CN102798650A - Method and device for detecting biochemical oxygen demand - Google Patents

Method and device for detecting biochemical oxygen demand Download PDF

Info

Publication number
CN102798650A
CN102798650A CN2012103130385A CN201210313038A CN102798650A CN 102798650 A CN102798650 A CN 102798650A CN 2012103130385 A CN2012103130385 A CN 2012103130385A CN 201210313038 A CN201210313038 A CN 201210313038A CN 102798650 A CN102798650 A CN 102798650A
Authority
CN
China
Prior art keywords
oxygen
oxygen electrode
water sample
electrode
obtains
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.)
Granted
Application number
CN2012103130385A
Other languages
Chinese (zh)
Other versions
CN102798650B (en
Inventor
刘长宇
董绍俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201210313038.5A priority Critical patent/CN102798650B/en
Publication of CN102798650A publication Critical patent/CN102798650A/en
Application granted granted Critical
Publication of CN102798650B publication Critical patent/CN102798650B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention provides a detection method for biochemical oxygen demand, which comprises the following steps: a), carrying out microculture on a water sample containing microorganisms to obtain a microbial film; b), enabling a water sample to be detected to sequentially pass through a first oxygen electrode, the microbial film in the step (a) and a second oxygen electrode, and obtaining first oxygen current and second oxygen current of the water sample to be detected through the detection of the oxygen electrodes; c), obtaining first oxygen content and second oxygen content of the water sample to be detected according to a calibration curve of the first oxygen current and the predetermined first oxygen electrode and a calibration curve of the second oxygen current and the predetermined second oxygen electrode; d), obtaining a difference value of the oxygen content of the water sample to be detected according to the first oxygen content and the second oxygen content of the water sample to be detected obtained in the step (c); and e), obtaining the biochemical oxygen demand of the sample to be detected according to the difference value of the oxygen content of the water sample to be detected in the step (d) and a predetermined standard curve. The oxygen content change obtained by the detected method can reflect the degree that a water body is polluted and play a role of early warning.

Description

A kind of method and device that detects biochemical oxygen demand
Technical field
The present invention relates to environmental protection technical field, relate in particular to a kind of method and device that detects biochemical oxygen demand.
Background technology
Biochemical oxygen demand (BOD) is meant the material that some can be oxidized in the microorganism decomposition water, the amount of the dissolved oxygen DO that particularly organic contaminant consumed.BOD is the important indicator of analyzing water body organic contaminant content, is one of most important parameter in the conventional water quality detection, and organic pollution materials is many more in the high more explanation water of its value, pollutes also just serious more.The standard method of measuring BOD in the world is that cultivation on the five (is BOD 5Method), its detailed process is: water sample to be measured is adopted the broad-spectrum micro-organisms inoculation, and dilution by a certain percentage, lucifuge constant temperature culture 5 days is according to the change calculations bod of dissolved oxygen content before and after cultivating.BOD 5Method adopts broad-spectrum micro-organisms, has realized organic efficient degradation, has farthest overcome the analysis result difference that causes because of the sample organism kinds and has generally been accepted.But in order to obtain accurate analytical results, BOD 5Method often needs many gradient dilutions, and length consuming time, big, the poor repeatability of workload, and can not in time reflect the variation of water quality, thereby can not realize the online detection of water quality.
In order to overcome BOD 5Many weak points of method disclose the method for multiple fast detecting BOD in the prior art.These methods all are to be purpose and with BOD to shorten detection time 5The method detected value is a benchmark.Like microbial membrane sensor method, microbial film reactor method, microbiological fuel cell method etc., wherein ripe with the technical development of microbiological sensor method, make that its application is more extensive.
The microbiological sensor method at first adopts physics or chemical embedding method to process biological membrane cultured microorganism, and makes said biological membrane be close to the surface of oxygen electrode; The biological membrane of being close to oxygen electrode surface runs into when containing organic water sample to be measured; Microbial respiratory effect in the biological membrane strengthens; Oxygen consumption increases, thereby makes the oxygen content reduction that arrives the water sample to be measured of oxygen electrode through biological membrane, thereby obtains the biochemical oxygen demand of water sample to be measured.This method is to utilize the power of microbial respiratory effect to be directly proportional with organic content, thereby calculates the BOD content of water sample.Adopt the biological membrane of embedding method preparation, increased dissolved oxygen DO and organism diffusional resistance, prolonged the response time at biofilm surface; Simultaneously, this method need adopt a kind of blank solution that a reference value of oxygen content is provided.Before measuring samples, need to measure earlier the dissolved oxygen DO of blank solution, and think that this dissolved oxygen levels is consistent with the dissolved oxygen levels of water sample to be measured.When sample flow is crossed microbial film, just can calculate the difference that the electrode surface dissolved oxygen DO changes.Therefore; Before measuring, need sample and blank solution be carried out the constant temperature processing, and the two is carried out the effective saturation of the air; So that the two dissolved oxygen content is consistent as far as possible; Make the BOD content of water sample not provide in real time, can not react organic situation of change in the water body timely, can not in the urgent early warning of water pollution, play an important role.
Summary of the invention
The object of the present invention is to provide a kind of method and device that detects biochemical oxygen demand; Method provided by the invention can realize the real time on-line monitoring to the water body biochemical oxygen demand; Can in time reflect organic variation in the water body, water pollution played the effect of urgent early warning.
The invention provides a kind of method that detects biochemical oxygen demand, may further comprise the steps:
The water sample that a) will contain microorganism carries out microbe culture, obtains microbial film;
B) microbial film and second oxygen electrode that water sample to be measured are obtained through first oxygen electrode, said step a) successively, oxygen electrode detects said water sample to be measured, obtains the first oxygen electric current and the second oxygen electric current;
C), obtain first oxygen content and second oxygen content of said water sample to be measured according to the said first oxygen electric current and the calibration curve of predetermined first oxygen electrode, the said second oxygen electric current calibration curve with predetermined second oxygen electrode;
First oxygen content and second oxygen content of the water sample to be measured that d) obtains according to said step c) obtain the difference of said water sample oxygen content to be measured;
The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.
Preferably, the calibration curve of first oxygen electrode obtains according to following step in the said step c):
The water of serial oxygen content is passed through first oxygen electrode respectively, obtain the first oxygen current value of the water of serial oxygen content respectively;
According to the oxygen content of the first oxygen current value of the water of the serial oxygen content that obtains and corresponding water thereof, obtain the calibration curve of first oxygen electrode;
The calibration curve of second oxygen electrode obtains according to following step in the said step c):
The water of serial oxygen content is passed through second oxygen electrode respectively, obtain the second oxygen current value of the water of serial oxygen content respectively;
According to the oxygen content of the second oxygen current value of the water of the serial oxygen content that obtains and corresponding water thereof, obtain the calibration curve of second oxygen electrode.
Preferably, the typical curve of the microbial film in the said step e) obtains according to following step:
With the microbial film and second oxygen electrode that the standard solution of series concentration obtains through first oxygen electrode, said step a) successively, oxygen electrode detects said standard solution, obtains the first oxygen electric current and the second oxygen electric current of the standard solution of said series concentration;
Calibration curve based on said first oxygen electric current and said first oxygen electrode; Obtain the first corresponding oxygen content of the said first oxygen electric current, the calibration curve of said first oxygen electrode is the oxygen content of the water sample measured of said first oxygen electrode and the relation curve of oxygen current value;
Calibration curve based on said second oxygen electric current and said second oxygen electrode; Obtain the second corresponding oxygen content of the said second oxygen electric current, the calibration curve of said second oxygen electrode is the oxygen content of the water sample measured of said second oxygen electrode and the relation curve of oxygen current value;
According to said first oxygen content and second oxygen content, the oxygen content of standard solution that obtains said series concentration respectively is poor;
According to the concentration of said oxygen content difference and corresponding standard solution thereof, obtain the typical curve of microbial film.
Preferably, said step a) is specially:
A1) will contain the microorganism water sample and carry out the elementary cultivation of microorganism, obtain elementary microbial film;
The standard solution that a2) will contain saturated air is successively through first oxygen electrode, said step a1) the elementary microbial film and second oxygen electrode that obtain, oxygen electrode detects first oxygen content and second oxygen content that obtains said standard solution;
A3) repeating step a1) and step a2) described process, first oxygen content of the standard solution that obtains until detection and the difference of second oxygen content are stable, accomplish the cultivation of microorganism, obtain microbial film.
Preferably, said standard solution is one or more in glucose solution, glutamic acid solution, glucose and glutamic acid mixed solution or the sucrose solution.
Preferably, the temperature of microbe culture is 20 ℃ ~ 45 ℃ in the said step a).
Preferably, the time of microbe culture is 20 h ~ 300 hours in the said step a).
Preferably, the microbe culture in the said step a) is for carrying out microbe culture in reactor.
Preferably, said reactor is a tubulose;
The material of said reactor is glass, ethylene-vinyl acetate copolymer, plastics, nylon, quartz or silica gel;
The length of said reactor is 30.0cm ~ 420.0cm;
The internal diameter of said reactor is 1.0mm ~ 4.0mm.
The invention provides a kind of device that detects biochemical oxygen demand, comprise sampling device, first oxygen electrode, reactor, second oxygen electrode, oxygen current sensing means and constant temperature water bath apparatus;
The outlet of said sampling device links to each other with the injection port of said first oxygen electrode;
The outlet of said first oxygen electrode links to each other with the injection port of said reactor;
The outlet of said reactor links to each other with the injection port of said second oxygen electrode;
Said first oxygen electrode, reactor and second oxygen electrode place said thermostat;
Said oxygen current sensing means links to each other with said second oxygen electrode with said first oxygen electrode, is used to detect the oxygen electric current at said first oxygen electrode place and the said second oxygen electrode place.
The invention provides a kind of detection biochemical oxygen demand method, may further comprise the steps: the water sample that a) will contain microorganism carries out microbe culture, obtains microbial film; B) microbial film and second oxygen electrode that water sample to be measured are obtained through first oxygen electrode, said step a) successively, oxygen electrode detects said water sample to be measured, obtains the first oxygen electric current and the second oxygen electric current of said water sample to be measured; C), obtain first oxygen content and second oxygen content of said water sample to be measured according to the said first oxygen electric current and the calibration curve of predetermined first oxygen electrode, the said second oxygen electric current calibration curve with predetermined second oxygen electrode; First oxygen content and second oxygen content of the water sample to be measured that d) obtains according to said step c) obtain the difference of said water sample oxygen content to be measured; The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.Method provided by the invention adopts two oxygen electrodes; Detect the initial oxygen content of water sample to be measured and the oxygen content after the degraded of process microbial film respectively; I.e. first oxygen content and second oxygen content; Thereby the oxygen content that obtains water sample to be measured is poor, according to the oxygen content difference that obtains and the typical curve of reservation, obtains the biochemical oxygen demand of water sample to be measured.Method provided by the invention need not to provide blank solution, also need not again water sample to be measured to be carried out the saturation of the air, has simplified the design and the operation steps of instrument, according to oxygen electrode E 1With oxygen electrode E 2The oxygen content change of the water sample of surveying to be measured; Directly draw the biochemical oxygen demand of water sample to be measured; In case organic content changes in the water sample to be measured; The oxygen content change that detection obtains can in time draw water sample biochemical oxygen demand to be measured, reflects the contaminated degree of water sample, thereby has realized the real-time monitoring to water sample biochemical oxygen demand to be measured.
Method provided by the invention need not to adopt blank sample, and need not water sample to be measured is carried out the saturation of the air, has solved previous methods empty sample dissolution oxygen and water sample dissolved oxygen DO to be measured because of the experimental error that the salt ionic concentration difference causes, and makes measurement result more accurate.And; Method provided by the invention need not to use buffer solution, solved pollution problem and the solution preparation of using buffer solution to bring and prepared process with pure water, solved the problem of using tap water need regular supplies; Labor savings can realize the on-line monitoring that nobody stands fast at.
Description of drawings
The schematic representation of apparatus of the detection biochemical oxygen demand that Fig. 1 provides for the embodiment of the invention;
The calibration curve of the oxygen electrode that Fig. 2 obtains for the embodiment of the invention 2;
The typical curve of the microbial film reactor that Fig. 3 obtains for the embodiment of the invention 3;
The monitoring result of the real-time water sample BOD that Fig. 4 obtains for the embodiment of the invention 5.
Embodiment
The invention provides a kind of method that detects biochemical oxygen demand, may further comprise the steps:
The water sample that a) will contain microorganism carries out microbe culture, obtains microbial film;
B) microbial film and second oxygen electrode that water sample to be measured are obtained through first oxygen electrode, said step a) successively, oxygen electrode detects said water sample to be measured, obtains the first oxygen electric current and the second oxygen electric current of said water sample to be measured;
C), obtain first oxygen content and second oxygen content of said water sample to be measured according to the said first oxygen electric current and the calibration curve of predetermined first oxygen electrode, the said second oxygen electric current calibration curve with predetermined second oxygen electrode;
First oxygen content and second oxygen content of the water sample to be measured that d) obtains according to said step c) obtain the difference of said water sample oxygen content to be measured;
The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.
The present invention provides a kind of method that detects biochemical oxygen demand, and method provided by the invention is passed through first oxygen electrode with water sample to be measured earlier, obtains the initial oxygen content of water sample to be measured, i.e. first oxygen content of water sample to be measured; Then it is carried out microbial degradation through microbial film; And then the water sample to be measured that will pass through degraded passes through second oxygen electrode; Detection obtains the oxygen content of water sample to be measured after microbial degradation, i.e. second oxygen content of water sample to be measured, thus obtain the oxygen content difference of water sample to be measured; According to the typical curve of the microbial film of oxygen content difference that obtains and reservation, obtain the biochemical oxygen demand of water sample to be measured.Method provided by the invention need not to provide blank solution again; Need not water sample to be measured is carried out the saturation of the air; The testing process of simplifying; The variation that can directly draw the water sample biochemical oxygen demand according to the oxygen change in current that obtains can realize the real-time online of water sample biochemical oxygen demand is detected, thereby forewarning function is played in water pollution.
In the present invention, said first oxygen electrode and second oxygen electrode are used for detecting the initial oxygen electric current and the oxygen electric current after the microbial film degraded of water sample respectively, in order to describe the aspect, in following argumentation, first oxygen electrode are defined as oxygen electrode E 1, second oxygen electrode is defined as E 2Oxygen electrode E 1The first oxygen electric current that detection obtains is defined as the oxygen electric current I 1, oxygen electrode E 2The oxygen electric current that detection obtains is defined as the oxygen electric current I 2According to the calibration curve of the oxygen current value that obtains with the oxygen electrode of being scheduled to, obtain the oxygen content of water sample, in this application, oxygen electrode E 1The oxygen content of the water sample that detection obtains i.e. first oxygen content is defined as [O 2] 1, oxygen electrode E 2The oxygen content of the water sample that detection obtains i.e. second oxygen content is defined as [O 2] 1
The water sample that the present invention at first will contain microorganism carries out microbe culture, obtains microbial film.The water sample that contains microorganism that the present invention adopts is preferably the water sample that contains microorganism that comes from occurring in nature; As can adopt active sludge, surface water or contain the industrial waste water of microorganism; Thereby kept the wherein intrinsic character of microorganism; The microorganism that obtains is more stable, and the kind of the microorganism in the microbial film that obtains has variation, in the process that organism is degraded, can not influence its degradation effect owing to organic kind is different; Can realize more effectively organic non-selective degraded, thereby make testing result more accurate.The present invention preferably carries out the cultivation of microorganism under 20 ℃ ~ 45 ℃ condition; It is that the cultivation of microorganism provides suitable temperature conditions that the present invention preferably adopts the mode of water bath with thermostatic control; Under said 20 ℃ ~ 45 ℃ temperature conditions; The present invention preferably will contain the microorganism water sample and carry out the saturation of the air, and the microorganism water sample that contains that contains saturated air that obtains is flow through oxygen electrode E successively 1, microbe carrier and oxygen electrode E 2The surface, oxygen electrode E 1Detection obtains the said [O that contains the microorganism water sample that contains saturated air 2] 1, the said microorganism that contains in the microorganism water sample is adsorbed gradually on the surface of said carrier and utilizes airborne oxygen to carry out the metabolism breeding, finally forms microbial film, oxygen electrode E 2Detection obtains the said [O that contains the microorganism water sample that contains saturated air 2] 2The present invention crosses the conditions such as flow velocity on microbe carrier surface and does not have special limitation the said microorganism aqueous sample stream that contains that contains saturated air; In the present invention; The flow velocity of microorganism aqueous sample stream through microbe carrier surface that contain of said saturated air is preferably 0.1mL/min ~ 10.0mL/mim, 1mL/mim ~ 5mL/mim more preferably, in the present invention; The temperature of said water bath with thermostatic control is preferably 20 ℃ ~ 45 ℃, more preferably 30 ℃ ~ 37 ℃.
The present invention is when carrying out the microbial film cultivation; Preferably the said microorganism water sample that contains is carried out microbe culture in reactor; Microorganism grows on the inwall of reactor and breeds, thereby on the inwall of reactor, forms microbial film, obtains the microbial film reactor.The present invention crosses reactor with the said microorganism water sample continuous stream that contains, and the said microorganism that contains in the microorganism water sample can be adsorbed on inwall and the growth and the breeding of said reactor, thereby obtains the microbial film reactor.The present invention is to the shape of said reactor, and parameters such as material and size do not have special limitation, adopts reactor well known to those skilled in the art to get final product.In the present invention, the material of said reactor can be for glass, also can be silica gel, can also be plastics, nylon, quartz or ethylene-vinyl acetate copolymer, and the material of reactor according to the invention is preferably glass; Said reactor can be tubulose, also can be the hollow prism shape, and the shape of reactor according to the invention is preferably tubulose; The length of reactor according to the invention is preferably 30.0cm ~ 420.0cm, and more preferably 50.0cm ~ 300.0cm most preferably is 75.0cm ~ 150.0cm; The internal diameter of said reactor is preferably 1.0mm ~ 4.0mm.
In order to make reactor wall be more suitable for absorption and the growth of microorganism, help the structure of microbial film, the present invention preferably carries out chemical modification to the inwall of said reactor, obtains having the reactor of roughening inwall.The present invention does not have special limitation to the method for said chemical modification, adopts the technical scheme of roughened well known to those skilled in the art to get final product.The present invention can adopt hydrofluorite that said reactor is carried out etching, obtains having the reactor of roughening inwall; Also can adopt strong base solution that said reactor wall is corroded, obtain having the reactor of roughening inwall; Can also on the inwall of said reactor, modify the special groups like hydroxyl, carboxyl or nanostructured etc., obtain having the reactor of roughening inwall, said nanostructured is preferably CNT.
In the process that microorganism is cultivated, the time of carrying out microbe culture according to the invention, there was certain difference the time of cultivation along with the source that contains the microorganism water sample is different.The present invention can be according to the incubation time of how much controlling microbial film that contains the amount that contains microorganism in the microorganism water sample; If the amount that contains the microorganism in the microorganism water sample that adopts is less; Then adopt the incubation time of long microorganism; If it is more to contain the amount of the microorganism in the microorganism water sample, the time of then carrying out microbe culture can shorten, as long as can access the saturated microbial film of absorption.In the present invention, the time that said microbial film is cultivated is preferably 20 h ~ 300 hours, and more preferably 30 h ~ are 250 hours, most preferably are 35 h ~ 150 hours.
When the present invention carries out microbe culture; With the said inside surface that contains the microorganism aqueous sample stream through microbe carrier; Obtain microbial film; When containing the microorganism aqueous sample stream through the inside surface of said carrier, said microbe carrier can adsorb the microorganism of some said, flows through when having adsorbed some microorganism carriers when containing organic water sample to be measured or standard solution; These microorganisms organism in said water sample to be measured or the standard solution of can degrading causes reducing from the terminal water sample to be measured after elementary microbial film degraded that flows out of said microbe carrier or the COD of standard solution.But cultivate the less stable of the microbial film that obtains through microbial film; Because when the organism in described water sample to be measured or the standard solution is degraded by microbial film; Microorganism still can grow on elementary microbial film reactor wall; The amount of microbial film constantly to be increased in the process of the cultivation of carrying out microbial film, therefore to have the saturated microorganism of absorption in the microbial film that obtains in order making, the present invention preferably carries out the cultivation of microbial film according to following steps:
A1) will contain the microorganism water sample and carry out the elementary cultivation of microorganism, obtain elementary microbial film;
The standard solution that a2) will contain saturated air is successively through oxygen electrode E 1, said step a1) the elementary microbial film and the oxygen electrode E that obtain 2, oxygen electrode detects the [O that obtains said standard solution 2] 1[O 2] 2
A3) repeating step a1) and step a2) described process, [the O of the standard solution that obtains until detection 2] 1[O 2] 2Difference stable, accomplish the cultivation of microorganism, obtain microbial film.
In order to obtain adsorbing the saturated microbial film of microorganism; The present invention is at first under the condition of the water bath with thermostatic control that technique scheme provides; Under promptly 20 ℃ ~ 45 ℃ the condition; The said microorganism water sample that contains is carried out the saturation of the air; The microorganism water sample that contains that obtains containing saturated air is flow through from the inside surface of microbe carrier continuously, make saidly to contain microorganism in the microorganism water sample in the inside surface absorption of said carrier and generate elementary microbial film, be adsorbed with elementary microorganism carrier and be elementary microbial film reactor.The present invention does not have special limitation to the method for the said saturation of the air, adopts technical scheme of carrying out the saturation of the air well known to those skilled in the art to get final product; The present invention does not have special limitation to the said flow velocity of microorganism aqueous sample stream through the microbe carrier surface that contain that contains saturated air; Adopt the flow velocity of the water sample that adopts in the detection water body biochemical oxygen demand process well known to those skilled in the art to get final product; In the present invention; The said flow velocity of microorganism aqueous sample stream through the microbe carrier surface that contain that contains saturated air is preferably 0.1mL/min ~ 10.0mL/mim, more preferably 1mL/mim ~ 5mL/mim; The said time of carrying out the elementary cultivation of microorganism is preferably 12 h ~ 150 hours.
After obtaining elementary microbial film, the present invention preferably will contain the blank aqueous sample stream of saturated air through said elementary microbial film, and said elementary microbial film is cleaned, and remove wherein residual organic.In to the said just process that level microbe cleans, said blank water sample is one or more in tap water, well water, precipitation or the underground water, is preferably in tap water or the underground water one or both.In the present invention, said blank aqueous sample stream is preferably 0.5mL/min ~ 10.0mL/min through the flow velocity of said elementary microbial film, more preferably 1.0mL/min ~ 3.0mL/min.
After the cleaning of completion to said elementary microbial film, the present invention is flow through oxygen electrode E successively with standard solution 1, said elementary microbial film and oxygen electrode E 2, oxygen electrode detects the [O that obtains said standard solution 2] 1[O 2] 2In this process, the organism in the microbial degradation standard solution in the elementary microbial film consumes dissolved oxygen DO wherein, thereby makes [the O that detection obtains 2] 2Reduce.
In the present invention, said standard solution is preferably international OECD specified standard solution (OECD solution), glucose solution, glutamic acid solution, glucose and glutamic acid mixed solution or sucrose solution.More preferably glucose solution or glucose and glutamic acid mixed solution most preferably are glucose and glutamic acid mixed solution, i.e. glucose glutamic acid (GGA) solution; Said OECD solution is the standard solution that uses in the BOD determination process of recommending in the standard of international OECD, and said OECD solution comprises beef extract, peptone and urea etc.In the present invention; Said standard solution all adopts in the described tap water of technique scheme, well water, precipitation or the underground water one or more to prepare and dilute; The biochemical oxygen demand concentration of standard solution of the present invention is meant the biochemical oxygen demand content of this standard solution under the finite concentration, and its unit is mg O 2/ L.The biochemical oxygen demand concentration of the standard solution that the present invention selected for use is preferably 1.0mg O 2/ L ~ 50mg O 2/ L.In the present invention, the flow velocity that said standard solution flows through said elementary microbial film is preferably 0.5mL/min ~ 10.0mL/min, more preferably 1.0mL/min ~ 3.0mL/min.
In order to obtain adsorbing the saturated microbial film of microorganism, repeat the elementary cultivation of microbial film and the step that standard solution is detected according to technique scheme, [the O of the standard solution that obtains until detection 2] 1[O 2] 2[O with the same standard solution that records in the step before 2] 1[O 2] 2Basically identical, this explanation microorganism is saturated in the absorption of reactor inside surface, and this moment, the cultivation of microbial film was accomplished, and obtained stable microbial film.
After obtaining stable microbial film, the present invention passes through oxygen electrode E successively with water sample to be measured 1, the technique scheme microbial film and the oxygen electrode E that obtain 2, oxygen electrode detects said water sample to be measured, obtains the oxygen electric current I of said water sample to be measured 1With the oxygen electric current I 2The present invention at first passes through oxygen electrode E with water sample to be measured 1, detect the oxygen electric current I that obtains said water sample to be measured 1, with its microbial film that obtains through technique scheme again, microorganism is wherein degraded to the organism in the water sample to be measured then, is partly dissolved oxygen thereby consume, and the water sample to be measured that will pass through degraded then is through oxygen electrode E 2, detect the oxygen electric current I that obtains said water sample to be measured 2The present invention does not have special limitation to the detection method of oxygen electric current, and the technical scheme that adopts employing oxygen electrode well known to those skilled in the art to detect water sample oxygen electric current gets final product.The present invention preferably adopts electrochemical workstation to link to each other with oxygen electrode, detects the oxygen electric current I that obtains water sample to be measured 1With the oxygen electric current I 2
Obtain the oxygen electric current I 1With the oxygen electric current I 2After, the present invention is according to said oxygen electric current I 1With the oxygen electrode E that subscribes 1Calibration curve, said oxygen electric current I 2With the oxygen electrode E that subscribes 2Calibration curve, obtain [the O of said water sample to be measured 2] 1[O 2] 2
In order to obtain [the O of said water sample to be measured 2] 1, the present invention at first sets up oxygen electrode E 1Calibration curve, said oxygen electrode E 1Calibration curve preferably obtain according to following method:
The water of serial oxygen content is passed through oxygen electrode E respectively 1, obtain the water oxygen electric current I of serial oxygen content respectively 1Value;
Oxygen electric current I according to the water of the serial oxygen content that obtains 1The oxygen content of the water of value and correspondence thereof obtains oxygen electrode E 1Calibration curve.
The present invention at first prepares the water of serial oxygen content, and the present invention does not have special limitation to the method for the water of the serial oxygen content of said preparation, adopts the technical scheme of the water of the serial oxygen content of preparation well known to those skilled in the art to get final product.The present invention preferably adopts the mixed gas that comprises nitrogen and oxygen that water is carried out the saturation of the air, obtains the water that contains dissolved oxygen DO of series concentration according to saturated degree.After obtaining containing the water of dissolved oxygen DO, the present invention detects the content of dissolved oxygen DO wherein, and the present invention does not have special limitation to the method for said detection dissolved oxygen content, adopts the method for detection dissolved oxygen content well known to those skilled in the art to get final product.The present invention does not have special limitation to the ratio of nitrogen in the mixed gas and oxygen, can make to contain oxygen in the water and get final product; For oxygen content is 0 water, i.e. the acquisition of oxygen-free water, the present invention preferably add excessive reductive agent in water; Consume dissolved oxygen DO wherein, thereby obtain oxygen-free water, in the present invention; Said reductive agent is preferably sodium sulphite and cobalt chloride, and said water is preferably deionized water.
After obtaining the water of serial oxygen content, the present invention passes through oxygen electrode E with the water of said serial oxygen content respectively 1, detection obtains the oxygen electric current I of the water of serial oxygen content respectively 1, according to the oxygen electric current I that obtains 1And the oxygen content of corresponding water, obtain oxygen electrode E 1Calibration curve, i.e. oxygen electrode E 1The oxygen electric current that detection obtains and the relation curve of oxygen content.
In order to obtain [the O of said water sample to be measured 2] 2, the present invention sets up oxygen electrode E 2Calibration curve, i.e. oxygen electrode E 2The oxygen electric current that detection obtains and the relation curve of oxygen content, said oxygen electrode E 2Calibration curve preferably according to the described oxygen electrode E of technique scheme 1The preparation method of calibration curve is set up.
Obtain [the O of water sample to be measured 2] 1[O 2] 2After, because through the water sample to be measured after the microbial degradation, dissolved oxygen DO wherein is consumed a part, makes [the O that obtains 2] 1Than [O 2] 2Low, the oxygen content of the said water sample to be measured that the present invention calculates is poor.
After obtaining the oxygen content of said water sample to be measured, the present invention obtains the biochemical oxygen demand of said water sample to be measured according to the oxygen content of said water sample to be measured and the typical curve of the microbial film of being scheduled to.In the present invention, said typical curve preferably obtains according to following method:
The standard solution of series concentration is passed through oxygen electrode E successively 1, the technique scheme microbial film and the oxygen electrode E that obtain 2, oxygen electrode detects said standard solution, obtains the oxygen electric current I of the standard solution of said series concentration 1With the oxygen electric current I 2
According to said oxygen electric current I 1With said oxygen electrode E 1Calibration curve, obtain said oxygen electric current I 1Corresponding [O 2] 1, said oxygen electrode E 1Calibration curve be said oxygen electrode E 1The oxygen content of the water sample of measuring and the relation curve of oxygen current value;
According to said oxygen electric current I 2With said oxygen electrode E 2Calibration curve, obtain said oxygen electric current I 2Corresponding [O 2] 2, said oxygen electrode E 2Calibration curve be said oxygen electrode E 2The oxygen content of the water sample of measuring and the relation curve of oxygen current value;
According to said [O 2] 1[O 2] 2, the oxygen content of standard solution that obtains said series concentration respectively is poor;
According to the concentration of said oxygen content difference and corresponding standard solution thereof, obtain the typical curve of microbial film.
The present invention at first prepares the standard solution of a series of biochemical oxygen demand concentration, and the present invention does not have special limitation to the method for preparing standard solution, adopts the technical scheme of preparing standard solution well known to those skilled in the art to get final product.In the present invention, the solvent of said preparing standard solution is preferably one or more in tap water, well water, precipitation or the underground water, is preferably tap water.The present invention does not have special limitation to the kind of said standard solution; Adopt the standard solution that detects as biochemical oxygen demand well known to those skilled in the art to get final product; In the present invention, said standard solution is preferably international OECD specified standard solution (OECD solution), glucose solution, glutamic acid solution, glucose and glutamic acid mixed solution or sucrose solution.More preferably glucose solution or glucose and glutamic acid mixed solution most preferably are glucose and glutamic acid mixed solution, i.e. the glucose glutamic acid solution; Said OECD solution is the standard solution that uses in the BOD determination process of recommending in the standard of international OECD, and said OECD solution comprises beef extract, peptone and urea.The biochemical oxygen demand concentration of standard solution of the present invention is meant the biochemical oxygen demand content of this standard solution under the finite concentration, and its unit is mg O 2/ L.In the present invention, the biochemical oxygen demand concentration of said standard solution is preferably 0.5mg O 2/ L ~ 100.0mg O 2/ L, more preferably 1.0mg O 2/ L ~ 50.0mg O 2/ L.
After obtaining the standard solution of series concentration, the present invention at first passes through oxygen electrode E with it 1, detect the oxygen electric current I that obtains said standard solution 1The microbial film that then standard solution of said series concentration is prepared through technique scheme again, microorganism is wherein degraded to the organism in the standard solution, makes the content of dissolved oxygen DO wherein descend; And then the standard solution through degraded that will obtain passes through oxygen electrode E 2, the oxygen electric current I of the standard solution of the said series concentration that detection obtains 2Obtain the oxygen electric current I of standard solution 1With the oxygen electric current I 2After, the present invention is according to said oxygen electric current I 1The oxygen electrode E that obtains with technique scheme 1Calibration curve, obtain [the O of said standard solution 2] 1, according to said oxygen electric current I 2The oxygen electrode E that obtains with technique scheme 2Calibration curve, obtain [the O of said standard solution 2] 2The present invention is again according to the [O of the standard solution that obtains 2] 1[O 2] 2, the oxygen content that calculates said standard solution is poor.
After obtaining the oxygen content difference of said standard solution, the present invention is an ordinate with said oxygen content difference preferably, is horizontal ordinate with the BOD concentration of standard solution, obtains the typical curve of microbial film.
After obtaining typical curve, the oxygen content difference of the said water sample to be measured that the present invention obtains according to technique scheme calculates the biochemical oxygen demand of said water sample to be measured.
The present invention provides a kind of method that detects biochemical oxygen demand, may further comprise the steps: the water sample that a) will contain microorganism carries out microbe culture, obtains microbial film; B) water sample to be measured is passed through oxygen electrode E successively 1, said the step a) microbial film and the oxygen electrode E that obtain 2, oxygen electrode detects water sample to be measured, obtains the oxygen electric current I of said water sample to be measured 1With the oxygen electric current I 2C) according to said oxygen electric current I 1With predetermined oxygen electrode E 1Calibration curve, said oxygen electric current I 2With predetermined oxygen electrode E 2Calibration curve, obtain [the O of said water sample to be measured 2] 1[O 2] 2[the O of the water sample to be measured that d) obtains according to said step c) 2] 1[O 2] 2, obtain the difference of said water sample oxygen content to be measured; The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.The present invention at first passes through oxygen electrode E with water sample to be measured 1, detect [the O that obtains said water sample to be measured 2] 1And then with it through microbial film, microorganism is wherein degraded to the organism in the water sample to be measured, and consumes dissolved oxygen DO wherein, makes the content of dissolved oxygen DO descend; And then will obtain passing through oxygen electrode E through the water sample to be measured of microbial degradation 2, detect [the O that obtains water sample to be measured 2] 2Thereby, obtain the difference of the oxygen content of water sample to be measured, according to the typical curve of difference that obtains and reservation, obtain the biochemical oxygen demand of water sample to be measured.Method provided by the invention need not to provide blank water sample; Also need not water sample to be measured is carried out the saturation of the air; Simplified operating process, and can reflect the variation of water sample organic content, thereby can realize real time on-line monitoring water body through oxygen content change; In time reflect the contaminated situation of water body, play the effect of early warning.
The present invention provides a kind of device that detects biochemical oxygen demand, comprising: sampling device, oxygen electrode E 1, reactor, oxygen electrode E 2, oxygen current sensing means and constant temperature water bath apparatus;
The outlet of said sampling device and said oxygen electrode E 1Injection port link to each other;
Said oxygen electrode E 1Outlet link to each other with the injection port of said reactor;
The outlet of said reactor and said oxygen electrode E 2Injection port link to each other;
Said oxygen electrode E 1, microbial film reactor and oxygen electrode E 2Place said thermostat;
Said oxygen current sensing means and said oxygen electrode E 1With said oxygen electrode E 2Link to each other, be used to detect said oxygen electrode E 1Place and said oxygen electrode E 2The oxygen electric current at place.
Referring to Fig. 1, the detection biochemical oxygen demand schematic representation of apparatus that Fig. 1 provides for the embodiment of the invention, wherein 1 is the water sample container, and 2 is the first sample introduction pipe, and 3 is peristaltic pump, and 4 is the second sample introduction pipe, 5 is oxygen electrode E 1, 6 is the 3rd sample introduction pipe, and 7 is reactor, and 8 is the 4th sample introduction pipe, and 9 is oxygen electrode E 2, 10 is constant temperature water bath apparatus, and 11 is first electrochemical workstation, and 12 is second electrochemical workstation, and 13 is first data line, 14 second data lines, 15 for going out the appearance pipe.
The device of detection biochemical oxygen demand provided by the invention comprises sampling device.For the robotization that realizes detecting in real time; In embodiments of the present invention; Said sampling device comprises water sample container 1, the first sample introduction pipe 2, peristaltic pump 3 and the second sample introduction pipe 4; The outlet of said water sample container 1 links to each other with the injection port of the said first sample introduction pipe 2, and the outlet of the said first sample introduction pipe 2 links to each other with the injection port of said peristaltic pump 3, and the outlet of said peristaltic pump 3 links to each other with the injection port of the said second sample introduction pipe 4;
The device of detection biochemical oxygen demand provided by the invention comprises oxygen electrode E 15, reactor 7, oxygen electrode E 29 with the oxygen current sensing means.In the present invention, said oxygen electrode E 15 injection port links to each other with the outlet of said sampling device, said oxygen electrode E 15 outlet links to each other with the injection port of said reactor 7, the outlet of said reactor 7 and said oxygen electrode E 29 injection port links to each other.In order to realize the connectedness of pick-up unit, in embodiments of the present invention, the device of said detection biochemical oxygen demand also comprises the 3rd sample introduction pipe 6 and the 4th sample introduction pipe 8, and said the 3rd sample introduction pipe 6 is arranged at said oxygen electrode E 15 and said reactor 7 between, said oxygen electrode E 16 injection port of 5 outlet and said the 3rd sample introduction pipe links to each other, and the outlet of said the 3rd sample introduction pipe 6 links to each other with the injection port of said reactor 7; Said the 4th sample introduction pipe 8 is arranged at said reactor 7 and said oxygen electrode E 2Between 9, the outlet of said reactor 7 links to each other with the injection port of said the 4th sample introduction pipe 8; The outlet of said the 4th sample introduction pipe 8 and said oxygen electrode E 29 injection port links to each other;
In the present invention, said pick-up unit comprises the oxygen current sensing means, said oxygen current sensing means respectively with said oxygen electrode E 1With said oxygen electrode E 2Link to each other, be used to detect said oxygen electrode E 1Place and said oxygen electrode E 2The oxygen electric current at place; In embodiments of the present invention, said oxygen current sensing means comprises first electrochemical workstation 11, second electrochemical workstation 12, first data line 13 and second data line 14, and said first electrochemical workstation 11 is through first data line 13 and said oxygen electrode E 15 link to each other, and are used to detect oxygen electrode E 1The oxygen electric current at place; Said second electrochemical workstation 12 is through second data line 14 and said oxygen electrode E 29 link to each other, and are used to detect oxygen electrode E 2The oxygen electric current at place.
In the present invention, in order to give the microorganism in the microbial film reactor suitable existence and breeding environment is provided, the device of detection biochemical oxygen demand provided by the invention comprises constant temperature water bath apparatus 10, said oxygen electrode E 15, microbial film reactor 7 and oxygen electrode E 29 are arranged in the said constant temperature water bath apparatus 10.
In embodiments of the present invention, in order to guarantee the continuity to water sample detection, biochemical oxygen demand pick-up unit provided by the invention also comprises appearance pipe 15, said injection port and the said oxygen electrode E that goes out appearance pipe 15 29 outlet links to each other.
For the detection method and the device of clearer explanation biochemical oxygen demand provided by the invention, with the application of said pick-up unit the detection method of biochemical oxygen demand provided by the invention is further explained below:
The present invention at first carries out oxygen electrode E 1With oxygen electrode E 2Calibration, obtain said oxygen electrode E 1With said oxygen electrode E 2Calibration curve, detailed process is following:
Deionized water is injected water sample container 1, adopt the mixed gas of the nitrogen oxygen of different volumes ratio that it is carried out the saturation of the air, and the employing model is the content that YSI modle 5B dissolved oxygen meter detects its dissolved oxygen DO.The deionized water that contains dissolved oxygen DO that obtains is passed through oxygen electrode E successively through the effect of peristaltic pump 1, reactor and oxygen electrode E 2, discharge from going out the appearance pipe at last.With said oxygen electrode E 1First electrochemical workstation that links to each other detects and obtains through oxygen electrode E 1The oxygen electric current I of the deionized water at place 1, with said oxygen electrode E 2Second electrochemical workstation that links to each other detects and obtains through oxygen electrode E 2The oxygen electric current I of the deionized water at place 2Thereby, obtain the oxygen current value of the deionized water of serial oxygen content;
Deionized water is injected water sample container 1, to wherein adding excessive sodium sulphite and a little cobalt chloride, obtain oxygen-free water, promptly oxygen content is zero deionized water.The oxygen-free water that obtains is passed through oxygen electrode E successively through the effect of peristaltic pump 1, reactor and oxygen electrode E 2, discharge from going out the appearance pipe at last.With said oxygen electrode E 1First electrochemical workstation that links to each other detects and obtains through oxygen electrode E 1The oxygen electric current I of the deionized water at place 1, with said oxygen electrode E 2Second electrochemical workstation that links to each other detects and obtains through oxygen electrode E 2The oxygen electric current I of the deionized water at place 2Thereby, obtain oxygen-free water oxygen current value;
Through oxygen electrode E 1With oxygen electrode E 2Detect the oxygen content of the oxygen electric current and the corresponding deionized water thereof of the water sample obtain respectively, obtain oxygen electrode E 1With oxygen electrode E 2Calibration curve.
In order to realize the detection to the water body biochemical oxygen demand, the present invention carries out the cultivation of microbial film in reactor 7, obtain the microbial film reactor.The present invention at first opens said constant temperature water bath apparatus 10, and said constant temperature water bath apparatus 10 is used for guaranteeing that the formation of microbial film reactor inside surface accomplishes under constant temperature.The water sample that the present invention will contain microorganism places water sample container 1, carries out utilizing the said water sample that contains microorganism of peristaltic pump 3 drivings to pass through oxygen electrode E from water sample container 1 successively through the first sample introduction pipe 2 and the second sample introduction pipe 4 after the saturation of the air 15, reactor 7 and oxygen electrode E 29.In the process of carrying out microbe culture,, in time replenish and contain the microorganism water sample in the water sample container 1 according to the consumption that contains the microorganism water sample.What contain saturated air contains the microorganism water sample when the reactor 7, and the microorganism in the water sample is adsorbed on the inwall of reactor 7 step by step and utilizes organism and airborne oxygen metabolism and the breeding in the water sample, and the training of microorganism begins; Peristaltic pump 3 control water sample flow velocitys are 1.0mL/min, and thermostat 10 design temperatures are 30 ℃, and the incubation time of elementary microbial film reactor is 12h.
After obtaining elementary microbial film reactor, the present invention adds tap water in water sample container 1, and the line space of going forward side by side gas is saturated, utilizes the tap water that peristaltic pump 3 controls contain saturated air to pass through oxygen electrode E successively 15, the microbial film reactor 7 and second reactor 9 cleaned 4 hours said reactor continuously.After cleaning completion, remaining tap water in the water sample container 1 is toppled over.
After the cleaning of completion to system, the present invention adopts above-mentioned 7 pairs of glucose glutamic acid solutions of reactor that are adsorbed with microorganism to detect.The glucose glutamic acid solution that the present invention will prepare in advance places water sample container 1, passes through oxygen electrode E successively through the glucose glutamic acid solution in the peristaltic pump 3 control water sample containers 1 1, be adsorbed with reactor and the oxygen electrode E of microorganism 2, and flow out by outlet.First electrochemical workstation and second electrochemical workstation detect oxygen electrode E respectively 1Place and oxygen electrode E 2Locate the oxygen electric current of water sample of flowing through, thereby detect the oxygen electric current I that obtains standard solution 1With the oxygen electric current I 2
In order to judge whether microorganism absorption is saturated in the reactor 7; The present invention repeats the elementary cultivation of mentioned microorganism, tap water cleans and the step of glucose glutamic acid solution detection, until [the O that said glucose glutamic acid solution is detected the glucose glutamic acid solution that obtains 2] 1[O 2] 2Difference consistent with preceding twice testing result, amount of microorganism of absorption reaches constant in this explanation reactor 7, accomplish the training of microorganism this moment, obtains stable microbial film reactor, uses it for the detection to biochemical oxygen demand;
After obtaining the microbial film reactor; The present invention detects the detection and the water sample to be measured of a series of biochemical oxygen demand concentration glucose glutamic acid solutions; The difference of the oxygen content of the glucose glutamic acid solution that obtains according to detection and the biochemical oxygen demand concentration of said glucose glutamic acid solution are drawn the typical curve that obtains the microbial film reactor; According to the testing result of said typical curve and said water sample to be measured, promptly the difference of the COD of said water sample to be measured calculates the biochemical oxygen demand of water sample to be measured;
In order to obtain the typical curve of microbial film reactor; The present invention at first prepares the glucose glutamic acid solution of a series of biochemical oxygen demand concentration; And said glucose glutamic acid solution placed said water sample container 1 respectively, pass through oxygen electrode E successively through the glucose glutamic acid solution in the peristaltic pump 3 control water sample containers 1 1, microbial film reactor and oxygen electrode E 2, the organism in the glucose glutamic acid solution is degraded by microorganisms, and obtains the glucose glutamic acid solution through microbial degradation; First electrochemical workstation and the second galvanochemistry work detect the oxygen electric current I that obtains the glucose glutamic acid solution respectively 1With the oxygen electric current I 2, according to said oxygen electric current I 1The oxygen electrode E that obtains with technique scheme 1Calibration curve, oxygen electric current I 2The oxygen electrode E that obtains with technique scheme 2Calibration curve, obtain [the O of glucose glutamic acid solution 2] 1[O 2] 2Thereby obtain the corresponding oxygen content difference of glucose glutamic acid solution of each biochemical oxygen demand concentration; According to the biochemical oxygen demand concentration of the said COD difference glucose glutamic acid solution corresponding, draw the typical curve that obtains the microbial film reactor with it;
After obtaining typical curve, the present invention detects water sample to be measured.The present invention places water sample container 1 with water sample to be measured, passes through oxygen electrode E successively through the water sample to be measured in the peristaltic pump 3 control water sample containers 1 1, microbial film reactor and oxygen electrode E 2, oxygen electrode detects the oxygen electric current I that obtains said water sample to be measured 1With the oxygen electric current I 2, the oxygen electrode E that obtains according to technique scheme 1With oxygen electrode E 2Calibration curve, calculate [the O of said water sample to be measured 2] 1[O 2] 2Thereby, obtain the oxygen content difference of said water sample to be measured, according to the difference and the typical curve of the oxygen content of the water sample to be measured that obtains, calculate the biochemical oxygen demand of water sample to be measured.
In order to further specify the present invention, below in conjunction with embodiment the method and apparatus of detection biochemical oxygen demand provided by the invention is elaborated, but can not they be interpreted as the qualification to protection domain of the present invention.
Embodiment 1
According to synoptic diagram shown in Figure 1, preparation microbial film reactor.
Constant temperature water bath apparatus 10 is opened, and adjusted the temperature to 30 ℃.In water sample container 1, inject the active sludge water sample, and said active sludge water sample is carried out the saturation of the air with the speed of 3.0L/min.With long for 105.0cm, internal diameter are that the reactor 7 of the glass material of 2.0mm is positioned in the water bath with thermostatic control, utilize peristaltic pump 3 with the active sludge water sample with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6 arrive reactor 7, again through the 4th sample introduction pipe 8 and oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Constantly from replenishing the active sludge water sample to water sample container 1, the microorganism in the active sludge is adsorbed on the inwall of reactor 7 simultaneously, and existence and breeding obtain elementary microbial film reactor.Through behind the 24h, clean water sample container 1 back to wherein injecting tap water.Under the control of peristaltic pump 33, with tap water with the speed of 1.0mL/min through successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6 arrive elementary microbial film reactor, again with the 4th sample introduction pipe 8 and oxygen electrode E 29, discharge from going out appearance pipe 15 at last.0.5h after, oxygen electrode E 15 with oxygen electrode E 2The current value of 9 outputs reaches stable, is respectively 652nA and 492nA.This difference can be explained the oxygen consumption degree of microorganism endogenous respiration when not having organism of microbial film reactor.Clean water sample container 1, and be 20.0mg O BOD concentration 2The glucose glutamic acid solution of/L injects water sample container 1, under the control of peristaltic pump 3, with the glucose glutamic acid solution with the data rate stream of 1.0mL/min through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6 arrive the microbial film reactor, again through the 4th sample introduction pipe 8 and oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Record oxygen electrode E 15 with oxygen electrode E 2The current value of 9 outputs reaches the current value when stablizing, and is respectively 659nA and 382nA.This difference can explain that the microorganism of microbial film reactor is 20.0mg O at organism for BOD concentration 2Endogenous respiration and external source are breathed common oxygen consumption degree during the glucose glutamic acid solution of/L.Repeat the incubation step of mentioned microorganism membrane reactor, after 12 hours, repeat that above-mentioned tap water cleans and be 20.0mg O BOD concentration 2The detection step of the glucose glutamic acid solution of/L writes down new oxygen electrode output current value.Continue the repetition above-mentioned steps, after cultivation proceeded to 62h, detecting BOD concentration was 20.0mg O 2During the glucose glutamic acid solution of/L, oxygen electrode E 15 with oxygen electrode E 29 output current is respectively 651nA and 332nA, oxygen electrode E when this result and 58h 15 with oxygen electrode E 29 output current value basically identical, the inwall of this explanation reactor 7 has adsorbed saturated microorganism, thereby judges the cultivation completion of microbial film reactor, obtains stable microbial film reactor.
Embodiment 2
According to synoptic diagram shown in Figure 1, microbial film reactor 7 is removed from system, substituted is that a segment length equates, the glass tube that internal diameter equates, appearance one end that goes out of this glass tube passes through the 4th sample introduction pipe 8 and oxygen electrode E 29 are connected, and carry out the calibration of oxygen electrode.
With oxygen electrode E 15 with oxygen electrode E 29 are connected with second electrochemical workstation 12 with first electrochemical workstation 11 with second data line 14 through first data line 13 respectively.Water sample container 1, peristaltic pump 3, oxygen electrode E 15, glass tube, oxygen electrode E 29 connect through the first sample introduction pipe, 2, the second sample introduction pipes, 4, the three sample introduction pipes, 6, the four sample introduction pipes 8 respectively, and by going out 15 waste discharges of appearance pipe.Oxygen electrode E 15, glass tube, oxygen electrode E 29 place constant temperature water bath apparatus 10.Said first electrochemical workstation 11 and second electrochemical workstation 12 are respectively applied for monitoring oxygen electrode E 15 with oxygen electrode E 29 electric current changes.
Constant temperature water bath apparatus 10 is opened, and adjusted the temperature to 30 ℃.
A) deionized water is injected water sample container 1, and adopt the mixed gas of nitrogen oxygen 8:1 that it is carried out the saturation of the air, and to adopt YSI modle 5B dissolved oxygen meter to record its dissolved oxygen content be 4.95mg L -1Utilize peristaltic pump 3 that dissolved oxygen content is 4.95mg L -1Deionized water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, glass tube, the 4th sample introduction pipe 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 399nA and 417nA.
B) deionized water is injected water sample container 1, and adopt the mixed gas of nitrogen oxygen 15:1 that it is carried out the saturation of the air, and to adopt YSI modle 5B dissolved oxygen meter to record its dissolved oxygen content be 2.66mg L -1Utilize peristaltic pump 3 that dissolved oxygen content is 2.66mg L -1Deionized water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, glass tube, the 4th sample introduction pipe 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 218nA and 222nA.
C) deionized water is injected water sample container 1, and adopt the mixed gas of nitrogen oxygen 5:1 that it is carried out the saturation of the air, and to adopt YSI modle 5B dissolved oxygen meter to record its dissolved oxygen content be 6.42mg L -1Utilize peristaltic pump 3 that dissolved oxygen content is 6.42mg L -1Deionized water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, glass tube, the 4th sample introduction pipe 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 560nA and 531nA.
D) deionized water is injected water sample container 1, and adopt air that it is carried out the saturation of the air, and to adopt YSI modle 5B dissolved oxygen meter to record its dissolved oxygen content be 8.76mg L -1Utilize peristaltic pump 3 that dissolved oxygen content is 8.76mg L -1Deionized water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, glass tube, the 4th sample introduction pipe 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 662nA and 671nA.
E) deionized water is injected water sample container 1, add excessive sodium sulphite and a little cobalt chloride therein, obtain oxygen-free water.Utilize peristaltic pump 3 with oxygen-free water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, glass tube, the 4th sample introduction pipe 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 9nA and 11nA.
F) according to above-mentioned oxygen content value and corresponding oxygen electrode E thereof 1With oxygen electrode E 2The current value that detection obtains obtains oxygen electrode E respectively 1With oxygen electrode E 2Oxygen content and the correlation curve of electric current, the result is as shown in Figure 2, the calibration curve of the electrode that Fig. 2 obtains for the embodiment of the invention 2, wherein curve 1 is oxygen electrode E 1Calibration curve, obtain its regression equation after the linear regression and be: y (nA)=74.75x (mg L -1)+15.058, coefficient R 2=0.9957, wherein y is a current value, and x is an oxygen content; Curve 2 is oxygen electrode E 2Calibration curve, after the linear regression, y (nA)=75.668x (mg L -1)+20.531, coefficient R 2=0.9941.Wherein y is a current value, and x is an oxygen content.
Embodiment 3
By the device that is used to detect biochemical oxygen demand that synoptic diagram shown in Figure 1 obtains, the glucose glutamic acid solution of series concentration is measured, obtain typical curve.
Constant temperature water bath apparatus 10 is opened, and adjusted the temperature to 30 ℃.Tap water is injected water sample container 1, utilize peristaltic pump 3 with tap water with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, microbial film reactor 7, the four sample introduction pipes 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 the monitoring outputting current steadily the time, current value is respectively 632nA and 512nA.The glucose glutamic acid solution of certain BOD content is injected water sample container 1, by above-mentioned steps, as oxygen electrode E 15 with oxygen electrode E 29 output currents reach when stablizing, and write down its current value.When changing the BOD content of glucose glutamic acid solution, oxygen electrode E 15 with oxygen electrode E 2The 9 stable current value correspondences that obtain also change.With the calibration curve of the stable current value that obtains, calculate corresponding oxygen content by the corresponding oxygen electrode that obtains among the embodiment 2.When sample is tap water, oxygen electrode E 15 with oxygen electrode E 2The difference of 9 oxygen contents that obtain is being represented the oxygen utilization of the microorganism endogenous respiration in the microbial film reactor 7.When sample when containing organic glucose glutamic acid solution, oxygen electrode E 15 with oxygen electrode E 2The 9 oxygen content differences that obtain are being represented the microorganism endogenous respiration and the common oxygen utilization of external sources breathing in the microbial film reactor 7.The present invention is an ordinate with the oxygen content difference that obtains; BOD content with the glucose glutamic acid solution of correspondence is horizontal ordinate; The relation curve that obtains of mapping i.e. the typical curve of microbial film reactor for this reason; The result is as shown in Figure 3, and the typical curve of the microbial film reactor that Fig. 3 obtains for the embodiment of the invention 3 with the linear equation that obtains after its linear regression is: y (mg L -1)=0.205x (mg L -1)+1.75, wherein, x is the BOD content of water sample, y is oxygen electrode E 15 with oxygen electrode E 29 detected oxygen content differences.
Embodiment 4
Adopt device shown in Figure 1, the microbial film reactor that adopts embodiment 1 to prepare carries out the mensuration of actual sample.Constant temperature water bath apparatus 10 is opened, and adjusted the temperature to 30 ℃.
Testing sample is injected water sample container 1, utilize peristaltic pump 3 with water sample to be measured with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, microbial film reactor 7, the four sample introduction pipes 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 detect outputting current steadily the time, current value is respectively 610nA and 305nA.The oxygen electrode E that obtains according to embodiment 2 15 with oxygen electrode E 29 calibration curve, calculating the oxygen content difference is 4.2mg L -1The typical curve and the above-mentioned oxygen content difference of the microbial film reactor that obtains according to embodiment 3, the BOD content that calculates this water sample to be measured is 11.9mg L -1
The present invention adopts BOD 5The biochemical oxygen demand value of this sample of method test, the result is 12.7mg L -1, the two is comparatively approaching, and this testing result of explaining that method provided by the invention obtains is comparatively accurate.
Embodiment 5
Adopt device shown in Figure 1, the microbial film reactor of embodiment 1 preparation carries out the mensuration of actual sample.
Constant temperature water bath apparatus 10 is opened, and adjusted the temperature to 30 ℃.The lake water sample is injected water sample container 1, utilize peristaltic pump 3 with said lake water sample with the speed of 1.0mL/min successively through the first sample introduction pipe 2, peristaltic pump 3, the second sample introduction pipes 4, oxygen electrode E 15, the three sample introduction pipes 6, microbial film reactor 7, the four sample introduction pipes 8, oxygen electrode E 29, discharge from going out appearance pipe 15 at last.Oxygen electrode E 15 with oxygen electrode E 29 detect outputting current steadily the time, current value is respectively 672nA and 489nA.In water sample container 1, continue to add sewage treatment plant's preliminary sedimentation tank sewage, after a period of time, oxygen electrode E 15 with oxygen electrode E 29 output currents reach stable, and current value is respectively 657nA and 324nA.In water sample container 1, continue to add rainwater, after a period of time, oxygen electrode E 15 with oxygen electrode E 29 output currents reach stable, and current value is respectively 688nA and 362nA.In water sample container 1, continue to add food factory's sewage, after a period of time, oxygen electrode E 15 with oxygen electrode E 29 output currents reach stable, and current value is respectively 652nA and 155nA.The oxygen electrode E that obtains according to embodiment 2 15 with oxygen electrode E 29 calibration curve calculates oxygen electrode E when measuring 4 kinds of water samples 15 with oxygen electrode E 29 oxygen content is respectively lake water sample (8.8mg L -1, 6.2mgL -1), preliminary sedimentation tank sewage (8.6mg L -1, 4.0mg L -1), rainwater (8.9mg L -1, 4.4mg L -1), food factory's sewage (8.6mg L -1, 1.8mg L -1).The typical curve of the microbial film reactor that obtains according to embodiment 3, the BOD content that obtains four kinds of water samples is respectively 4.1mg L -1, 18.8mg L -1, 13.4mgL -1With 29.5mg L -1The result is as shown in Figure 4; The monitoring result of the real-time water sample BOD that Fig. 4 obtains for the embodiment of the invention 4, wherein curve 1 is the monitoring result behind the adding preliminary sedimentation tank sewage in the lake water sample, curve 2 is the monitoring result that adds rainwater in the lake water; By finding out among Fig. 4; Obtain the directly variation of organic content in the response sample of oxygen content change, when analyzed water sample is contaminated, the early warning that this method can rapid sensitive.
The present invention adopts the BOD method to measure the biochemical oxygen demand of four kinds of water samples, and the result is respectively 4.5mgL -1, 15.1mg L -1, 11.4mg L -1With 27.2mg L -1, the gained result is comparatively approaching, and this testing result of explaining that method provided by the invention obtains is comparatively accurate.
Can be known that by above embodiment the present invention provides a kind of method that detects biochemical oxygen demand, may further comprise the steps: the water sample that a) will contain microorganism carries out microbe culture, obtains microbial film; B) microbial film and second oxygen electrode that water sample to be measured are obtained through first oxygen electrode, said step a) successively, oxygen electrode detects said water sample to be measured, obtains the first oxygen electric current and the second oxygen electric current of said water sample to be measured; C), obtain first oxygen content and second oxygen content of said water sample to be measured according to the said first oxygen electric current and the calibration curve of predetermined first oxygen electrode, the said second oxygen electric current calibration curve with predetermined second oxygen electrode; First oxygen content and second oxygen content of the water sample to be measured that d) obtains according to said step c) obtain the difference of said water sample oxygen content to be measured; The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.The present invention at first passes through first oxygen electrode with water sample to be measured, detects first oxygen content that obtains said water sample to be measured; And then with it through microbial film, microorganism is wherein degraded to the organism in the water sample to be measured, and consumes dissolved oxygen DO wherein, makes the content of dissolved oxygen DO descend; And then will obtain passing through second oxygen electrode through the water sample to be measured of microbial degradation; Detection obtains second oxygen content of water sample to be measured; Thereby obtain the difference of the oxygen content of water sample to be measured,, obtain the biochemical oxygen demand of water sample to be measured according to the typical curve of difference that obtains and reservation.Method provided by the invention need not to provide blank water sample; Also need not water sample to be measured is carried out the saturation of the air; Simplified operating process, and can reflect the variation of water sample organic content, thereby can realize real time on-line monitoring water body through oxygen content change; In time reflect the contaminated situation of water body, play the effect of early warning.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.

Claims (10)

1. method that detects biochemical oxygen demand may further comprise the steps:
The water sample that a) will contain microorganism carries out microbe culture, obtains microbial film;
B) microbial film and second oxygen electrode that water sample to be measured are obtained through first oxygen electrode, said step a) successively, oxygen electrode detects said water sample to be measured, obtains the first oxygen electric current and the second oxygen electric current of said water sample to be measured;
C), obtain first oxygen content and second oxygen content of said water sample to be measured according to the said first oxygen electric current and the calibration curve of predetermined first oxygen electrode, the said second oxygen electric current calibration curve with predetermined second oxygen electrode;
First oxygen content and second oxygen content of the water sample to be measured that d) obtains according to said step c) obtain the difference of said water sample oxygen content to be measured;
The typical curve of the difference of the water sample oxygen content to be measured that e) obtains according to said step d) and predetermined microbial film obtains the biochemical oxygen demand of said water sample to be measured.
2. method according to claim 1 is characterized in that, the calibration curve of first oxygen electrode obtains according to following step in the said step c):
The water of serial oxygen content is passed through first oxygen electrode respectively, obtain the first oxygen current value of the water of serial oxygen content respectively;
According to the oxygen content of the first oxygen current value of the water of the serial oxygen content that obtains and corresponding water thereof, obtain the calibration curve of first oxygen electrode;
The calibration curve of second oxygen electrode obtains according to following step in the said step c):
The water of serial oxygen content is passed through second oxygen electrode respectively, obtain the second oxygen current value of the water of serial oxygen content respectively;
According to the oxygen content of the second oxygen current value of the water of the serial oxygen content that obtains and corresponding water thereof, obtain the calibration curve of second oxygen electrode.
3. method according to claim 1 is characterized in that, the typical curve of the microbial film in the said step e) obtains according to following step:
With the microbial film and second oxygen electrode that the standard solution of series concentration obtains through first oxygen electrode, said step a) successively, oxygen electrode detects said standard solution, obtains the first oxygen electric current and the second oxygen electric current of the standard solution of said series concentration;
Calibration curve based on said first oxygen electric current and said first oxygen electrode; Obtain the first corresponding oxygen content of the said first oxygen electric current, the calibration curve of said first oxygen electrode is the oxygen content of the water sample measured of said first oxygen electrode and the relation curve of oxygen current value;
Calibration curve based on said second oxygen electric current and said second oxygen electrode; Obtain the second corresponding oxygen content of the said second oxygen electric current, the calibration curve of said second oxygen electrode is the oxygen content of the water sample measured of said second oxygen electrode and the relation curve of oxygen current value;
According to said first oxygen content and second oxygen content, the oxygen content of standard solution that obtains said series concentration respectively is poor;
According to the concentration of said oxygen content difference and corresponding standard solution thereof, obtain the typical curve of microbial film.
4. according to the described method of said claim 1, it is characterized in that said step a) is specially:
A1) will contain the microorganism water sample and carry out the elementary cultivation of microorganism, obtain elementary microbial film;
The standard solution that a2) will contain saturated air is successively through first oxygen electrode, said step a1) the elementary microbial film and second oxygen electrode that obtain, oxygen electrode detects first oxygen content and second oxygen content that obtains said standard solution;
A3) repeating step a1) and step a2) described process, first oxygen content of the standard solution that obtains until detection and the difference of second oxygen content are stable, accomplish the cultivation of microorganism, obtain microbial film.
5. according to any described method of claim 3 ~ 4, it is characterized in that said standard solution is one or more in glucose solution, glutamic acid solution, glucose and glutamic acid mixed solution or the sucrose solution.
6. method according to claim 1 is characterized in that, the temperature of microbe culture is 20 ℃ ~ 45 ℃ in the said step a).
7. method according to claim 1 is characterized in that, the time of microbe culture is 20 h ~ 300 hours in the said step a).
8. method according to claim 1 is characterized in that, the microbe culture in the said step a) is for carrying out microbe culture in reactor.
9. method according to claim 8 is characterized in that, said reactor is a tubulose;
The material of said reactor is glass, ethylene-vinyl acetate copolymer, plastics, nylon, quartz or silica gel;
The length of said reactor is 30.0cm ~ 420.0cm;
The internal diameter of said reactor is 1.0mm ~ 4.0mm.
10. a device that detects biochemical oxygen demand comprises sampling device, first oxygen electrode, reactor, second oxygen electrode, oxygen current sensing means and constant temperature water bath apparatus;
The outlet of said sampling device links to each other with the injection port of said first oxygen electrode;
The outlet of said first oxygen electrode links to each other with the injection port of said reactor;
The outlet of said reactor links to each other with the injection port of said second oxygen electrode;
Said first oxygen electrode, reactor and second oxygen electrode place said thermostat;
Said oxygen current sensing means links to each other with said second oxygen electrode with said first oxygen electrode, is used to detect the oxygen electric current at said first oxygen electrode place and the said second oxygen electrode place.
CN201210313038.5A 2012-08-29 2012-08-29 A kind of method and device detecting biochemical oxygen demand Active CN102798650B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210313038.5A CN102798650B (en) 2012-08-29 2012-08-29 A kind of method and device detecting biochemical oxygen demand

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210313038.5A CN102798650B (en) 2012-08-29 2012-08-29 A kind of method and device detecting biochemical oxygen demand

Publications (2)

Publication Number Publication Date
CN102798650A true CN102798650A (en) 2012-11-28
CN102798650B CN102798650B (en) 2015-08-05

Family

ID=47197828

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210313038.5A Active CN102798650B (en) 2012-08-29 2012-08-29 A kind of method and device detecting biochemical oxygen demand

Country Status (1)

Country Link
CN (1) CN102798650B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103645224A (en) * 2013-12-02 2014-03-19 中山欧麦克仪器设备有限公司 On-line BOD (biochemical oxygen demand) measurer
CN105116031A (en) * 2015-08-25 2015-12-02 中国科学院长春应用化学研究所 Online biochemical oxygen demand detection method and online biochemical oxygen demand detection device
CN108663427A (en) * 2018-05-23 2018-10-16 燕山大学 A kind of seawater BOD online auto monitoring systems based on microbial film reactor
CN109709197A (en) * 2019-01-24 2019-05-03 天津市赛普新锐仪器科技有限公司 BOD Quick testing instrument and accurately compensate measuring method
CN113075280A (en) * 2021-03-22 2021-07-06 北京石油化工学院 Biochemical oxygen demand BOD and toxicity integrated detection method
CN113337390A (en) * 2021-05-10 2021-09-03 北京工商大学 BOD detection device and BOD detection method
CN113466311A (en) * 2021-06-16 2021-10-01 五邑大学 Seawater measurement method based on seawater in-situ culture microbial film
CN113504264A (en) * 2021-06-23 2021-10-15 武汉新烽光电股份有限公司 Rapid BOD detection system and detection method thereof
CN113562851A (en) * 2021-06-23 2021-10-29 武汉新烽光电股份有限公司 Quick BOD detects normal position biomembrane subassembly
CN113504275B (en) * 2021-07-21 2023-11-14 武汉新烽光电股份有限公司 Device and method for quickly measuring BOD
CN113655191B (en) * 2021-07-23 2023-11-14 武汉新烽光电股份有限公司 Microbial membrane reactor for detecting BOD of water quality, preparation method thereof and membrane forming method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0369490A2 (en) * 1988-11-18 1990-05-23 Kao Corporation Method of bod measurement and apparatus thereof
US5017496A (en) * 1986-02-17 1991-05-21 Ecotechniek B.V. Method for determining the respiration rate of a respiring material in the form of a continuous process current, as well as a device suitable for such an application
JPH03156360A (en) * 1989-11-14 1991-07-04 Kao Corp Bod measuring apparatus
CN101000341A (en) * 2006-12-29 2007-07-18 中国科学院长春应用化学研究所 Sensor type on-line monitor of biochemical oxygen demand
CN102288653A (en) * 2011-05-06 2011-12-21 湖北博凡生物科技有限公司 Online biochemical oxygen demand (BOD) detector and detection method of same
CN102608181A (en) * 2012-04-10 2012-07-25 中国科学院长春应用化学研究所 Method for detecting biochemical oxygen demand

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017496A (en) * 1986-02-17 1991-05-21 Ecotechniek B.V. Method for determining the respiration rate of a respiring material in the form of a continuous process current, as well as a device suitable for such an application
EP0369490A2 (en) * 1988-11-18 1990-05-23 Kao Corporation Method of bod measurement and apparatus thereof
JPH03156360A (en) * 1989-11-14 1991-07-04 Kao Corp Bod measuring apparatus
CN101000341A (en) * 2006-12-29 2007-07-18 中国科学院长春应用化学研究所 Sensor type on-line monitor of biochemical oxygen demand
CN102288653A (en) * 2011-05-06 2011-12-21 湖北博凡生物科技有限公司 Online biochemical oxygen demand (BOD) detector and detection method of same
CN102608181A (en) * 2012-04-10 2012-07-25 中国科学院长春应用化学研究所 Method for detecting biochemical oxygen demand

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HASSAPIS G: "Biological oxygen demand (BOD) monitoring by a multiprocessing system", 《IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT》 *
RIEGLER G: "Kontinuierliche Kurzzeit-BSB-Messung", 《KORRESPONDENZ ABWASSER》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103645224A (en) * 2013-12-02 2014-03-19 中山欧麦克仪器设备有限公司 On-line BOD (biochemical oxygen demand) measurer
CN105116031A (en) * 2015-08-25 2015-12-02 中国科学院长春应用化学研究所 Online biochemical oxygen demand detection method and online biochemical oxygen demand detection device
CN108663427A (en) * 2018-05-23 2018-10-16 燕山大学 A kind of seawater BOD online auto monitoring systems based on microbial film reactor
CN109709197A (en) * 2019-01-24 2019-05-03 天津市赛普新锐仪器科技有限公司 BOD Quick testing instrument and accurately compensate measuring method
CN109709197B (en) * 2019-01-24 2024-01-12 天津市赛普新锐仪器科技有限公司 BOD rapid tester and accurate compensation testing method
CN113075280B (en) * 2021-03-22 2023-04-11 北京石油化工学院 Biochemical oxygen demand BOD and toxicity integrated detection method
CN113075280A (en) * 2021-03-22 2021-07-06 北京石油化工学院 Biochemical oxygen demand BOD and toxicity integrated detection method
CN113337390A (en) * 2021-05-10 2021-09-03 北京工商大学 BOD detection device and BOD detection method
CN113466311A (en) * 2021-06-16 2021-10-01 五邑大学 Seawater measurement method based on seawater in-situ culture microbial film
CN113504264A (en) * 2021-06-23 2021-10-15 武汉新烽光电股份有限公司 Rapid BOD detection system and detection method thereof
CN113562851A (en) * 2021-06-23 2021-10-29 武汉新烽光电股份有限公司 Quick BOD detects normal position biomembrane subassembly
CN113504275B (en) * 2021-07-21 2023-11-14 武汉新烽光电股份有限公司 Device and method for quickly measuring BOD
CN113655191B (en) * 2021-07-23 2023-11-14 武汉新烽光电股份有限公司 Microbial membrane reactor for detecting BOD of water quality, preparation method thereof and membrane forming method

Also Published As

Publication number Publication date
CN102798650B (en) 2015-08-05

Similar Documents

Publication Publication Date Title
CN102798650B (en) A kind of method and device detecting biochemical oxygen demand
CN102608181B (en) Method for detecting biochemical oxygen demand
CN101413915B (en) Method for rapidly detecting biochemical oxygen demand by using on site culture organism
CN102735812B (en) Biochemical oxygen demand detection method
CN101620201B (en) Measuring method of biochemical oxygen demand and BOD sensor and applications
CN101907596B (en) Method for monitoring and estimating inlet water toxicity of urban wastewater treatment plant on line
CN102636545B (en) Early warning device for biomass with comprehensive toxicity in water
CN206804514U (en) A kind of ammonia nitrogen water quality in-line analyzer
CN104880504A (en) Pressure difference final motion liquid column balance type coulometry BOD measuring device
CN108368471B (en) Identification of calibration offset for PH measuring devices
CN104316572B (en) A kind of fast and convenient method for evaluating Source water and drinking water microorganism pollution risk
US9423373B2 (en) Method for detecting biochemical oxygen demand
CN105588831A (en) Method for detecting acute toxicity of rare earth tailing pond surrounding groundwater pollution by using freshwater luminescent bacteria
CN104090014B (en) The detection method and its device of a kind of acute toxicity of water quality
CN104330455A (en) Method and device of on-line monitoring nitrate nitrogen through microbial electrolytic tank technology
CN102288653A (en) Online biochemical oxygen demand (BOD) detector and detection method of same
CN204945047U (en) A kind of online fluorescence method dissolved oxygen sensor
CN105116031A (en) Online biochemical oxygen demand detection method and online biochemical oxygen demand detection device
CN201935910U (en) Water quality toxicity detecting device
CN202710513U (en) Biological warning device for comprehensive water toxicity
CN205506808U (en) Oxygen absorption rate on -line measuring device
CN104034785A (en) On-line biologic detection and automatic alarm device for toxic substances in water body
CN210953907U (en) Sewage treatment plant toxicity of intaking on-line measuring device
CN101625317A (en) Full-automatic online chemical oxygen demand (BOD) and biological oxygen demand (BOD) monitor and use method thereof
CN104673664A (en) Blood sample culture device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant