US3854877A - Combination tod-tc analysis method - Google Patents

Combination tod-tc analysis method Download PDF

Info

Publication number
US3854877A
US3854877A US00278531A US27853172A US3854877A US 3854877 A US3854877 A US 3854877A US 00278531 A US00278531 A US 00278531A US 27853172 A US27853172 A US 27853172A US 3854877 A US3854877 A US 3854877A
Authority
US
United States
Prior art keywords
oxygen
carbon dioxide
combustion zone
detector
total
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.)
Expired - Lifetime
Application number
US00278531A
Other languages
English (en)
Inventor
E Csaky
C Thompson
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Priority to US00278531A priority Critical patent/US3854877A/en
Priority to DE2339229A priority patent/DE2339229A1/de
Priority to NL7310698A priority patent/NL7310698A/xx
Priority to CA178,112A priority patent/CA990190A/en
Priority to FR7328701A priority patent/FR2195794A1/fr
Priority to BE134329A priority patent/BE803324A/xx
Priority to JP48088088A priority patent/JPS49133090A/ja
Application granted granted Critical
Publication of US3854877A publication Critical patent/US3854877A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Organic contamination in water
    • 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
    • Y10T436/23—Carbon containing
    • Y10T436/235—In an aqueous solution [e.g., TOC, etc.]

Definitions

  • the combined capabilities of the instrument provide means for determining an index of the degree of nitrification in certain waste treatment processes.
  • Apparatus for carrying out the foregoingprocess will be better understood by reference to the accompanying which comprises the steps of flowing a feed gas stream composed of an inert gas containing-a minor proportion of oxygen into a heated combustion zone at a constant rate.'Within the combustion zone, the feed gas is passed through a combustion supporting, porous-catalyst bed. The combustion zone is heated at a combus tion-supporting temperature within the-range from about 600 up to about 1200C., preferably within the range from about 800 to about l0O0C. From the heated combustion zone, the gas stream is fed into a detector train.
  • First in this train is means for cooling the gas, which may be simply the gas conduit itself as cooled by the surrounding atmosphere, and means for separating any condensate that may be formed as a result of the intermittent introduction of combustion products.
  • the feed gas stream is then passed through a detector for carbon dioxide. Subsequently, the gas stream is passed through a continuous, quantitative oxygen detector.
  • a small amount of an aqueous dispersion containing a combustible material is injected into the combustion zone upstream from the porous catalyst bed. This sample is vaporized and any combustibles contained therein are oxidized to produce carbon dioxide. In addition, nitrogenous compounds will be oxidized to some degree.
  • the carbon dioxide detector measures the amount of total carbon (TC) that was contained in the injected sample. Subsequently, within the oxygen detector, the total oxygen demand, which includes the oxygen used in forming the carbon dioxide and in oxidizing oxidizable nitrogen compounds, is measured in terms of the decrease in the amount of oxygen relative to the background oxygen content of the feed gas stream. This measurement yields what is termed herein the total oxygen demand (TOD) of the aqueous dispersion.
  • TOD total oxygen demand
  • the difference between the measured TOD and the calculated TOD from the measured TC measurements yields an indication of the amount of oxidizable nitrogenous materials present in the sample analyzed.
  • The-depicted apparatus comprises a dilute oxygen feed stream supply means 2, which in this particu- -lar illustration is composed of an arrangement of an inert gas (for example, nitrogen) supply tank 3 and an oxygen supply tank 4 integrally feeding a feed gas line.
  • an inert gas for example, nitrogen
  • Nitrogen and oxygen are metered into the feed gas line 6 through pressure and flow control valves 7 and 8. Any known means for producing a carrier gas stream containing a controlled amount of oxygen may be used in place of the particular means illustrated.
  • Line 6 feeds the mixed gas stream into a confined combustion zone defined by that portion of the combustion tube 15 within the heating zone 13 of an electric furnace 9. Within the heated combustion zone is a gas permeable, catalyst bed 16 of an oxidation supporting catalyst material. The temperature of the heating 'zone 13 is controlled by a variable power control 10 feeding through the electrical input lines 11' and 12 which are connected to the terminalsof a resistanceheating coil 14.
  • suitable injection means such as the illustrated syringe 17.
  • suitable injection means such as the illustrated syringe 17.
  • pneumaticaut'omatic injection valves may be used.
  • the trajectory for sample injection is such that the sample will be deposited within the heating zone 13 on the upstream side of the catalyst bed 16.
  • Gaseous products from the heated zone 13 of the combustion conduit 15 are passed through cooling means, which in the illustration is simply conduit 19' as cooled at ambient air conditions.
  • the gas is passed through a water trap 54 which is vented as required through valve 52 to remove condensate. From the water trap 54, the gas ispassed through conduit 33 into the carbon dioxide-sensitized, infrared analyzer 35 containing a detection cell 36.
  • the variable voltage signal from the carbon dioxide detector is amplified by means of a low voltage amplifier 38 connected to said detector by electrical leads 63 and 64.
  • the enhanced electrical signal is then fed through leads 61 and 62 into a continuous graphic recorder 39, which produces a curve 41 on a continuous strip of recording paper 42.
  • the amplitude of, and the area under, the curve 41 are each a function of the carbon dioxide concentration continuously measured in the detection cell 36 of the infrared analyzer 35.
  • the degree of amplification and After passing through the detection cell 36 the gaseous product is passed through conduit 37 into an oxygen detector 21 and from this detector exhausts into the atmosphere through vent 20.
  • the oxygen detector 21 produces an electrical signal which is fed through electrical connections 23 to read out means 30, which is a graphic recorder 26.
  • the signal from the oxygen detector which may be measured as voltage or current, is proportional to, and therefore correlative with, the oxygen content of the gaseous effluent. If desired, the recorded signal can be calibrated for direct reading of the signal as the oxygen content of the effluent gas stream.
  • TOD total oxygen demand
  • Q is a function of t, which is time, and Q, is the oxygen content of the feed gas stream, or in other terms the oxygen content of the effluent gas under steady state conditions.
  • t and are the timesot' sampleinjection and return of the oxygen content of the effluent gas to that of the feed gas stream, respectively.
  • a graphic illustration of the value of the above equation solved for TOD is shown in the drawing by the shaded area 3l between the base line 29 representing the oxygen content of the feed gas stream and curve 27 plotted by the graphic recorder 26 between 1 and
  • variations in the oxygen content of the gaseous effluent from the combustion zone are reflected in the amplitude or displacement of the curve 27 from the recorder base line 29.
  • the displacement of the recorded curve 27 from the base line '29 is directly proportional to the amount of oxygen used in the combustion of the sample, i.e., the total oxygen demand of the aqueous dispersion.
  • the output results from recorders 26 and 39 can be tabulated in conventional fashion and stored in a computer for re-v above patents incorporated herein by reference. It will be apparent from reading these teachings that numerous changes in equipment'can be made without detracting from the benefit of achieving both TOD and TC measurements on a given aqueous sample plus the capability of differential measurement of oxidiieree nitrogenous materials as will be described in detail below.
  • the present invention provides a method for determining the degree of oxidation occurring in a process stream such as, for example,-the degree of nitrification occurring in the biooxidation of a waste stream.
  • the computer is programmed to read out a function such as the ratio of TC to TOD. of 'the influent minus the ratio of TC to TOD of the effluent and the values of this function serve as an index of the degree of nitrification occurring in the oxidative process.
  • a function such as the ratio of TC to TOD. of 'the influent minus the ratio of TC to TOD of the effluent and the values of this function serve as an index of the degree of nitrification occurring in the oxidative process.
  • the apparatus is calibrated with samples of known composition and/or compared with analyses of like samples by standard methods of analysis.
  • the foregoing method can be considered as comprising generating a first signal proportional to the TC and a second signal proportional to the TOD of an influent stream of a process and combining said first and second signals to generate a third signal proportional to a ratio of said first and second signals. Similar first, second and third signals are generated from a sample of the effluent stream from said process and the third signals from the influent and effluent streams are combined to generate a signal having a value which serves as an index of the degree of oxidation occurring in said process.
  • Conventional electronic equipment is available for storing, reproducing and combining the above signals and for producing a readout of the resultant index value either in numerical or graphical form.
  • a processfor simultaneously measuring the total oxygen demand and total carbon of an aqueous dispersion of combustible material which comprises the steps l. flowinga feed gas stream containing a relatively small amount of oxygen at a constant rate through a confined combustion zone heated at a combustion supporting temperature within the range from about 600 to about l200C. and, within the combustion zone, flowing the feed gas stream through a combustion supporting catalyst bed,
  • a method as in claim 1 including the additional step of calibrating each of the signals obtained from the carbon dioxide detector and oxygen detector to yield a measurement of carbon and total oxidizable material contained in the aqueous dispersion.
  • a method for determining the degree of oxidation change in a process stream which comprises generating signals proportional, respectively, to a ratio of the total oxygen demand and the total carbon in the influent stream to an oxidative reaction zone and in the effluent stream from said zone and combining said signals to generate a signal the value of which is an index of the degree of oxidation occurring in said zone.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Molecular Biology (AREA)
  • Combustion & Propulsion (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Biomedical Technology (AREA)
  • Emergency Medicine (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
US00278531A 1972-08-07 1972-08-07 Combination tod-tc analysis method Expired - Lifetime US3854877A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00278531A US3854877A (en) 1972-08-07 1972-08-07 Combination tod-tc analysis method
DE2339229A DE2339229A1 (de) 1972-08-07 1973-08-02 Kombiniertes tod-tc-analysenverfahren
NL7310698A NL7310698A (de) 1972-08-07 1973-08-02
CA178,112A CA990190A (en) 1972-08-07 1973-08-03 Combination tod-tc analysis method
FR7328701A FR2195794A1 (de) 1972-08-07 1973-08-06
BE134329A BE803324A (fr) 1972-08-07 1973-08-07 Procede et appareil d'analyse du carbone total et de la demande totale en oxygene d'une dispersion aqueuse
JP48088088A JPS49133090A (de) 1972-08-07 1973-08-07

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00278531A US3854877A (en) 1972-08-07 1972-08-07 Combination tod-tc analysis method

Publications (1)

Publication Number Publication Date
US3854877A true US3854877A (en) 1974-12-17

Family

ID=23065334

Family Applications (1)

Application Number Title Priority Date Filing Date
US00278531A Expired - Lifetime US3854877A (en) 1972-08-07 1972-08-07 Combination tod-tc analysis method

Country Status (7)

Country Link
US (1) US3854877A (de)
JP (1) JPS49133090A (de)
BE (1) BE803324A (de)
CA (1) CA990190A (de)
DE (1) DE2339229A1 (de)
FR (1) FR2195794A1 (de)
NL (1) NL7310698A (de)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958941A (en) * 1975-02-06 1976-05-25 Sybron Corporation Apparatus for measuring content of organic carbon
US3960498A (en) * 1974-08-01 1976-06-01 Instrumentation Laboratory, Inc. Electrochemical analysis system
US3985505A (en) * 1974-11-21 1976-10-12 Leco Corporation Combustion system
US4095951A (en) * 1974-05-24 1978-06-20 Raytheon Company Organic carbon analyzer system
WO1980001108A1 (en) * 1978-11-16 1980-05-29 Metropolitan Sanitary District In-line distillation system
US4277438A (en) * 1979-09-04 1981-07-07 Astro Resources Corporation Method and apparatus for measuring the amount of carbon and other organics in an aqueous solution
US4293522A (en) * 1979-05-21 1981-10-06 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrophotolysis oxidation system for measurement of organic concentration in water
US4344918A (en) * 1980-03-05 1982-08-17 Xertex Corporation Determination of total carbon in liquid samples
US4540468A (en) * 1983-09-26 1985-09-10 Board Of Trustees Of The University Of Maine Method for determining the degree of completion and pulp yield
US4666860A (en) * 1984-01-10 1987-05-19 Anatel Instrument Corporation Instrument for measurement of the organic carbon content of water
US4868127A (en) * 1984-01-10 1989-09-19 Anatel Corporation Instrument for measurement of the organic carbon content of water
US5047212A (en) * 1984-01-10 1991-09-10 Anatel Corporation Instrument for measurement of the organic carbon content of water
US5271900A (en) * 1990-03-09 1993-12-21 Shimadzu Corporation Carbon analyzer for both aqueous solutions and solid samples
US5275957A (en) * 1984-01-10 1994-01-04 Anatel Corporation Instrument and method for measurement of the organic carbon content of water
US5677190A (en) * 1994-12-14 1997-10-14 Anatel Corporation Cell and circuit for monitoring photochemical reactions
EP1914546A2 (de) * 2006-10-19 2008-04-23 IAV GmbH Ingenieurgesellschaft Auto und Verkehr Vorrichtung und Verfahren zur Bestimmung der Gebrauchseigenschaften eines Schmiermittels
US20170343523A1 (en) * 2014-12-08 2017-11-30 Lar Process Analysers Ag Analysis system for analyzing water and wastewater

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296435A (en) * 1964-07-06 1967-01-03 Dow Chemical Co Method and apparatus for determining the total carbon content of aqueous systems
US3421856A (en) * 1965-12-29 1969-01-14 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials
US3528800A (en) * 1966-02-14 1970-09-15 Leeds & Northrup Co Optimized blowing control for basic oxygen furnaces
US3560156A (en) * 1965-05-03 1971-02-02 Dow Chemical Co Determining the oxygen demand of combustible materials in aqueous dispersions
US3567386A (en) * 1969-02-03 1971-03-02 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials
US3567385A (en) * 1969-02-03 1971-03-02 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials
US3607230A (en) * 1969-01-21 1971-09-21 Koppers Co Inc Process for controlling the carbon content of a molten metal bath

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3296435A (en) * 1964-07-06 1967-01-03 Dow Chemical Co Method and apparatus for determining the total carbon content of aqueous systems
US3560156A (en) * 1965-05-03 1971-02-02 Dow Chemical Co Determining the oxygen demand of combustible materials in aqueous dispersions
US3421856A (en) * 1965-12-29 1969-01-14 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials
US3528800A (en) * 1966-02-14 1970-09-15 Leeds & Northrup Co Optimized blowing control for basic oxygen furnaces
US3607230A (en) * 1969-01-21 1971-09-21 Koppers Co Inc Process for controlling the carbon content of a molten metal bath
US3567386A (en) * 1969-02-03 1971-03-02 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials
US3567385A (en) * 1969-02-03 1971-03-02 Dow Chemical Co Method and apparatus for determining the oxygen demand of oxidizable materials

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4095951A (en) * 1974-05-24 1978-06-20 Raytheon Company Organic carbon analyzer system
US3960498A (en) * 1974-08-01 1976-06-01 Instrumentation Laboratory, Inc. Electrochemical analysis system
US3985505A (en) * 1974-11-21 1976-10-12 Leco Corporation Combustion system
US3958941A (en) * 1975-02-06 1976-05-25 Sybron Corporation Apparatus for measuring content of organic carbon
WO1980001108A1 (en) * 1978-11-16 1980-05-29 Metropolitan Sanitary District In-line distillation system
US4265857A (en) * 1978-11-16 1981-05-05 The Metropolitan Sanitary District Of Greater Chicago In-line distillation system
US4293522A (en) * 1979-05-21 1981-10-06 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Electrophotolysis oxidation system for measurement of organic concentration in water
US4277438A (en) * 1979-09-04 1981-07-07 Astro Resources Corporation Method and apparatus for measuring the amount of carbon and other organics in an aqueous solution
US4344918A (en) * 1980-03-05 1982-08-17 Xertex Corporation Determination of total carbon in liquid samples
US4540468A (en) * 1983-09-26 1985-09-10 Board Of Trustees Of The University Of Maine Method for determining the degree of completion and pulp yield
US4666860A (en) * 1984-01-10 1987-05-19 Anatel Instrument Corporation Instrument for measurement of the organic carbon content of water
US4868127A (en) * 1984-01-10 1989-09-19 Anatel Corporation Instrument for measurement of the organic carbon content of water
US5047212A (en) * 1984-01-10 1991-09-10 Anatel Corporation Instrument for measurement of the organic carbon content of water
US5275957A (en) * 1984-01-10 1994-01-04 Anatel Corporation Instrument and method for measurement of the organic carbon content of water
US5271900A (en) * 1990-03-09 1993-12-21 Shimadzu Corporation Carbon analyzer for both aqueous solutions and solid samples
US5677190A (en) * 1994-12-14 1997-10-14 Anatel Corporation Cell and circuit for monitoring photochemical reactions
EP1914546A2 (de) * 2006-10-19 2008-04-23 IAV GmbH Ingenieurgesellschaft Auto und Verkehr Vorrichtung und Verfahren zur Bestimmung der Gebrauchseigenschaften eines Schmiermittels
EP1914546A3 (de) * 2006-10-19 2009-04-22 IAV GmbH Ingenieurgesellschaft Auto und Verkehr Vorrichtung und Verfahren zur Bestimmung der Gebrauchseigenschaften eines Schmiermittels
US20170343523A1 (en) * 2014-12-08 2017-11-30 Lar Process Analysers Ag Analysis system for analyzing water and wastewater

Also Published As

Publication number Publication date
NL7310698A (de) 1974-02-11
FR2195794A1 (de) 1974-03-08
CA990190A (en) 1976-06-01
BE803324A (fr) 1974-02-07
JPS49133090A (de) 1974-12-20
DE2339229A1 (de) 1974-02-21

Similar Documents

Publication Publication Date Title
US3854877A (en) Combination tod-tc analysis method
US3296435A (en) Method and apparatus for determining the total carbon content of aqueous systems
Johansson et al. Production of nitric oxide in loam under aerobic and anaerobic conditions
US4066402A (en) Analytical method and apparatus for determination of total nitrogen and/or carbon contents in aqueous systems
EP0670490A3 (de) Verfahren und Vorrichtung zum Messen eines Gasmediums mit einem chemischen Sensor.
US4332591A (en) Analytical method and apparatus for the determination of total nitrogen contents in aqueous systems
US3819499A (en) Device for detecting one or more oxidizable components in a sample
US3560156A (en) Determining the oxygen demand of combustible materials in aqueous dispersions
Alberti et al. Amperometric solid-state sensor for NO and NO2 based on protonic conduction
DE3632480C2 (de)
US3420636A (en) Carbon monoxide analyzer
US3880722A (en) Potentiometric CO detector
US3567385A (en) Method and apparatus for determining the oxygen demand of oxidizable materials
US1375933A (en) Apparatus and process for gas analysis
US3421856A (en) Method and apparatus for determining the oxygen demand of oxidizable materials
US3681032A (en) Carbon content analysis
Young et al. Biochemical oxygen demand (BOD), chemical oxygen demand (COD), and total oxygen demand (TOD)
Nakajima Simultaneous determination of dissolved organic carbon and phosphorus in waters using flame ionization and photometric detectors
US20030205077A1 (en) Continuous on-line carbon analyzer
Helms Rapid measurement of organic pollution by total organic carbon and comparisons with other techniques
JPH02195255A (ja) 還元性雰囲気炉における炉気中のカーボンポテンシャル測定装置
JPS60142257A (ja) 無機炭素測定法及び測定器
Via 3RD INTERNATIONAL CONGRESS ON MARINE MUNICIPAL AND INDUSTRIAL WASTEWATER DISPOSAL
Scott et al. The characteristics of a Zirconia solid electrolyte detector for oxygen
CA1054036A (en) Analytical method and apparatus for determination of total nitrogen and/or carbon contents in aqueous systems