CN109626864A - A kind of composition for electrolytic manganese residues harmless treatment - Google Patents

A kind of composition for electrolytic manganese residues harmless treatment Download PDF

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Publication number
CN109626864A
CN109626864A CN201811511750.XA CN201811511750A CN109626864A CN 109626864 A CN109626864 A CN 109626864A CN 201811511750 A CN201811511750 A CN 201811511750A CN 109626864 A CN109626864 A CN 109626864A
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electrolytic manganese
manganese residues
parts
residues
electrolytic
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李京鸿
李秀梅
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Wudao Environmental Protection Technology Co Ltd
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Wudao Environmental Protection Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B7/00Fertilisers based essentially on alkali or ammonium orthophosphates
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of compositions for electrolytic manganese residues harmless treatment, composition includes calcium hydroxide, silica flour, sodium dihydrogen phosphate, unsaturated polyester resin and isobutyl triethoxy silane, in parts by weight, the electrolytic manganese residues of every 100 parts of processing, calcium hydroxide are 5~10 parts;Silica flour is 5~10 parts;Sodium dihydrogen phosphate is 0.1~0.5 part;Unsaturated polyester resin is 40~55 parts;Isobutyl triethoxy silane is 0.01~0.15 part.Electrolytic manganese residues are handled using the composition, obtain innoxious electrolytic manganese residues, 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

A kind of composition for electrolytic manganese residues harmless treatment
Technical field
The invention belongs to manganese production technical field, especially a kind of pair of electrolytic manganese residues carry out the composition that processing is used.
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 use In the composition of electrolytic manganese residues harmless treatment, electrolytic manganese residues are handled using the composition, obtain innoxious electrolysis Manganese slag, processing cost is low, and low energy consumption, and processing step is simple, easily operated, avoids the stacking of electrolytic manganese residues to the dirt of ambient enviroment Dye.
In order to solve the above technical problems, the technical scheme adopted by the invention is that:
A kind of composition for electrolytic manganese residues harmless treatment, it is characterised in that: including calcium hydroxide, silica flour, di(2-ethylhexyl)phosphate Hydrogen sodium, unsaturated polyester resin and isobutyl triethoxy silane, in parts by weight, the electrolytic manganese residues of every 100 parts of processing, Calcium hydroxide is 5~10 parts;Silica flour is 5~10 parts;Sodium dihydrogen phosphate is 0.1~0.5 part;Unsaturated polyester resin be 40~ 55 parts;Isobutyl triethoxy silane is 0.01~0.15 part.
The calcium hydroxide, silica flour, sodium dihydrogen phosphate, unsaturated polyester resin and isobutyl triethoxy silane are independent Separately packaging.
The present invention also provides use above-mentioned composition processing electrolytic manganese residues method, specifically: first 100 parts be electrolysed It is added in manganese slag after calcium hydroxide and silica flour after stirring 30min and stands 2h, and control moisture content between 35~45%;Add 5min is stirred after entering disodium hydrogen phosphate;Unsaturated polyester resin is added, is stirred 1~2min;It is 60~85 DEG C of items in temperature Isobutyl triethoxy silane is added under part, stirs 8~20min, obtains innoxious electrolytic manganese residues.
Compared with prior art, the invention has the following advantages:
For electrolytic manganese residues after compositions-treated provided by the invention, the harmful substance (manganese ion and ammonia nitrogen) in electrolytic manganese residues is equal It is processed, become innoxious electrolytic manganese residues.Obtained electrolytic manganese residues are no longer noxious materials, harmless to ambient enviroment.? The electrolytic manganese residues production all-sided fertilizer arrived will not contaminated soil, endanger human health, produce roadbed material, rain penetration will not be passed through Soil near to roadbed, to influence its surrounding enviroment.Materials for wall is made, distributes, influences without worry harmful substance Health.And the technological operation step is simple, does not also need to roast electrolytic manganese residues under 450~900 DEG C of hot conditions It burns 0.5~4 hour, 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
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
30min is stirred after 5 parts of calcium hydroxide and 5 parts of silica flour is added in the container that label is 1 first, stands 2h, and And control moisture content is 35%;It is added after 0.1 part of disodium hydrogen phosphate after stirring 5min, obtains product one;
Then 40 parts of unsaturated polyester resins are added in product one, is stirred 1min, obtains product two;
Finally by product two temperature be 60 DEG C under the conditions of be added 0.01 part of isobutyl triethoxy silane, stir 20min, obtain To innoxious electrolytic manganese residues.
Embodiment 2
30min is stirred after 6 parts of calcium hydroxide, 6 parts of silica flour is added in the container that label is 2 first, stands 2h, and Moisture content is controlled 40%;After 0.2 part of disodium hydrogen phosphate stirring 5min is added, product one is obtained;
Then 42 parts of unsaturated polyester resins are added in product one, is stirred 1.2min, obtains product two;
Finally by product two temperature be 62 DEG C under the conditions of be added 0.05 part of isobutyl triethoxy silane, stir 15min, obtain To innoxious electrolytic manganese residues.
Embodiment 3
30min is stirred after 8 parts of calcium hydroxide, 8 parts of silica flour is added in the container that label is 3 first, stands 2h, and Moisture content is controlled 42%;After 0.3 part of disodium hydrogen phosphate stirring 5min is added, product one is obtained;
Then 50 parts of unsaturated polyester resins are added in product one, is stirred 1.5min, obtains product two;
Finally by product two temperature be 70 DEG C under the conditions of be added 0.8 part of isobutyl triethoxy silane, stir 12min, obtain To innoxious electrolytic manganese residues.
Embodiment 4
9 parts of calcium hydroxide, 9 parts of silica flour stirring 30min is added in the container that label is 4 first, stands 2h, and control Moisture content processed is 45%;0.4 part of disodium hydrogen phosphate is added, after stirring 5min, obtains product one;
Then 52 parts of unsaturated polyester resins are added in product one, is stirred 1.8min, obtains product two;
Finally by product two temperature be 80 DEG C under the conditions of be added 0.1 part of isobutyl triethoxy silane, stir 10min, obtain To innoxious electrolytic manganese residues.
Embodiment 5
10 parts of calcium hydroxide, 10 parts of silica flour stirring 30min is added in the container that label is 5 first, stands 2h, and Moisture content is controlled 38%;0.5 part of disodium hydrogen phosphate is added, after stirring 5min, obtains product one;
Then 55 parts of unsaturated polyester resins are added in product one, is stirred 2min, obtains product two;
Finally by product two temperature be 85 DEG C under the conditions of be added 0.15 part of isobutyl triethoxy silane, stir 8min, obtain To innoxious electrolytic manganese residues.
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 (1)

1. a kind of composition for electrolytic manganese residues harmless treatment, it is characterised in that: including calcium hydroxide, silica flour, phosphoric acid Sodium dihydrogen, unsaturated polyester resin and isobutyl triethoxy silane, in parts by weight, the electrolytic manganese of every 100 parts of processing Slag, calcium hydroxide are 5~10 parts;Silica flour is 5~10 parts;Sodium dihydrogen phosphate is 0.1~0.5 part;Unsaturated polyester resin is 40~55 parts;Isobutyl triethoxy silane is 0.01~0.15 part.
CN201811511750.XA 2018-12-11 2018-12-11 A kind of composition for electrolytic manganese residues harmless treatment Pending CN109626864A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105236899A (en) * 2015-09-25 2016-01-13 湖南省小尹无忌环境能源科技开发有限公司 Harmless resource utilization method of zinc electrolysis acid leaching residue

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105236899A (en) * 2015-09-25 2016-01-13 湖南省小尹无忌环境能源科技开发有限公司 Harmless resource utilization method of zinc electrolysis acid leaching residue

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李登新: "《固体废物处理与处置》", 31 July 2014, 中国环境出版社 *

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