CN101880773A

CN101880773A - Manufacturing process for producing synthetic reducing agent by using waste slag of electrolytic manganese and application of synthetic reducing agent

Info

Publication number: CN101880773A
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: 2010-11-10
Anticipated expiration: 2030-06-13
Also published as: CN101880773B

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 has been in short supply, add local government and repeat to impose resource compensation, go out the county and will receive dozens of yuan/ton, 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 only surplus at present half, and resource recovery is very low, has only 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 big 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 an electrolytic metal Mn; Another kind is to be raw material with rich manganese ore and high silicon manganese-silicon alloy, 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---the 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 big more, and is increasing to the harm and the pressure of environment protection; The 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 to reduce manganese product such as electrolytic metal Mn with Electrolytic Manganese Metal Residues, 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: with the manufacture craft that Electrolytic Manganese Metal Residues is produced composite reductant, its step is as follows:

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

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

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 circulation is applied 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 gained behind the barium sulphide usefulness water extraction press filtration removal cinder.

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

A, with Manganse Dioxide oven dry, pulverize the back and mix with sulfuric acid, anolyte;

B, in above-mentioned mixing solutions, add composite reductant, behind the question response, will can obtain purified 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, the mass consumption waste manganese slag, 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 reduction dioxide ore for manganese (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 manufacturing 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 technology is extracted, utilized; Most of reclaim (in the manganese slag) of ammonia nitrogen through further handling, can reach relevant national standard.Utilize the manganese product of the production of this composite reductant reduction Manganse Dioxide significantly to improve production efficiency on the basis of original production technique and reduce production costs not changing simultaneously.

Embodiment:

With the manufacture craft that Electrolytic Manganese Metal Residues is produced composite reductant, 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 treat after the fully reaction it is carried out press filtration and handle and obtain waste residue (being mainly lime powder) and a feed liquid;

B, be 1 by the mass ratio of barium sulfate and ammonium sulfate with barium sulfide solution and ammonium sulfate: (0.4-0.5) mix, reaction back press filtration with throw out remove obtain No. two feed liquids (described barium sulfide solution be barium sulphide with water extraction press filtration cinder after the solution of gained);

In above-mentioned preparation process, except that 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 obtain process white when obtaining No. two feed liquids, this barium sulfate promptly is contained in the above-mentioned throw out, as long as will obtain the process white 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 reduction Manganse Dioxide 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),, make preliminary electrolytic solution through deironing, removing heavy metals, neutralization, press filtration, again behind deep purifying qualified electrolytic solution, add additive and carry out electrolysis, again through passivation, washing, dry, peel off, pack the electrolytic metal Mn finished product.

The method of producing other manganese products with this composite reductant reduction dioxide ore for manganese 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 sulfur acid ammonium) in the abundant certain density manganese sulfate solution of reaction back system, obtain purified manganese sulfate solution (most of manganese chemical product is that intermediate makes each relevant manganese product with this solution all) through deironing, removing heavy metals, neutralization, press filtration again, but this solution direct evaporation condensing crystal and dehydration or oven dry obtain manganous sulfate; Perhaps react to such an extent that the manganous carbonate of manganous carbonate precipitation after solid-liquid separation cleaned back dewatered drying acquisition manganous carbonate with soluble carbon hydrochlorate (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 be by other corresponding manganese products of manganous sulfate, manganous carbonate or Manganous chloride tetrahydrate refabrication.

By using this synthetic reducing agent manganese dioxide reduction ore deposit to produce electrolytic manganese metal following advantage is arranged:

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

2, utilize efficiently the manganese 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 reducing agent primary raw material, substantially anhydrous solube metallic in the waste residue after our technology 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 reaction speed is fast;

6, significantly reduce the discharging of carbon dioxide and waste residue, reach the requirement of national recycling economy;

7, production technology 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 reducing 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:

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

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 manganese slag, 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 is characterized in that: in described step b, to be barium sulphide press the solution of removing gained behind the filter cinder with water extraction to described barium sulfide solution.

4. produce the application of composite reductant of the manufacture craft preparation of composite reductant with Electrolytic Manganese Metal Residues, it is characterized in that: be used to prepare the method for manganese sulfate solution, described method is as follows: