CN102120601A - Method for preparing carbonate and strontium sulfate mixed product from manganese-containing waste liquid - Google Patents
Method for preparing carbonate and strontium sulfate mixed product from manganese-containing waste liquid Download PDFInfo
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- CN102120601A CN102120601A CN2010106158379A CN201010615837A CN102120601A CN 102120601 A CN102120601 A CN 102120601A CN 2010106158379 A CN2010106158379 A CN 2010106158379A CN 201010615837 A CN201010615837 A CN 201010615837A CN 102120601 A CN102120601 A CN 102120601A
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- carbonate
- sulfate
- strontium
- manganese
- waste liquid
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Abstract
The invention provides a method for preparing a carbonate and strontium sulfate mixed product from manganese-containing waste liquid, comprising the steps of: leaching manganese-containing waste liquid obtained from hydroquinone production to obtain clear filter liquor containing manganese sulfate, ammonium sulfate and sulfuric acid and a filter cake containing elementary-substance residues; making the filter cake containing elementary-substance residues react with an excessive amount of sulfuric acid to obtain a solution containing calcium sulfate, manganese sulfate, zinc sulfate, sodium sulfate, aluminum sulfate, cadmium sulfate and nickel sulfate; then making the obtained solution react with a strontium carbonate solution to obtain a strontium sulfate and carbonate mixed solution containing calcium carbonate, manganese carbonate, zinc carbonate, sodium carbonate, aluminum carbonate, cadmium carbonate and nickel carbonate; filtering to obtain a calcium carbonate filter cake and a filer liquor containing the carbonate and the strontium sulfate; washing, drying and crushing the calcium carbonate filter cake to obtain a calcium carbonate product; and carrying out reduced-pressure distillation and cooling crystallization on the filter liquor containing the carbonate and the strontium sulfate to obtain the carbonate and strontium sulfate mixed product.
Description
Technical field
The present invention relates to contain the technical field of the improvement and the utilization of manganese waste liquid, especially with containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained.
Background technology
Resorcinol is important organic intermediate, and China is in the development seventies in 20th century and dropped into suitability for industrialized production.Advantages such as at present domestic mainly taking used aniline-Manganse Dioxide explained hereafter Resorcinol, and this technology is compared with external phenol-hydrogen peroxide process, has the product purity height, and impurity is few.But its shortcoming is that the quantity discharged of waste liquid is big.Under the common state, one ton of Resorcinol of every production has 40 tons of Mn-bearing waste waters approximately.The chemical composition that production Resorcinol gained contains manganese waste liquid the inside is the content 11-12% of manganous sulfate, and ammonium sulfate content is 1.4-1.6%, and sulfuric acid content is 1.8-2.2%, simple substance element residue 5-6%, and the simple substance element is: calcium, magnesium, zinc, sodium, aluminium, cadmium and nickel.
At present domestic factories' utilizations contain the manganese waste liquid and produce crystal manganous sulfate or common carbonate, and high-purity manganese carbonate etc.High-purity manganese carbonate is an ideal high performance strong magneticsubstance, is the main raw material of the manganese-silicon that developed rapidly modern age, mangal, high-performance manganese dioxide product.High-purity manganese carbonate mainly is as soft magnet oxygen magneticsubstance at present, is that raw material is produced with electrolytic manganese or manganous sulfate, bicarbonate of ammonia etc. generally.The utilization of domestic existing factory contains the manganese waste liquid and produces the manganous sulfate crystal through a series of purification process, carries out replacement(metathesis)reaction with bicarbonate of ammonia again and produces high-purity manganese carbonate.
Yet, but be not used with other chemical ingredients in the Resorcinol, thereby, resource wasted.
Summary of the invention
The chemical composition that production Resorcinol gained contains the manganese waste liquid is the content 11-12% of manganous sulfate, and ammonium sulfate content is 1.4-1.6%, and sulfuric acid content is 1.8-2.2%, simple substance element residue 5-6%, and the simple substance element is: calcium, magnesium, zinc, sodium, aluminium, cadmium and nickel.For it is fully utilized, the invention provides with containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, this method is simple to operate, facility investment is few, will produce the Resorcinol gained and contain the comprehensive utilization of manganese waste liquid, turns waste into wealth, eliminated and contained of the pollution of manganese waste liquid, improved economic benefit of enterprises environment.
Technical scheme of the present invention is as follows: with containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, comprises following concrete steps:
Steps A: will produce the Resorcinol gained and contain the filter cake that obtains clarifying sulfur acid manganese, ammonium sulfate, vitriolic filtrate behind the manganese waste liquid suction filtration and contain the simple substance residue, described filtrate is developed other products separately;
Step B: described filter cake and the excess sulfuric acid reaction that contains the simple substance residue, obtain sulfur acid calcium, sal epsom, zinc sulfate, sodium sulfate, the solution of Tai-Ace S 150, Cadmium Sulphate and single nickel salt, then mix with Strontium carbonate powder solution again, and to make the ratio of molar content sum and the molar content of Strontium carbonate powder of the material of vitriol in the solution be 1: 0.8-1.2 obtains containing the carbonate of lime carbonate, magnesiumcarbonate, zinc carbonate, yellow soda ash, aluminium carbonate, cadmium carbonate and nickelous carbonate and the mixing solutions of Strontium Sulphate;
Step C: with the mixing solutions of step B gained carbonate and Strontium Sulphate after filtration, obtain the filtrate of calcium carbonate filter cake and carbonate containing and Strontium Sulphate;
Step D: calcium carbonate filter cake obtains calcium carbonate product through washing, dry and pulverizing;
Step e: contain mix carbonate and Strontium Sulphate filtrate through underpressure distillation, crystallisation by cooling, separate out carbonate crystal and Strontium Sulphate crystal, separate after filtration, obtain carbonate and Strontium Sulphate mixing prod.
Usefulness of the present invention contains the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, its chemical equation:
CaSO
4+SrCO
3=====CaCO
3+SrSO
4
MgSO
4+SrCO
3=====MgCO
3+SrSO
4
ZnSO
4+SrCO
3=====ZnCO
3+SrSO
4
Na
2SO
4+SrCO
3=====Na
2CO
3+SrSO
4
Al
2(SO
4)
3+3SrCO
3=====Al
2(CO
3)
3+3SrSO
4
CdSO
4+SrCO
3=====CdCO
3+SrSO
4
NiSO
4+SrCO
3=====NiCO
3+SrSO
4
Beneficial effect of the present invention is: usefulness of the present invention contains the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, this method is simple to operate, facility investment is few, to produce the Resorcinol gained and contain the comprehensive utilization of manganese waste liquid, turn waste into wealth, eliminated and contain of the pollution of manganese waste liquid, improved economic benefit of enterprises environment.
Embodiment
Embodiment 1:
With containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, comprises following concrete steps:
Steps A: 500kg is produced the Resorcinol gained contain the filter cake that obtains clarifying sulfur acid manganese, ammonium sulfate, vitriolic filtrate behind the manganese waste liquid suction filtration and contain the simple substance residue, described filtrate is developed other products separately;
Step B: described filter cake and the excess sulfuric acid reaction that contains the simple substance residue, obtain sulfur acid calcium, sal epsom, zinc sulfate, sodium sulfate, the solution of Tai-Ace S 150, Cadmium Sulphate and single nickel salt, then mix with Strontium carbonate powder solution again, and to make the ratio of molar content sum and the molar content of Strontium carbonate powder of the material of vitriol in the solution be 1: 0.8, obtains containing the carbonate of lime carbonate, magnesiumcarbonate, zinc carbonate, yellow soda ash, aluminium carbonate, cadmium carbonate and nickelous carbonate and the mixing solutions of Strontium Sulphate;
Step C: with the mixing solutions of step B gained carbonate and Strontium Sulphate after filtration, obtain the filtrate of calcium carbonate filter cake and carbonate containing and Strontium Sulphate;
Step D: calcium carbonate filter cake obtains calcium carbonate product through washing, dry and pulverizing;
Step e: contain mix carbonate and Strontium Sulphate filtrate through underpressure distillation, crystallisation by cooling, separate out carbonate crystal and Strontium Sulphate crystal, separate after filtration, obtain carbonate and Strontium Sulphate mixing prod.
Embodiment 2:
With containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, comprises following concrete steps:
Steps A: 500kg is produced the Resorcinol gained contain the filter cake that obtains clarifying sulfur acid manganese, ammonium sulfate, vitriolic filtrate behind the manganese waste liquid suction filtration and contain the simple substance residue, described filtrate is developed other products separately;
Step B: described filter cake and the excess sulfuric acid reaction that contains the simple substance residue, obtain sulfur acid calcium, sal epsom, zinc sulfate, sodium sulfate, the solution of Tai-Ace S 150, Cadmium Sulphate and single nickel salt, then mix with Strontium carbonate powder solution again, and to make the ratio of molar content sum and the molar content of Strontium carbonate powder of the material of vitriol in the solution be 1: 1, obtains containing the carbonate of lime carbonate, magnesiumcarbonate, zinc carbonate, yellow soda ash, aluminium carbonate, cadmium carbonate and nickelous carbonate and the mixing solutions of Strontium Sulphate;
Step C: with the mixing solutions of step B gained carbonate and Strontium Sulphate after filtration, obtain the filtrate of calcium carbonate filter cake and carbonate containing and Strontium Sulphate;
Step D: calcium carbonate filter cake obtains calcium carbonate product through washing, dry and pulverizing;
Step e: contain mix carbonate and Strontium Sulphate filtrate through underpressure distillation, crystallisation by cooling, separate out carbonate crystal and Strontium Sulphate crystal, separate after filtration, obtain carbonate and Strontium Sulphate mixing prod.
Embodiment 3:
With containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, comprises following concrete steps:
Steps A: 500kg is produced the Resorcinol gained contain the filter cake that obtains clarifying sulfur acid manganese, ammonium sulfate, vitriolic filtrate behind the manganese waste liquid suction filtration and contain the simple substance residue, described filtrate is developed other products separately;
Step B: described filter cake and the excess sulfuric acid reaction that contains the simple substance residue, obtain sulfur acid calcium, sal epsom, zinc sulfate, sodium sulfate, the solution of Tai-Ace S 150, Cadmium Sulphate and single nickel salt, then mix with Strontium carbonate powder solution again, and to make the ratio of molar content sum and the molar content of Strontium carbonate powder of the material of vitriol in the solution be 1: 1.2, obtains containing the carbonate of lime carbonate, magnesiumcarbonate, zinc carbonate, yellow soda ash, aluminium carbonate, cadmium carbonate and nickelous carbonate and the mixing solutions of Strontium Sulphate;
Step C: with the mixing solutions of step B gained carbonate and Strontium Sulphate after filtration, obtain the filtrate of calcium carbonate filter cake and carbonate containing and Strontium Sulphate;
Step D: calcium carbonate filter cake obtains calcium carbonate product through washing, dry and pulverizing;
Step e: contain mix carbonate and Strontium Sulphate filtrate through underpressure distillation, crystallisation by cooling, separate out carbonate crystal and Strontium Sulphate crystal, separate after filtration, obtain carbonate and Strontium Sulphate mixing prod.
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 product.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 (1)
1. with containing the method that the manganese waste liquid prepares carbonate and Strontium Sulphate mixing prod, it is characterized in that the described manganese waste liquid that contains contains the manganese waste liquid for producing the Resorcinol gained, comprises following concrete steps:
Steps A: will produce the Resorcinol gained and contain the filter cake that obtains clarifying sulfur acid manganese, ammonium sulfate, vitriolic filtrate behind the manganese waste liquid suction filtration and contain the simple substance residue, described filtrate is developed other products separately;
Step B: described filter cake and the excess sulfuric acid reaction that contains the simple substance residue, obtain sulfur acid calcium, sal epsom, zinc sulfate, sodium sulfate, the solution of Tai-Ace S 150, Cadmium Sulphate and single nickel salt, then mix with Strontium carbonate powder solution again, and to make the ratio of molar content sum and the molar content of Strontium carbonate powder of the material of vitriol in the solution be 1: 0.8-1.2 obtains containing the carbonate of lime carbonate, magnesiumcarbonate, zinc carbonate, yellow soda ash, aluminium carbonate, cadmium carbonate and nickelous carbonate and the mixing solutions of Strontium Sulphate;
Step C: with the mixing solutions of step B gained carbonate and Strontium Sulphate after filtration, obtain the filtrate of calcium carbonate filter cake and carbonate containing and Strontium Sulphate;
Step D: calcium carbonate filter cake obtains calcium carbonate product through washing, dry and pulverizing;
Step e: contain mix carbonate and Strontium Sulphate filtrate through underpressure distillation, crystallisation by cooling, separate out carbonate crystal and Strontium Sulphate crystal, separate after filtration, obtain carbonate and Strontium Sulphate mixing prod.
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CN2010106158379A CN102120601A (en) | 2010-12-30 | 2010-12-30 | Method for preparing carbonate and strontium sulfate mixed product from manganese-containing waste liquid |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103910372A (en) * | 2014-04-23 | 2014-07-09 | 河北辛集化工集团有限责任公司 | Novel method for preparing strontium carbonate for industrial use by using strontium salt residues |
-
2010
- 2010-12-30 CN CN2010106158379A patent/CN102120601A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103910372A (en) * | 2014-04-23 | 2014-07-09 | 河北辛集化工集团有限责任公司 | Novel method for preparing strontium carbonate for industrial use by using strontium salt residues |
CN103910372B (en) * | 2014-04-23 | 2016-01-13 | 河北辛集化工集团有限责任公司 | A kind of novel method adopting strontium salt residue to prepare industrial magnesium strontium |
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Application publication date: 20110713 |