CN102115039A - Method for preparing sulfide and mixed product of sodium sulfide and ammonium sulfate by manganese-containing waste liquid - Google Patents

Abstract

The invention provides a method for preparing sulfide and mixed product of sodium sulfide and ammonium sulfate by manganese-containing waste liquid, which comprises the steps of: leaching the manganese-containing waste liquid obtained by producing hydroquinone, and obtaining clear filtrate containing manganese sulfate, the ammonium sulfate and sulfuric acid as well as a filter cake containing simple substance residue; leading the filter cake containing simple substance residue to have reaction with the excess sulfuric acid, and obtaining solution containing calcium sulfate, magnesium sulfate, zinc sulfate, sodium sulfate, aluminum sulfate, cadmium sulfate and nickel sulfate; then, mixing the obtained solution and ammonium sulfide solution for reaction, and obtaining mixed solution of the ammonium sulfate and the sulfide containing calcium sulfide, magnesium sulfide, zinc sulfide, sodium sulfide, aluminium sulfide, cadmium sulfide and nickel sulfide; filtering the obtained mixed solution, and obtaining a mixed sulfide filter cake of the calcium sulfide, the magnesium sulfide, the zinc sulfide, the aluminium sulfide, the cadmium sulfide and the nickel sulfide as well as filtrate containing the sodium sulfide and the ammonium sulfate; washing, drying and grinding the mixed sulfide filter cake, and obtaining the sulfide product; and finally, carrying out reduced pressure distillation and cooling crystallization on the filtrate containing the sodium sulfide and the ammonium sulfate, and obtaining the mixed product of the sodium sulfide and the ammonium sulfate.

Description

With containing the method that the manganese waste liquid prepares sulfide and sodium sulphite and sulfate of ammoniac mixing prod

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 sulfide and sodium sulphite and sulfate of ammoniac 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 sulfide and sodium sulphite and sulfate of ammoniac 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 sulfide and sodium sulphite and sulfate of ammoniac 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 the sulfuration ammonia solution again, and to make the ratio of molar content of molar content sum and sulfuration ammonia of the material of vitriol in the solution be 1: 0.8-1.2 obtains the mixed sulfides of Containing Sulfur calcium, magnesium sulfide, zinc sulphide, sodium sulphite, aluminium sulfide, Cadmium Sulfide and nickelous sulfide and the mixing solutions of sulfate of ammoniac;

Step C: with the mixing solutions of step B gained mixed sulfides and sulfate of ammoniac after filtration, obtain the filtrate of mixed sulfides filter cake and the Containing Sulfur sodium and the sulfate of ammoniac of sulfurated lime, magnesium sulfide, zinc sulphide, aluminium sulfide, Cadmium Sulfide and nickelous sulfide;

Step D: the mixed sulfides filter cake through washing, dry and pulverizing, is obtained the sulfide product;

Step e: the filtrate of Containing Sulfur sodium and sulfate of ammoniac through underpressure distillation, crystallisation by cooling, separate out and mix sodium sulfide crystal and sulfate of ammoniac crystal, separate after filtration, obtain sodium sulphite and sulfate of ammoniac mixing prod.

Usefulness of the present invention contains the method that the manganese waste liquid prepares sulfide and sodium sulphite and sulfate of ammoniac mixing prod, its chemical equation:

CaSO ₄+(NH ₄) ₂S＝＝＝＝＝CaS+(NH ₄) ₂SO ₄

MgSO ₄+(NH ₄) ₂S ₃＝＝＝＝＝MgS+(NH ₄) ₂SO ₄

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

ZnSO ₄+(NH ₄) ₂S＝＝＝＝＝ZnS+(NH ₄) ₂SO ₄

Al ₂(SO ₄) ₃+3(NH ₄) ₂S＝＝＝＝＝Al ₂S ₃+3(NH ₄) ₂SO ₄

CdSO ₄+(NH ₄) ₂S＝＝＝＝＝CdS+(NH ₄) ₂SO ₄

NiSO ₄+(NH ₄) ₂S＝＝＝＝＝NiS+(NH ₄) ₂SO ₄

Beneficial effect of the present invention is: usefulness of the present invention contains the method that the manganese waste liquid prepares sulfide and sodium sulphite and sulfate of ammoniac 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 sulfide and sodium sulphite and sulfate of ammoniac 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 the sulfuration ammonia solution again, and to make the ratio of molar content of molar content sum and sulfuration ammonia of the material of vitriol in the solution be 1: 0.8, obtains the sulfide of Containing Sulfur calcium, magnesium sulfide, zinc sulphide, sodium sulphite, aluminium sulfide, Cadmium Sulfide and nickelous sulfide and the mixing solutions of sulfate of ammoniac;

Step C: with the mixing solutions of step B gained mixed sulfides and sulfate of ammoniac after filtration, obtain the filtrate of mixed sulfides filter cake and the Containing Sulfur sodium and the sulfate of ammoniac of sulfurated lime, magnesium sulfide, zinc sulphide, aluminium sulfide, Cadmium Sulfide and nickelous sulfide;

Step D: the mixed sulfides filter cake through washing, dry and pulverizing, is obtained the sulfide product;

Step e: the filtrate of Containing Sulfur sodium and sulfate of ammoniac through underpressure distillation, crystallisation by cooling, separate out and mix sodium sulfide crystal and sulfate of ammoniac crystal, separate after filtration, obtain sodium sulphite and sulfate of ammoniac mixing prod.

Embodiment 2:

With containing the method that the manganese waste liquid prepares sulfide and sodium sulphite and sulfate of ammoniac 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 the sulfuration ammonia solution again, and to make the ratio of molar content of molar content sum and sulfuration ammonia of the material of vitriol in the solution be 1: 1, obtains the sulfide of Containing Sulfur calcium, magnesium sulfide, zinc sulphide, sodium sulphite, aluminium sulfide, Cadmium Sulfide and nickelous sulfide and the mixing solutions of sulfate of ammoniac;

Step C: with the mixing solutions of step B gained mixed sulfides and sulfate of ammoniac after filtration, obtain the filtrate of mixed sulfides filter cake and the Containing Sulfur sodium and the sulfate of ammoniac of sulfurated lime, magnesium sulfide, zinc sulphide, aluminium sulfide, Cadmium Sulfide and nickelous sulfide;

Step D: the mixed sulfides filter cake through washing, dry and pulverizing, is obtained the sulfide product;

Step e: the filtrate of Containing Sulfur sodium and sulfate of ammoniac through underpressure distillation, crystallisation by cooling, separate out and mix sodium sulfide crystal and sulfate of ammoniac crystal, separate after filtration, obtain sodium sulphite and sulfate of ammoniac mixing prod.

Embodiment 3:

With containing the method that the manganese waste liquid prepares sulfide and sodium sulphite and sulfate of ammoniac 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 the sulfuration ammonia solution again, and to make the ratio of molar content of molar content sum and sulfuration ammonia of the material of vitriol in the solution be 1: 1.2, obtains the sulfide of Containing Sulfur calcium, magnesium sulfide, zinc sulphide, sodium sulphite, aluminium sulfide, Cadmium Sulfide and nickelous sulfide and the mixing solutions of sulfate of ammoniac;

Step C: with the mixing solutions of step B gained mixed sulfides and sulfate of ammoniac after filtration, obtain the filtrate of mixed sulfides filter cake and the Containing Sulfur sodium and the sulfate of ammoniac of sulfurated lime, magnesium sulfide, zinc sulphide, aluminium sulfide, Cadmium Sulfide and nickelous sulfide;

Step D: the mixed sulfides filter cake through washing, dry and pulverizing, is obtained the sulfide product;

Step e: the filtrate of Containing Sulfur sodium and sulfate of ammoniac through underpressure distillation, crystallisation by cooling, separate out and mix sodium sulfide crystal and sulfate of ammoniac crystal, separate after filtration, obtain sodium sulphite and sulfate of ammoniac 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 sulfide and sodium sulphite and sulfate of ammoniac 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 the sulfuration ammonia solution again, and to make the ratio of molar content of molar content sum and sulfuration ammonia of the material of vitriol in the solution be 1: 0.8-1.2 obtains the mixed sulfides of Containing Sulfur calcium, magnesium sulfide, zinc sulphide, sodium sulphite, aluminium sulfide, Cadmium Sulfide and nickelous sulfide and the mixing solutions of sulfate of ammoniac;

Step C: with the mixing solutions of step B gained mixed sulfides and sulfate of ammoniac after filtration, obtain the filtrate of mixed sulfides filter cake and the Containing Sulfur sodium and the sulfate of ammoniac of sulfurated lime, magnesium sulfide, zinc sulphide, aluminium sulfide, Cadmium Sulfide and nickelous sulfide;

Step D: the mixed sulfides filter cake through washing, dry and pulverizing, is obtained the sulfide product;

Step e: the filtrate of Containing Sulfur sodium and sulfate of ammoniac through underpressure distillation, crystallisation by cooling, separate out and mix sodium sulfide crystal and sulfate of ammoniac crystal, separate after filtration, obtain sodium sulphite and sulfate of ammoniac mixing prod.