CN107144649A - Biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine - Google Patents
Biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine Download PDFInfo
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- CN107144649A CN107144649A CN201710283852.XA CN201710283852A CN107144649A CN 107144649 A CN107144649 A CN 107144649A CN 201710283852 A CN201710283852 A CN 201710283852A CN 107144649 A CN107144649 A CN 107144649A
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- sulfamethyldiazine
- solution
- ultrasonic
- beaker
- ultraviolet
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- QPPBRPIAZZHUNT-UHFFFAOYSA-N sulfamerazine Chemical compound CC1=CC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 QPPBRPIAZZHUNT-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 40
- 238000002604 ultrasonography Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 230000033228 biological regulation Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 description 23
- 150000003254 radicals Chemical class 0.000 description 21
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 20
- 229940124530 sulfonamide Drugs 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 6
- -1 iodine free radical Chemical class 0.000 description 6
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 6
- 229960002178 thiamazole Drugs 0.000 description 6
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 150000003230 pyrimidines Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229960000468 sulfalene Drugs 0.000 description 4
- KXRZBTAEDBELFD-UHFFFAOYSA-N sulfamethopyrazine Chemical compound COC1=NC=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 KXRZBTAEDBELFD-UHFFFAOYSA-N 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- LNJMHEJAYSYZKK-UHFFFAOYSA-N 2-methylpyrimidine Chemical compound CC1=NC=CC=N1 LNJMHEJAYSYZKK-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LVILGAOSPDLNRM-UHFFFAOYSA-N 4-methylpyrimidine Chemical compound CC1=CC=NC=N1 LVILGAOSPDLNRM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- GHCFWKFREBNSPC-UHFFFAOYSA-N 2-Amino-4-methylpyrimidine Chemical compound CC1=CC=NC(N)=N1 GHCFWKFREBNSPC-UHFFFAOYSA-N 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention discloses a kind of biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, specifically implement according to following steps：Step 1：Prepare certain density sulfamethyldiazine storing solution；Step 2：Measured amounts sulfamethyldiazine storing solution is placed in volumetric flask, constant volume, shake up, stand after be transferred in beaker；Step 3：To adding certain density NaOH solution or H in beaker2SO4Solution adjusts pH value；Step 4：To a certain amount of KI solution is added in the sulfamethyldiazine storing solution for regulating PH, stir；Step 5, it is to be mixed it is uniform after, then to adding a certain amount of H in beaker2O2Stir, form mixed solution；Step 6, carry out the ultrasound wave irradiation regular hour at normal atmospheric pressure to the mixed solution in beaker using ultrasonic cell disruptor or the irradiation regular hour is carried out to the mixed solution in beaker using ultraviolet light at normal atmospheric pressure.Solve the problem of degradation rate is too low present in prior art.
Description
Technical field
The invention belongs to antibiotic contaminant removal process technical field, it is related to a kind of based on ultrasonic or ultraviolet enhanced sulphur
The biodegrading process of amine methylpyrimidine.
Background technology
Sulfa drugs refers to the medicine general name with P-aminobenzene-sulfonamide structure, is widely used in animal for a long time
Prevention and treatment of diseases.In recent years, sulfa drugs is frequently detected in natural water body and secondary effluent, with certain
Eco-toxicity, potential ecological hazard is produced safely to environmental organism.Therefore, its environmental behaviour and control technology receive the country
The extensive concern of outer scholar.
High-level oxidation technology is to handle one of effective means of intractable organic pollution.It is currently based on hydroxyl radical free radical oxygen
Changing the method for degraded sulfa drugs has O3、UV/H2O2、Fenton、UV-A/TiO2、Fe3+With gamma-rays/H2O2Deng.In recent years, base
The synthesis for absorbing Visible Light Induced Photocatalytic and photochemical catalyst in molecular iodine is paid close attention to by related scholar, molecular iodine I2[E0(I2/I-)=
0.54V] break to form I [E under visible ray (λ >=450nm) or other energy excitations0(I·/I-)=1.33V].It is existing
Biodegrading process degradation rate is too low, it is impossible to the effective pollution problem for solving sulfa drugs to natural water body and secondary effluent.
The content of the invention
It is an object of the invention to provide a kind of biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, solve
The problem of degradation rate present in prior art is too low.
The technical solution adopted in the present invention is, based on the biodegrading process of ultrasonic or ultraviolet enhanced sulfamethyldiazine,
Specifically implement according to following steps：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution that prepared by the step 1 of measured amounts is placed in volumetric flask, constant volume, is shaken
It is transferred to after even, standing in beaker；
Step 3, to adding certain density NaOH solution or H in beaker2SO4Solution adjusts pH value；
Step 4, to a certain amount of KI is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH, stir；
Step 5, after step 4 stirs, then to adding a certain amount of H in beaker2O2Stir, form mixing molten
Liquid；
Step 6, after step 5 stirs, using ultrasonic cell disruptor to the mixed solution in beaker in standard
The ultrasound wave irradiation regular hour is carried out under atmospheric pressure or using ultraviolet light at normal atmospheric pressure to the mixed solution in beaker
Carry out the irradiation regular hour.
It is a feature of the present invention that
The concentration that quantifying in step 2 shakes up rear sulfamethyldiazine is 0.0095~0.076mmolL-1。
The solution concentration of NaOH solution in step 3 is 0.90molL-1~1.10molL-1。
H in step 32SO4The solution concentration of solution is 0.90molL-1~1.10molL-1。
It is to use NaOH solution or H to be given in step 3 in beaker and add concentration2SO4Solution adjusts pH value
2.6~5.6.
KI concentration in step 4 is 2.4mmolL-1~4.8mmolL-1。
H in step 52O2Concentration is 30mmolL-1~180mmolL-1。
The N of ultrasonic cell disruptor model JY92- II in step 6, ultrasonic power is 65W~390W.
The wavelength of ultraviolet light is 320nm~380nm in step 6.
Exposure time in step 6 is not less than 10min.
The beneficial effects of the invention are as follows the biodegrading process of the invention based on ultrasonic or ultraviolet enhanced sulfamethyldiazine leads to
Cross ultrasonic, ultraviolet enhanced H2O2/ KI systems degraded sulfamethyldiazine, by adjusting the initial pH of sulfamethyldiazine solution,
The removal of sulfamethyldiazine is realized, the degradation rate of sulfamethyldiazine is substantially increased.
Brief description of the drawings
Fig. 1 be the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention ultrasound system under sulfanilamide (SN)
The resolution ratio figure of methylpyrimidine；
Fig. 2 be the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention ultraviolet system under sulfanilamide (SN)
The resolution ratio figure of methylpyrimidine；
Fig. 3 is degraded under the ultrasound system of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Uv absorption spectra during sulfamethyldiazine；
Fig. 4 is degraded under the ultraviolet system of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Uv absorption spectra during sulfamethyldiazine；
Fig. 5 is the sulfamethyldiazine point of the biodegrading process of the invention based on ultrasonic or ultraviolet enhanced sulfamethyldiazine
Not in ultrasound/H2O2/ KI, ultraviolet/H2O2The A of reaction solution in/KI systems460nm(I2) and A350nm(I3 -) changing trend diagram；
Fig. 6 is degraded under the ultrasound system of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Influence figures of the initial pH of solution to degradation rate during sulfamethyldiazine；
Fig. 7 is degraded under the ultraviolet system of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Influence figures of the initial pH of solution to degradation rate during sulfamethyldiazine；
Fig. 8 is the sulfalene under different pH of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Yl pyrimidines are in ultrasound/H2O2The A of reaction solution in/KI systems460nm(I2) changing trend diagram；
Fig. 9 is the sulfalene under different pH of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Yl pyrimidines are in ultrasound/H2O2The A of reaction solution in/KI systems350nm(I3 -) changing trend diagram；
Figure 10 is the sulfanilamide (SN) under different pH of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Methylpyrimidine is in ultraviolet/H2O2The A of reaction solution in/KI systems460nm(I2) changing trend diagram；
Figure 11 is the sulfanilamide (SN) under different pH of the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the invention
Methylpyrimidine is in ultraviolet/H2O2The A of reaction solution in/KI systems350nm(I3 -) changing trend diagram；
Figure 12 is methanol, the methimazole of the biodegrading process of the invention based on ultrasonic or ultraviolet enhanced sulfamethyldiazine
To the suppression situation curve map of ultrasound system degraded sulfamethyldiazine；
Figure 13 is methanol, the methimazole of the biodegrading process of the invention based on ultrasonic or ultraviolet enhanced sulfamethyldiazine
To the suppression situation curve map for sulfamethyldiazine of being degraded under ultraviolet system；
Figure 14 is two kinds of enhancing systems of the biodegrading process of the invention based on ultrasonic or ultraviolet enhanced sulfamethyldiazine
The HPLC spectrograms of degraded sulfamethyldiazine.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine of the present invention, it is specifically real according to following steps
Apply：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution that prepared by the step 1 of measured amounts is placed in volumetric flask, constant volume, is shaken
It is transferred to after even, standing in beaker, the concentration for quantitatively shaking up rear sulfamethyldiazine is 0.0095~0.076mmolL-1；
Step 3, it is 0.90molL to concentration is added in beaker-1~1.10molL-1NaOH solution or H2SO4Solution
PH value is adjusted between 2.6~5.6；
Step 4, it is 2.40mmolL to concentration is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH-1~
4.80mmol·L-1KI, stir；
Step 5, after step 4 stirs, then in beaker add concentration be 30mmolL-1~180mmolL-1
H2O2Stir, form mixed solution；
Step 6, it is molten to the mixing in beaker using the N ultrasonic cell disruptors of JY92- II after step 5 stirs
Liquid at normal atmospheric pressure, ultrasonic power be that ultrasound wave irradiation not less than 10min or uses wavelength for 320nm under 65W~390W
~380nm ultraviolet light is not less than 10min to the mixed solution irradiation in beaker at normal atmospheric pressure.
Experiment material in the specific embodiment of the present invention is as follows：KI (analyzes pure, Tianjin good fortune morning chemical reagent
Factory)；30%H2O2(top pure grade, Chemical Reagent Co., Ltd., Sinopharm Group)；(analysis is pure, Tianjin day power for sodium hydroxide, sulfuric acid
Chemical reagent Co., Ltd)；(99.5%) Tianjin good fortune morning chemical reagent factory, purity be more than sulfamethyldiazine；Methanol (analysis
It is pure, Guangdong Guanghua Science and Technology Co., Ltd.)；(98%) Shanghai Yan Chen Industrial Co., Ltd.s, purity be more than methimazole；Acetonitrile
(chromatographically pure)；Ultra-pure water.
Laboratory apparatus in the specific embodiment of the present invention is as follows：PHs-25 digital displays acidometer (the upper beneficial instrument and meter of marine rainbow
Co., Ltd) with E-201-C-9 type pH combination electrodes (Shanghai Russell science and technology)；The N ultrasonic cell disruptors of JY92- II (are equipped with
Diameter 8mm titanium probe, Ningbo Xin Zhi Instrument Ltd.)；18W uviol lamp models UVA-365nm (Beijing Zhong Yifuteng sections
Skill Co., Ltd)；Aglient1200 liquid chromatographs, are equipped with G1311A quaternary pumps, 30 DEG C of column oven, the variable ripples of G1314CXL
Long UV-detector.The flight matter of UltiMate3000 liquid chromatograies (Dionex branch companies of the U.S.)-micrOTOF-Q II 10280
Compose (German Bruker companies).
Embodiment 1
Based on the biodegrading process of ultrasonic or ultraviolet enhanced sulfamethyldiazine, specifically implement according to following steps：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution that prepared by the step 1 of measured amounts is placed in volumetric flask, constant volume, is shaken
It is transferred to after even, standing in beaker, the concentration for quantitatively shaking up rear sulfamethyldiazine is 0.038mmolL-1；
Step 3, it is 1.0molL to concentration is added in beaker-1NaOH solution or H2SO4Solution adjusts pH value to 2.6；
Step 4, it is 2.40mmolL to concentration is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH-1's
KI, stirs；
Step 5, after step 4 stirs, then in beaker add concentration be 30mmolL-1H2O2Stir,
Form mixed solution；
Step 6, it is molten to the mixing in beaker using the N ultrasonic cell disruptors of JY92- II after step 5 stirs
Liquid at normal atmospheric pressure, ultrasonic power be that ultrasound wave irradiation not less than 10min or uses wavelength for the ultraviolet of 365nm under 195W
Light is not less than 10min to the mixed solution irradiation in beaker at normal atmospheric pressure.
Embodiment 2
Based on the biodegrading process of ultrasonic or ultraviolet enhanced sulfamethyldiazine, specifically implement according to following steps：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution that prepared by the step 1 of measured amounts is placed in volumetric flask, constant volume, is shaken
It is transferred to after even, standing in beaker, the concentration for quantitatively shaking up rear sulfamethyldiazine is 0.038mmolL-1；
Step 3, it is 1.0molL to concentration is added in beaker-1NaOH solution or H2SO4Solution adjusts pH value to 3.2；
Step 4, it is 3.60mmolL to concentration is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH-1's
KI, stirs；
Step 5, after step 4 stirs, then in beaker add concentration be 105mmolL-1H2O2Stirring is equal
It is even, form mixed solution；
Step 6, it is molten to the mixing in beaker using the N ultrasonic cell disruptors of JY92- II after step 5 stirs
Liquid at normal atmospheric pressure, ultrasonic power be that ultrasound wave irradiation not less than 10min or uses wavelength for the ultraviolet of 365nm under 195W
Light is not less than 10min to the mixed solution irradiation in beaker at normal atmospheric pressure.
Embodiment 3
Based on the biodegrading process of ultrasonic or ultraviolet enhanced sulfamethyldiazine, specifically implement according to following steps：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution that prepared by the step 1 of measured amounts is placed in volumetric flask, constant volume, is shaken
It is transferred to after even, standing in beaker, the concentration for quantitatively shaking up rear sulfamethyldiazine is 0.038mmolL-1；
Step 3, it is 1.10molL to concentration is added in beaker-1NaOH solution or H2SO4Solution adjust pH value to
4.2；
Step 4, it is 4.80mmolL to concentration is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH-1's
KI, stirs；
Step 5, after step 4 stirs, then in beaker add concentration be 180mmolL-1H2O2Stirring is equal
It is even, form mixed solution；
Step 6, it is molten to the mixing in beaker using the N ultrasonic cell disruptors of JY92- II after step 5 stirs
Liquid at normal atmospheric pressure, ultrasonic power be that ultrasound wave irradiation not less than 10min or uses wavelength for the ultraviolet of 365nm under 195W
Light is not less than 10min to the mixed solution irradiation in beaker at normal atmospheric pressure.
Embodiment 4
Based on the biodegrading process of ultrasonic or ultraviolet enhanced sulfamethyldiazine, specifically implement according to following steps：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, the sulfamethyldiazine storing solution for measuring two groups of a certain amount of steps 1 preparations is placed in 200ml volumetric flasks,
Constant volume, shake up, stand after be transferred to respectively in 250mL beaker, constant volume shake up after concentration range be 0.038mmolL-1；
Step 3, it is 1.0molL to concentration is added in two groups of beakers-1NaOH solution or H2SO4Solution adjusts pH value
To 3.2；
Step 4, it is 4.8mmolL to concentration is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH-1's
KI, stirs；
Step 5, after step 4 stirs, then in beaker add concentration be 120mmolL-1H2O2Stirring is equal
It is even, form mixed solution；
Step 6, after step 5 stirs, by two groups of identical mixed solutions,
First group using the N ultrasonic cell disruptors of JY92- II to the mixed solution in beaker at normal atmospheric pressure, it is super
Acoustical power is not less than 10min for ultrasound wave irradiation under 195W；It is designated as：Ultrasound/H2O2/ KI groups；
Second group uses wavelength not small to the mixed solution irradiation in beaker at normal atmospheric pressure for 365nm ultraviolet light
In 10min；It is designated as ultraviolet/H2O2/KI。
It is experimental group with embodiment 4,
First group of control group is respectively：Only under ultrasound condition, ultrasound/KI, ultrasound/H2O2、H2O2、KI/H2O2, it is super
Sound/KI/H2O2；
Second group of control group is respectively：Only under ultraviolet light conditions, ultraviolet/KI, ultraviolet/H2O2、H2O2、KI/H2O2, it is purple
Outside/KI/H2O2；
Probe is immersed in beaker, soaking depth about 1.0cm, the sampling per 10min passes through HPLC after crossing 0.22 μm of filter membrane
The concentration of sulfamethyldiazine is analyzed, the degradation rate of sulfamethyldiazine, degradation rate=(c is calculated0-ct)/c0× 100%, formula
In, c0And ctRespectively start the concentration (mmolL with t sulfamethyldiazine-1)。
HPLC analyzes the concentration of sulfamethyldiazine：
Sulfamethyldiazine concentration is analyzed by Aglient1200 liquid chromatographs, using quantified by external standard method.Chromatographic isolation
Condition is chromatographic column：EclipsePlusC18(4.6×150mm；5μm)；Mobile phase is acetonitrile: ultra-pure water=25: 75 (volumes
Than)；Sample size is 10.0 μ L；Flow velocity is 0.30mLmin-1；Detection wavelength 269nm；Column temperature is 30 DEG C.On this condition, sulphur
The retention time t of amine methylpyrimidineR=6.585min.
As shown in figure 1, independent H2O2Oxidation to sulfamethyldiazine is little, and degradation rate is only 1.6%, and this is main
It is because sulfamethyldiazine contains reactive species (- SO simultaneously2-) and reproducibility group (- NH2,-NH -), limit
H2O2Oxidation.Individually the degradation effect of ultrasound is not also obvious, and this is relevant with the quantity of HO free radicals in system.Ultrasound/H2O2One
Determine to improve the removal effect to sulfamethyldiazine in degree, the yield for essentially consisting in HO free radicals in system has increased
Plus.Ultrasound/KI is even below direct ultrasound to the clearance of sulfamethyldiazine, and this is due to I-HO is caught under ultrasonication
Free radical and discharge iodine, degrade to form competition with sulfamethyldiazine.
As shown in Fig. 2 individually under ultraviolet irradiation, 60min, the degraded clearance of sulfamethyldiazine is only 5.7%.Sulfanilamide (SN)
Methylpyrimidine structure is relatively stablized, and characteristic absorption wavelength is 291nm, therefore can not directly effective photodissociation.Ultraviolet/H2O2Under the conditions of
Degradation rate is 10.2%, and this is due to H2O2HO free radicals could be produced in λ ＜ 260nm.Ultraviolet/KI is to sulfamethyldiazine
Remove almost without influence.KI/H2O2The clearance of sulfamethyldiazine is 43.5% in system.H under acid condition2O2It is with KI
Molecular iodine (I2) main source, H2O2By I-Oxidation generation I2, shown in conversion type such as formula (1), while I in solution-With I2With reference to
As I3 -, shown in conversion type such as formula (2), I3 -Generation further improve I2Solubility in water.In I2And I3 -Common work
Under, sulfamethyldiazine is effectively degraded.But due to I2[E0(I2/I-)=0.54V] and I3 -[E0(I3 -/I-)=0.53V]
Oxidability it is relatively low, therefore limit H2O2Degradation effects of/the KI to sulphadiazine.
Ultrasonic H is can be seen that from Fig. 1 and Fig. 22O2/ KI and ultraviolet/H2O2Degradeds of/the KI to sulfamethyldiazine, 60min
Degradation rate be respectively 85.2% and 65.9%.This essentially consists in the generation of molecular iodine and iodine free radical, and conversion type such as (3)~
(5) shown in.
H2O2+2H++2I-→I2+2H2O (1)
I2+I-→I3 - (2)
The present invention further compares ultrasound/H by ultra-violet absorption spectrum2O2/ KI and ultraviolet/H2O2/ KI systems decompose sulphur
I during amine methylpyrimidine2And I3 -Generation situation, as a result as Figure 3-Figure 4, the sulfanilamide (SN) it can be seen from Fig. 3 and Fig. 4
Methylpyrimidine has obvious absorption in λ=291nm or so, is constantly reduced as reaction carries out peak height, illustrates that sulfamethyldiazine exists
Ultrasonic, ultraviolet enhancing H2O2Effective degraded is there occurs in/KI systems, the UV absorption at 350nm and 460nm gradually drops in addition
It is low.Due to I2It is respectively ε in λ=350nm and λ=460nm molar absorption coefficient350nm=30M-1cm-1And ε460nm=730M- 1cm-1, I3 -Molar absorption coefficient be respectively ε350nm=25800M-1cm-1And ε460nm=980M-1cm-1, therefore can use
A460nmAnd A350nmTo analyze I in experimentation2And I3 -Generation and Expenditure Levels.
Ultrasound/H2O2/ KI, ultraviolet/H2O2The A of reaction solution in/KI systems460nm(I2) and A350nm(I3 -) result of variations such as
Shown in Fig. 5, Fig. 5 shows, the I during two kinds of system degraded sulfamethyldiazines2(A460nm) and I3 -(A350nm) carried out with reaction
Decrease, illustrate I3 -And I2Constantly reduce, have I in two kinds of systems2And I3 -Generate and take part in reaction.T=0, two kinds of bodies
I in system2And I3 -Growing amount it is essentially identical, with the progress of reaction, ultrasound, ultraviolet irradiation promote I2And I3 -Decompose generation activity
Higher I free radicals and I2 -, iodine free radical is the chief active free radical of degraded sulfamethyldiazine.Ultrasound/H2O2/ KI systems
Middle I2And I3 -Consumption faster, be more beneficial for the degraded of sulfamethyldiazine.On the one hand, under ultraviolet irradiation, I in solution2Release
Put and react can regard as heterogeneous system, i.e. system normal agitation effect under light can not be by solution uniform pickup.Ultrasonic procedure
Formation, vibration, collapse of hollow bubble etc. can provide effective stirring action, promote effective progress of heterogeneous reaction.This
Temperature, which rises, in outer ultrasonic reaction system may cause I2Volatilization.
(1) influence of the sulfamethyldiazine solution initial pH value to its degradation effect
The sulfamethyldiazine initial concentration of preparation is 0.038mmolL-1, H2O2Addition concentration with KI is respectively
120mmol·L-1、4.8mmol·L-1, addition concentration is 1.0molL-1NaOH solution or H2SO4Solution adjusts solution ph
Respectively 2.6,3.2,4.2,5.6, it is ultrasonic, ultraviolet right respectively in the case where ultrasonic power is 195W and a length of 365nm of ultraviolet light wave
H2O2The influence of/KI degraded sulfamethyldiazines.
As shown in fig. 6, as shown in fig. 7, degraded of the initial pH value on sulfamethyldiazine influences clearly.PH is 2.6
~5.6 scopes, the degradation rate of sulfamethyldiazine is reduced with the rise of initial pH value, solution ph is followed successively by 2.6,3.2,
When 4.2 and 5.6,60min, as shown in fig. 6, under ultrasonication, degradation rate is respectively 92.3%, 85.2%, 43.4% and
36.5%；As shown in fig. 7, under the conditions of ultraviolet, degradation rate is respectively 85.4%, 65.9%, 48.9% and 38.9%.Acid condition
Substantially it is more conducive to the degraded of sulfamethyldiazine.
On the basis of influence of the analysis sulfamethyldiazine solution initial pH value to its degradation effect, different PH are analyzed
Under, ultrasound/H2O2/ KI, ultraviolet/H2O2Under/KI systems, the A of reaction solution460nm(I2) and A350nm(I3 -) change.
As shown in figures s-11, show that solution initial pH value influences I2Yield, I2Generation dropped with the rise of pH value
It is low.Because H+H can be effectively improved2O2The progress that promotes of oxidisability, more iodine are generated in sound, light enhancing system free
Base.As pH value from 2.6 increases to 5.6, I3 -Amount reduce therewith (pH=4.2 exceptions).Therefore I is limited to a certain extent certainly
By base and I2 -The generation of free radical, the clearance of sulfamethyldiazine is with the increased reduction of pH value.
Compare the form of iodine in different pH value in ultrasonic, ultraviolet enhancing system, ultraviolet/H2O2I in/KI systems2And I3 -
Amount it is relatively stable.In weak acid environment, H2O2Oxidisability is reduced, and itself is decomposed into H2O and O2, I3 -Based on its photodissociation.It is super
Sound/H2O2I in/KI systems2Growing amount it is obvious in pH=2.6~3.2 ranges.Due to more I-Participate in oxidation reaction, drop
Low I-With I2And the reaction probabilities of I free radicals, I3 -Yield reduce, I is inhibited to a certain extent2 -The generation of free radical.
With the progress of ultrasonic reaction, I2Consumption substantially increase, more I2Reaction generation I free radicals, with I2 -·[E0(I2 -·/I-)
=1.03V] compare, I [E0(I·/I-)=1.33V] have higher oxidation activity, sulfamethyldiazine effectively degrade from
The structural analysis of sulfamethyldiazine in itself, its pKa1=2.5 ± 0.7, pKa1=7 ± 1, in the scope of pH2.6~5.6, sulfalene
Yl pyrimidines exist in equal neutral molecule form, therefore influence of the pH value to reaction essentially consists in the life of iodine molecule and its free radical
Into.
(2) free radical suppresses
Ultrasound/H2O2/ KI, ultraviolet/H2O2The living radical type of/KI systems degraded sulfamethyldiazine, to sulfalene
Yl pyrimidines initial concentration is 0.038mmolL-1, H2O2It is respectively 120mmolL with KI addition concentration-1、2.4mmol·L-1,
Addition concentration is 1.0molL-1NaOH solution or H2SO4When solution regulation solution ph is 3.2, it is in ultrasonic power respectively
It is ultrasonic, ultraviolet to H under 195W and a length of 365nm of ultraviolet light wave2O2The influence of/KI degraded sulfamethyldiazines.
Using methanol and methimazole as ultrasonotomography and the inhibitor of ultraviolet degradation, as shown in Figure 12-Figure 13,
Figure 12-Figure 13 shows, as the inhibitor of HO free radicals, and methanol inhibits ultrasound/H to a certain extent2O2/ KI, purple
Outside/H2O2The degraded of sulfamethyldiazine in/KI systems, 60min degradation rate respectively by 85.2% be reduced to 78.75% and
65.9% to 54.91%.Methimazole is used as iodine free radical (I free radicals, I2 -Free radical) inhibitor, have to sulfamethyldiazine
Obvious inhibitory action.The addition concentration of methimazole is respectively 0.0,12.0,24.0 and 48mmolL-1, 60min, ultrasound/
H2O2The clearance of/KI system sulfamethyldiazines is respectively 85.2%, 58.95%, 23.95% and 3.98%；Ultraviolet/H2O2/
The clearance of KI system sulfamethyldiazines is respectively 65.9%, 27.0%, 10.9% and 1.84%.Therefore iodine free radical is drawn
(I free radicals, I2 -Free radical) be two reaction systems chief active free radical.
(3) product of sulfamethyldiazine degraded
It is 0.038mmolL to sulfamethyldiazine initial concentration-1, H2O2It is respectively 120mmol with KI addition concentration
L-1、2.4mmol·L-1, addition concentration is 1.0molL-1NaOH solution or H2SO4When solution regulation solution ph is 3.2,
Respectively in the case where ultrasonic power is 195W and a length of 365nm of ultraviolet light wave, sulfamethyldiazine degradation process under ultrasound, ultraviolet irradiation
In HPLC change, as shown in figure 14, under the conditions of experimental analysis HPLC, the retention time t of sulfamethyldiazineR=
6.585min, with the progress of reaction, peak area reduces, and illustrates sulfamethyldiazine in ultrasound/H2O2/ KI, ultraviolet/H2O2/KI
Effective degraded is there occurs in system.
Further the product in degradation process is analyzed using HPLC/MS/MS, the analysis of sulfamethyldiazine product
Completed by the LC-MS instrument of Bruker micrOTOF-Q II 10280.HPLC analysis conditions：Zorbax SB-Aq chromatographic columns
(150mm × 4.6mm, 5 μm)；Using acetonitrile as mobile phase A, ultra-pure water is Mobile phase B, acetonitrile: ultra-pure water=25: 75 (volumes
Than)；Detection wavelength 269nm；Flow velocity 0.3mLmin-1；30 DEG C of column temperature；The μ L of sample size 10；Mass Spectrometry Conditions：ESI+Electron spray ion
Change mode, dries gas N2, flow 6Lmin-1, atomization gas pressure 50psi, dry 350 DEG C of temperature degree.Scan mode：Full scan
(scan), scanning range (m/z)：50~20000.Concrete outcome is as shown in table 1.
The main degradation products of the sulfamethyldiazine of table 1
As can be seen from Table 1, the main m/z of sulfamethyldiazine is 265.In the degraded aoxidized based on hydroxyl radical free radical
Cheng Zhong, by the attack of HO free radicals, C-N keys that pyrimidine ring is connected with amino disconnect, and generate corresponding sulfanilyl
Amine and 4- methylpyrimidine -2- amine.In 4- methylpyrimidine -2- amine-NH2Replaced by HO free radicals, can further generate 4- first
Base -2- hydroxy pyrimidines, this paper only detects P-aminobenzene-sulfonamide.In addition, sulfanilamide (SN) key (S-N) in sulfamethyldiazine compared with
Easily attacked by free radical, produce sulfanilamide (SN) acid groups, and make during subsequent degradation through peroxidating, desulfurization etc. are a series of
With being degraded, research finds that the reaction of sulfa drugs 40%~70% starts from the fracture of sulfanilamide (SN) key.The life of phenyl-monoiodide
Into this and ultrasound/H2O2/ KI, ultraviolet/H2O2The contribution of iodine free radical is relevant in/KI systems.
Claims (10)
1. the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, it is characterised in that specifically according to following steps
Implement：
Step 1, certain density sulfamethyldiazine storing solution is prepared；
Step 2, measured amounts step 1 prepare sulfamethyldiazine storing solution be placed in volumetric flask, constant volume, shake up, it is quiet
Postpone and be transferred in beaker；
Step 3, to adding certain density NaOH solution or H in beaker2SO4Solution adjusts pH value；
Step 4, to a certain amount of KI is added in the sulfamethyldiazine storing solution that step 3 is regulated to pH, stir；
Step 5, after step 4 stirs, then to adding a certain amount of H in beaker2O2Stir, form mixed solution；
Step 6, after step 5 stirs, using ultrasonic cell disruptor to the mixed solution in beaker in normal atmosphere
Pressure is carried out the ultrasound wave irradiation regular hour or the mixed solution in beaker is carried out at normal atmospheric pressure using ultraviolet light
Irradiate the regular hour.
2. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the concentration that quantifying described in step 2 shakes up rear sulfamethyldiazine is 0.0095~0.076mmolL-1。
3. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the solution concentration of the NaOH solution described in step 3 is 0.90molL-1~1.10molL-1。
4. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the H described in step 32SO4The solution concentration of solution is 0.90molL-1~1.10molL-1。
5. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In it is to use NaOH solution or H to be given in step 3 in beaker and add concentration2SO4Solution regulation pH value is 2.6~5.2.
6. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the KI concentration described in step 4 is 2.4mmolL-1~4.8mmolL-1。
7. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the H described in step 52O2Concentration is 30mmolL-1~180mmolL-1。
8. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the N of ultrasonic cell disruptor model JY92- II described in step 6, ultrasonic power is 65W~390W.
9. the biodegrading process according to claim 1 based on ultrasonic or ultraviolet enhanced sulfamethyldiazine, its feature exists
In the wavelength of ultraviolet light described in step 6 is 320nm~380nm.
10. the biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine according to claim 8 or claim 9, it is special
Levy and be, the exposure time described in step 6 is not less than 10min.
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|---|---|---|---|---|
| CN102285703A (en) * | 2011-06-15 | 2011-12-21 | 南京信息工程大学 | Method for ultrasonic removal of sulfadiazine in water |
| CN104556292A (en) * | 2013-10-28 | 2015-04-29 | 张军伟 | Method for photochemical degradation of sulfonamide in water by using freshwater algae |
| CN105502776A (en) * | 2016-01-21 | 2016-04-20 | 中华人民共和国济南出入境检验检疫局 | Method for removing antibiotics in water by using UV/H2O2 combination |
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|---|---|---|---|---|
| CN102285703A (en) * | 2011-06-15 | 2011-12-21 | 南京信息工程大学 | Method for ultrasonic removal of sulfadiazine in water |
| CN104556292A (en) * | 2013-10-28 | 2015-04-29 | 张军伟 | Method for photochemical degradation of sulfonamide in water by using freshwater algae |
| CN105502776A (en) * | 2016-01-21 | 2016-04-20 | 中华人民共和国济南出入境检验检疫局 | Method for removing antibiotics in water by using UV/H2O2 combination |
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