JPS6093952A - Continuous measurement of bod - Google Patents
Continuous measurement of bodInfo
- Publication number
- JPS6093952A JPS6093952A JP58203155A JP20315583A JPS6093952A JP S6093952 A JPS6093952 A JP S6093952A JP 58203155 A JP58203155 A JP 58203155A JP 20315583 A JP20315583 A JP 20315583A JP S6093952 A JPS6093952 A JP S6093952A
- Authority
- JP
- Japan
- Prior art keywords
- bod
- solution
- standard solution
- electrode
- standard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005259 measurement Methods 0.000 title claims abstract description 39
- 239000012086 standard solution Substances 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000007853 buffer solution Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- SPLIXMVCDRBRKV-BCLLBKCYSA-N (2s)-2-aminopentanedioic acid;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC(=O)[C@@H](N)CCC(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPLIXMVCDRBRKV-BCLLBKCYSA-N 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 24
- 230000000813 microbial effect Effects 0.000 claims description 21
- 230000007935 neutral effect Effects 0.000 claims description 14
- 239000005416 organic matter Substances 0.000 claims description 11
- 238000000691 measurement method Methods 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims 1
- 244000005700 microbiome Species 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000007774 longterm Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1893—Water using flow cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Immunology (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Emergency Medicine (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
Description
【発明の詳細な説明】
この発明はBOD連続測定方法に関する。さらに詳しく
は、隔膜式酸素電極と微生物膜とを組合せてなる微生物
電極を用いてEODを連続的にしかも長期間に亘って測
定する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a continuous BOD measurement method. More specifically, the present invention relates to a method of measuring EOD continuously over a long period of time using a microbial electrode formed by combining a diaphragm-type oxygen electrode and a microbial membrane.
従来から微生物電極を用いてBODを測定する方法が種
々提案されている。これらの一つとして微生物電極を備
えたフローセル中に、中性緩衝液を流しておいて中性条
件に保つと共に空気を吹き込んで実質的に空気飽和の条
件に保ち、この条件下で被測定液を供給して該被測定液
中のBOD成分に対応する七μ中の溶存酸素低下量すな
わち微生物の代謝によって消費される溶存酸素量を隔膜
式酸素電極の出力として検出して測定する方法が行なわ
れている。そしてかような測定は上記被測定液の代りに
、BOD既知の有機物含有標準液を供給した際の出力を
基準とし°て行われており、すなわち所定の測定数経過
毎に出力とBODと検量m管較正することにより行われ
ている。Conventionally, various methods for measuring BOD using microbial electrodes have been proposed. As one of these, a neutral buffer solution is flowed into a flow cell equipped with a microbial electrode to maintain neutral conditions, and air is blown into the flow cell to maintain a substantially air-saturated condition. A method is carried out in which the amount of dissolved oxygen decreased in the 7μ corresponding to the BOD component in the liquid to be measured, that is, the amount of dissolved oxygen consumed by the metabolism of microorganisms, is detected and measured as the output of the diaphragm oxygen electrode. It is. Such measurements are performed based on the output when an organic matter-containing standard solution with a known BOD is supplied instead of the above-mentioned liquid to be measured.In other words, the output, BOD, and calibration are calculated every predetermined number of measurements. This is done by calibrating the m tube.
そして、上記有機物含有標準液として、従来、J工S
KOlog −210BOD測定の際の標準液として用
いられている中性のグμコースーグμタミン酸混合標準
液が適用されている。Conventionally, as the organic matter-containing standard solution, J.
A neutral glucose-g-tamic acid mixed standard solution, which is used as a standard solution for KOlog-210BOD measurement, is used.
しかし、かような従来の有機物含有標準液を用いてBO
Dの連続測定管行う際に種々の問題があった。その一つ
は、長時間の連続測定用として所定量貯留しである有機
物含有標準液のBODが時間経過と共に徐々に低下して
測定値に大きな誤差を与えるという問題である。この原
因は明らかではないが、徐々に標準液中のBOD成分が
分解消費されていくためと考えられる。そのため、貯留
した各標準液を短期間で新たな標準液と取り換える必要
があった。一方、かような標準液は管路を通じて前記フ
ローセル中に所定周期で導びかれるが、長時間の連続測
定においてはこの管路内に微生物が標準液を基質として
摂取することにより増殖し多量のスライムが発生し、配
管系を徐々に閉塞し流量を減少させたシ完全な閉塞を招
き、又はスライムによって被検液のBOD成分が消費さ
れるという問題もあった。However, using such conventional organic matter-containing standard solutions, BO
There were various problems when conducting continuous measurement tube D. One of the problems is that the BOD of an organic matter-containing standard solution, which is stored in a predetermined amount for long-term continuous measurement, gradually decreases over time, giving a large error to the measured value. Although the cause of this is not clear, it is thought that the BOD component in the standard solution is gradually decomposed and consumed. Therefore, it was necessary to replace each stored standard solution with a new standard solution within a short period of time. On the other hand, such a standard solution is guided into the flow cell through a pipe at a predetermined period, but during long-term continuous measurements, microorganisms in this pipe take in the standard solution as a substrate and proliferate, resulting in a large amount of microorganisms. There is also the problem that slime is generated, gradually blocking the piping system and reducing the flow rate, leading to complete blockage, or that the BOD component of the test liquid is consumed by the slime.
この発明は、かような従来の問題点を解消すべくなされ
たものであシ、長時間の連続測定においても標準液の変
化による測定誤差を生じず、しかも標準液の管路内のス
ライムの発生を抑制しつつBODを連続的に測定できる
方法を提供することを目的とするものである。This invention was made in order to solve these conventional problems, and it does not cause measurement errors due to changes in the standard solution even during long-term continuous measurements, and it also eliminates slime in the standard solution pipe. It is an object of this invention to provide a method that can continuously measure BOD while suppressing its occurrence.
この発明の発明者らは、種々検討を行った結果、従来の
中性で用いられていた有機物含有標準液のpHを約2〜
3に調整する仁とによシ、長時間使用による標準液自体
のBOD低下を招くことなく測定を行うことができ、し
かもか\る標準液を用いることにより管路のスライム障
害をも減少するξとができる事実を見出しこの発明に到
達した。As a result of various studies, the inventors of this invention found that the pH of the organic matter-containing standard solution, which was conventionally used as a neutral solution, was increased from about 2 to
By adjusting the standard solution to 3, it is possible to perform measurements without causing a decrease in the BOD of the standard solution itself due to long-term use, and by using such a standard solution, slime problems in the pipes are also reduced. This invention was achieved by discovering the fact that ξ is possible.
かくしてこの発明によれば、隔膜式酸素電極と微生物膜
からなる微生物電極を備えた測定用フローセル中に、中
性緩衝液の存在下でかつS気処理下、被測定液を管路を
通じて供給して微生物電極 3−
の出力を検知し、この出力と、所定の測定数経過毎に測
定されるBOD既知の有機物含有標準液供給時の基準出
力、とを比較して被測定液のBODを連続的に測定する
ことからなシ、上記有機物含有標準液としてpHFJ2
〜3にail整された有機物水溶液を用いたことを特徴
とするBOD連続測定方法が提供される。Thus, according to the present invention, a liquid to be measured is supplied through a pipe in the presence of a neutral buffer and under S gas treatment into a measurement flow cell equipped with a diaphragm-type oxygen electrode and a microbial electrode consisting of a microbial membrane. Detect the output of the microbial electrode 3- by using the microbial electrode 3-, and compare this output with the reference output when supplying a standard solution containing organic matter with a known BOD, which is measured every predetermined number of measurements, to continuously determine the BOD of the liquid to be measured. pHFJ2 is used as the organic matter-containing standard solution for measurement.
A continuous BOD measurement method is provided, which is characterized in that it uses an aqueous organic matter solution that has been conditioned to ail.
この発明に用いる有機物水溶液としては膨水化物及び/
又はアミノ酸の水溶液が好適であシ、具体的にはグμコ
ース、フラクトース、サッカロース、2クトース、可溶
性澱粉、グリシン、グルタミン酸、ヒスチジン等が挙げ
られる。これらのうち代表的なものとして、グμコース
ーグIタミン酸混合水溶液が挙げられる。ただしこれ以
外の脂肪酸、アyコーμ類等の有機化合物も場合によっ
ては使用可能である。これらの濃度は供給量や微生物活
性等に応じて適宜決定される。The organic aqueous solution used in this invention is a swollen product and/or
Alternatively, an aqueous solution of an amino acid is suitable, and specific examples thereof include glucose, fructose, sucrose, 2-ctose, soluble starch, glycine, glutamic acid, histidine, and the like. A representative example of these is a mixed aqueous solution of Glucosug I tamic acid. However, organic compounds other than these, such as fatty acids and ayco-μ compounds, may also be used depending on the case. These concentrations are appropriately determined depending on the supply amount, microbial activity, etc.
この発明において、上記有機物水溶液のpHは約2〜3
に調整される。pHの調整は通常、上記有機物を水に溶
解すると共に、塩酸、硫酸、硝酸4−
等の鉱酸を少量添加することにより簡便に行われる。な
お、pHを約2未満(例えばpHユ)とすると酸性が強
すぎて、フローセル中に導びかれた際に通常用いられる
中性緩衝液の存在下においても系が酸性となって正常な
微生物の活性が抑制される惧れがあシ、従って中性緩衝
液中の塩の量を増加させる必要があ夛不適当である。ま
た、pE(を約3を越える(例えばI)H4)とBOD
低下やスライムの発生の防止又は抑制効果は期待できな
い。In this invention, the pH of the organic substance aqueous solution is about 2 to 3.
is adjusted to The pH is usually easily adjusted by dissolving the organic substance in water and adding a small amount of a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid. Note that if the pH is less than about 2 (for example, pH 2), the acidity is too strong, and when introduced into the flow cell, the system becomes acidic even in the presence of a commonly used neutral buffer solution, and normal microorganisms cannot survive. There is a risk that the activity of the neutral buffer may be inhibited, and therefore it may be inappropriate to increase the amount of salt in the neutral buffer. Also, pE (exceeding about 3 (e.g. I)H4) and BOD
No effect can be expected to prevent or suppress deterioration or slime generation.
通常、pHを約3に調整するのが好ましい。It is usually preferred to adjust the pH to about 3.
この発明に用いる微生物電極としては、特開昭54−4
T16998公報や特開昭56−108951号公報な
どで用いられる所謂微生物電極を適用することができる
。As the microbial electrode used in this invention, JP-A No. 54-4
A so-called microbial electrode used in publications such as T16998 and JP-A-56-108951 can be used.
また、中性緩衝液としては、pH1のリン酸塩緩衝液が
適当であJ)、0.0IM程度の濃度のものが好適であ
る。Further, as the neutral buffer, a phosphate buffer with a pH of 1 is suitable (J), and one with a concentration of about 0.0 IM is suitable.
なお、測定毎に測定管路にpH3程度の洗浄液を供給す
ることが、スライム発生防止の点でより好ましい。Note that it is more preferable to supply a cleaning liquid with a pH of about 3 to the measurement pipe for each measurement in order to prevent slime generation.
以下、この発明の方法を添付図面に従ってさらに詳説す
る。Hereinafter, the method of the present invention will be explained in more detail with reference to the accompanying drawings.
第1図に示す(1)は、BOD連続測定装置であシ、こ
の発明の方法を実施する測定装置の一実施例でおる。(1) shown in FIG. 1 is a BOD continuous measuring device, which is an embodiment of the measuring device that implements the method of the present invention.
(2)は微生物電極で、隔膜式酸素電m (3)と微生
物膜(4)とを組合せてなる公知の構成である。(2) is a microbial electrode, which has a known configuration consisting of a combination of a diaphragm type oxygen electrode (3) and a microbial membrane (4).
微生物電極(2)の下部には測定セ/L/(5)が取り
付けられておシ、測定セル(5)の液入口(5a)から
流入して液出口(5b)へ流出する液が微生物膜(4)
と接しうるようになっている。液が微生物A11(4)
K効果的に接するように1液入口(δa)pよ液出口(
5b)よシ下の段ちがいの位置に設けである。A measurement cell/L/(5) is attached to the lower part of the microorganism electrode (2), and the liquid flowing into the measurement cell (5) from the liquid inlet (5a) and flowing out to the liquid outlet (5b) collects microorganisms. Membrane (4)
It is now possible to come into contact with The liquid is microorganism A11 (4)
K Make sure that the 1st liquid inlet (δa) and P are in effective contact with the liquid outlet (
5b) It is installed at a different position on the lower floor.
これら微生物電極(2)および測定セ/L/(5)は、
恒温水槽(6)中で所定温度(九とえば30℃)に保た
れている。(′1)は、コイμ状の流路で、この中を通
過する間に液がほぼ所定温度となるよう長さが定められ
ている。These microorganism electrodes (2) and measurement cell/L/(5) are
It is maintained at a predetermined temperature (for example, 30° C.) in a constant temperature water bath (6). ('1) is a carp-shaped flow path, and the length is determined so that the liquid reaches approximately a predetermined temperature while passing through the channel.
(8)はマイクロコンピュータのごとき制御回路で、予
め設定された手順に従ってH街液(B)、試料液(S)
、標準液(C1)〜CC5)、洗浄液(N)および空気
を測定セル(5)に供給すべく、ポンプ(9)(10)
、エアポンプ(12)および切換パルプ(13)をル
リ御する。また微生物電極(2)の出力電流に基いてB
OD値の算出を行う。(8) is a control circuit such as a microcomputer, which controls the H street solution (B) and sample solution (S) according to preset procedures.
, standard solutions (C1) to CC5), cleaning solution (N) and air to the measuring cell (5), pumps (9) (10)
, air pump (12) and switching pulp (13). Also, based on the output current of the microbial electrode (2), B
Calculate the OD value.
そして標準液CC1)〜(Ca)は塩酸でpf(3にそ
れぞれ調整され貯留されたグμコースーグpタミン酸混
合水溶液であり、BODはそれぞれ25ダ/1.5o1
ag/、g及び1ooq//?に調整された標準液を示
す0
なお、洗浄液(N)は上水道水に塩酸を加えてpH3に
調整されたものである。Standard solutions CC1) to (Ca) are a mixed aqueous solution of glucose μ-sug p-tamic acid adjusted to pf (3) with hydrochloric acid and stored, and each has a BOD of 25 Da/1.5o1.
ag/, g and 1ooq//? 0 indicates a standard solution adjusted to pH 3. Note that the cleaning solution (N) was adjusted to pH 3 by adding hydrochloric acid to tap water.
次に動作を説明すると、まずリン酸緩衝液(0,01M
、pH7)のごとき中性緩衝液(B)がローラーポンプ
(9)によって測定セA/(5)に供給されてセル内は
中性条件とされ、かつ洗浄液(N)が切換バルブ(13
)およびローラーポンプ(9〕を介して測定セル(5)
に供給される。また常時エアポンプ(12)から空気が
供給されこれによってセ/l/(5)内は曝−7=
気処理下となる。緩衝液(E)の流量はたとえば1.0
d/分、洗浄液(N)の流量はたとえばlnwl1分、
空気流量はたとえば1000114/分である。Next, to explain the operation, first, phosphate buffer (0.01M
, pH 7) is supplied to the measuring cell A/(5) by the roller pump (9) to maintain neutral conditions in the cell, and the washing liquid (N) is supplied to the measuring cell A/(5) by the roller pump (9).
) and the measuring cell (5) via the roller pump (9)
supplied to In addition, air is constantly supplied from the air pump (12), so that the inside of the cell/l/(5) is exposed to air. The flow rate of the buffer solution (E) is, for example, 1.0
d/min, the flow rate of the cleaning solution (N) is, for example, lnwl1 min,
The air flow rate is, for example, 1000114/min.
試料測定時には、切換バルブ(13)が切換えられて、
洗浄液(N)の代りに工場廃水のごとき試料液(S)が
採取ポンプ(No)およびフイルタ(18)を介して供
給される。緩衝液(B)の供給などは前と同様である。When measuring a sample, the switching valve (13) is switched,
Instead of the cleaning liquid (N), a sample liquid (S) such as factory wastewater is supplied via a collection pump (No) and a filter (18). The supply of buffer solution (B) etc. are the same as before.
黴佑物電極(2)の出力電流は、試料液(S)のBOD
に比例した減少値を示す。The output current of the mold electrode (2) is the BOD of the sample solution (S).
shows a decrease value proportional to .
上記のように測定セル(5)に試料液CF3)を供給す
るのはたとえば30分毎に5分間くらい行われ゛、他の
時間は洗浄液(N)が供給される。As mentioned above, the sample liquid CF3) is supplied to the measurement cell (5) for about 5 minutes every 30 minutes, and the cleaning liquid (N) is supplied at other times.
所定の較正設定時刻Kfkると、切換パルプ(13)が
切換えられて、洗浄液(N)の代シに標準液(Ct)。At a predetermined calibration set time Kfk, the switching pulp (13) is switched to use the standard solution (Ct) instead of the cleaning solution (N).
(Ox) 、 (Os)が測定セtv(りにそれぞれ供
給され、各々について測定が行われる。各標準液(C1
)、(Os)。(Ox) and (Os) are respectively supplied to the measurement set and measured for each. Each standard solution (C1
), (Os).
(C3)のBOD値は既知であるから、これらに対する
微生物電極(2)の出力値に′1&き、制御回路(8)
は検量線を較正する。この較正は所定の測定数経過毎に
、たとえば1日数回行われる。Since the BOD value of (C3) is known, the output value of the microbial electrode (2) for these is set to '1&', and the control circuit (8)
calibrates the standard curve. This calibration is performed every predetermined number of measurements, for example several times a day.
8−
上記較正に基いて各試料液のBODが連続的に測定され
ることとなる。そして標準液(Ct)〜(C3)はpH
3に調整されているため、長時間の連続測定においても
それぞれのBODは低下することなく、正確な測定を行
うことができる。また、ことに標準液の供給管路におい
てスライムの発生が抑制されており長時間の測定時に有
利である。8- Based on the above calibration, the BOD of each sample solution will be measured continuously. And the standard solutions (Ct) to (C3) have pH
3, each BOD does not decrease even during long-term continuous measurements, making it possible to perform accurate measurements. In addition, the generation of slime is particularly suppressed in the standard solution supply pipeline, which is advantageous during long-term measurements.
実施例1
グμコースーグμタミン酸混合水溶液からなる従来の2
種の濃度の中性水溶液を作製し、1m間室内で放置し、
この間のBODの変化をJIS法に準じて測定した。こ
の結果は第1表の通りであった。Example 1 Conventional method 2 consisting of a mixed aqueous solution of glucose-sug μ-tamic acid
Prepare a neutral aqueous solution of the seed concentration and leave it indoors for 1 m.
Changes in BOD during this time were measured according to the JIS method. The results were as shown in Table 1.
第1表(比較例〕
このように1週間の放置においてBODは減少しておシ
、BODの連続測定用に貯留する標準液としては不適当
であることが判る。Table 1 (Comparative Example) As can be seen, the BOD decreased after being left for one week, and it was found that the solution was unsuitable as a standard solution to be stored for continuous BOD measurement.
これに対し、BOD調製濃度150 w/43 (BO
D夾測値121.’? )に調製しかつ塩酸を添加して
pHを3に調整したグμコースーグμタンン酸混合水溶
液について同様な測定を行ったところ、1週間後のBO
D値は1211と実質的に変らず、BODの連続測定用
の標準液として適していることが判明し友。On the other hand, BOD preparation concentration 150 w/43 (BO
D-measured value 121. '? ) and added hydrochloric acid to adjust the pH to 3. Similar measurements were performed on a mixed aqueous solution of gucose-sug μ tannic acid, and the results showed that the BO
The D value was 1211, which was virtually unchanged, and it was found to be suitable as a standard solution for continuous BOD measurements.
実施例2
第1図に示した装置でBODの連続測定上行った結果、
1週間後に初めて標準液供給管内にスライムが発生する
のが認められたが、その後の増殖も遅く14日程度の連
続測定に支障がないことが判明した。Example 2 Results of continuous measurement of BOD using the device shown in Figure 1.
Slime was first observed to grow inside the standard solution supply tube after one week, but it was found that the growth thereafter was slow and there was no problem with continuous measurement for about 14 days.
辷れに対し、pH1の標準液を用いる以外同様に連続測
定を行ったところ、3日日でスライムが発生し1週間で
測定困難な状助となった。Continuous measurements were performed in the same way except for using a pH 1 standard solution for the slippage, and slime was formed after 3 days, making measurements difficult after 1 week.
実施例3
実施例2の効果をより定量的に確劇する丸めに第2図の
ごときサイホン滴下系を設定し「つまシ度」を測定した
。Example 3 In order to more quantitatively demonstrate the effect of Example 2, a siphon dripping system as shown in FIG. 2 was set up to measure the "degree of crushing".
ここで(21)は連続測定用に用いた内径1關のビニー
ルチューブでありA−B間の長さは2mであり% (2
0)は上水道水であシ、(23)はメスシリンダーであ
る。ここにおいて「つまシ度」Xは:連続測定前の滴下
量(wl/mj−n)×100
の式によシ算出した。Here, (21) is a vinyl tube with an inner diameter of 1 inch used for continuous measurement, and the length between A and B is 2 m, and % (2
0) is tap water, and (23) is a graduated cylinder. Here, the "stiffness" X was calculated using the formula: Dropped amount before continuous measurement (wl/mj-n) x 100.
この結果を第2表に示す。The results are shown in Table 2.
第2表
−このようにこの発明の方法によればスライム障害も抑
制され有利であることが判る。Table 2 - It can be seen that the method of the present invention is advantageous in that it suppresses slime damage.
実施例4
第1図の装置を用いて某下水処理場初沈流出水のEOD
を測定した。ここで中性緩衝液は0.OIM。Example 4 EOD of initial sedimentation effluent of a certain sewage treatment plant using the device shown in Figure 1.
was measured. Here, the neutral buffer is 0. OIM.
1l−
pHマのリン酸塩M衡液を用い、ポンプ(9)による流
量は標準液側、緩衝液側共に1.66 d/minとし
た。A phosphate M balanced solution of 1 l-pH was used, and the flow rate by the pump (9) was 1.66 d/min for both the standard solution side and the buffer solution side.
この測定で得られたBOD値とJIS法によるBOD値
とは測定数26点において相関係数0.88と良好でお
った。このことから、標準液のpHを2〜3程度に下け
ても微生物電極自体への悪影響は生じないことが判る。The BOD value obtained by this measurement and the BOD value determined by the JIS method had a good correlation coefficient of 0.88 at 26 measurement points. This shows that even if the pH of the standard solution is lowered to about 2 to 3, there will be no adverse effect on the microbial electrode itself.
第1図は、この発明のBOD連続測定方法の実施に適し
た測定装置を例示する構成説明図、第2図は実施例3に
おける「つまシ度」を測定する器具を説明する概略図で
ある。
(1)・・・BOD連続測定装置、
(2)・・・微生物電極、(3)・・・隔膜式酸素電極
、(4)・・・微生物層、 (5)・・・測定上p、(
5a)・・・液入口、 (5b)・・・液出口、(9)
・・・ローラーポンプ、(10)・・・採取ポンプ、(
12)・・・エアポンプ、(13)・・・切換パルプ、
12−
(B)・・・中性緩衝液、(S)・・・試料液、(N)
・・・洗浄液、 (Ct)(Cz)(Cm) ・・・
41早液。FIG. 1 is a configuration explanatory diagram illustrating a measuring device suitable for carrying out the BOD continuous measurement method of the present invention, and FIG. 2 is a schematic diagram illustrating an instrument for measuring "Tsumashi degree" in Example 3. . (1)...BOD continuous measuring device, (2)...microbial electrode, (3)...diaphragm oxygen electrode, (4)...microbial layer, (5)...measurement p, (
5a)...Liquid inlet, (5b)...Liquid outlet, (9)
... Roller pump, (10) ... Collection pump, (
12)...Air pump, (13)...Switching pulp,
12- (B)... Neutral buffer solution, (S)... Sample solution, (N)
...Cleaning liquid, (Ct) (Cz) (Cm) ...
41 Early liquid.
Claims (3)
備えた測定用70−セル中に、中性緩衝液の存在下でか
つ曝気処理下、被測定液を管路を通じて供給して微生物
電極の出力を検知し、この出力と、所定の測定数経過値
に測定されるBOD既知の有機物含有標準液供給時の基
準出力、とを比較して被測定液のBODを連続的に測定
することからなシ、上記有機物含有標準液としてpH約
2〜3に調整された有機物水溶液を用いたことを%徴と
するBOD連続測定方法。(1) Into a measurement cell 70 equipped with a microbial electrode consisting of a diaphragm-type oxygen electrode and a microbial membrane, in the presence of a neutral buffer solution and under aeration treatment, a liquid to be measured is supplied through a pipe to the microbial electrode. The BOD of the liquid to be measured is continuously measured by detecting the output of the sample and comparing this output with the standard output when supplying a standard solution containing organic matter whose BOD is known and which is measured over a predetermined number of measurements. KARANASHI: A continuous BOD measurement method in which the organic matter aqueous solution adjusted to pH approximately 2 to 3 is used as the organic matter-containing standard solution.
の水溶液である特許請求の範囲第1項記載の測定方法。(2) The measuring method according to claim 1, wherein the organic substance aqueous solution is a rehydrated product and/or an amino acid aqueous solution.
水溶液である特許請求の範囲第1項又は第2項記載の測
定方法。(3) The measuring method according to claim 1 or 2, wherein the organic substance aqueous solution is a glucose-glutamic acid mixed aqueous solution.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58203155A JPS6093952A (en) | 1983-10-28 | 1983-10-28 | Continuous measurement of bod |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58203155A JPS6093952A (en) | 1983-10-28 | 1983-10-28 | Continuous measurement of bod |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6093952A true JPS6093952A (en) | 1985-05-25 |
Family
ID=16469337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58203155A Pending JPS6093952A (en) | 1983-10-28 | 1983-10-28 | Continuous measurement of bod |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6093952A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04136760A (en) * | 1990-09-28 | 1992-05-11 | Haimo Kk | Method for preventing generation of slime of piping in quality analyser of water |
JPH056363U (en) * | 1991-07-10 | 1993-01-29 | 日新電機株式会社 | BOD standard solution storage device |
KR100483587B1 (en) * | 2002-10-30 | 2005-04-19 | 한국바이오시스템(주) | BOD Analyzer using Biochemical Fuel Cells with installed Membrane-Electrode Assembly |
KR100502885B1 (en) * | 2002-05-15 | 2005-07-25 | 한국과학기술연구원 | Method for Monitoring BOD of Waste Water Continuously Using Microbial Fuel Cell |
CN105486830A (en) * | 2016-01-08 | 2016-04-13 | 深圳市清时捷科技有限公司 | Online water quality project alternating detection device and method thereof |
JP2021507246A (en) * | 2017-12-21 | 2021-02-22 | シーメンス・ヘルスケア・ダイアグノスティックス・インコーポレイテッド | Composition containing stabilized oxygen and method for producing the same |
-
1983
- 1983-10-28 JP JP58203155A patent/JPS6093952A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04136760A (en) * | 1990-09-28 | 1992-05-11 | Haimo Kk | Method for preventing generation of slime of piping in quality analyser of water |
JPH056363U (en) * | 1991-07-10 | 1993-01-29 | 日新電機株式会社 | BOD standard solution storage device |
KR100502885B1 (en) * | 2002-05-15 | 2005-07-25 | 한국과학기술연구원 | Method for Monitoring BOD of Waste Water Continuously Using Microbial Fuel Cell |
KR100483587B1 (en) * | 2002-10-30 | 2005-04-19 | 한국바이오시스템(주) | BOD Analyzer using Biochemical Fuel Cells with installed Membrane-Electrode Assembly |
CN105486830A (en) * | 2016-01-08 | 2016-04-13 | 深圳市清时捷科技有限公司 | Online water quality project alternating detection device and method thereof |
JP2021507246A (en) * | 2017-12-21 | 2021-02-22 | シーメンス・ヘルスケア・ダイアグノスティックス・インコーポレイテッド | Composition containing stabilized oxygen and method for producing the same |
US11549936B2 (en) | 2017-12-21 | 2023-01-10 | Siemens Healthcare Diagnostics Inc. | Compositions comprising stabilized oxygen and methods of forming the same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5503720A (en) | Process for the quantitative determination of electrochemically reducible or oxidizable substances, particularly peracetic acid mixed with other oxidizing substances | |
JPH0785072B2 (en) | Toxic substance detection device and water quality monitoring system using the same | |
JPS6093952A (en) | Continuous measurement of bod | |
JP4999742B2 (en) | Toxic substance detection method and toxic substance detection apparatus | |
Yoshioka et al. | Evaluation of the test method “activated sludge, respiration inhibition test” proposed by the OECD | |
JP3664888B2 (en) | BOD biosensor measuring device | |
JP3721087B2 (en) | Biosensor type abnormal water quality detection device | |
JPH08145981A (en) | Bod measuring instrument | |
JPS59222753A (en) | Measuring apparatus using microorganism electrode | |
CN115639333A (en) | Method for detecting ammonia nitrogen content by using nitration biological reaction | |
JP5347711B2 (en) | Detection method of harmful substances in water | |
JPH0735741A (en) | Bod measuring equipment | |
JPH0637324Y2 (en) | Measuring device using microbial electrode | |
JP2001228110A (en) | Biosensor-applied water quality meter | |
JP2004037273A (en) | Water analyzing method and device | |
JP3077461B2 (en) | How to monitor hazardous substances in water | |
JPH0545352A (en) | Bod measuring apparatus | |
JPH07101217B2 (en) | BOD measurement method | |
JP3032831B2 (en) | Hazardous substance detection device | |
JPS5852558A (en) | Ammonia densitometer | |
JPH04502275A (en) | Continuous monitoring of effluent | |
KR100363438B1 (en) | Continuous activated sludge respiration and short term BOD analyzer based on tubular flow respiration chamber | |
JP2001165893A (en) | Detecting method for toxic substance in environmental water | |
Pratt et al. | Comparison of methods for the determination of KL a O2 for respirometric measurements | |
CN117448415A (en) | On-line monitoring method, system and application of biotoxicity of groundwater quality |