CN1260137C - Method for treating urban drinking water by radiation - Google Patents
Method for treating urban drinking water by radiation Download PDFInfo
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- CN1260137C CN1260137C CN200410044885.1A CN200410044885A CN1260137C CN 1260137 C CN1260137 C CN 1260137C CN 200410044885 A CN200410044885 A CN 200410044885A CN 1260137 C CN1260137 C CN 1260137C
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- 239000003651 drinking water Substances 0.000 title claims abstract description 22
- 230000005855 radiation Effects 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000010894 electron beam technology Methods 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 230000002285 radioactive effect Effects 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 abstract description 18
- 238000005660 chlorination reaction Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000004659 sterilization and disinfection Methods 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000008399 tap water Substances 0.000 description 12
- 235000020679 tap water Nutrition 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 10
- 230000015271 coagulation Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
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- 238000001728 nano-filtration Methods 0.000 description 5
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- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 238000000108 ultra-filtration Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical class O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
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- Physical Water Treatments (AREA)
Abstract
The present invention discloses a treatment method for drinking water. City drinking water is treated by an irradiation method so as to achieve the purposes of degrading chlorination by products in the city drinking water with high efficiency and meeting the requirements of high quality drinking water of people. Water which is treated by chlorination is irradiated using high-energy electron beams or gamma rays to remove halogenating organics in the water and obtain high quality yield water.
Description
Technical field
The present invention relates to a kind of treatment process of tap water, specifically utilize irradiation urban drinking water to be carried out the method for advanced processes.
Background technology
Chlorination is the sterilization means that extensively adopt during city water is handled always.Chlorination mainly works by hypochlorous acid (HOCl).The hypochlorous acid volume is little, neutral charge, and the cell walls that can see through bacterium is penetrated into bacterium inside, and oxidation destroys the enzyme system of bacterium and makes bacterium death.The chlorine disinfectant applicating history is long, use, convenient transportation, and cost is lower, chlorine has the very strong ability of killing to bacterium, it can keep some amount for a long time in water chlorine residue has lasting disinfecting power, is present most widely used general and the most cost-effective disinfectant.Yet its serious disadvantage of chlorine disinfectant is when organic content in the water source is high slightly, to produce chlorinatedorganic, and most of chlorinatedorganics all have " three cause " property (carcinogenic, teratogenesis, mutagenesis), serve as typical case's representative with haloform (THM) and halogen acetic acid (HAA) especially wherein.Western developed country has been listed the THM limit index in the Drinking Water national standard.With industrial development, the drinking water source quality constantly descends, and disinfectant consumption continues to increase, and disinfection byproduct (DBP) content is heightened, and is therefore, imperative to the removal of cholorination by product (DBPs).
The medium cholorination by product of tap water is removed in research, and the general processing mode of considering has: reduce precursor before chloridized; Form the back in disinfection byproduct (DBP) and reduce their concentration.Because it is bigger that disinfection byproduct (DBP) forms difficulty of post-processing, existing research is mostly considered from method improvement water treatment method two aspects of improving the tap water cholorination.
Remove precursor before the method for improvement tap water cholorination mainly contains chlorination, reduce chlorine dosage and duration of contact etc.
Drinking water hygiene the scholar mostly think, the essential measure of eliminating DBPs in the tap water is the condition of water quality that improves former water, promptly removes the precursor that may form DBPs in the water.Wherein mainly be solubility colourity and the total organic carbon of removing in the former water (TOC).The U.S.'s three kinds of methods that recommendation is adopted in the process of implementing the D/DBP regulations are enhanced coagulation method, granular carbon absorption method and membrane filter method at present, in addition, the biological oxidation process of employing and photochemical oxidation method are also arranged as pre-treating process.
1. enhanced coagulation method
The enhanced coagulation method is meant that under the common process flow process coagulating agent that adds excess is to improve organic clearance in the former water.It is removed mechanism and mainly contains 3 points: (1) charge neutrality, (2) precipitation, (3) co-precipitation.Because this method and technology is less demanding, need not to drop into substantial contribution, generally believed it is the optimal path of realizing the D/DBP regulations fs by the water treatment worker.The factor that influences coagulation effect has coagulating agent kind, consuming amount of concrete, coagulation pH value, mixes hydraulics, raw water quality variation and medicament dosing method etc.The THMs that this method forms chlorination is though through coagulation, precipitation and filtration, remove very few.In practice, also should consider the increase of the increase of sludge quantity in the water treatment procedure, the increase of turbidity, total pharmaceutical quantities and regulate the sulfuric acid consumption of coagulation and the soda-lime consumption of adjusting water outlet etc.
2. grain active carbon (GAC) filters
GAC is a kind of good water conditioner, and it mainly contains two kinds to organic removal mechanism: physisorption and microbiological deterioration.The GAC adsorption filtration not only can be removed dissolved organic matter content in the water, reduces the output of DBPs, and can directly remove DBPs, also can reduce the requirement of chlorine.But GAC filters the disinfection byproduct (DBP) of not degrading, and simultaneously, (Maximum Contamination Level when MCL) very low, needs often to change the charcoal core, and required expense is than higher when greatest contamination thing permissible level.In addition, delivery turbidity greatly also is the weak point of this method.
3. membrane filtration
Membrane filtration be one existing decades history maturation process, it is in recent years new development that this technology is used to the tap water the removal of disinfection byproduct (DBP) presoma.Film device can be divided into four kinds of nanofiltration (NF), reverse osmosis (RO), ultrafiltration (UF) and micro-filtrations (MF).Organism in the natural water mainly is a humic acids, and their molecular weight is less relatively, and the molecular weight variation range is paused in 100～1000 roads, thereby nanofiltration (NF) is best to removal effect of organic matter in the source water.The film softening process is in nanofiltration again, and its molecular weight cut-off is that 200～1000 roads pause, and organism can keep the mineral ion to the human body beneficial simultaneously in removing water.Remove organism in the water with membrane filtration and have that energy consumption is low, the simple advantage of equipment, but the work-ing life of film short, easily pollute, the difficult cleaning and the higher extensive utilization that has limited this technology of cost of film.
4. Biological Pretreatment
The Biological Pretreatment method generally is to set up biological treatment device (or structures) before conventional treatment process, metabolism by means of the microbial population (microbial film) of enrichment in this device, the condition of constantly inflation go down absorption, decomposition, oxidation, utilize all contaminations matter (mainly being organism) in the water source, coagulation, the sedimentation function of water have so promptly been improved, follow-up common process is carried out smoothly, reduce alum consumption and chlorine consumption, reduce the amount of " three cause " thing precursor in the water again, improved effluent characteristics.The main bio-contact oxidation technology that adopts in the tap water pre-treatment at present, filler has quartz sand, haydite and elastic stereo etc.Result of study shows that the bio-oxidation technology makes the organic concentration in the water that tangible reduction be arranged, and particularly ammonia nitrogen is had tangible clearance.But Biological Pretreatment need be built special structures, increases investment and working cost, promotes acquiring a certain degree of difficulty in existing water factory.
5. chemical oxidation
Chemical oxidization method is to utilize the higher oxygenant of oxidation potential energy (as O
3, KMnO
4, H
2O
2) etc., or photon and oxygenant, catalyst action are (as UV-H
2O
2, UV-O
3, UV-TiO
2) and oxygenant between the (O that interacts
3-H
2O
2) the free radical effect of the strong oxidizing property that produces, reach the organic purpose of oxygenolysis.As potassium permanganate (KMnO
4) pre-treatment, part TOC in the former water can be decomposed, formed Manganse Dioxide and other suspended substances are removed in coagulation, precipitation and filtration subsequently, thereby can reduce more than total DBPs50% in chloridized.
With KMnO
4Organism in the control water needn't change conventional water-purifying process flow process, only need or add KMnO before dosing coagulant simultaneously
4Solution, easy to operation.But not with O
3The organism of reaction can not be by KMnO
4Oxidation; KMnO
4Can not with the organism permineralization of its oxidation CO also
2And H
2O often generates many intermediate products; To the oxidation of humic class material in the surface water even may generate a small amount of THMs; KMnO
4Price is higher.Therefore, this method is still difficult promotes.
More than in the various removal tap water method of disinfection byproduct (DBP) such as DBPs all have separately relative merits, certain limitation is arranged in actual applications.Therefore it is imperative to develop new drinking water treatment technology.
Summary of the invention
The objective of the invention is problem, adopt the method for irradiation that urban drinking water is handled, reach cholorination by product in the efficient degradation urban drinking water, satisfy the demand of people the high quality tap water at above-mentioned prior art existence.
The objective of the invention is to realize by following measure:
The method of utilizing irradiation that urban drinking water is handled is characterized in that utilizing high-power electron beam or gamma-rays to carry out radiation treatment to the water body after handling through cholorination, removes wherein halogen acetic acid and haloform.
Described gamma-rays is a radioactive atom
60Co or
137Radiate during the Cs decay.
Described high-power electron beam is produced by high-energy electron accelerator.
The gamma-rays that radiates during the radioactive atom decay has great penetrating force, and industrial modal irradiation source is a radionuclide
60Co (cobalt) and
137Cs (caesium).And the controllability of high-power electron beam is good, and speed of reaction is fast, and penetration power is strong.High-power electron beam and gamma-rays can both produce the similar activity intermediate, and major different is that the dosage release rate of cobalt source gamma-radiation is relatively low.
It is basic identical that high-power electron beam and gamma-rays enter the reaction that water body takes place.After high-power electron beam or gamma-rays enter water body, 10
-7With water molecules following reaction taking place in second generates various active substances:
During the energy of the every absorption of the numeral in bracket 100eV, the quantity of the various free radicals that produce in the water.Irradiation is exactly that the moment and the water molecule reaction that utilize high-power electron beam or gamma-rays to enter water body produce active free radical e
Aq -, OH, H etc. handle water body.These free radicals OH, H, e
Aq -All be the high reactivity material, can be rapidly with water body in organism react, thereby reach the organic purpose of Degradation and Transformation.Because OH and e that reaction produces
Aq -Quantity is suitable substantially, also may be reductive action so the removal of pollutent may be an oxygenizement, and this depends primarily on concentration, chemical structure and the condition of water quality of pollutent.e
Aq -Be the intensive nucleophilic reagent, can and have the alkene and the phenyl ring kickback of electron-withdrawing group.For example: it and halogen-containing organism can have certain reaction, and its reaction pattern is generally:
。OH is a typical oxidizing agents, and it can bring out the chain reaction of back as the intermediate product of reaction, and in OH and the water most organic reaction velocity constants all 10
8～10
10M
-1S
-1Order of magnitude scope mainly is addition and proposes H-H reaction with the organism reaction.Addition mainly is and the organism that contains unsaturated link(age), as contains the organism of ethylene linkage and aromatic ring.Proposing H-H reaction mainly is and saturated fatty compounds of group and the reaction of many unsaturated compounds, as aldehydes and ketone organism.
The present invention compares with other traditional treatment method, and its irradiation technique carries out senior being in to urban drinking water and has the following advantages:
Its treating processes of urban drinking water generally comprises following steps in the prior art: former water → coagulation → precipitation → sand filtration → cholorination → water outlet, and radiation treatment of the present invention is the advanced treatment that the water body behind the cholorination is carried out, and has further improved the quality of tap water.
The standard oxidation of the free radical OH that produces in the present invention reaction also original position is only second to fluorine (2.87V) up to 2.80V, is the known the strongest oxygenant that can use in water treatment at present, and in OH and the water most organic reaction velocity constants all 10
8～10
10M
-1S
-1Order of magnitude scope; It can bring out the chain reaction of back as the intermediate product of reaction; OH does not have selectively direct and pollutant reaction is degraded to carbonic acid gas, water and mineral salt with it, can not produce secondary pollution; Because it is a kind of physical chemical process, be easy to be controlled, handle needs to satisfy, even can degrade 10
-9M
-1S
-1The pollutent of level; It both can be used as individual curing, can be complementary with other treating processes again, to reduce cost, satisfied processing requirements; The reaction conditions gentleness can effectively reduce the growing amount of DBP, is a kind of drinking water treatment technology of high-efficiency and energy-saving type.
The present invention need not the existing facility of the water factory of traditional tap water treatment process is changed on a large scale.After treatment, the clearance of main disinfection byproduct (DBP) halomethane (THMs) in the water outlet and halogen acetic acid (HAAs) is all near 100%; And this kind treatment process can also be removed the precursor of disinfection byproduct (DBP) effectively, has reduced the danger that raises in pipe network in disinfection byproduct (DBP) concentration, has improved the quality of the terminal resident's tap water of pipe network.
Embodiment
Embodiment 1: to the urban drinking water chlorine dosage is 6mg/L, pH value is 7.5, TOC concentration is 7.0mg/L, haloform concentration is about 40 μ g/L, and halogen acetic acid concentration is about the conventional waterworks water outlet of 30 μ g/L, through 1.5MeV, the high-power electron beam that the 50mA high-energy electron accelerator produces, under the irradiation dose of 3kGy, haloform concentration is brought down below 4 μ g/, and halogen acetic acid concentration is brought down below 5 μ g/L.And, when handling, also removed the precursor of part disinfection byproduct (DBP), when in pipe network, transporting, pass the increase of disinfection byproduct (DBP) concentration in time seldom, guaranteed the drinking water quality of pipe network end.Rise at 8.5 o'clock going out water ph value, the irradiation dose of 2kGy just can reach similar treatment effect, therefore, in the higher area of water quality pH value, can consider to reduce irradiation dose to reduce processing cost.
Embodiment 2: when the irradiation dose among the embodiment 1 changes 5kGy into, this two classes disinfection byproduct (DBP) of halomethane and halogen acetic acid can reach fully to be removed, for microorganism and the viral clearance that can reach 5log, but the irradiation cost significantly improves, and should look various places drinking water treatment requirement and choose irradiation dose.
Embodiment 3: it is 500 that the irradiation among the embodiment 1 adopts source strength, 000Ci
60The Co ray carries out irradiation, and other condition is constant, and treatment effect is constant substantially.
Embodiment 4: it is 500 that the irradiation among the embodiment 2 adopts source strength, 000Ci
60The Co ray carries out irradiation, and other condition is constant, and this two classes disinfection byproduct (DBP) of halomethane and halogen acetic acid can reach fully to be removed.
Embodiment 5: because the difference of urban drinking water source water water quality, and causes and the variation of chlorine dosage, TOC concentration under identical irradiation dose, can not produce remarkably influenced among the embodiment 1 the irradiation effect, and also constant substantially to the clearance of cholorination by product.
Claims (3)
1, the method for utilizing irradiation that urban drinking water is handled is characterized in that utilizing high-power electron beam or gamma-rays to carry out radiation treatment to the water body after handling through cholorination, removes wherein halogen acetic acid and haloform.
2, treatment process according to claim 1 is characterized in that what described high-power electron beam was produced by high-energy electron accelerator.
3, treatment process according to claim 1 is characterized in that described gamma-rays is a radioactive atom
60Co or
137Radiate during the Cs decay.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410044885.1A CN1260137C (en) | 2004-06-03 | 2004-06-03 | Method for treating urban drinking water by radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410044885.1A CN1260137C (en) | 2004-06-03 | 2004-06-03 | Method for treating urban drinking water by radiation |
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| Publication Number | Publication Date |
|---|---|
| CN1583580A CN1583580A (en) | 2005-02-23 |
| CN1260137C true CN1260137C (en) | 2006-06-21 |
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| CN200410044885.1A Expired - Fee Related CN1260137C (en) | 2004-06-03 | 2004-06-03 | Method for treating urban drinking water by radiation |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320677B (en) * | 2011-08-29 | 2013-05-08 | 上海大学 | Device for treating waste water by electron beam irradiation method |
| CN102351273A (en) * | 2011-09-23 | 2012-02-15 | 河南师范大学 | Closed wastewater treatment device utilizing high-energy photon |
| CN104326523A (en) * | 2014-10-22 | 2015-02-04 | 陕西华陆化工环保有限公司 | Method for degrading drinking water chlorination disinfection by-products |
| CN109592855B (en) * | 2019-01-21 | 2021-11-02 | 南华大学 | Method for strengthening advanced treatment of tail water of sewage treatment plant by using irradiation-artificial wetland combined process |
| CN109867324B (en) * | 2019-03-27 | 2021-10-19 | 湖北顶新环保生物质材料有限公司 | Method for improving sewage flocculation treatment effect |
| CN111020617A (en) * | 2019-12-26 | 2020-04-17 | 初强 | Technology and method for preparing hydrogen-oxygen combustible mixed gas by impacting water molecules with high-energy electrons |
| CN112897635A (en) * | 2021-01-27 | 2021-06-04 | 同济大学 | Method for removing organic chloramine in drinking water |
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2004
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