CN102115132A - Method for producing series chlorides and sulfuric acid by using manganese-containing waste liquid from production of hydroquinone - Google Patents

Abstract

The invention relates to the technical field of utilization of manganese-containing waste liquid from the production of hydroquinone, in particular to a method for producing series chlorides and sulfuric acid 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 the vacuum filter, reacting obtained filter cake with hydrochloric acid, filtering again, distilling filtrate under reduced pressure, cooling by a stage cooler to obtain series chlorides respectively, and deeply processing the series chlorides respectively to obtain corresponding products. In the invention, waste liquid can be removed completely, so the pollution of waste residue to the environment is reduced; valuable series chlorides and sulfuric acid 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 ofly make serial muriate and vitriolic method with producing the manganese waste liquid 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 ofly make serial muriate and vitriolic method with producing the manganese waste liquid 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 sulphide salt, and high-purity manganese sulfide etc.High-purity manganese sulfide 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.Present high-purity manganese sulfide mainly is as soft magnet oxygen magneticsubstance, is that raw material is produced with electrolytic manganese or manganous sulfate, hydrogen sulfide ammonium etc. generally.But do not have a kind of at present with producing the relevant report that the manganese waste liquid is made serial muriate and vitriolic method that contains that Resorcinol produced yet.

Summary of the invention

The invention provides and a kind ofly make serial muriate and vitriolic method with producing the manganese waste liquid that contains that Resorcinol produced, this method not only technology is simple, 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 ofly make serial muriate and vitriolic method, comprise being prepared as follows step with producing the manganese waste liquid that contains that Resorcinol produced:

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 residue filtrate in the steps A is used to develop other products;

Step C, suction filtration gained filter cake in the steps A is transferred in the reactor, drops into hydrochloric acid simultaneously and react, the mass ratio between filter cake and the hydrochloric acid is 1: 0.34～0.74; Reaction generates serial muriate and vitriolic mixture I;

Step D, the mixture I of gained among the step C is filtered with strainer;

Step e, the clarifying filtrate of sulphur of gained among the step D is carried out underpressure distillation, gradient cooling, crystallization through the underpressure distillation device, obtain serial muriate crystal respectively;

Step G, with step e gained series muriate respectively through wash drying, crushing packing becomes different chloride products;

Step H, remaining liquid in the step e gained underpressure distillation device is obtained sulfuric acid product through shallow distillation.

The present invention carries out suction filtration with the waste liquid that Resorcinol produced with the suction filtration machine earlier, obtain filtering and reacting with hydrochloric acid, after after filtering once more filtrate being carried out underpressure distillation, cool off with the gradient cooling device, obtain serial muriate respectively, serial muriate deep processing respectively obtains corresponding product; The present invention can as clean as a pennyly gulp down waste liquid, alleviates the pollution of waste liquid to environment; Can make valuable serial muriate and sulfuric 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:

CaSO ₄+2HCl＝＝＝＝＝CaCl ₂+H ₂SO ₄

MgSO ₄+2HCl＝＝＝＝＝MgCl ₂+H ₂SO ₄

Na ₂SO ₄+2HCl＝＝＝＝＝MgCl ₂+H ₂SO ₄

ZnSO ₄+2HCl＝＝＝＝＝ZnCl ₂+H ₂SO ₄

Al ₂(SO ₄) ₃+6HCl＝＝＝＝＝2AlCl ₃+3H ₂SO ₄

CdSO ₄+2HCl＝＝＝＝＝CdCl ₂+H ₂SO ₄

NiSO ₄+2HCl＝＝＝＝＝NiCl+H ₂SO ₄

Concrete embodiment

Embodiment 1

A kind ofly make serial muriate and vitriolic method, comprise being prepared as follows step with producing the manganese waste liquid that contains that Resorcinol produced:

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 C, suction filtration gained filter cake in the steps A is transferred in the reactor, drops into hydrochloric acid simultaneously and react, the mass ratio between filter cake and the hydrochloric acid is 1: 0.34; Reaction generates serial muriate and vitriolic mixture I;

Step D, the mixture I of gained among the step C is filtered with strainer;

Step e, the clarifying filtrate of sulphur of gained among the step D is carried out underpressure distillation, gradient cooling, crystallization through the underpressure distillation device, obtain serial muriate crystal respectively;

Step G, with step e gained series muriate respectively through wash drying, crushing packing becomes products such as calcium chloride, magnesium chloride, sodium-chlor, aluminum chloride, zinc chloride, Cadmium chloride fine powder, nickelous chloride.

Step H, remaining liquid in the step e gained underpressure distillation device is obtained sulfuric acid product through shallow distillation.

Embodiment 2

A kind ofly make serial muriate and vitriolic method, comprise being prepared as follows step with producing the manganese waste liquid that contains that Resorcinol produced:

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 C, suction filtration gained filter cake in the steps A is transferred in the reactor, drops into hydrochloric acid simultaneously and react, the mass ratio between filter cake and the hydrochloric acid is 1: 0.54; Reaction generates serial muriate and vitriolic mixture I;

Step D, the mixture I of gained among the step C is filtered with strainer;

Step e, the clarifying filtrate of sulphur of gained among the step D is carried out underpressure distillation, gradient cooling, crystallization through the underpressure distillation device, obtain serial muriate crystal respectively;

Step G, with step e gained series muriate respectively through wash drying, crushing packing becomes products such as calcium chloride, magnesium chloride, sodium-chlor, aluminum chloride, zinc chloride, Cadmium chloride fine powder, nickelous chloride.

Step H, remaining liquid in the step e gained underpressure distillation device is obtained sulfuric acid product through shallow distillation.

Embodiment 3

A kind ofly make serial muriate and vitriolic method, comprise being prepared as follows step with producing the manganese waste liquid that contains that Resorcinol produced:

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 C, suction filtration gained filter cake in the steps A is transferred in the reactor, drops into hydrochloric acid simultaneously and react, the mass ratio between filter cake and the hydrochloric acid is 1: 0.74; Reaction generates serial muriate and vitriolic mixture I;

Step D, the mixture I of gained among the step C is filtered with strainer;

Step e, the clarifying filtrate of sulphur of gained among the step D is carried out underpressure distillation, gradient cooling, crystallization through the underpressure distillation device, obtain serial muriate crystal respectively;

Step G, with step e gained series muriate respectively through wash drying, crushing packing becomes products such as calcium chloride, magnesium chloride, sodium-chlor, aluminum chloride, zinc chloride, Cadmium chloride fine powder, nickelous chloride.

Step H, remaining liquid in the step e gained underpressure distillation device is obtained sulfuric acid product through 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. make serial muriate and vitriolic method with producing the manganese waste liquid that contains that Resorcinol produced for one kind, it is characterized in that, 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 residue filtrate in the steps A is used to develop other products;

Step C, suction filtration gained filter cake in the steps A is transferred in the reactor, drops into hydrochloric acid simultaneously and react, the mass ratio between filter cake and the hydrochloric acid is 1: 0.34～0.74; Reaction generates serial muriate and vitriolic mixture I;

Step D, the mixture I of gained among the step C is filtered with strainer;

Step e, the clarifying filtrate of sulphur of gained among the step D is carried out underpressure distillation, gradient cooling, crystallization through the underpressure distillation device, obtain serial muriate crystal respectively;

Step G, with step e gained series muriate respectively through wash drying, crushing packing becomes different chloride products;

Step H, remaining liquid in the step e gained underpressure distillation device is obtained sulfuric acid product through shallow distillation.