CN110174398A - Water body total chrome content on-line measuring device and method based on high-level oxidation technology - Google Patents
Water body total chrome content on-line measuring device and method based on high-level oxidation technology Download PDFInfo
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- CN110174398A CN110174398A CN201910586194.0A CN201910586194A CN110174398A CN 110174398 A CN110174398 A CN 110174398A CN 201910586194 A CN201910586194 A CN 201910586194A CN 110174398 A CN110174398 A CN 110174398A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000011651 chromium Substances 0.000 claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000005587 bubbling Effects 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000006396 nitration reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000008676 import Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 9
- 230000003139 buffering effect Effects 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 8
- BYPCTJNKNKPFPG-UHFFFAOYSA-N CC(=O)C.C1(=CC=CC=C1)N(C(N(N)C1=CC=CC=C1)=O)N Chemical group CC(=O)C.C1(=CC=CC=C1)N(C(N(N)C1=CC=CC=C1)=O)N BYPCTJNKNKPFPG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 33
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 5
- 238000010561 standard procedure Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 4
- 230000006698 induction Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 235000012721 chromium Nutrition 0.000 description 32
- 239000000523 sample Substances 0.000 description 32
- 238000002835 absorbance Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 9
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 8
- 238000002798 spectrophotometry method Methods 0.000 description 8
- 239000012286 potassium permanganate Substances 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000012738 dissolution medium Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 231100000089 gene mutation induction Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of water body total chrome content on-line measuring device and method based on high-level oxidation technology.The present invention is dissolved in the ozone gas of high concentration in water sample more to be measured using electrolysis type ozone generator and quartz glass bubbler formula reactor；The present invention generates rapidly the hydroxyl radical free radical OH of strong oxidizing property using uv induction ozone in water, and under normal temperature conditions in the short time complete oxidation different valence state and form chromium, reduce the use of chemical reagent in oxidation process and the generation of secondary pollution；The present invention solves the problems, such as to be difficult to remove excessive oxidant in National Standard Method, and by the pH of adjusting sample, the hydrogen peroxide for avoiding ozone from generating promotes the reduction of hexavalent chromium in acid condition, improves the accuracy of water body total chrome content measurement.
Description
Technical field
The present invention relates to water quality monitoring technical fields, and in particular to a kind of water body total chrome content based on high-level oxidation technology
On-line measuring device and method.
Background technique
Total chromium refers to the total content of various valence states and form chromium concn in 1L water body, be measure water quality important indicator it
One.Chromium is a kind of heavy metal that toxicity is very big, is easily accessible human body cell, causes to damage to the internal organs such as liver, kidney and DNA,
Accumulation has carcinogenicity and may induce gene mutation in human body.With the development of economy, especially plating, process hides and weaving
Etc. industries development, produce a large amount of industrial wastewater containing chromiums, cause serious environmental pollution.Therefore, chromium total in water body is contained
The on-line checking of amount has important practical usage.
Diphenylcarbazide can be divided mainly into according to the difference of testing principle for the detection method of water body total chrome content
Spectrophotometry, ferrous ammonium sulfate titration and atomic absorption spectrophotometry.Common total chromium water quality currently on the market
Online automatic monitor is mainly based upon diphenyl carbazide spectrophotometry, i.e., in acidic dissolution medium, certain temperature and
Under pressure, the chromium of different valence state and form is oxidized to Cr VI by potassium permanganate or potassium persulfate solution in water sample, Cr VI from
Son is reacted with diphenylcarbazide generates aubergine complex, carries out spectrophotometry at Yu Bochang 540nm.
Diphenyl carbazide spectrophotometry has selectivity strong, high sensitivity, accurate and reliable, low in cost, anti-because of it
The advantages that interfering and being easily used, such online automatic monitor are online in total chromium of surface water, sanitary sewage and industrial wastewater
It is widely applied in automatic monitoring.
National Standard Method (HJ 798-2016) uses potassium permanganate and potassium peroxydisulfate as oxidant, excessive in the detection process
Potassium permanganate or potassium persulfate oxidation agent can all influence to develop the color, therefore, excessive potassium permanganate need to drip under the shielding of urea
Add sodium nitrite to restore, and excessive potassium peroxydisulfate need to heat removal under the high temperature conditions, cause operating process cumbersome, and when to
It surveys in water sample and needs to carry out pre- resolution processing when containing large amount of organic, to eliminate influence of the organic matter to absorbance, to lead
Detection cycle is caused further to lengthen.So National Standard Method measures water body total chrome content, there are reaction temperature height, pre- resolution and oxidation are anti-
Long, more using chemical reagent between seasonable, the problems such as operation and maintenance cost is high, cumbersome with it is insufficient.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art, a kind of water body based on high-level oxidation technology is provided
Total chrome content detection device and method make the ozone gas of high concentration using electrolysis type ozone generator and quartzy bubbling style reactor
Body is more sufficiently uniformly dissolved in water sample to be measured；The hydroxyl of strong oxidizing property is generated rapidly certainly using uv induction ozone in water
By base OH, and under normal temperature conditions in the short time complete oxidation different valence state and form chromium, reduce in oxidation process and change
Learn the use of reagent and the generation of secondary pollution.
It is another object of the present invention to solve the problems, such as to be difficult to remove excessive oxidant in National Standard Method, while passing through adjusting
The pH of sample, the hydrogen peroxide for avoiding ozone from generating promote the reduction of hexavalent chromium in acid condition, improve the total chromium of water body
The accuracy of assay.
According to technical solution provided by the invention, a kind of water body total chrome content on-line checking dress based on high-level oxidation technology
It sets, including quartzy bubbling style reactor, hangs the first ultraviolet lamp and second respectively in the both sides external of quartzy bubbling style reactor
Ultraviolet lamp；The setting water sample import of top two sides and buffer inlet in the quartzy bubbling style reactor；The water sample import
It is connect with water sample storage tank, the first syringe pump is set at water sample outlet end；The buffer inlet and buffering flow container connect
It connects, the second syringe pump is set in the buffering flow container outlet end；It is set in the upper end (i.e. top) of the quartzy bubbling style reactor
Set ozone gas bubbling pipe and tail gas outlet；It is anti-that one end of the ozone gas bubbling pipe extend into the quartzy bubble type
It answers and is exported inside device as the ozone gas bubbling pipe, the other end of the ozone gas bubbling pipe stays in the quartz drum
The ozone gas bubbling pipe import, the ozone gas bubbling pipe import and the electrolysis method ozone are used as outside bubble reactor
The first solenoid valve is arranged in the gas output end of the ozone generator by electrolytic process in generator connection；In the quartzy bubble type
The bottom of reactor is equipped with outlet, which is connect by pipeline with first input end in pond of developing the color, in the quartz drum
Second solenoid valve is arranged in the outlet end of bubble reactor；The second input end of the colour developing pond is connect with nitration mixture tank, in the nitration mixture
Third syringe pump is arranged in tank outlet end；Colour developing pond third input end is connect with total chromium color developing agent tank, is developed the color in total chromium
The 5th syringe pump is arranged in agent tank outlet end；The first exit end in the colour developing pond is connect with spectrophotometer, in the colour developing pond
First exit end be arranged the 4th syringe pump；The second outlet end in the colour developing pond is connect with waste liquid tank, in the colour developing pond
Third solenoid valve is arranged in second outlet end.
The electrolysis type ozone generator is that the ozone generation module of applying solid polymer dielectric film (PEM) formula passes through
It is electrolysed distilled water and generates the high-concentrated ozone gas that mass concentration is 18-20wt%, and PEM ozone generation module is 4.
The total chromium matter amount concentration range of water sample to be measured in the water sample storage tank is 0-1mg/L.
The quartz bubbling style reactor is cylinder, and material is quartz glass, size are as follows: height 140~160mm, interior
15~25mm of diameter, 18~28mm of outer diameter.Most preferably, the quartzy bubbling style reactor is cylinder, and material is quartz glass,
Size are as follows: height 150mm, internal diameter 20mm, outer diameter 23mm.
The ozone gas bubbling pipe is quartz material, and internal diameter is 1.5~2.5mm, and outer diameter is 3~5mm, the ozone gas
Distance is 15~25mm between the outlet of body bubbling pipe and quartzy bubbling style reactor bottom.Most preferably, the ozone gas drum
Bubble pipe is also quartz material, internal diameter 2mm, outer diameter 4mm, the outlet of ozone gas bubbling pipe and quartzy bubbling style reactor bottom
Between distance be 20mm.
The watt level of first ultraviolet lamp and the second ultraviolet lamp is 12~24W, and the ultraviolet light wave irradiated is a length of
254nm.Most preferably, the watt level of first ultraviolet lamp and the second ultraviolet lamp is 18W, and the ultraviolet light wave irradiated is a length of
254nm。
Buffer solution in the buffering flow container is borax-sodium hydroxide buffer solution, and pH is about that 12, pH is
11.5~12.5.
Mixed acid solution in the nitration mixture tank is the mixed solution of phosphoric acid, sulfuric acid and water, wherein the body of phosphoric acid, sulfuric acid and water
Product is than being 1:0.8~1.2:1.5~2.5.Most preferably, the mixed acid solution in the nitration mixture tank is the mixed of phosphoric acid, sulfuric acid and water
Solution is closed, wherein the volume ratio of phosphoric acid, sulfuric acid and water is 1:1:2.
Color developing agent in total chromium color developing agent tank is diphenylcarbazide-acetone that mass concentration is 1.5~2.5g/L
Solution.Most preferably, the color developing agent in total chromium color developing agent tank is that diphenylcarbazide-acetone that mass concentration is 2g/L is molten
Liquid.
A kind of water body total chrome content online test method is examined online using the water body total chrome content based on high-level oxidation technology
Survey device, comprising the following steps:
(1) the first solenoid valve is closed, electrolysis type ozone generator is started, so that being generated in electrolysis type ozone generator enough
High-concentrated ozone gas, and be produced as the static pressure of 8~12cm (preferably 10cm) water-column；
(2) 15~25mL (preferably 20mL) water sample to be measured is injected into quartzy bubbling from water sample storage tank by the first syringe pump
It is anti-to be injected into quartzy bubble type from buffer tank by the second syringe pump by formula reactor for 3~7mL (preferably 5mL) buffer solution
Device is answered, so that mixed sample pH value of solution is greater than 11.5, is controlled between 11.5~12；
(3) the first ultraviolet lamp, the second ultraviolet lamp and the first solenoid valve are opened, so that electrolysis type ozone generator generation 8~
The high-concentrated ozone gas of 12cm (preferably 10cm) water-column static pressure passes through the first solenoid valve and ozone gas bubbling pipe
Entered in quartzy bubbling style reactor in a manner of bubbling, the first ultraviolet lamp and the are set in the two sides of quartzy bubbling style reactor
Two ultraviolet lamps issue 254nm ultraviolet light, and ozone gas, which reacts rapidly under the irradiation of 254nm ultraviolet light with water sample, generates Strong oxdiative
Property hydroxyl radical free radical OH, so that aoxidizing in water sample to be measured (0-1mg/L) chromium of different valence state and form is Cr VI, oxidation
The resolution reaction time is 3~7min (preferably 5min)；
(4) oxidation resolution after reaction, opens second solenoid valve, and the water sample to be measured after reaction is completed is discharged into colour developing
Chi Zhong；
(5) by third syringe pump that 0.5~1.0mL (preferably 0.7mL) nitration mixture is molten after water sample is discharged into colour developing pond completely
Liquid (volume ratio of phosphoric acid, sulfuric acid and water be 1:1:2) is injected into colour developing pond from nitration mixture tank, by the 5th syringe pump by 0.5~
1.5mL (preferably 1mL) diphenylcarbazide-acetone soln is injected into colour developing pond from total chromium color developing agent tank, and chromogenic reaction 3~
8min (preferably 5min)；
(6) after to chromogenic reaction, by the 4th syringe pump by 3~8mL (preferably 5mL) colour developing after solution from colour developing pond
It is injected into spectrophotometer；Solution after remaining colour developing is discharged into waste liquid tank；Spectrophotometer test after the colour developing solution in
Absorbance value at 540nm wavelength, is calculated total chrome content.
Compared with prior art, the present invention has the advantage that
The present invention is compared to the advantage of potassium permanganate and potassium peroxydisulfate that National Standard Method uses: oxidation resolution reaction temperature
Low, room temperature can react rapidly under uv induction；Oxidation digestion time is short, and 5min can all aoxidize the chromium solution of 1mg/L；
Initiator of the ozone as hydroxyl radical free radical is selected, excessive ozone reduces the use of chemical reagent without tail processing；It generates
Ozone gas, itself can be decomposed into oxygen, and secondary pollution is few.
For the present invention simultaneously by the pH of adjusting sample, the hydrogen peroxide for avoiding ozone from generating promotes sexavalence in acid condition
The reduction of chromium ion improves the accuracy of water body total chrome content measurement.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the water body total chrome content on-line measuring device the present invention is based on high-level oxidation technology；
Wherein, 1. electrolysis type ozone generator；2. water sample storage tank；3. the first syringe pump；4. the first solenoid valve；5. first is purple
Outer lamp；6. second solenoid valve；7. waste liquid tank；8. ozone gas bubbling pipe；9. quartzy bubbling style reactor；10. the second ultraviolet lamp；
11. third solenoid valve；12. tail gas outlet；13. the second syringe pump；14. buffering flow container；15. nitration mixture tank；16. third is injected
Pump；17. the 4th syringe pump；18. pond of developing the color；19. total chromium color developing agent tank；20. the 5th syringe pump；21. spectrophotometer；
Fig. 2 is the matched curve figure of water body total chrome content online test method of the present invention.
Specific embodiment
As shown in Figure 1, for the present invention is based on the water body total chrome content on-line measuring devices of high-level oxidation technology, including quartz
Bubbling style reactor 9 hangs the first ultraviolet lamp 5 and the second ultraviolet lamp 10 in the both sides external of quartzy bubbling style reactor 9 respectively；
In the top two sides of quartzy bubbling style reactor 9, water sample import and buffer inlet are set；Water sample import and water sample storage tank 2 connect
It connects, the first syringe pump 3 is set in 2 outlet end of water sample storage tank；Buffer inlet is connect with buffering flow container 14, is gone out in buffering flow container 14
The second syringe pump 13 is arranged in mouth end；In the upper end of quartzy bubbling style reactor 9,8 import of ozone gas bubbling pipe and tail gas row are set
Outlet 12；It is connect in 8 import of ozone gas bubbling pipe with ozone generator by electrolytic process 1, in the gas of ozone generator by electrolytic process 1
The first solenoid valve 4 is arranged in output end；The bottom of quartzy bubbling style reactor 9 be equipped with outlet, the outlet by pipeline with
Second solenoid valve 6 is arranged in the outlet end of quartzy bubbling style reactor 9 in the first input end connection in colour developing pond 18；Colour developing pond 18
Second input end is connect with nitration mixture tank 15, and third syringe pump 16 is arranged in 15 outlet end of nitration mixture tank；Develop the color 18 third input end of pond
It is connect with total chromium color developing agent tank 19, the 5th syringe pump 20 is set in total 19 outlet end of chromium color developing agent tank；The first of colour developing pond 18 goes out
Mouth end is connect with spectrophotometer 21, and the 4th syringe pump 17 is arranged in the first exit end in colour developing pond 18；The second of colour developing pond 18
Outlet end is connect with waste liquid tank 7, and third solenoid valve 11 is arranged at the second outlet end in colour developing pond 18.
Electrolysis type ozone generator 1 generates the ozone gas that mass concentration is 18-20% using electrolysis distilled water.
Quartzy bubbling style reactor 9 is cylinder, and material is quartz glass, size are as follows: height 150mm, internal diameter 20mm, outer
Diameter 23mm, ozone gas bubbling pipe 8 also be quartz material, internal diameter 2mm, outer diameter 4mm, ozone gas bubbling pipe 8 outlet with
Distance is 20mm between quartzy 9 bottom of bubbling style reactor.
The watt level of first ultraviolet lamp 5 and the second ultraviolet lamp 10 be 18W, and irradiate a length of 254nm of ultraviolet light wave.
The buffer solution buffered in flow container 14 is borax-sodium hydroxide mixed solution, and pH is about 12.
It is phosphoric acid in nitration mixture tank 15, the mixed solution of sulfuric acid and water, wherein the volume ratio of phosphoric acid, sulfuric acid and water is 1:1:2.
It is concentration in total chromium color developing agent tank 19 is 2g/L diphenylcarbazide-acetone soln.
Light absorption value under 21, spectrophotometer output 540nm wavelength.
Using the present invention is based on the water body total chrome content on-line measuring devices of high-level oxidation technology to detect water body total chrome content
It sequentially includes the following steps:
(1) the first solenoid valve 4 is closed, electrolysis type ozone generator 1 is started, so that being generated in electrolysis type ozone generator 1
Enough high-concentrated ozone gas, and generate the static pressure of about 10cm water-column；
(2) 20mL water sample to be measured is injected into quartzy bubbling style reactor 9 from water sample storage tank 2 by the first syringe pump 3, by
5mL buffer solution is injected into quartzy bubbling style reactor 9 from buffer tank 14 by two syringe pumps 13, so that mixed sample pH value of solution
Greater than 11.5；
(3) the first ultraviolet lamp 5, the second ultraviolet lamp 10 and the first solenoid valve 4 are opened, so that electrolysis type ozone generator 1 produces
The high-concentrated ozone gas of raw 10cm water-column static pressure is by the first solenoid valve 4 and ozone gas bubbling pipe 8 with bubbling
Mode enters in quartzy bubbling style reactor 9, purple in the first ultraviolet lamp of the two sides of quartzy bubbling style reactor 9 setting 5 and second
Outer lamp 10 issues 254nm ultraviolet light, and ozone gas, which reacts rapidly under the irradiation of 254nm ultraviolet light with water sample, generates strong oxidizing property
Hydroxyl radical free radical OH, so that aoxidizing in water sample to be measured (0-1mg/L) chromium of different valence state and form is Cr VI, oxidation disappears
The solution reaction time is 5min；
(4) oxidation resolution after reaction, opens second solenoid valve 6, and the water sample to be measured after reaction is completed is discharged into aobvious
In color pond 18；
(5) after water sample completely be discharged into colour developing pond 18 after, by third syringe pump 16 by 0.7mL mixed acid solution (phosphoric acid, sulfuric acid and
The volume ratio of water is 1:1:2) it is injected into colour developing pond 18 from nitration mixture tank 15, by the 5th syringe pump 20 by 1mL diphenylcarbazide-
Acetone soln is injected into colour developing pond 18 from total chromium color developing agent tank 19, chromogenic reaction 5min；
(6) after to chromogenic reaction, solution is injected into light splitting from colour developing pond 18 after 5mL is developed the color by the 4th syringe pump 17
Photometer 21；Solution after remaining colour developing is discharged into waste liquid tank 7；Solution is in 540nm after spectrophotometer 21 tests the colour developing
Absorbance value at wavelength, is calculated total chrome content.
The present invention uses the diphenyl carbazide spectrophotometry based on high-level oxidation technology, is by ozone-ultraviolet in alkali
Property solution condition under be quickly generated the hydroxyl radical free radical OH of strong oxidizing property aoxidize the chromium of different valence state and form be Cr VI,
PH value of solution is adjusted to acidity by nitration mixture, and hexavalent chromium is reacted with diphenylcarbazide generates aubergine complex, Yu Bochang
Spectrophotometry is carried out at 540nm.
The theoretical basis that diphenyl carbazide spectrophotometry quantitative determines total chromium water quality is Lambert-Beer's law, fortune
Basic principle for total chromium water quality detection is to establish linear model between the absorbance and hexavalent chromium concentration of solution.It is wherein bright
Primary-Beer law is indicated by formula (1) are as follows:
A=KCL (1)
In formula (1), A is absorbance value；K is absorptivity, unit Lmg/mm, with lambda1-wavelength and extinction material
The factors such as property it is related；C is extinction material concentration, unit mg/L；L is absorbing liquid thickness, unit mm.Then with extinction
Angle value A corresponds to standard hexavalent chromium concentration C and finds out relationship between absorbance and hexavalent chromium concentration, and fit hexavalent chromium concentration with
Relation curve between absorbance can finally can be calculated the hexavalent chromium concentration of water sample to be measured according to curvilinear equation.Blank
Experimental result is as shown in table 1.
1 blank assay result table of table
Wherein, it is required according to HJ168, the detection limit calculation of the detection method are as follows:
MDL=t(n-1,0.99)×S (2)
In formula (2), MDL is method detection limit；S is the standard deviation of the multiple measured value of blank sample；T is freedom degree n-1,
T distribution when confidence level is 99%；N is the parallel determination number of sample.Therefore, according to the resulting data of table 1, method detection limit
The ≈ of MDL=2.355 × 0.0003 7 × 10-4mg/L。
The Cr VI standard for preparing 0.04,0.08,0.12,0.16,0.20,0.40,0.60,0.80 and 1.00mg/L is molten
Liquid carries out 3 groups of parallel laboratory tests to each Cr VI standard specimen, obtains the absorbance values of various concentration standard specimen, standard specimen experiment knot
Fruit is as shown in table 2.
2 standard specimen experimental result table of table
| Cr VI standard specimen (mg/L) | Absorbance values |
| 0.04 | 0.0284 |
| 0.08 | 0.0589 |
| 0.12 | 0.0882 |
| 0.16 | 0.1180 |
| 0.20 | 0.1483 |
| 0.40 | 0.2913 |
| 0.60 | 0.4484 |
| 0.80 | 0.6050 |
| 1.00 | 0.7564 |
Experimental data is subjected to linear fit on Origin software, matched curve is as shown in Figure 2.
According to linear fit result: the relationship of the hexavalent chromium concentration C and absorbance value A of 0~1mg/L of concentration range can
It is indicated with formula (3):
A=0.75661C-0.00292 (Rf=0.9998) (3)
By the coefficient R of formula (3)fIt is found that hexavalent chromium concentration has good with absorbance value in entire measurement range
Linear relationship.
The trivalent chromium standard solution for further preparing 0.2mg/L and 0.8mg/L carries out 6 to various concentration trivalent chromium standard specimen
Group parallel laboratory test substitutes into the total chromium concn of formula (3) calculating actual measurement after obtaining the final absorbance value of standard specimen.Finally certainly according to total chromium water quality
The precision and the error of indication of the performance Index Calculation data of dynamic on-line computing model, final result are as shown in table 3.
3 standard specimen experimental result table of table
By table (3) it is found that the essence based on the diphenyl carbazide spectrophotometry of high-level oxidation technology in range ability
Density and the error of indication are respectively 1.16% and 2.50%, meet total chromium Water Quality on-line Automatic Monitor performance indicator requirement:
Precision≤5% and the error of indication are in ± 5%.
Claims (10)
1. a kind of water body total chrome content on-line measuring device based on high-level oxidation technology, including quartzy bubbling style reactor (9),
The first ultraviolet lamp (5) and the second ultraviolet lamp (10) are hung respectively in the both sides external of quartzy bubbling style reactor (9)；In the stone
The top two sides setting water sample import of English bubbling style reactor (9) and buffer inlet；The water sample import and water sample storage tank (2)
The first syringe pump (3) are arranged in water sample storage tank (2) outlet end in connection；The buffer inlet and buffering flow container (14) are even
It connects, the second syringe pump (13) is set in the buffering flow container (14) outlet end；In the upper end of the quartzy bubbling style reactor (9)
Ozone gas bubbling pipe (8) and tail gas outlet (12) are set；One end of the ozone gas bubbling pipe (8) extend into described
It is exported inside quartzy bubbling style reactor (9) as the ozone gas bubbling pipe (8), the ozone gas bubbling pipe (8)
The other end stay in the quartzy bubbling style reactor (9) outside as ozone gas bubbling pipe (8) import, the ozone gas
(8) import of body bubbling pipe is connect with the ozone generator by electrolytic process (1), the gas in the ozone generator by electrolytic process (1)
The first solenoid valve (4) are arranged in output end；It is equipped with outlet in the bottom of the quartzy bubbling style reactor (9), the outlet is logical
It crosses pipeline to connect with the first input end of colour developing pond (18), in the outlet end setting second of the quartzy bubbling style reactor (9)
Solenoid valve (6)；(18) second input end of colour developing pond is connect with nitration mixture tank (15), is arranged in nitration mixture tank (15) outlet end
Third syringe pump (16)；Colour developing pond (18) the third input end is connect with total chromium color developing agent tank (19), is developed the color in total chromium
The 5th syringe pump (20) is arranged in agent tank (19) outlet end；The first exit end of colour developing pond (18) and spectrophotometer (21) are even
It connects, the 4th syringe pump (17) is set in the first exit end of colour developing pond (18)；The second outlet end of colour developing pond (18)
It is connect with waste liquid tank (7), third solenoid valve (11) is set at the second outlet end of colour developing pond (18).
2. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
The quartz bubbling style reactor (9) is cylinder, and material is quartz glass, size are as follows: 140~160mm of height, internal diameter 15~
25mm, 18~28mm of outer diameter.
3. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
The ozone gas bubbling pipe (8) is quartz material, and internal diameter is 1.5~2.5mm, and outer diameter is 3~5mm, the ozone gas drum
Distance is 15~25mm between bubble pipe (8) outlet and quartzy bubbling style reactor (9) bottom.
4. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
The watt level of first ultraviolet lamp (5) and the second ultraviolet lamp (10) is 12~24W, and the ultraviolet light wave irradiated is a length of
254nm。
5. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
Buffer solution in buffering flow container (14) is borax-sodium hydroxide buffer solution.
6. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
Mixed acid solution in the nitration mixture tank (15) is the mixed solution of phosphoric acid, sulfuric acid and water, wherein the volume ratio of phosphoric acid, sulfuric acid and water
For 1:0.8~1.2:1.5~2.5.
7. the water body total chrome content on-line measuring device based on high-level oxidation technology as described in claim 1, which is characterized in that
Color developing agent in total chromium color developing agent tank is diphenylcarbazide-acetone soln that mass concentration is 1.5~2.5g/L.
8. a kind of water body total chrome content online test method, which is characterized in that use the described in any item bases of claim 1~7
In the water body total chrome content on-line measuring device of high-level oxidation technology, comprising the following steps:
(1) the first solenoid valve is closed, electrolysis type ozone generator is started, so that generating enough height in electrolysis type ozone generator
Concentration of ozone gas, and it is produced as the static pressure of 8~12cm water-column；
(2) 15~25mL water sample to be measured is injected into quartzy bubbling style reactor from water sample storage tank by the first syringe pump, by second
3~7mL buffer solution is injected into quartzy bubbling style reactor from buffer tank by syringe pump, so that mixed sample pH value of solution is greater than
11.5；
(3) the first ultraviolet lamp, the second ultraviolet lamp and the first solenoid valve are opened, so that electrolysis type ozone generator generates 8~12cm
The high-concentrated ozone gas of water-column static pressure is entered in a manner of being bubbled the first solenoid valve and ozone gas bubbling pipe
In quartzy bubbling style reactor, the first ultraviolet lamp is set in the two sides of quartzy bubbling style reactor and the second ultraviolet lamp issues
254nm ultraviolet light, ozone gas react the hydroxyl for generating strong oxidizing property under the irradiation of 254nm ultraviolet light with water sample oxidation resolution
Free radical OH；
(4) oxidation resolution after reaction, opens second solenoid valve, and the water sample to be measured after reaction is completed is discharged into colour developing pond
In；
(5) after water sample is discharged into colour developing pond completely, 0.5~1.0mL mixed acid solution is injected into from nitration mixture tank by third syringe pump
It develops the color in pond, is injected into 0.5~1.5mL diphenylcarbazide-acetone soln from total chromium color developing agent tank by the 5th syringe pump aobvious
In color pond, 3~8min of chromogenic reaction；
(6) after to chromogenic reaction, solution after 3~8mL colour developing is injected into spectrophotometric from colour developing pond by the 4th syringe pump
Meter；Solution after remaining colour developing is discharged into waste liquid tank；Spectrophotometer tests suction of the solution at 540nm wavelength after the colour developing
Total chrome content is calculated in shading value.
9. water body total chrome content online test method as claimed in claim 8, which is characterized in that in step (2), so that mixing
Water sample pH value of solution is greater than 11.5, controls between 11.5~12.
10. water body total chrome content online test method as claimed in claim 8, which is characterized in that described in step (3)
The oxidation resolution reaction time is 3~7min.
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