CN102115058A - Method for co-production of manganese phosphate, lithium sulfate and ammonium phosphate from manganese-containing waste liquid generated during hydroquinone production - Google Patents

Abstract

The invention relates to the technical field of utilization of a manganese-containing waste liquid generated during hydroquinone production, in particular to a method for co-production of manganese phosphate, lithium sulfate and ammonium phosphate from a manganese-containing waste liquid generated during the production of hydroquinone. The method mainly comprises the following steps: the waste liquid generated during the production of hydroquinone is filtered through a filtration machine, the resulting filtrate is distilled and filtered, and the resulting filter cake is highly processed to obtain a manganese phosphate product; and the filtrate is further distilled under a reduced pressure and then the distillation products are separately and highly processed to obtain a lithium sulfate product and an ammonium phosphate product respectively. The method can not only completely handle the waste liquid to reduce the air pollution due to the waste liquid but also produce the valuable products of manganese phosphate, lithium sulfate and ammonium phosphate. The method is significant in social benefit and economic benefit, in simple in process, needs simple production equipment, and is a relatively practical method for handling and utilization.

Description

A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 phosphoric acid salt, and high-purity phosphoric acid manganese etc.High-purity phosphoric acid manganese is 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 phosphoric acid manganese mainly is as soft magnet oxygen magneticsubstance at present, is that raw material is produced with electrolytic manganese or manganous sulfate, ammonium hydrogen phosphate 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 phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.31～0.71; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;

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 phosphate product;

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

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

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes the ammonium phosphate 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 phosphate product; Further respectively deep processing obtained Lithium Sulphate and ammonium phosphate 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 phosphate, Lithium Sulphate and ammonium phosphate 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:

3MnSO ₄+2Li ₃PO ₄＝＝＝＝＝Mn ₃(PO ₄) ₂+3Li ₂SO ₄

3(NH ₄) ₂SO ₄+2Li ₃PO ₄＝＝＝＝＝2(NH ₄) ₃PO ₄+3Li ₂SO ₄

3H ₂SO ₄+2Li ₃PO ₄＝＝＝＝＝3Li ₂SO ₄+H ₃PO ₄

Concrete embodiment

Embodiment 1

A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.31; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;

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 56.90kg manganous phosphate product;

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

Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 68.37kg Lithium Sulphate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 5.25kg ammonium phosphate product.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.51; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;

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 93.61kg manganous phosphate product;

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

Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 112.46kg Lithium Sulphate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 8.64kg ammonium phosphate product.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.71; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;

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 130.32kg manganous phosphate product;

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

Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 156.57kg Lithium Sulphate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 12.03kg ammonium phosphate 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 phosphate co-producing sulfuric acid lithium and ammonium phosphate 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 Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.31～0.71; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;

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 phosphate product;

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

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

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