CN102115178A - Method for co-production of manganese sulfide, magnesium sulfate and ammonium sulfide from manganese-containing waste liquid generated during hydroquinone production - Google Patents
Method for co-production of manganese sulfide, magnesium sulfate and ammonium sulfide from manganese-containing waste liquid generated during hydroquinone production Download PDFInfo
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- CN102115178A CN102115178A CN201010615793XA CN201010615793A CN102115178A CN 102115178 A CN102115178 A CN 102115178A CN 201010615793X A CN201010615793X A CN 201010615793XA CN 201010615793 A CN201010615793 A CN 201010615793A CN 102115178 A CN102115178 A CN 102115178A
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Abstract
The invention relates to the technical field of utilization of manganese-containing waste liquid generated during the production of hydroquinone, in particular to a method for co-production of manganese sulfide, magnesium sulfate and ammonium sulfide from manganese-containing waste liquid generated during the hydroquinone production. The method mainly comprises the following steps: firstly the waste liquid generated during the hydroquinone production is filtered by a filtering machine to produce a filtrate, the filtrate is distilled and filtered to produce a filter cake and a filtrate, and the filter cake is deep-processed to obtain a manganese sulfide product; and the filtrate is further distilled under a reduced pressure and then deep-processed to obtain a magnesium sulfate product and an ammonium sulfide product respectively. The method can not only completely eliminate the waste liquid to reduce the environmental pollution due to the waste liquid but also provide the valuable products of manganese sulfide, magnesium sulfate and ammonium sulfide. The method not only has significant social and economic benefits but also simplifies the production process and the production equipment, and is a relatively practical method for treatment and utilization.
Description
Technical field
The present invention relates to produce the technical field that contains the manganese waste water utilization that Resorcinol produces, particularly a kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced.
Technical background
Resorcinol is important organic intermediate, and China has also dropped into suitability for industrialized production in the development seventies in 20th century.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 contains manganese waste liquid the inside of Resorcinol 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%.At present domestic factories' utilizations contain the manganese waste liquid and produce crystal manganous sulfate or common sulphide salt, and high-purity manganese sulfide etc.High-purity manganese sulfide 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.Present high-purity manganese sulfide mainly is as soft magnet oxygen magneticsubstance, is that raw material is produced with electrolytic manganese or manganous sulfate, hydrogen sulfide ammonium etc. generally.But do not have a kind of at present with producing the relevant report that the manganese waste liquid is made the method for manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced yet.
Summary of the invention
The invention provides that a kind of this method not only technology is simple with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, and can also make multiple value product when can effectively dispose waste liquid.
To achieve the above object, technical scheme of the present invention is:
A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the waste liquid that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into magnesium sulfide solution simultaneously and react, the mass ratio between filtrate and the magnesium sulfide solution is 1: 0.17～0.57; Reaction generates the mixture I of manganese sulfide and sal epsom and ammonium sulfide;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes the manganese sulfide product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain magnesium sulfate crystals and ammonium sulfide crystal respectively;
Step G, with step F gained magnesium sulfate crystals through wash drying, crushing packing becomes the sal epsom product;
Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes the ammonium sulfide product.
The present invention carries out suction filtration with the waste liquid that Resorcinol produced with the suction filtration machine earlier, obtains filtrate and carries out distillating filtering, and the filter cake deep processing obtains the manganese sulfide product; Further respectively deep processing obtained sal epsom and ammonium sulfide product respectively after filtrate was carried out underpressure distillation again; The present invention can as clean as a pennyly gulp down waste liquid, alleviates the pollution of waste liquid to environment; Can make valuable manganese sulfide, sal epsom and ammonium sulfide product again, not only have remarkable social benefit and economic benefit, and technology and production unit are simple, be a kind of relatively actual processing and utilize method.
Its chemical equation is:
MnSO
4+MgS＝＝＝＝＝MnS+MgSO
4
(NH
4)
2SO
4+MgS＝＝＝＝＝(NH
4)
2S+MgSO
4
H
2SO
4+MgS＝＝＝＝＝MgSO
4+H
2S
Concrete embodiment
Embodiment 1
A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into magnesium sulfide solution simultaneously and react, the mass ratio between filtrate and the magnesium sulfide solution is 1: 0.17; Reaction generates the mixture I of manganese sulfide and sal epsom and ammonium sulfide;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 31.49kg manganese sulfide product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain magnesium sulfate crystals and ammonium sulfide crystal respectively;
Step G, with step F gained magnesium sulfate crystals through wash drying, crushing packing becomes 56.25kg sal epsom product;
Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 3.08kg ammonium sulfide product.
Embodiment 2
A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into magnesium sulfide solution simultaneously and react, the mass ratio between filtrate and the magnesium sulfide solution is 1: 0.37; Reaction generates the mixture I of manganese sulfide and sal epsom and ammonium sulfide;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 68.53kg manganese sulfide product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain magnesium sulfate crystals and ammonium sulfide crystal respectively;
Step G, with step F gained magnesium sulfate crystals through wash drying, crushing packing becomes 122.4kg sal epsom product;
Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 6.70kg ammonium sulfide product.
Embodiment 3
A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into magnesium sulfide solution simultaneously and react, the mass ratio between filtrate and the magnesium sulfide solution is 1: 0.57; Reaction generates the mixture I of manganese sulfide and sal epsom and ammonium sulfide;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 105.57kg manganese sulfide product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain magnesium sulfate crystals and ammonium sulfide crystal respectively;
Step G, with step F gained magnesium sulfate crystals through wash drying, crushing packing becomes 188.57kg sal epsom product;
Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 10.32kg ammonium sulfide product.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (1)
1. one kind with producing the method that the manganese waste liquid is made manganese sulfide co-producing sulfuric acid magnesium and ammonium sulfide that contains that Resorcinol produced, and it is characterized in that, comprises being prepared as follows step:
Steps A, will produce the waste liquid that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into magnesium sulfide solution simultaneously and react, the mass ratio between filtrate and the magnesium sulfide solution is 1: 0.17～0.57; Reaction generates the mixture I of manganese sulfide and sal epsom and ammonium sulfide;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes the manganese sulfide product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain magnesium sulfate crystals and ammonium sulfide crystal respectively;
Step G, with step F gained magnesium sulfate crystals through wash drying, crushing packing becomes the sal epsom product;
Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes the ammonium sulfide product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010615793XA CN102115178A (en) | 2010-12-30 | 2010-12-30 | Method for co-production of manganese sulfide, magnesium sulfate and ammonium sulfide from manganese-containing waste liquid generated during hydroquinone production |
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| CN201010615793XA CN102115178A (en) | 2010-12-30 | 2010-12-30 | Method for co-production of manganese sulfide, magnesium sulfate and ammonium sulfide from manganese-containing waste liquid generated during hydroquinone production |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
-
2010
- 2010-12-30 CN CN201010615793XA patent/CN102115178A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
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Application publication date: 20110706 |