CN102115065A - Method for producing manganese phosphate, zinc sulfate and ammonium phosphate by using manganese-containing waste liquid from production of hydroquinone - Google Patents

Abstract

The invention relates to the technical field of the utilization of manganese-containing waste liquid from the production of hydroquinone, in particular to a method for producing manganese phosphate, zinc sulfate and ammonium phosphate by using the manganese-containing waste liquid from the production of hydroquinone, which mainly comprises: performing suction-filtration on the waste liquid from the production of hydroquinone by using a vacuum filter, distilling and filtering the obtain filtrate, and deeply processing the filter cake to obtain a manganese phosphate product; and distilling the filtrate under reduced pressure, and further deeply processing respectively to obtain zinc sulfate and ammonium phosphate products. In the invention, waste liquid can be removed completely, so the pollution of waste residue to the environment is reduced; valuable manganese phosphate, zinc sulfate and ammonium phosphate products are produced; and thus, obvious social and economic benefit is created. The process and production equipment are simple, and the method is a practical treatment and utilization method.

Description

A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid zinc 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 zinc 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 zinc 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 zinc 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 zinc 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 zinc phosphate solution simultaneously and react, the mass ratio between filtrate and the zinc phosphate solution is 1: 0.65～1.05; Reaction generates the mixture I of manganous phosphate and zinc sulfate 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 zinc sulfate crystal and ammonium phosphate crystal respectively;

Step G, with step F gained zinc sulfate crystal through wash drying, crushing packing becomes the zinc sulfate 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 zinc sulfate 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, zinc sulfate 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+Zn ₃(PO ₄) ₂＝＝＝＝＝Mn ₃(PO ₄) ₂+3ZnSO ₄

3(NH ₄) ₂SO ₄+Zn ₃(PO ₄) ₂＝＝＝＝＝2(NH ₄) ₃PO ₄+3ZnSO ₄

3H ₂SO ₄+Zn ₃(PO ₄) ₂＝＝＝＝＝3ZnSO 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 zinc 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 zinc phosphate solution simultaneously and react, the mass ratio between filtrate and the zinc phosphate solution is 1: 0.65; Reaction generates the mixture I of manganous phosphate and zinc sulfate 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 72.25kg manganous phosphate product;

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

Step G, with step F gained zinc sulfate crystal through wash drying, crushing packing becomes 127.36kg zinc sulfate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 6.67kg 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 zinc 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 zinc phosphate solution simultaneously and react, the mass ratio between filtrate and the zinc phosphate solution is 1: 0.85; Reaction generates the mixture I of manganous phosphate and zinc sulfate 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 94.48kg manganous phosphate product;

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

Step G, with step F gained zinc sulfate crystal through wash drying, crushing packing becomes 166.82kg zinc sulfate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 8.72kg 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 zinc 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 zinc phosphate solution simultaneously and react, the mass ratio between filtrate and the zinc phosphate solution is 1: 1.05; Reaction generates the mixture I of manganous phosphate and zinc sulfate 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 116.89kg manganous phosphate product;

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

Step G, with step F gained zinc sulfate crystal through wash drying, crushing packing becomes 205.94kg zinc sulfate product;

Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 10.77kg 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 zinc 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 zinc phosphate solution simultaneously and react, the mass ratio between filtrate and the zinc phosphate solution is 1: 0.65～1.05; Reaction generates the mixture I of manganous phosphate and zinc sulfate 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 zinc sulfate crystal and ammonium phosphate crystal respectively;

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

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