CN101880773B

CN101880773B - Manufacturing process for producing synthetic reducing agent by using waste slag of electrolytic manganese and application of synthetic reducing agent

Info

Publication number: CN101880773B
Application number: CN2010102000760A
Authority: CN
Inventors: 不公告发明人
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-06-13
Filing date: 2010-06-13
Publication date: 2013-01-30
Anticipated expiration: 2030-06-13
Also published as: CN101880773A

Abstract

The invention relates to a manufacturing process for producing a synthetic reducing agent by using waste slag of electrolytic manganese and application of the synthetic reducing agent. The manufacturing process comprises the following steps of: adding manganese slag into mixed liquid of sulfuric acid and lixivium and performing pressure filtration after a reaction is finished to obtain the waste slag and feed liquid 1; b, mixing solution of barium sulfide with ammonium sulfate in a mass ratio of barium sulfide to ammonium sulfate of 1:(0.4-0.5), and performing pressure filtration after reaction and removing precipitate to obtain feed liquid 2; and c, adding the feed liquid 1 into the feed liquid 2, performing pressure filtration to separate out the synthetic reducing agent after a reaction is finished and the lixivium, and then recycling the lixivium into the step a. The synthetic reducing agent has the advantages of efficiently reducing and utilizing manganese dioxide ore, using the waste slag of the electrolytic manganese as a main raw material, largely consuming the waste manganese, and largely reducing the waste slag and carbon dioxide generated in the manufacturing process for leaching and producing the electrolytic manganese by using manganese carbonate and reducing the manganese dioxide ore and by other reduction methods.

Description

Produce the manufacture craft of composite reductant and the application of this composite reductant with Electrolytic Manganese Metal Residues

Technical field:

The present invention relates to produce the manufacture craft of composite reductant and the application of this composite reductant with Electrolytic Manganese Metal Residues.

Background technology:

In the electrolytic manganese industry of China, the manganese triangle that Hunan, Guizhou, Chongqing have a common boundary is the concentrated area of taking as own duty, because exploitation is early fast with development, now manganese carbonate ore in the Xiushan Mountain, Song Tao is in short supply, add local government and repeat to impose resource compensation, go out the county and will receive tens yuan/tons, ore price accounts for 1/3 of electrolytic manganese cost.The mine in Chongqing, Song Tao, the western Hunan all exists disorderly adopts the phenomenon of disorderly digging, several ten thousand tons of reserves at present only surplus half, and resource recovery is very low, only has about 50%, adopting richness in the exploitation, to abandon poor phenomenon serious, ore grade drops to below 16% from 19%.But the manganese oxide ore in Guangxi is in plentiful supply, and large new reserves have 100,000,000 tons, and use enough decades.The production method of manganese metal has two kinds.A kind of is to adopt electrolytic process, and products obtained therefrom is electrolytic metal Mn; Another kind is take rich manganese ore and high silicon manganese-silicon alloy as raw material, produces with electric furnace desiliconization purifying method, and product claims manganese metal.

And along with the electrolytic metal manganese industry existing main production raw material---grade and the reserves of manganous carbonate mineral resources are more and more lower, the production cost of electrolytic metal Mn is more and more higher thereupon, the waste manganese slag amount of bringing aborning is larger, and is increasing to harm and the pressure of environment protection; Reserves and the grade of opposite Manganse Dioxide are very high, but the well solution because the reducing process of dioxide ore for manganese is failed always, so the Manganse Dioxide mineral resources is never utilized well.

Summary of the invention:

Thereby the objective of the invention is for the production cost that provides the application of producing the manufacture craft of composite reductant and this composite reductant with Electrolytic Manganese Metal Residues to reduce the manganese product such as electrolytic metal Mn, enhance productivity, reduce Carbon emission, reduce waste manganese slag discharging, improve the utilization ratio of resource;

The technical solution adopted for the present invention to solve the technical problems is: produce the manufacture craft of composite reductant with Electrolytic Manganese Metal Residues, its step is as follows:

A, the manganese slag is joined in the mixed solution of sulfuric acid and leach liquor, after abundant reaction, it is carried out press filtration and process and obtain waste residue and a feed liquid;

B, be 1 with barium sulfide solution and ammonium sulfate by the mass ratio of barium sulphide and ammonium sulfate: (0.4-0.5) mix, press filtration is removed throw out and is obtained No. two feed liquids (the described throw out that leaches is by-product precipitation barium sulfate crude product) after the reaction;

C, an above-mentioned feed liquid is added in No. two feed liquids, behind the question response composite reductant and leach liquor is isolated in its press filtration, more described leach liquor circulating is used among the step a.

In above-mentioned steps a, the mass ratio of described manganese slag, sulfuric acid and leach liquor is: 1: (0.1-0.15): 4.

In above-mentioned steps b, described barium sulfide solution is the solution of removing gained behind the cinder after the barium sulphide water dissolves fully with pressure filter.

When the manganese products such as manufacturing electrolytic metal Mn, it mainly is to become first the output manganese sulfate solution, the invention allows for thus the method that this composite reductant prepares manganese sulfate solution of using:

A, mix with sulfuric acid, anolyte with Manganse Dioxide oven dry, after pulverizing;

B, in above-mentioned mixing solutions, add composite reductant, behind the question response, will can obtain pure manganese sulfate solution after its deironing, neutralization, removing heavy metals, the press filtration.

The present invention utilizes the leaching waste residue in the electrolytic metal Mn production process to be raw material, produces the novel process of efficient composite reductant; This composite reductant can reduce efficiently, utilize dioxide ore for manganese, and utilize the manganese slag as main raw material, a large amount of waste manganese slags that consume, a large amount of reduce with manganese carbonate ore and leach the waste residue that produces in production electrolytic metal Mn manufacturing processedes and carbonic acid gas with other method of reducing manganese dioxide reduction ore deposits (one ton of electrolytic metal Mn of every production can reduce about 1.4 tons of Carbon emissions, whole nation electrolytic metal Mn output is more than 2,000,000 tons/year, continue to use existing production technique, to discharge 2,800,000 tons more than the carbonic acid gas every year in atmosphere), meet macroscopical requirement of national recycling economy and low-carbon (LC); And substantially anhydrous solube metallic in the waste residue after technique is extracted, utilized; Most of reclaim (in the manganese slag) of ammonia nitrogen through further processing, can reach relevant national standard.Utilize simultaneously the manganese product of the production of this composite reductant manganese dioxide reduction significantly to improve production efficiency and reducing production costs on the basis of original production technique not changing.

Embodiment:

Produce the manufacture craft of composite reductant with Electrolytic Manganese Metal Residues, its step is as follows:

A, the manganese slag is joined in the mixed solution of sulfuric acid and leach liquor, its mass ratio is 1: (0.1-0.15): 4, and after abundant reaction, it is carried out press filtration and process and obtain waste residue (being mainly lime powder) and a feed liquid;

B, be 1 with barium sulfide solution and ammonium sulfate by the mass ratio of barium sulphide and ammonium sulfate: (0.4-0.5) mix, press filtration is removed throw out and is obtained No. two feed liquids (described barium sulfide solution is the solution of removing gained behind the cinder after the barium sulphide water dissolves fully with pressure filter) after the reaction;

In above-mentioned preparation process, except obtaining composite reductant, also can be directly or carry out a little after some simple processing also can the byproduct that obtains other, as: in step b, we also can be precipitated barium sulfate when obtaining No. two feed liquids, this barium sulfate namely is contained in the above-mentioned throw out, as long as will be precipitated the barium sulfate crude product after its washing, purification, the dehydration, and then then can obtain the process white of content more than 97% after washing, purify, dewatering.

The method of producing electrolytic metal Mn with this composite reductant manganese dioxide reduction is: add a certain amount of sulfuric acid in the waste electrolyte (being anolyte) that the production electrolytic metal Mn generates, (for example it contains Mn to add the dioxide ore for manganese of drying, pulverizing and the leach liquor of reductive agent reaction generation certain content ²⁺: 36-42g/L, (NH ₄) ₂SO ₄: 100-120g/L), through deironing, removing heavy metals, neutralization, press filtration, make preliminary electrolytic solution, again behind deep purifying qualified electrolytic solution, add additive and carry out electrolysis, again through passivation, washing, dry, peel off, pack and to get the electrolytic metal Mn finished product.

The method of producing other manganese products with this composite reductant manganese dioxide reduction ore deposit is: with reductive agent, dioxide ore for manganese, sulfuric acid adds the aqueous solution (or specific solution with order by a certain percentage, as produce manganous carbonate can be with the aqueous solution of liquid containing ammonium sulfate) in the abundant certain density manganese sulfate solution of system after the reaction, again through deironing, removing heavy metals, neutralization, press filtration obtains pure manganese sulfate solution (most of manganese chemical product all makes each relevant manganese product take this solution as intermediate), but this solution direct evaporation condensing crystal and dehydration or oven dry obtain manganous sulfate; Perhaps react to such an extent that manganous carbonate precipitation dewatered drying after the manganous carbonate after the solid-liquid separation is cleaned obtains manganous carbonate with soluble carbonate salt (routine bicarbonate of ammonia); Or making manganese chloride solution with calcium sulfate precipitation and after solid-liquid separation with calcium chloride reaction, filtrate (Manganous chloride tetrahydrate) evaporating, concentrating and crystallizing and dewatered drying obtain Manganous chloride tetrahydrate, must byproduct calcium sulfate after the washing of precipitate dehydration; Also can prepare again other corresponding manganese products by manganous sulfate, manganous carbonate or Manganous chloride tetrahydrate.

By using this composite reductant manganese dioxide reduction ore deposit to produce electrolytic metal Mn following advantage is arranged:

1, do not change main production and the main equipment of the original production of electrolytic metal Mn manufacturer;

2, utilize efficiently the Manganse Dioxide ore resources, leach recovery rate and reach more than 93%;

3, significantly reduce the amount of waste residue, and waste residue also is that we produce the reductive agent main raw material, substantially anhydrous solube metallic in the waste residue after our technique is extracted, processed reaches the relevant environmental requirement of country;

4, reduce production costs widely (compare and to reduce more than 15% with traditional reducing process according to mineral resources is different) enhance productivity (compare with traditional reducing process, can improve more than 20%);

5, Leaching reaction is cold reaction, needn't heat, and speed of response is fast;

6, significantly reduce the discharging of carbonic acid gas and waste residue, reach the requirement of national recycling economy;

7, production technique is simple, practical, with low cost;

8, most manganese in the recyclable waste residue, but and byproduct bring the substantially production and application cost of offset reductive agent of new benefit.

Claims

1. produce the manufacture craft of composite reductant with Electrolytic Manganese Metal Residues, it is characterized in that: described manufacture craft is as follows:

A, Electrolytic Manganese Metal Residues is joined in the mixed solution of sulfuric acid and leach liquor, after abundant reaction, it is carried out press filtration and process and obtain waste residue and a feed liquid;

B, be 1 with barium sulfide solution and ammonium sulfate by the mass ratio of barium sulphide and ammonium sulfate: (0.4-0.5) mix, press filtration is removed throw out and is obtained feed liquid No. two after the reaction;

2. manufacture craft of producing composite reductant with Electrolytic Manganese Metal Residues according to claim 1, it is characterized in that: in described step a, the mass ratio of described Electrolytic Manganese Metal Residues, sulfuric acid and leach liquor is: 1: (0.1-0.15): 4.

3. manufacture craft of producing composite reductant with Electrolytic Manganese Metal Residues according to claim 1,

It is characterized in that: in described step b, described barium sulfide solution is the solution of gained behind the barium sulphide usefulness water extraction press filtration removal cinder.

4. according to claim 1 and 2 or the application of the composite reductant of 3 described manufacture craft preparations of producing composite reductant with Electrolytic Manganese Metal Residues, it is characterized in that: for the preparation of the method for manganese sulfate solution, described method is as follows:

A, will Manganse Dioxide oven dry, mix with sulfuric acid, the waste electrolyte of producing the electrolytic metal Mn generation after pulverizing;