate permanent white and zinc chloride; Through filtering, obtain permanent white filter cake and the solution that contains zinc chloride;
Step D: after permanent white filter cake washing, pulverizing and drying, obtain barium sulfate product;
Step e: with the solution distillation that contains zinc chloride of step C gained is the zinc chloride supersaturated solution, and the zinc chloride crystallization is separated out, and obtains zinc chloride product
.
Embodiment 3:
Prepare the method for barium sulfate and co-produced zinc chloride with 500kg bariumchloride waste residue, the said waste residue that uses the bariumchloride waste residue as hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained comprises following concrete steps:
Steps A: the bariumchloride waste residue fully is dissolved in water, is mainly contained the solution of bariumchloride and barium sulphide, convert the wherein molar content of barium sulphide;
Step B: the steps A gained mainly contained bariumchloride and barium sulfide solution and mixed in hydrochloric acid; The molar content that makes barium sulphide is 1:2.4 with the ratio of the molar content of hydrogenchloride; Hydrochloric acid and barium sulphide reaction generate bariumchloride and hydrogen sulfide, after hydrogen sulfide is overflowed from solution, obtain containing the solution of bariumchloride; The effusion hydrogen sulfide feeds in the sodium hydroxide solution and absorbs, in order to avoid contaminate environment;
Step C: the solution that contains bariumchloride and small amount of hydrochloric acid of step B gained is mixed with zinc sulfate, and making the bariumchloride and the ratio of the molar content of the material of zinc sulfate is 1:0.8; Zinc sulfate and bariumchloride reaction generate permanent white and zinc chloride; Through filtering, obtain permanent white filter cake and the solution that contains zinc chloride;
Step D: after permanent white filter cake washing, pulverizing and drying, obtain barium sulfate product;
Step e: with the solution distillation that contains zinc chloride of step C gained is the zinc chloride supersaturated solution, and the zinc chloride crystallization is separated out, and obtains the zinc chloride product.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be regarded as belonging to the scope of patent protection that the present invention is confirmed by claims of being submitted to.
Claims (1)
1. prepare the method for barium sulfate and co-produced zinc chloride with the bariumchloride waste residue, it is characterized in that, said bariumchloride waste residue is the waste residue of hydrochloric acid and barium sulphide prepared in reaction thiocarbamide gained, comprises following concrete steps:
Steps A: the bariumchloride waste residue fully is dissolved in water, is mainly contained the solution of bariumchloride and barium sulphide, convert the wherein molar content of barium sulphide;
Step B: the steps A gained mainly contained bariumchloride and barium sulfide solution and mixed in hydrochloric acid; The molar content that makes barium sulphide is 1:1.6-2.4 with the ratio of the molar content of hydrogenchloride; Hydrochloric acid and barium sulphide reaction generate bariumchloride and hydrogen sulfide, after hydrogen sulfide is overflowed from solution, obtain containing the solution of bariumchloride; The effusion hydrogen sulfide feeds in the sodium hydroxide solution and absorbs, in order to avoid contaminate environment;
Step C: the solution that contains bariumchloride and small amount of hydrochloric acid of step B gained is mixed with zinc sulfate, and making the bariumchloride and the ratio of the molar content of the material of zinc sulfate is 1:0.8-1.2; Zinc sulfate and bariumchloride reaction generate permanent white and zinc chloride; Through filtering, obtain permanent white filter cake and the solution that contains zinc chloride;
Step D: after permanent white filter cake washing, pulverizing and drying, obtain barium sulfate product;
Step e: with the solution distillation that contains zinc chloride of step C gained is the zinc chloride supersaturated solution, and the zinc chloride crystallization is separated out, and obtains the zinc chloride product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106154537A CN102115137B (en) | 2010-12-31 | 2010-12-31 | Method for co-production of barium sulfate and zinc chloride from barium chloride waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106154537A CN102115137B (en) | 2010-12-31 | 2010-12-31 | Method for co-production of barium sulfate and zinc chloride from barium chloride waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102115137A CN102115137A (en) | 2011-07-06 |
| CN102115137B true CN102115137B (en) | 2012-08-01 |
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|---|---|---|---|
| CN2010106154537A Expired - Fee Related CN102115137B (en) | 2010-12-31 | 2010-12-31 | Method for co-production of barium sulfate and zinc chloride from barium chloride waste |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107743A (en) * | 1985-10-18 | 1986-10-15 | 太原工业大学 | Co-producing sulfuric acid barium and magnesian hydrochloric acid cyclic method |
| CN101643233A (en) * | 2009-06-08 | 2010-02-10 | 王嘉兴 | Method for preparing co-production sodium chloride of precipitated barium sulfate |
| CN101792167A (en) * | 2010-01-29 | 2010-08-04 | 张颖 | Method for preparing modified micro-barium sulfate |
-
2010
- 2010-12-31 CN CN2010106154537A patent/CN102115137B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107743A (en) * | 1985-10-18 | 1986-10-15 | 太原工业大学 | Co-producing sulfuric acid barium and magnesian hydrochloric acid cyclic method |
| CN101643233A (en) * | 2009-06-08 | 2010-02-10 | 王嘉兴 | Method for preparing co-production sodium chloride of precipitated barium sulfate |
| CN101792167A (en) * | 2010-01-29 | 2010-08-04 | 张颖 | Method for preparing modified micro-barium sulfate |
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|---|---|
| CN102115137A (en) | 2011-07-06 |
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