CN1138855C - Method for monitoring biological activity in fluids - Google Patents

Method for monitoring biological activity in fluids Download PDF

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CN1138855C
CN1138855C CNB971925453A CN97192545A CN1138855C CN 1138855 C CN1138855 C CN 1138855C CN B971925453 A CNB971925453 A CN B971925453A CN 97192545 A CN97192545 A CN 97192545A CN 1138855 C CN1138855 C CN 1138855C
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variation
dissolved oxygen
velocity
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CN1212053A (en
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X
X·扬
J·F·李
S·K·曼尼辛
T·J·玛
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Biochem Technology Inc
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • C12Q1/04Determining presence or kind of microorganism; Use of selective media for testing antibiotics or bacteriocides; Compositions containing a chemical indicator therefor
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483Physical analysis of biological material
    • G01N33/497Physical analysis of biological material of gaseous biological material, e.g. breath

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Abstract

A method of monitoring a microbiological process in a fluid supply involving isolation of a fluid sample from a fluid supply, measuring the pH of the fluid sample at selected time intervals, then analyzing changes in pH, if any, to determine a pH variation rate for the sample. The dissolved oxygen in the sample is also measured at selected time intervals substantially synchronously with the pH measurements, and changes in dissolved oxygen, if any, are analyzed to determine a biological oxygen consumption rate for the sample.

Description

Bioactive method in the monitoring fluid
Invention field
The present invention relates to the monitoring method of important metabolism transition point in the organic and inorganic matrix process of microbial metabolism and the control method of microbiological treatment program.
Background of invention
In the process of microorganism and inorganic matrix organic in metabolism, location parameter such as pH, consumption rate changes but for example can make.
In the microorganisms cultures based on nitrification, as ammonium ion (NH 4 +) to be consumed to metabolism below the mark, the hydrogen ion (H that nitrifying process produces +) can significantly reduce.Therefore, hydrogen ion activity (being pH) also changes thereupon in the solution.
Similarly, the situation that is lower than some metabolism standard with matrix content is compared, and obtains easily in the situation of a large amount of multiple outside organic substrates, and the consumption rate of microorganisms cultures is higher.In the both of these case, detectable pH velocity of variation (being sometimes referred to as " pH production rate " or " pHPR " herein) and consumption rate (being sometimes referred to as " biological consumption rate " or " BOCR " herein) directly are subjected to the influence of matrix metabolism rate in time.Therefore, suppose that the variation of pH and consumption rate is only caused by microbial metabolic activity in the matrix, in theory can pHPR and BOCR as the index of important metabolism transition point in the microbiological treatment program.PHPR be defined as d (pH)/dt or-Δ (pH)/Δ t; BOCR is defined as d (DO)/dt, or-Δ (DO)/Δ t.When the slope of pH and/or DO when negative, the value of pHPR and/or BOCR is for just.
Summary of the invention
Method of the present invention comprises tells fluid sample (for example waste water in the purifying treatment) in the fluid feeder.Measure the pH of fluid sample, calculate pHPR and analysis, with the generation of the important metabolism transition point of rapid test.By analysis as can be known, need which kind of controlled step, when carry out this controlled step so that the processing tool maximum efficiency of monitoring fluid feeder.
Specifically, contain the monitoring method of microbiological treatment program in the fluid feeder of microbial population, it comprises: a) tell fluid sample in the fluid feeder; B) the fixed interval period is measured the pH of fluid sample; C) change as pH, then analyze its variable quantity, to measure the pH velocity of variation of sample; D) the fixed interval period, when measuring pH, measure the dissolved oxygen content of sample substantially; And e) changes as dissolved oxygen content, then analyze its variable quantity, to measure the biological consumption rate of sample; Or a) in the fluid feeder, tell fluid sample; B) the fixed interval period is measured the pH of fluid sample; C) change as pH, then analyze its variable quantity, to measure the pH velocity of variation of sample; D) when measure the pH velocity of variation is 1) transfer zero and/or 2 to from negative value) transfer zero for the second time to; And e) shows measurement result.
The accompanying drawing summary
Accompanying drawing 1 is the diagram of Michaelis-Menten reaction kinetics theory.
Accompanying drawing 2 is in the microbiological treatment process, and consumption rate of mixed solution sample (BOCR) and pH velocity of variation (pHPR) are in time to ammonium (NH 4 +) concentration and organic carbon source (be generically and collectively referred to as BOD; Biochemical oxygen demand (BOD)) theory changes situation.
Accompanying drawing 3 is in the microbiological treatment process, and consumption rate of mixed solution sample (BOCR) and pH velocity of variation (pHPR) are in time to ammonium (NH 4 +) concentration and organic carbon source (be generically and collectively referred to as BOD; Biochemical oxygen demand (BOD)) theory changes situation.
Accompanying drawing 4 is in the biological reaction tank, is used for the positive sectional view from a kind of embodiment of sampling of fluid feeder and device for monitoring according to the present invention.
Accompanying drawing 5 finishes when beginning aeration for aeration, therebetween the relation of oxygen velocity of variation and BOCR (the variation per-cent with the per minute Oxygen saturation is represented).
Accompanying drawing 6 finishes when beginning aeration for aeration, and pH changes and the relation of pHPR (with the ammonia change in concentration time, per minute pH variable quantity is represented) therebetween.
Accompanying drawing 7 is when COD (chemical oxygen demand (COD)) is not the metabolic restrictions factor, the relation of pHPR (representing with per minute pH variable quantity) and ammonia concentration.
Accompanying drawing 8 is when COD is not the metabolic restrictions factor, the relation of BOCR (the variation per-cent with the per minute Oxygen saturation is represented) and ammonia concentration.
When accompanying drawing 9 different ammonia concentration and COD, the variation situation of pHPR (representing) with per minute pH variable quantity.
When accompanying drawing 10 is different ammonia concentration and COD, the relation of pHPR (representing), BOCR (the variation per-cent with the per minute Oxygen saturation is represented), ammonia concentration and COD with per minute pH variable quantity.
When accompanying drawing 11 is continuous aeration, the time dependent relation of DO and pH.
Accompanying drawing 12 is pH, NH 3-N concentration and d (pH)/dt relation in time.
Accompanying drawing 13 is DO and d (DO)/dt relation in time.
When biochemical reaction carries out, its reaction rate, part can be by theoretical (such as the accompanying drawing 1) explanation of Michaelis-Menten. State in this theory that when substrate concentration was extremely low, biochemical reaction rate was extremely low, increase biochemical reaction rate with substrate concentration and also increase to a fixed point surpass this fixed point, no matter how substrate concentration increases, the increase of reaction rate is extremely low. In other words, surpass this fixed point, substrate concentration is high again, and reaction speed only can approach and can not reach flat-top. This flat-top is highest response speed or Vmax It is with linear extrapolation, is 2K at substrate concentrationsThe time reaction rate. KsFor metabolic response speed is highest response speed (Vmax) substrate concentration of a half.
Therefore, with regard to the metabolism viewpoint, 2KsImportant concentration for matrix. When substrate concentration surpasses 2KsThe time, microorganism is with the highest and near the fixed rate metabolism matrix. Substrate concentration is lower than 2KsThe time, the microbial metabolism reaction rate then changes with substrate concentration, and is subject to 2Ks Therefore, when the specific inorganic and organic substrate of microbial metabolism, but affected by it and/or the variation of relative some location parameter, will change with the particular substrate change in concentration. In particular, be equal to or greater than 2K when substrate concentrationsThe time, but location parameter and/or this parameter of recording over time rate will be relatively constant. When substrate concentration is down to 2KsWhen following, but location parameter and/or this parameter of recording rate over time is equal to or greater than 2K with substrate concentrationsThe time, be remarkable difference.
In many biological respinses, wish to predict when particular substrate concentration can be down to this important metabolite concentration 2KsBelow. When specific organic and inorganic matrix concentration changes, but can learn the change type of culture of microorganism metabolism behavior by the variation of monitoring certain relevant location parameter.
For example, in many purification of waste water degree of treatments, purpose is to reduce to specific organic and concentration inorganic matrix minimum.These matrix generally include the organic nutrient substance with BOD (biochemical oxygen demand (BOD)) and/or COD (chemical oxygen demand (COD)) expression and detection, and inorganic ammonium salt (NH 4 +).Suppose that nitration reaction and BOD/COD reduction reaction are topmost two reactions, when BOD and ammonia are consumed to its 2K separately sWhen following, consumption rate (BOCR) and pH velocity of variation (pHPR) all can demonstrate its characteristic variations.
With BOCR and pHPR is that the main drawback of controlled variable is, when the continous way purification of waste water is handled, the variation of pH and DO and multiple parameter correlations such as for example nutrition (biodegradable carbon, nitrogen, phosphorus compound or the like) concentration, biomass concentration, basicity in the fluid medium.When waste water was flowed through treatment facility, these parameters often changed.Owing to be subjected to too many unknown and changed factor interference, so be difficult to set up the dependency of location parameter and purification of waste water processing efficiency.Unless when measuring pH and DO, predict these interference parameters or it be maintained at definite value, measure pHPR and BOCR value and can't provide valuable information to waste water treatment efficiency.
Use for example biological activity determination device of the 5th, 466, No. 604 (it classifies reference in this article as) middle statements of United States Patent (USP), can from the waste water main body handling, original position tell wastewater sample.Certainly, according to the present invention, also can use other devices.Herein, so-called " original position " is meant any instant fluid sample partition method, and no matter whether sample is present in the bodies of fluid, for example waste water.In other words, measure, just can use the actual device that in bodies of fluid, takes out sample as long as can accomplish " immediately " and/or " online " substantially.
Accompanying drawing 2 and 3 shows that BOCR and pHPR are with BOD and ammonia (NH 4 +) theory that changes of concentration changes, and in hereinafter explaining.The single sample that accompanying drawing mixes for fluid of telling from the waste water main body (being waste water) and the microorganism that carries out biological nutrition removal (BNR), the variation situation of generation.To telling sample aeration or aeration not.The beginning aeration also proceeds to dissolved oxygen content one limit value that sample dissolution oxygen amount exceeds the waste water main body.In case reach this value, stop aeration, when the dissolved oxygen content of sample is lower than dissolved oxygen content one limit value of waste water main body, just begin aeration again.In the stage of not carrying out aeration, BOCR and pHPR are estimated by following method and calculate:
BOCR=-(Δ DO)/(Δ t) wherein Δ DO is in certain period Δ t, records the variable quantity of saturation dissolved oxygen, and it is represented with percent saturation; And
PHPR=-(Δ pH)/(Δ t) wherein Δ pH is in certain period Δ t, records the variable quantity of pH.
Shown in the A stage of accompanying drawing 2 and 3, work as NH 4 +Be higher than its 2K separately with the concentration of BOD sDuring value, because BOD is with top speed consumption, and be better than nitrated oxygen consumption reaction, so BOCR is constant at its relative maximum.Therefore, pHPR also is constant at the place, centre.This BOCR/pHPR type and hereinafter described those, all based on hypothesis 1) in the biological material, principal reaction is nitration reaction and BOD consumption reaction, 2) hydrionic generation and its active relevant with nitration reaction speed and 3) react and not limited by the oxygen amount of obtaining.
Then, the metabolism of Chi Xuing makes NH 4 +Concentration is reduced to its 2K sBelow, this moment nitration reaction speed, hydrogen ion produces speed and is reduced to than low rate by the highest, wherein ammonia concentration is the metabolic restrictions factor.Shown in the B stage of accompanying drawing 2, pHPR significantly reduces to relative low value, and BOCR then reduces to relative intermediate value, the oxygen demand that this demonstration is caused owing to nitration reaction speed declines to a great extent and the decline of usage quantity.Ammonia concentration is by being higher than 2K sGo to and be lower than 2K s, this A and B transformation between the stage in accompanying drawing 2 illustrate.
Accompanying drawing 2 and C stage of 3, show and work as NH 4 +Concentration is lower than its 2K sAnd BOD also consumes to being lower than its 2K sThe time, the minimum width of cloth of pHPR rises, the variation of this clean metabolism behavior of reflection mixed biologic colony, and BOCR then reduces to its dead slow, and this reflection consumes the extremely low oxygen-consumption of BOD and nitration reaction, and its B and C transformation between the stage in accompanying drawing 2 illustrate.
In the D stage of accompanying drawing 3, show that working as BOD concentration is lower than its 2K s, but NH 4 +Concentration is higher than its 2K sThe time, pHPR rises to maximum, and this reflects high nitration reaction speed; BOCR then reduces to intermediate value, and this reflection is descended only by total oxygen-consumption that the decline of BOD consumption reaction is caused.At this moment, pHPR is maximum value, is because due to the cushioning effect of no BOD consumption reaction.Usually, the carbonic acid gas that is generated by the BOD consumption reaction forms part pH surge capability through the carbonic acid system in sample.Therefore, when the carbonic acid gas of no BOD consumption reaction and its generation, pHPR is than much higher under other conditions.
Based on last example, but because of BOCR and pHPR are the important relevant location parameter of microbial metabolic activity, so can learn biological material for information about by trend and/or the level of monitoring and comparison BOCR and pHPR.In particular, illustrate in this example, when 1) nitrated and BOD removes simultaneously when its top speed is carried out 2) BOD is lower than its 2K s, when carrying out nitration reaction, 3) and ammonia concentration is lower than its 2K s, carry out BOD when removing reaction and 4) ammonia and BOD be lower than 2K separately sThe time, how to make a strategic decision.
The B parameter OCR and the pHPR of direct and continuous comparative measurement can learn several conclusions of relevant waste water situation.During continuous monitoring mixed solution sample, when pHPR significantly rises and BOCR descends simultaneously, expression BOD has reduced to its 2K sBelow, and ammonia is still sufficient.During continuous monitoring mixed solution sample, reduce near zero the time when BOCR reduces to intermediate value and pHPR, expression ammonia has been reduced to its 2K sBelow, and BOD is still sufficient.During continuous monitoring mixed solution sample, when BOCR reduces to low value and pHPR also reduces to low value, expression ammonia and BOD have reduced to its 2K sBelow.When BOCR reduces to low value and pHPR by slightly rising to high slightly low value near zero place, also represent same case.
Table I has been summed up these types, but and how to illustrate by the relative value of comparison location parameter BOCR and pHPR and type and in conjunction with the accompanying drawings 2 and 3 obtain for information about above-mentioned,
Table I
Stage Concentration BOD NH 4 + Location parameter The relative value of location parameter
A >2K s >2K s BOCR High
pHPR Medium
B >2K s <2K s BOCR Medium
pHPR Near zero
C <2K s <2K s BOCR Low
pHPR Low
D <2K s >2K s BOCR Medium
pHPR High
Accompanying drawing 4 illustrates the example of a preferred embodiment that is used for telling wastewater sample.Device 11 is dipped in wastewater trough (only part illustrates), and comprises the sensing chamber 8 of tool removable cover 32.Axle 56 in the apical axis 57 that is connected with motor 53 drives makes removable cover 32 release towards direction shown in the arrow " A ".In the open site, the paddle 48 of rotation makes sensing chamber's 8 inside and outside waste water exchanges, and the waste water fresh sample is full of sensing chamber 8.Through for some time (as 30 seconds), motor 53 backwards rotation make removable cover 32 draw back towards direction shown in the arrow " B ", and are airtight fully to sensing chamber 8.Removable hood 32 and paddle 48 all drive interior axle 56 and outer shaft 55 and 53 coaxial connections of motor by same reversible slow speed of revolution motor 53.This coaxial module is placed in the stainless steel tube 54.
After the waste water fresh sample is full of sensing chamber 8, detect DO concentration, be lower than waste water main body oxygen concn one set(ting)value, then air and/or oxygen are pumped into sensing chamber 8, till reaching this DO concentration through aeration tube 13 as dissolved oxygen content with DO probe 10.Be higher or lower than the dissolved oxygen content of waste water main body oxygen concn one set(ting)value, can guarantee that the aerobic metabolism reaction is identical or approaching with nutrient removal process in the waste water main body in the sensing chamber 8.Similarly, measure the variation of pH with pH probe 12.In addition, paddle 48 can be periodically or persistence rotate, to keep sample in good mixing and be suspended state.
When dissolved oxygen concentration reaches the highest, stop to last the measuring interval period to installing 11 aerations.In this stage, monitor remaining DO concentration and pH with probe, and remaining DO concentration and pH are not influenced by a large amount of aerations of waste water.The pH and the remaining DO signal that are recorded by separately probe 12 and 10 are sent to controller, and press aforesaid equation by it, through numerical differentiation, and with DO and pH over time, are converted to BOCR and pHPR respectively.
Most waste water treatment plant, the BOD and the ammonium concentration of final discharge water all are lower than its 2K sValue.BOD and NH in the sensing chamber 4 +Concentration is brought down below its 2K sThe time, BOCR and pHPR value can significantly change, and this expression is removed nutraceutical aerobic metabolism reaction and is finished.According to the standard shown in the Table I, BOCR and pHPR remove nutraceutical aerobic metabolism reaction as can be known and finish by analysis.In the other biological handling procedure, medium mesostroma concentration is much higher than 2K usually s, make the generation of microorganism growth and object be maintained at top speed.Therefore, by measuring finishing of metabolic reaction, need to add nutrition and matrix as can be known, or when stop the biological treatment program, or when gather in the crops the object that makes.
The relevant information of removing nutraceutical aerobic metabolism reaction such as nitration reaction deadline (NT), denitration time (DNT) etc., all can be used to regulate and control purification of waste water program and other aerobic metabolism programs.For example the waste water treatment plant can compare the average hydraulic detention time of waste water in NT that measures and the aeration tank.When NT is shorter than HRT greatly, then the aerobism nutrient removal is promptly finished at the aeration tank middle section.In fact all the other zones, aeration tank behind this zone are in idle state, and purification of waste water is not had any help.At this moment, the adoptable adequate measure in waste water treatment plant is: some zone of (I) cutting down the aeration tank, with the save operation cost, and/or (2) increase the wastewater feed amount, and increase the treatment capacity of waste water treatment plant effectively, and/or (3) reduce the air feed rate of aeration tank, and aerobism metabolic reaction speed is reduced, so then NT can with hydraulic detention time tight connecting in the aeration tank, and reduce the power consumption of air-blaster.
Embodiment
Embodiment 1
From being positioned at Oaks, the mixed solution sample that take out the senior biological effluent treatment factory aeration tank of Pennsylvania places and is furnished with equipment and the aeration of measuring sample pH, saturation dissolved oxygen and the container of keeping the equipment of sample well blend state.Derive from the data of the equipment of measuring pH and saturation dissolved oxygen, also analyze to calculate BOCR and pHPR with computer record.Sample is in fixing period, and aeration and stop aeration hocketing.The beginning aeration, the dissolved oxygen content of waste water main body adds that a limit value is a standard, when the dissolved oxygen content of sample reaches this standard, stops aeration when obtaining sample.To deduct a limit value be standard to the dissolved oxygen content of waste water main body when obtaining sample, only when the dissolved oxygen content of sample is reduced to this standard, just begins aeration once again.Measure NH 4 +With solvable organic carbon substrate concn, and represent with chemical oxygen demand (COD) (COD).There is linear relationship between COD and BOD.Therefore, represent BOD concentration with the COD analytical value.In aeration phase not, for example indicated with arrow in the accompanying drawing 5 and 6, all converse BOCR and pHPR with the aforesaid method estimation and by numerical differentiation.
Accompanying drawing 5 illustrates, and keeps that (it is much larger than the 2K of COD greater than 150 milligrams of COD/ liters recording COD concentration sValue) and ammonia concentration by greater than 2K sBe changed to and be lower than 2K sCondition under in the process of the test of carrying out, saturation dissolved oxygen and BOCR.By accompanying drawing 5 as can be known, the raw data of dissolved oxygen promptly stops and beginning the relation of the velocity of variation and the BOCR of oxygen between aeration.Accompanying drawing 5 also illustrates, when ammonia concentration is reduced to its 2K sBelow the value, in important metabolism transition process, BOCR is reduced to the transformation of intermediate value by height.BOCR represents with the variation per-cent of per minute oxygen saturation.
Accompanying drawing 6 is in identical period as shown in Figure 5, the pH of sample and pHPR.In this stage, record COD concentration and keep that (it is much larger than the 2K of COD greater than 150 milligrams of COD/ liters sValue), and ammonia concentration by greater than its 2K sBe changed to and be lower than 2K sAccompanying drawing 6 is expressed the raw data of pH, that is stops and beginning the relation of variable quantity and the pHPR of pH between aeration.Accompanying drawing 6 also illustrates, when ammonia concentration is reduced to its 2K sBelow the value, in important metabolism transition process, pHPR is reduced near zero transformation by intermediate value.PHPR represents with the variable quantity of per minute pH.
Accompanying drawing 7 shows, in the identical period as shown in Figure 6, records the variation of ammonia concentration and the pHPR that calculates.Accompanying drawing 7 illustrates, when ammonia concentration from being higher than 2K sReduce to 2K sBelow, pHPR is converted near zero by intermediate value.PHPR represents with the variable quantity of per minute pH.
Accompanying drawing 8 shows, in the identical period as shown in Figure 5, records the variation of ammonia concentration and the BOCR that calculates.Accompanying drawing 8 illustrates, when ammonia concentration from being higher than 2K sReduce to 2K sBelow, BOCR by high-transformation to intermediate value.BOCR represents with the variation per-cent of per minute oxygen saturation.
Accompanying drawing 9 shows the variation consistence of pHPR and ammonia concentration.This is when the contained ammonia of sample exhausts, and promptly when T=120 and T=170 minute, adds ammonia solution and record in the mixed solution sample.At T=0 with between T=195 minute, COD concentration is far above its 2K sTreat after the T=195 that COD concentration is reduced to its 2K sUnder.In the time of about T=90 minute, when ammonia concentration is reduced to its 2K sBelow, can find the remarkable transformation of pHPR.
Then be during at pHPR, add ammonia near the T=120 of null value and T=170 minute.Accompanying drawing 9 illustrates, pHPR by each follow-up interpolation before slightly near null value, jump to as T=0 and the intermediate value between T=90 minute.Work as ammonia after the interpolation ammonia and be consumed to its 2K sBe worth when following, pHPR returns back near zero or low value.When adding ammonia first in T=120 minute, COD measures sufficient, and with the consumption of ammonia, pHPR drops near null value.COD concentration was also reduced to its 2K when adding ammonia once more in T=170 minute sExhausting of ammonia taken place when following.Therefore, pHPR reduces to low value, and non-zero, it is shown in the C stage of accompanying drawing 2 and 3.
Accompanying drawing 10 is to the more complete explanation of the data of accompanying drawing 9, and it comprises pHPR calculated value, BOCR calculated value, ammonia and COD concentration.Clearly illustrate in the accompanying drawing 10 that when important metabolism incident took place, pHPR changed between level different relatively with BOCR.
Example according to the present invention, by the relative level of monitoring BOCR and pHPR, can learn quickly and accurately when the concentration of organic substrate and/or inorganic matrix can reduce to its 2K as can be known thus sBelow.When particular substrate concentration is reduced to its important metabolite concentration 2K sWhen following, have significant change, or contain the change of metabolic type in the sample of living microorganism and/or behavior by expression microbial population or its ambient conditions.
Can use various controlled step according to specified handler.For example, exhaust particular substrate in the microbial population, then represent its metabolic variation, guarantee that required secondary metabolite forms, this represents that promptly handling procedure need have separation, collection and/or purification step.Similarly, in some biological treatment program, microbial population need be used matrix stage feeding, detects this substrate concn and is lower than its 2K sAnd/or when detection interpolation matrix makes its concentration surpass 2K sAbility, all can be used to decision need to increase or reduces the feeding amount.
Embodiment 1 is the oxybiotic organism waste water purification method, and its order ground is by biomechanism, reduces specific inorganic and organic substrate, for example reduces solvable ammonia and organic carbon.Because 2K sConcentration be usually less than to many matrix the fixed horizontal standard of lower concentration, so can be lower than its 2K according to one or more substrate concns sThe situation of concentration adopts various controlled step.For example, all be lower than its 2K separately as organic and inorganic (ammonia) substrate concn sConcentration value then can increase the flow velocity of waste water by the waste water treatment plant, and wastewater treatment capacity also promotes thereupon.All be higher than its 2K separately as organic and amino matter concentration sConcentration value then can reduce the flow velocity of waste water by the waste water treatment plant.When amino matter is lower than its 2K s, and organic substrate is higher than its 2K sThe time, because of the demand reduction of nitration reaction, can reduce the aeration rate of batch processed.At last, if organic substrate concentration is lower than its 2K s, and amino matter concentration is higher than its 2K s, then need increase aeration rate, carry out in order to nitration reaction.
Embodiment 2
Among the embodiment 2,, tell the mixed solution sample with embodiment 1 described same procedure.Continue mixed solution sample aeration to confinement period.Select aeration speed to make the dissolved oxygen concentration of sample be higher than biological removal carbon and the required threshold value of amino matter.By dissolved oxygen probe and pH probe monitoring oxygen concn and pH variable quantity, the result as shown in Figure 11.
Then, in the self-isolation sample, periodically extract mixed with little amount liquid sample out, and analyze its ammonia concentration.Accompanying drawing 12 shows, isolated mixed solution sample, and in whole aeration process, the variation of pH and ammonia concentration.When nitration reaction finishes (ammonia concentration is lower than limit of detection, i.e. 0.1ppm), follow the slow increase of pH value.
PH is to the derivative relation of time, and d (pH)/dt is shown in accompanying drawing 12.When ammonia concentration levels off to zero the time, d (pH)/dt value passed through for the 2nd zero point.D (pH)/dt value also can be considered the position of d (pH)/dt by the negative value vanishing by the 2nd zero point.Reach the required time of this position, be called the nitration reaction deadline of mixed solution sample, or be called NT.At embodiment 2, as shown in Figure 12, recording NT is about 75 minutes.Among the embodiment 2, d (pH)/dt measures different with embodiment 1.Among the embodiment 1, d (pH)/dt measures at aeration phase not, and the d of embodiment 2 (pH)/dt measures when continuous aeration.Owing in the mixed solution sample, remove carbonic acid gas continuously, when measuring pH, may find that pH descends.Thereby pHPR is a negative value sometimes.
Accompanying drawing 13 is that the dissolved oxygen content of same sample distributes and its derivative d (DO)/dt.When ammonia exhausts, the first derivative values of DO, d (DO)/dt, beginning is significantly risen.By the nitration reaction time (NT) that DO records, it also is about 75 minutes.
In this, illustrate that how will measure the nitration reaction time is applied to the biological nitration time variable control.In the bio-reactor or series of biologic reactor that carry out the biological nitration reaction, at bio-reactor foremost, or first bio-reactor front end in the series of biologic reactor, sampling unit is set.The NT that records, being illustrated in present biomass concentration and ammonia load needs to finish nitration reaction through the time of NT down.
The hydraulic detention time (HRT) of mixed solution in bio-reactor or the series of biologic reactor is to consider the flow of mixed solution and the geometrical shape of flow problem and bio-reactor or series of biologic reactor, calculates and gets.The HRT that compares NT and mixed solution then.Suitable nitration reaction, it is when regular job, and NT and HRT are suitable.As NT during much smaller than HRT, in bio-reactor or series of biologic reactor, nitration reaction is finished ahead of time than promptly deciding HRT, and this expression handling procedure has extra nitration reaction capacity.When other pollutents had promptly been removed before ammonia is nitrated fully, NT detected and is indicating wastewater treatment program termination point.This shows that under the same operation condition, used treatment trough volume can be handled more waste water, or the cell body that this program can reduce in the operation is long-pending, to reduce running cost.
On the other hand, if NT much larger than HRT, ammonia concentration can be greater than zero, but not necessarily can surpass emission standard.For guaranteeing the quality of factory's discharge water, improve aeration speed to bio-reactor or series of biologic reactor, and/or the concentration of mixed solution.When NT is higher than HRT for a long time the time, this expression handling procedure overload concerning ammonia is removed, desire is handled the waste water of this specified rate, needs to enlarge waste water disposal facility.
Generally speaking,, can provide information such as the required aeration speed of nitration reaction capacity, bio-reactor or the series of biologic reactor of handling procedure for example, bio-reactor discharge water quality, adjust the nitration treatment program for plant operator through relatively NT and HRT.
The present invention can be applicable to the microbiological treatment program of any kind of, and it includes, but is not limited to purification of waste water (city, trade effluent or the like), medicine/biotechnology manufacturing, brewages, fermentation or any handling procedure that comprises purifying or mixing microorganisms colony.

Claims (19)

1. contain the monitoring method of microbiological treatment program in the fluid feeder of microbial population, it comprises:
A) in the fluid feeder, tell fluid sample;
B) the fixed interval period is measured the pH of fluid sample;
C) change as pH, then analyze its variable quantity, to measure the pH velocity of variation of sample;
D) the fixed interval period, when measuring pH, measure the dissolved oxygen content of sample substantially; With
E) change as dissolved oxygen content, then analyze its variable quantity, to measure the biological consumption rate of sample;
Or
A) in the fluid feeder, tell fluid sample;
B) the fixed interval period is measured the pH of fluid sample;
C) change as pH, then analyze its variable quantity, to measure the pH velocity of variation of sample;
D) when measure the pH velocity of variation is 1) transfer zero and/or 2 to from negative value) transfer zero for the second time to; With
E) show measurement result.
2. change when measuring the pH velocity of variation by analyzing pH according to the process of claim 1 wherein, according to following equation:
pHPR=(dpH)/(dt)
Wherein, pHPR is the pH velocity of variation, and dpH is the variation of pH, and dt is the variation of time, and dpH and dt the two all level off to zero.
3. according to the process of claim 1 wherein that the mensuration of pH and dissolved oxygen content is successive substantially.
4. change when measuring biological consumption rate by analyzing dissolved oxygen according to the process of claim 1 wherein, according to following equation:
BOCR=(dDO)/(dt)
The BOCR thing consumption rate of making a living wherein, dDO is the variation of dissolved oxygen content, dt is the variation of time, and dDO and dt the two all level off to zero.
5. according to the method for claim 1, it further comprises the fixed interval period, repeating step b) to e), and pH velocity of variation that newly records and biological consumption rate compared with pH velocity of variation that had before recorded and biological consumption rate.
6. according to the method for claim 5, wherein the pH velocity of variation that newly records and biological consumption rate are compared with pH velocity of variation that had before recorded and biological consumption rate and determine in the fluid feeder organic and content mineral compound be greater than or less than its 2K separately sConcentration.
7. according to the method for claim 1, further comprise if pH velocity of variation and/or biological consumption rate are when changing and the controlled step of carrying out thereupon.
8. according to the method for claim 7, wherein controlled step comprises by measuring from telling sample to pH velocity of variation and transfers zero and/or transfer zero required time for the second time to and measure the nitration reaction time to by negative value, measure hydraulic detention time in the fluid feeder, and compare nitration reaction time and hydraulic detention time.
9. method according to Claim 8, wherein controlled step further comprise when the nitration reaction time less than hydraulic detention time, then increase the fluid input rate of fluid feeder or reduce fluid feeder aeration speed; When the nitration reaction time greater than hydraulic detention time, then increase the aeration speed of fluid feeder.
10. the method arbitrary according to claim 7-9, wherein the fluid feeder is handled and is had the fluid feeder through aeration and handles stream, and wherein controlled step is that at least a being selected from increases fluid feeder aeration rate, reduces fluid feeder aeration rate, increases the fluid feeder and handle flow, reduce the processing that the fluid feeder is handled flow.
11. the method arbitrary according to claim 7-9 wherein adopts the microbial population feeding method of adding matrix, wherein controlled step comprises change matrix addition.
12. the method arbitrary according to claim 7-9, wherein the microbiological treatment program produces required metabolite, and wherein controlled step is at least a step of separating metabolite from the fluid feeder, collecting metabolite and purifying metabolite that is selected from.
13. according to the process of claim 1 wherein that the step of described separation of the fluid sample is that original position is carried out.
14. according to the process of claim 1 wherein that fluid sample contains required dissolved oxygen content before measuring pH and dissolved oxygen content.
15. tell fluid sample according to the process of claim 1 wherein in the fluid sample container, this fluid sample container comprises can be with the aerator and the sample agitator of air and/or oxygen supply fluid sample.
16. according to the method for claim 15, it further comprises, in sample receiver in the whole process of separating sample with aerator to described fluid sample aeration, its dissolved oxygen content of METHOD FOR CONTINUOUS DETERMINATION and pH when continuing the stirred fluid sample.
17. method according to claim 15, it further comprised the following steps: before the step of pH that measures described fluid sample and dissolved oxygen content, with aerator to described fluid sample aeration till sample contains required saturation dissolved oxygen, in the step of pH that measures fluid sample and dissolved oxygen content with agitator intermittently or continue to stir sample.
18. according to the process of claim 1 wherein that wherein the microbiological treatment program is selected from purification of waste water, medicine or biotechnology manufacturing, brewages and ferments.
19. according to the method for claim 1, it further comprises substantially fluid samples aeration continuously.
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US6106718A (en) * 1998-07-01 2000-08-22 Biochem Technology, Inc. Enhanced denitrification process by monitoring and controlling carbonaceous nutrient addition
US6143246A (en) 1998-08-18 2000-11-07 Biochem Technology, Inc. Apparatus for measuring ammonia in biochemical processes
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US8012758B2 (en) * 2007-02-16 2011-09-06 Nalco Company Method of monitoring microbiological activity in process streams
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