CN100541172C - The method of fastly analyzing chemical oxygen demand by high-pressure flowing injection - Google Patents
The method of fastly analyzing chemical oxygen demand by high-pressure flowing injection Download PDFInfo
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- CN100541172C CN100541172C CNB2007100223921A CN200710022392A CN100541172C CN 100541172 C CN100541172 C CN 100541172C CN B2007100223921 A CNB2007100223921 A CN B2007100223921A CN 200710022392 A CN200710022392 A CN 200710022392A CN 100541172 C CN100541172 C CN 100541172C
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- 239000000126 substance Substances 0.000 title claims abstract description 23
- 238000002347 injection Methods 0.000 title claims abstract description 20
- 239000007924 injection Substances 0.000 title claims abstract description 20
- 239000001301 oxygen Substances 0.000 title claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000498 cooling water Substances 0.000 claims abstract description 4
- 238000010790 dilution Methods 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 241000276438 Gadus morhua Species 0.000 claims abstract 3
- 235000019516 cod Nutrition 0.000 claims abstract 3
- 230000005693 optoelectronics Effects 0.000 claims abstract 2
- 238000005070 sampling Methods 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005755 formation reaction Methods 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 210000001736 Capillaries Anatomy 0.000 abstract description 7
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N Potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 27
- 229940069002 Potassium Dichromate Drugs 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 4
- SGSXYQPXIVHYON-UHFFFAOYSA-M azanium;iron;sulfate Chemical compound [NH4+].[Fe].[O-]S([O-])(=O)=O SGSXYQPXIVHYON-UHFFFAOYSA-M 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002572 peristaltic Effects 0.000 description 3
- 230000002829 reduced Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L Silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940074994 mercuric sulfate Drugs 0.000 description 2
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CIWXFRVOSDNDJZ-UHFFFAOYSA-L Ferroin Chemical compound [Fe+2].[O-]S([O-])(=O)=O.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 CIWXFRVOSDNDJZ-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- YUVLVONHNMXKBW-UHFFFAOYSA-L [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ag+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O YUVLVONHNMXKBW-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The present invention relates to a kind of method of fastly analyzing chemical oxygen demand by high-pressure flowing injection, with potassium dichromate-dilution heat of sulfuric acid is current-carrying liquid, by constant flow pump the continuous high-pressure delivery of current-carrying liquid is injected pipeline capillaceous, by fillup valve quantitative water sample is injected current-carrying liquid, water sample spreads in the current-carrying liquid of directed flow and with the current-carrying liquid isothermal reactor of flowing through successively, cooling water tank and colorimetric flow cell, record COD by monochromatic light photograph and opto-electronic conversion, outlet kapillary from flow cell flows out at last, discharge pressure 〉=the 0.6MPa of control constant flow pump, 170 ℃～190 ℃ of the temperature of reaction of isothermal reactor; Internal diameter 0.5-1mm capillaceous, pipe thickness 〉=0.8mm, the capillary extending of the flow cell endpiece in this method is the pipeline more than 30 meters, this kapillary is coiled continuously form the back pressure pipe, forms bigger damping, make and clear up reaction and under high pressure carry out, the interference of bubble to light absorption eliminated in the generation of inhibitory reaction liquid gas bubble, and test data is accurate, test period shortens greatly, is applicable to the COD fast detecting.
Description
Technical field
The present invention relates to a kind of chemical oxygen demand analysis method that water-quality COD detects that is used for, particularly be used for method, belong to the monitoring water environment analysis field the fastly analyzing chemical oxygen demand by high-pressure flowing injection of water COD on-line monitoring.
Background technology
Chemical oxygen demand (COD) (Chemical Oxygen Demand) is called for short COD, oxidized dose of oxygen amounts that potassium dichromate oxidation consumed of reductive pollutants such as organism, nitrite, ferrous salt, sulfide in the expression water are represented with the oxygen consumption weight mg/L of unit bodies ponding.The degree that chemical oxygen demand (COD) reflection water quality is polluted by reducing substances is an important indicator of determining the water pollution degree in the environmental protection field, also is one of controlling index of China's enforcement total emission volumn.
COD
CrMethod (potassium dichromate survey COD method) is to be considered to detect COD at present the most accurately and effective method, this method be make potassium dichromate in strongly acidic solution with water sample in reducing substances reaction, reducing substances in the oxidation water sample is calculated the amount of reducing substances oxygen consumed in the water sample according to the actual consumption of potassium dichromate.
The oxidation reaction formula of potassium dichromate in the highly acid medium is:
Traditional COD
CrDetection method is manual carrying out in conical flask.Water sample and potassium dichromate standard solution mixing in sulfuric acid-silver sulfate solution of certain metering, heating (about 145 ℃) backflow 2h, after the solution cooling, add 3 ferroin indicator solutions, with the unreacted excessive potassium dichromate of iron ammonium sulfate standard solution titration, until the color of solution by yellow through blue-green till the bronzing, the consumption V of record test water sample iron ammonium sulfate standard solution
1Calculate iron ammonium sulfate standard solution volume value V with blank test
0Poor V
0-V
1, calculate COD by formula
Cr(O
2Mg/L) value.
Along with expanding economy, water pollution is on the rise, and need carry out online monitoring water quality to tap water, rivers, lake water and various industrial discharge water, high-concentration waste water etc., to guarantee the sewage qualified discharge, avoids pollution of waterhead, and guarantees the quality of domestic water.And traditional COD
CrManual inspection method preface is many, troublesome poeration, and sense cycle length can not be applicable to the online detection needs of COD.At present the COD quick analytic instrument that uses of laboratory is a sealed digestion formula quick analytic instrument, and the single measuring samples time needs one hour, and when insoluble suspended particle is arranged in the water, measures inaccurately, can not really satisfy the requirement of on-line quick detection.
Flow Injection Analysis is a kind of new express-analysis technology, and it is that quantity of sample is cut into by valve in the current-carrying liquid of a continuous flow, is advanced to a flow cell by Photoelectric Detection after sample and the reaction of current-carrying liquid, obtains testing result.In recent years, people have carried out a lot of researchs to the COD flowing injecting analysis technology, but because COD measure to need long-time high temperature to clear up, digestion solution and sample can produce a large amount of microbubbles in the kapillary under condition of normal pressure, make colorimetric estimation be subjected to disturbing greatly and can not realizing.There is human to go bubbler to remove bubble, but too many because of bubble, go bubbler meeting fluid flow state and light absorption process to produce and disturb, make flow cell can't obtain the test solution stream of constant current, measuring accuracy is very poor.
Summary of the invention
The purpose of this invention is to provide a kind of analytical approach that is used for detecting the chemical oxygen demand (COD) of water COD content, method especially for the fastly analyzing chemical oxygen demand by high-pressure flowing injection of on-line analysis and laboratory express-analysis, its easy economy, can guarantee the constant flow of current-carrying system and not have bubble interference, measuring accuracy height.
The method of this fastly analyzing chemical oxygen demand by high-pressure flowing injection is a current-carrying liquid with potassium dichromate-dilution heat of sulfuric acid, by constant flow pump current-carrying liquid is injected pipeline capillaceous continuously, by sampling valve quantitative water sample is injected current-carrying liquid, water sample in the current-carrying liquid of directed flow, spread and with current-carrying liquid successively through isothermal reactor, cooling water tank and colorimetric flow cell, outlet kapillary from flow cell flows out at last, feature of the present invention is that the output pressure 〉=0.6MPa of control constant flow pump is generally 0.6～0.8MPa, 170 ℃～190 ℃ of the temperature of reaction of isothermal reactor; Internal diameter 0.5-1mm capillaceous, pipe thickness 〉=0.8mm,, the capillary extending of said flow cell endpiece also is coiled into back pressure pipe (big or small and different according to capillary inner diameter, as generally to select 30～60 meters) continuously more than 30 meters.
Water sample is quantitatively cut in the current-carrying liquid by fillup valve, and the sample loop that only needs rotational valve core can will be connected in fillup valve inserts test macro, and water sample is promptly promoted to advance by current-carrying liquid.
The current-carrying liquid that flows out from the back pressure pipe can return the repeated use of current-carrying liquid reagent bottle.But when the water sample chlorinity is high, to add a small amount of mercuric sulfate in the current-carrying liquid, under few situation, when containing the material that difficulty clears up in the sample, add silver sulfate in the current-carrying liquid as catalyzer, the mercurous or silver-colored not reproducible use of current-carrying liquid.
For the water sample that contains solid impurity, remove a large amount of impurity except that adopting general filtration treatment, for prevent＞the 0.8mm granule foreign enters detection system, water sample was delivered to one earlier respectively vertical can differs from outflow downwards behind separator tube and the ejector by the submersible pump that has filter screen before feeding sampling valve, can differ from the downward current of formation in the separator tube at vertical, sampling valve is drawn water sample by the negative pressure that from up to down stretches into the sampling pipe utilization that can differ from the separator tube and ejector and produce from downward current.In the water＞granule foreign of 0.8mm moves downward because of gravity, avoids entering in the water sample.
The constant flow pump of carrying current-carrying liquid also must have the function of anti-potassium dichromate and 60% sulfuric acid corrosion except that requiring to produce the elevated pressures.
In this method, quantitatively water sample is promoted to advance and limited diffusion in current-carrying liquid by potassium dichromate current-carrying liquid, enter well heater after, the reducing substances that water sample contains under heating with potassium dichromate reaction, portion C r
6+Be reduced into Cr
3+, after being cooled by refrigeratory, enter the colorimetric flow cell and accept illumination, because Cr
6+The difference of reduction according to the changing value that sees through light intensity, obtains to have the response curve of corresponding peak height and peak width to the difference that is absorbed with of ultraviolet light (380-410mm), with peak height or peak width, through relatively calculating the content of trying to achieve COD in the water sample.
This method adopts high-pressure delivery current-carrying liquid, because boiling point of liquid is with the also corresponding raising of pressure, thereby can avoid bubble to produce, in addition, the back pressure pipe that employing of the present invention is consistent with the import capillary diameter, prolong flow cell endpiece capillary pipe length significantly, to increase damping action to system's current-carrying liquid, guarantee that the detection system before the flow cell endpiece keeps the above high pressure of 0.6MPa, rather than adopt and to reduce the outlet bore and increase the damping method method, thereby do not influence the smooth and easy discharge of molecule in the sample.
The present invention is because the system pressure raising, the generation of reactant liquor bubble when having contained high temperature, corresponding temperature of reaction can be brought up to 170～190 ℃, under such high temperature, react required big shortening of time, finished the shortest need of a water sample detection analysis 7 minutes, and made " on-line monitoring " be able to real realization.Can or carry out the on-line monitoring of COD at random to timings such as the source water of rivers and lakes, water factory or industrial discharge water, easy and obtain instant analysis data apace, particularly for the great water pollution accident of spy's property sent out, can in time find, in time report, in time handle, striven for valuable time for removing a hidden danger.
This method can contain effectively that the bubble in the detection system generates, and test result is accurate; Measurement range is wide, and COD concentration is low to moderate 3.5mg/L, and high water sample to the scope of 100000mg/L all need not to concentrate or dilution just can directly detect.Because measurement range is very wide, can use the ultraviolet source of wavelength 380～410nm, avoid near the ratio color light source of normally used 640nm to measure Cr
3+The incompatibility that causes to water body chroma.Because this method improved temperature of reaction, the clearing up to be reflected at of potassium dichromate need not to add the silver sulfate catalyzer in most cases; And, clearing up reaction and can contain Cl in the water under the High Temperature High Pressure
-To Cl
0Transform, therefore except that a few cases, need not to use mercuric sulfate in the reagent; Both fall expending of low mercury, argentum reagent, reagent is reused, reduced the secondary pollution of reagent discharging.The water sample of the each incision of this method is micro-, has only about 50 μ l, and the consumption of reagent also is extremely low.The capillary extending of the flow cell endpiece in this method is the pipeline more than 30 meters, this kapillary is coiled formation back pressure pipe continuously, form bigger damping, make and clear up reaction and under high pressure carry out, the interference of bubble to light absorption eliminated in the generation of inhibitory reaction liquid gas bubble, and test data is accurate, test period shortens greatly, is applicable to the COD fast detecting.
Description of drawings
Fig. 1 is a high-pressure flow injection rapid analysis COD method schematic diagram.
Fig. 2 is the embodiment flow circuit diagram of high-pressure flow injection rapid analysis COD.
Fig. 3 is another embodiment flow circuit diagram of high-pressure flow injection rapid analysis COD.
Among the figure, V1-current-carrying liquid retaining valve, V2-standard specimen transfer valve, V3-water sample transfer valve, V4-water sample fillup valve, Ls-sample loop, Lo-valve arc groove, 1,2,3,4,5,6-sampling valve interface, the 7-isothermal reactor, the 8-cooling tank, 9-flow cell, 10-back pressure pipe, 11,12,13-current-carrying liquid valve interface, 14-high pressure constant flow pump, 15-current-carrying liquid storage bottle, the 16-peristaltic pump, 17-water sample bottle, 17 '-the water sample waste liquid bottle, the 18-solenoid valve, 19-combination block, 20-current-carrying liquid waste liquid bottle, 21,22,23-standard specimen valve interface, the 24-ejector, 25-vertically can differ from separator tube, 26-sampling pipe, the 27-variable valve, the 28-submersible pump, 29-retaining valve, 30-water tank, 31,32,33-sampling valve interface, the 34-run-down pipe.
Embodiment
Below in conjunction with accompanying drawing 1 explanation principle of the present invention
Fig. 1 represents the principle process flow diagram of this method, and the pipeline among the figure is corrosion resistant fluoroplastic kapillary, is connected to the water sample fillup valve on the capillary pipeline.Potassium dichromate reagent is carried continuously by constant flow pump that (pressure 〉=0.6MPa), the constent temperature heater of flowing through, cooling water tank, colorimetric flow cell come out from flow cell to form the potassium dichromate current-carrying liquid of continuous flow after return in the reagent bottle behind the tens meters long back pressure pipe.During detection, the water sample fillup valve goes to the test position, after fillup valve is cut water sample in the reacting pipe, the sample band is advanced by current-carrying liquid and diffusion gradually in progradation, and sample and reagent present gradient and mixes (seeing Fig. 1 lower-left figure), and the gradient mixed zone enters in the constent temperature heater (or claiming reactor) and is heated to 170～190 ℃, under high-temperature and high-pressure conditions, after clearing up fast, flowing through flow cell, is that 380-410nm light source irradiation and colorimetric are surveyed Cr by wavelength
6+The changing value of amount obtains to have the response curve (seeing Fig. 1 bottom-right graph) of corresponding peak height and peak width, with peak height or peak width through with the curve ratio of blank test, calculate the content of trying to achieve COD in the water sample.
Fig. 2 is one of the embodiment of a fastly analyzing chemical oxygen demand by high-pressure flowing injection method of the present invention flow circuit diagram.
Pipeline in this example is internal diameter 0.8mm, the kapillary of external diameter 2.5mm; 40 meters of back pressure pipe 10 length;
The reagent component concentration of preparation is in the current-carrying liquid 15: sulfuric acid 60% (weight), potassium dichromate 0.025～0.08mol/L.
Water sample fillup valve V4 is a six-way valve, and six interfaces 1～6 that valve seat is provided with, valve gap are provided with and six three deep-slotted chip breaker Lo that interface is corresponding, and sample loop Ls is one section kapillary, and its two ends are connected in 2 and 5 two interfaces; In all the other two docking ports of valve V4, interface 3 and 4 connects sampling system, and 1 and 6 carry streaming system.Rotary spool makes deep-slotted chip breaker Lo forward or reversely turn over radian at interval, sample loop Ls can be selected switching between two systems.
Interface 4 is connected with water sample bottle 17 (or standard specimen bottle) by the solenoid valve of selecting to connect 18, and interface 3 is by peristaltic pump 16 and water sample waste liquid bottle 17 ' join; Interface 1 connects with high pressure constant flow pump 14 (this example adopts electronic ceramic injection pump, down together), and interface 6 joins with the import of isothermal reactor 7.Two interfaces that are positioned at same deep-slotted chip breaker Lo communicate, and the position of groove Lo changes by the rotation of spool, and the annexation between the interface also changes with the position change of groove Lo.
Among Fig. 2, the solid line position of groove Lo is represented the sampling state, represents test mode when going to dotted line position.
Test process is, earlier water sample fillup valve V4 gone to the sample states of Fig. 2, and at this moment, sample loop Ls two ends 2 and 5 communicate with interface 3 and 4 respectively, do not communicate with interface 1 and 6; Communicate between the interface 1 and 6.Select opens solenoid valve 18, make the suction of water sample 17 by peristaltic pump 16, form 17 → 19 → 4 → 5 → Ls → 2 → 3 → 17 ' stream; Stop peristaltic pump 16, be full of water sample among the sample loop Ls.Earlier ceramic injection pump 14 is communicated with current-carrying liquid storage bottle 15 (interface 12 communicates with 11, with 13 obstructed) by valve V1, unlatching ceramic injection pump 14, with current-carrying liquid in the chamber of 15 → 11 → 12 suction pumps 14; Be full of termination of pumping behind the reagent in pump 14 chambeies; Switch V1, interface 12 is led to 13, with 11 obstructed.The deep-slotted chip breaker Lo that will inject sample valve V4 this moment goes to the dotted line position of Fig. 2, two interfaces that be positioned at same dotted line groove this moment communicate, be interface 3 and 4,1 and 2,6 communicate respectively with 5, interface 3 and 2,1 and 6,4 and 5 is obstructed respectively, sample loop Ls and sampling system disconnect, the gauge water sample has entered in the path of current-carrying liquid in the ring, oppositely start syringe pump 14 this moment, reagent promptly injects the flowing reactive system to high pressure (more than the 0.6MPa) constant current in the following order in the pump chamber: 14 → 12 → 13 → 1 → 2 → Ls → 5 → 6 → 7 → 8 → 9 → 10 are disposed in the waste liquid bottle 20 at last; Water sample is promoted to advance by the current-carrying liquid of continuous flow, through high temperature (170～190 ℃) reaction, cooling, rayed, after the back pressure pipe outflow system of long distance, from photoelectric commutator curve of output collection of illustrative plates, with the standard sample spectrum contrast that records under the same operating conditions, calculate the content value of COD in the water sample.
Fig. 3 is two flow circuit diagrams of the embodiment of fastly analyzing chemical oxygen demand by high-pressure flowing injection method of the present invention.
Present embodiment is provided with the jet flow negative pressure sampling system, sampling pipe 26 from up to down stretches in the vertical energy difference separator tube 25, the sampling pipe upper end joins by the interface 32,31 of valve V3 and the interface 4 of injection sampling valve V4, and the negative pressure suction inlet of ejector 24 and the interface 3 of fillup valve V4 join.Open two variable valve 27 of sampling system, source water (for example rivers water) 28 fens two-way of submersible pump by having filter screen are respectively through two valves 27, one the road from ejector 24, and another road can flow in the water tank 30 downwards respectively by difference separator tube 25 from vertical, and ejector 24 promptly produces negative pressure.Fillup valve V4 is gone to the sample states of Fig. 3, water sample forms stream: 26 → 32 → 31 → 4 → 5 → Ls → 2 → 3 → 24 → 30 in the following order because of the negative pressure swabbing action of ejector 24, sampling pipe 26 is to draw water sample in the current downward from vertical tube 25, make in the sample loop Ls and be full of water sample, then sampling valve V4 is gone to the measurement state, make in the sample loop Ls incision current-carrying system, the operation of test process is identical with Fig. 2 embodiment, just this example turns back to the current-carrying liquid that back pressure pipe 10 flows out in the reagent bottle 15, for reusing.It is standard specimen or water sample to be checked that valve V2 and V3 can select sample objects by the rotation of spool.
During submersible pump 28 work, retaining valve 29 is closed automatically, water tank 30 liquid levels rise to behind the certain altitude promptly to overflow from run-down pipe 34 and flow back to water source (rivers) or sewage row mouthful, when submersible pump 28 quit work after sampling finished, retaining valve is opened left because of the static pressure effect of water in the water tank 30, and water is promptly discharged from submersible pump 28 in the water tank.
The advantage of the sampling system that this is routine is, water sample is to take in the downward current that vertically can differ from separator tube 25, in the water greater than the molecule of kapillary bore because of gravity sink with moisture from, and can be inhaled in the current-carrying system less than the molecule of kapillary bore, make the COD testing process more close specifications of surveys, more reliable, more accurate.
Dotted line is represented automatic control system among Fig. 3, by controller the action of pressure, temperature and each valve of each parts of detection system is controlled automatically.
Claims (5)
1. the method for fastly analyzing chemical oxygen demand by high-pressure flowing injection, with potassium dichromate-dilution heat of sulfuric acid is current-carrying liquid, by constant flow pump current-carrying liquid is injected pipeline capillaceous continuously, by fillup valve quantitative water sample is injected current-carrying liquid, water sample in the current-carrying liquid of directed flow, spread and with current-carrying liquid successively through isothermal reactor, cooling water tank and colorimetric flow cell, record COD by ultraviolet lighting and opto-electronic conversion, last current-carrying liquid flows out from the outlet kapillary of flow cell, output pressure 〉=the 0.6MPa that it is characterized in that the constant flow pump system of controlling, 170 ℃～190 ℃ of the temperature of reaction of isothermal reactor; Internal diameter 0.5-1mm capillaceous, pipe thickness 〉=0.8mm, the kapillary of said flow cell endpiece extend also to be coiled into the back pressure pipe more than 30 meters continuously.
2. the method for fastly analyzing chemical oxygen demand by high-pressure flowing injection according to claim 1, it is characterized in that said water sample was delivered to one earlier respectively and vertical can differs from outflow downwards behind separator tube and the ejector by the submersible pump that has filter screen before feeding sampling valve, can differ from the downward current of formation in the separator tube at vertical, sampling valve is drawn water sample by the negative pressure that from up to down stretches into the sampling pipe utilization that can differ from the separator tube and ejector and produce from downward current.
3. the method for fastly analyzing chemical oxygen demand by high-pressure flowing injection according to claim 1, the length that it is characterized in that the back pressure pipe is 30～60 meters.
4. the method for fastly analyzing chemical oxygen demand by high-pressure flowing injection according to claim 1, the output pressure that it is characterized in that constant flow pump is 0.6～0.8MPa.
5. according to the method for claim 1 or 2 or 3 or 4 described fastly analyzing chemical oxygen demand by high-pressure flowing injection, it is characterized in that returning current-carrying liquid reagent bottle from the current-carrying liquid that the back pressure pipe flows out reuses.
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|---|---|---|---|
| CNB2007100223921A CN100541172C (en) | 2007-05-16 | 2007-05-16 | The method of fastly analyzing chemical oxygen demand by high-pressure flowing injection |
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| CNB2007100223921A CN100541172C (en) | 2007-05-16 | 2007-05-16 | The method of fastly analyzing chemical oxygen demand by high-pressure flowing injection |
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| CN101226153B (en) * | 2007-12-25 | 2010-09-08 | 洪陵成 | Colorimetric assay apparatus for testing flow injection ammonia nitrogen |
| CN101936977B (en) * | 2009-07-02 | 2012-01-25 | 杭州慕迪科技有限公司 | Method for recycling mixed reagent in COD (Chemical Oxygen Demand) online measuring process |
| CN102539796B (en) * | 2010-12-30 | 2013-10-16 | 北京吉天仪器有限公司 | Automatic analysis meter and method for amylose |
| CN102410942A (en) * | 2011-07-25 | 2012-04-11 | 迈瑞尔实验设备（上海）有限公司 | Online sampling system |
| CN103969348B (en) * | 2013-01-29 | 2018-01-09 | 深圳普门科技有限公司 | The bubble suppressing method and its testing instruments of a kind of medical test instrument |
| CN103399110B (en) * | 2013-07-19 | 2015-12-23 | 安徽皖仪科技股份有限公司 | The design of a kind of pressure of the back adjustable for ultraviolet spectrometry detecting device flow cell |
| CN104820078B (en) * | 2014-01-30 | 2018-01-12 | 株式会社岛津制作所 | A kind of multrirange detecting system |
| CN107179263A (en) * | 2017-05-26 | 2017-09-19 | 南京大学 | Puddle influences on Contaminants Transport in a kind of simulation pipeline device and method of work |
| CN109540597A (en) * | 2017-09-21 | 2019-03-29 | 贵港市厚顺信息技术有限公司 | A kind of sulfuric acid sampler |
| TW202004169A (en) | 2018-06-04 | 2020-01-16 | 國立交通大學 | Color chart, test kit, and method for determining chemical oxygen demand of water and wastewater |
| CN110780084B (en) * | 2019-09-17 | 2022-10-21 | 浙江省海洋水产研究所 | Pump structure for flow injection analyzer |
| CN110763859B (en) * | 2019-09-17 | 2022-10-21 | 浙江省海洋水产研究所 | Constant flow pump for flow injection analyzer |
| CN111505202A (en) * | 2020-04-26 | 2020-08-07 | 广东省测试分析研究所（中国广州分析测试中心） | Multifunctional dilution/titration device |
| CN112129959B (en) * | 2020-09-25 | 2021-06-25 | 上海安杰环保科技股份有限公司 | Full-automatic chemical oxygen demand analyzer based on different liquid transfer flow paths |
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2007
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