WO2000034773A1 - APPARATUS AND METHOD FOR MEASURING NOx AND NITRIFICATION/DENITRIFICATION RATES IN BIOCHEMICAL PROCESSES - Google Patents

APPARATUS AND METHOD FOR MEASURING NOx AND NITRIFICATION/DENITRIFICATION RATES IN BIOCHEMICAL PROCESSES Download PDF

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Publication number
WO2000034773A1
WO2000034773A1 PCT/US1999/010120 US9910120W WO0034773A1 WO 2000034773 A1 WO2000034773 A1 WO 2000034773A1 US 9910120 W US9910120 W US 9910120W WO 0034773 A1 WO0034773 A1 WO 0034773A1
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WO
WIPO (PCT)
Prior art keywords
sample
liquid
method defined
ammonia
measuring
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Ceased
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PCT/US1999/010120
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English (en)
French (fr)
Inventor
Jaw Fang Lee
Sergey K. Maneshin
Marcus E. Kolb
Xin Yang
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Biochem Technology Inc
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Biochem Technology Inc
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Publication date
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Priority to BR9916024-2A priority Critical patent/BR9916024A/pt
Priority to JP2000587177A priority patent/JP4365038B2/ja
Priority to DE69929686T priority patent/DE69929686T2/de
Priority to EP99920405A priority patent/EP1141702B1/en
Priority to AU37908/99A priority patent/AU765651B2/en
Priority to CA002353991A priority patent/CA2353991C/en
Publication of WO2000034773A1 publication Critical patent/WO2000034773A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0037—NOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/12—Condition responsive control
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173076—Nitrite or nitrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173845—Amine and quaternary ammonium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173845—Amine and quaternary ammonium
    • Y10T436/174614—Tertiary amine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/173845—Amine and quaternary ammonium
    • Y10T436/175383—Ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/177692—Oxides of nitrogen
    • Y10T436/178459—Only nitrogen dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/17—Nitrogen containing
    • Y10T436/177692—Oxides of nitrogen
    • Y10T436/179228—Both nitrogen oxide and dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/25—Chemistry: analytical and immunological testing including sample preparation
    • Y10T436/25875—Gaseous sample or with change of physical state

Definitions

  • the present invention relates to apparatus and methods for measuring amounts of NO x (nitrate (N0 3 ) and/or nitrite (N0 2 )) and nitrification/denitrification rates in liquid and controlling the treatment thereof.
  • BNR biological nutrient removal
  • contaminants in liquids such as wastewater, particularly carbon sources (measured as biochemical oxygen demand or BOD), ammonia, nitrates, phosphates and the like are digested by activated sludge in anaerobic, anoxic and aerobic (oxic) stages, also known in the art.
  • activated sludge in anaerobic, anoxic and aerobic (oxic) stages, also known in the art.
  • wastewater with or without passing through a preliminary settlement process, is mixed with return activated sludge (RAS), sometimes hereinafter referred to as “mixed liquor.
  • RAS return activated sludge
  • One aspect of the invention includes a method of measuring the nitrification rate for a liquid including isolating a first liquid sample at t 0 ; recording a value of ammonia [NH 3 ] ⁇ present in the first sample at a predetermined time t t ; isolating a second liquid sample and introducing air into the second liquid sample after another predetermined time t 2 ; terminating the introduction of air into the second liquid sample and adjusting the p ⁇ of the second sample at t 3 ; recording another value of ammonia [NH 3 ] 2 in the second sample at a predetermined time t 4 ; and determining the nitrification rate of the liquid according to the following formula:
  • NR is the nitrification rate
  • At is t 2 -t 3 and ⁇ [NH 3 ] is [NH 3 ] 1 -[NH 3 ] 2 .
  • Another aspect of the invention includes another method of measuring a nitrification rate for liquids including isolating first and second liquid samples and introducing air into the second liquid sample at t 0 ; recording a value of ammonia [NH 3 ] ⁇ present in the first sample and terminating introduction of air into the second sample at t x ; recording a value of ammonia [NH 3 ] 2 present in the second sample at t 2 ; and determining the nitrification rate of the liquid according to the following formula:
  • NR At wherein NR is the nitrification rate, At is t r t 2 and ⁇ [NH 3 ] is [NH 3 ],-[NH 3 ] 2 .
  • ammonia [NH 3 ] and ammonium [NH 4 + ] are substantially equivalent so long as the p ⁇ value of the solution is known. It is advantageous to measure ammonium concentration, [NH 4 + ], at a lower p ⁇ (p ⁇ ⁇ 6), while the measurement of ammonia concentration, [NH 5 ], is more convenient at an elevated p ⁇ (p ⁇ > 8).
  • the discussion of this invention often refers to the ammonia concentration as [NH 3 ] measured with an ammonia selective probe, with the understanding that at a lower pH, it can be replaced by [NH 4 + ] measured with an ammonium ion selective probe.
  • the invention also includes a method of measuring ⁇ x in liquids, especially wastewater. This method is different from other analyzing methods in that there is no need to prepare the sample by filtration or other method of solids removal.
  • the method includes isolating a wastewater sample; adjusting the pH and/or ionic strength of the sample to a predetermined level for a predetermined time interval t, ; recording a value of [N ⁇ J, present in the sample with an NO x selective probe(s); recording another value of [NO x ] 2 present in the sample after another predetermined time interval t 2 ; determining NO x concentrations in the sample at each predetermined time interval t, and t 2 according to the following formula:
  • ⁇ [NO X ] [NO X ] 2 - [NO x ] ⁇ ; and determining the ⁇ x concentration of the sample according to the following formula: ⁇ [NO X ]
  • the rate of denitrification may be determined.
  • the denitrification rate (DR) may be determined as follows: isolating a liquid sample at t 0 ; recording a value of [NO x ⁇ present in the sample at a predetermined time t 7 ; recording a value of [NO X ] 2 present in the sample at a predetermined time t 2 ; and determining the denitrification rate of the liquid according to the following formula:
  • Fig. 1 is a schematic of a typical wastewater treatment process utilizing embodiments of the invention and shows the many locations that detectors can be installed through out the system.
  • Fig. 2 shows a schematic front elevational view of an embodiment of apparatus of the invention used to monitor a bioreactor tank.
  • Fig. 3 shows a schematic front elevational view of another embodiment of apparatus of the invention used to monitor a bioreactor tank.
  • Fig. 4 shows an exploded schematic view, partially taken in section, of wastewater sampling apparatus in accordance with aspects of the invention.
  • Fig. 5 shows an exploded schematic view, partially taken in section, of wastewater sampling apparatus in accordance with another embodiment of the invention.
  • Fig. 6 shows a schematic view, partially taken in section, of solution dispenser apparatus in accordance with aspects of the invention.
  • Fig. 7 is a block diagram of a method to measure ⁇ O x and a method of calibrating an NO x analyzer in accordance with aspects of the invention.
  • Fig. 8 is a block diagram of a method of determining the rate of denitrification of wastewater.
  • Fig. 9 is a block diagram of a method of determining the rate of nitrification of wastewater.
  • Fig. 10 is a block diagram of another method of determining the rate of nitrification of wastewater. Detailed Description of the Invention
  • Wastewater treatment plants are often subjected to severe transient conditions, such as diurnal variations in organic loads.
  • the proper evaluation and control of a BNR process requires an accurate and current assessment of the amount of NO x and ammonia in the mixed liquor, the nitrification rate and the denitrification rate, among other things, in a variety of environments and under a number of conditions.
  • the apparatus for quantifying ammonia and/or NO x and/or nitrification rate and/or denitrification rate can be used in all stages of a WWTP or any combination thereof. Incorporation of the apparatus into a typical WWTP is shown schematically in Fig. 1. NO x and/or ammonia measurements may be taken at any point or location in the system shown in Fig. 1. This includes multiple measurement locations within a selected stage, if desired.
  • the general application and use of the apparatus in the anaerobic, anoxic and/or aerobic stages of a typical wastewater treatment plant will now be discussed.
  • a bioreactor tank 1 (or, alternatively, a wastewater channel) contains wastewater 2 and/or sludge.
  • Detection apparatus is mounted on the top of bioreactor tank 1 and extends into wastewater 2.
  • the apparatus includes a central control and analysis unit 20 connected to optional computer/monitor 13 by wire or wireless connection 22.
  • central control and analysis unit 20 connects to detection probe 10 by way of wire connection 24.
  • Motor container 26 also connects to central control and analysis unit 20 by way of connection wire 28. Power is supplied to motor container 26 also by wire connection 28.
  • Detection probe 10 is positioned in detection chamber 8 and electrically connected to central control and analysis unit 20 to detect changes in the quantity of ammonia or ammonium or NO x concentration in wastewater samples depending on the configuration.
  • a preferred ammonium ion selective probe 10 is an ammonium probe manufactured by HACH or NICO.
  • a preferred ammonia detection probe 10 is an ammonia gas probe also manufactured by NICO or HACH.
  • a preferred NO 3 and/or NO 2 ion selective probe(s) are manufactured by NICO.
  • Optional computer/monitor 13 may be of any suitable type such as a personal computer or the like.
  • Device 52 consists of two containers (one storing ammonia or NO x calibration solution and the other storing pH adjustment solution and/or ionic strength adjustment solution) and a delivery device for each, for example, a pump.
  • Device 52 is connected to central control and analysis unit 20 by wire 54.
  • Device 52 provides ammonia or NO x calibration and pH adjustment solution and/or ionic strength adjustment solution to the liquid (e.g. wastewater) in detection chamber 8 by connection tube 53 through feed ports 55.
  • the pH adjustment solution typically a base for mid to high pH and an acid for low pH, may be selected from a wide variety of pH altering solutions.
  • Bases include NaOH, KOH and the like.
  • Acids include HC1, acetic acid and the like.
  • the ionic strength adjustment solution typically A1 2 (S0 4 ) 3 solution, or solution of Al 2 (SO 4 ) 3 , Ag 2 SO 4 , H 3 BO 3 , and sulfamic acid, can be selected from a wide variety of solutions for the adjustment of ionic strength of the wastewater sample.
  • Device 52 is described in detail below in conjunction with Fig. 6.
  • Sampling unit 11 is mounted onto a movable carriage 30 which is capable of moving substantially vertically upwardly and downwardly to move sampling unit 11 into and out of wastewater 2.
  • the precise structure of movable carriage 30 is not critical so long as the preferred capability or movability of sampling unit 11 is achieved.
  • Detection probe 10 has its detection end located in detection chamber 8.
  • Detection chamber 8 has an opening 66 and an adjacent movable cover 32 which moves vertically upwardly and downwardly along guide channels 34 and closes or seals opening 66.
  • Fig. 3 shows another embodiment of apparatus for sampling wastewater.
  • FIG. 3 The embodiment shown in Fig. 3 is similar to that shown in Fig. 2 except that apparatus providing for additional sampling capability is provided. Specifically, another detection chamber 8 having a probe 10 is mounted adjacent to the detection chamber/probe configuration shown in Fig. 2. Of course, additional connections are provided to the control and analysis unit 20 and solution supplied by device 52.
  • Fig. 4 shows detection chamber 8 having a detection probe 10A with a detection end 50 A.
  • Detection probe 10A may be an ammonia, ammonium or an
  • Detection chamber 8 also has an optional detection probe 10B with a detection end 50B.
  • Optional detection probe 1 OB is a pH probe.
  • Detection chamber 8 still further has feed ports 55 A and 55B.
  • Feed device 52 feeds pH adjustment solution and/or ionic strength adjustment solution into detection chamber 8 through feed port 55B.
  • Feed device 52 feeds ammonia or
  • Propeller 48 is located interiorly of detection chamber 8 and stirs or agitates samples when probes 10A and 10B are in operation.
  • Cover 32 is in an open position which, when closed, covers opening 66.
  • Propeller 48 is connected to motor container 26 by way of a series of coaxial tubes 102, 104 and 106.
  • An adaptor 108 and a thrust bearing sleeve 112 are contained in and attached to middle tube 104.
  • Outside tube 102 is mounted to base 101.
  • Adaptor 108 is attached to threaded rod 110 to either open or close cover 32 depending on motor direction of linear actuator motor 116.
  • Middle tube 104 travels axially only if induced drag on middle tube 104 exceeds an amount of torque required for linear actuator motor 116 to turn on threaded rod 110. This drag can be induced by propeller 48 attached to middle tube 104 and/or any bushings or other hardware in contact with middle tube 104.
  • Thrust bearing sleeve 112 holds bearing 114 which carries axial tension of central tube 106 when cover 32 is closed. Bearing 114 allows middle tube 104 to rotate independently of central tube 106 and transfers axial motion of tube 104 to central tube 106.
  • Outside tube 102 supports both base 101 and chamber 8 while protecting the internal parts. Chamber 8 is substantially sealed to outside tube 102 and when cover 32 is pulled against chamber 8 the space inside chamber 8 is sealed.
  • FIG. 5 shows another embodiment of a chamber 8 configuration containing an optional additional detection probe. All other components are the same as shown in Fig. 4.
  • Optional detection probe 10C has a detection end 50.
  • Optional detection probe 10C is a dissolved oxygen probe. It connects to central control and analysis unit 20 by way of connection 24C. Referring to Fig.
  • device 52 is constructed to accurately dispense various solutions to other components of the overall system.
  • Device 52 includes a housing 198 and preferably contains two solution containers 200 and 202, although it may be configured to contain only one or more than two solution containers.
  • the containers 200 and 202 have corresponding solution pumps 204 and 206 connected to their respective solution containers with pump feeding lines
  • the pump feeding lines are preferably equipped with a sharp or needle-type device 212 and 214 that extend though housing 198.
  • Each solution container is preferably made of a plastic material that is pierceable by the needle or sharp device, whereby when the solution container is lowered onto the needle, it punctures the container to provide access to the solution.
  • the container is shaped to urge liquid in the solution container to flow towards the needle device.
  • the needle-type device 216 and 218 are connected to air lines 230 and 232.
  • Each pump 204 and 206 connected to the respective solution containers connects control and analysis unit 20 (not shown in Fig. 6), by line 222 and 224.
  • the pumps 204 and 206 also connect to detection chamber(s) 8 (not shown in
  • the solution within the containers may vary.
  • the preferred solution(s) are ammonium chloride or sodium nitrate.
  • the pH and/or ionic strength adjustment solution(s) also can also be held in the containers.
  • one aspect of the invention involves measuring the amount of NO x in the wastewater. This is performed by a method of measuring
  • NO x in liquid including isolating a liquid sample; adjusting the pH and/or ionic strength of the sample at time t 0 ; recording a value of NO x present in the sample with an NO x selective probe(s) at a predetermined time t ⁇ ; recording another value of NO x present in the sample after another predetermined time t 2 ; determining NO x concentrations in the sample at each predetermined time t x and t 2 according to the following formula:
  • the NO x analyzer can be calibrated according to the lower portion of the block diagram shown in Fig. 7 and according to the following method: a) Collect a mixed liquor sample from the wastewater treatment tank and conduct NO x analysis as described above, except that the sample is not discharged to the treatment tank after the NO x concentration is measured. Parameters and intermediate results such as [NO t, [NO X ] 2 , mVj, mV 2 , ⁇ [NO X ]/ ⁇ t are saved for use in the calibration step.
  • c) Wait to t 3 seconds to read the third mV reading from the probe
  • the method includes: a) isolating a first liquid sample at t 0 ; b) measuring the concentration of ammonia [NH 3 ] ⁇ or ammonium [NH 4 + ] !
  • NR ⁇ t At wherein NR is the nitrification rate, ⁇ t is t 3 -t 2 and ⁇ [NH 3 ] is [NH 3 ] r [NH 3 ] 2 or
  • the method includes: a) isolating first and second liquid samples and introducing air into the second liquid sample at t 0 ; b) measuring the concentration of ammonia [NH 3 ] ⁇ or ammonium [NH 4 + ] present in the first sample; c) terminating introduction of air into the second sample at t ⁇ ;
  • NR is the nitrification rate
  • ⁇ t is t x -t and ⁇ [NH 3 ] is [NH 3 ],-[NH 3 ] 2 or ⁇ [NH ] is [NH ] r [NH ] 2 .
  • the preferred operation of the ammonia analyzer in the measurement mode is as follows: a) Collect a mixed liquor sample from the wastewater treatment tank. b) Inject p ⁇ adjustment solution to bring the p ⁇ of the water phase to about 12.0. This can be done either through a predetermined amount or feedback control by way of a p ⁇ probe. This is recorded as time zero, c) Wait to t x seconds to read the first mW l reading from the ammonia probe. d) Wait to t 2 seconds to read the second mV 2 reading from the ammonia probe. e) Use the following equation to calculate ammonia concentrations from mV, and mV 2 , where a and b are linear coefficients of the ammonia probe.
  • the sample is discharged to the treatment tank, and a fresh sample is taken for the next analysis.
  • the ammonia analyzer is preferably calibrated according to the following method: a) Collect a mixed liquor sample from the wastewater treatment tank and conduct ammonia analysis as described above, except that the sample is not discharged to the treatment tank after the ammonia concentration is measured. Parameters and intermediate results such as [NH 3J 1 , [NH 3 ] 2 , rnVj, mV 2 , ⁇ [NH 3 ]/ ⁇ t are saved for use in the calibration step. b) After the ammonia concentration is measured, a predetermined volume of ammonia solution is injected into the sample container so that the concentration of ammonia in the container increases by a ⁇ [NH 3 ] cl , (e.g.
  • the calibration of the ammonia analyzer can be performed as frequently as every measurement cycle, or everyday.
  • the default calibration frequency is preferably once a day.
  • DR denitrification rate
  • the method includes: a) isolating a liquid sample at t 0 ; b) measuring the concentration of NO x ([NO xJ1 ) present in the sample at a predetermined time t , c) measuring the concentration of ⁇ x ([NO x ] 2 ) present in the sample at a predetermined time t 2 ; and d) determining the denitrification rate of the liquid according to the following formula: ⁇ [NO X ]
  • ⁇ R nitrification rate
  • the NR measurement also allows the operator of the wastewater treatment plant to estimate how much wastewater influent the plant can treat with the existing facility, therefore planning for plant expansion or modification.
  • Denitrification rate can be used in the monitoring and control of biological denitrification within the wastewater treatment process.
  • the information can answer the following:
  • the DR measurement allows the evaluation of denitrification activity in terms of carbonaceous nutrient and nitrate loading.
  • a lower DR indicates an endogenous denitrification, as carbonaceous nutrient is limited. Increased carbonaceous nutrient loading enhances the denitrification process.
  • a higher DR predicts an active denitrification process. Increasing the internal recycle improves the total nitrogen removal from the wastewater stream.
  • the invention may be applied to any kind of microbial process including, but not limited to, wastewater purification (municipal, industrial and the like), pharmaceutical/biotechnology production, brewing, fermentation or any other process involving pure or mixed populations of micro organisms.

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  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Activated Sludge Processes (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
PCT/US1999/010120 1998-12-07 1999-05-07 APPARATUS AND METHOD FOR MEASURING NOx AND NITRIFICATION/DENITRIFICATION RATES IN BIOCHEMICAL PROCESSES Ceased WO2000034773A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR9916024-2A BR9916024A (pt) 1998-12-07 1999-05-07 Aparelho e método para medição de nox e taxas de nitrificação/desnitrificação em processos bioquìmicos
JP2000587177A JP4365038B2 (ja) 1998-12-07 1999-05-07 生化学的工程中のNOx及び硝化/脱窒素化速度を測定するための装置と方法
DE69929686T DE69929686T2 (de) 1998-12-07 1999-05-07 Verfahren zum messen der nitrifikationsraten in biochemischen prozessen
EP99920405A EP1141702B1 (en) 1998-12-07 1999-05-07 Method for measuring nitrification rates in biochemical processes
AU37908/99A AU765651B2 (en) 1998-12-07 1999-05-07 Apparatus and method for measuring NOx and Nitrification/Denitrification rates in biochemical processes
CA002353991A CA2353991C (en) 1998-12-07 1999-05-07 Apparatus and method for measuring nox and nitrification/denitrification rates in biochemical processes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/206,543 US5976888A (en) 1998-12-07 1998-12-07 Method for measuring NOx in biochemical processes
US09/206,543 1998-12-07

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WO2000034773A1 true WO2000034773A1 (en) 2000-06-15

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US (2) US5976888A (enExample)
EP (1) EP1141702B1 (enExample)
JP (1) JP4365038B2 (enExample)
CN (1) CN1153967C (enExample)
AR (1) AR018384A1 (enExample)
AT (1) ATE317121T1 (enExample)
AU (1) AU765651B2 (enExample)
BR (1) BR9916024A (enExample)
CA (1) CA2353991C (enExample)
DE (1) DE69929686T2 (enExample)
RU (1) RU2224251C2 (enExample)
TW (1) TW513572B (enExample)
WO (1) WO2000034773A1 (enExample)
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Publication number Priority date Publication date Assignee Title
US6706171B2 (en) 2000-10-12 2004-03-16 Biochem Technology, Inc. Systems for treating wastewater in a series of filter-containing tanks
US8415141B2 (en) * 2007-08-17 2013-04-09 Qimin You Enclosed unit for rapid detection of a target nucleic acid amplification product
JP2012200705A (ja) * 2011-03-28 2012-10-22 Swing Corp 窒素含有排水の処理方法及び装置
JP5685504B2 (ja) * 2011-08-10 2015-03-18 川崎重工業株式会社 水処理システムおよびその曝気風量制御方法
JP2013039538A (ja) * 2011-08-18 2013-02-28 Hitachi Plant Technologies Ltd 廃水処理装置
EP2795295B1 (en) 2011-12-12 2017-10-11 Step Ahead Innovations, Inc. Water-quality monitoring system
WO2013133443A1 (ja) * 2012-03-09 2013-09-12 メタウォーター株式会社 排水の処理装置、排水の処理方法、および排水の処理システム、並びに制御装置、制御方法、およびプログラム
GB201217350D0 (en) * 2012-09-28 2012-11-14 Strathkelvin Instr Ltd Device for monitoring wastewater treatment
WO2014205230A1 (en) 2013-06-19 2014-12-24 Step Ahead Innovations Inc. Aquatic environment water parameter testing systems and methods
FR3064625A1 (fr) 2017-03-30 2018-10-05 Suez Groupe Procede et dispositif de traitement d'eau residuaire
CN109239142B (zh) * 2018-09-14 2020-07-28 华东师范大学 一种沉积物反硝化速率的测定方法及测定装置

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043936A (en) * 1976-02-24 1977-08-23 The United States Of America As Represented By United States Energy Research And Development Administration Biological denitrification of high concentration nitrate waste
US4059499A (en) * 1975-11-20 1977-11-22 Bifok Ab Nitrate ion selective electrode
GB2139610A (en) * 1983-05-10 1984-11-14 Cory & Son Limited Wm Treatment of an aqueous medium to reduce ammonia content thereof
US5304308A (en) * 1992-06-08 1994-04-19 Fuji Electric Co., Ltd. Control method in double-tank-type intermittent aeration activated sludge process
US5401412A (en) * 1993-07-20 1995-03-28 Biochem Technology, Inc. Method and apparatus for monitoring biological activity in wastewater and controlling the treatment thereof
US5403488A (en) * 1989-09-29 1995-04-04 Orpegen Medizinisch-Molekular-Biologische Forschungsgesellschaft Mbh Process for the regulation of an activated sludge clarification plan
EP0745562A2 (en) * 1995-05-31 1996-12-04 Masatoshi Matsumura Purification system for groundwater or wastewater; biochemical reactor and liquid-transport stirring apparatus
BE1010432A5 (nl) * 1996-03-15 1998-08-04 Aquafin N V Een automatisch meetinstrument voor het bepalen van de koolstofstikstof stoichiometrie en de reactiesnelheid van het denitrificatieproces en dat gebaseerd is op een ph-regelaar.

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3348409A (en) * 1963-09-19 1967-10-24 Robert M Arthur Method and apparatus for analyzing gas absorption and expiration characteristics
US3354057A (en) * 1963-09-27 1967-11-21 Allied Chem Method and apparatus for determination of water in liquid ammonia
US3374065A (en) * 1963-12-20 1968-03-19 Toyo Giken Company Ltd Biochemical oxygen demand continual detecting apparatus
US3565583A (en) * 1968-01-15 1971-02-23 Dohrmann Instr Co Method and apparatus for determination of nitrogen in water and in oxygenated hydrocarbon matrices
US3616273A (en) * 1968-04-01 1971-10-26 Standard Oil Co Nitrogen determination and apparatus therefor
US3854877A (en) * 1972-08-07 1974-12-17 Dow Chemical Co Combination tod-tc analysis method
US3877875A (en) * 1973-07-19 1975-04-15 Beckman Instruments Inc Nitrogen constituent analysis
US4162195A (en) * 1974-04-04 1979-07-24 Aktiebolaget Kalle-Regulatorer Biological testing device and method of measuring toxicity of sewage
US4209299A (en) * 1978-02-21 1980-06-24 The Regents Of The University Of California Method and apparatus for determination of volatile electrolytes
US4220715A (en) * 1978-08-03 1980-09-02 Johnston Laboratories, Inc. Apparatus for and method of detection of significant bacteriuria in urine samples through measurement of head space gas oxygen consumption in a closed-vial system
US4277343A (en) * 1979-03-13 1981-07-07 Paz Jacob D Method for continuously monitoring and controlling alkalinity for environmental purposes using a pCO2 probe
US4216065A (en) * 1979-06-18 1980-08-05 University Of Delaware Bio-selective electrode probes using tissue slices
US4288229A (en) * 1980-03-07 1981-09-08 Envirotech Corporation Determination of total organic carbon in a plurality of aqueous samples containing halide ion
US4297173A (en) * 1980-05-22 1981-10-27 Ajinomoto Company, Incorporated Method for determining ammonia and sensor therefor
JPS5999353A (ja) * 1982-11-30 1984-06-08 Agency Of Ind Science & Technol Bodの測定方法及びその装置
US4666610A (en) * 1985-05-28 1987-05-19 Aquascience Research Group, Inc. Method and product for removal of chloramines, chlorine and ammonia from aquaculture water
US4845025A (en) * 1987-11-10 1989-07-04 Coulter Corporation Biological sample mixing apparatus and method
DE3811540A1 (de) * 1988-04-06 1989-10-19 Gimat Verfahren zur bestimmung des chemischen sauerstoffbedarfs von brauchwaessern und vorrichtung zur durchfuehrung des verfahrens
DK374889D0 (da) * 1989-07-28 1989-07-28 Koege Kemisk Vaerk Fremgangsmaade til procesovervaagning
US5013442A (en) * 1990-02-09 1991-05-07 Davis Water & Waste Industries, Inc. Aerobic wastewater treatment with alkalinity control
US5702951A (en) * 1990-07-04 1997-12-30 Commonwealth Scientific And Industrial Research Organisation Continuous RBCOD measurement
DE4224901A1 (de) * 1992-07-28 1994-02-03 Peter Dr Junghans Anordnung und Verfahren zur Bestimmung des Nitrosierungspotentials in einem biochemischen Reaktionssystem mittels der stabilisotopen ·1··5·N-Markierungstechnik
SE509036C2 (sv) * 1993-06-29 1998-11-30 Foss Tecator Ab Förfarande för mätning av kemiska och fysikaliska parametrar för att karakterisera och klassificera vattensuspensioner
US5466604A (en) * 1994-03-08 1995-11-14 Biochem Technology, Inc. Apparatus for monitoring biological activity in wastewater and controlling the treatment thereof
US5552319A (en) * 1993-07-20 1996-09-03 Biochem Technology, Inc. Apparatus and method for monitoring and controlling biological activity in wastewater and controlling the treatment thereof
US5629202A (en) * 1994-07-19 1997-05-13 Development Center For Biotechnology Computer-controlled bioreactor system for enzymatic synthesis of L-tryptophan
DE19509777A1 (de) * 1995-03-17 1996-09-19 Grundig Emv Verfahren zur Bestimmung des Kohlenstoffabbaus und der Nitrifikation in biologischen Systemen
US5658802A (en) * 1995-09-07 1997-08-19 Microfab Technologies, Inc. Method and apparatus for making miniaturized diagnostic arrays
US5698412A (en) * 1996-11-07 1997-12-16 Biochem Technology, Inc. Method for monitoring and controlling biological activity in fluids
US5856119A (en) * 1996-01-22 1999-01-05 Biochem Technology, Inc. Method for monitoring and controlling biological activity in fluids
US6143246A (en) * 1998-08-18 2000-11-07 Biochem Technology, Inc. Apparatus for measuring ammonia in biochemical processes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059499A (en) * 1975-11-20 1977-11-22 Bifok Ab Nitrate ion selective electrode
US4043936A (en) * 1976-02-24 1977-08-23 The United States Of America As Represented By United States Energy Research And Development Administration Biological denitrification of high concentration nitrate waste
GB2139610A (en) * 1983-05-10 1984-11-14 Cory & Son Limited Wm Treatment of an aqueous medium to reduce ammonia content thereof
US5403488A (en) * 1989-09-29 1995-04-04 Orpegen Medizinisch-Molekular-Biologische Forschungsgesellschaft Mbh Process for the regulation of an activated sludge clarification plan
US5304308A (en) * 1992-06-08 1994-04-19 Fuji Electric Co., Ltd. Control method in double-tank-type intermittent aeration activated sludge process
US5401412A (en) * 1993-07-20 1995-03-28 Biochem Technology, Inc. Method and apparatus for monitoring biological activity in wastewater and controlling the treatment thereof
EP0745562A2 (en) * 1995-05-31 1996-12-04 Masatoshi Matsumura Purification system for groundwater or wastewater; biochemical reactor and liquid-transport stirring apparatus
BE1010432A5 (nl) * 1996-03-15 1998-08-04 Aquafin N V Een automatisch meetinstrument voor het bepalen van de koolstofstikstof stoichiometrie en de reactiesnelheid van het denitrificatieproces en dat gebaseerd is op een ph-regelaar.

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BR9916024A (pt) 2005-01-04
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US5976888A (en) 1999-11-02
ZA993303B (en) 1999-11-15
TW513572B (en) 2002-12-11
AU765651B2 (en) 2003-09-25
CA2353991C (en) 2009-01-06
CA2353991A1 (en) 2000-06-15
AU3790899A (en) 2000-06-26
RU2224251C2 (ru) 2004-02-20
JP2003526771A (ja) 2003-09-09
DE69929686D1 (de) 2006-04-13
US6248595B1 (en) 2001-06-19
CN1333872A (zh) 2002-01-30
JP4365038B2 (ja) 2009-11-18
ATE317121T1 (de) 2006-02-15
DE69929686T2 (de) 2006-09-21
AR018384A1 (es) 2001-11-14
EP1141702A1 (en) 2001-10-10

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