US20050000832A1 - Measuring apparatus for monitoring residual oxygen in an exhaust gas - Google Patents

Measuring apparatus for monitoring residual oxygen in an exhaust gas Download PDF

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Publication number
US20050000832A1
US20050000832A1 US10/866,404 US86640404A US2005000832A1 US 20050000832 A1 US20050000832 A1 US 20050000832A1 US 86640404 A US86640404 A US 86640404A US 2005000832 A1 US2005000832 A1 US 2005000832A1
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United States
Prior art keywords
oxygen
phase
partial pressure
reaction chamber
pump
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Abandoned
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US10/866,404
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English (en)
Inventor
Philip Holoch
Thomas Gamper
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Hexis AG
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Hexis AG
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Publication date
Application filed by Hexis AG filed Critical Hexis AG
Assigned to SULZER HEXIS AG reassignment SULZER HEXIS AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAMPER, THOMAS, KOLOCH, PHILIP
Publication of US20050000832A1 publication Critical patent/US20050000832A1/en
Priority to US12/209,118 priority Critical patent/US8366906B2/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/41—Oxygen pumping cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
    • G01N27/4175—Calibrating or checking the analyser
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
    • G01N27/419—Measuring voltages or currents with a combination of oxygen pumping cells and oxygen concentration cells

Definitions

  • the invention relates to a measuring apparatus for monitoring residual oxygen in an exhaust gas in accordance with the pre-characterising part of claim 1 , to a method for operating the measuring apparatus and also to a use of the method.
  • the measuring apparatus is a modified lambda probe (broad band lambda probe) such as is used in cars for monitoring the exhaust gases.
  • the measuring apparatus includes a sensor and in the interior of this a “reaction chamber” in which the partial pressure of molecular oxygen is influenced via electrode reactions.
  • This oxygen partial pressure can be changed or adjusted by means of an oxygen ion pump working electrochemically between the reaction chamber and an exhaust space.
  • a transport of molecular oxygen takes place through a “diffusion gap” into the reaction chamber or out of it.
  • the diffusion gap joins the reaction chamber with the measuring point in the exterior region of the probe at which the concentration of the residual oxygen in the exhaust gas (or its partial pressure) is determined as a desired value.
  • the oxygen partial pressure in the reaction chamber is preset as the desired value of a regulating circuit.
  • the actual value of this regulating circuit is determined electrochemically by means of a Nernst cell with respect to a reference value which is given by the oxygen partial pressure of the atmosphere.
  • An electrical “pump current” with which an oxygen outflow or inflow is brought about in the oxygen ion pump is the set value of the regulating current.
  • a steady state sets in which the diffusion current of the molecular oxygen through the diffusion gap and the oxygen ion current in the ion pump are the same size.
  • the difference between the oxygen partial pressure in the exhaust gas and that of the reaction chamber results in a pump current which can not only be positive but also negative.
  • the Nernst cell and the oxygen ion pump respectively include an oxygen ion conducting solid electrolyte layer and electrode layers applied on this layer by means of which redox processes result with molecular oxygen, with oxygen ions of the solid electrolyte layer and with electrons.
  • the solid electrolytes are only conductive for the oxygen ions at a high temperature.
  • the electrons in the oxygen ion pump are introduced or removed via an electrical circuit at the electrodes; in this arrangement they form the pump current.
  • the strength of the pump current can be used as a measure for the concentration of the residual oxygen in the exhaust gas which is to be measured.
  • the voltage determined using the Nernst cell is compared in an electronic measuring apparatus with a reference voltage which corresponds to the desired value of the partial pressure in the reaction chamber.
  • the strength of the pump current is regulated to adapt the actual value to the desired value.
  • an energy saving procedure consists of producing electrical energy by means of fuel cells in addition to the production of thermal energy.
  • precautionary measures are prescribed.
  • a measure of this kind can be the use of a measuring apparatus for monitoring the residual oxygen in the exhaust gases which arise during the production of energy in order to avoid a less than stoichiometric combustion and a formation of explosive or toxic gases.
  • An example of a system with a Lamda probe is described in EP-A-0 818 840 ( FIG. 7 ).
  • a reliable “intrinsically safe” functional reliability of the probe used for the measurement is of great importance. At any time during the operation of the fuel cell unit, one has to know whether the measuring apparatus is carrying out the monitoring correctly.
  • the object of the invention is to produce a measuring apparatus for monitoring the residual oxygen in an exhaust gas, the condition of which is monitored by a supplementary procedure in order to facilitate a timely intervention using remedial measures if defects in the measuring apparatus occur. This object is satisfied by the measuring apparatus defined in claim 1 .
  • a Lambda probe is used with the measuring apparatus for monitoring residual oxygen in an exhaust gas in which a measuring point for oxygen at a sensor is connected with a reaction chamber via a diffusion gap.
  • the reaction chamber drives a stream of oxygen I O2 along the diffusion gap by means of a controllably adjustable oxygen partial pressure p i .
  • An oxygen partial pressure p i pre-determined as a desired value is set up in the reaction chamber by means of an electro-chemical oxygen ion pump driven by an electrical pump current I p .
  • the pump current the strength of which is proportional to the strength of the oxygen current driven along the diffusion gap, can be used as a measured variable for the partial pressure p m of the residual oxygen in the exhaust gas or its concentration.
  • phase N the residual oxygen can be monitored.
  • the Lamda probe can be operated temporarily, in particularly intermittently in a phase H or a phase L.
  • the oxygen partial pressure p i in the reaction chamber assumes a largely minimum value or a largely maximum value.
  • the dependent claim 2 relates to an advantageous embodiment of the measuring apparatus in accordance with the invention.
  • Methods for operating this measuring apparatus are respectively the subject of the claims 3 to 7 .
  • Claim 8 relates to applications of the method in accordance with the invention.
  • FIG. 1 a section through a part of a Lambda probe
  • FIG. 2 a graphic illustration of the pump current in the dynamic operation of the measuring apparatus in accordance with the invention for a lean exhaust gas ( ⁇ >>1) and
  • a Lamda probe 1 as schematically illustrated in FIG. 1 , includes a sensor 2 and an electronic part 3 . These two components 2 and 3 form a part of the measuring apparatus in accordance with the invention with which the residual oxygen in an exhaust gas can be measured.
  • a reaction chamber 25 is located in the interior of the sensor 2 in which the partial pressure pi can be influenced by molecular oxygen by means of electrochemical reactions which take place on an electrode. This oxygen partial pressure pi can be changed by means of an electrochemical oxygen ion pump working between the reaction chamber 25 and the exhaust gas.
  • a transport of molecular oxygen takes place through a diffusion gap 22 into the reaction chamber 25 or out of it.
  • the diffusion gap 22 which can consist of a porous material containing, fine and communicating pores, connects the reaction chamber 25 with a measuring point 24 at which the partial pressure p m of the residual oxygen in the exhaust gas is determined.
  • the stream of the oxygen diffused by the diffusion gap 22 is termed I O2 .
  • the oxygen partial pressure p m is determined electrochemically by means of a Nernst cell with reference to a reference value which is given by means of the partial pressure p 0 of the atmospheric oxygen existing in the environment.
  • the relative proportion of the oxygen in the atmosphere amounts to 21% by volume.
  • the oxygen pump and the Nernst cell respectively include a negative ion conducting solid electrolyte layer 20 a , or 20 b .
  • the solid electrolytes are only conductive for the oxygen ions at a high temperature.
  • a temperature of preferably 750° C. is produced by means of a heater 27 integrated in the sensor 2 .
  • An electric heating element 27 ′ made of platinum is embedded in an outer base plate 20 d , which is thermally conductively adjacent to an inner base plate 20 c.
  • Electrodes 21 a , 21 b and 21 c and 21 d are applied to the relatively thick solid electrolyte layers 20 a and 20 b as thin layers.
  • the electrode 21 b of the oxygen ion pump is electrically conductingly connected to the electrode 21 c of the Nernst cell. These two electrodes 21 b and 21 c cover a large part of the inner surface of the reaction chamber 25 .
  • Redox processes take place on the electrodes between molecular oxygen, oxygen ions of the solid electrolyte layers and electrons.
  • the electrons are respectively supplied by and led away by an electrical circuit 3 ′ at the electrodes 21 a and 21 b ; in this arrangement they form a pump current I p . If a steady state is present for the oxygen ion pump, the strength of the pump current I p can be used as a measurement for the concentration of the residual oxygen to be measured in the exhaust gas.
  • the oxygen stream I O2 flowing through the diffusion gap 22 is driven due to the difference of the partial pressures p m and p i .
  • I o2 is proportional to the pump current I p .
  • the oxgen partial pressure p i in the reaction chamber is adjusted to a desired value using the Nernst cell.
  • the voltage determined using the Nernst cell which corresponds to the actual value of p i is compared in the electronic part 3 with a reference voltage which corresponds to the desired value of p i .
  • the reference voltage is produced in a component 31 which is arranged on a connection 34 between ground 32 and the input of an operational amplifier.
  • the pump current I p flows through a line 23 to the electrode 21 a of the oxygen ion pump.
  • the line 23 contains an ohmic resistance 33 at which the pump current I p can be measured as voltage U p .
  • the strength of the pump current I p is regulated to adapt the actual value to the desired value of p i .
  • the known Lambda probe 1 is usually operated using a fixed reference voltage (450 mV for example) of the component 31 so that a constant oxygen partial pressure p i sets in in the reaction chamber 25 .
  • the reference voltage is dynamically driven in a large range by respectively changing from one reference voltage to the next one after short phases (time intervals).
  • new values are continually set for the oxygen partial pressure p i in the reaction chamber.
  • phase N a normal operating phase
  • the partial pressure p m of the residual oxygen is measured.
  • the Lamda probe 1 is operated from time to time in a phase H or in a phase L. In these phases H and L, p i assumes a largely minimum value (p H ⁇ p m ) or a largely maximum value (p L ⁇ p 0 ) in the reaction chamber 25 .
  • the phases are termed phase H, phase N and phase L (based on “high”, “normal” and “low”).
  • the reference voltages typically amount to 900 mV (for H), 450 mV (for N) and 20 mV (for L).
  • the oxygen partial pressure p i in the reaction chamber 25 assumes values which differ by several powers of ten. Thanks to the large differences an amplification results for the pump current I p , which, when compared with the usual amplification of pump currents, is very much greater. Due to this amplification, defects which have an influence of the transport of the molecular oxygen into the reaction chamber 25 are easily recognisable.
  • Temperature swings have an influence on the permeability of the diffusion gap 22 and on the ion mobility of the oxygen pump and thus on the probe signal. For this reason, the power of the electrical heating 27 with which the sensor 2 is kept at the pre-given temperature, is regulated. To this end the internal resistance of the Nernst cell is not used, as is common, since this is subjected to severe aging. Instead a heating current is briefly interrupted in phases and during this interruption the resistance of the heating element 27 ′ is measured. This measured value is a measurement for the temperature of the sensor 2 . In the new state the temperature control can be calibrated with regard to the inner resistance because the value of this inner resistance is known for the new state.
  • a regulation is effected once to the inner resistance of the Nernst cell. As soon as this corresponds with a desired value, the actual value of the resistance of the heating element is taken/recorded. This value can subsequently be taken as a desired value for the heating power control during the whole life of the sensor 2 .
  • a corresponding correction in the strength of the thermal flow is carried out by means of a control circuit, in order to maintain a pre-given operating temperature (750° C.) of the sensor.
  • the Lambda probe is operated in the phase H or in the phase L, with the oxygen partial pressure in the reaction chamber 25 assuming largely extreme values in these operating phases.
  • FIG. 2 shows the dynamic signal of a pump current I p , if a lean exhaust gas ( ⁇ >>1) forms an oxygen source at the measuring point 24 which has a high oxygen partial pressure p m of about 10 4 Pa.
  • the reference voltage of the component 31 which determines the desired value in relation to p i is continually varied step-by-step with the progress of time from low to medium (normal), from medium to high and from high to low and periodically in this manner so that a periodic sequence of the phases L, N and H sets in.
  • the reference voltage of the component 31 is left unchanged at each step during a time interval, at least until a steady state has set in. The settling requires 3 seconds for example.
  • the operating phases N, L and/or H can last for different lengths of time.
  • the pump current I p which is proportional to the difference between p m and p i , relatively large values result for the all three operating phases L, N and H.
  • the pump current I p is only disrupted for a short while during the transition from the phase H to the phase L and even shows a change in the flow direction.
  • the oxygen partial pressure pi in the reaction chamber has to be increased considerably, from practically zero to around 102 Pa. This increase mainly results from an inflow of molecular oxygen from the exhaust gas of the measuring point 24 .
  • the phases N and H can not be distinguished from each other on the basis of the graph in the diagram of FIG. 2 .
  • the measuring point 24 even forms a negative oxygen source in the phase L, in other words an oxygen sink.
  • the phases N and L can only be distinguished from one another on the basis of the graph at the profile directly after the transitions from L to N and from H to L.
  • the method in accordance with the invention can be used in an apparatus in which exhaust gases in have to be monitored during combustion or in an electrochemical reaction.
  • the apparatus can be a vehicle or a heating apparatus.
  • the method in accordance with the invention is particularly suitable in a fuel cell system with which not only thermal energy but also electrical energy can be produced simultaneously from one fuel.
US10/866,404 2003-07-03 2004-06-10 Measuring apparatus for monitoring residual oxygen in an exhaust gas Abandoned US20050000832A1 (en)

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US12/209,118 US8366906B2 (en) 2003-07-03 2008-09-11 Measuring method for monitoring residual oxygen in an exhaust gas

Applications Claiming Priority (2)

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EP03405495.7 2003-07-03
EP03405495 2003-07-03

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US (2) US20050000832A1 (da)
EP (1) EP1494025B1 (da)
JP (1) JP4796756B2 (da)
KR (1) KR20050004004A (da)
CN (1) CN1576837A (da)
AT (1) ATE368850T1 (da)
AU (1) AU2004202985A1 (da)
DE (1) DE502004004491D1 (da)
DK (1) DK1494025T3 (da)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008025631A1 (de) * 2006-09-01 2008-03-06 Robert Bosch Gmbh Schaltungsanordnung zum betreiben einer führungssonde
US20090152113A1 (en) * 2004-05-04 2009-06-18 Kuo-Chuang Chiu Gas detection system
US20100281854A1 (en) * 2007-07-23 2010-11-11 Jia Huang Fault analysis method for a lambda probe
US20110314898A1 (en) * 2008-07-10 2011-12-29 Dirk Liemersdorf Sensor element and method for determining gas components in gas mixtures, and use thereof
WO2012007238A1 (de) * 2010-06-15 2012-01-19 Robert Bosch Gmbh Schaltungsanordnung zum betreiben einer gassonde
US20130186169A1 (en) * 2010-06-08 2013-07-25 Claudius Bevot Method for detecting the type of lambda probes
US20140287519A1 (en) * 2013-03-19 2014-09-25 Robert Bosch Gmbh Method, Control Device and Device for Analyzing a Gas
CN110530951A (zh) * 2018-05-25 2019-12-03 罗伯特·博世有限公司 用于诊断废气传感器的方法

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DE102005032456A1 (de) * 2005-07-12 2007-01-25 Robert Bosch Gmbh Verfahren zur Dynamikdiagnose einer Abgassonde
DE102005056515A1 (de) * 2005-11-28 2007-05-31 Robert Bosch Gmbh Verfahren zur Erkennung der Diffusionsgaszusammensetzung in einer Breitband-Lambdasonde
DE102007009157A1 (de) * 2007-02-26 2008-08-28 Robert Bosch Gmbh Verfahren zum Betreiben einer Lambdasonde
DE102009026418B4 (de) 2009-05-22 2023-07-13 Robert Bosch Gmbh Konditionierung eines Sensorelements in einem Brennerprüferstand bei mindestens 1000°C und Konditionierungsstrom
DE102009027378A1 (de) * 2009-07-01 2011-01-05 Robert Bosch Gmbh Verfahren und Diagnosevorrichtung zur Diagnose einer beheizbaren Abgassonde einer Brennkraftmaschine
CN101811870B (zh) * 2009-07-21 2012-09-05 哈尔滨理工大学 铝合金熔体含氢量快速测定仪用探头及制造方法
DE102013223049A1 (de) * 2013-11-13 2015-05-13 Robert Bosch Gmbh Verfahren zur Diagnose einer Lambda-Sonde im laufenden Betrieb
CN110308190A (zh) * 2019-07-30 2019-10-08 苏州禾苏传感器科技有限公司 一种带扩散障片式氧传感器芯片
DE102022209840A1 (de) * 2022-09-19 2024-03-21 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zum Betrieb einer elektrochemische Vorrichtung sowie elektrochemische Vorrichtung

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US5558752A (en) * 1995-04-28 1996-09-24 General Motors Corporation Exhaust gas sensor diagnostic
US6059947A (en) * 1997-07-14 2000-05-09 Ngk Insulators, Ltd. Gas sensor
US6471840B1 (en) * 1998-12-21 2002-10-29 Kabushiki Kaisha Riken Composite sensor
US20030116433A1 (en) * 2001-11-15 2003-06-26 Lothar Diehl Sensor for measuring the concentration of a gas component in a gas mixture
US20040089279A1 (en) * 2002-11-12 2004-05-13 Woodward Governor Company Apparatus for air/fuel ratio control

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090152113A1 (en) * 2004-05-04 2009-06-18 Kuo-Chuang Chiu Gas detection system
US20090223819A1 (en) * 2006-09-01 2009-09-10 Robert Bosch Gmbh Circuit arrangement for operating a guide probe
WO2008025631A1 (de) * 2006-09-01 2008-03-06 Robert Bosch Gmbh Schaltungsanordnung zum betreiben einer führungssonde
US20100281854A1 (en) * 2007-07-23 2010-11-11 Jia Huang Fault analysis method for a lambda probe
US8386155B2 (en) 2007-07-23 2013-02-26 Continental Automotive Gmbh Fault analysis method for a lambda probe
US8940144B2 (en) * 2008-07-10 2015-01-27 Robert Bosch Gmbh Sensor element and method for determining gas components in gas mixtures, and use thereof
US20110314898A1 (en) * 2008-07-10 2011-12-29 Dirk Liemersdorf Sensor element and method for determining gas components in gas mixtures, and use thereof
US9347903B2 (en) * 2010-06-08 2016-05-24 Robert Bosch Gmbh Method for detecting the type of lambda probes
US20130186169A1 (en) * 2010-06-08 2013-07-25 Claudius Bevot Method for detecting the type of lambda probes
CN102939532A (zh) * 2010-06-15 2013-02-20 罗伯特·博世有限公司 用于运行气体探测器的电路布置
WO2012007238A1 (de) * 2010-06-15 2012-01-19 Robert Bosch Gmbh Schaltungsanordnung zum betreiben einer gassonde
US9983157B2 (en) 2010-06-15 2018-05-29 Robert Bosch Gmbh Circuit assembly for operating a gas probe
US20140287519A1 (en) * 2013-03-19 2014-09-25 Robert Bosch Gmbh Method, Control Device and Device for Analyzing a Gas
CN110530951A (zh) * 2018-05-25 2019-12-03 罗伯特·博世有限公司 用于诊断废气传感器的方法

Also Published As

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JP4796756B2 (ja) 2011-10-19
AU2004202985A1 (en) 2005-01-20
JP2005024561A (ja) 2005-01-27
US8366906B2 (en) 2013-02-05
EP1494025B1 (de) 2007-08-01
KR20050004004A (ko) 2005-01-12
US20090057163A1 (en) 2009-03-05
DK1494025T3 (da) 2007-09-17
DE502004004491D1 (de) 2007-09-13
CN1576837A (zh) 2005-02-09
EP1494025A1 (de) 2005-01-05
ATE368850T1 (de) 2007-08-15

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