CN101723488A - 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 PDFInfo
- Publication number
- CN101723488A CN101723488A CN200910218398.5A CN200910218398A CN101723488A CN 101723488 A CN101723488 A CN 101723488A CN 200910218398 A CN200910218398 A CN 200910218398A CN 101723488 A CN101723488 A CN 101723488A
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- Prior art keywords
- iron
- medicament
- preparation
- carbon
- treatment
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003814 drug Substances 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 100
- 229910052742 iron Inorganic materials 0.000 claims description 39
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003245 coal Substances 0.000 claims description 13
- 239000012141 concentrate Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 4
- 231100000719 pollutant Toxicity 0.000 abstract 4
- -1 and the like Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000008394 flocculating agent Substances 0.000 abstract 1
- 239000010842 industrial wastewater Substances 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001465 metallisation Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
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
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 seventies in 20th century, the scientific worker of USSR (Union of Soviet Socialist Republics) was used for the processing of dyeing waste water to cast iron filing, and the electrolysis treatment waster water process was updated in the iron charcoal in the last few years, was widely used.This method utilizes iron and carbon component to constitute small galvanic cell, is electrolyte solution with waste water, based on multiple effects such as electrochemical reaction and set redox, absorption, flocculation, displacements, handles trade effluent.
When being immersed in iron and carbon in the waste water, if waste water has stronger tart words, reduced iron can and acid-respons generation Fe
2+, under weak acid or the neutrallty condition because the difference in Electrode Potential between iron and the carbon can form numerous little galvanic cell in the waste water.Wherein the iron that current potential is low becomes anode, and the carbon that current potential is high becomes negative electrode, and electrochemical reaction takes place, 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 take place:
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 structures and characteristic in the waste water, make effects such as organism generation chain rupture, open loop.
Iron loss H in the reaction
+And the OH of interior electrolytic reaction generation
-Be the reason that water outlet pH value raises, and by Fe
2+The Fe that oxidation generates
3+Hydrolysis generates the big 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 characteristics such as use range is wide, technology 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 remarkable advantages more than other technologies.BOD/COD improved greatly after the waste water of difficult for biological degradation electrolysis process in iron carbon was handled, and helped the raising of subsequent biological treatment effect.But there are some shortcomings in electrolysis process in the iron carbon at present:
1, the iron carbon granule is big, contact is insufficient, long reaction time;
2, the passivation of iron carbon surface and the problem that hardens;
Problems such as 3, the power consumption of fluidisation aeration iron carbon technology, 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 handled.Electrolysis process or material improve to some extent inside the Pass can seeing mutually, and treatment effect is strengthened, but all exists filtrate easily to harden, and easily run off problems such as interior electrolysis electrode associativity difference.Problems such as seen still not thorough solution adds quantification based on iron carbon internal electrolysis principle Study on wastewater treatment, hardens, and activity is low.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of particulate state or Powdered water treatment agent and preparation method thereof based on iron carbon internal electrolysis principle is 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 weight %: direct-reduced iron 60～90, surplus is the gac and the small amount of impurities of combining closely with direct-reduced iron, and the form of said medicament is a particulate state or Powdered, its granularity≤0.5mm.
The present invention can also add the flocculation agent of 0～10 weight %, and said flocculation agent is any one in polymerize aluminum chloride, the polyacrylamide.
Medicaments preparation method 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, dried mixed material places in the High Temperature Furnaces Heating Apparatus in the baking oven, in 1000～1200 ℃ of following 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 weight % flocculation agent are made the novel water-treatment medicament finished product based on internal electrolysis principle.
Employed carbon raw material is a carbon content greater than 70% coal, coke or its combination among the above-mentioned preparation method, and when coal and coke combination, the ratio between the two is 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.
Compare with prior art, the present invention has following advantage or positively effect:
1, fe is a direct-reduced iron, and specific surface area is big, and the absorption removal effect is good;
2, carbon combines 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 below.The present invention is higher in order to carbon content, contain the higher material of ferric oxide is raw material, and extra large bright and beautiful iron carbon is produced in high-temperature roasting under reducing environment, adds small amount of flocculant again, constitutes 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, be crushed to after the cooling below the diameter 0.5mm, add 2% polyacrylamide, promptly make said water treatment agent in 1100 ℃ of following roasting 10 clocks.
After tested, the degree of metalization of iron is 82.6% in the above-mentioned preparation, contains reduced iron 88 weight %, and specific surface area is 490m
2/ g.
Embodiment 2.
Raw material: low sulphur coal (carbon containing 78.8%), chemical industry 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, and be crushed to after the cooling below the diameter 0.5mm, and add 10% polymerize aluminum chloride in 1030 ℃ of following roastings 22 minutes.
After tested, the degree of metalization of iron is 83.5% in the above-mentioned preparation, contains reduced iron 69 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, and be crushed to after the cooling below the diameter 0.3mm, and add 5% polymerize aluminum chloride in 1180 ℃ of following roastings 30 minutes.
After tested, the degree of metalization of iron is 87.2% in the above-mentioned preparation, contains reduced iron 81 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, and be crushed to after the cooling below the diameter 0.3mm, and not add flocculation agent in 1200 ℃ of following roastings 30 minutes.
After tested, the degree of metalization of iron is 80.3% in the above-mentioned preparation, contains reduced iron 72 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, and be crushed to after the cooling below the diameter 0.3mm, and not add flocculation agent in 1110 ℃ of following roastings 20 minutes.
After tested, the degree of metalization of iron is 86.3% in the above-mentioned preparation, contains reduced iron 80 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 effect is obvious under neutral and weak basic condition.
Claims (4)
1. novel water-treatment medicament based on internal electrolysis principle, contain direct-reduced iron and gac in the said medicament, it is characterized in that, the composition of said medicament is counted with weight %: direct-reduced iron 60～90, surplus is the gac and the small amount of impurities of combining closely with direct-reduced iron, the form of said medicament is a particulate state or Powdered, its granularity≤0.5mm.
2. according to the medicament of claim 1, it is characterized in that adding the flocculation agent of 0～10 weight %, described flocculation agent is any one in polymerize aluminum chloride, the polyacrylamide.
3. claim 1 and 2 medicaments preparation method 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, dried mixed material places in the High Temperature Furnaces Heating Apparatus in the baking oven, in 1000～1200 ℃ of following 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 weight % flocculation agent are made the novel water-treatment medicament finished product based on internal electrolysis principle.
4. preparation method according to claim 3 is characterized in that employed carbon raw material is a carbon content greater than 70% coal, coke or its combination, and when coal and coke combination, the ratio between the two is arbitrarily; Employed iron-bearing material is an iron-holder 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910218398.5A CN101723488B (en) | 2009-12-21 | 2009-12-21 | Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910218398.5A CN101723488B (en) | 2009-12-21 | 2009-12-21 | Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101723488A true CN101723488A (en) | 2010-06-09 |
| CN101723488B CN101723488B (en) | 2013-01-16 |
Family
ID=42445144
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910218398.5A Expired - Fee Related CN101723488B (en) | 2009-12-21 | 2009-12-21 | Novel water-treatment medicament based on internal electrolysis principle and preparation method thereof |
Country Status (1)
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557201A (en) * | 2010-12-17 | 2012-07-11 | 上海洗霸科技股份有限公司 | Micro-electrolysis filling material and preparation method thereof |
| 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 |
| WO2013056500A1 (en) * | 2011-10-18 | 2013-04-25 | 成都快典科技有限公司 | Malachite green dye waste water treatment method |
| CN105502593A (en) * | 2016-01-25 | 2016-04-20 | 山西德恒机电科技有限公司 | Method for synthesizing electrolytic packing in iron carbon through in-situ carbothermic reduction |
| CN107930605A (en) * | 2017-11-30 | 2018-04-20 | 重庆精创联合环保工程有限公司 | Adsorbent for electroplating wastewater adsorption treatment |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN100540477C (en) * | 2007-11-28 | 2009-09-16 | 河北理工大学 | A kind of high-carbonaceous metallized pellet and preparation method who is used to handle waste water |
| CN101318726A (en) * | 2008-07-08 | 2008-12-10 | 无锡林信环保工程有限公司 | Iron-carbon filling material |
| CN101402479B (en) * | 2008-10-31 | 2012-09-05 | 山东锦程工贸有限公司 | Process for producing fine electrolyser for wastewater treatment |
-
2009
- 2009-12-21 CN CN200910218398.5A patent/CN101723488B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557201A (en) * | 2010-12-17 | 2012-07-11 | 上海洗霸科技股份有限公司 | Micro-electrolysis filling material and preparation method thereof |
| WO2013056500A1 (en) * | 2011-10-18 | 2013-04-25 | 成都快典科技有限公司 | Malachite green dye waste water treatment method |
| 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 |
| CN105502593A (en) * | 2016-01-25 | 2016-04-20 | 山西德恒机电科技有限公司 | Method for synthesizing electrolytic packing in iron carbon through in-situ carbothermic reduction |
| CN107930605A (en) * | 2017-11-30 | 2018-04-20 | 重庆精创联合环保工程有限公司 | Adsorbent for electroplating wastewater adsorption treatment |
| 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 |
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