CN112777677A - Method for degrading smelly substances in water based on disinfection technology - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910001868 water Inorganic materials 0.000 title claims abstract description 86
- 239000000126 substance Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 30
- 230000000593 degrading effect Effects 0.000 title claims abstract description 21
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- LFYXNXGVLGKVCJ-FBIMIBRVSA-N 2-methylisoborneol Chemical group C1C[C@@]2(C)[C@](C)(O)C[C@@H]1C2(C)C LFYXNXGVLGKVCJ-FBIMIBRVSA-N 0.000 claims abstract description 51
- LFYXNXGVLGKVCJ-UHFFFAOYSA-N 2-methylisoborneol Natural products C1CC2(C)C(C)(O)CC1C2(C)C LFYXNXGVLGKVCJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 claims abstract description 51
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical group ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims abstract description 49
- JLPUXFOGCDVKGO-TUAOUCFPSA-N (-)-geosmin Chemical compound C1CCC[C@]2(O)[C@@H](C)CCC[C@]21C JLPUXFOGCDVKGO-TUAOUCFPSA-N 0.000 claims abstract description 46
- 239000001075 (4R,4aR,8aS)-4,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol Substances 0.000 claims abstract description 46
- JLPUXFOGCDVKGO-UHFFFAOYSA-N dl-geosmin Natural products C1CCCC2(O)C(C)CCCC21C JLPUXFOGCDVKGO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229930001467 geosmin Natural products 0.000 claims abstract description 46
- 238000006731 degradation reaction Methods 0.000 claims abstract description 42
- 230000015556 catabolic process Effects 0.000 claims abstract description 36
- 239000000645 desinfectant Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003651 drinking water Substances 0.000 claims description 17
- 235000020188 drinking water Nutrition 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 33
- 239000003814 drug Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005070 sampling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- 239000000460 chlorine Substances 0.000 description 29
- 238000009303 advanced oxidation process reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000003205 fragrance Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010813 internal standard method Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 238000013494 PH determination Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for degrading smelly substances in water based on a disinfection technology, which comprises the following steps: and adding a disinfectant solution into the water containing the smelly substances, then carrying out ultraviolet irradiation, and carrying out sampling analysis after a period of reaction to obtain the degradation effect of the smelly substances in the water. The odor substance is 2-methylisoborneol or geosmin, the disinfectant is chloramine solution, and the irradiation intensity of ultraviolet irradiation is 1.42-4.26 multiplied by 10‑6Einstein·L‑1·S‑1. The method has the advantages of simple operation, obvious effect, safe use and environmental protection. Can achieve better degradation effect in a short time under the normal temperature condition, and has good degradation effect under the neutral, acidic or alkaline conditionsThe application is as follows. The technology does not need to additionally increase other equipment and medicaments, is simple to operate, can realize the high-efficiency degradation of smelly substances in water, and can play the synergy of ultraviolet and chloramine combined disinfection.
Description
Technical Field
The invention relates to the field of water treatment technology application, in particular to a method for degrading smelly substances in water based on a disinfection technology.
Background
At present, the problem of smell of drinking water is a hot spot of general attention of researchers all over the world. 2-methylisoborneol (2-MIB) and Geosmin (GSM) are secondary metabolites produced by specific microorganisms and are the most common oxytetracycline-causing substances in drinking water sources. When the content of the above-mentioned substances is more than 10ng/L, unpleasant peculiar smell is generated, sensory indexes and drinkability of water are influenced, and worry about drinking water safety of consumers are caused. Therefore, the removal of these two typical odorants is of great significance for improving the quality of drinking water.
Scholars at home and abroad carry out a great deal of research on the removal technology of 2-MIB and GSM in drinking water, wherein the method mainly comprises the following steps: conventional treatment processes (coagulation, precipitation, filtration), adsorption, chemical oxidation, biological treatment and the like.
In general, the conventional treatment processes such as coagulation, precipitation, filtration and the like have poor removal effects on the 2-MIB and the GSM; powdered Activated Carbon (PAC) adsorption is the most common method for removing 2-MIB and GSM in water at present, but natural organic matters existing in natural water greatly reduce the adsorption capacity of the activated carbon on the 2-MIB and the GSM, a large amount of PAC is required to be added to achieve the expected target, and the treatment cost of water supply enterprises is greatly increased; common oxidants such as chlorine, chlorine dioxide and potassium permanganate hardly remove the 2-MIB and the GSM, and can kill the algae cells, so that the 2-MIB and the GSM in the algae cells are released into water, and further serious odor is caused; compared with other methods, the biological treatment method has the advantages of low cost, no need of adding chemical substances, no generation of new pollution and the like, but further research on the practical application of the technology is needed.
To solve the odor problem of 2-MIB and GSM in drinking water, advanced oxidation process has become a hot point of research, because the high activity free radical generated by the process can efficiently degrade the odor substances in drinking water. For example UV/H2O2，UV/TiO2，O3/H2O2And the like. However, these independent advanced oxidation processes require the construction of separate water treatment structures and the continuous addition of additional chemicals, which increases the operational burden of water supply enterprises and limits the popularization and application of the advanced oxidation processes. Aiming at the defect of an independent advanced oxidation process, the existing process of the drinking water plant is optimized and coupled to become an advanced oxidation system, and becomes one of new trends in the development of drinking water treatment processes.
At present, main water supply enterprises and newly built drinking water plants adopt chloramine or ultraviolet rays as a main disinfection mode. However, chloramine has weak oxidizing ability, low reactivity with 2-MIB and GSM, and is difficult to remove 2-MIB and GSM in drinking water; the intensity of the ultraviolet radiation during the ultraviolet disinfection process is difficult to degrade the 2-MIB and the GSM in the water. Although researches show that the vacuum ultraviolet can degrade the 2-MIB and the GSM, water molecules have strong absorption effect on the vacuum ultraviolet, so that the penetration thickness of the vacuum ultraviolet in a water layer is limited, a large number of active species are generated in a relatively limited space, and the ratio of self-recombination quenching is large, thereby influencing the efficiency of the vacuum ultraviolet and limiting the application of the vacuum ultraviolet in practical production.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides the method for degrading the smelly substances in the water based on the disinfection technology, does not need to add extra equipment and agents, is simple to operate, can play the synergy of the ultraviolet and chloramine combined disinfection, and can realize the efficient degradation of the smelly substances in the water.
The purpose of the invention is realized by the following technical scheme.
A method for degrading smelly substances in water based on a disinfection technology comprises the following steps:
firstly, adding a disinfectant solution into water containing smelly substances under the condition of ultraviolet lamp irradiation;
and secondly, continuously irradiating the ultraviolet lamp until the odor substances are degraded to be below the limit value specified by the water quality standard of the drinking water.
Preferably, the chloramine solution is formulated from sodium hypochlorite and ammonium sulfate or sodium hypochlorite and ammonium chloride.
Preferably, in any of the above embodiments, the disinfectant is a chloramine solution, and the concentration of the chloramine solution is 0.014 × 10-3mol/L～0.07×10-3mol/L。
Preferably, according to any of the above embodiments, the concentration of the chloramine solution is 0.025 × 10-3mol/L。
Preferably, in any of the above schemes, the irradiation intensity of the ultraviolet irradiation is 1.42-4.26 × 10- 6Einstein·L-1·S-1And the reaction time is 0.5-15 min.
Preferably, according to any of the above schemes, the irradiation intensity of the ultraviolet irradiation is 1.42 × 10-6Einstein·L-1·S-1And the reaction time is 5 min.
According to any scheme, the reaction pH value of the method is preferably 5-9.
An application of a method for degrading smelly substances in water based on a disinfection technology is applied to degrading 2-methylisoborneol and/or geosmin in water.
Preferably, the concentration of the 2-methylisoborneol and/or the geosmin is 10-150 ng/L.
The invention has the beneficial effects that:
by coupling ultraviolet disinfection with chloramine disinfection (i.e. the water after chloramine disinfection passes through an ultraviolet device), not only can the disinfection aim be achieved, but also chloramine in the water can be activated by ultraviolet rays to generate free radicals to form an advanced oxidation system (i.e. ultraviolet/chloramine (UV/NH))2Cl) advanced oxidation system) to achieve efficient removal of 2-MIB and GSM.
Compared with other advanced oxidation methods, the method has the advantages of simple operation, wide applicable pH range and the like, and can degrade odor substances in water and other organic matters.
The method of the invention irradiates ultraviolet light in water to excite chloramine solution to generate high-activity free radicals, and the free radicals can efficiently degrade odor substances in water in a short time and can also improve the sterilization and disinfection effects.
The method disclosed by the invention can be used for carrying out reaction at normal temperature, and can be used for efficiently degrading smelly substances in water without adding other activating agents.
In the method, the sodium hypochlorite solution, the ammonium sulfate solution and the ammonium chloride solution are all used for daily disinfection of a water plant, no additional medicament is needed to be purchased, and the method is easy to store and transport and convenient to use; the ultraviolet irradiation is simple to operate and easy to popularize and apply in practical application.
Under the irradiation of ultraviolet light, the disinfectant solution is put into the water body to be degraded, so that a good degradation effect can be achieved in a short time at normal temperature, and the disinfectant solution has good degradation effect under neutral, acidic or alkaline conditions.
The method disclosed by the invention is environment-friendly and simple to operate, can realize efficient degradation of smelly substances in water without additionally adding other equipment and medicaments, and can be used for deodorizing the water body before or after the conventional process of a water plant, so that the effective removal of the smelly substances is ensured, the synergy of ultraviolet and chloramine combined disinfection is also exerted, and the overall operation is simple and convenient.
Drawings
FIG. 1 is a standard curve for measuring 2-MIB prepared by the internal standard method according to an embodiment of the present invention, wherein the internal standard substance is 2-isobutyl-3-methoxy-pyrazolazine (IBMP);
FIG. 2 is a standard curve for GSM measurements made by the internal standard method according to an embodiment of the present invention, where the internal standard is 2-isobutyl-3-methoxy-pyrazolazine (IBMP);
FIG. 3 is a schematic diagram of the effect of using UV light and disinfectant to degrade the odorant in pure water according to the embodiment of the present invention;
FIG. 4 shows UV/NH under different UV irradiation2Degradation of 2-MIB by Cl;
FIG. 5 shows UV/NH under different UV irradiation2Degradation of GSM by Cl;
FIG. 6 shows UV/NH at different chloroamine concentrations2Degradation of 2-MIB by Cl;
FIG. 7 UV/NH at different chloramine concentrations2Degradation of GSM by Cl;
FIG. 8 UV/NH at different pH values2Degradation of 2-MIB by Cl;
FIG. 9 UV/NH at different pH values2Degradation of GSM by Cl.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
1. A method for degrading smelly substances in water based on a disinfection technology comprises the following steps:
firstly, adding a disinfectant solution into water containing smelly substances under the condition of ultraviolet lamp irradiation;
and secondly, continuously irradiating the ultraviolet lamp until the odor substance is degraded to be below the limit value specified in the sanitary Standard for Drinking Water (GB 5749-.
The method has a reaction pH value of 5-9 and adopts phosphoric acid buffer solution for adjustment.
The disinfectant is chloramine solution with the concentration of 0.014 multiplied by 10-3mol/L～0.07×10- 3mol/L; preference is given toThe concentration of the chloramine solution is 0.025 x 10-3And the chloramine solution is prepared from sodium hypochlorite and ammonium sulfate or sodium hypochlorite and ammonium chloride in mol/L.
The irradiation intensity of the ultraviolet irradiation is 1.42-4.26 multiplied by 10-6Einstein·L-1·S-1The reaction time is 0.5-15 min; preferably, the irradiation intensity of the ultraviolet irradiation is 1.42 × 10-6Einstein·L-1·S-1And the reaction time is 5 min.
2. Verification experiment of scheme for degrading smelly substances in pure water by combining ultraviolet with chloramine solution
The average degradation effect in the following table is the average result of three parallel tests.
(1) Taking 4 20mL CTC special sample bottles containing 2.50g NaCl, preparing 10mL standard solutions of smelling substances with Mass concentrations of 10, 50, 100 and 200ng/L with ultrapure water, adding 20 μ L of an internal standard substance (2-isobutyl-3-methoxy-pygmine (IBMP)) with a concentration of 10mg/L, measuring by a headspace solid phase microextraction-Gas Chromatography-Mass Spectrometer (GC-MS) and drawing a standard working curve by taking the ratio of peak areas of the target substance to the internal standard substance as an abscissa and the concentration of the target substance as an ordinate, as shown in FIG. 1 and FIG. 2.
FIG. 1 is a standard curve for measuring 2-MIB prepared by internal standard method according to the embodiment of the present invention, and the abscissa is A2-MIB/AIBMPThe ratio of the peak area of the substance measured by GC-MS is shown, and the ordinate thereof is C2-MIBThe concentration of 2-MIB formulated is shown, and the equation fitted to the trend line of the measured data is y 7.2903x +1.4483, with a linear coefficient R2The measurement requirement can be met by 0.9995.
FIG. 2 is a standard curve for measuring GSM prepared by internal standard method according to the embodiment of the present invention, and the abscissa is AGSM/AIBMPWith ordinate C2-MIBThe fitting equation of the measured data trend line is y-51.747 x-0.6113, wherein the linear coefficient is R2The measurement requirement can be met by 0.9995.
(2) By purePreparing 500ml mixed solution with chloramine concentration of 0.07mM and odorous substance concentration of 100-150 ng/L by using water, adjusting the pH of the solution to 7 by using PBS buffer solution, adding the prepared odorous substance solution into a reactor provided with an ultraviolet lamp tube, and irradiating by using ultraviolet lamp light to obtain the product with the ultraviolet lamp light irradiation of 4.26 multiplied by 10-6Einstein·L-1·S-1At times of 0.5, 1, 1.5, 2, 3, 5min, respectively, 10ml of the sample was added to a CTC-only sample bottle already containing 2.5g of NaCl, and 100. mu.l of sodium thiosulfate at a concentration of 0.1M was added as a quencher, and 20. mu.l of IBMP at a concentration of 10mg/L was added.
(3) The concentrations of IBMP and 2-MIB at different times were measured on GC-MS by internal standard method, and the degradation effect of the smelly substance during the reaction time is shown in Table 1.
The degradation effect of the disinfectant is changed along with time as shown in fig. 3, and fig. 3 is a schematic diagram of the effect of degrading 2-MIB in water by using ultraviolet and the disinfectant in combination according to the embodiment of the invention. The experimental procedure for GSM degradation was as above.
In FIG. 3, C represents the residual concentration (ng/L), C0The initial concentration (ng/L) is expressed and the ordinate is the ratio of the residual concentration to the initial concentration, thereby reflecting the degradation effect.
TABLE 1 degradation of odorants in reaction time
| Time (min) | Average degradation effect of 2-MIB | Average degradation effect of |
| 0 | 0 | 0 |
| 0.5 | 26.45％ | 36.94％ |
| 1 | 38.91％ | 51.26％ |
| 1.5 | 53.14％ | 61.80％ |
| 2 | 61.57％ | 71.80％ |
| 3 | 71.41％ | 81.35％ |
| 5 | 80.00％ | 85.59％ |
In summary, UV combined with disinfectants (chloramine solutions) can degrade the odor substances in pure water and UV/NH2The reaction principle of the Cl advanced oxidation system is as follows:
NH2Cl+hv→·NH2+·Cl
HOCl/OCl-+hv→·OH+·Cl
·Cl+OH-/H2O→ClOH·-→Cl-+·OH
ultraviolet combined with chloramine can generate highly active free radicals (Cl, OH and NH)2Etc.) can efficiently degrade 2-MIB and GSM which are difficult to degrade in water, can reduce the odor of the water, has the degradation rate of over 80 percent, and can effectively purify the water quality.
3. Ultraviolet and chloramine solution combined degradation of smelly substance in pure water, determination of UV irradiation condition
Separately preparing NH by pure water2Adding 500ml of mixed solution with the Cl solution concentration of 0.07mM and the odor substance concentration of 60-80 ng/L into a reactor provided with an ultraviolet lamp tube, adjusting the pH of the solution to 7 by using PBS buffer solution, and adding the prepared odor substance solution into the reactor, wherein the ultraviolet radiation intensity is 1.42 multiplied by 10 respectively-6、2.84×10-6、4.26×10-6Einstein·L-1·S-1At times 0, 1, 3, 5, 8, 10min respectively, 10ml of the sample was added to a CTC-only sample bottle already containing 2.50g of NaCl, and 100. mu.l of sodium thiosulfate as a quencher at a concentration of 0.1M and 20. mu.l of IBMP at a concentration of 10mg/L were added. The effect of the degradation of odorants during the reaction time is shown in FIGS. 4 and 5.
Under different UV irradiation, UV/NH2The Cl advanced oxidation process has good removal effect on both 2-MIB and GSM, the removal rates of the 2-MIB and the GSM are increased along with the increase of the irradiation intensity, and under three different ultraviolet irradiation conditions, after reaction for 10min, the removal rates of the 2-MIB and the GSM are 77.7 percent and 86.8 percent, 83.6 percent and 90.4 percent, 87.0 percent and 97.8 percent respectively. 1.42X 10-6Einstein·L-1·S-1Under the condition, the 2-MIB and the GSM have higher removal rate, and the light intensity of a low range is preferred from the viewpoint of energy saving.
4. Ultraviolet and chloramine solution combined degradation of smelly substance in pure water, determination of chloramine concentration condition
Preparing 500ml of mixed solution with chloramine concentration of 0.007mM, 0.014mM, 0.025mM, 0.05mM, 0.07mM, 0.1mM and odor substance concentration of 60-80 ng/L with pure water, and using ultraviolet lamp with light irradiation intensity of 1.42 × 10 to save energy to the maximum-6Einstein·L-1·S-1The olfactive substance degradation experiment is carried out, and other experimental methods are the same as the determination experiment of the UV radiation condition. The effect of the degradation of odorants during the reaction time is shown in FIGS. 6 and 7.
From the viewpoint of energy saving, a lower UV irradiation intensity (1.42X 10) is selected-6Einstein·L-1·S-1) To reduce the smell of the substancesAnd (5) performing solution experiments.
When the concentration of chloramine is less than 0.014mM, the removal rate of 2-MIB and GSM is still low after the continuous reaction for 10min, and the effluent can not meet the standard specified by drinking water, so that the concentration of chloramine less than 0.014mM is not suitable for being applied in actual production; when the concentration of chloramine is more than 0.07mM, the removal rate of 2-MIB and GSM after the continuous reaction for 10min is lower than that of 0.07mM, which indicates that the removal rate of 2-MIB and GSM is not improved by increasing the concentration of chloramine, and the high dosage of chloramine in the actual production can generate a large amount of disinfection byproducts and cause unnecessary waste, so the concentration of chloramine more than 0.07mM is not suitable for the actual production.
At 0.014X 10-3mol/L-0.07×10-3UV/NH at different chloramine concentrations between mol/L2The Cl advanced oxidation process has good removal effect on both 2-MIB and GSM, 0.025mM NH2Under Cl conditions, UV/NH2The Cl has the best removal effect on the 2-MIB and the GSM, the removal rates of the 2-MIB and the GSM after 10min reaction reach 92.2 percent and 92.8 percent respectively, and the 2-MIB and the GSM are almost completely removed, so 0.025mM is selected as NH2The optimum concentration of Cl.
In the actual operation of the water plant, the concentration of the inlet water 2-MIB and the GSM of the water plant generally does not exceed 30ng/L, so when the removal rate reaches more than 70%, the outlet water 2-MIB and the GSM can meet the standard limit value specified in the sanitary Standard for Drinking Water (GB5749 and 2006) in China. 0.025mM NH2After 5min of reaction under Cl condition, UV/NH2The removal rates of Cl to 2-MIB and GSM reach 74.0 percent and 83.9 percent respectively, and NH with certain concentration still remains in the water2Cl, can meet the requirements of the subsequent disinfection process. Therefore, 0.025mM is selected as NH2The optimal concentration of Cl is 5min, the optimal reaction time is 5min, namely the effluent concentration reaches the standard limit value specified in sanitary Standard for Drinking Water (GB 5749-.
5. Ultraviolet and chloramine solution combined degradation of odor substances in pure water, and determination of pH value condition
Preparing three groups of 500ml mixed solutions with chloramine concentration of 0.025mM and olfactory substance concentration of 60-80 ng/L by using pure water, adjusting the pH values to be 5, 7 and 9 respectively by using a phosphoric acid buffer solution, and carrying out an olfactory substance degradation experiment. The effect of the degradation of odorants during the reaction time is shown in FIGS. 8 and 9.
UV/NH at pH 52The Cl advanced oxidation process is best for the removal of 2-MIB and GSM, while UV/NH at pH 7 and 92The Cl advanced oxidation process also provides high removal of 2-MIB and GSM, thus, UV/NH at different pH ranges2The Cl advanced oxidation process has good removal effect on both 2-MIB and GSM.
Example 1
According to the optimum experimental conditions determined by the pure water experiment, the ultraviolet radiation intensity is 1.42 multiplied by 10- 6Einstein·L-1·S-1UV/NH was carried out at a chloramine concentration of 0.025mM and a pH of 72And (3) Cl advanced oxidation process for removing odor substances in an actual water source. Preparing 500ml of mixed solution with the concentration of the smelly substances of 100-150 ng/L by using a water source of Yangtze river, adding the prepared smelly substance solution into a reactor provided with an ultraviolet lamp tube, adding 10ml of sample into a CTC special sample bottle already containing 2.50g of NaCl when the time is 0, 1, 2, 5, 10 and 15min, respectively, adding 100 mu L of sodium thiosulfate with the concentration of 0.1M as a quenching agent and 20 mu L of IBMP with the concentration of 10mg/L, and carrying out a degradation experiment on the smelly substances, wherein the degradation effect of the smelly substances within the reaction time is shown in Table 2.
TABLE 2 degradation of odorants in Yangtze river Water during the reaction time
| Time (min) | Average degradation effect of 2-MIB | Average degradation effect of |
| 0 | 0 | 0 |
| 1 | 19.81％ | 24.07％ |
| 2 | 30.76％ | 38.09％ |
| 5 | 51.30％ | 61.17％ |
| 10 | 61.63％ | 71.89％ |
| 15 | 66.84％ | 76.75％ |
The embodiment is characterized in that the combination of ultraviolet and a disinfectant (chloramine solution) is used for degrading smelly substances in Yangtze river water, the combination of ultraviolet and chloramine can effectively degrade 2-MIB and GSM which are difficult to degrade in Yangtze river water, the ultraviolet/chloramine coupling process can be used as a pretreatment process for removing the smelly substances in an actual water source, but natural organic matters existing in the actual water source Yangtze river water can reduce UV/NH2The Cl advanced oxidation process has the effect of removing smelly substances.
Example 2
At an intensity of ultraviolet radiation of 1.42X 10-6Einstein·L-1·S-1And chloramine concentration of 0.025mM, pH 7, coagulation, precipitation and filtration in pilot plant treatment to obtain a river water (28390; 2-MI is present in river water)B) 500ml of a mixed solution with an odorant concentration of 100 to 150ng/L was prepared, and the degradation test of odorant in river water was performed by the method similar to that in example 1 at 28390, and the effect of degradation of odorant in reaction time is shown in Table 3.
TABLE 3 reaction time 28390 effect on degradation of odor substances in river water
| Time (min) | Average degradation effect of 2- |
| 0 | 0 |
| 1 | 9.56％ |
| 2 | 16.44％ |
| 5 | 44.36％ |
| 10 | 71.32％ |
| 15 | 81.64％ |
The embodiment combines ultraviolet and disinfectant (chloramine solution) to degrade the < lambda > 28390processed by the coagulation, precipitation and filtration pilot plant, the < lambda > 28390can effectively degrade the < lambda > 28390processed by the coagulation, precipitation and filtration pilot plant when the < lambda > ultraviolet and chloramine are used together, and the < lambda > 28390can be seen from the < lambda > 2-MIB </lambda > which is difficult to degrade in the < lambda > 2-MIB </lambda > river waterAfter the water is treated by the conventional process of a water plant, the deep treatment adopts an ultraviolet/chloramine coupling process, and well removes odor substances in the water of \28390river, so that the UV/NH is2The Cl advanced oxidation process can be used as an advanced treatment process of a water plant to further purify the water quality of an actual water body, and has a certain application prospect.
The two embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A method for degrading smelly substances in water based on a disinfection technology is characterized by comprising the following steps: the method comprises the following steps:
firstly, adding a disinfectant solution into water containing smelly substances under the condition of ultraviolet lamp irradiation;
and secondly, continuously irradiating the ultraviolet lamp until the odor substances are degraded to be below the limit value specified in the sanitary Standard for Drinking Water (GB5749-2006) in China.
2. The method for degrading smelling substances in water based on disinfection technology as claimed in claim 1, wherein: the chloramine solution is prepared from sodium hypochlorite and ammonium sulfate or sodium hypochlorite and ammonium chloride.
3. The method for degrading smelling substances in water based on disinfection technology as claimed in claim 2, wherein: the disinfectant is chloramine solution with the concentration of 0.014 multiplied by 10-3mol/L～0.07×10-3mol/L。
4. The method for degrading smelling substances in water based on disinfection technology as claimed in claim 3, wherein: the concentration of the chloramine solution is 0.025 x 10-3mol/L。
5. The base of claim 1The method for degrading smelly substances in water by using a disinfection technology is characterized by comprising the following steps of: the irradiation intensity of the ultraviolet irradiation is 1.42-4.26 multiplied by 10-6Einstein·L-1·S-1And the reaction time is 0.5-15 min.
6. The method for degrading smelling substances in water based on disinfection technology as claimed in claim 5, wherein: the irradiation intensity of the ultraviolet irradiation is 1.42 multiplied by 10-6Einstein·L-1·S-1And the reaction time is 5 min.
7. The method for degrading smelling substances in water based on disinfection technology as claimed in claim 1, wherein: the method has a reaction pH value of 5-9.
8. Use of a method for the degradation of smelling substances in water based on disinfection technology according to any of claims 1-7, characterized in that: the method is applied to degrading 2-methylisoborneol and/or geosmin in water.
9. Use of a method for the degradation of smelling substances in water based on disinfection technology according to claim 8, characterized in that: the concentration of the 2-methylisoborneol and/or the geosmin is 10-150 ng/L.
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