CN102115059A - Method for preparing manganese phosphate coproduced with ammonium sulfate and phosphoric acid by using manganese-containing waste liquor produced during production of hydroquinone - Google Patents

Abstract

The invention relates to the technical field of utilization of manganese-containing waste liquor produced during production of hydroquinone, in particular to a method for preparing manganese phosphate coproduced with ammonium sulfate and phosphoric acid by using manganese-containing waste liquor produced during production of hydroquinone. The method comprises the following steps of: performing suction filtration on the waste liquor produced by hydroquinone by using a suction filtration machine to obtain filtrate, distilling and filtering the filtrate, and performing deep processing on a filter cake to obtain a manganese phosphate product; and distilling the filtrate under a reduced pressure and performing further deep processing respectively to obtain an ammonium sulfate product and a phosphoric acid product. By adopting the method, waste liquor can be treated completely, environmental pollution caused by the waste liquor is relieved, valuable manganese phosphate, ammonium sulfate and phosphoric acid products can be obtained, remarkable social benefit and economic benefit are achieved, and process and production equipment are simple. The method is a relatively practical treatment and utilization method.

Description

A kind of with producing the method that the manganese waste liquid is made manganous phosphate coproduction of ammonia sulfate and phosphoric acid 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 coproduction of ammonia sulfate and phosphoric acid 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 coproduction of ammonia sulfate and phosphoric acid 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 coproduction of ammonia sulfate and phosphoric acid 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 coproduction of ammonia sulfate and phosphoric acid 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 phosphoric acid solution simultaneously and react, the mass ratio between filtrate and the phosphoric acid solution is 1: 0.46～0.86; Reaction generates the mixture I of manganous phosphate and ammonium sulfate and phosphoric acid;

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 the ammonium sulfate crystalline substance respectively;

Step G, remaining liquid in the underpressure distillation in the step F is obtained phosphoric acid product after shallow distillation.

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 ammonium sulfate and phosphoric acid 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, ammonium sulfate and phosphoric acid 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+2(NH ₄) ₃PO ₄＝＝＝＝＝Mn ₃(PO ₄) ₂+3(NH ₄) ₂SO ₄

3H ₂SO ₄+2(NH ₄) ₃PO ₄＝＝＝＝＝3(NH ₄) 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 coproduction of ammonia sulfate and phosphoric acid 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 phosphoric acid solution simultaneously and react, the mass ratio between filtrate and the phosphoric acid solution is 1: 0.46; Reaction generates the mixture I of manganous phosphate and ammonium sulfate and phosphoric acid;

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 74.76kg manganous phosphate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain 97.93kg ammonium sulfate crystalline substance respectively;

Step G, remaining liquid in the underpressure distillation in the step F is obtained the 6.88kg phosphoric acid product after shallow distillation.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganous phosphate coproduction of ammonia sulfate and phosphoric acid 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 phosphoric acid solution simultaneously and react, the mass ratio between filtrate and the phosphoric acid solution is 1: 0.66; Reaction generates the mixture I of manganous phosphate and ammonium sulfate and phosphoric acid;

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 107.26kg manganous phosphate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain 139.69kg ammonium sulfate crystalline substance respectively;

Step G, remaining liquid in the underpressure distillation in the step F is obtained the 9.87kg phosphoric acid product after shallow distillation.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganous phosphate coproduction of ammonia sulfate and phosphoric acid 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 phosphoric acid solution simultaneously and react, the mass ratio between filtrate and the phosphoric acid solution is 1: 0.86; Reaction generates the mixture I of manganous phosphate and ammonium sulfate and phosphoric acid;

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 139.77kg manganous phosphate product;

Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain 182.02kg ammonium sulfate crystalline substance respectively;

Step G, remaining liquid in the underpressure distillation in the step F is obtained the 12.87kg phosphoric acid product after shallow distillation.

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 coproduction of ammonia sulfate and phosphoric acid 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 phosphoric acid solution simultaneously and react, the mass ratio between filtrate and the phosphoric acid solution is 1: 0.46～0.86; Reaction generates the mixture I of manganous phosphate and ammonium sulfate and phosphoric acid;

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 the ammonium sulfate crystalline substance respectively;

Step G, remaining liquid in the underpressure distillation in the step F is obtained phosphoric acid product after shallow distillation.