EP0334779A1 - Verfahren und Einrichtung um die gesamte Natur von Brenngasen festzustellen mit dem Ziel, diese zu optimieren und Anwendungen dieser Einrichtungen - Google Patents

Verfahren und Einrichtung um die gesamte Natur von Brenngasen festzustellen mit dem Ziel, diese zu optimieren und Anwendungen dieser Einrichtungen Download PDF

Info

Publication number
EP0334779A1
EP0334779A1 EP89430005A EP89430005A EP0334779A1 EP 0334779 A1 EP0334779 A1 EP 0334779A1 EP 89430005 A EP89430005 A EP 89430005A EP 89430005 A EP89430005 A EP 89430005A EP 0334779 A1 EP0334779 A1 EP 0334779A1
Authority
EP
European Patent Office
Prior art keywords
phthalocyanine
detector
combustion
temperature
burner
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89430005A
Other languages
English (en)
French (fr)
Other versions
EP0334779B1 (de
Inventor
André De Haan
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to AT89430005T priority Critical patent/ATE77486T1/de
Publication of EP0334779A1 publication Critical patent/EP0334779A1/de
Application granted granted Critical
Publication of EP0334779B1 publication Critical patent/EP0334779B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23NREGULATING OR CONTROLLING COMBUSTION
    • F23N5/00Systems for controlling combustion
    • F23N5/003Systems for controlling combustion using detectors sensitive to combustion gas properties
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02DCONTROLLING COMBUSTION ENGINES
    • F02D41/00Electrical control of supply of combustible mixture or its constituents
    • F02D41/02Circuit arrangements for generating control signals
    • F02D41/14Introducing closed-loop corrections
    • F02D41/1438Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor
    • F02D41/1444Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases
    • F02D41/1454Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being an oxygen content or concentration or the air-fuel ratio
    • F02D41/1455Introducing closed-loop corrections using means for determining characteristics of the combustion gases; Sensors therefor characterised by the characteristics of the combustion gases the characteristics being an oxygen content or concentration or the air-fuel ratio with sensor resistivity varying with oxygen concentration
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23NREGULATING OR CONTROLLING COMBUSTION
    • F23N5/00Systems for controlling combustion
    • F23N5/18Systems for controlling combustion using detectors sensitive to rate of flow of air or fuel

Definitions

  • the present invention relates to methods and devices for globally detecting the nature of the combustion gases with a view to optimizing the latter and applications of these devices.
  • Detectors comprising a layer of metallic phthalocyanine placed in contact with the gases resulting from a combustion, for example in contact with the fumes of a burner or the exhaust gases of an internal combustion engine to globally measure the nature and the proportions of the combustion gases.
  • the electrical resistance of the phthalocyanine layer which is a semiconductor varies with the nature and proportions of the combustion gases, which depends on the respective proportions of air and fuel which combine in combustion.
  • Such a detector emits an electrical signal which generally depends on the mixture of gases contained in the combustion gases and which can be used to indicate the ratio between the quantity of air and fuel and / or to optimize this ratio when the signal delivered by the detector is used in a control loop which regulates the amount of air or the amount of fuel.
  • US Patent 4,381,922 describes combustion detectors comprising an insulating plate, electrodes deposited on this plate and a thin layer of an amorphous or crystalline metallophthalocyanine deposited between said electrodes, which is composed of ferrous, ferric phthalocyanine particles , Nickel, cobalt or copper, which have been suspended in a liquid solvent taken from the group of carbon tetrachloride, ether and acetone to be applied in a thin layer.
  • This patent teaches in particular that a copper or iron phthalocyanine, which has been suspended for 24 hours in carbon tetrachloride or in a chlorinated solvent gives rise to a compound whose electrical resistance is ten times lower than that of the same metallic phthalocyanine not treated with carbon tetrachloride or with a chlorinated solvent.
  • This patent also teaches the use of detectors comprising a sensitive layer of copper phthalocyanine, treated with ether to control the proper functioning of a burner.
  • the resistance variation curve as a function of the excess combustion air passes through a fairly flat minimum in the vicinity of the stoichiometric proportions and the detector can be used to regulate the admission of air to the burner.
  • phthalocyanines are p-type semiconductors.
  • water vapor is an electron donor gas which reduces the conductivity of phthalocyanine.
  • the positive charges are stabilized by water vapor and the number of positive carriers capable of ensuring conduction decreases.
  • the semiconductor can become n-type.
  • the gases produced by combustion in particular by the combustion of hydrocarbons necessarily contain water vapor which results of the combination of hydrogen from hydrocarbons with oxygen from the air.
  • US Patent 4,381,922 teaches that, when a phthalocyanine-based detector is used to control a burner in order to regulate the ratio between the quantities of air and of fuels, the detector is placed in a cell heated to a temperature of 95 ° C, to avoid condensation on the combustion water detector by keeping the burner at a temperature above the dew point.
  • detectors based on phthalocyanines are kept at a temperature above the dew point. In fact, if conductive water condenses on the detector, the electrodes of the latter are short-circuited and the electrical signal between the electrodes does not depend on the nature of the combustion gases.
  • U.S. Patent 4,381,922 teaches that one of the problems encountered when using phthalocyanine detectors is their sensitivity to atmospheric humidity. He teaches one way to solve this problem which is to add silica gel or a finely ground molecular sieve saturated with water in a mixture of phthalocyanines and carbon tetrachloride used to make the detectors.
  • the silica gel or molecular sieve powder then acts as a buffer which regulates and stabilizes the reaction to humidity of the detectors.
  • FIG. 10 of this same U.S. patent shows that the logarithm of the resistance of a detector obtained by this method passes through a minimum for a value of the excess of combustion air close to the stoichiometry but this minimum is relatively flat.
  • This flattening of the resistance variation curve near the minimum is due, in particular to the addition of silica gel or a molecular sieve which fix the water and which cause the resistance variations due to a change in composition of gases are masked by the action of water on phthalocyanines.
  • An object of the present invention is to provide new means which make it possible to use phthalocyanine-based detectors to globally detect the nature of the combustion gases which contain water vapor by eliminating the effects of this water vapor on the resistance of said phthalocyanines, which new means have the advantage, compared to known means, that the curve which represents the resistance variations of the detector as a function of the excess combustion air has a very acute minimum peak which coincides with an excess of air corresponding to the combustion optimum of the burner considered.
  • a method for globally detecting the nature of the gases produced by combustion comprises, in known manner, a detector comprising a layer of a metallic phthalocyanine placed between two electrodes which is arranged in the combustion gases and an electrical circuit which one connects to the electrodes between which an electrical signal is collected which varies as a function of the overall nature of the combustion gases, which itself varies as a function of the air / fuel ratio.
  • the objective of the invention is achieved by a process according to which curves of variation of the resistance of metallic phthalocyanine are plotted as a function of the inverse of the temperature thereof expressed in degrees Celsius for various hygrometric degrees of the gases , which curves have a point of convergence and said detector is maintained at a temperature above a minimum threshold, which may be slightly lower than the temperature corresponding to said point of convergence.
  • the phthalocyanine is copper phthalocyanine and the temperature of the detector is maintained above a minimum threshold substantially equal to 40 ° C.
  • the phthalocyanine is cobalt phthalocyanine and the temperature of the detector is maintained at a minimum threshold substantially equal to 30 ° C.
  • a detector according to the invention comprises, in a known manner, a plate made of an insulating material, on which are deposited two electrodes and a film of a metallic phthalocyanine connecting the two electrodes together.
  • the insulating plate also carries electrical heating resistors which are connected to a voltage source.
  • the phthalocyanine film is obtained by applying to said support a thin layer of a suspension of metal phthalocyanine particles in a solvent taken from the group of carbon tetrachloride, ether or acetone, in which has dissolved a very small amount of a hydrophobic material, preferably a liquid or solid alkane whose molecules contain more than ten carbon atoms, for example paraffin oil.
  • a hydrophobic material preferably a liquid or solid alkane whose molecules contain more than ten carbon atoms, for example paraffin oil.
  • the invention results in new detectors comprising a semiconductor layer of a metallic phthalocyanine connecting together two electrodes between which an electrical signal is collected which depends on the composition of the oxygenated gases resulting from combustion in contact with which the detector is placed and which does not depend on the water vapor content of said gases.
  • Phthalocyanines are very sensitive to water vapor which modifies the semiconductor of phthalocyanines by passing it from a p type (electron recipient) to an n type (electron donor).
  • the method according to the invention according to which the temperature of the point of convergence of the curves each representing the evolution of the resistance of a sample of a determined metallic phthalocyanine is determined, as a function of the inverse of the temperature expressed in degrees Celsius, when this phthalocyanine sample is placed in contact with a gaseous atmosphere having a determined hygrometric degree, and the detector made up of this phthalocyanine is kept at a temperature above a minimum threshold which is close to the temperature of said point of convergence and which can be slightly lower than this temperature, makes the detector insensitive to water vapor contained in the combustion gas and therefore to obtain an electrical signal representative of the composition of the combustion gases, which depends on the air / combustible.
  • the method according to the invention has the advantage that the phthalocyanine retains a high sensitivity to variations in the composition of the combustion gases and that the variation curve the resistance of phthalocyanine as a function of the excess air coefficient has a more acute minimum situated in the range of positive air excess coefficients and corresponding to the combustion burner optimum considered for a given load, that is to say for a given fuel flow. It therefore makes it possible to obtain a more precise regulation of combustion, that is to say to maintain the air / fuel ratio closer to the optimum of the burner.
  • the detector By keeping the temperature of the detector near or above the temperature of the point of convergence, the detector is made insensitive to the water vapor contained in the combustion gases, without seeking to avoid the condensation which does not occur if the temperature is higher than the dew point corresponding to the humidity of the combustion gases or if the partially condensed water is trapped.
  • FIG. 1 is a graph drawn up by the inventor which represents on the ordinate the resistance R expressed in ohms of a sample of copper phthalocyanine of type ⁇ and on the abscissa the inverse 1 / t of the temperature t ° of the sample expressed in degrees Celsius.
  • Phthalocyanine type ⁇ corresponds to the monoclinic crystallographic form.
  • This graph represents the resistance variation curves corresponding to different hygrometric degrees staggered between 10% and 70%.
  • This graph shows that, for a determined hygrometric degree, the resistance varies linearly according to the inverse of the temperature and decreases when the temperature increases. It shows that the lines corresponding to different hygrometric degrees are concurrent at a point, called point P of convergence, which corresponds to a value of 1 / t of the order of 0.023, that is to say a temperature of the order of 44 ° C.
  • the present invention is a practical application of this discovery to detectors based on phthalocyanines intended to emit an electrical signal which indicates the nature of the combustion gases charged with water vapor without being influenced by this humidity.
  • This application consists in constantly maintaining the detector at a temperature higher than a value slightly lower than the temperature of the point of convergence P defined by the curves of FIG. 1.
  • the temperature of the phthalocyanine is maintained above 40 ° C.
  • the graph in FIG. 1 shows that for 1 / t ⁇ 0.25, that is to say for t> 40 ° C., the variations in resistance due to variations in humidity of the order of 20% remain low and the electrical signal delivered by the detector is therefore disrupted to a negligible extent by the variations in humidity which are usually encountered.
  • Measurements of variation of the resistance as a function of the inverse of the temperature and the hygrometry carried out on a sample of phthalocyanine of cobalt monoclinic show that one also obtains straight lines which converge at a point which corresponds substantially to a temperature of 36 ° C and which are substantially confused for higher temperatures.
  • the temperature of the detector is kept above approximately 30 ° C. and the effect of a change in the hygrometric degree of the combustion gases becomes negligible.
  • FIG. 2 is a graph which represents the variations of the logarithm of the resistance R plotted on the ordinates of a sample of phthalocyanine of copper, cobalt or iron, maintained at a temperature higher than that of the point of convergence as a function of the coefficient d 'excess air E plotted on the abscissa;
  • FIG. 2 shows that the resistance of a detector composed of metallic phthalocyanine maintained at a temperature higher than a minimum determined according to the nature of the phthalocyanine and placed in contact with the gases of combustion decreases very rapidly when the excess of air increases in the zone corresponding to an air defect, passes through a minimum in the vicinity of optimal combustion, that is to say for slightly positive values depending on the burner and its load and increases again when the excess air increases.
  • FIG. 3 is a graph which represents values measured by means of a detector according to the invention in copper phthalocyanine, maintained at a temperature above 40 ° C. and placed in the fumes emitted by an industrial boiler burner, having a 9.3 MW power.
  • the dashed curve C1 represents the variations in the carbon monoxide (CO) content expressed in parts per million (ppm) as a function of the percentage of oxygen in the flue gases.
  • Curve C2 in solid lines represents the concomitant variations in the resistance expressed in mega-ohms of the detector. This graph shows that the resistance of the detector presents a very accentuated minimum for an excess of air of the order of 3% which corresponds to optimum combustion for which the carbon monoxide content reaches a value substantially zero.
  • FIGS. 2 and 3 show that a detector according to the invention placed in contact with the gases of combustion produces an electrical signal which varies very quickly as a function of the coefficient excess air. On the other hand, the signal does not vary or varies very little as a function of the hydrometric degree of the combustion gases.
  • This signal indicates the quality of combustion. It can be used, for example, to indicate whether a burner fitted to a boiler, an oven or any type of fireplace is operating in good conditions. In this case, it suffices to set a threshold higher than the minimum, to compare the signal emitted by the detector to this threshold and to trigger an alarm signal when this threshold is exceeded to warn the user that the burner is operating in bad conditions. conditions due to either a defect or an excess of air.
  • the signal delivered by a detector composed of metallic phthalocyanines placed in contact with the gases emitted by a combustion device, for example by a burner or by an internal combustion engine can also be used to automatically regulate the coefficient of excess air and to keep it around the optimal value corresponding to the minimum of the electrical resistance value.
  • FIG. 4 schematically represents an exemplary embodiment of a device according to the invention used to optimize the operation of a burner.
  • the reference 1 represents a combustion chamber, for example the hearth of a boiler, equipped with a burner 2 which is supplied with fuel, for example in liquid or gaseous hydrocarbons, by a line 3 which is connected to a source of food 5.
  • a combustion chamber for example the hearth of a boiler, equipped with a burner 2 which is supplied with fuel, for example in liquid or gaseous hydrocarbons, by a line 3 which is connected to a source of food 5.
  • Line 3 may include a flow meter 4 for measuring the fuel flow.
  • the burner 2 is supplied with combustion air through a pipe 7 connected to an air source, for example a fan.
  • Line 7 may include a flow meter 8.
  • a pipe 12 is connected to said flue pipe and to the suction of a fan 13.
  • a chamber or enclosure 11 containing a detector 14 is placed in the path of the pipe 12, so that the detector 14 is constantly in contact with combustion gases which are renewed.
  • the detector 14 includes a semiconductor pad composed of a metallic phthalocyanine, the resistance of which varies as a function of the composition of the combustion gases and in particular, if no precautions were taken, of the water vapor contained in these gases.
  • the semiconductor pad is placed between two electrodes which are connected to a measuring device 15 which emits a signal which varies with the resistance of the detector 14.
  • This signal is used in a servo loop comprising for example an electrical circuit 16 which automatically controls an automatic adjustment means 18 of the air flow arriving at the burner via line 7 or of the fuel flow supplying the burner through line 3 .
  • the electrical circuit 16 can be an analog regulator with derivative action.
  • the electronic circuit 16 can also be a computer coupled to an analog to digital converter. In this case, the computer automatically reduces to the minimum the value of the resistance of the detector 14. For this, it controls the register 18 in one direction, for example that which increases the air flow and it compares the value of the resistance of the detector to a previous value.
  • FIG. 5 represents a preferred embodiment of the detector 14.
  • This detector comprises an insulating support 25 which is for example a plate made of sintered alumina or of epoxy resin or of any rigid material, such as a plastic material coated with a film made of a copolymer of aromatic anhydride and aromatic diamine sold under the name "KAPTON".
  • the material composing the wafer 25 has a very high resistivity for example greater than 1015 ⁇ .cm, much greater than that of the phthalocyanine that makes up the active layer.
  • the plate 25 has an area of the order of cm2.
  • the plate 25 carries two electrodes 26, 27 which for example have the shape of two combs whose teeth are parallel and interposed.
  • the electrodes 26 and 27 can be deposited on the wafer by one of the techniques well known for the production of printed circuits.
  • a thin layer of metallic phthalocyanine is deposited which is preferably a phthalocyanine comprising a central ion Fe2+, Fe3+, Co2+, Cu2+ or Ni2+.
  • the phthalocyanine layer can be applied directly above the electrodes or directly on the support 25.
  • the electrodes 26 and 27 are first printed on the insulating support 25.
  • a small quantity of phthalocyanine powder is mixed with a solvent which is taken from the group consisting of carbon tetrachloride, ether or acetone.
  • a thin film of metallic phthalocyanine is deposited on the insulating plate by evaporation under vacuum, that is to say by sublimation.
  • This vacuum deposition is carried out for example by heating the phthalocyanine to a temperature of the order of 350 ° C., under a reduced pressure of the order of 0.1 Pas (10 ⁇ 3mbars).
  • the latter is kept at a temperature constantly above a threshold determined according to the nature of the phthalocyanine used, for example a temperature above 40 ° C. for a copper phthalocyanine or higher than 30 ° C for a cobalt phthalocyanine.
  • One means of keeping the temperature of the detector above the desired threshold consists in providing the insulating board 25 with a heating resistor which may for example be a resistor printed on the back of the board and connected to a voltage source.
  • Another means for keeping the temperature of the detector above a threshold consists in placing the detector 14 in a chamber 11 whose temperature is regulated so as never to fall below the fixed threshold.
  • Another means consists in treating the phthalocyanine to block it on a p-type conductivity.
  • a method of preparing a detector 14 has been set out above in which a suspension of phthalocyanine particles is formed in a solvent which is preferably carbon tetrachloride.
  • this solvent which is preferably a liquid or solid alkane, the molecules of which contain more than ten carbon atoms.
  • a few milliliters of a liquid alkane are added per liter of solvent.
  • the responses obtained are more uniform from one combustion to another because the effect due to temperature variations is smaller and the minimum of the signal corresponds to the optimum of the burner considered.
  • FIG. 5 schematically represents an application of a detector based on metallic phthalocyanine to regulate the good combustion of an internal combustion engine.
  • the figure shows a single cylinder 20, a piston 21 and the connecting rod 22 which connects the piston to crankshaft 22a.
  • the elements corresponding to those of FIG. 3 are designated by the same references.
  • the reference 3 designates the fuel supply which is provided for example by an injector 23.
  • the reference 10 represents the exhaust duct.
  • the reference 24 represents a spark plug.
  • the detector 14 is placed in a chamber 11 which is interposed on a duct 12 connected in bypass to the exhaust duct 10.
  • the regulator 16 controls a means 18 for adjusting the air intake which is for example a motorized throttle valve placed in the intake duct.
  • the regulator 16 can control the fuel injection pump.
  • FIG. 7 schematically represents an installation for measuring the calorific value of a combustible gas.
  • Fuel gas distributed by a network to subscribers is billed for a specified calorific value (PC).
  • PC calorific value
  • FIG. 7 represents an installation allowing a subscriber to measure the real calorific power of the gas delivered to him.
  • Reference 28 represents a combustion chamber equipped with a small gas burner 29.
  • Reference 30 represents a detector according to the invention based on metallic phthalocyanine which is placed in contact with the gases produced by combustion.
  • the reference 31 represents a smoke rejection chimney.
  • the detector 30 is placed on a conduit connected in bypass to the chimney which leads to a suction device 32, for example a fan or a water pump.
  • a suction device 32 for example a fan or a water pump.
  • the detector 30 is placed inside a thermally insulated chamber 33.
  • the electrical signal emitted by the detector 30 is sent to electronic circuits 34.
  • the electronic circuits control an ignition electrode 35 of the burner and receive a signal from a flame detector 36 which is for example a photoelectric cell.
  • Reference 37 represents a bottle containing a standard combustible gas, for example methane.
  • the outlet duct of the bottle 37 is equipped with a solenoid valve 37a.
  • the reference 38 represents a stop valve which is placed on a pipe 39 connected to the distribution network of a combustible gas for which it is desired to check the calorific value.
  • the reference 38a is a solenoid valve.
  • the reference 40 represents a filter.
  • Reference 41 represents a heated chamber maintained at a constant temperature which is for example 45 ° C.
  • the gas pipe 39 passes through the chamber 40 and it includes, inside this chamber, a coil 41, a pressure regulator 42, a capillary tube 43 and a flow meter 44.
  • the output of the flow meter is connected to the power supply in burner gas 29.
  • the reference 45 represents an air duct which is connected to a source of compressed air, for example to a compressor.
  • the pipe 45 is equipped with a stop valve 46, a solenoid valve 46a, a filter coupled to a pressure reducer 47 and a second filter called the coalescer filter 48.
  • the pipe 45 comprises, in the passage through the chamber 40, a coil 49, a mass flow meter 50 and an automatic valve 51 for regulating the air flow.
  • the assembly formed by the mass flow meter 50 and the control valve 51 is connected to the electronic circuits 34.
  • the air duct leaving the chamber 40 is connected to the air supply to the burner 29.
  • the outlet of the bottle of standard gas 37 is connected in bypass on line 39.
  • the operation is as follows.
  • the burner In a calibration phase, the burner is first operated by supplying it with standard gas and with air and the detector 30 automatically adjusts the position of the automatic valve 51 so that combustion is optimum, that is to say -to say that the air / fuel ratio is equal to the optimum combustion of the burner for the standard gas considered. Knowing the stoichiometric air / fuel ratio of the standard gas, we can thus calculate the deviation from the stoichiometry due to the burner and calibrate the installation.
  • the burner 29 is supplied with an unknown fuel gas, for example the gas delivered by a network of distribution.
  • the detector 30, in cooperation with the electronic circuits 34 and with the regulating valve 51, automatically regulates the air flow to the optimum value corresponding to the combustion optimum.
  • the position of the automatic valve 51 compared to the position it occupied during calibration indicates the amount of air corresponding to the stoichiometric proportions for the gas to be controlled and makes it possible to calculate the lower calorific value of this gas.
EP89430005A 1988-03-21 1989-03-16 Verfahren und Einrichtung um die gesamte Natur von Brenngasen festzustellen mit dem Ziel, diese zu optimieren und Anwendungen dieser Einrichtungen Expired - Lifetime EP0334779B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89430005T ATE77486T1 (de) 1988-03-21 1989-03-16 Verfahren und einrichtung um die gesamte natur von brenngasen festzustellen mit dem ziel, diese zu optimieren und anwendungen dieser einrichtungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8803604A FR2628827B1 (fr) 1988-03-21 1988-03-21 Procede pour optimiser une combustion, dispositif pour la mise en oeuvre de ce procede, ainsi que detecteur equipant un tel dispositif
FR8803604 1988-03-21

Publications (2)

Publication Number Publication Date
EP0334779A1 true EP0334779A1 (de) 1989-09-27
EP0334779B1 EP0334779B1 (de) 1992-06-17

Family

ID=9364432

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89430005A Expired - Lifetime EP0334779B1 (de) 1988-03-21 1989-03-16 Verfahren und Einrichtung um die gesamte Natur von Brenngasen festzustellen mit dem Ziel, diese zu optimieren und Anwendungen dieser Einrichtungen

Country Status (8)

Country Link
EP (1) EP0334779B1 (de)
JP (1) JPH0210257A (de)
AT (1) ATE77486T1 (de)
CA (1) CA1334109C (de)
DE (1) DE68901798T2 (de)
ES (1) ES2033123T3 (de)
FR (1) FR2628827B1 (de)
GR (1) GR3005556T3 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1467149A1 (de) * 2003-04-11 2004-10-13 E.ON Ruhrgas AG Verfahren zum Überwachen der Verbrennung in einer Verbrennungseinrichtung
RU2493488C1 (ru) * 2012-03-07 2013-09-20 Общество с ограниченной ответственностью Научно-Инновационное предприятие СКГМИ (ГТУ) "Стройкомплект-Инновации" ООО НИП СКГМИ Способ оптимизации процесса горения топлива

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2156073B1 (es) * 1999-03-26 2002-03-01 Univ Valladolid Dispositivo sensor con base peliculas delgadas de ftalocianinas depositadas sobre microelectrodos.
DE10001251B4 (de) * 2000-01-14 2005-01-27 Robert Bosch Gmbh Verfahren zum Steuern oder Regeln eines Gasbrenners

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1145077A (en) * 1965-04-19 1969-03-12 Honeywell Inc Improvements in or relating to burner control apparatus
FR2383440A1 (fr) * 1977-03-11 1978-10-06 Frey Yvan Procede de preparation d'une tete de detection
GB2065280A (en) * 1979-12-10 1981-06-24 Measurex Corp Method of controlling the opacity of the exhaust of the combustion of solid fuel and air in a furnace
GB2077437A (en) * 1980-06-07 1981-12-16 Emi Ltd Ammonia gas sensors
EP0047008A1 (de) * 1980-09-02 1982-03-10 Erhard Grolitsch Verfahren zum vollkommenen schadstoffarmen Verbrennen (Oxidation) von kohlenstoffhaltigen Brennstoffen
US4392813A (en) * 1979-08-20 1983-07-12 Matsushita Electric Industrial Co., Ltd. Combustion appliance with safety device
GB2111987A (en) * 1981-12-01 1983-07-13 Nat Res Dev Heterocyclic semiconductors and gas sensors
EP0156958A1 (de) * 1984-03-21 1985-10-09 Hartmann & Braun Aktiengesellschaft Regelverfahren für die Verbrennungsluftmenge einer Feuerungseinrichtung
US4636767A (en) * 1985-08-21 1987-01-13 The United States Of America As Represented By The Secretary Of The Navy Mixed semiconductor film device for monitoring gases

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5818020A (ja) * 1981-07-27 1983-02-02 Sharp Corp 燃焼制御安全装置
JPS58102024A (ja) * 1981-12-11 1983-06-17 Sumitomo Metal Ind Ltd ボイラ−の燃焼制御方法
JPS59125330A (ja) * 1982-12-29 1984-07-19 Matsushita Electric Ind Co Ltd 石油燃焼器

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1145077A (en) * 1965-04-19 1969-03-12 Honeywell Inc Improvements in or relating to burner control apparatus
FR2383440A1 (fr) * 1977-03-11 1978-10-06 Frey Yvan Procede de preparation d'une tete de detection
US4392813A (en) * 1979-08-20 1983-07-12 Matsushita Electric Industrial Co., Ltd. Combustion appliance with safety device
GB2065280A (en) * 1979-12-10 1981-06-24 Measurex Corp Method of controlling the opacity of the exhaust of the combustion of solid fuel and air in a furnace
GB2077437A (en) * 1980-06-07 1981-12-16 Emi Ltd Ammonia gas sensors
EP0047008A1 (de) * 1980-09-02 1982-03-10 Erhard Grolitsch Verfahren zum vollkommenen schadstoffarmen Verbrennen (Oxidation) von kohlenstoffhaltigen Brennstoffen
GB2111987A (en) * 1981-12-01 1983-07-13 Nat Res Dev Heterocyclic semiconductors and gas sensors
EP0156958A1 (de) * 1984-03-21 1985-10-09 Hartmann & Braun Aktiengesellschaft Regelverfahren für die Verbrennungsluftmenge einer Feuerungseinrichtung
US4636767A (en) * 1985-08-21 1987-01-13 The United States Of America As Represented By The Secretary Of The Navy Mixed semiconductor film device for monitoring gases

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 7, no. 203 (M-241)[1348], 8 septembre 1983, page 113 M 241; & JP-A-58 102 024 (SUMITOMO KINZOKU KOGYO K.K.) 17-06-1983 *
PATENT ABSTRACTS OF JAPAN, vol. 7, no. 95 (M-209)[1240], 21 avril 1983, page 46 M 209; & JP-A-58 018 020 (SHARP K.K.) 02-02-1983 *
PATENT ABSTRACTS OF JAPAN, vol. 8, no. 249 (M-338)[1686], 15 novembre 1984, page 101 M 338; & JP-A-59 125 330 (MATSUSHITA DENKI SANGYO K.K.) 19-07-1984 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1467149A1 (de) * 2003-04-11 2004-10-13 E.ON Ruhrgas AG Verfahren zum Überwachen der Verbrennung in einer Verbrennungseinrichtung
RU2493488C1 (ru) * 2012-03-07 2013-09-20 Общество с ограниченной ответственностью Научно-Инновационное предприятие СКГМИ (ГТУ) "Стройкомплект-Инновации" ООО НИП СКГМИ Способ оптимизации процесса горения топлива

Also Published As

Publication number Publication date
FR2628827A1 (fr) 1989-09-22
CA1334109C (en) 1995-01-24
JPH0210257A (ja) 1990-01-16
ES2033123T3 (es) 1993-03-01
DE68901798T2 (de) 1993-02-04
ATE77486T1 (de) 1992-07-15
FR2628827B1 (fr) 1990-07-06
EP0334779B1 (de) 1992-06-17
GR3005556T3 (de) 1993-06-07
DE68901798D1 (de) 1992-07-23

Similar Documents

Publication Publication Date Title
FR2951499A1 (fr) Procede d'evaluation de l'etat d'un capteur de suie dans un vehicule automobile
FR2777075A1 (fr) Procede de conduite d'un four et dispositif pour la mise en oeuvre du procede
EP0334779B1 (de) Verfahren und Einrichtung um die gesamte Natur von Brenngasen festzustellen mit dem Ziel, diese zu optimieren und Anwendungen dieser Einrichtungen
EP0664449B1 (de) Verfahren und Vorrichtung zur Lieferung von Gas an eine Vorrichtung zur Analyse von Verunreinigungsspuren in einem Gas
Adamian et al. Smoke sensor on the base of Bi2O3 sesquioxide
US5248617A (en) Processes and apparatus for detecting the nature of combustion gases
FR2817966A1 (fr) Detecteur de gaz multicouches et systeme associe de detection de concentration de gaz
FR2626673A1 (fr) Procede et dispositif de mesurage de la puissance calorifique vehiculee par un courant de matiere combustible
FR2462706A1 (fr) Dispositif de production d'un signal pour le reglage par reaction du rapport d'un melange air/carburant
EP0077724B1 (de) Verfahren, Fühler und Vorrichtung zur Feststellung von Gasspuren in einem gasartigen Medium
EP2078190A1 (de) Verbrennungsgassensor
FR2465426A1 (fr) Procede de fermentation endothermique du tabac
Demin et al. Effect of composition on properties of In2O3–Ga2O3 thin films
FR2579754A1 (fr) Nitrures et oxynitrures utiles comme detecteurs selectifs de gaz reducteurs dans l'atmosphere, et dispositif de detection les contenant
EP0030979B1 (de) Brennstoff-einspritzvorrichtung
US4796590A (en) Rapid-response method and devices for detection of poor combustion
FR2712961A1 (fr) Réglage en temps réel d'un brûleur à combustible de caractéristiques variables, notamment pour four métallurgique de réchauffage.
WO1989008245A1 (fr) Grossisseur de particules d'aerosol par enrobage de liquide
FR2779826A1 (fr) Detecteur d'ozone, de dioxyde d'azote ou de tout autre gaz polluant et son utilisation
EP0536271A1 (de) Sensor zum nachweis der anwesenheit von flüchtigen stoffen und nicht verbrannten gasen in einem gasfluss oder einer gasförmigen umgebung.
EP4285016A1 (de) Vorrichtung und verfahren zum spülen eines mit kohlenwasserstoffdämpfen beladenen gasstroms
FR2652652A1 (fr) Procede et dispositif de detection d'especes chimiques au moyen d'un film mince de semiconducteur inorganique.
BE873578A (fr) Moteur a combustion interne utilisant in combustible gazeux liquefie
Fasoli et al. Analysis of tin oxide thin films fabricated via sol-gel and delayed ignition of combustion processes
EP1041039A1 (de) Neue Metalloxid-Zusammenzetzungen, daraus erhaltene halbleitende Sensoren und deren Verwendung zur Gas-Detektion

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19900108

17Q First examination report despatched

Effective date: 19910606

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 77486

Country of ref document: AT

Date of ref document: 19920715

Kind code of ref document: T

REF Corresponds to:

Ref document number: 68901798

Country of ref document: DE

Date of ref document: 19920723

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2033123

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3005556

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 89430005.2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970307

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970311

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970319

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970320

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19970324

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970325

Year of fee payment: 9

Ref country code: ES

Payment date: 19970325

Year of fee payment: 9

Ref country code: CH

Payment date: 19970325

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19970328

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970410

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19970509

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980316

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980316

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980316

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980317

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

BERE Be: lapsed

Owner name: DE HAAN ANDRE

Effective date: 19980331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980316

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19981001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981201

EUG Se: european patent has lapsed

Ref document number: 89430005.2

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050316