CN101723488B - Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof - Google Patents

Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof Download PDF

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Publication number
CN101723488B
CN101723488B CN200910218398.5A CN200910218398A CN101723488B CN 101723488 B CN101723488 B CN 101723488B CN 200910218398 A CN200910218398 A CN 200910218398A CN 101723488 B CN101723488 B CN 101723488B
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iron
preparation
treatment
carbon
pollutant
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CN101723488A (en
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徐晓军
李新征
罗发生
陈映雪
张瑾
邱珉
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a water-treatment medicament and a preparation method thereof. The preparation method comprises the following steps of: uniformly coordinating a material containing carbon with a material containing iron oxide in a proper proportion; mixing and crushing coordination compounds, and then placing into a high temperature furnace; roasting at the temperature of 1000-1200 DEG C in a reduction or weak reduction environment for 10-30 minutes; cooling and then crushing to grain diameters less than or equal to 0.5 mm; and adding 0-10 percent of flocculants. The invention can be used for the treatment of poisonous and harmful pollutants with high COD and difficult degradation, i.e. a printing and dyeing pollutant, an electrofacing pollutant, a pharmaceutical pollutant, a surface active agent, and the like, and industrial waste water with higher chrominance and has the advantages of high treatment speed, quantitative addition, high treatment efficiency and stability.

Description

A kind of water treatment agent based on internal electrolysis principle and preparation method thereof
Technical field
The present invention relates to a kind of water treatment agent and preparation method thereof, particularly environment protection and metallurgical product technical field.
Background technology
The scientific worker of 20 century 70 USSR (Union of Soviet Socialist Republics) is the processing of cast iron filing for dyeing waste water, and the electrolysis treatment waster water process was updated in the iron charcoal in the last few years, was widely used.The method utilizes iron and carbon component to consist of small galvanic cell, take waste water as electrolyte solution, take electrochemical reaction as multiple effects such as main and set redox, absorption, flocculation, displacements, processes trade effluent.
When being immersed in iron and carbon in the waste water, if waste water has stronger acidity, reduced iron can and acid-respons generate Fe2+, under weak acid or the neutrallty condition because the difference in Electrode Potential between iron and the carbon, can the numerous little galvanic cell of formation in the waste water.The iron that wherein current potential is low becomes anode, and the carbon that current potential is high becomes negative electrode, and electrochemical reaction occurs, and its reaction process is as follows:
Anode (Fe): Fe-2e → Fe 2+,
Negative electrode (C): 2H ++ 2e → 2[H] → H 2, organic difficult degradation pollutent+ne → easily biodegradable organics, heavy metal ion+ne → heavy metal simple substance
The all right lower heavy metal ion of direct replacement activity of iron, as:
Fe+Cu 2+→Cu+Fe 2+
If aerobic exists in the water, following reaction can also occur:
O 2+4H ++4e→2H 2O;
O 2+2H 2O+4e→4OH -
2Fe 2++O 2+4H +→2H 2O+Fe 3+
From reaction, find out the Fe of the status nascendi of generation 2+With atom H, they have high chemically reactive, can change many organic structure and characteristics in the waste water, make the effects such as organism generation chain rupture, open loop.
Iron loss H in the reaction +And the OH of interior electrolytic reaction generation -The reason that water outlet pH value raises, and by Fe 2+The Fe that oxidation generates 3+Hydrolysis generates the large Fe (OH) of the polymerization degree gradually 3The colloid throw out can adsorb, condense the pollutent in the water effectively, thereby strengthens the decontamination effect improving to waste water.
Iron carbon internal electrolysis has the characteristics such as use range is wide, technique is simple, treatment effect is good, and especially the processing for the higher trade effluent of printing and dyeing, plating, pharmacy, the contour COD of tensio-active agent, difficult degradation, hazardous contaminant and colourity has more significantly advantage than other techniques.The waste water of difficult for biological degradation BOD/COD after iron carbon internal electrolysis process is processed improves greatly, is conducive to the raising of subsequent biological treatment effect.But there are some shortcomings in iron carbon internal electrolysis process at present:
1, the iron carbon granule is large, contact is insufficient, long reaction time;
2, the passivation of iron carbon surface and the problem that hardens;
The problems such as 3, the power consumption of fluidisation aeration iron carbon technique, technology controlling and process, the loss of iron carbon
Chinese patent CN101318726A discloses " a kind of iron-carbon filling material ", and it utilizes simple substance greying free state charcoal to be distributed to the interior electrolysis effectiveness of enhancing in the irony.Chinese patent CN1167627C discloses a kind of " method for the treatment of used water difficult to degradate by catalytic internal electrolysis of iron ", and it mixes by a certain percentage with copper iron, and adds surfactant-modified zeolite, makes filtrate, and waste water is processed.Can see the problems such as relevant internal electrolysis process or material improve to some extent, and treatment effect is strengthened, but all exists filtrate easily to harden, and easily runs off, and interior electrolysis electrode associativity is poor.The problems the such as seen research based on iron carbon internal electrolysis principle processing waste water does not still have thoroughly solution to add quantification, hardens, and activity is low.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, a kind of particulate state based on iron carbon internal electrolysis principle or Powdered water treatment agent and preparation method thereof are provided, be characterized in that processing speed is fast, quantitatively add, processing efficiency is high and stable.
Contain iron in the medicament of the present invention, it is characterized in that: the composition of said medicament is counted with % by weight: direct-reduced iron 60~90, surplus is gac and a small amount of impurity of combining closely with direct-reduced iron, and the form of said medicament is particulate state or Powdered, its granularity≤0.5mm.
The present invention can also add the flocculation agent of 0~10 % by weight, and said flocculation agent is any one in polymerize aluminum chloride, the polyacrylamide.
The preparation method of medicament of the present invention is characterized in that, preparation section is as follows:
A, be that 1/9~2/3 ratio mixes carbon raw material and iron-bearing material according to carbon and ferric oxide weight ratio;
B, miscellany are crushed to below 120 orders;
C, the B operation is made, the mixture in the baking oven after the oven dry places in the High Temperature Furnaces Heating Apparatus, in 1000~1200 ℃ of lower roastings 10~30 minutes, is crushed to particle diameter≤0.5mm after the cooling under reducing environment, makes particulate state or powdered medicament;
D, adding 0~10 % by weight flocculation agent are made the novel water-treatment medicament finished product based on internal electrolysis principle.
Employed carbon raw material is carbon content greater than 70% coal, coke or its combination among the above-mentioned preparation method, and when Coal and coke made up, the ratio between the two was arbitrarily; Employed iron-bearing material is to contain the ferric oxide amount greater than 1~3 kind in 60% iron ore concentrate, iron mud, the slag, and during 2~3 kinds of combinations in using iron ore concentrate, iron mud, slag, the ratio between its composition is arbitrarily.
Be compared with existing technology, the present invention has the following advantages or positively effect:
1, fe is direct-reduced iron, and specific surface area is large, and Adsorption is effective;
2, carbon is combined with iron evenly closely, and interior electrolytic action is strong and complete, applicable to neutral and weak basic condition waste water;
3, be swift in response, can quantitatively add, do not harden, the production quantity of slag is few.
Embodiment
The invention will be further described with embodiment for the below.The present invention is higher in order to carbon content, contain ferric oxide higher building material is raw material, and extra large bright and beautiful iron carbon is produced in high-temperature roasting under reducing environment, adds a small amount of flocculation agent again, consists of this novel water-treatment medicament.
Embodiment 1.
Water treatment agent preparation method of the present invention is as follows:
Raw material: low sulphur coal (carbon containing 72%), iron ore concentrate (containing ferric oxide 68%), polymerize aluminum chloride.Low sulphur coal and iron ore concentrate cooperate by weight 0.15.
Preparation: above-mentioned low sulphur coal and iron ore concentrate are mixed, be crushed to below 120 orders, put into High Temperature Furnaces Heating Apparatus after the oven dry in 1100 ℃ of lower roasting 10 clocks, be crushed to after the cooling below the diameter 0.5mm, add 2% polyacrylamide, namely make said water treatment agent.
After tested, the degree of metalization of iron is 82.6% in the above-mentioned preparation, contains reduced iron 88 % by weight, and specific surface area is 490m 2/ g.
Embodiment 2.
Raw material: low sulphur coal (carbon containing 78.8%), chemical iron mud (containing ferric oxide 81%), polymerize aluminum chloride.
Weight ratio: low sulphur coal and iron ore concentrate cooperate by 0.20/1.
Preparation: will cooperate below raw material pulverizing to 120 order, and put into High Temperature Furnaces Heating Apparatus after the oven dry in 1030 ℃ of lower roastings 22 minutes, and be crushed to after the cooling below the diameter 0.5mm, and add 10% polymerize aluminum chloride.
After tested, the degree of metalization of iron is 83.5% in the above-mentioned preparation, contains reduced iron 69 % by weight, and specific surface area is 590m 2/ g.
Embodiment 3.
Raw material: coke (carbon containing 84.6%), slag and iron ore concentrate mixture (containing ferric oxide 91%), polymerize aluminum chloride.
Weight ratio: low sulphur coal and iron ore concentrate cooperate by 0.30/1.
Make: will cooperate below raw material pulverizing to 120 order, and put into High Temperature Furnaces Heating Apparatus after the oven dry in 1180 ℃ of lower roastings 30 minutes, and be crushed to after the cooling below the diameter 0.3mm, and add 5% polymerize aluminum chloride.
After tested, the degree of metalization of iron is 87.2% in the above-mentioned preparation, contains reduced iron 81 % by weight, and specific surface area is 620m 2/ g.
Embodiment 4.
Raw material: 1: 1 mixture (carbon containing 84.6%) of coke and coal mass ratio, iron mud and slag mixture (containing ferric oxide 65%).
Weight ratio: low sulphur coal and iron ore concentrate cooperate by 0.35/1.
Make: will cooperate below raw material pulverizing to 120 order, and put into High Temperature Furnaces Heating Apparatus after the oven dry in 1200 ℃ of lower roastings 30 minutes, and be crushed to after the cooling below the diameter 0.3mm, and not add flocculation agent.
After tested, the degree of metalization of iron is 80.3% in the above-mentioned preparation, contains reduced iron 72 % by weight, and specific surface area is 620m 2/ g.
Embodiment 5
Raw material: coke (carbon containing 86%), iron ore concentrate, iron mud and slag mixture (containing ferric oxide 82%).
Weight ratio: low sulphur coal and iron ore concentrate cooperate by 0.32/1.
Make: will cooperate below raw material pulverizing to 120 order, and put into High Temperature Furnaces Heating Apparatus after the oven dry in 1110 ℃ of lower roastings 20 minutes, and be crushed to after the cooling below the diameter 0.3mm, and not add flocculation agent.
After tested, the degree of metalization of iron is 86.3% in the above-mentioned preparation, contains reduced iron 80 % by weight, and specific surface area is 610m 2/ g.
Show that by embodiment wastewater treatment experiment the present invention under equal conditions can improve 55% to COD, heavy metal ion average removal rate at the stirring aeration condition with respect to common iron carbon bed process; The removal time reduces about half under the effect same; Average water outlet BOD/COD value improves 20%.And successful under neutral and weak basic condition.

Claims (1)

1. the water treatment agent based on internal electrolysis principle is characterized in that,
Raw material: carbon containing is 72% low sulphur coal, contains ferric oxide and be 68% iron ore concentrate and polyacrylamide; Low sulphur coal and iron ore concentrate be 0.15 cooperation by weight,
Preparation section: above-mentioned low sulphur coal and iron ore concentrate are mixed, be crushed to below 120 orders, put into High Temperature Furnaces Heating Apparatus after the oven dry in 1100 ℃ of lower roasting 10 clocks, be crushed to after the cooling below the diameter 0.5mm, add 2% polyacrylamide, make powdered medicament, be i.e. said water treatment agent.
CN200910218398.5A 2009-12-21 2009-12-21 Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof Expired - Fee Related CN101723488B (en)

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Publication number Priority date Publication date Assignee Title
CN102557201B (en) * 2010-12-17 2014-02-26 上海洗霸科技股份有限公司 Micro-electrolysis filling material and preparation method thereof
CN103058310A (en) * 2011-10-18 2013-04-24 成都快典科技有限公司 Treatment method of malachite green dye wastewater
CN102807269A (en) * 2012-08-30 2012-12-05 张家港市三星净化设备制造有限公司 Microelectrolysis catalytic device for sewage treatment equipment
CN105502593B (en) * 2016-01-25 2019-01-01 山西德恒机电科技有限公司 The method of carbon thermal reduction synthesis Iron carbon reduction filler in situ
CN107930605B (en) * 2017-11-30 2021-05-04 重庆精创联合环保工程有限公司 Adsorbent for adsorption treatment of electroplating wastewater
CN109851002A (en) * 2019-02-12 2019-06-07 陕西煤业化工技术研究院有限责任公司 A kind of micro-electrolysis stuffing and its preparation method and application for realizing iron cement recycling
CN111439819A (en) * 2020-04-19 2020-07-24 东北石油大学 Flocculating agent for quickly and efficiently purifying strong-acid mine wastewater

Citations (4)

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CN101007671A (en) * 2006-01-26 2007-08-01 清远市灵捷制造化工有限公司 Powdery microelectrode for microelectrolysis treatment of indegradable industrial effluent
CN101200320A (en) * 2007-11-28 2008-06-18 河北理工大学 High-carbonaceous metallized pellet for treating waste water and preparation method
CN101318726A (en) * 2008-07-08 2008-12-10 无锡林信环保工程有限公司 Iron-carbon filling material
CN101402479A (en) * 2008-10-31 2009-04-08 山东锦程工贸有限公司 Process for producing fine electrolyser for wastewater treatment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101007671A (en) * 2006-01-26 2007-08-01 清远市灵捷制造化工有限公司 Powdery microelectrode for microelectrolysis treatment of indegradable industrial effluent
CN101200320A (en) * 2007-11-28 2008-06-18 河北理工大学 High-carbonaceous metallized pellet for treating waste water and preparation method
CN101318726A (en) * 2008-07-08 2008-12-10 无锡林信环保工程有限公司 Iron-carbon filling material
CN101402479A (en) * 2008-10-31 2009-04-08 山东锦程工贸有限公司 Process for producing fine electrolyser for wastewater treatment

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