CN102115244A - Method for preparing co-product of manganese sulfide and sodium sulfate as well as ammonium sulfide by manganese-containing waste liquid obtained by producing hydroquinone - Google Patents

Abstract

The invention relates to the technical field of the utilization of manganese-containing waste liquid obtained by producing hydroquinone, in particular to a method for preparing co-product of manganese sulfide and sodium sulfate as well as ammonium sulfide by manganese-containing waste liquid obtained by producing hydroquinone. The method mainly comprises the steps of: firstly, leaching the manganese-containing waste liquid obtained by producing hydroquinone by a leaching machine, and obtaining filtrate for distilling and filtering; carrying out deep processing on a filter cake, and obtaining the manganese sulfide product; and then carrying out reduced pressure distillation on the filtrate, respectively carrying out further deep processing, and obtaining the sodium sulfate and the ammonium sulfide. The method leads the waste liquid to be cleanly removed so as to reduce the pollution of the waste liquid for the environment, and can be used for preparing the valuable manganese sulfide, sodium sulfate and ammonium sulfide, thus not only being remarkable in social benefit and economic benefit, but also being simple in technique and production equipment; therefore, the invention is a more practical processing and utilizing method.

Description

A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sodium sulfate and ammonium sulfide that contains that Resorcinol produced

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 sodium sulfate 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 sodium sulfate 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 sodium sulfate 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 sodium sulfate 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 sodium sulfide solution simultaneously and react, the mass ratio between filtrate and the sodium sulfide solution is 1: 0.32～0.72; Reaction generates the mixture I of manganese sulfide and sodium sulfate 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 sodium sulfate crystal and ammonium sulfide crystal respectively;

Step G, with step F gained sodium sulfate crystal through wash drying, crushing packing becomes the sodium sulfate 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 sodium sulfate 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, sodium sulfate 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+Na ₂S＝＝＝＝＝MnS+Na ₂SO ₄

(NH ₄) ₂SO ₄+Na ₂S＝＝＝＝＝(NH ₄) ₂S+Na ₂SO ₄

H ₂SO ₄+Na ₂S＝＝＝＝＝Na ₂SO 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 sodium sulfate 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 sodium sulfide solution simultaneously and react, the mass ratio between filtrate and the sodium sulfide solution is 1: 0.32; Reaction generates the mixture I of manganese sulfide and sodium sulfate 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 42.81kg manganese sulfide product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain sodium sulfate crystal and ammonium sulfide crystal respectively;

Step G, with step F gained sodium sulfate crystal through wash drying, crushing packing becomes 90.23kg sodium sulfate product;

Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 4.19kg ammonium sulfide product.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sodium sulfate 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 sodium sulfide solution simultaneously and react, the mass ratio between filtrate and the sodium sulfide solution is 1: 0.52; Reaction generates the mixture I of manganese sulfide and sodium sulfate 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 69.56kg manganese sulfide product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain sodium sulfate crystal and ammonium sulfide crystal respectively;

Step G, with step F gained sodium sulfate crystal through wash drying, crushing packing becomes 146.64kg sodium sulfate product;

Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 6.80kg ammonium sulfide product.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganese sulfide co-producing sodium sulfate 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 sodium sulfide solution simultaneously and react, the mass ratio between filtrate and the sodium sulfide solution is 1: 0.72; Reaction generates the mixture I of manganese sulfide and sodium sulfate 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 96.32kg manganese sulfide product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain sodium sulfate crystal and ammonium sulfide crystal respectively;

Step G, with step F gained sodium sulfate crystal through wash drying, crushing packing becomes 202.04kg sodium sulfate product;

Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes 9.42kg 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 sodium sulfate 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 sodium sulfide solution simultaneously and react, the mass ratio between filtrate and the sodium sulfide solution is 1: 0.32～0.72; Reaction generates the mixture I of manganese sulfide and sodium sulfate 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 sodium sulfate crystal and ammonium sulfide crystal respectively;

Step G, with step F gained sodium sulfate crystal through wash drying, crushing packing becomes the sodium sulfate product;

Step H, with step F gained ammonium sulfide crystal through wash drying, crushing packing becomes the ammonium sulfide product.