CN101625317A - Full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) monitor and use method thereof - Google Patents
Full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) monitor and use method thereof Download PDFInfo
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Abstract
The invention relates to a full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) monitor and a use method thereof. The monitor comprises a BOD aeration device, an ultraviolet scanning device and a computer control device and is characterized by also comprising a sampling device, a sample-storing device and a water-replenishing device, wherein the computer control device controls the sampling device, the sample-storing device, the BOD aeration device, the water-replenishing device and the ultraviolet scanning device. The monitor confirms BOD by the change of COD based on a concept that a COD difference before and after biodegradation is equal to the BOD. The invention does not use chemical reagents and does not cause secondary pollution, has rapid and accurate measurement, simple and convenient operation, simple structure, wide range of application and extremely low failure rate and can realize full-automatic remote control.
Description
Technical field
The present invention relates to chemical analysis field, relate in particular to the monitor and the using method thereof of a kind of full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD).
Background technology
Classical biological oxygen demand (BOD) (BOD) assay method is the dilution inocalation method, i.e. BOD5 is that the difference with dissolved oxygen DO before and after the biodegradation is a principle, since five days consuming time of this method, complicated operation, and extension rate is big, dilution error is big, can't measure for some industrial sewage, can't realize automation equipment.So, BOD method on the one appears in succession, differential pressure method etc., but all be unable to do without dilution, cultivation, and complicated operation, the defective of length consuming time, the difference that be unable to do without dissolved oxygen DO is as quantitative foundation.
In recent years external, domestic prevailing measured BOD with biomembrance process, and some country also is decided to be national standard abroad, and China also is decided to be national standard under the influence of this academic viewpoint.This method some water body abroad is adaptable, because external water body, comprise industrial waste water, all passed through one-level, secondary, tertiary treatment, sewage is very clean, and China's concentration of wastewater height, complicated component, change fast, be can not with abroad can with method copy everything mechanically China and use, reason is exactly that this method also is not suitable for China's actual conditions.Analyze theoretically, problem is also a lot: 1. microbial film electrode method is as standard method but do not have supporting emission standard, design standards, and it is standard that the emission standard of China, design standards remain with BOD5, be converted into BOD5, and its workload is very big; 2. the different microorganisms film different organism of can only degrading, and do not have a kind of microbial film can be general, i.e. ten million kind of corresponding ten million kind of organism of microorganism, its permutation and combination also is ten million kind of possibility, its data reliability, practicality also are suspicious; 3. biological membrane also is a kind of biology, in use can wear out, death, and an electrode is limited service time, constantly change electrode,, and electrode has changed, parameter has also become, and the continuity of data also has problems; 4. microbial film is easy to poison, and as PH, heavy metal membrane poisoning is lost efficacy, other the microorganism of also may on film, grow, and like this, variation has also just taken place in the property condition of microbial film.She Ji instrument also much can't have been promoted with regard to problem in this way.
Solve the problem that BOD5 method and microorganism film technique exist, realize the requirement of instrumentation, robotization, must fundamentally change " dissolved oxygen DO is poor before and after the biodegradation " method as quantitative basis, foundation " chemical oxygen consumption (COC)s (COD) is poor before and after the biodegradation " is the method for quantitative basis.And it is irrelevant with oxygen in water to measure COD, and bubble is not afraid of in dilution, and temperature can be set in the optimum temperature of growth of microorganism.According to the biological chemistry principle of dynamics: the organic speed of microbial degradation is to be directly proportional with the organism amount that exists in the water, is directly proportional with temperature, is directly proportional with the water oxygen amount, also is directly proportional with activation of microorganism and absolute magnitude.Therefore in operation, can not dilute, can stir inflation, temperature is used the microorganism that is grown in logarithmic phase through domestication between 25 °-30 °, improved degradation speed greatly, can be in 1-2 hour that degradable organic matter degradation is intact.We measure before the biodegradation and the COD after the degraded, try to achieve difference DELTA COD, have just drawn BODS, again BODS are scaled BOD5, are connected with emission standard, the design standards of BOD5.
Chemical oxygen consumption (COC) assay method and device: classical chemical oxygen consumption (COC) assay method is a potassium bichromate titrimetric method, in addition, the method that different oxygenants are arranged, as cerium salt method, manganese salt method, also having with the potassium dichromate is the photometry of pre-treatment, coulometry etc., the also coulometry of useful different oxygenants: as ozone method, active OH method etc.Common ground of these methods is exactly all will use oxygenant, acid, and is also long on the time.Will use oxygenant, strong acid, heating with these principle design instruments, make pipeline, valve damages easily, self-reacting device failure rate height, and simultaneously, minute is also longer, can not go out data in good time.
Summary of the invention
Technical matters to be solved by this invention provides the monitor and the using method thereof of full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD), has overcome the shortcoming of above-mentioned prior art.
Technical matters to be solved by this invention is achieved through the following technical solutions:
The monitor of a kind of full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) comprises BOD aerator, UV scanning device and Computer Control Unit, it is characterized in that: also comprise sampling apparatus, sample storage device and water replanishing device; Described Computer Control Unit is controlled described sampling apparatus, sample storage device, BOD aerator, water replanishing device and UV scanning device; Described sampling apparatus, the sample storage device, the BOD aerator is connected with T-valve by pipeline between water replanishing device and the UV scanning device; Described sampling apparatus comprises sampling thief and backpurge system, and water sample enters the sample storage bottle of sample storage device through sampling thief and backpurge system; The sample storage bottle of described sample storage device places semiconductor cooler, temperature controller on the described semiconductor cooler, and described sample storage position of bottleneck is equipped with stop; Water sample in the described BOD aerator and the water in the water replanishing device enter the UV scanning device after mixing.
Described backpurge system is made up of sample introduction barrier, sampling valve, recoil valve, utilizes the pressure reversal flushing of tap water.
On described BOD aerator, sample storage device and the water replanishing device atmospheric valve and air pump are housed all; Atmospheric valve and the air pump air pressure in can regulating device reaches the purpose of sample introduction and setting-out.
Water drain valve all is equipped with in the semiconductor cooler bottom and the BOD aerator bottom of described sample storage device; Be used for bleeding off the part that the post precipitation water sample contains suspended impurity.All there are sedimentation of suspension in sample storage bottle, each mensuration cycle of aeration bottle in these bottles, therefore all need emptying and flushing.Therefore sample storage bottle is finished at 0～4 ℃ sample retention so that be BOD in order to preserve sample by semiconductor cooler, its heat-insulation layer is made up of stainless steel and insulation material.
Described BOD aerator is equipped with heating constant-temperature system.The cultivation of dominant bacteria domestication in the BOD aerator, the majority of organic pollutants of degrading within a short period of time must guarantee growth of microorganism in logarithmic phase, and is to tame cultivation with determined sewage.The growth of microorganism optimum temperature is 30～35 ℃, so must rapidly solution be heated to 30～35 ℃ after adding dominant bacteria, and automatic constant-temperature.During the microbial degradation organism, its degradation rate is directly proportional with oxygen in water concentration, because of will constantly filling air, also can play beating action simultaneously.Water vapor is constantly overflowed under the condition of water temperature more than 30 ℃ and constantly inflation, has played an inspissation, therefore, needs water replanishing device to replenish clear water to original level.
The cuvette of described UV scanning device is provided with ultrasonic unit, and described cuvette is provided with computer-controlled automatic dilution device; Described scanister is provided with the formula xenon lamp that glitters, and adopting light source is the formula xenon lamp that glitters, and the double light path complementation increases the service life.
Described sampling apparatus adopts the technology of equal proportion sampling; Amplitude of variation according to enterprise's average discharge and flow calculates " threshold " of sampling each time, thereby reaches the purpose of equal proportion sampling, if promptly flow is big, can sample more, and flow is little, can sample less.
Described scanister is the CCD technology and the optical fiber technology of uses advanced, guarantees to scan to finish in the several seconds.
The using method of the monitor of a kind of full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD), the principle of work of described method is: the theory that the lambert-law of Beer of single wavelength mensuration pure material is expanded to the sweep measuring amount of the mixture, length scanning between promptly adopting from 200nm to 800nm for a kind of organic mixture solution, form peak area through integrated absorbance, this area is directly proportional with the concentration of determinand.
Described COD/BOD adopts the difference of biodegradation front and back COD to equal the notion of BOD, adopts the poor of biodegradation front and back COD, has changed the standard method of measuring BOD with " oxygen in water is poor before and after the biodegradation ";
Described computing formula is: COD=Kc ∑ A+B;
Before the COD-COD after=Δ COD=BODs;
BOD5＝BODs·Kb
Flow before COD total amount=COD
BOD5 total amount=BOD5 flow
Kc, Kb are that the water sample with reality is a standard model;
Kc measures with national standard method and UV scanning method simultaneously, is theoretical value with the standard method measured value, returns with the peak area that scans and tries to achieve, and A is a scan area in the formula, and B is for cutting a square; Kc specifically asks method: the theoretical COD value of being obtained same water sample by the GB volumetric method, obtain the theoretical value of five dilute concentrations again, scan, obtain corresponding peak area with these five dilute samples, carry out linear regression with peak area and theoretical COD value, promptly draw the computing formula of COD.
And Kb is simultaneously to one group of sample with a kind of sewage, measures with standard dilution method and UV method and tries to achieve; Flow is the actual flow of sewage.
Kb specifically asks method: make 4 parallel samples by a certain sewage sample, with GB dilution method on the five, obtain BOD5, the difference Δ COD with the COD before and after the biodegradation obtains BODS simultaneously; Kb is compared with the mean value of four BODS by the mean value of BOD5 and tries to achieve.
At normal temperature or 30～35 ℃ of aerations, the inoculation dominant bacteria uses active sludge, biological membrane, even the suspension that carries disease germs in the sewage, comes degradation of organic substances when measuring BOD.
Suspension in the water body is interference measurement to be that the sweep interval number of wavelengths is multiply by in the absorption of selecting 350nm between ultraviolet region and visible region, deducts in total absorption, to revise the interference of suspension.
The characteristics that UV scanning method of the present invention is measured COD are:
1. according to the additive property of dullness, the various organic dullness under a certain wavelength can addition, and the value of the dullness under the different wave length can add up to area, thereby has expanded Lambert-Beer's law.Classical Lambert-Beer's law is measured at pure material, and new method can be measured potpourri, and classical Lambert-Beer's law is quantitative according to wave height, and new method is quantitative according to area.
2. do not carry out chemical pre-treatment, directly water sample is scanned, its quantivative approach is with same water sample, tries to achieve area with scanning method, simultaneously, use potassium bichromate titrimetric method, try to achieve COD, two groups of data are tried to achieve formula through recurrence: COD=Kc ∑ A+B, and wherein Kc is a reduction coefficient, A is a scan area, and B is for cutting square.
3. with the absorption under the near visible wavelength, eliminate the interference of turbidity.
4. colourity is disturbed and can be eliminated automatically, and the colourity that the inorganics ion produces can not produce absorption at ultraviolet region, thereby not disturb; And organism colourity, one fixes on ultraviolet region absorbs, and is the part of COD, and it doesn't matter disturbs.
It is the Lambert-Beer's law height that the present invention will scan that quantitative principle rises to.Clear and definite, the former law by single wavelength mensuration pure material develops into the new Lambert-Beer's law of multi-wavelength sweep measuring potpourri.With the active sludge biological degraded, develop into multiple biodegradation method.As the plastic carrier biomembrance process, varicosity polyfoam carrier organism method has solved active sludge and has wanted centrifuging, repeatedly Xi Di a difficult problem.
The optical signature of monitor of the present invention is the CCD technology and the optical fiber technology of uses advanced, guarantees to scan to finish in the several seconds; Light source is the formula xenon lamp that glitters, and the double light path complementation reaches more than 2 years its serviceable life; CCD has heat sink, to guarantee to eliminate the influence of the temperature difference.
The CCD technology of uses advanced improves the sweep velocity of UV photometry greatly simultaneously.Adopt computer technology then, equal proportion sampling technology, remote data transmission technology have realized remote data transmission, telemonitoring, total amount, the device that concentration can both be measured.
Described COD/BOD total amount monitor device, its software programming comprise and being characterized as: a. utilizes the variation of UV scanning technology determination sewage composition; B. utilize the UV scanning technology to seek the computing formula that is complementary in the database; C. utilize the contaminated degree of UV scanning technology determination cuvette; D. utilize UV scanning technology determination cuvette whether to clean up, when need pickling or wiping; E. utilize the UV scanning technology determination biodegradable " terminal point "; F. utilize the UV scanning technology to eliminate the interference of suspension.
When water-quality constituents changed, all there was the inaccurate problem of a determination data in photometry.Though scanning method is wanted accurately also to have error.For this reason, adopt computer technology, resolve multiple scanning patter, in database, depositing corresponding reduction formula, thereby can correlativity reached more than 0.9.
Can survey COD, BOD, TOC mineral oil according to the lambert-law of Beer of above-mentioned expansion, residual toxicity, total organic contaminant etc. in the atmosphere.
The present invention has following advantage:
The present invention is without chemical reagent, and non-secondary pollution is measured quick and precisely, and easy and simple to handle, simple in structure, applied widely, failure rate is extremely low, can realize full-automatic Long-distance Control; It is short serviceable life to have solved the photometer lamp, changes the frequent problem of lamp, and apparatus guarantee is reached more than eight months interval time.
Description of drawings
Fig. 1 flow diagram of the present invention
Fig. 2 apparatus of the present invention schematic diagram
Embodiment
Embodiment 1
As depicted in figs. 1 and 2, the present invention includes and comprise sampling apparatus, sample storage device, water replanishing device, BOD aerator, UV scanning device and Computer Control Unit.
The sewage sample enters the sample storage bottle 5 of sample storage device through the sampling thief 1 of sampling apparatus through water pump 2 and T-valve 3 back-purge system 4 of flowing through; Described sample storage bottle 5 places semiconductor cooler 6, and temperature controller 7 on the semiconductor cooler 6, and described sample storage position of bottleneck is equipped with stop 8; Atmospheric valve 9 and air pump 10 are housed on the sample storage device, and the sample storage bottom of device is equipped with water drain valve 11.Water sample part in the sample storage bottle enters the BOD aeration bottle 13 of BOD aerator through T-valve 12, and a part directly enters UV scanning device 21 through T-valve 20.Atmospheric valve 14 and air pump 15 are housed on the BOD aerator, and water drain valve 16 is equipped with in BOD aerator bottom, and the BOD aerator is equipped with 17 pairs of BOD aerations of heating constant-temperature equipment bottle 13 and carries out temperature control.Atmospheric valve 18 and air pump 19 are housed on the water replanishing device 20, and the water sample in clear water in the water replanishing device and the BOD aeration bottle 13 is mixed into normal concentration and enters UV scanning device 22 through T-valve 21.The operation of computer installation 23 control sampling apparatuses, sample storage device, water replanishing device, BOD aerator and UV scanning device.
Embodiment 2
The concrete operation steps of the rapid assay methods of monitor of the present invention is:
1. target waste water is carried out UV scanning with monitor of the present invention, find out the highest absorption peak, determine sweep interval thus.
2. determine the Kc value.Obtain the theoretical COD value of target waste water by the GB volumetric method; Obtain four dilute concentrations of this target waste water again, 80%, the theoretical value of 60%, 40% and 20% concentration, scan with these five samples, obtain corresponding peak area, carry out linear regression with peak area and theoretical COD value, promptly draw the Kc value, again by before formula COD=Kc ∑ A+B and the formula COD-COD after=Δ COD=BODs, can obtain COD value and BODs value.
3. determine the Kb value.Target wastewater sample sample, with GB dilution method on the five do 4 parallel, obtain average BOD5, the difference Δ COD with the COD before and after the biodegradation obtains BODS simultaneously, is 4 parallel BODS; Kb is compared with the mean value of four BODS by the mean value of BOD5 and tries to achieve.
4. the actual flow by flow before formula COD total amount=COD and BOD5 total amount=BOD5 flow and waste water can calculate COD total amount and BOD5 total amount.
Embodiment 3
The instrument of utilization embodiment 1 is the using method of 2 these instruments in conjunction with the embodiments, and the present invention tests different wastewater samples, determines the Kc value, and is as shown in table 1 below:
Table 1 the present invention determines the Kc value to different wastewater sample tests
Embodiment 4
The instrument of utilization embodiment 1 is the using method of 2 these instruments in conjunction with the embodiments, and the present invention tests different wastewater samples, and contrast is the test result of BOD reason and BOD5 of the present invention with the BOD of GB dilution method on the five, and the mg/l of unit is as shown in table 2 below:
The test result of table 2 GB dilution method BOD5 on the five and BODS of the present invention
The instrument using method of 2 these instruments in conjunction with the embodiments of utilization embodiment 1, the present invention is to different wastewater sample test results, and the mg/l of unit is as shown in table 3 below:
Table 3 the present invention is to different wastewater sample test results
Claims (9)
1, the monitor of a kind of full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) comprises BOD aerator, UV scanning device and Computer Control Unit, it is characterized in that: also comprise sampling apparatus, sample storage device and water replanishing device;
Described Computer Control Unit is controlled described sampling apparatus, sample storage device, BOD aerator, water replanishing device and UV scanning device;
Described sampling apparatus, the sample storage device, the BOD aerator is connected with T-valve by pipeline between water replanishing device and the UV scanning device;
Described sampling apparatus comprises sampling thief and backpurge system, and water sample enters the sample storage bottle of sample storage device through sampling thief and backpurge system;
The sample storage bottle of described sample storage device places semiconductor cooler, temperature controller on the described semiconductor cooler, and described sample storage position of bottleneck is equipped with stop;
Water sample in the described BOD aerator and the water in the water replanishing device enter the UV scanning device after mixing.
2, the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), it is characterized in that: described backpurge system is made up of sample introduction barrier, sampling valve, recoil valve, utilizes the pressure reversal flushing of tap water.
3, the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD) is characterized in that: on described BOD aerator, sample storage device and the water replanishing device atmospheric valve and air pump are housed all; Water drain valve all is equipped with in the semiconductor cooler bottom and the BOD aerator bottom of described sample storage device.
4, the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD) is characterized in that: described BOD aerator is equipped with heating constant-temperature system.
5, the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), it is characterized in that: the cuvette of described UV scanning device is provided with ultrasonic unit, and described cuvette is provided with computer-controlled automatic dilution device; Described scanister is provided with the formula xenon lamp that glitters.
6, the using method of the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), described sampling apparatus adopts the technology of equal proportion sampling; Described scanister is the CCD technology and the optical fiber technology of uses advanced, guarantees to scan to finish in the several seconds.
7, the using method of the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), described method is to length scanning between a kind of organic mixture solution employing is from 200nm to 800nm, form peak area through integrated absorbance, this area is directly proportional with the concentration of determinand, calculates measurement result by formula again;
Described computing formula is: COD=Kc ∑ A+B;
Before the COD-COD after=Δ COD=BODs;
BOD5＝BODs·Kb
Flow before COD total amount=COD
BOD5 total amount=BOD5 flow
Kc, Kb are that the water sample with reality is a standard model; Kc measures with national standard method and UV scanning method simultaneously, is theoretical value with the standard method measured value, returns with the peak area that scans and tries to achieve, and A is a scan area in the formula, and B is for cutting a square; And Kb is simultaneously to one group of sample with a kind of sewage, measures with standard dilution method and ultraviolet photometry and tries to achieve; Flow refers to the actual flow of sewage.
8, the using method of the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), at normal temperature or 30～35 ℃ of aerations, the inoculation dominant bacteria uses active sludge, biological membrane when measuring BOD, even the suspension that carries disease germs in the sewage, come degradation of organic substances.
9, the using method of the monitor of a kind of full-automatic online chemical oxygen demand (BOD) as claimed in claim 1 and biological oxygen demand (BOD), the suspension of interference measurement is that the sweep interval number of wavelengths is multiply by in the absorption of selecting 350nm between ultraviolet region and visible region in the water body, in total absorption, deduct, to revise the interference of suspension.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102735812A (en) * | 2012-06-15 | 2012-10-17 | 中国科学院长春应用化学研究所 | Biochemical oxygen demand detection method |
| CN108872121A (en) * | 2018-06-25 | 2018-11-23 | 代堂刚 | The water quality rapid assay methods of five-day BOD in a kind of indirect determination water |
| CN109061208A (en) * | 2018-08-02 | 2018-12-21 | 上海宝中盈仪器仪表有限公司 | Full-automatic biochemical oxygen demand detector |
| CN114047228A (en) * | 2021-11-09 | 2022-02-15 | 同济大学 | Device and method for analyzing sediment oxygen-consuming pollutants |
-
2009
- 2009-08-19 CN CN200910163017A patent/CN101625317A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102735812A (en) * | 2012-06-15 | 2012-10-17 | 中国科学院长春应用化学研究所 | Biochemical oxygen demand detection method |
| CN102735812B (en) * | 2012-06-15 | 2015-05-20 | 中国科学院长春应用化学研究所 | Biochemical oxygen demand detection method |
| CN108872121A (en) * | 2018-06-25 | 2018-11-23 | 代堂刚 | The water quality rapid assay methods of five-day BOD in a kind of indirect determination water |
| CN109061208A (en) * | 2018-08-02 | 2018-12-21 | 上海宝中盈仪器仪表有限公司 | Full-automatic biochemical oxygen demand detector |
| CN114047228A (en) * | 2021-11-09 | 2022-02-15 | 同济大学 | Device and method for analyzing sediment oxygen-consuming pollutants |
| CN114047228B (en) * | 2021-11-09 | 2023-08-04 | 同济大学 | Device and method for analyzing oxygen-consuming pollutants of sediment |
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Application publication date: 20100113 |