CN109650760A - A kind of method for innocent treatment of electrolytic manganese residues - Google Patents
A kind of method for innocent treatment of electrolytic manganese residues Download PDFInfo
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- CN109650760A CN109650760A CN201811513353.6A CN201811513353A CN109650760A CN 109650760 A CN109650760 A CN 109650760A CN 201811513353 A CN201811513353 A CN 201811513353A CN 109650760 A CN109650760 A CN 109650760A
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- electrolytic manganese
- parts
- manganese residues
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- innocent treatment
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
Abstract
The invention discloses a kind of method for innocent treatment of electrolytic manganese residues, characterized by the following steps: step 1,0.05 part~0.5 part phosphate is added in 100 parts of electrolytic manganese residues in parts by weight, product one is obtained after being stirred to react；Step 2,5~20 parts of magnesium hydroxides and magnesia mixture are added in product one, product two is obtained after being stirred to react；Step 3,0.05~0.3 part of carboxylic acid is added in product two, innoxious electrolytic manganese residues are obtained after being stirred to react.The present invention handles electrolytic manganese residues, and processing cost is low, and low energy consumption, and processing step is simple, easily operated, avoids the stacking of electrolytic manganese residues to the pollution of ambient enviroment.
Description
Technical field
The invention belongs to the methods that manganese production technical field, especially a kind of pair of electrolytic manganese residues are handled.
Background technique
China is currently the first Chan Meng big country in the world, and manganese metal is used for steel and iron industry, there is saying for " no manganese not Cheng Gang ", manganese
It is one of the important basic supplies of Chinese national economy and national grand strategy resource, therefore the production of manganese is particularly significant.
The production technology of manganese mainly includes electrolysis method, aluminothermic process and electro silicothermic process, and the method for industrial production manganese is electrolysis method.
The production cost of electrolysis method is higher, and the purity for the manganese that can be generated a large amount of electrolytic manganese residues, but produce is good.
Electrolytic manganese residues are the pollution sources that electrolytic manganese industry is maximum, most dangerous, and it is a generation that Electrolytic Manganese Metal Residues, which recycle,
Criticality problem.China is the maximum electrolytic manganese metal production in the whole world, consumption and exported country, and production capacity is more than 2,000,000 tons, Zhan Quanqiu
The 98% of electrolytic manganese aggregated capacity.Electrolytic manganese residues are the filtering acid sludges generated after electrolytic manganese metal, are the emphasis pollutions of electrolytic manganese industry
Object.For electrolytic manganese residues yield up to 7 ~ 11 ton/ton manganese, annual yield is about 20,000,000 tons, is accumulated over 80,000,000 tons over the years, deposits
It measures huge.Currently, enterprise not yet finds the method for dealing carefully with electrolytic manganese residues, generally electrolytic manganese residues are transported to stockyard and are built a dam heap
It puts.Domestic electrolytic manganese residues tailing dam takes up a large area, and safety coefficient is low, and for a long time under the action of Weathering And Leaching Behavior, polluted big
Piece arable land and underground water source, do great damage to ecological environment.
There are mainly two types of for the conventional process mode of electrolytic manganese residues:
First is that electrolytic manganese residues sorting process technology.The technology utilizes the alternate different physicochemical characteristics of each mine of electrolytic manganese residues, will
Various composition separates, and the magnetic separation fine fodder such as obtained using the magnetism of manganese can become the acceptable material of production electrolytic manganese.
Second is that electrolytic manganese residues solidification technology.Inertia is fixed or be wrapped in harmful components in electrolytic manganese residues by the technology
Solidification basic material in, be a kind of method for innocent treatment.It is generally using cement as the basic material for solidifying addition, cement
Additive amount be no less than 45%.
In recent years, the grade of manganese ore gradually decreases.Meanwhile with the raising of production technology level, the effect of production link
Rate is continuously improved, and the content of manganese in electrolytic manganese residues further decreases, and the manganese in electrolytic manganese residues has been difficult through sorting process
Method recycles again.Although curing process effect is good, for being piled into the electrolytic manganese residues on mountain, this method may disappear
A large amount of cement is consumed, the increase of processing cost certainly will be will cause, industrial applications prospect is general.
A large amount of electrolytic manganese residues are hoarded, and bring very big pressure to Environmental Protection in China work.Recycling is carried out to electrolytic manganese residues
It utilizes, not only can solve its pollution problem to environment, additionally it is possible to create benefit for enterprise, reduce production cost.Currently, electric
The resource utilization of solution manganese slag is mainly the following mode:
One, valuable metal is recycled.Manganese in electrolytic manganese residues resource accounting reaches 9%~13%.The recovery method of manganese mainly have bioanalysis,
Acidic leaching method and three kinds of water washing and precipitating method.Bioanalysis mainly utilizes sulfur-oxidizing bacteria and iron-oxidizing bacterium to leach in electrolytic manganese residues
Manganese, the leaching rate of manganese is up to 90% or more.Acidic leaching rule adds acid leaching solution, leaching auxiliary agent in electrolytic manganese residues, surpasses
The higher manganese sulfate product of purity can be obtained after sound, removal of impurities.The method that water washing and precipitating method uses " clear water washery slag+ammonium salt precipitating "
Soluble manganese is recycled, the rate of recovery of manganese can reach 99% or more, and in the rich manganese precipitating material recycled, the content of manganese can reach 30%
More than.Acidic leaching method and water washing and precipitating method due to complex process, higher cost and will cause secondary pollution, cause using by
Limit.Bioanalysis is the method for the recycling manganese in electrolytic manganese residues and other metal ions of a great potential, but to strain and leaching
Condition it is more demanding, and the bioleaching time is generally longer.In addition, the cultivation of strain is also more complicated, still fail at present
Find most suitable strain.
Two, all-sided fertilizer is prepared.Rich in macronutrient required for organic substance and plant in electrolytic manganese residues, as manganese,
Selenium, potassium, sodium, iron, boron etc., this provides possibility to prepare all-sided fertilizer using electrolytic manganese residues.Currently, the full price of electrolytic manganese residues preparation
Though fertilizer can increase certain fertilizer efficiency, its fertilizer efficiency is not so good as common nitrogenous fertilizer and phosphate fertilizer.In addition, also containing many harmful members in electrolytic manganese residues
Element, promote crop growth while also can contaminated soil, endanger human health.If can be right before applying electrolytic manganese residues fertilizer
It carries out harmless treatment, then electrolytic manganese residues fertilizer will be widely adopted in agriculture actual production.
Three, materials for wall is produced.Electrolytic manganese residues mainly contain silica, calcium oxide, iron oxide and aluminium oxide etc., are suitble to
For brickmaking.Currently, having non-burning brick, fired brick, Ceramic Tiles, steam-pressing brisk and heat preservation using the major product that electrolytic manganese residues produce
Brick.Electrolytic manganese residues have in the main problem for preparing materials for wall: first is that the mixed ratio of electrolytic manganese residues is relatively fewer, increasing and add
Amount will lead to the intensity decline of brick body；Second is that heavy metal and poisonous impurities need to be removed further in electrolytic manganese residues.
Four, roadbed material is produced.Electrolytic manganese ground-slag is free of the asphalt of clinker with addition of flyash and carbide slurry preparation,
Stability, intensity, adhesion and the anti-corrosion property energy of asphalt can be effectively improved.The asphalt uses anti-after 1 year
Compressive Strength still can reach 10 megapascal, meet the requirement of traffic construction.It is prepared when the additive amount of electrolytic manganese residues reaches 80%
Asphalt mastic and asphalt performance and economy it is best.Certainly, electrolytic manganese residues are promoted on a large scale in highway subgrade
Application in terms of material must consider that " poisoning " of heavy metal ion in electrolytic manganese residues influences.Heavy metal in electrolytic manganese residues from
Son can be by the soil near rain penetration to roadbed, to influence its surrounding enviroment.
Currently, the application technology as the second resource research of electrolytic manganese residues is in theoretical research stage mostly, in actual industrial
What is be applied is very few, and reason mainly has following two points: first is that recycling electrolytic manganese residues in manganese metal can not obtain it is good
Good economic benefit, and secondary use value is little.Second is that electrolytic manganese residues in cement industry, materials for wall, prepare all-sided fertilizer etc.
During the resource utilization in field, it is required to consider the harmless treatment to harmful element or heavy metal, higher cost.
Application publication number is CN107649488A, and date of publication is on 2 2nd, 2018, applies for the China of artificial Tsinghua University
Application for a patent for invention discloses a kind of innoxious method of processing electrolytic manganese residues, method includes the following steps: (1) is by electrolytic manganese
Slag is 450~900 DEG C in temperature, partial pressure of oxygen 10-2Pa~1040.5~4 hour is roasted under conditions of Pa；(2) use contains
The aqueous solution of chelating agent or obtained using dilute sulfuric acid impregnation steps (1) electrolytic manganese residues 0.5~2 hour；(3) step (2) are obtained
The product filters pressing arrived obtains innoxious electrolytic manganese residues after filter cake drying.This method can make the electrolytic manganese after harmless treatment
For the color of slag as native clay, the concentration of the harmful substance including heavy metal reaches national agricultural soil standard.Nothing
The soil that electrolytic manganese residues after evilization can be used as improvement arable land uses, and can be used for the second ploughing of local Desertification Soil.But
Be this method roasts 0.5~4 hour firstly the need of to electrolytic manganese residues under 450~900 DEG C of hot conditions, and energy consumption is high；Place
Manage higher cost.
Summary of the invention
The present invention is in order to solve drawbacks described above existing for existing harmless treatment electrolytic manganese residues, and the present invention provides a kind of electricity
The method for innocent treatment for solving manganese slag handles electrolytic manganese residues by this method, and processing cost is low, and low energy consumption, and processing step is simple,
It is easily operated, avoid the stacking of electrolytic manganese residues to the pollution of ambient enviroment.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of method for innocent treatment of electrolytic manganese residues, characterized by the following steps:
Step 1,0.05 part~0.5 part phosphate is added in 100 parts of electrolytic manganese residues in parts by weight, after being stirred to react
To product one；
Step 2,5~20 parts of magnesium hydroxides and magnesia mixture are added in product one, product two is obtained after being stirred to react；
Step 3,0.05~0.3 part of carboxylic acid is added in product two, innoxious electrolytic manganese residues are obtained after being stirred to react.
The phosphate includes following ingredient based on parts by weight:
40~50 parts of tripolyphosphate
40~50 parts of hexametaphosphate
10~20 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
20~30 parts of tartaric acid
70~80 parts of citric acid.
In the magnesium hydroxide and magnesia mixture, the mass ratio of magnesium hydroxide and magnesia are as follows: 1~4:6~9.
In step 1, the time being stirred to react is 0.5~3min.
In step 1, it is 0.1 part that phosphatic parts by weight, which are added,.
In step 2, the time being stirred to react is 25~35min.
In step 2, the parts by weight that magnesium hydroxide and magnesia mixture is added are 10 parts.
In step 3, the time being stirred to react is 1~3min.
In step 3, the parts by weight that carboxylic acid is added are 0.1 part.
Compared with prior art, the invention has the following advantages:
Harmful substance (manganese ion and ammonia nitrogen) quilt of the electrolytic manganese residues after process provided by the invention, in electrolytic manganese residues
Processing, becomes innoxious electrolytic manganese residues.Obtained electrolytic manganese residues are no longer noxious materials, harmless to ambient enviroment.And have
Have certain gelling property, not the risk with dam break also for the resource circulation utilization of next step provide one it is relatively good
Filler.Obtained electrolytic manganese residues production all-sided fertilizer will not contaminated soil, endanger human health, produce roadbed material, will not pass through
Soil near rain penetration to roadbed, to influence its surrounding enviroment.Materials for wall is made, it is scattered without harmful substance is worried
Hair, influences health.And the technological operation step is simple, does not also need the high temperature item to electrolytic manganese residues at 450~900 DEG C
0.5~4 hour is roasted under part, energy consumption significantly reduces, and processing cost significantly reduces.
Specific embodiment
The present invention will be further described with reference to the examples below, and described embodiment is only present invention a part
Embodiment is not whole embodiment.Based on the embodiments of the present invention, those skilled in the art are not making
Other embodiments used obtained, belong to protection scope of the present invention under the premise of creative work.
500 parts of untreated electrolytic manganese residues are taken first, and 500 parts of electrolytic manganese residues are divided into 5 parts, are attached separately to container
In, each container difference labelled 1,2,3,4,5.
Harmful substance in electrolytic manganese residues is contained in harmful substance contents and standard GB8978-1996 in electrolytic manganese residues
Amount requires as shown in Table 1:
Harmful substance contents in one electrolytic manganese residues of table
| Harmful substance | Standard limited value (mg/L) | Content (mg/L) |
| Manganese ion | 5.0 | 2270 |
| Ammonia nitrogen | 25 | 678.12 |
| Copper ion | 2.0 | 0.047 |
| Zinc ion | 5.0 | 1.72 |
| Chromium particle | 1.5 | 0.802 |
| Nickel particles | 1.0 | 0.44 |
| Arsenic particle | 0.5 | 0.00114 |
| Silver ion | 0.5 | 0.268 |
| Se particle | 0.5 | 0.019 |
As can be seen from Table I, the harmful substance in electrolytic manganese residues is in addition to the content of manganese particle and ammonia nitrogen is much higher than standard requirements
Outside, other harmful substances are below standard limited value, therefore need to only handle manganese particle and the ammonia nitrogen in electrolytic manganese residues.
Embodiment 1
Step 1,0.1 part of phosphate is added in the container 1, obtains product one after being stirred to react 1min；
Step 2, the mixture of 10 parts of magnesium hydroxides and magnesia, mixing ratio are as follows: 1:6 is stirred to react are added in product one
Product two is obtained after 30min；
Step 3,0.1 part of carboxylic acid is added in product two, obtains innoxious electrolytic manganese residues after being stirred to react 2min.
The compounding phosphate includes following ingredient based on parts by weight:
40 parts of tripolyphosphate
40 parts of hexametaphosphate
10 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
20 parts of tartaric acid
70 parts of citric acid.
Embodiment 2
Step 1,0.05 part of phosphate is added in container 2, obtains product one after being stirred to react 0.5min；
Step 2, the mixture of 5 parts of magnesium hydroxides and magnesia is added in product one, mixed proportion 1:8 stirs anti-25min
After obtain product two；
Step 3,0.05 part of carboxylic acid is added in product two, obtains innoxious electrolytic manganese residues after being stirred to react 1min.
The compounding phosphate includes following ingredient based on parts by weight:
50 parts of tripolyphosphate
50 parts of hexametaphosphate
20 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
30 parts of tartaric acid
80 parts of citric acid.
Embodiment 3
Step 1,0.2 part of phosphate is added in container 3, obtains product one after being stirred to react 2min；
Step 2, the mixture of 15 parts of magnesium hydroxides and magnesia, mixed proportion are as follows: 1:9 is stirred to react are added in product one
28min obtains product two；
Step 3,0.2 part of carboxylic acid is added in product two, is stirred to react 2min and obtains innoxious electrolytic manganese residues.
The compounding phosphate includes following ingredient based on parts by weight:
50 parts of tripolyphosphate
40 parts of hexametaphosphate
20 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
20 parts of tartaric acid
70 parts of citric acid.
Embodiment 4
Step 1,0.4 part of phosphate is added in container 4, obtains product one after being stirred to react 2.5min；
Step 2, the mixture of 18 parts of magnesium hydroxides and magnesia, mixed proportion are as follows: 2:7 is stirred to react are added in product one
32min obtains product two；
Step 3,0.25 part of carboxylic acid is added in product two, obtains innoxious electrolytic manganese residues after being stirred to react 2.5min.
The compounding phosphate includes following ingredient based on parts by weight:
45 parts of tripolyphosphate
45 parts of hexametaphosphate
15 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
25 parts of tartaric acid
75 parts of citric acid.
Embodiment 5
Step 1,0.5 part of phosphate is added in container 5, obtains product one after being stirred to react 3min；
Step 2, the mixture of 20 parts of magnesium hydroxides and magnesia, mixed proportion are as follows: 4:9 is stirred to react are added in product one
Product two is obtained after 35min；
Step 3,0.3 part of carboxylic acid is added in product two, obtains innoxious electrolytic manganese residues after being stirred to react 3min.
The compounding phosphate includes following ingredient based on parts by weight:
48 parts of tripolyphosphate
50 parts of hexametaphosphate
18 parts of tertiary sodium phosphate.
The carboxylic acid includes following ingredient based on parts by weight:
22 parts of tartaric acid
78 parts of citric acid.
The electrolytic manganese residues obtained after above-described embodiment processing are detected, the result obtained is as shown in Table 2:
There is a small amount of precipitation by metallic ion object in the innoxious electrolytic manganese residues that above-described embodiment obtains, there is no free heavy metals
99% or more, remaining ammonia root generates micro ammonium magnesium phosphate for ion, free manganese ion and ammonia root removal rate.No longer have
There is harmful substance, either stacks that be also used as the raw material of other substances be nontoxic.It has been really achieved electrolytic manganese
The harmless treatment effect of slag.
It will treated that electrolytic manganese residues inject available electrolytic manganese residues base in corresponding mold by above-described embodiment
Craftwork, while solving the problems, such as innoxious latter step resources circulation.Electrolytic manganese residues can be recycled and utilized.
Claims (10)
1. a kind of method for innocent treatment of electrolytic manganese residues, characterized by the following steps:
Step 1,0.05 part~0.5 part phosphate is added in 100 parts of electrolytic manganese residues in parts by weight, after being stirred to react
To product one；
Step 2,5~20 parts of magnesium hydroxides and magnesia mixture are added in product one, product two is obtained after being stirred to react；
Step 3,0.05~0.3 part of carboxylic acid is added in product two, innoxious electrolytic manganese residues are obtained after being stirred to react.
2. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: the phosphate with
Parts by weight meter includes following ingredient:
40~50 parts of tripolyphosphate
40~50 parts of hexametaphosphate
10~20 parts of tertiary sodium phosphate.
3. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: the carboxylic acid is with weight
Measuring number meter includes following ingredient:
20~30 parts of tartaric acid
70~80 parts of citric acid.
4. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: the magnesium hydroxide
In magnesia mixture, the mass ratio of magnesium hydroxide and magnesia are as follows: 1~4:6~9.
5. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 1, stirring
The time of reaction is 0.5~3min.
6. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 1, be added
Phosphatic parts by weight are 0.1 part.
7. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 2, stirring
The time of reaction is 25~35min.
8. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 2, be added
The parts by weight of magnesium hydroxide and magnesia mixture are 10 parts.
9. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 3, stirring
The time of reaction is 1~3min.
10. a kind of method for innocent treatment of electrolytic manganese residues according to claim 1, it is characterised in that: in step 3, add
The parts by weight for entering carboxylic acid are 0.1 part.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103286116A (en) * | 2013-06-27 | 2013-09-11 | 重庆大学 | Harmless treatment method of electrolytic manganese residue |
| CN104307849A (en) * | 2014-10-13 | 2015-01-28 | 中国环境科学研究院 | Electrolytic manganese residue curing/stabilizing treatment method |
| CN104690080A (en) * | 2015-03-28 | 2015-06-10 | 重庆大学 | Method for directly carrying out innocent treatment on electrolytic manganese residues in filter pressing plate frames |
| CN108246777A (en) * | 2018-02-24 | 2018-07-06 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
-
2018
- 2018-12-11 CN CN201811513353.6A patent/CN109650760A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103286116A (en) * | 2013-06-27 | 2013-09-11 | 重庆大学 | Harmless treatment method of electrolytic manganese residue |
| CN104307849A (en) * | 2014-10-13 | 2015-01-28 | 中国环境科学研究院 | Electrolytic manganese residue curing/stabilizing treatment method |
| CN104690080A (en) * | 2015-03-28 | 2015-06-10 | 重庆大学 | Method for directly carrying out innocent treatment on electrolytic manganese residues in filter pressing plate frames |
| CN108246777A (en) * | 2018-02-24 | 2018-07-06 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
Non-Patent Citations (1)
| Title |
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| 杜兵等: "稳定剂对电解锰废渣中高浓度可溶性锰稳定效果的影响", 《中国环境科学》 * |
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Application publication date: 20190419 |