WO2017143992A1 - 一种控制水中氯代含氮消毒副产物的方法 - Google Patents

一种控制水中氯代含氮消毒副产物的方法 Download PDF

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WO2017143992A1
WO2017143992A1 PCT/CN2017/074505 CN2017074505W WO2017143992A1 WO 2017143992 A1 WO2017143992 A1 WO 2017143992A1 CN 2017074505 W CN2017074505 W CN 2017074505W WO 2017143992 A1 WO2017143992 A1 WO 2017143992A1
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water
disinfection
persulfate
products
aeration
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French (fr)
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楚文海
李冬梅
高乃云
丁顺克
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Tongji University
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/32—Details relating to UV-irradiation devices
    • C02F2201/322—Lamp arrangement
    • C02F2201/3221—Lamps suspended above a water surface or pipe
    • 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
    • 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
    • C02F2303/18—Removal of treatment agents after treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the invention belongs to the technical field of water treatment and relates to a method for controlling chlorinated nitrogen-containing disinfection by-products in water.
  • Drinking water safety is a major liability issue for thousands of households.
  • Drinking water disinfection is an indispensable treatment for drinking water safety.
  • the widely used chlorine disinfection process can effectively kill bacterial viruses, but it also produces harmful disinfectants.
  • Products DBPs.
  • C-DBPs carbon-containing disinfection by-products
  • chloroform carbon-containing disinfection by-products
  • N-DBPs nitrogen-containing disinfection by-products
  • the chlorinated N-DBPs which are currently receiving more attention include: halogenated acetonitrile (HANs), haloacetamide (HAcAms) and halogenated nitromethane (HNMs). They are often present in drinking water after chlorination (free chlorine, chloramine disinfection, etc.) at a level of ⁇ g/L, and their studies have found that their chronic cytotoxicity and acute genotoxicity are hundreds to thousands of times that of THMs.
  • the three types of halogenated N-DBPs of HANs, HNMs and HAcAms include chlorinated, brominated and iodine.
  • chlorinated N-DBPs have the highest concentration in drinking water after chlorination, so it needs to be taken seriously. And control.
  • Chlorinated HANs include dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN)
  • chlorinated HAcAms include dichloroacetamide (DCAcAm) and trichloroacetamide (TCAcAm)
  • chlorinated HNMs include dichloronitromethane. (DCNM) and trichloronitromethane (TCNM).
  • the structure of chlorinated N-DBPs is as follows:
  • the object of the present invention is to provide a method for controlling chlorinated nitrogen-containing disinfection by-products in water, which starts from the source control angle and utilizes highly oxidizing sulfate radicals to efficiently remove chlorinated N.
  • Precursors of DBPs, and the possibility of subsequent chlorination of chloroform concentration after oxidation of sulfate radicals increase the rapid aeration measures, and achieve the purpose of removing chlorinated N-DBPs and chloroform simultaneously.
  • the N-DBPs control technology with the same effect is low in cost, easy to implement, easy to control, and free from secondary pollution, which improves the safety of drinking water and ensures the health of people drinking water.
  • a method for controlling chlorinated nitrogen-containing disinfection by-products in water comprises the following steps:
  • the water sample is drinking water.
  • the pH is 6-10, and the pH is controlled by at least one of concentrated sulfuric acid, sodium hydroxide, and phosphate buffer solution.
  • the ultraviolet light has a wavelength of 180 to 290 nm, an irradiation dose of 15 to 600 mJ/cm 2 , and an irradiation time of 1 to 30 min.
  • the ultraviolet light is a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a halogen lamp. At least one of them provides ultraviolet light, and the arrangement of the ultraviolet lamp adopts a suspended irradiation type, and the distance between the ultraviolet lamp and the water body is not more than 100 cm.
  • the persulfate is at least one of sodium persulfate, potassium persulfate, and ammonium persulfate.
  • the hydrogen persulfate is at least one of potassium hydrogen persulfate, sodium hydrogen persulfate, and ammonium hydrogen persulfate.
  • the persulfate or persulfate is added in an amount of 10 to 200 mg/L.
  • the chlorination is performed by adding a hypochlorite solution or liquid chlorine.
  • the hypochlorite is sodium hypochlorite.
  • the concentration of available chlorine in the chlorination disinfection is 5 to 30 mg/L.
  • the chlorination sterilization terminates the chlorination reaction by adding a dechlorination reagent at the time of the test, and the dechlorination reagent is preferably at least one of ascorbic acid, sodium sulfite, and sodium thiosulfate.
  • the flow rate of the aeration treatment is 2 to 60 L/h, and the aeration time is 1 to 10 minutes.
  • the aeration device used in the aeration treatment is a small air pump that blows air aeration, and the aeration air source uses air.
  • the present invention has the following advantages and benefits:
  • N-DBPs This application solves the problem of disinfection by-products in drinking water from the perspective of source control.
  • the control method of N-DBPs can be summarized into three aspects: (1) source control: the precursor substance of N-DBPs in water is removed before disinfection, and the disinfectant (chlorine and chloramine, etc.) added during disinfection cannot be combined with The precursor material reacts to form N-DBPs. (2) Process control: mainly to reduce the formation of N-DBPs in the disinfection process by changing the disinfection process parameters or disinfection methods.
  • N-DBPs Change the disinfection process parameters, that is, on the basis of ensuring the disinfection and sterilization effect, the formation of N-DBPs can be reduced by reducing the parameters such as the amount of disinfectant used; changing the disinfection method means replacing the existing disinfection process or A new disinfection process is added based on the existing disinfection process.
  • End control The N-DBPs that have been formed are removed.
  • N-DBPs such as chlorinated HANs and HAcAms
  • end control may be a palliative method.
  • the present application removes chlorinated N-DBPs precursors by activating the persulfate (sodium persulfate) by ultraviolet irradiation to produce highly oxidizing sulfate radicals.
  • Sulfate radicals produced by UV irradiation of persulfate have high oxidation potential and can efficiently oxidize and remove chlorinated N-DBPs precursors, thereby inhibiting the formation of chlorinated N-DBPs during subsequent chlorination. .
  • the present application is directed to the problem that the chlorination of the sulfate radical may cause an increase in the concentration of the subsequent chlorination of the chloroform, and the rapid aeration can be achieved, and the purpose of removing the chlorinated N-DBPs and the chloroform can be achieved at the same time.
  • the high oxidative nature of sulfate radicals may damage the structure of dissolved organic matter in the water, which in turn leads to an increase in the concentration of chloroform during subsequent chlorination. Due to the strong volatility of chloroform, the concentration of chloroform in the water can be reduced by rapid aeration, thereby achieving the simultaneous removal of chlorinated N-DBPs and chloroform.
  • the method of the present application does not require high ultraviolet light and does not generate high energy costs; the chemical used is cheap, and does not affect the water quality sensory; the aeration device is simple and easy to use, and the air source is economical and applicable.
  • the reactor used is simple in design and convenient to use, can effectively control the formation of chlorinated N-DBPs, and can effectively reduce the amount of chloroform in the subsequent chlorination process. Therefore, it is a safe, efficient and economical method for controlling the disinfection by-products of chlorinated nitrogen in drinking water.
  • FIG. 1 is a view showing the results of a method for controlling a chlorinated nitrogen-containing disinfection by-product in water according to Example 1 of the present invention.
  • Fig. 2 is a view showing the results of a method for controlling chlorinated nitrogen-containing disinfection by-product in water according to Example 2 of the present invention.
  • Fig. 3 is a view showing the results of a method for controlling chlorinated nitrogen-containing disinfection by-product in water according to Example 3 of the present invention.
  • FIG. 4 is a process flow diagram of a method for controlling chlorinated nitrogen-containing disinfection by-products in water according to Embodiment 1 of the present invention.
  • FIG. 4 is a process flow diagram of a method for controlling chlorinated nitrogen-containing disinfection by-products in water according to Embodiment 1 of the present invention.
  • the following steps are carried out: the actual water body pH of the initial dissolved organic nitrogen concentration is about 0.5 mg/L is controlled to 6, the pH is adjusted by a concentrated sulfuric acid solution, and the ultraviolet light is irradiated with a low-pressure mercury lamp having a wavelength of 180 nm, and the ultraviolet light is irradiated.
  • the dosage is 500mJ/cm 2 and the irradiation time is 1min.
  • the arrangement of the UV lamp is suspended irradiation.
  • the distance between the UV lamp and the water body is not more than 100cm and the power is 15W.
  • sodium persulfate and persulfate are added to the water.
  • the dosage of sodium is 200mg/L.
  • the ultraviolet light excites sodium persulfate to produce highly oxidizing sulfate radicals, and the precursor of chlorinated N-DBPs is oxidized and removed, thereby inhibiting the chlorination in the subsequent chlorination process.
  • N-DBPs The formation of N-DBPs; then chlorination, the water sample was transferred to a 40mL brown ampule during disinfection, adding 9.1mg / L of available chlorine, that is, NaClO solution (diluted to the effective chlorine content when used) 10g/L or so as a mother , Placed in a brown reagent bottle and stored at 4 °C protected from light). Immediately after the chlorine is added, it is sealed with a screw cap with a Teflon gasket. After thorough mixing, it is stored in an incubator for 24 hours and kept at a temperature of 24 ⁇ 1 °C. After the end of the 24 h reaction, 1.6 mg/L of ascorbic acid was added to terminate the chlorination reaction, and the chlorination step was completed.
  • available chlorine that is, NaClO solution (diluted to the effective chlorine content when used) 10g/L or so as a mother , Placed in a brown reagent bottle and stored at 4 °C protected from light.
  • the chlorine
  • Aeration is then carried out to remove volatile volatile by-products such as trichloromethane which may be added.
  • the aeration device uses a small air pump to blow air aeration, the aeration gas source uses air, the aeration flow rate is 60L/h, and the aeration time is 5 minutes.
  • Determination method of disinfection by-products First, the liquid sample after aeration is subjected to liquid-liquid extraction operation, the water sample is passed through a 0.45 ⁇ m microporous membrane, and ascorbic acid is added to the water sample to eliminate residual chlorine in the water (ascorbic acid is added) The amount [in molar concentration] is 2 to 3 times that of residual chlorine in water), and then 4 g of anhydrous sodium sulfate is added to a test tube containing 20 mL of water, and shaken on a test tube shaker for 1 min to make anhydrous sodium sulfate. When it is fully dissolved, the water level rises.
  • the carrier gas is high-purity helium; the carrier gas flow control mode is pressure control; the carrier gas flow rate is 56.9mL/min; the injection volume is 1.0 ⁇ L; the injection mode is no-split; the inlet temperature is 180°C.
  • the mass spectrometer temperature is 250 ° C; the ion source is an electron bombardment ion source (EI); the electron energy is 70 eV; the scanning mass range m/z is 20 to 200; and the detection mode is selective ion detection (SIM).
  • Temperature program The initial temperature was 40 ° C, held for 10 min, and then heated to 150 ° C at a rate of 40 ° C / min for 5 min.
  • Fig. 1 is a view showing the results of a method for controlling the disinfection by-product of chlorinated nitrogen in water according to the embodiment 1 of the present invention.
  • Disinfection after UV persulfate treatment can well inhibit the formation of chlorinated nitrogen-containing disinfection by-products in water; dichloroacetonitrile, trichloroacetonitrile, dichloronitromethane, trichloronitromethane, dichloroacetamide
  • the production of trichloroacetamide was reduced by 59%, 46%, 50%, 58%, 61%, and 52%, respectively; after micro-aeration treatment, the produced chloroform (TCM) also had a good removal effect. The removal rate reached 90%.
  • PS described in Figure 1 refers to persulfate
  • the specific aeration mode, aeration amount and aeration time of the present invention can be determined according to a combination of the amount of treated water, the concentration of volatile disinfection by-products, and economic conditions.
  • the specific ultraviolet light time or light dose and the persulfate dosage of the present invention may be based on comprehensive characteristics of the actual water body characteristics (soluble organic nitrogen concentration, turbidity, color), light source characteristics (irradiation light intensity, light depth), and the like. to make sure.
  • the disinfecting dose and the disinfecting time of the present invention can be determined based on comprehensive factors such as the characteristics of the actual water body (dissolved organic carbon concentration, dissolved organic nitrogen concentration, and halogen ion concentration).
  • the method of the present application does not require high ultraviolet light and does not generate high energy costs; the chemical used is cheap, and does not affect the water quality sensory; the aeration device is simple and easy to use, and the air source is economical and applicable.
  • the reactor used is simple in design and convenient to use, can effectively control the formation of chlorinated N-DBPs, and can effectively reduce the amount of chloroform in the subsequent chlorination process. Therefore, it is a safe, efficient and economical method for controlling the disinfection by-products of chlorinated nitrogen in drinking water.
  • the ultraviolet persulfate oxidation system of the present invention there are mainly three ways to remove the precursor of the chlorinated N-DBPs: one is to use the precursor to absorb light in the ultraviolet spectral range for photolysis; the other is to use persulfuric acid.
  • the oxidizing property of the salt directly oxidizes and removes the precursor of the chlorinated N-DBPs; the third is the use of ultraviolet light to excite the sulfate radical generated by the persulfate, as follows:
  • the background substance in the water body such as suspended matter, humus, total bacteria, dissolved organic nitrogen (DON), pH, etc.
  • the background substance in the water body should be adjusted according to these factors to reasonably adjust the dosage of persulfate and ultraviolet irradiation. Dose and aeration.
  • the turbidity and chromaticity of the water have certain influence on the ultraviolet light irradiation.
  • the absorbance of the actual water body under ultraviolet light can be measured, and then the reactor is rationally designed according to the Lambert Beer's law to achieve the designed ultraviolet light dose requirement ( That is, 15 to 500 mJ/cm 2 ).
  • a method for controlling chlorinated nitrogen-containing disinfection by-products in drinking water is achieved by the following steps: containing 0.615 mg/L chloramphenicol (belonging to dissolved organic nitrogen, equivalent to a dissolved organic nitrogen concentration of 0.05 mg/L)
  • the pH of the water body was adjusted to 7, and the pH was adjusted with a phosphate buffer solution.
  • the volume of the water sample was 40 mL, and then irradiated with a medium-pressure mercury lamp having a wavelength of 270 nm.
  • the irradiation dose of ultraviolet light was 585 mJ/cm 2 , and the irradiation time was 15min, the arrangement of the UV lamp is to use a UV lamp to suspend the parallel irradiation reactor.
  • the distance between the UV lamp and the water body is no more than 100cm, and the power is 15W.
  • the concentration of sodium persulfate is 78mg/L, that is, the chlorine content is completed. Degradation of nitrogen disinfection by-product precursors, thereby inhibiting the formation of chlorinated N-DBPs during subsequent chlorination.
  • chlorination disinfection the water sample was transferred to a 40mL brown ampule during disinfection, adding 5.1mg / L of effective chlorine, that is, NaClO solution (diluted to a mother liquor with an effective chlorine content of 10g / L when used) And placed in a brown reagent bottle at 4 ° C protected from light), immediately sealed with a screw cap with a Teflon gasket, fully mixed, stored in an incubator in the dark for 24h and kept at a temperature of 24 After ⁇ 1 ° C, after 24 h of reaction, 1.0 mg/L of ascorbic acid was added to terminate the chlorination reaction. The solution is then aerated to remove volatile volatile by-products such as chloroform, which may be added.
  • the aeration device uses a small air pump to blow air aeration, the aeration gas source uses air, the aeration flow rate is 40L/h, and the aeration time is 10 minutes.
  • Determination method of disinfection by-products First, the liquid sample after aeration is subjected to liquid-liquid extraction operation, the water sample is passed through a 0.45 ⁇ m microporous membrane, and ascorbic acid is added to the water sample to eliminate residual chlorine in the water (ascorbic acid is added) The amount [in molar concentration] is 2 to 3 times that of residual chlorine in water), and then 4 g of anhydrous sodium sulfate is added to a test tube containing 20 mL of water, and shaken on a test tube shaker for 1 min to make anhydrous sodium sulfate. When it is fully dissolved, the water level rises.
  • the carrier gas is high-purity helium; the carrier gas flow control mode is pressure control; the carrier gas flow rate is 56.9mL/min; the injection volume is 1.0 ⁇ L; the injection mode is no-split; the inlet temperature is 180°C.
  • the mass spectrometer temperature is 250 ° C; the ion source is an electron bombardment ion source (EI); the electron energy is 70 eV; the scanning mass range m/z is 20 to 200; and the detection mode is selective ion detection (SIM).
  • Temperature program The initial temperature was 40 ° C, held for 10 min, and then heated to 150 ° C at a rate of 40 ° C / min for 5 min.
  • Fig. 2 is a view showing the results of a method for controlling the disinfection by-product of chlorinated nitrogen in water according to Example 2 of the present invention.
  • Disinfection after UV persulfate treatment can well inhibit the formation of chlorinated nitrogen-containing disinfection by-products in water; dichloroacetonitrile, trichloroacetonitrile, dichloronitromethane, trichloronitromethane, dichloroacetamide
  • the amount of trichloroacetamide produced was reduced by 58%, 46%, 49%, 58%, 63%, and 42%, respectively.
  • the formation of chloroform was also well removed. It reached 82%.
  • a method for controlling chlorinated nitrogen-containing disinfection by-products in drinking water is achieved by adjusting the pH of the actual water body with an initial dissolved organic nitrogen concentration of about 0.5 mg/L to 9, and adjusting the pH with NaOH solution, drinking water
  • the volume of the water body is 40mL, and then irradiated with high-pressure mercury lamp ultraviolet light with a wavelength of 290nm.
  • the irradiation dose of ultraviolet light is 585mJ/cm 2 and the irradiation time is 30min.
  • the arrangement of the ultraviolet lamp is suspended by parallel irradiation of the UV lamp.
  • the distance between the lamp and the water body is not more than 100cm, and the power is 15W.
  • the concentration of sodium persulfate is 119mg/L, which completes the degradation of the precursor of the chlorinated nitrogen-containing disinfection by-product, thereby inhibiting the subsequent chlorination process.
  • Add 7.1 mg/L of available chlorine, ie NaClO solution diluted to a mother liquor with an effective chlorine content of 10 g/L when used, and stored in a brown reagent bottle at 4 ° C in the dark). Immediately after the effective chlorine was added, it was sealed with a screw cap with a Teflon gasket.
  • the chlorination reaction was terminated by adding 1.4 mg/L of ascorbic acid. Then, the water sample is micro-aerated, the aeration device uses a small air pump to blow air aeration, the aeration gas source uses air, the aeration flow rate is 50L/h, and the aeration time is 10 minutes, which is used to remove the volatile disinfection. by-product.
  • Determination method of disinfection by-products First, the liquid sample after aeration is subjected to liquid-liquid extraction operation: the water sample is passed through a 0.45 ⁇ m microporous membrane, and ascorbic acid is added to the water sample to eliminate residual chlorine in the water (ascorbic acid is added) The amount [in molar concentration] is 2 to 3 times that of residual chlorine in water), and then 4 g of anhydrous sodium sulfate is added to a test tube containing 20 mL of water, and shaken on a test tube shaker for 1 min to make anhydrous sodium sulfate. When it is fully dissolved, the water level rises.
  • the carrier gas is high-purity helium; the carrier gas flow control mode is pressure control; the carrier gas flow rate is 56.9mL/min; the injection volume is 1.0 ⁇ L; the injection mode is no-split; the inlet temperature is 180°C.
  • the mass spectrometer temperature is 250 ° C; the ion source is an electron bombardment ion source (EI); the electron energy is 70 eV; the scanning mass range m/z is 20 to 200; and the detection mode is selective ion detection (SIM).
  • Temperature program The initial temperature was 40 ° C, held for 10 min, and then heated to 150 ° C at a rate of 40 ° C / min for 5 min.
  • Fig. 3 is a schematic diagram showing the results of a method for controlling the disinfection by-product of chlorinated nitrogen in water according to Example 3 of the present invention. Disinfection after UV persulfate treatment can well inhibit the formation of chlorinated nitrogen-containing disinfection by-products in water; dichloroacetonitrile, trichloroacetonitrile, dichloronitromethane, trichloronitromethane, dichloroacetamide The amount of trichloroacetamide produced was reduced by 53%, 42%, 53%, 60%, 64%, and 55%, respectively; after micro-aeration treatment, the produced chloroform also had a good removal effect, and the removal rate was It reached 81%.
  • a method for controlling chlorinated nitrogen-containing disinfection by-products in drinking water is achieved by adjusting the pH of the actual water body with an initial dissolved organic nitrogen concentration of about 0.5 mg/L to 10, and adjusting the pH with NaOH solution, drinking water
  • the volume of the water body is 40 mL, and then irradiation is carried out by using a xenon lamp ultraviolet light having a wavelength of 225 nm.
  • the irradiation dose of the ultraviolet light is 15 mJ/cm 2 and the irradiation time is 30 min.
  • the arrangement of the ultraviolet lamp is carried out by using a UV lamp to suspend the parallel irradiation reactor, the ultraviolet lamp and The distance between the water body is not more than 100cm and the power is 15W.
  • the potassium persulfate is added to make the concentration of 10mg/L, that is, the degradation of the precursor of the chlorinated nitrogen-containing disinfection by-product is completed, thereby inhibiting the chlorine in the subsequent chlorination process.
  • the formation of N-DBPs is carried out; then chlorination is carried out, and the water sample to be tested is transferred into a 40 mL ampule when disinfecting.
  • Add 30 mg/L of available chlorine, ie NaClO solution diluted to a mother liquor with an effective chlorine content of 10 g/L when used, and placed in a brown reagent bottle and stored at 4 ° C in the dark).
  • the effective chlorine was added, it was sealed with a screw cap with a Teflon gasket. After thorough mixing, it was stored in an incubator for 24 h in the dark and kept at a temperature of 24 ⁇ 1 °C. After the end of the 24 h reaction, the chlorination reaction was terminated by adding 1.4 mg/L of sodium sulfite. Then, the water sample is micro-aerated, the aeration device uses a small air pump to blow air aeration, the aeration gas source uses air, the aeration flow rate is 2L/h, and the aeration time is 10 minutes, which is used to remove the volatile disinfection. by-product.
  • Determination method of disinfection by-products First, the liquid sample after aeration is subjected to liquid-liquid extraction operation: the water sample is passed through a 0.45 ⁇ m microporous membrane, and ascorbic acid is added to the water sample to eliminate residual chlorine in the water (ascorbic acid is added) The amount [in molar concentration] is 2 to 3 times that of residual chlorine in water), and then 4 g of anhydrous sodium sulfate is added to a test tube containing 20 mL of water, and shaken on a test tube shaker for 1 min to make anhydrous sodium sulfate. When it is fully dissolved, the water level rises.
  • the carrier gas is high-purity helium; the carrier gas flow control mode is pressure control; the carrier gas flow rate is 56.9mL/min; the injection volume is 1.0 ⁇ L; the injection mode is no-split; the inlet temperature is 180°C.
  • the mass spectrometer temperature is 250 ° C; the ion source is an electron bombardment ion source (EI); the electron energy is 70 eV; the scanning mass range m/z is 20 to 200; and the detection mode is selective ion detection (SIM).
  • Temperature program The initial temperature was 40 ° C, held for 10 min, and then heated to 150 ° C at a rate of 40 ° C / min for 5 min.
  • Disinfection after UV persulfate treatment can well inhibit the formation of chlorinated nitrogen-containing disinfection by-products in water; dichloroacetonitrile, trichloroacetonitrile, dichloronitromethane, trichloronitromethane, dichloroacetamide
  • the amount of trichloroacetamide produced was reduced by 39%, 28%, 30%, 33%, 41%, 30%, respectively; after micro-aeration treatment, the produced chloroform also had a good removal effect, and the removal rate was It reached 63%.
  • a method for controlling chlorinated nitrogen-containing disinfection by-products in drinking water is achieved by adjusting the pH of the actual water body with an initial dissolved organic nitrogen concentration of about 0.5 mg/L to 8 and adjusting the pH with sodium hydroxide.
  • the volume of the water sample is 40mL, and then irradiated with ultraviolet light of a halogen lamp with a wavelength of 250nm.
  • the irradiation dose of ultraviolet light is 300mJ/cm 2 and the irradiation time is 30min.
  • the arrangement of the ultraviolet lamp is suspended by parallel irradiation of the UV lamp.
  • the distance between the lamp and the water body is not more than 100cm, and the power is 15W.
  • the concentration of sodium persulfate is 150mg/L, that is, the degradation of the precursor of the chlorinated nitrogen-containing disinfection by-product is completed, thereby inhibiting subsequent chlorination. Formation of chlorinated N-DBPs during the process. Then chlorination is carried out.
  • the water sample is transferred to a 40 mL brown ampule bottle, and 17 mg/L of available chlorine, that is, NaClO solution is added (diluted to a mother liquor having an effective chlorine content of about 10 g/L when used.
  • the chlorination reaction was terminated by adding 1.0 mg/L of sodium thiosulfate.
  • the solution is then aerated to remove volatile volatile by-products such as chloroform, which may be added.
  • the aeration device uses a small air pump to blow air aeration, the aeration gas source uses air, the aeration flow rate is 30L/h, and the aeration time is 5 minutes.
  • Determination method of disinfection by-products First, the liquid sample after aeration is subjected to liquid-liquid extraction operation, the water sample is passed through a 0.45 ⁇ m microporous membrane, and ascorbic acid is added to the water sample to eliminate residual chlorine in the water (ascorbic acid is added) The amount [in molar concentration] is 2 to 3 times that of residual chlorine in water), and then 4 g of anhydrous sodium sulfate is added to a test tube containing 20 mL of water, and shaken on a test tube shaker for 1 min to make anhydrous sodium sulfate. When it is fully dissolved, the water level rises.
  • the carrier gas is high-purity helium; the carrier gas flow control mode is pressure control; the carrier gas flow rate is 56.9mL/min; the injection volume is 1.0 ⁇ L; the injection mode is no-split; the inlet temperature is 180°C.
  • the mass spectrometer temperature is 250 ° C; the ion source is an electron bombardment ion source (EI); the electron energy is 70 eV; the scanning mass range m/z is 20 to 200; and the detection mode is selective ion detection (SIM).
  • Temperature program The initial temperature was 40 ° C, held for 10 min, and then heated to 150 ° C at a rate of 40 ° C / min for 5 min.
  • Disinfection after UV persulfate treatment can well inhibit the formation of chlorinated nitrogen-containing disinfection by-products in water; dichloroacetonitrile, trichloroacetonitrile, dichloronitromethane, trichloronitromethane, dichloroacetamide
  • the amount of trichloroacetamide produced was reduced by 43%, 37%, 38%, 41%, 49%, and 34%, respectively.
  • the formation of chloroform was also well removed. It reached 65%.

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Abstract

一种控制水中氯代含氮消毒副产物的方法，包括以下步骤：首先，控制水样的pH值，采用紫外光照射处理，并同时投加过硫酸盐或过硫酸氢盐，然后进行氯化消毒，最后进行曝气处理，得到去除了水中氯代含氮消毒副产物的水样；该方法能有效控制氯代N-DBPs的形成，并能有效减少后续氯化消毒过程中三氯甲烷的量。

Description

一种控制水中氯代含氮消毒副产物的方法 技术领域
本发明属于水处理技术领域，涉及一种控制水中氯代含氮消毒副产物的方法。
背景技术
饮水安全是关乎千家万户的重大民生问题，饮用水消毒是保障饮水安全不可或缺的处理措施，被广泛采用的氯消毒工艺可有效杀灭细菌病毒，但也会产生对人体有害的消毒副产物(DBPs)。40年来，三氯甲烷等含碳消毒副产物(C-DBPs)已得到大量研究和报道。然而，由于世界人口的持续增长、工农业的快速发展以及对环境问题认识和管理的缺乏，全球水体富营养化问题日益严重，我国亦不例外，污染物排放量超过受纳水体环境容量，部分水源地水质恶化，水源水中溶解性有机氮(DON)水平升高，且部分DON化合物(氨基酸等)亲水性强，无法通过混凝、沉淀和过滤等常规净水工艺去除，从而与后续消毒时所投加的消毒剂(氯等)反应生成含氮消毒副产物(N-DBPs)。研究表明，N-DBPs的毒性远高于三氯甲烷(TCM)等C-DBPs，且普遍存在于水厂氯消毒后的出水中，对人们的饮水健康非常不利，成为目前国际上市政、环境和公共卫生领域的一大研究热点。
目前得到较多关注的氯代N-DBPs主要包括：卤代乙腈(HANs)、卤代乙酰胺(HAcAms)和卤代硝基甲烷(HNMs)三类。它们常以μg/L的水平存在于氯化消毒(自由氯、氯胺消毒等)后的饮用水中，且研究发现它们的慢性细胞毒性和急性遗传毒性是THMs的数百至数千倍，严重危害人们的饮水健康。HANs、HNMs和HAcAms三类卤代N-DBPs都包括氯代、溴代和碘代三类，其中氯代N-DBPs在氯化消毒后的饮用水中的浓度水平最高，因此，需要加以重视和控制。氯代类HANs包括二氯乙腈(DCAN)和三氯乙腈(TCAN)，氯代类HAcAms包括二氯乙酰胺(DCAcAm)和三氯乙酰胺(TCAcAm)，氯代类HNMs包括二氯硝基甲烷(DCNM)和三氯硝基甲烷(TCNM)。氯代N-DBPs的结构如下所示：
Figure PCTCN2017074505-appb-000001
Figure PCTCN2017074505-appb-000002
发明内容
针对现有技术的问题，本发明的目的是提供一种控制水中氯代含氮消毒副产物的方法，该方法从源头控制角度入手，利用强氧化性的硫酸根自由基来高效去除氯代N-DBPs的前体物，并针对硫酸根自由基氧化后可能造成后续氯化消毒三氯甲烷浓度增高的问题，增加快速曝气措施，可以同时达到去除氯代N-DBPs和三氯甲烷的目的；较同等效果的N-DBPs控制技术成本低、易于实现、便于管控、无二次污染，提高了饮用水的安全性，保障了人们的饮水健康。
为了实现上述目的，本发明采用的技术方案如下：
一种控制水中氯代含氮消毒副产物的方法，包括以下步骤：
首先，控制水样的pH值，采用紫外光照射处理，并同时投加过硫酸盐或过硫酸氢盐，然后进行氯化消毒，最后进行曝气处理，得到去除了水中氯代含氮消毒副产物的水样。
所述水样为饮用水。
所述pH值为6-10，采用浓硫酸、氢氧化钠、磷酸盐缓冲溶液中的至少一种控制pH值。
所述紫外光的波长为180～290nm，照射剂量为15～600mJ/cm2，照射时间为1～30min，所述紫外光采用低压汞灯、中压汞灯、高压汞灯、氙灯、卤灯中的至少一种来提供紫外光，紫外灯的布置方式采用悬空辐照式，紫外灯与水体的距离不大于100cm。
所述过硫酸盐为过硫酸钠、过硫酸钾、过硫酸铵中的至少一种。
所述过硫酸氢盐为过硫酸氢钾、过硫酸氢钠、过硫酸氢铵中的至少一种。
所述过硫酸盐或过硫酸氢盐的投加量为10～200mg/L。
所述氯化消毒是投加次氯酸盐溶液或液氯进行消毒，优选的，所述次氯酸盐为次氯酸钠。
所述氯化消毒中有效氯的浓度为5～30mg/L。
所述氯化消毒在试验时投加脱氯试剂终止氯化反应，所述脱氯试剂优选为抗坏血酸、亚硫酸钠、硫代硫酸钠中的至少一种。
所述曝气处理的流量为2～60L/h，曝气时间为1～10min。
所述曝气处理采用的曝气装置为小型气泵鼓吹空气曝气，曝气气源采用空气。
由于采用了上述技术方案，本发明具有以下优点和有益效果：
本申请从源头控制的角度去解决饮用水中的消毒副产物问题。目前N-DBPs的控制方法可以概括为三个方面：(1)源头控制：消毒之前去除水中N-DBPs的前体物质，消毒时所投加的消毒剂(氯和氯胺等)便无法与前体物质反应生成N-DBPs。(2)过程控制：主要是通过改变消毒工艺参数或消毒方式来降低N-DBPs在消毒过程中的形成。改变消毒工艺参数，即是在保证消毒杀菌效果的基础上，可以通过降低消毒剂的使用量等参数的方式，来降低N-DBPs的形成；改变消毒方式，即是替换现有消毒工艺或在现有消毒工艺的基础上增加新的消毒工艺。(3)末端控制：对已经形成的N-DBPs进行去除。
从末端控制角度对已生成的氯代HANs和HAcAms等N-DBPs开展控制，在一定程度上可以有效消减它们的浓度，但在前体物和余氯存在时无法抑制其再度生成。因此，末端控制可能是治标不治本的方法。
对于过程控制，有一些研究考察了不同消毒剂量、反应时间和溶液pH等因素对氯代N-DBPs的过程控制效果，在特定消毒条件和方式下，可以控制某类N-DBPs的形成，但同时也造成了另外一类N-DBPs的产生。
因此，在消毒之前，结合水厂实际情况，通过增加预处理措施来高效去除N-DBPs前体物，从而实现氯代N-DBPs的源头控制，是一种行之有效的N-DBPs控制方法。
本申请通过利用紫外辐照激活过硫酸盐(过硫酸钠)产生高氧化性的硫酸根自由基来去除氯代N-DBPs前体物。紫外辐照过硫酸盐所产生的硫酸根自由基具有很高的氧化电位，能高效地氧化去除氯代N-DBPs前体物，从而抑制了后续氯化消毒过程中氯代N-DBPs的形成。
本申请针对硫酸根自由基氧化后可能造成后续氯化消毒三氯甲烷浓度增高的问题，增加快速曝气，可以同时达到去除氯代N-DBPs和三氯甲烷的目的。硫酸根自由基的高氧化性可能会破坏水体中的溶解性有机物的结构，继而造成后续氯化消毒过程中三氯甲烷浓度的增高。由于三氯甲烷具有较强的挥发性，通过快速曝气，可以降低水体中三氯甲烷的浓度，从而达到同时去除氯代N-DBPs和三氯甲烷的目的。本申请的方法对紫外光的要求不高，不会产生高昂的能源费用；所采用的化学药剂价格便宜，对水质感官不会产生影响；曝气装置简单易行，采用空气气源，经济适用，所用反应器设计简单，使用方便，能有效控制氯代N-DBPs的形成，并能有效减少后续氯化消毒过程中三氯甲烷的量。因此，是一项安全、高效、经济的控制饮用水中氯代含氮消毒副产物的方法。
附图说明
图1是本发明实施例1实施控制水中氯代含氮消毒副产物的方法的结果示意图。
图2是本发明实施例2实施控制水中氯代含氮消毒副产物的方法的结果示意图。
图3是本发明实施例3实施控制水中氯代含氮消毒副产物的方法的结果示意图。
图4是本发明实施例1实施控制水中氯代含氮消毒副产物的方法的工艺流程图。
具体实施方式
下面结合附图所示实施例对本发明作进一步详细的说明。
实施例1
一种控制饮用水中氯代含氮消毒副产物的方法(如图4所示，图4是本发明实施例1实施控制水中氯代含氮消毒副产物的方法的工艺流程图。)，通过以下步骤实现：将初始溶解性有机氮浓度为0.5mg/L左右的实际水体pH控制为6，采用浓硫酸溶液调节pH，采用波长为180nm的低压汞灯紫外光进行照射处理，紫外光的照射剂量为500mJ/cm2，照射时间为1min，紫外灯的布置方式采用悬空辐照式，紫外灯与水体的距离不大于100cm，功率为15W；同时，向水体中投加过硫酸钠，过硫酸钠的投加量为200mg/L，紫外光激发过硫酸钠产生高氧化性的硫酸根自由基，对氯代N-DBPs的前体物进行氧化去除，从而抑制后续氯化消毒过程中氯代N-DBPs的形成；然后进行氯化消毒，消毒时将水样移至40mL的棕色安培瓶中，投加9.1mg/L的有效氯，即NaClO溶液(使用时将其稀释到有效氯含量为10g/L左右作为母液，并置于棕色试剂瓶中在4℃下避光保存)。待氯投加后，立即用带有聚四氟乙烯垫片的螺旋盖密封，充分混合后，存放于恒温箱中避光反应24h并保持温度为24±1℃。24h反应结束后，投加1.6mg/L的抗坏血酸终止氯化反应，氯化消毒步骤完成。然后进行曝气，去除可能增加的三氯甲烷等挥发性强的消毒副产物。曝气装置采用小型气泵鼓吹空气曝气，曝气气源采用空气，曝气的流量采用60L/h，曝气时间为5min。
消毒副产物测定方法：首先是将曝气后的水样进行液液萃取操作，将水样过0.45μm微孔滤膜，向水样中投加抗坏血酸，以消去水中余氯(抗坏血酸的投加量[以摩尔浓度计]是水中余氯的2～3倍)，再向放有20mL水样的试管中投加4g无水硫酸钠，置于试管振荡器上振荡1min，使得无水硫酸钠充分溶解，水样液面有所上升。之后投加2mL萃取剂乙酸乙酯，并置于试管振荡器上振荡3min，静置10min，用移液枪吸取上层萃取剂溶液1mL置于1.5mL进样瓶中，将进样瓶放于AOC-20i自动进样器中，等待气相色谱质谱(GC/MS)(日本Shimazu GC/MS-QP2010S)测定。仪器设置条件如下：RTX-5MS毛细管柱(柱长30m，内径0.25mm，膜后0.25μm)，AOC-20i自动进样器。检测条件：载气为高纯氦气；载气流量控制方式为压力控制；载气流速为56.9mL/min；进样量为1.0μL；进样方式为无分流；进样口温度为180℃；质谱检测器温度为250℃；离子源为电子轰击离子源(EI)；电子能量为70eV；扫描质量范围m/z为20～200；检测模式为选择离子检测(SIM)。升温程序：初始温度为40℃，保持10min，再以40℃/min的速率升温至150℃,保持5min。
实验结果如图1所示，图1是本发明实施例1实施控制水中氯代含氮消毒副产物的方法的结果示意图。经过紫外过硫酸盐处理之后再消毒可以很好的抑制水体中氯代含氮消毒副产物的生成；二氯乙腈、三氯乙腈、二氯硝基甲烷、三氯硝基甲烷、二氯乙酰胺、三氯乙酰胺的生成量分别降低了59％、46％、50％、58％、61％、52％；经过微曝气处理对于生成的三氯甲烷(TCM)也有着很好的去除效果，去除率达到了90％。(图1中所描述的PS指过硫酸盐)
本发明的具体曝气方式、曝气量和曝气时间可以根据处理水量、挥发性消毒副产物浓度以及经济条件等综合因素来确定。本发明的具体紫外光照时间或光照剂量以及过硫酸盐投加剂量可以根据实际水体的特性(溶解性有机氮浓度、浊度、色度)、光源特性(照射光强度、光照深度)等综合因素来确定。本发明的消毒剂量以及消毒时间可以根据实际水体的特性(溶解性有机碳浓度、溶解性有机氮浓度以及卤素离子浓度)等综合因素来确定。
本申请的方法对紫外光的要求不高，不会产生高昂的能源费用；所采用的化学药剂价格便宜，对水质感官不会产生影响；曝气装置简单易行，采用空气气源，经济适用；所用反应器设计简单，使用方便，能有效控制氯代N-DBPs的形成，并能有效减少后续氯化消毒过程中三氯甲烷的量。因此，是一项安全、高效、经济的控制饮用水中氯代含氮消毒副产物的方法。
本发明中的紫外过硫酸盐氧化体系中，去除氯代N-DBPs前体物的途径主要有三种：一是利用前体物在紫外光谱范围内有吸收性进行光解；二是利用过硫酸盐的氧化性直接氧化去除氯代N-DBPs的前体物；三是利用紫外光激发过硫酸盐所产生的硫酸根自由基，如下所示：，
S2O8 2-+hv→2SO4 .-
氧化去除水体中氯代N-DBPs的前体物，从源头抑制氯代N-DBPs的形成，如下所示：
SO4 .-+前体物→非前体物+SO4 2-
本发明中水体中的本底物质，如悬浮物、腐殖质、细菌总量、溶解性有机氮(DON)、pH等，需根据这几个因素合理调控过硫酸盐的投加量、紫外辐照剂量以及曝气量。水体的浊度、色度对紫外光照射也有一定的影响，可以通过测定实际水体在紫外光下的吸光度，然后按照朗伯比尔定律计算，合理设计反应器，以达到设计的紫外光剂量要求(即15～500mJ/cm2)。实施例2
一种控制饮用水中氯代含氮消毒副产物的方法，通过以下步骤实现：将含有0.615mg/L氯霉素(属于溶解性有机氮，相当于溶解性有机氮浓度为0.05mg/L)的水体pH调节至7，采用磷酸盐缓冲溶液调节pH，水样的体积为40mL，然后采用波长为270nm的中压汞灯紫外光进行照射，紫外光的照射剂量585mJ/cm2，照射时间为15min，紫外灯的布置方式采用紫外灯悬空平行照射反应器，紫外灯与水体的距离不大于100cm，功率为15W；同时投加过硫酸钠 使其浓度为78mg/L，即完成对氯代含氮消毒副产物前体物的降解，从而抑制后续氯化消毒过程中氯代N-DBPs的形成。然后进行氯化消毒，消毒时将水样移至40mL的棕色安培瓶中，投加5.1mg/L的有效氯，即NaClO溶液(使用时将其稀释到有效氯含量为10g/L左右的母液，并置于棕色试剂瓶中在4℃下避光保存)，立即用带有聚四氟乙烯垫片的螺旋盖密封，充分混合后，存放于恒温箱中避光反应24h并保持温度为24±1℃，24h反应结束后，投加1.0mg/L的抗坏血酸终止氯化反应。然后对溶液进行曝气，去除可能增加的三氯甲烷等挥发性强的消毒副产物。曝气装置采用小型气泵鼓吹空气曝气，曝气气源采用空气，曝气的流量采用40L/h，曝气时间为10min。
消毒副产物测定方法：首先是将曝气后的水样进行液液萃取操作，将水样过0.45μm微孔滤膜，向水样中投加抗坏血酸，以消去水中余氯(抗坏血酸的投加量[以摩尔浓度计]是水中余氯的2～3倍)，再向放有20mL水样的试管中投加4g无水硫酸钠，置于试管振荡器上振荡1min，使得无水硫酸钠充分溶解，水样液面有所上升。之后投加2mL萃取剂乙酸乙酯，并置于试管振荡器上振荡3min，静置10min，用移液枪吸取上层萃取剂溶液1mL置于1.5mL进样瓶中，将进样瓶放于AOC-20i自动进样器中，等待气相色谱质谱(GC/MS)(日本Shimazu GC/MS-QP2010S)测定。仪器设置条件如下：RTX-5MS毛细管柱(柱长30m，内径0.25mm，膜后0.25μm)，AOC-20i自动进样器。检测条件：载气为高纯氦气；载气流量控制方式为压力控制；载气流速为56.9mL/min；进样量为1.0μL；进样方式为无分流；进样口温度为180℃；质谱检测器温度为250℃；离子源为电子轰击离子源(EI)；电子能量为70eV；扫描质量范围m/z为20～200；检测模式为选择离子检测(SIM)。升温程序：初始温度为40℃，保持10min，再以40℃/min的速率升温至150℃,保持5min。
实验结果如图2所示，图2是本发明实施例2实施控制水中氯代含氮消毒副产物的方法的结果示意图。经过紫外过硫酸盐处理之后再消毒可以很好的抑制水体中氯代含氮消毒副产物的生成；二氯乙腈、三氯乙腈、二氯硝基甲烷、三氯硝基甲烷、二氯乙酰胺、三氯乙酰胺的生成量分别降低了58％、46％、49％、58％、63％、42％；经过微曝气处理对于生成的三氯甲烷也有着很好的去除效果，去除率达到了82％。
实施例3
一种控制饮用水中氯代含氮消毒副产物的方法，通过以下步骤实现：将初始溶解性有机氮浓度为0.5mg/L左右的实际水体pH调节至9，采用NaOH溶液调节pH，饮用水水体的体积为40mL，然后采用波长为290nm的高压汞灯紫外光进行照射，紫外光的照射剂量585mJ/cm2，照射时间为30min，紫外灯的布置方式采用紫外灯悬空平行照射反应器，紫外灯与水体的距离不大于100cm，功率为15W；同时投加过硫酸钠使其浓度为119mg/L，即完成 对氯代含氮消毒副产物前体物的降解，从而抑制后续氯化消毒过程中氯代N-DBPs的形成；然后进行氯化消毒，消毒时将待测水样移入40mL安培瓶中。投加7.1mg/L的有效氯，即NaClO溶液(使用时将其稀释到有效氯含量为10g/L左右的母液，并置于棕色试剂瓶中在4℃下避光保存)。有效氯投加之后，立即用带有聚四氟乙烯垫片的螺旋盖密封，充分混合后，存放于恒温箱中避光反应24h并保持温度为24±1℃。24h反应结束后，投加1.4mg/L的抗坏血酸终止氯化反应。然后对水样进行微曝气，曝气装置采用小型气泵鼓吹空气曝气，曝气气源采用空气，曝气的流量采用50L/h，曝气时间为10min，用以去除生成易挥发性消毒副产物。
消毒副产物测定方法：首先是将曝气后的水样进行液液萃取操作：将水样过0.45μm微孔滤膜，向水样中投加抗坏血酸，以消去水中余氯(抗坏血酸的投加量[以摩尔浓度计]是水中余氯的2～3倍)，再向放有20mL水样的试管中投加4g无水硫酸钠，置于试管振荡器上振荡1min，使得无水硫酸钠充分溶解，水样液面有所上升。之后投加2mL萃取剂乙酸乙酯，并置于试管振荡器上振荡3min，静置10min，用移液枪吸取上层萃取剂溶液1mL置于1.5mL进样瓶中，将进样瓶放于AOC-20i自动进样器中，等待气相色谱质谱(GC/MS)(日本Shimazu GC/MS-QP2010S)测定。仪器设置条件如下：RTX-5MS毛细管柱(柱长30m，内径0.25mm，膜后0.25μm)，AOC-20i自动进样器。检测条件：载气为高纯氦气；载气流量控制方式为压力控制；载气流速为56.9mL/min；进样量为1.0μL；进样方式为无分流；进样口温度为180℃；质谱检测器温度为250℃；离子源为电子轰击离子源(EI)；电子能量为70eV；扫描质量范围m/z为20～200；检测模式为选择离子检测(SIM)。升温程序：初始温度为40℃，保持10min，再以40℃/min的速率升温至150℃,保持5min。
实验结果如图3所示，图3是本发明实施例3实施控制水中氯代含氮消毒副产物的方法的结果示意图。经过紫外过硫酸盐处理之后再消毒可以很好的抑制水体中氯代含氮消毒副产物的生成；二氯乙腈、三氯乙腈、二氯硝基甲烷、三氯硝基甲烷、二氯乙酰胺、三氯乙酰胺的生成量分别降低了53％、42％、53％、60％、64％、55％；经过微曝气处理对于生成的三氯甲烷也有着很好的去除效果，去除率达到了81％。
实施例4
一种控制饮用水中氯代含氮消毒副产物的方法，通过以下步骤实现：将初始溶解性有机氮浓度为0.5mg/L左右的实际水体pH调节至10，采用NaOH溶液调节pH，饮用水水体的体积为40mL，然后采用波长为225nm的氙灯紫外光进行照射，紫外光的照射剂量15mJ/cm2，照射时间为30min，紫外灯的布置方式采用紫外灯悬空平行照射反应器，紫外灯与水体的距离不大于100cm，功率为15W；同时投加过硫酸钾使其浓度为10mg/L，即完成对氯代含氮消毒副产物前体物的降解，从而抑制后续氯化消毒过程中氯代N-DBPs的形成；然后进行氯化 消毒，消毒时将待测水样移入40mL安培瓶中。投加30mg/L的有效氯，即NaClO溶液(使用时将其稀释到有效氯含量为10g/L左右的母液，并置于棕色试剂瓶中在4℃下避光保存)。有效氯投加之后，立即用带有聚四氟乙烯垫片的螺旋盖密封，充分混合后，存放于恒温箱中避光反应24h并保持温度为24±1℃。24h反应结束后，投加1.4mg/L的亚硫酸钠终止氯化反应。然后对水样进行微曝气，曝气装置采用小型气泵鼓吹空气曝气，曝气气源采用空气，曝气的流量采用2L/h，曝气时间为10min，用以去除生成易挥发性消毒副产物。
消毒副产物测定方法：首先是将曝气后的水样进行液液萃取操作：将水样过0.45μm微孔滤膜，向水样中投加抗坏血酸，以消去水中余氯(抗坏血酸的投加量[以摩尔浓度计]是水中余氯的2～3倍)，再向放有20mL水样的试管中投加4g无水硫酸钠，置于试管振荡器上振荡1min，使得无水硫酸钠充分溶解，水样液面有所上升。之后投加2mL萃取剂乙酸乙酯，并置于试管振荡器上振荡3min，静置10min，用移液枪吸取上层萃取剂溶液1mL置于1.5mL进样瓶中，将进样瓶放于AOC-20i自动进样器中，等待气相色谱质谱(GC/MS)(日本Shimazu GC/MS-QP2010S)测定。仪器设置条件如下：RTX-5MS毛细管柱(柱长30m，内径0.25mm，膜后0.25μm)，AOC-20i自动进样器。检测条件：载气为高纯氦气；载气流量控制方式为压力控制；载气流速为56.9mL/min；进样量为1.0μL；进样方式为无分流；进样口温度为180℃；质谱检测器温度为250℃；离子源为电子轰击离子源(EI)；电子能量为70eV；扫描质量范围m/z为20～200；检测模式为选择离子检测(SIM)。升温程序：初始温度为40℃，保持10min，再以40℃/min的速率升温至150℃,保持5min。
经过紫外过硫酸盐处理之后再消毒可以很好的抑制水体中氯代含氮消毒副产物的生成；二氯乙腈、三氯乙腈、二氯硝基甲烷、三氯硝基甲烷、二氯乙酰胺、三氯乙酰胺的生成量分别降低了39％、28％、30％、33％、41％、30％；经过微曝气处理对于生成的三氯甲烷也有着很好的去除效果，去除率达到了63％。
实施例5
一种控制饮用水中氯代含氮消毒副产物的方法，通过以下步骤实现：将初始溶解性有机氮浓度为0.5mg/L左右的实际水体pH调节至8，采用氢氧化钠调节pH值，水样的体积为40mL，然后采用波长为250nm的卤灯紫外光进行照射，紫外光的照射剂量300mJ/cm2，照射时间为30min，紫外灯的布置方式采用紫外灯悬空平行照射反应器，紫外灯与水体的距离不大于100cm，功率为15W；同时投加过硫酸氢钠使其浓度为150mg/L，即完成对氯代含氮消毒副产物前体物的降解，从而抑制后续氯化消毒过程中氯代N-DBPs的形成。然后进行氯化消毒，消毒时将水样移至40mL的棕色安培瓶中，投加17mg/L的有效氯，即NaClO溶液(使用时将其稀释到有效氯含量为10g/L左右的母液，并置于棕色试剂瓶中在4℃下避光保存)， 立即用带有聚四氟乙烯垫片的螺旋盖密封，充分混合后，存放于恒温箱中避光反应24h并保持温度为24±1℃，24h反应结束后，投加1.0mg/L的硫代硫酸钠终止氯化反应。然后对溶液进行曝气，去除可能增加的三氯甲烷等挥发性强的消毒副产物。曝气装置采用小型气泵鼓吹空气曝气，曝气气源采用空气，曝气的流量采用30L/h，曝气时间为5min。
消毒副产物测定方法：首先是将曝气后的水样进行液液萃取操作，将水样过0.45μm微孔滤膜，向水样中投加抗坏血酸，以消去水中余氯(抗坏血酸的投加量[以摩尔浓度计]是水中余氯的2～3倍)，再向放有20mL水样的试管中投加4g无水硫酸钠，置于试管振荡器上振荡1min，使得无水硫酸钠充分溶解，水样液面有所上升。之后投加2mL萃取剂乙酸乙酯，并置于试管振荡器上振荡3min，静置10min，用移液枪吸取上层萃取剂溶液1mL置于1.5mL进样瓶中，将进样瓶放于AOC-20i自动进样器中，等待气相色谱质谱(GC/MS)(日本Shimazu GC/MS-QP2010S)测定。仪器设置条件如下：RTX-5MS毛细管柱(柱长30m，内径0.25mm，膜后0.25μm)，AOC-20i自动进样器。检测条件：载气为高纯氦气；载气流量控制方式为压力控制；载气流速为56.9mL/min；进样量为1.0μL；进样方式为无分流；进样口温度为180℃；质谱检测器温度为250℃；离子源为电子轰击离子源(EI)；电子能量为70eV；扫描质量范围m/z为20～200；检测模式为选择离子检测(SIM)。升温程序：初始温度为40℃，保持10min，再以40℃/min的速率升温至150℃,保持5min。
经过紫外过硫酸盐处理之后再消毒可以很好的抑制水体中氯代含氮消毒副产物的生成；二氯乙腈、三氯乙腈、二氯硝基甲烷、三氯硝基甲烷、二氯乙酰胺、三氯乙酰胺的生成量分别降低了43％、37％、38％、41％、49％、34％；经过微曝气处理对于生成的三氯甲烷也有着很好的去除效果，去除率达到了65％。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种控制水中氯代含氮消毒副产物的方法，其特征在于：包括以下步骤：
    首先，控制水样的pH值，采用紫外光照射处理，并同时投加过硫酸盐或过硫酸氢盐，然后进行氯化消毒，最后进行曝气处理，得到去除了水中氯代含氮消毒副产物的水样。
  2. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述水样为饮用水。
  3. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述pH值为6-10，采用浓硫酸、氢氧化钠、磷酸盐缓冲溶液中的至少一种控制pH值。
  4. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述紫外光的波长为180～290nm，照射剂量为15～600mJ/cm2，照射时间为1～30min，所述紫外光采用低压汞灯、中压汞灯、高压汞灯、氙灯、卤灯中的至少一种来提供紫外光，紫外灯的布置方式采用悬空辐照式，紫外灯与水体的距离不大于100cm。
  5. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述过硫酸盐为过硫酸钠、过硫酸钾、过硫酸铵中的至少一种；
    优选的，所述过硫酸氢盐为过硫酸氢钾、过硫酸氢钠、过硫酸氢铵中的至少一种。
  6. 根据权利要求5所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述过硫酸盐或过硫酸氢盐的投加量为10～200mg/L。
  7. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述氯化消毒是投加次氯酸盐溶液或液氯进行消毒，优选的，所述次氯酸盐为次氯酸钠。
  8. 根据权利要求7所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述氯化消毒中有效氯的浓度为5～30mg/L。
  9. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述氯化消毒在试验时投加脱氯试剂终止氯化反应，所述脱氯试剂优选为抗坏血酸、亚硫酸钠、硫代硫酸钠中的至少一种。
  10. 根据权利要求1所述的控制水中氯代含氮消毒副产物的方法，其特征在于：所述曝气处理的流量为2～60L/h，曝气时间为1～10min；
    优选的，所述曝气处理采用的曝气装置为小型气泵鼓吹空气曝气，曝气气源采用空气。
PCT/CN2017/074505 2016-02-26 2017-02-23 一种控制水中氯代含氮消毒副产物的方法 Ceased WO2017143992A1 (zh)

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