EP0645527B1 - Méthode pour la réduction de la température d'allumage d'une réaction catalytique et exothermique - Google Patents

Méthode pour la réduction de la température d'allumage d'une réaction catalytique et exothermique Download PDF

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Publication number
EP0645527B1
EP0645527B1 EP94114279A EP94114279A EP0645527B1 EP 0645527 B1 EP0645527 B1 EP 0645527B1 EP 94114279 A EP94114279 A EP 94114279A EP 94114279 A EP94114279 A EP 94114279A EP 0645527 B1 EP0645527 B1 EP 0645527B1
Authority
EP
European Patent Office
Prior art keywords
channels
gas
process gas
diameter channels
ignition temperature
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
EP94114279A
Other languages
German (de)
English (en)
Other versions
EP0645527A1 (fr
Inventor
Ivar Ivarsen Primdahl
Thomas Sandahl Christensen
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.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP0645527A1 publication Critical patent/EP0645527A1/fr
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Anticipated expiration legal-status Critical
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2053—By-passing catalytic reactors, e.g. to prevent overheating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2340/00—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2350/00—Arrangements for fitting catalyst support or particle filter element in the housing
    • F01N2350/02—Fitting ceramic monoliths in a metallic housing
    • F01N2350/06—Fitting ceramic monoliths in a metallic housing with means preventing gas flow by-pass or leakage

Definitions

  • the present invention relates to exothermic catalytic reactions in gaseous reactants passing through a monolithic catalyst body.
  • the invention is concerned with reduction of the ignition temperature during oxidation and combustion processes.
  • catalytic combustors are usually equipped with preheaters operating either on support fuel or electrical energy for the preheating of the feed gas. Compression of the feed gas also increases the gas temperature and partly or completely provides necessary preheating to the compressed gas.
  • preheating As a major drawback of preheating during catalytic processes in general, necessary supply of extraneous energy results in poorer process economy and higher investment costs for preheating equipment. Furthermore, preheating by burners causes formation of nitrogen oxides and reduces strongly the environmental advantage of catalytic combustion. This is, in particular, a problem in the catalytic combustion of gases with high ignition temperature such as methane and other hydrocarbons, which demand extensive preheating.
  • a catalyst body with reduced back pressure resistance and improved warming up performance is disclosed in JP 63 11 3112.
  • the body is composed of 3 monolithic sections with increasing inner peripheral surface of each monolith section in the direction of gas flow.
  • a general object of this invention is directed to the improvement of exothermic catalytic processes being carried out in monolithic structured catalyst, by reducing the ignition temperature of the reactions proceeding on the catalyst and, thereby, substantially reducing energy consumption during those processes.
  • Ignition temperature as used herein defines the lowest temperature at which the exothermic reactions begin and continue in a process gas passing through the monolithic catalyst body.
  • Critical parameters which influence the ignition temperature, comprise concentration of the reactants in the process gas and space velocity of the gas through the catalyst. Other parameters include concentration and type of the catalytic material used.
  • catalytic processes of the above art including catalytic oxidation and catalytic combustion, are a function of this parameter since lower velocities mean longer residence time and an increased conversion rate of reactants. This in turn decreases ignition temperatures by heat evolving due to the exothermic nature of the reactions.
  • space velocity is mainly controlled by the hydraulic diameter of channels for passage of the gas at a given pressure drop across the unit.
  • Channels with a small hydraulic diameter have a higher surface to volume ratio than large hydraulic diameter channels. Because of the higher surface to volume ratio, the catalytic surface area per unit of length is larger in the small diameter channels than in the large diameter channels.
  • a lower space velocity is obtained in the small diameter channels, and, therefore, the residence time of reactants in the channels and on the catalyst is much longer, which in combination with the larger catalytic surface results in much higher reaction rates than in the large diameter channels at a given gas pressure at the inlet of the catalyst unit.
  • this invention provides a process for the reduction of ignition temperature during exothermic catalytic reactions in gaseous reactants in a process gas being passed through a monolithic structured catalyst unit provided with a plurality of small hydraulic diameter channels and a plurality of large hydraulic diameter channels, which method comprises passing a first portion of the process gas through the small diameter channels and a second portion of the process gas through the large diameter channels, so that the first gas portion flows at a low flow velocity and a high reaction rate in the unit and excess of heat evolving during the catalytic reactions proceeding at the high rate in the small diameter channels is transferred to the second portion of the process gas to reduce the ignition temperature of the catalytic reactions proceeding in the large diameter channels.
  • Transfer of heat from the hot process gas in the small diameter channels to reactions in the large diameter channels may be accomplished by direct or indirect heat transfer. Usage of direct or indirect heat transfer depends, thereby, mostly on the heat conducting properties of the monolithic body.
  • a catalytic body for use in the inventive process may be prepared conventionally by corrugating e.g. metallic foils or heat resistant materials in a corrugating machine, or by extruding of ceramic material.
  • the corrugated or extruded bodies are then loaded with catalytic active material by methods well-known in the art and include impregnation or wash coating the body with a solution containing the active material or a precursor thereof.
  • the invention further provides a monolithic catalyst body (Fig. 1) being useful in carrying out the above process.
  • the catalyst body comprises a section with small diameter 2 and a section with large diameter channels 4.
  • sections 2 and 4 are connected in series and separated by a mixing chamber 6 between the sections.
  • a hot gas portion 8 from small diameter channels 2 is mixed with residual process gas 10 being by-passed the small diameter channels in order to reduce pressure drop in the process gas.
  • the temperature of the mixed gas portion 12 will be at or slightly above the ignition temperature necessary for the reactions in the large diameter channels 4.
  • a monolithic catalyst unit of the above kind may be manufactured by arranging e.g. extruded catalyst bodies with the appropriated channel size and length in a reactor tube with a mixing unit established between the bodies.
  • heat evolved by reaction in the small channels may be transferred by indirect exchange through the channel walls.
  • a monolithic catalyst unit is provided with a plurality of small diameter and large diameter channels in parallel, so that each small diameter channel is contiguous to at least a large diameter channel. Heat is, thereby, transferred through the walls between the channel.
  • Such catalyst unit may be prepared by corrugating sheets of suitable material with different corrugation height piling and/or rolling up the sheets to a cylindrical or sandwiched body optionally with a liner between the sheets.
  • the size of hydraulic diameters, the distribution and proportional number of small and large diameter channels is determined on the gas composition and the actual ignition temperature of reactions to be carried out in the unit.
  • the Example is a calculation model related to catalytic combustion of natural gas for gas turbine.
  • the ignition temperature for this reaction depends on the resistance time, and, thereby, the linear gas velocity and the space velocity through the catalyst. For a fixed pressure drop the space velocity will decrease by decreasing the hydraulic diameter of the monolith.
  • the ignition temperature and distance from channel inlet to the point in the channel, where the ignition temperature is obtained, are calculated for different hydraulic diameters (D h ) of 2 mm, 3.5 mm and 5 mm, respectively. Eventual heat transfer between channels has been neglected in this Example.
  • the monolithic catalysts on which the calculations are carried out consist of a spinel carrier with outer diameter of 150 mm and a length of 1000 mm including parallel channels with the above hydraulic diameters and a wall thickness of 0.5 mm.
  • the ignition temperature is defined by 5% methane conversion.
  • the distance for obtaining 5% conversion is listed in Table 1.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (3)

  1. Procédé d'abaissement de la température d'allumage au cours de réactions catalytiques exothermiques dans des réactifs gazeux dans un gaz de procédé que l'on fait passer à travers une unité de catalyseur à structure monolithique munie de plusieurs canaux de petit diamètre hydraulique et de plusieurs canaux de grand diamètre hydraulique, caractérisé par l'étape consistant à faire passer une première partie du gaz de procédé à travers les canaux de petit diamètre et une seconde partie du gaz de procédé à travers les canaux de grand diamètre, de manière que la première partie de gaz s'écoule avec une faible vitesse d'écoulement et une grande vitesse de réaction dans l'unité, et en ce qu'on transfère l'excès de chaleur qui se dégage au cours des réactions catalytiques qui se déroulent à vitesse élevée dans les canaux de petit diamètre à la seconde partie du gaz de procédé afin de réduire la température d'allumage des réactions catalytiques qui se déroulent dans les canaux de grand diamètre.
  2. Procédé de la revendication 1, dans lequel la chaleur est transférée directement à la seconde partie du gaz de procédé par mélange de cette partie avec la première partie de gaz quittant les canaux de petit diamètre.
  3. Procédé de la revendication 1, dans lequel la chaleur est transférée indirectement à la seconde partie du gaz de procédé en faisant passer les première et seconde parties du gaz dans une relation de conduction de chaleur à travers les canaux.
EP94114279A 1993-09-27 1994-09-12 Méthode pour la réduction de la température d'allumage d'une réaction catalytique et exothermique Expired - Lifetime EP0645527B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK931089A DK108993D0 (da) 1993-09-27 1993-09-27 Fremgangsmaade til reduktion af taendingstemperatur
DK1089/93 1993-09-27

Publications (2)

Publication Number Publication Date
EP0645527A1 EP0645527A1 (fr) 1995-03-29
EP0645527B1 true EP0645527B1 (fr) 1997-07-09

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EP94114279A Expired - Lifetime EP0645527B1 (fr) 1993-09-27 1994-09-12 Méthode pour la réduction de la température d'allumage d'une réaction catalytique et exothermique

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Country Link
EP (1) EP0645527B1 (fr)
JP (1) JPH07208743A (fr)
DE (1) DE69404104T2 (fr)
DK (1) DK108993D0 (fr)
ES (1) ES2105452T3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI107828B (fi) * 1999-05-18 2001-10-15 Kemira Metalkat Oy Dieselmoottoreiden pakokaasujen puhdistusjärjestelmä ja menetelmä dieselmoottoreiden pakokaasujen puhdistamiseksi
US6179608B1 (en) * 1999-05-28 2001-01-30 Precision Combustion, Inc. Swirling flashback arrestor
ZA200306075B (en) * 2001-02-16 2004-09-08 Battelle Memorial Institute Integrated reactors, methods of making same, and methods of conducting simultaneous exothermic and endothermic reactions.
DE10219747B4 (de) * 2002-05-02 2005-06-23 Daimlerchrysler Ag Verfahren zur Vermeidung einer Rückzündung in einem einen Reaktionsraum anströmenden Gemisch und Reaktor zur Durchführung des Verfahrens

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002716A1 (fr) * 1990-08-06 1992-02-20 Emitec Gesellschaft Für Emissionstechnologie Mbh Corps metallique monolithique en nid d'abeilles a nombre variable de canaux

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH086582B2 (ja) * 1986-10-31 1996-01-24 マツダ株式会社 エンジンの排気ガス浄化用触媒装置
DE3828644A1 (de) * 1988-08-24 1990-03-01 Bayerische Motoren Werke Ag Verzweigte abgasleitung einer brennkraftmaschine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002716A1 (fr) * 1990-08-06 1992-02-20 Emitec Gesellschaft Für Emissionstechnologie Mbh Corps metallique monolithique en nid d'abeilles a nombre variable de canaux

Also Published As

Publication number Publication date
DK108993D0 (da) 1993-09-27
JPH07208743A (ja) 1995-08-11
DE69404104D1 (de) 1997-08-14
ES2105452T3 (es) 1997-10-16
EP0645527A1 (fr) 1995-03-29
DE69404104T2 (de) 1997-10-30

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