CN102616942A - Method for removing perchlorate from drinking water - Google Patents
Method for removing perchlorate from drinking water Download PDFInfo
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- CN102616942A CN102616942A CN2012101118660A CN201210111866A CN102616942A CN 102616942 A CN102616942 A CN 102616942A CN 2012101118660 A CN2012101118660 A CN 2012101118660A CN 201210111866 A CN201210111866 A CN 201210111866A CN 102616942 A CN102616942 A CN 102616942A
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- perchlorate
- autotrophy
- reduction
- water
- reduction process
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Abstract
The invention provides a method for removing perchlorate from drinking water. Based on a two-dimensional electrode-biofilm reactor, a mixed filler of elemental S<0> and activated carbon is added between a cathode and an anode to form a bipolar three-dimensional electrode-biofilm reactor. In the sulfur-based autotrophic reduction process of the perchlorate, the elemental S<0> is taken as an electron donor, the perchlorate is reduced to Cl<->, and H<+> and SO4<2-> are generated. The H<+> is reduced to H2 through electrochemical reaction of the activated carbon and an electrode in the reactor, and the H2 is taken as an electron donor in the hydrogen-based autotrophic reduction process of the perchlorate, so that the problems that the pH value of effluent is relatively low and the content of the SO4<2-> of the effluent exceeds the standard in the sulfur-based autotrophic reduction process of the perchlorate are effectively solved. The method is economical, efficient and easy to operate.
Description
Technical field
The invention belongs to field of environment engineering technology; Relating to a kind of method and reactor drum thereof of removing perchlorate in the tap water, specifically is sulphur autotrophy perchlorate reduction process and electrochemical hydrogen autotrophy perchlorate reduction process to be combined form multiple three-diemsnional electrode-biofilm reactor.
Background technology
Perchlorate is a kind of persistence toxic pollutant with high diffusion property; Be widely used in fields such as rocket propellant, pyrotechnics manufacturing and munitions industry, also be applied to lubricating oil, fabric fixing agent, electroplate liquid, magnesium cell, automotive air bag, highway safety Flash board, leather processing, rubber manufacturing, dyestuff and coating material production as additive.Perchlorate is mainly derived from discharge and the waste of producing and using perchlorate factory in the water body.Perchlorate is the material that belongs to non-volatile, soluble in water, the adsorptive power on most soil and mineral substance very a little less than, in case the entering environment will be with underground water and surface water rapid diffusion, thereby cause large-area underground water and surface water pollution.The chemical property of perchlorate is highly stable, is difficult for decomposing, and under the general environment condition, can long-term stability have many decades.Perchlorate's electric charge and the ionic radius that gets into human body through tap water is very close with iodide ion, and the Tiroidina with iodide ion competition entering human body causes thyroid function to lack of proper care; Cause the minimizing of Triiodothyronine and trilute resultant quantity; Final growth, the especially baby's who influences human body the metabolism and the growth of cns cause amentia; When serious marrow, muscle tissue are produced the pathology influence, bring out thyroid carcinoma.
Since nineteen ninety-seven, American National EPA (USEPA) has successively monitored out perchlorate in underground water, surface water and the tap water in 42 states such as California, and lists it in candidate pollution substance table, and regulation safe concentration scope is 4-18 μ g/L.Environmental pollution that perchlorate causes and HUMAN HEALTH safety-problems have caused international research person's great attention.Subsequently, American scholar such as Coates have systematically been analyzed the harm of perchlorate and have been repaired control strategy, thereby have led the research direction of perchlorate control techniques in the tap water.At present, China is the big country of fireworks manufacturing and consumption, production potassium perchlorate and oxidation additive, exists potential perchlorate contaminated source.Because the high resolution of perchlorate, traditional handling technology of water supply can not be removed perchlorate in the tap water effectively.Therefore, from ensureing the angle of drinking water safety, research and develop that perchlorate removal technology is necessary in efficient, the safe and economic tap water.
Perchlorate removal technology mainly contains ion exchange method, membrane separation process and biological reducing method.Ion exchange method can be removed the perchlorate in the water effectively, is widely used in the removal of perchlorate in the tap water.Need regeneration after but anionite-exchange resin is saturated, produce the perchlorate regenerated liquid of high density, the problem of subsequent disposal need be further carried out in existence.Membrane filter method can be removed the perchlorate in the tap water effectively, but processing cost is higher, and spissated perchlorate waste water also needs further to handle.The biological reducing method is a kind of economy, effective and safe perchlorate removal technology.In the biological reducing method, perchlorate reduction bacterium and electron donor are the keys of accomplishing the micro-reduction perchlorate.Big quantity research shows, can realize the reduction of perchlorate reduction bacterium to perchlorate with organism such as acetate, ethanol, lactic acid salts effectively as electron donor.But have following problem with organism as electron donor reduction perchlorate: (1) breeds the interior mikrobe of reactor drum as the organism sustainable supply of electron donor in a large number, can cause " microbial contamination " problem of water outlet; (2) organism that is not utilized by mikrobe in the water outlet is prone to cause microbial growth in the distribution system of water supply, and can produce deleterious chlorine disinfection by-product.In order to address the above problem, people have successfully carried out with H in succession
2Make the research of chemoautotrophy perchlorate reduction bacterium reduction perchlorate as electron donor.But, hydrogen as the electron donor process in, exist that hydrogen solubility is low, the shortcoming of explosive, storage and hard transportation, limited should technology large-scale promotion application.Simple substance S
0Not only having water-fast characteristics, in reduction process, can also discharge electronics as electron donor as required lentamente, and have and be easy to safeguard the advantage low with working cost, is a kind of inorganic electronic donor of efficient, economic autotrophy reduction perchlorate.But with S
0In the process as electron donor reduction perchlorate, because following reaction has taken place:: 2.87S
0+ 3.32H
2O+ClO
4 -+ 1.85CO
2+ 0.462HCO
3 -+ 0.462NH
4 +→ 5.69H
++ 2.87SO
4 2-+ Cl
-+ 0.462C
5H
7O
2On the low side and the SO of pH can appear in N in the water outlet
4 2-The problem that exceeds standard; If add CaCO
3Regulate the pH value, can occur the problem that the water hardness increases again.
Summary of the invention
Process to sulphur autotrophy reduction perchlorate exists the on the low side and SO of water outlet pH
4 2-The problem that exceeds standard, the present invention provides a kind of multiple three-diemsnional electrode-biofilm reactor to remove the method and the reactor drum thereof of perchlorate in the tap water.Its principle of work is following: on two-dimensional electrode biofilm reactor basis, between negative and positive the two poles of the earth, add simple substance S
0And gac.Simple substance S
0As electron donor and sulphur autotrophy reduction perchlorate microorganism carrier, gac is as hydrogen autotrophy reduction perchlorate microbe carrier.Sulphur autotrophy perchlorate reduction bacterium utilizes simple substance S
0The electronics that provides is reduced to Cl with perchlorate
-, and produce H
+And SO
4 2-Each activated carbon granule is equivalent to numerous small electrode-biofilm reactor, and electrochemical action is with the H that produces
+Be reduced to H
2, hydrogen autotrophy perchlorate reduction bacterium utilizes H
2Part perchlorate in the reductive water has been avoided the on the low side and SO of water outlet pH effectively
4 2-The problem that exceeds standard is removed technology thereby form in the low tap water of a kind of highly economical, working cost perchlorate.
Advantage of the present invention is following:
(1) H that in sulphur autotrophy perchlorate reduction bacterium reduction perchlorate process, produces
+, be reduced to H through electrochemical action
2,, avoided water outlet pH problem of lower effectively as the electron donor of hydrogen autotrophy reduction perchlorate;
(2) the activated carbon granule surface forms numerous small electrode-biofilm reactor, utilizes H
2As electron donor, reduction part perchlorate has been avoided water outlet SO effectively
4 2-The problem that exceeds standard;
(3) mikrobe in the reactor drum is with the autotrophic bacteria of inorganics as electron donor and nutritive substance, and the mud generation is little, is convenient to maintenance management;
(4) simple substance S
0Cheap with gac, and be easy to obtain.
Description of drawings
For accompanying drawing is seen in technical process of the present invention.
The former water that contains perchlorate in the former pond 1 is taken out liter by volume pump 2, gets into the packed column 4 that sulphur/gac carbon mixed fillers is arranged through water-in 3, simultaneously energized 8.Perchlorate in the water inlet produces H under the effect of sulphur autotrophy perchlorate reduction bacterium
+, it is reduced to H under the electrochemical action of positive pole 7 and negative electrode 5
2, the hydrogen autotrophy perchlorate reduction bacterium that is filled carbon granule surface adsorption in the post 4 is used to reduce perchlorate, and water is after treatment discharged through reactor outlet 6.
Embodiment
The present invention adopts the enforcement of technical scheme may further comprise the steps:
(1) gets the returned sluge or the anaerobic sludge of municipal sewage plant's secondary sedimentation basins, remove the impurity that is contained in the mud earlier, it is joined in the batch culture apparatus that contains the former water of higher concentration perchlorate, through adding certain density inorganic carbon source, simple substance S
0And inorganic nutrient substance, and regularly in the batch culture apparatus, feed hydrogen, sulphur autotrophy perchloric acid reduction bacterium and hydrogen autotrophy perchlorate reduction bacterium are tamed enrichment.In cultivation and domestication process, perchlorate, pH, Cl in the periodic monitor batch culture apparatus
-, SO
4 2-And redox potential (ORP) is cultivated the variation of acclimation period at each.When the perchlorate reduction effect after different cycles is stable, cultivate the domestication end of processing.
(2) will cultivate good sulphur autotrophy of domestication and the multiple three-diemsnional electrode-biofilm reactor of hydrogen autotrophy perchlorate reduction bacterium mixing sludge inoculation.Concrete grammar is following: sulfur-bearing autotrophy and hydrogen autotrophy perchlorate reduction bacterium mixing sludge are mixed according to 1: 5 volume proportion with water distribution, and perchlorate is greater than 5mg/L in the suggestion water distribution.Mud mixture is passed through in the peristaltic pump injecting reactor submergence simple substance S
0With the activated carbon granule filtrate, make perchlorate reduction bacterium attached to filtrate or be trapped in the space between the filtrate.After soaking 72h, the beginning low discharge is intake continuously, connects power supply and hangs film, and the perchlorate reduction efficiency reaches more than 85%, hangs film work and accomplishes.
(3) after multiple three-diemsnional electrode-biofilm reactor sludge seeding was accomplished, the former water that contains perchlorate got into the packed column 4 that sulphur/gac carbon mixed fillers is arranged from former pond 1 by volume pump 2 and water-in 3.Energized 8, the perchlorate in the water inlet produces H under the effect of sulphur autotrophy perchlorate reduction bacterium
+, it is reduced to H under the electrochemical action of positive pole 7 and negative electrode 5
2, and the hydrogen autotrophy perchlorate reduction bacterium that is filled carbon granule surface adsorption in the post 4 utilizes the reduction perchlorate, water is after treatment discharged through reactor outlet 6.
With following said embodiment the present invention is further specified.
Adopt multiple three-diemsnional electrode-biofilm reactor to be processed by stainless material in the instance, with the negative electrode of stainless steel cylinder as reactor drum, graphite carbon rod is as anode.Wherein, the internal diameter of negative electrode, height and area are respectively 7.5cm, 30cm and 706.5cm
2, anode internal diameter, height and interelectrode distance are respectively 35cm, 2.5cm and 2.5cm.This reactor drum FCV all is 1.324L.Select for use particle diameter be after the sulfur granules of 2～4mm and activated carbon granule that particle diameter is 1.5～2.5mm mix as the medium filler of reactor drum, sulphur in the reactor drum/gac carbon granule volume ratio is about 2: 1.In strength of current is that 50mA is under the situation of 9.3～14.8mg/L with water inlet perchlorate concentration; Hydraulic detention time is 6h; The clearance of perchlorate is more than 99.9%, and water outlet perchloric acid hydrochlorate concentration is in 4-18 μ g/L scope, and the scope of water outlet pH is 7.72～8.84.
Claims (5)
1. a method of removing perchlorate in the tap water is characterized in that, in same reactor drum, sulphur autotrophy perchlorate reduction process and electrochemical hydrogen autotrophy perchlorate reduction process is combined.
2. require described method according to right 1, wherein, sulphur autotrophy perchlorate reduction process is with simple substance S
0As electron donor.
3. require described method according to right 1, wherein, hydrogen autotrophy perchlorate reduction process is that the hydrogen that produces with electrochemistry is as electron donor.
4. according to right 1 described method, wherein, reduction of sulphur autotrophy perchlorate and electrochemical hydrogen autotrophy reduction perchlorate are to adopt simple substance S
0Particle and gac (or hard coal) carry out simple substance S for the fixed bed of filler
0The two ratio of particle and gac is 3: 1～2: 1.
5. according to right 3 described methods, wherein, electrochemical hydrogen autotrophy reduction perchlorate be with graphite as anode, stainless steel plate is as negative electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101118660A CN102616942A (en) | 2012-04-17 | 2012-04-17 | Method for removing perchlorate from drinking water |
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|---|---|---|---|
| CN2012101118660A CN102616942A (en) | 2012-04-17 | 2012-04-17 | Method for removing perchlorate from drinking water |
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|---|---|
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ID=46557224
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193317A (en) * | 2013-04-21 | 2013-07-10 | 北京工业大学 | Reinforced denitrification method for three-dimensional electrode biological film |
| CN103951054A (en) * | 2014-04-30 | 2014-07-30 | 华南理工大学 | Method for treating perchlorate in inorganic water body by using continuous flow anaerobic bioreactor |
| CN105236590A (en) * | 2015-11-11 | 2016-01-13 | 河南工业大学 | Method for deep degrading perchlorate in water through synergism of microorganism heterotrophism and electrochemistry hydrogen autotrophy |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN106830355A (en) * | 2017-02-07 | 2017-06-13 | 福建三炬生物科技股份有限公司 | A kind of minimizing technology and its device of the perchlorate of tea place irrigation water |
| CN107162117A (en) * | 2017-05-31 | 2017-09-15 | 南开大学 | A kind of method that electrochemical reduction removes perchlorate in water body |
| CN108946917A (en) * | 2018-06-21 | 2018-12-07 | 南京大学 | A kind of enhanced sulphur autotrophic denitrification sewage deep nitrogen rejection facility and method |
| CN111115842A (en) * | 2019-12-19 | 2020-05-08 | 西安交通大学 | Method for treating ammonium perchlorate wastewater |
| CN111943365A (en) * | 2020-08-19 | 2020-11-17 | 中国科学院烟台海岸带研究所 | Synchronous removing device and method for nitrate and sulfate in low-carbon high-nitrogen high-sulfur water body |
-
2012
- 2012-04-17 CN CN2012101118660A patent/CN102616942A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193317A (en) * | 2013-04-21 | 2013-07-10 | 北京工业大学 | Reinforced denitrification method for three-dimensional electrode biological film |
| CN103951054A (en) * | 2014-04-30 | 2014-07-30 | 华南理工大学 | Method for treating perchlorate in inorganic water body by using continuous flow anaerobic bioreactor |
| CN105236590A (en) * | 2015-11-11 | 2016-01-13 | 河南工业大学 | Method for deep degrading perchlorate in water through synergism of microorganism heterotrophism and electrochemistry hydrogen autotrophy |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN106830355A (en) * | 2017-02-07 | 2017-06-13 | 福建三炬生物科技股份有限公司 | A kind of minimizing technology and its device of the perchlorate of tea place irrigation water |
| CN107162117A (en) * | 2017-05-31 | 2017-09-15 | 南开大学 | A kind of method that electrochemical reduction removes perchlorate in water body |
| CN107162117B (en) * | 2017-05-31 | 2020-11-24 | 南开大学 | Method for removing perchlorate in water body through electrochemical reduction |
| CN108946917A (en) * | 2018-06-21 | 2018-12-07 | 南京大学 | A kind of enhanced sulphur autotrophic denitrification sewage deep nitrogen rejection facility and method |
| CN108946917B (en) * | 2018-06-21 | 2020-12-29 | 南京大学 | Enhanced sulfur autotrophic denitrification sewage deep denitrification device and method |
| CN111115842A (en) * | 2019-12-19 | 2020-05-08 | 西安交通大学 | Method for treating ammonium perchlorate wastewater |
| CN111943365A (en) * | 2020-08-19 | 2020-11-17 | 中国科学院烟台海岸带研究所 | Synchronous removing device and method for nitrate and sulfate in low-carbon high-nitrogen high-sulfur water body |
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Application publication date: 20120801 |