CN102115249A - Method for preparing manganese hydroxide, as well as cobaltous sulfate and aqueous ammonia with manganese-containing waste liquor obtained in production of hydroquinone - Google Patents

Abstract

The invention belongs to the technical field of utilization of manganese-containing waste liquor obtained in the production of hydroquinone and particularly relates to a method for preparing manganese hydroxide, as well as cobaltous sulfate and aqueous ammonia with the manganese-containing waste liquor obtained in the production of hydroquinone. The method mainly comprises the following steps: the manganese-containing waste liquor obtained in the production of hydroquinone is filter through a filter to obtain a filtrate; the filtrate is distilled and filtered to obtain a filter cake; the filter cake is deeply processed to obtain manganese hydroxide; and then the filtrate is distilled under reduced pressure and then further deeply processed to obtain cobaltous sulfate and aqueous ammonia. The waste liquor can be fully utilized, so that environmental pollutions are reduced; valuable manganese hydroxide, as well as cobaltous sulfate and aqueous ammonia products can be prepared; and the method not only has remarkable social and economical benefits, but also is simple in process and production equipment, and is classified as a more practical treatment and utilization method.

Description

A kind of with producing the method that the manganese waste liquid is made manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 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.But do not have a kind of at present with producing the relevant report that the manganese waste liquid is made the method for manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 cobaltous hydroxide solution simultaneously and react, the mass ratio between described filtrate and the cobaltous hydroxide solution is 1: 0.42～0.82; Reaction generates the mixture I of manganous hydroxide and rose vitriol and ammoniacal liquor;

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 manganous hydroxide product;

Step F, the clarifying filtrate of sulphur of gained among the step D is packaged to be the ammoniacal liquor product through underpressure distillation, condensation;

Step G, with the remaining liquid of underpressure distillation in the step e distill, cooling, crystallization, packing become the rose vitriol crystal 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 manganous hydroxide product; Further respectively deep processing obtained rose vitriol and ammoniacal liquor 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 manganous hydroxide, rose vitriol and ammoniacal liquor 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+Co(OH) ₂＝＝＝＝＝Mn(OH) ₂+CoSO ₄

(NH ₄) ₂SO ₄+Co(OH) ₂＝＝＝＝＝2NH ₄OH+CoSO ₄

H ₂SO ₄+Co(OH) ₂＝＝＝＝＝CoSO ₄+H ₂O

Concrete embodiment

Embodiment 1

A kind of with producing the method that the manganese waste liquid is made manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 cobaltous hydroxide solution simultaneously and react, the mass ratio between described filtrate and the cobaltous hydroxide solution is 1: 0.42; Reaction generates the mixture I of manganous hydroxide and rose vitriol and ammoniacal liquor;

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 48.38kg manganous hydroxide product;

Step F, the clarifying filtrate of sulphur of gained among the step D is packaged to be 4.73kg ammoniacal liquor product through underpressure distillation, condensation;

Step G, with the remaining liquid of underpressure distillation in the step e distill, cooling, crystallization, packing become 108.66kg rose vitriol crystal product.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 cobaltous hydroxide solution simultaneously and react, the mass ratio between described filtrate and the cobaltous hydroxide solution is 1: 0.62; Reaction generates the mixture I of manganous hydroxide and rose vitriol and ammoniacal liquor;

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 71.42kg manganous hydroxide product;

Step F, the clarifying filtrate of sulphur of gained among the step D is packaged to be 6.98kg ammoniacal liquor product through underpressure distillation, condensation;

Step G, with the remaining liquid of underpressure distillation in the step e distill, cooling, crystallization, packing become 144.99kg rose vitriol crystal product.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 cobaltous hydroxide solution simultaneously and react, the mass ratio between described filtrate and the cobaltous hydroxide solution is 1: 0.82; Reaction generates the mixture I of manganous hydroxide and rose vitriol and ammoniacal liquor;

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 94.46kg manganous hydroxide product;

Step F, the clarifying filtrate of sulphur of gained among the step D is packaged to be 9.23kg ammoniacal liquor product through underpressure distillation, condensation;

Step G, with the remaining liquid of underpressure distillation in the step e distill, cooling, crystallization, packing become 212.15kg rose vitriol crystal 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 manganous hydroxide co-producing sulfuric acid cobalt and ammoniacal liquor 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 cobaltous hydroxide solution simultaneously and react, the mass ratio between described filtrate and the cobaltous hydroxide solution is 1: 0.42～0.82; Reaction generates the mixture I of manganous hydroxide and rose vitriol and ammoniacal liquor;

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 manganous hydroxide product;

Step F, the clarifying filtrate of sulphur of gained among the step D is packaged to be the ammoniacal liquor product through underpressure distillation, condensation;

Step G, with the remaining liquid of underpressure distillation in the step e distill, cooling, crystallization, packing become the rose vitriol crystal product.