CN102745781A - Method for carrying out in-situ remediation on underground water nitrate pollution by adopting iron fuel cell - Google Patents
Method for carrying out in-situ remediation on underground water nitrate pollution by adopting iron fuel cell Download PDFInfo
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- CN102745781A CN102745781A CN2012102603983A CN201210260398A CN102745781A CN 102745781 A CN102745781 A CN 102745781A CN 2012102603983 A CN2012102603983 A CN 2012102603983A CN 201210260398 A CN201210260398 A CN 201210260398A CN 102745781 A CN102745781 A CN 102745781A
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Abstract
The invention discloses a method for carrying out in-situ remediation on underground water nitrate pollution by adopting an iron fuel cell. The method is characterized in that a double-chamber iron fuel cell is constructed, wherein an anode is arranged in an anode chamber filled with a pH buffer solution, an underground water-containing layer polluted by nitrate in an anaerobic environment is used as a cathode chamber, and a cathode is arranged in the cathode chamber; the anode and the cathode are connected by a lead, and a connecting resistor is connected in the lead in series; and both ends of a salt bridge are respectively soaked in the solutions of the anode chamber and the cathode chamber. The method has the advantages of simple structure, no organic carbon source, microbial strain or any other chemical substance needs to be added into the underground water, operation and maintenance are convenient, the method is quick to start, the nitrate degradation speed is high, the pollution remediation period of the underground water is short, the construction investment and the running cost are low, and no secondary pollution is generated.
Description
Technical field
The present invention relates to the method that a kind of groundwater azotate pollution original position is repaired, be specifically related to a kind ofly under the situation that lifeless matter is participated in, the method for nitrate nitrogen in underground water is removed in the electron reduction effect that utilizes the rail fuel battery to provide.
Background technology
Underground water is not only important component part of hydrology round-robin; Still human a kind of important Freshwater resources; Or even the only drinking water source of many people, fresh water 68% that in the world can be for people to use is underground water, about 50% population is the drinking water source with underground water.But because sewage and the discharging of trade effluent and the excessive use of seepage, agrochemical and agricultural chemicals; And soil has than high mineral solvability and low retentiveness; Nitrate salt very easily is penetrated into rainwater or field irrigation causes irreversible azotate pollution in the underground water, and pollution level constantly increases.Because nitrate concentration is too high in the tap water; Can bring out the carcinogenic substance that water body produces some nitrosaminess; Cause cancer, methemoglobinemia (claiming blue baby's syndromes again), lymphoma disease, therefore, carry out groundwater nitrate pollution remediation technology research and more and more receive publicity.
At present, groundwater azotate pollution reparation technology commonly used has physical removal method, chemical reduction method and biological denitrificaion method.The physical removal method comprises ion exchange method, reverse osmosis method, electroosmose process, absorption method etc.; These methods all can be removed the nitrate salt in the underground water effectively; But poor selectivity to nitrate removal; The liquid concentrator of handling the back generation needs further aftertreatment, and cost is expensive, and generally can only be used for the dystopy reparation.It mainly is to utilize reductive agent that the nitrate nitrogen reduction is removed that technology is removed in chemical reduction, and employed reductive agent and catalyzer contain heavy metal and organic pollutant, and not only cost is expensive, and very easily causes secondary pollution.Be CN101805065A, open day be that the Chinese patent on August 18th, 2010 discloses a kind of " a kind of method of repairing pollution of nitrate nitrogen in underground water " like publication number; It is to adopt substep liquid phase reduction and magnetic method preparation and select nanometer Fe/Cu particle; Add in the anoxybiotic nitrate soln; Remove nitrate salt,, operate also more convenient though the efficient of this method reparation pollution of nitrate nitrogen in underground water is higher; But the complex manufacturing technology of nanometer Fe/Cu particle, cost height, reacted heavy metal ion remains in the underground water can cause even more serious groundwater pollution.The biological denitrification denitride technology be research at present at most, the hottest groundwater azotate pollution based technique for in-situ remediation method; The biology in situ denitride technology needs in polluted underground water, to add reparation matrix; Like pretreated cotton, wheat straw waste, sawdust, old and useless newspaper; Or elemental sulfur, Zero-valent Iron, acetate, ethanol, sucrose, starch, hydrogen and methane etc., the advantage of groundwater azotate pollution biology in situ recovery technique is: need not underground water to be extracted out energy efficient; Receive other impurity in the underground water to disturb less; Invest lower; Equip simpler.Its shortcoming is: process monitoring and pollution repairing effect assessment difficulty; Operation and control difficulty are big; Be prone to cause secondary pollution; Microorganism culturing, domestication and maintenance process complicacy etc.The Chinese patent that is on July 29th, 2009 like publication number CN101492206, open day discloses a kind of " utilizing the corn straw original position to repair the method for groundwater azotate pollution "; It is in the underground water of azotate pollution; With corn straw or/and the corn straw hydrolyzed solution as denitrifying carbon source; Add the enriching floras liquid that is rich in the denitrifying bacterium flora; Remove the nitric nitrogen in the underground water through biological denitrification ", this invention gets final product the innoxious use stalk, can effectively eliminate groundwater azotate pollution again.But because stalk contains Persistent organic pollutants such as a large amount of xylogen, pectin, fat are cured, secondary pollution is serious; Need construct permeable reactive wall, construction costs is high, and later maintenance is difficult; Need add, cultivate and keep the special efficacy mikrobe of higher concentration, operational conditions is harsh, the engineering poor operability; Microbial growth is slow, and it is long to pollute repairing efficiency; Stalk need be through pre-treatment such as wet oxidation, acid-alkali treatment, steam explosions, and cost is high; Relict matter very easily causes ground water aquifer obstruction etc.
Summary of the invention
The objective of the invention is to overcome the weak point of existing groundwater nitrate pollution remediation technology, provide a kind of and need not that mikrobe is participated in, need not add organic carbon source, treatment effect is good, cost is low, control the method for repairing groundwater azotate pollution with employing rail fuel battery original position easy to maintenance, non-secondary pollution.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics that the present invention adopts rail fuel battery original position to repair the method for groundwater azotate pollution are: make up two chambers rail fuel battery; Anode places in the anolyte compartment that is full of the pH damping fluid; With the underground reservoir that receives azotate pollution under the anaerobic environment is cathode compartment, and negative electrode places in the cathode compartment, is connected with lead between anode and the negative electrode; The resistance that is connected in series in the lead, the two ends of salt bridge are dipped in respectively in the solution of anolyte compartment and cathode compartment.
The characteristics that the present invention adopts rail fuel battery original position to repair the method for groundwater azotate pollution also are:
Said anode is made up of a plurality of steel wire lump polyphones, hangs in the anolyte compartment.
Cylindrical or the square container that said anolyte compartment places the face of land, made by non-conducting material, or for adopting Steel Concrete on the ground, half or the pond of underground structure on the ground.
Said negative electrode adopts Stainless Steel Cloth, silk group or thin plate; Or be material with corrosion-resistant and the good graphite cake of conductivity, graphite rod or carbon cloth.
Said cathode compartment or for being filled with the encloses container that contains nitrate soln.
Said lead adopts the copper conductor or the stainless steel lead of outsourcing insulating material, applies with insullac at the tie point place of lead and anode and negative electrode.
Said resistance is that resistance is the resistance unit of 100-1000 Ω.
Said salt bridge is that to adopt mass concentration by transparent vinyl pipe filling heat of solution be 3% aqueous phosphate solution, after condensation, is cut into required length.
The present invention utilizes electrochemical principle; Make up the rail fuel battery, the electronics that iron anode produces constantly is transferred to cathode surface through lead, is reduced to nitrogen after the nitrate salt in the cathode compartment gets electronics; Realize denitrogenation; The hydrogen ion that denitrification process produces is in salt bridge transfers to the anolyte compartment, with in the pH damping fluid and remove.Compared with present technology, beneficial effect of the present invention is embodied in:
1, to adopt Zero-valent Iron be electron donor in the present invention, need not in underground water, to add organic carbon source, and not only easy to operate, cost is low, and can not cause secondary pollution.
2, the present invention does not need mikrobe to participate in, and running maintenance is easy, starts soon, and the nitrate salt degradation rate is high, and the groundwater pollution repairing efficiency is short.
3, the present invention adopts inert cathode, in the process of removing nitrate salt, can not introduce any other material to underground water, no any residual contaminants after the groundwater pollution reparation.
4, electrode materials of the present invention is cheap and easy to get, need not in underground water, to make up facilities such as reaction wall, after negative electrode places underground water; No longer need in underground water, increase or change any material in the operational process; The anolyte compartment places the face of land, only needs regular replenishment or changes a spot of pH damping fluid, convenient operating maintenance; Quantities is minimum, reduced investment.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is a lab scale result of study of the present invention.
Label among the figure: 1 anode, 2 anolyte compartments, 3 negative electrodes, 4 cathode compartments, 5 leads, 6 resistance, 7 salt bridges.
Embodiment
Referring to Fig. 1, anolyte compartment 2 is the cylindrical or square containers that place the face of land, made by non-conducting material in the present embodiment, or for adopting Steel Concrete on the ground, half or the pond of underground structure on the ground; Anode 1 adopts the steel wire lump of polyphone to hang in the anolyte compartment, charges into the pH damping fluid in the anolyte compartment 2, and the pH damping fluid is that mass concentration is 1% disodium phosphate soln or sodium carbonate solution.Cathode compartment 4 can be the container that airtight non-conductive material is made; Also can directly utilize underground reservoir, promptly, directly negative electrode 3 is positioned in the underground water through punching; Negative electrode 3 can adopt Stainless Steel Cloth, silk group, thin plate; Or the material that other is corrosion-resistant, conductivity is good formation, like graphite cake, graphite rod, carbon cloth etc., negative electrode 3 is immersed in the solution that contains nitrate salt in the cathode compartment 4.Anode 1 adopts the copper conductor or the stainless steel lead of outsourcing insulating material to be connected with negative electrode 3, and lead and electrode tie point place apply with insullac, and itself and the aqueous solution are isolated, and a resistance unit that resistance is 100-1000 Ω is connected in series in the lead 5.Adopt salt bridge 7 to connect between anolyte compartment 2 and the cathode compartment 4; The mass concentration that salt bridge 7 adopts the transparent vinyl pipe to load heat of solution is 3% aqueous phosphate solution; Cut into required length after the condensation and use, when loading the aqueous phosphate solution of heat of solution, avoid entrapped air; Prevent after the condensation residual bubble in the middle of salt bridge, the two ends of salt bridge 7 are immersed in respectively in the solution in anolyte compartment 2 and the cathode compartment 4.
In the present embodiment, the working process that rail fuel battery original position is repaired groundwater azotate pollution is:
Iron anode in the anolyte compartment 2 is pressed galvanic principles, and electrolysis produces electronics, and transfers to the cathode surface in the cathode compartment through lead; After nitrate ion in the cathode compartment obtains electronics; Be reduced into nitrogen, from underground water, discharge, realize the removal of groundwater azotate pollution; The proton that produces in the nitrate reduction process (hydrogen ion) then transfers in the anolyte compartment through salt bridge, is neutralized by the damping fluid in the anolyte compartment.
Utilize the simulated groundwater that contains nitrate salt of present embodiment two rail fuel Battery disposal laboratories, chamber configuration, cathode compartment and anolyte compartment all adopt the wide mouth of 225ml that the vial of sealing cover is arranged, and negative electrode adopts carbon cloth; Anode adopts steel wire lump, connects the resistance of the 1k Ω that is connected in series in the Stainless Steel Wire between negative electrode and the anode with Stainless Steel Wire; The internal diameter of salt bridge is that 1.5cm, length are 35cm; The anolyte compartment charges into sterilized buffered soln, and cathode compartment injects nitrate soln, and before experiment, uses N
2Stripping carried out deoxidation in 10 minutes.Two chambers rail fuel battery is seen Fig. 2 to the removal effect of nitrate salt, and when initial nitrate concentration was 365mg/L, the residue nitrate concentration after 28 days was 90.8mg/L, and the nitrate removal rate reaches 75.1%, and degradation speed is 9.79mgNO
3-/ Ld, and under the equal conditions, the interior nitrate salt residual concentration of cathode compartment that does not connect external circuit is 359.5mg/L, promptly the nitrate removal rate under the anaerobic condition has only 1.5%, and degradation speed is merely 0.19mgNO
3-/ Ld.Therefore, the rail fuel battery is 51 times of nitrate salt degradation rate under the natural surroundings to the degradation rate of nitrate salt in the underground water.In the experimentation, the voltage at the resistance two ends of external 1000 Ω of two chamber rail fuel batteries reaches 60mV.
Claims (8)
1. method that adopts rail fuel battery original position to repair groundwater azotate pollution; It is characterized in that making up two chambers rail fuel battery; Anode (1) places in the anolyte compartment (2) that is full of the pH damping fluid; With the underground reservoir that receives azotate pollution under the anaerobic environment is cathode compartment (4), and negative electrode (3) places in the cathode compartment (4), is connected with lead (5) between anode (1) and the negative electrode (3); The resistance (6) that is connected in series in the lead (5), the two ends of salt bridge (7) are dipped in respectively in the solution of anolyte compartment (2) and cathode compartment (4).
2. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution, it is characterized in that said anode (1) is made up of a plurality of steel wire lumps polyphones, hangs in the anolyte compartment (2).
3. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution; It is characterized in that: the cylindrical or square container that said anolyte compartment (2) place the face of land, made by non-conducting material, or for adopting Steel Concrete on the ground, half or the pond of underground structure on the ground.
4. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution, it is characterized in that: said negative electrode (3) adopts Stainless Steel Cloth, silk group or thin plate; Or be material with corrosion-resistant and the good graphite cake of conductivity, graphite rod or carbon cloth.
5. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution, it is characterized in that: said cathode compartment (4) or for being filled with the encloses container that contains nitrate soln.
6. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution; It is characterized in that: said lead (5) adopts the copper conductor or the stainless steel lead of outsourcing insulating material, and the tie point place with anode (1) and negative electrode (3) applies with insullac at lead (5).
7. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution, and it is characterized in that: said resistance (6) is that resistance is the resistance unit of 100-1000 Ω.
8. employing rail fuel battery original position according to claim 1 is repaired the method for groundwater azotate pollution; It is characterized in that: said salt bridge (7) is that to adopt mass concentration by transparent vinyl pipe filling heat of solution be 3% aqueous phosphate solution, after condensation, is cut into required length.
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| CN2012102603983A CN102745781A (en) | 2012-07-25 | 2012-07-25 | Method for carrying out in-situ remediation on underground water nitrate pollution by adopting iron fuel cell |
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| CN2012102603983A CN102745781A (en) | 2012-07-25 | 2012-07-25 | Method for carrying out in-situ remediation on underground water nitrate pollution by adopting iron fuel cell |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104330451A (en) * | 2014-08-28 | 2015-02-04 | 天能集团江苏科技有限公司 | Manufacturing method of salt bridge used in low temperature environment |
| CN104722570A (en) * | 2013-12-19 | 2015-06-24 | 中国科学院沈阳应用生态研究所 | Electric restoration method and device utilizing salt bridge to improve soil organic pollutant removal |
| CN104944532A (en) * | 2014-03-26 | 2015-09-30 | 宝山钢铁股份有限公司 | Treatment device and treatment method of cold rolling phosphorus-containing wastewater |
| CN108314147A (en) * | 2018-03-15 | 2018-07-24 | 大连理工大学 | A method of using fluffy steel wire lump as electrode original position treatment for reuse bath wastewater |
| CN112811528A (en) * | 2021-01-07 | 2021-05-18 | 北京化工大学 | Method for electrochemically reducing nitrate nitrogen and simultaneously outputting voltage |
| CN113526621A (en) * | 2020-07-07 | 2021-10-22 | 叶涛 | Method and device for treating nitrate radical-containing waste liquid |
-
2012
- 2012-07-25 CN CN2012102603983A patent/CN102745781A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722570A (en) * | 2013-12-19 | 2015-06-24 | 中国科学院沈阳应用生态研究所 | Electric restoration method and device utilizing salt bridge to improve soil organic pollutant removal |
| CN104722570B (en) * | 2013-12-19 | 2017-12-19 | 中国科学院沈阳应用生态研究所 | A kind of electric repair method and its device using salt bridge reinforced soil organic pollutant removal |
| CN104944532A (en) * | 2014-03-26 | 2015-09-30 | 宝山钢铁股份有限公司 | Treatment device and treatment method of cold rolling phosphorus-containing wastewater |
| CN104944532B (en) * | 2014-03-26 | 2018-03-09 | 宝山钢铁股份有限公司 | A kind of processing unit and processing method of cold rolling phosphorus-containing wastewater |
| CN104330451A (en) * | 2014-08-28 | 2015-02-04 | 天能集团江苏科技有限公司 | Manufacturing method of salt bridge used in low temperature environment |
| CN104330451B (en) * | 2014-08-28 | 2017-04-05 | 天能集团江苏科技有限公司 | The salt bridge manufacture method that a kind of low temperature environment is used |
| CN108314147A (en) * | 2018-03-15 | 2018-07-24 | 大连理工大学 | A method of using fluffy steel wire lump as electrode original position treatment for reuse bath wastewater |
| CN113526621A (en) * | 2020-07-07 | 2021-10-22 | 叶涛 | Method and device for treating nitrate radical-containing waste liquid |
| CN113526621B (en) * | 2020-07-07 | 2024-04-19 | 叶涛 | Method and device for treating nitrate-containing waste liquid |
| CN112811528A (en) * | 2021-01-07 | 2021-05-18 | 北京化工大学 | Method for electrochemically reducing nitrate nitrogen and simultaneously outputting voltage |
| CN112811528B (en) * | 2021-01-07 | 2022-03-01 | 北京化工大学 | Method for electrochemically reducing nitrate nitrogen and simultaneously outputting voltage |
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Application publication date: 20121024 |