CN109626852A - A kind of electrolytic manganese residues harmless treatment composition - Google Patents
A kind of electrolytic manganese residues harmless treatment composition Download PDFInfo
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- CN109626852A CN109626852A CN201811511775.XA CN201811511775A CN109626852A CN 109626852 A CN109626852 A CN 109626852A CN 201811511775 A CN201811511775 A CN 201811511775A CN 109626852 A CN109626852 A CN 109626852A
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- electrolytic manganese
- manganese residues
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- residues
- product
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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
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/02—Calcareous fertilisers from limestone, calcium carbonate, calcium hydrate, slaked lime, calcium oxide, waste calcium products
Abstract
The invention discloses a kind of electrolytic manganese residues harmless treatment compositions, composition includes calcium hydroxide and liquid substance, calcium hydroxide and liquid substance are separately packed, liquid substance is the mixture of the sodium chloride solution that concentration is 10~25% and compounding agent, and the compounding agent includes 0.5~2 portion of citrate and 10~25 parts of aluminum sulfate in parts by weight.Electrolytic manganese residues are handled using the present invention, processing cost is low, and low energy consumption, and processing step is simple, and it is easily operated, avoid the stacking of electrolytic manganese residues to the pollution of ambient enviroment.
Description
Technical field
The invention belongs to manganese production technical field, the composition used when 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
Manganese slag harmlessness composition for treating is solved, electrolytic manganese residues are handled by the composition, processing cost is low, and low energy consumption, place
It is simple to manage step, 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 electrolytic manganese residues harmless treatment composition, it is characterised in that: including calcium hydroxide and liquid substance, calcium hydroxide
It is separately packed with liquid substance,
Based on parts by weight, liquid substance includes:
The sodium chloride solution that concentration is 10~25%: 400~600 parts
Compounding agent: 0.5~2 part；
The compounding agent includes 0.5~2 portion of citrate and 10~25 parts of aluminum sulfate in parts by weight.
Based on parts by weight, when handling 100 parts of electrolytic manganese residues, calcium hydroxide dosage is 20~30 parts.
The dosage of liquid substance are as follows: be added in 100 parts of electrolytic manganese residues after 20~30 parts of calcium hydroxides obtained product with
The solid-to-liquid ratio of liquid substance are as follows: 1:3.5~5.5.
The present invention also provides use above-mentioned composition to electrolytic manganese residues carry out harmless treatment method, specifically:
Step 1, calcium hydroxide, the additional amount of calcium hydroxide are added into electrolytic manganese residues are as follows: be added in every 100 parts of electrolytic manganese residues
20~30 parts of calcium hydroxide；
Step 2, liquid substance is added into the product that step 1 obtains, stirs 1~2min, the specific additional amount of liquid substance are as follows:
The solid-to-liquid ratio of product and liquid substance that step 1 obtains is 1:3.5~5.5；
Step 3, the substance Jing Guo step 2 is heated, washs filtering with hot water after heating, obtains innoxious electrolysis after dry
Manganese slag.
In step 1, the water content of electrolytic manganese residues is controlled 40~50%.
It in step 1, is stirred after calcium hydroxide is added in electrolytic manganese residues, mixing time is 20~40min, has been stirred
At rear standing 2h or more.
In step 3, heating and temperature control is 90~130 DEG C, and heating time is 3~5h.
In step 3, the temperature of hot water is greater than or equal to 93 DEG C.
Compared with prior art, the invention has the following advantages:
Harmful substance of the electrolytic manganese residues after composition provided by the invention is handled according to processing step, in electrolytic manganese residues
(manganese ion and ammonia nitrogen) is processed, becomes innoxious electrolytic manganese residues.Obtained electrolytic manganese residues are no longer noxious materials,
It is harmless to ambient enviroment.The substance with gelling property is formed, to provide manganese slag toward the application of powder of lacquer putty for use on, decorative panel etc.
The raw material of base.Obtained electrolytic manganese residues production all-sided fertilizer will not contaminated soil, endanger human health, produce roadbed material, will not
By the soil near rain penetration to roadbed, to influence its surrounding enviroment.Materials for wall is made, without worry nuisance
Matter distributes, and influences health, and the technological operation step is simple, does not also need the height to electrolytic manganese residues at 450~900 DEG C
0.5~4 hour is roasted under the conditions of temperature, 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 in container, often
A 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
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
It is 40% by the water content control of the electrolytic manganese residues in container 1,20 parts of calcium hydroxide stirring is then added in the container 1
20min stands 2h product one derived above；
Configuration concentration is 400 parts of sodium chloride solution of 10%, and 0.5 part of compounding agent is added in sodium chloride solution, obtains product two；
Contain 0.5 portion of citrate and 10 parts of aluminum sulfate in compounding agent；
Product one is added in product two, 1min is stirred, the mixed liquor that configuration solid-to-liquid ratio is 1:3.5 obtains product three；
Product three is heated, heating and temperature control is 90 DEG C, after heating 5h, washs filtering with the hot water that temperature is 93 DEG C, dry
After obtain product four, obtained product four be harmless treatment after electrolytic manganese residues.
Embodiment 2
It is 42% by the water content control of the electrolytic manganese residues in container 2,22 parts of calcium hydroxide, stirring is then added in container 2
25min stands 2h product one derived above；
Configuration concentration is 450 parts of sodium chloride solution of 15%, and 1 part of compounding agent is added in sodium chloride solution, obtains product two；It is multiple
Contain 1 portion of citrate and 15 parts of aluminum sulfate in ingredients；
Product one is added in product two, 1.2min is stirred, the mixed liquor that configuration solid-to-liquid ratio is 1:4 obtains product three；
Product three is heated, heating and temperature control is 100 DEG C, after heating 4.5h, washs filtering with the hot water that temperature is 94 DEG C, does
Product four is obtained after dry, obtained product four is the electrolytic manganese residues after harmless treatment.
Embodiment 3
It is 45% by the water content control of the electrolytic manganese residues in container 3,25 parts of calcium hydroxide, stirring is then added in container 3
30min stands 2h product one derived above；
Configuration concentration is 500 parts of sodium chloride solution of 20%, and 1.5 parts of compounding agent are added in sodium chloride solution, obtains product two；
Contain 1.5 portions of citrates and 20 parts of aluminum sulfate in compounding agent；
Product one is added in product two, 1.5min is stirred, the mixed liquor that configuration solid-to-liquid ratio is 1:4.5 obtains product three；
Product three is heated, heating and temperature control is 110 DEG C, after heating 4h, washs filtering with the hot water that temperature is 95 DEG C, dry
After obtain product four, obtained product four be harmless treatment after electrolytic manganese residues.
Embodiment 4
It is 48% by the water content control of the electrolytic manganese residues in container 4,28 parts of calcium hydroxide, stirring is then added in container 4
35min stands 2h product one derived above；
Configuration concentration is 550 parts of sodium chloride solution of 23%, and 1.8 parts of compounding agent are added in sodium chloride solution, obtains product two；
Contain 1.8 portions of citrates and 22 parts of aluminum sulfate in compounding agent；
Product one is added in product two, 1.8min is stirred, the mixed liquor that configuration solid-to-liquid ratio is 1:5 obtains product three；
Product three is heated, heating and temperature control is 125 DEG C, after heating 3.5h, filtering is washed with the hot water that temperature is 100 DEG C,
Product four is obtained after drying, obtained product four is the electrolytic manganese residues after harmless treatment.
Embodiment 5
It is 50% by the water content control of the electrolytic manganese residues in container 5,30 parts of calcium hydroxide, stirring is then added in container 5
40min stands 2h product one derived above；
Configuration concentration is 600 parts of sodium chloride solution of 25%, and 2 parts of compounding agent are added in sodium chloride solution, obtains product two；It is multiple
Contain 2 portions of citrates and 25 parts of aluminum sulfate in ingredients；
Product one is added in product two, 2min is stirred, the mixed liquor that configuration solid-to-liquid ratio is 1:5.5 obtains product three；
Product three is heated, heating and temperature control is 130 DEG C, after heating 3h, washs filtering with the hot water that temperature is 110 DEG C, does
Product four is obtained after dry, obtained product four is the electrolytic manganese residues after harmless treatment.
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 (3)
1. a kind of electrolytic manganese residues harmless treatment composition, it is characterised in that: including calcium hydroxide and liquid substance, hydroxide
Calcium and liquid substance are separately packed,
Based on parts by weight, liquid substance includes:
The sodium chloride solution that concentration is 10~25%: 400~600 parts
Compounding agent: 0.5~2 part；
The compounding agent includes 0.5~2 portion of citrate and 10~25 parts of aluminum sulfate in parts by weight.
2. a kind of electrolytic manganese residues harmless treatment composition according to claim 1, it is characterised in that: with parts by weight
Meter, when handling 100 parts of electrolytic manganese residues, calcium hydroxide dosage is 20~30 parts.
3. a kind of electrolytic manganese residues harmless treatment composition according to claim 1, it is characterised in that: liquid substance
Dosage are as follows: the solid-to-liquid ratio of the product and liquid substance that obtain after 20~30 parts of calcium hydroxides is added in 100 parts of electrolytic manganese residues are as follows:
1:3.5~5.5.
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| CN201811511775.XA CN109626852A (en) | 2018-12-11 | 2018-12-11 | A kind of electrolytic manganese residues harmless treatment composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258269A (en) * | 1997-05-29 | 2000-06-28 | 派里克累斯有限公司 | Encapsulation of hazardous waste materials |
| 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 |
| CN107649488A (en) * | 2017-09-30 | 2018-02-02 | 北京秀山丽水环保科技有限责任公司 | It is a kind of to handle the innoxious method of electrolytic manganese residues |
-
2018
- 2018-12-11 CN CN201811511775.XA patent/CN109626852A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258269A (en) * | 1997-05-29 | 2000-06-28 | 派里克累斯有限公司 | Encapsulation of hazardous waste materials |
| 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 |
| CN107649488A (en) * | 2017-09-30 | 2018-02-02 | 北京秀山丽水环保科技有限责任公司 | It is a kind of to handle the innoxious method of electrolytic manganese residues |
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