CN102115200A - Method for producing manganese nitrate and co-producing potassium sulfate and ammonium nitrate by using manganese-containing waste liquid generated by producing hydroquinone - Google Patents

Abstract

The invention relates to the technical field of utilization of a manganese-containing waste liquid generated by producing hydroquinone, and in particular relates to a method for producing manganese nitrate and co-producing potassium sulfate and ammonium nitrate by using a manganese-containing waste liquid generated by producin hydroquinone. The method mainly comprises the following steps: leaching the waste liquid generated by producing the hydroquinone through a leaching machine so as to obtain a filtrate, and carrying out distillation filtration on the filtrate; carrying out deep processing on a filter cake so as to obtain the manganese nitrate product; and distilling the filtrate at reduced pressure, and then respectively carrying out further deep processing on the distilled filtrate so as to respectively obtain the potassium sulfate and ammonium nitrate products. By using the method, the waste liquid can be clearly treated, and the pollution of the waste liquid on environment is alleviated; and the method has the advantages of obvious social benefits and economic benefits as well as simple process and production equipment, thus the method is a practicable processing and utilizing method.

Description

A kind of with producing the method that the manganese waste liquid is made manganous nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 nitrate, and high pure nitric acid manganese etc.High pure nitric 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 pure nitric acid manganese mainly is as soft magnet oxygen magneticsubstance at present, is that raw material is produced with electrolytic manganese or manganous sulfate, nitric acid hydrogen ammonium 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 nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 potassium nitrate solution simultaneously and react, the mass ratio between filtrate and the potassium nitrate solution is 1: 1.14～1.54; Reaction generates the mixture I of manganous nitrate and vitriolate of tartar and ammonium nitrate;

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 nitrate product;

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

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

Step H, with step F gained ammonium nitrate crystal through wash drying, crushing packing becomes ammonium nitrate 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 nitrate product; Further respectively deep processing obtained vitriolate of tartar and ammonium nitrate 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 nitrate, vitriolate of tartar and ammonium nitrate 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+2KNO ₃＝＝＝＝＝Mn(NO ₃) ₂+K ₂SO ₄

(NH ₄) ₂SO ₄+2KNO ₃＝＝＝＝＝2NH ₄NO ₃+K ₂SO ₄

H ₂SO ₄+2KNO ₃＝＝＝＝＝K ₂SO ₄+H ₂O

Concrete embodiment

Embodiment 1

A kind of with producing the method that the manganese waste liquid is made manganous nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 potassium nitrate solution simultaneously and react, the mass ratio between filtrate and the potassium nitrate solution is 1: 1.14; Reaction generates the mixture I of manganous nitrate and vitriolate of tartar and ammonium nitrate;

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 120.75kg manganous nitrate product;

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

Step G, with step F gained potassium sulfate crystal through wash drying, crushing packing becomes the 170.42kg potassium product;

Step H, with step F gained ammonium nitrate crystal through wash drying, crushing packing becomes the 13.51kg ammonium nitrate product.

Embodiment 2

A kind of with producing the method that the manganese waste liquid is made manganous nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 potassium nitrate solution simultaneously and react, the mass ratio between filtrate and the potassium nitrate solution is 1: 1.34; Reaction generates the mixture I of manganous nitrate and vitriolate of tartar and ammonium nitrate;

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 141.93kg manganous nitrate product;

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

Step G, with step F gained potassium sulfate crystal through wash drying, crushing packing becomes the 200.32kg potassium product;

Step H, with step F gained ammonium nitrate crystal through wash drying, crushing packing becomes the 15.88kg ammonium nitrate product.

Embodiment 3

A kind of with producing the method that the manganese waste liquid is made manganous nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 potassium nitrate solution simultaneously and react, the mass ratio between filtrate and the potassium nitrate solution is 1: 1.54; Reaction generates the mixture I of manganous nitrate and vitriolate of tartar and ammonium nitrate;

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 163.11kg manganous nitrate product;

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

Step G, with step F gained potassium sulfate crystal through wash drying, crushing packing becomes the 229.28kg potassium product;

Step H, with step F gained ammonium nitrate crystal through wash drying, crushing packing becomes the 18.25kg ammonium nitrate 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 nitrate co-producing sulfuric acid potassium and ammonium nitrate 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 potassium nitrate solution simultaneously and react, the mass ratio between filtrate and the potassium nitrate solution is 1: 1.14～1.54; Reaction generates the mixture I of manganous nitrate and vitriolate of tartar and ammonium nitrate;

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 nitrate product;

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

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

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