CN1719233A - Fast determination method of chemical oxygen demand - Google Patents
Fast determination method of chemical oxygen demand Download PDFInfo
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- CN1719233A CN1719233A CN 200510043933 CN200510043933A CN1719233A CN 1719233 A CN1719233 A CN 1719233A CN 200510043933 CN200510043933 CN 200510043933 CN 200510043933 A CN200510043933 A CN 200510043933A CN 1719233 A CN1719233 A CN 1719233A
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Abstract
The present invention relates to a determination method of chemical oxygen demand. Said method includes the following steps: firstly, using potassium acid phthalate standard liquor (1200mg/L) to make standard curve; making the waste water undergo the process of ultrasonic water bath treatment, then further homogenizing; heating for 30min; using spectrophotometry to determine the absorbancy of trivalent chromium ion after the water sample is reacted at the place of 620 nm wavelength: then making colorimetry of water sample determination so as to obtain the absorbancy and correspondent COD value.
Description
One, technical field: the assay method that the present invention relates to a kind of chemical oxygen demand (COD).
Two, background technology: chemical oxygen demand (COD) (COD) is meant that under certain condition the amount of the oxygenant that consumes is represented with the mg/litre of oxygen when handling water sample with strong oxidizer.Chemical oxygen demand (COD) has reflected the degree that polluted by reducing substances.Reducing substances comprises organism, nitrite, ferrous salt, sulfide etc. in the water, and water is very general by organic pollutants, so chemical oxygen demand (COD) is also as one of index of organism relative content.
The method that generally adopts is national standard method (GB11914-89) at present.Be oxygenant with the potassium dichromate promptly, in acid medium, silver sulfate is a catalyzer, is the chlorion screening agent with the mercuric sulfate, measures the COD value of water sample, and the mensuration process needs reflux 2h.It detects numerical stability, favorable reproducibility.But still there are many deficiencies: (1) energy resource consumption big (heating 2 hours).(2) complicated operation.(3) toxic drugs consumption big (mercuric sulfate, potassium dichromate, silver sulfate).(4) operational danger big (sulfuric acid adds from recirculatory pipe).(5) sense cycle long (generally needing about 4 hours just can obtain the result).Owing to above reason, its batch quantity analysis in the sewage operational management is restricted.
For solving the problem that standard method exists, people have done a large amount of research on the fast measuring of COD for a long time, have occurred spectrophotometric method (replacing titration determination with colorimetricization), the quick resolution method of catalysis new detection methods such as (with by the new catalyzer accelerated reaction speed of exploitation).These methods shortened much than standard method on detection time, the detection numerical value of Potassium Hydrogen Phthalate standard model is compared relative error generally at 1-5% with GB, may reach more than 10% and the reappearance extreme difference but in the detection of actual water sample, compare its relative error with standard method.Main cause have following some:
(1) contain suspension in the actual water sample, the fast method sampling amount is few, the representative variation of water sample.
(2) these rapid assay methods shorten heat time heating time for accelerated oxidation speed, mostly strengthened the consumption of catalyzer and screening agent, so easy generation mercury salt precipitation, the small part of this deposit seed easily suspends, be subjected to interference when making the spectrophotometric colorimetric estimation, gained COD numerical value extremely instability is difficult to reading, and its measurement result is higher easily.
Three, summary of the invention: purpose of the present invention is exactly the defective that exists at prior art, and a kind of rapid assay methods of chemical oxygen demand (COD) accurately and rapidly is provided.
Technical scheme of the present invention is: formulate typical curve with the stupid diformazan potassium hydrogen phthalate mark liquid of neighbour (1200mg/L) earlier; Waste water is further homogenizing after ultrasound bath is handled; Waste water is guaranteeing that sulfuric acid-silver sulfate solution volume accounts under 1/2nd the condition of reactant liquor cumulative volume, heat time heating time 30min; Sentence the absorbance of spectrophotometry water sample reaction back trivalent chromic ion at wavelength 620nm; Can obtain absorbance and corresponding C OD value when carrying out the colorimetric of water determination again.
Specifically comprise the steps:
(1) medicine preparation
(1) potassium dichromate standard solution (1/6K
2Cr
2O
7=0.2500mol/L): take by weighing in advance and dissolve in immigration 1000ml volumetric flask in the water, be diluted to graticule, shake up at the 120 ℃ of pure potassium dichromate of benchmark or pure potassium dichromate 12.258g of top grade of drying 2h down;
(2) sulfuric acid-silver sulfate solution: in 500ml concentration 98% concentrated sulphuric acid, add the 5g silver sulfate.Placed 1-2 days, and made its dissolving;
(3) mercuric sulfate: take by weighing mercuric sulfate 100g in the 500ml volumetric flask, add about 400ml water, add concentrated sulphuric acid 50ml again and make its dissolving, be settled to graticule, shake up standby with distilled water;
(4) adjacent stupid diformazan potassium hydrogen phthalate mark liquid (1200mg/L);
(2) formulate typical curve
Get 6 of COD analyzer randomized response pipes, clean up and add adjacent stupid diformazan potassium hydrogen phthalate mark liquid 0,0.5,1.0,1.5,2.0,3.0ml respectively, obtain that the COD theoretical value is respectively 0,200,400,600,800,1200mg/L;
(1) with distilled water each reaction tube is complemented to 4ml successively;
(2) add potassium dichromate standard solution 2ml in every by-reaction pipe;
(3) every by-reaction pipe adds sulfuric acid-silver sulfate solution 6ml, airtight shaking up;
(4) reaction tube is inserted in the firehole of ultrasound bath machine successively, when temperature is lower than 165 ℃, clear up 30min;
(5) take out reaction tube to reacting pipe support, be cooled to room temperature, airtight shaking up;
(6) utilize the COD analyzer in wavelength 620nm place colorimetric, with joining standard specimen with the least square method calibration curve and the storage, try to achieve regression equation;
(3) water determination
(1) water sample is handled 5min in ultrasound bath;
(2) draw 4ml distilled water (making blank sample) and the uniform water sample of 3ml respectively and place the reaction tube that has cleaned up;
(3) in the water sample reaction tube, add mercuric sulfate 1ml;
(4) add potassium dichromate standard solution 2ml in every by-reaction pipe;
(5) add sulfuric acid-silver sulfate solution 6ml, airtight shaking up in every by-reaction pipe;
(6) reaction tube is inserted in the firehole of ultrasound bath machine successively, when temperature is lower than 165 ℃, clear up 30min;
(7) take out reaction tube to pipe support, be cooled to room temperature;
(8) utilize the COD analyzer by [function] [2] method of operating,, directly determine the absorbance and the COD value of actual water sample in wavelength 620nm place colorimetric.
Effect of the present invention:
(1) by the relation between suitable medicine combination, heat time heating time, the COD extent of reaction, the optimization top condition has been avoided the generation of precipitation, the solution clarification of reaction back, colorimetric numerical stability.This is the crucial part of present technique.
(2) solved the problem of sample representation difference, adopted ultrasound wave that water sample is handled earlier, make suspension be subjected in following time of action of ultrasonic waves, the time and tension forms small one by one cavity, i.e. what is called " cavitation bubble ".Because the pressure of cavitation bubble differs very greatly different, has very big impulsive force when " cavitation bubble " disappears, make bulky grain division, homogenizing in the liquid.Meanwhile ultrasound wave can play the effect of accelerate dissolution again in liquid.Like this, only need 5 minutes time of less than just can make original bigger suspension pulverize powder, equally distributed suspension small particle, so far water sample can reach the degree of mixing, homogenizing fully, at this moment has representativeness with the pipette, extract water sample.
(3) various chemicals consumptions only be equivalent to national standard method 1/5th to sixth, save medicine.Shorten to 30 minutes heat time heating time, energy savings has improved detection speed.Several water samples can provide testing result in 1h; 20 water samples can provide testing result in 1.5 hours.
(4) interpolation of oxygenant and screening agent can adopt buret to add, and dosing is accurate and operating speed is fast, extremely is fit to measure in batches.
(5) to compare relative error little for measurement result and GB, below 3%, and favorable reproducibility as a result.
Four, description of drawings: accompanying drawing is a chemical oxygen demand rapid measurement method standard curve of the present invention.
Five, specific embodiment:
Principle of the present invention is: adopt the sealed digestion colourimetry to measure down at 165 ℃.Waste water is handled further homogenizing of back through ultrasound bath, makes composition homogeneous such as solid particle in the water sample, colloidal solid, the raising sample representation; In addition, waste water is guaranteeing that sulfuric acid-silver sulfate solution volume accounts under 1/2nd the condition of reactant liquor cumulative volume, the COD of the COD of heating 30min and standard method heating 120min has good correlativity, 94-96% when its extent of reaction can reach the standard method terminal point and stable is so select 30min the most suitable as heat time heating time; Sentence the absorbance of spectrophotometry water sample reaction back trivalent chromic ion at wavelength 620nm; Earlier formulate typical curve, can obtain absorbance and corresponding C OD value when carrying out the colorimetric of water determination again with the stupid diformazan potassium hydrogen phthalate mark liquid of neighbour (1200mg/L).
(1) medicine and instrument
(1) potassium dichromate standard solution (1/6K
2Cr
2O
7=0.2500mol/L): take by weighing in advance and dissolve in immigration 1000ml volumetric flask in the water, be diluted to graticule, shake up at 120 ℃ of benchmark or pure potassium dichromate 12.258g of top grade of drying 2h down.
(2) sulfuric acid-silver sulfate solution: in the 500ml concentrated sulphuric acid, add the 5g silver sulfate.Place 1-2d, shake frequently and make its dissolving.
(3) mercuric sulfate: take by weighing mercuric sulfate 100g in the 500ml volumetric flask, add about 400ml water, add concentrated sulphuric acid 50ml again and make its dissolving, be settled to graticule, shake up standby with distilled water.
(4) adjacent stupid diformazan potassium hydrogen phthalate mark liquid (1200mg/L).
Use instrument: HH-6 type COD analyzer, DL-720A ultrasound bath.
(2) measurement range
The scope of detecting is the water sample of COD at 50-1200mg/L, and chlorion is sheltered scope and is≤2000mg/L.Higher or chlorine ion concentration water sample of high detects after can doing suitable dilution again to COD.
(3) formulate typical curve
Get 6 of HH-6 type COD analyzer randomized response pipes and perform mark, clean up (after cleaning with cleansing solution, wash down with tap water, soaking 5-12 hour taking-up back with dilute sulfuric acid cleans with distilled water, oven dry), add adjacent stupid diformazan potassium hydrogen phthalate mark liquid 0,0.5,1.0,1.5,2.0,3.0ml respectively, obtain that the COD theoretical value is respectively 0,200,400,600,800,1200mg/L.
(1) with distilled water each reaction tube is complemented to 4ml successively.
(2) add potassium dichromate standard solution 2ml in every by-reaction pipe.
(3) every by-reaction pipe adds sulfuric acid-silver sulfate solution 6ml, and the tool plug shakes up.(lid must screw, and must not leak gas, otherwise heating back test solution can overflow, and the corrosion instrument also causes danger.)
(4) reaction tube is inserted in the firehole of DL-720A ultrasound bath machine successively, treat that temperature is brought down below after 165 ℃ of the setting values by [clearing up], the instrument self-timing is cleared up, and 30min clears up the buzzing that finishes and reports to the police.
(5) take out reaction tube to reacting pipe support, natural cooling 2 minutes, water-cooled is to room temperature again.(carefully operate during cooling, prevent that chilled water from entering reaction tube or staiing mouth of pipe pipe close, influences measurement result.)
(6) the tool plug shakes up, and is to be measured.
(7) utilize HH-6 type COD analyzer by [function] [1] method of operating, in wavelength 620nm place colorimetric, with joining standard specimen with the least square method calibration curve and the storage, try to achieve regression equation.
1, formulates typical curve
| Numbering | 0 | 1 | 2 | 3 | 4 | 5 |
| COD mg/L | 0 | 200 | 400 | 600 | 800 | 1000 |
| Absorbance A | 0 | 0.1484 | 0.2917 | 0.4469 | 0.5982 | 0.7474 |
COD is tried to achieve in recurrence and the absorbance relational expression is: y=1335.3x+3.1217 R
2=0.9999 correlativity is fine.Y:COD x in the formula: water sample absorbance R
2: dependence among equations
(4) water determination
(1) water sample is handled 5min in ultrasound bath.
(2) draw 4ml distilled water (doing blank) or the uniform water sample of 3ml respectively and place the reaction tube that has cleaned up.
(3) add mercuric sulfate 1ml (blank does not add) in every by-reaction pipe.
(4) add potassium dichromate standard solution 2ml in every by-reaction pipe.
(5) add sulfuric acid-silver sulfate solution 6ml in every by-reaction pipe, the tool plug shakes up.(lid must cover tightly, must not leak gas, otherwise heating back test solution can overflow, and the corrosion instrument also causes danger)
(6) reaction tube is inserted in the firehole of DL-720A ultrasound bath machine successively, treat that temperature is brought down below after 165 ℃ of the setting values by [clearing up], the instrument self-clocking is cleared up, and 30min clears up the buzzing that finishes and reports to the police.
(7) take out reaction tube to pipe support, natural cooling 2 minutes, water-cooled is to room temperature again.(carefully operate during cooling, prevent that chilled water from entering reaction tube or staining mouth of pipe pipe close, influences measurement result.)
(8) utilize HH-6 type COD analyzer by [function] [2] method of operating,, directly determine the absorbance and the COD value of actual water sample in wavelength 620nm place colorimetric.
(5) points for attention
(1) in order to improve the accuracy of detection, should reduce sample influencing each other when detecting as far as possible, before each application of sample, use distilled water, testing sample cleans colorimetric pool successively.In addition, the used lid of the reaction tube of blank, standard specimen, sample and reaction tube as far as possible separately uses, to reduce the error that operation brings.
(2) the interior solution of reaction tube must shake up before the heating; The interior solution of reaction tube must shake up before the colorimetric.
The useable glass rod tilted to drain into the colorimetric pool wall when (3) solution moved into the colorimetric pool of HH-6 type COD analyzer from reaction tube, in case pour deposit seed into or form air bubble.
COD reading when (4) stablizing for a long time with absorbance during colorimetric is as the criterion.
The testing result contrast of several paper-making effluents
| Water sample | The GB testing result | Express method | Relative error |
| Straw pulp waste water | 3818 | 3894 | 1.99％ |
| 3898 | 2.10％ | ||
| The deinking pulp waste water | 3767 | 3792 | 0.66％ |
| 3790 | 0.61％ | ||
| Works liquor | 324 | 324 | 0 |
| 325 | 0.3％ |
By above data as seen, this method detects not only favorable reproducibility, and to compare relative error very little with national standard, and within claimed range, control takes this method can obtain COD numerical value accurately at short notice as process operation fully.
Claims (2)
1, a kind of rapid assay methods of chemical oxygen demand (COD) is characterized in that: formulate typical curve with the stupid diformazan potassium hydrogen phthalate mark liquid of neighbour (1200mg/L) earlier; Waste water is further homogenizing after ultrasound bath is handled; Waste water is guaranteeing that sulfuric acid-silver sulfate solution volume accounts under 1/2nd the condition of reactant liquor cumulative volume, heat time heating time 30min; Sentence the absorbance of spectrophotometry water sample reaction back trivalent chromic ion at wavelength 620nm; Can obtain absorbance and corresponding C OD value when carrying out the colorimetric of water determination again.
2, the rapid assay methods of chemical oxygen demand (COD) according to claim 1 is characterized in that comprising the steps:
(1) medicine preparation
(1) potassium dichromate standard solution (1/6K
2Cr
2O
7=0.2500mol/L): take by weighing in advance and dissolve in immigration 1000ml volumetric flask in the water, be diluted to graticule, shake up at the 120 ℃ of pure potassium dichromate of benchmark or pure potassium dichromate 12.258g of top grade of drying 2h down;
(2) sulfuric acid-silver sulfate solution: in 500ml concentration 98% concentrated sulphuric acid, add the 5g silver sulfate.Placed 1-2 days, and made its dissolving;
(3) mercuric sulfate: take by weighing mercuric sulfate 100g in the 500ml volumetric flask, add about 400ml water, add concentrated sulphuric acid 50ml again and make its dissolving, be settled to graticule, shake up standby with distilled water;
(4) adjacent stupid diformazan potassium hydrogen phthalate mark liquid (1200mg/L);
(2) formulate typical curve
Get 6 of COD analyzer randomized response pipes, clean up and add adjacent stupid diformazan potassium hydrogen phthalate mark liquid 0,0.5,1.0,1.5,2.0,3.0ml respectively, obtain that the COD theoretical value is respectively 0,200,400,600,800,1200mg/L;
(1) with distilled water each reaction tube is complemented to 4ml successively;
(2) add potassium dichromate standard solution 2ml in every by-reaction pipe;
(3) every by-reaction pipe adds sulfuric acid-silver sulfate solution 6ml, airtight shaking up;
(4) reaction tube is inserted in the firehole of ultrasound bath machine successively, when temperature is lower than 165 ℃, clear up 30min;
(5) take out reaction tube to reacting pipe support, be cooled to room temperature, airtight shaking up;
(6) utilize the COD analyzer in wavelength 620nm place colorimetric, with joining standard specimen with the least square method calibration curve and the storage, try to achieve regression equation;
(3) water determination
(1) water sample is handled 5min in ultrasound bath;
(2) draw 4ml distilled water (making blank sample) and the uniform water sample of 3ml respectively and place the reaction tube that has cleaned up;
(3) in the water sample reaction tube, add mercuric sulfate 1ml;
(4) add potassium dichromate standard solution 2ml in every by-reaction pipe;
(5) add sulfuric acid-silver sulfate solution 6ml, airtight shaking up in every by-reaction pipe;
(6) reaction tube is inserted in the firehole of ultrasound bath machine successively, when temperature is lower than 165 ℃, clear up 30min;
(7) take out reaction tube to pipe support, be cooled to room temperature;
(8) utilize the COD analyzer by [function] [2] method of operating,, directly determine the absorbance and the COD value of actual water sample in wavelength 620nm place colorimetric.
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| CN 200510043933 CN1719233A (en) | 2005-06-24 | 2005-06-24 | Fast determination method of chemical oxygen demand |
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| CN 200510043933 CN1719233A (en) | 2005-06-24 | 2005-06-24 | Fast determination method of chemical oxygen demand |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462949A (en) * | 2007-12-17 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing primary standard reagent potassium hydrogen phthalate |
| CN102721654A (en) * | 2011-11-16 | 2012-10-10 | 深圳市世纪天源环保技术有限公司 | Background absorption correction method for CODcr measurement |
| CN103175805A (en) * | 2013-03-11 | 2013-06-26 | 楚广诣 | Method for determining indexes of COD and BOD5 in sewage through near infrared spectrometry |
| CN103592242A (en) * | 2013-11-11 | 2014-02-19 | 天津大学 | Method for measuring COD (chemical oxygen demand) of seawater |
| CN103611553A (en) * | 2013-10-19 | 2014-03-05 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Catalyst for chemical oxygen consumption tester, and preparation method and application method of catalyst |
| CN103645186A (en) * | 2013-12-24 | 2014-03-19 | 南京中锗科技股份有限公司 | Method for analyzing content of COD (chemical oxygen demand) in sewage with high chloride ion concentration |
| CN106290758A (en) * | 2015-05-20 | 2017-01-04 | 中国石油天然气股份有限公司 | The detection device of the acquisition methods of organic compound theoretical COD, the detection method of COD of sewage and COD of sewage |
| CN107144534A (en) * | 2017-04-21 | 2017-09-08 | 苏州源泓环保科技有限公司 | COD water quality online test method |
| CN107589086A (en) * | 2017-08-29 | 2018-01-16 | 南京工业大学 | A kind of hydrogen peroxide remover composition, removing method and quick COD assay methods for COD measure |
| CN108680716A (en) * | 2018-02-13 | 2018-10-19 | 华测检测认证集团股份有限公司 | A kind of chlorine-contained wastewater COD prescreening method |
| CN108931491A (en) * | 2018-07-25 | 2018-12-04 | 东南大学 | A kind of Multifunctional water portable remote monitor and water quality monitoring method |
| CN108956495A (en) * | 2018-07-11 | 2018-12-07 | 东盛科兴环保科技河北有限公司 | A kind of method that dual wavelength internal standard method measures lower range COD in water body |
| CN108956509A (en) * | 2018-07-06 | 2018-12-07 | 郭壮 | A kind of reagent and its detection method of quick measurement high-chloride wastewater COD |
| CN109254112A (en) * | 2018-11-07 | 2019-01-22 | 武汉中粮食品科技有限公司 | A kind of COD of sewage rapid detection method |
| CN111103389A (en) * | 2019-12-19 | 2020-05-05 | 福建省高创环境科技股份有限公司 | Sewage pipeline COD rapid detector and method thereof |
| CN112485099A (en) * | 2020-11-23 | 2021-03-12 | 陕西彩虹新材料有限公司 | Preparation method of COD mixed digesting agent |
| US11474091B2 (en) | 2018-06-04 | 2022-10-18 | National Yang Ming Chiao Tung University | Color chart, test kit, and method of estimating chemical oxygen demand of water |
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2005
- 2005-06-24 CN CN 200510043933 patent/CN1719233A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462949A (en) * | 2007-12-17 | 2009-06-24 | 天津市化学试剂研究所 | Method for preparing primary standard reagent potassium hydrogen phthalate |
| CN101462949B (en) * | 2007-12-17 | 2013-06-19 | 天津市化学试剂研究所 | Method for preparing primary standard reagent potassium hydrogen phthalate |
| CN102721654A (en) * | 2011-11-16 | 2012-10-10 | 深圳市世纪天源环保技术有限公司 | Background absorption correction method for CODcr measurement |
| CN102721654B (en) * | 2011-11-16 | 2014-11-05 | 深圳市世纪天源环保技术有限公司 | Background absorption correction method for CODcr measurement |
| CN103175805A (en) * | 2013-03-11 | 2013-06-26 | 楚广诣 | Method for determining indexes of COD and BOD5 in sewage through near infrared spectrometry |
| CN103175805B (en) * | 2013-03-11 | 2015-04-29 | 楚广诣 | Method for determining indexes of COD and BOD5 in sewage through near infrared spectrometry |
| CN103611553A (en) * | 2013-10-19 | 2014-03-05 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Catalyst for chemical oxygen consumption tester, and preparation method and application method of catalyst |
| CN103592242A (en) * | 2013-11-11 | 2014-02-19 | 天津大学 | Method for measuring COD (chemical oxygen demand) of seawater |
| CN103592242B (en) * | 2013-11-11 | 2016-01-06 | 天津大学 | A kind of method measuring seawater cod |
| CN103645186A (en) * | 2013-12-24 | 2014-03-19 | 南京中锗科技股份有限公司 | Method for analyzing content of COD (chemical oxygen demand) in sewage with high chloride ion concentration |
| CN106290758B (en) * | 2015-05-20 | 2019-03-12 | 中国石油天然气股份有限公司 | The detection device of the acquisition methods of organic compound theoretical COD, the detection method of COD of sewage and COD of sewage |
| CN106290758A (en) * | 2015-05-20 | 2017-01-04 | 中国石油天然气股份有限公司 | The detection device of the acquisition methods of organic compound theoretical COD, the detection method of COD of sewage and COD of sewage |
| CN107144534A (en) * | 2017-04-21 | 2017-09-08 | 苏州源泓环保科技有限公司 | COD water quality online test method |
| CN107589086A (en) * | 2017-08-29 | 2018-01-16 | 南京工业大学 | A kind of hydrogen peroxide remover composition, removing method and quick COD assay methods for COD measure |
| CN107589086B (en) * | 2017-08-29 | 2019-08-23 | 南京工业大学 | A kind of hydrogen peroxide remover composition, removing method and quick COD measuring method for COD measurement |
| CN108680716A (en) * | 2018-02-13 | 2018-10-19 | 华测检测认证集团股份有限公司 | A kind of chlorine-contained wastewater COD prescreening method |
| US11474091B2 (en) | 2018-06-04 | 2022-10-18 | National Yang Ming Chiao Tung University | Color chart, test kit, and method of estimating chemical oxygen demand of water |
| US11808749B2 (en) | 2018-06-04 | 2023-11-07 | National Yang Ming Chiao Tung University | Method of estimating chemical oxygen demand of water |
| CN108956509A (en) * | 2018-07-06 | 2018-12-07 | 郭壮 | A kind of reagent and its detection method of quick measurement high-chloride wastewater COD |
| CN108956495A (en) * | 2018-07-11 | 2018-12-07 | 东盛科兴环保科技河北有限公司 | A kind of method that dual wavelength internal standard method measures lower range COD in water body |
| CN108931491A (en) * | 2018-07-25 | 2018-12-04 | 东南大学 | A kind of Multifunctional water portable remote monitor and water quality monitoring method |
| CN109254112A (en) * | 2018-11-07 | 2019-01-22 | 武汉中粮食品科技有限公司 | A kind of COD of sewage rapid detection method |
| CN111103389A (en) * | 2019-12-19 | 2020-05-05 | 福建省高创环境科技股份有限公司 | Sewage pipeline COD rapid detector and method thereof |
| CN112485099A (en) * | 2020-11-23 | 2021-03-12 | 陕西彩虹新材料有限公司 | Preparation method of COD mixed digesting agent |
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