CN102115177A - Method for co-production of manganese carbonate, cobalt sulfate and ammonium carbonate from manganese-containing waste liquid generated during hydroquinone production - Google Patents

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 carbonate, cobalt sulfate and ammonium carbonate from manganese-containing waste liquid generated during the hydroquinone production. The method mainly comprises the following steps: 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 carbonate product; and the filtrate is further distilled under a reduced pressure and then deep-processed to obtain a cobalt sulfate product and an ammonium carbonate 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 carbonate, cobalt sulfate and ammonium carbonate. 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

A kind of with producing the method that the manganese waste liquid is made manganous carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate solution simultaneously and react, the mass ratio between filtrate and the cobaltous carbonate solution is 1: 0.59～0.99; Reaction generates the mixture I of manganous carbonate and rose vitriol and volatile salt;

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 manganese carbonate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain rose vitriol crystal and volatile salt crystal respectively;

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

Step H, with step F gained volatile salt crystal through wash drying, crushing packing becomes the volatile salt 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 manganese carbonate product; Further respectively deep processing obtained rose vitriol and volatile salt 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 carbonate, rose vitriol and volatile salt 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+CoCO ₃＝＝＝＝＝MnCO ₃+CoSO ₄

(NH ₄) ₂SO ₄+CoCO ₃＝＝＝＝＝(NH ₄) ₂CO ₃+CoSO ₄

H ₂SO ₄+CoCO ₃＝＝＝＝＝CoSO ₄+H ₂O

Concrete embodiment

Embodiment 1

A kind of with producing the method that the manganese waste liquid is made manganous carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate solution simultaneously and react, the mass ratio between filtrate and the cobaltous carbonate solution is 1: 0.59; Reaction generates the mixture I of manganous carbonate and rose vitriol and volatile salt;

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 68.68kg manganese carbonate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain rose vitriol crystal and volatile salt crystal respectively;

Step G, with step F gained rose vitriol crystal through wash drying, crushing packing becomes 119.67kg rose vitriol product;

Step H, with step F gained volatile salt crystal through wash drying, crushing packing becomes 5.84kg volatile salt product.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganous carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate solution simultaneously and react, the mass ratio between filtrate and the cobaltous carbonate solution is 1: 0.79; Reaction generates the mixture I of manganous carbonate and rose vitriol and volatile salt;

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 91.96kg manganese carbonate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain rose vitriol crystal and volatile salt crystal respectively;

Step G, with step F gained rose vitriol crystal through wash drying, crushing packing becomes 160.24kg rose vitriol product;

Step H, with step F gained volatile salt crystal through wash drying, crushing packing becomes 7.82kg volatile salt product.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganous carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate solution simultaneously and react, the mass ratio between filtrate and the cobaltous carbonate solution is 1: 0.99; Reaction generates the mixture I of manganous carbonate and rose vitriol and volatile salt;

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 115.24kg manganese carbonate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain rose vitriol crystal and volatile salt crystal respectively;

Step G, with step F gained rose vitriol crystal through wash drying, crushing packing becomes 200.81kg rose vitriol product;

Step H, with step F gained volatile salt crystal through wash drying, crushing packing becomes 9.80kg volatile salt 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 carbonate co-producing sulfuric acid cobalt and volatile salt 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 carbonate solution simultaneously and react, the mass ratio between filtrate and the cobaltous carbonate solution is 1: 0.59～0.99; Reaction generates the mixture I of manganous carbonate and rose vitriol and volatile salt;

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 manganese carbonate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain rose vitriol crystal and volatile salt crystal respectively;

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

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