EP0803580A1 - Verfahren und Anlage zum Herstellen einer Wärmebehandlungsatmosphäre - Google Patents

Verfahren und Anlage zum Herstellen einer Wärmebehandlungsatmosphäre Download PDF

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Publication number
EP0803580A1
EP0803580A1 EP97400801A EP97400801A EP0803580A1 EP 0803580 A1 EP0803580 A1 EP 0803580A1 EP 97400801 A EP97400801 A EP 97400801A EP 97400801 A EP97400801 A EP 97400801A EP 0803580 A1 EP0803580 A1 EP 0803580A1
Authority
EP
European Patent Office
Prior art keywords
reactor
gas mixture
mixture
catalytic reactor
gas
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.)
Ceased
Application number
EP97400801A
Other languages
English (en)
French (fr)
Inventor
Klaus c/o Air Liquide GmbH Bucker
Pascale Pourtalet Mcsweeney
Philippe Poynot
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.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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 Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0803580A1 publication Critical patent/EP0803580A1/de
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C21D1/763—Adjusting the composition of the atmosphere using a catalyst

Definitions

  • the present invention relates to the field of atmospheres used in heat treatment furnaces. It is more particularly interested in the atmospheres obtained by deoxygenation of a gaseous mixture comprising oxygen (such as for example consisting of air, or of a mixture of air and nitrogen obtained by cryogenic route, or of an impure nitrogen produced by air separation by permeation or adsorption), by reaction of this mixture with a hydrocarbon in a catalytic deoxygenation reactor.
  • a gaseous mixture comprising oxygen such as for example consisting of air, or of a mixture of air and nitrogen obtained by cryogenic route, or of an impure nitrogen produced by air separation by permeation or adsorption
  • atmospheres most often contain a majority species which is generally nitrogen, supplemented if necessary, according to the type of heat treatment practiced and the nature of the materials treated, by additional more or less active species such as H 2 , CO, H 2 O, CO 2 , or even hydrocarbons.
  • the catalytic reactor is positioned substantially vertically, the incoming gas mixtures (comprising oxygen and hydrocarbon) approach the reactor in its lower part, the heat treatment atmosphere resulting from the reaction between the two species being recovered. and discharged from the top of the reactor.
  • reaction process occurring within the catalytic reactor, between oxygen and the hydrocarbon in fact comprises several elementary reactions.
  • the residual hydrocarbon from the atmosphere reacts with carbon dioxide and the water formed during the reactions mentioned above.
  • the reactions that occur at during this second reaction stage are highly endothermic.
  • the catalytic reactor is traditionally heated to a temperature which can reach several hundred ° C. or even more than 1000 ° C. depending on the type of catalyst used.
  • the upper part of the reactor is then that which is the most strongly heated. However, to this heat due to electric heating, there is added the heat given off by the exothermic reactions occurring precisely in the upper part of the reactor.
  • This upper part of the reactor is therefore subjected to particularly high temperatures, which can cause a phenomenon of sintering of the catalyst grains, therefore an alteration which can lead to a reduction in reactivity of the catalyst; -ii) Furthermore, this heat which therefore accumulates in the upper part of the reactor actually accumulates in the zone where the exothermic reactions which consume little energy take place, which consequently does not favor not the endothermic reactions which, as we have seen, are mainly located in the lower part of the reactor.
  • the configuration of the catalytic reactor according to the invention overcomes these two drawbacks.
  • the reactive gases mixture comprising oxygen and mixture comprising hydrocarbon
  • the heat treatment atmosphere produced is recovered in the upper part of the reactor.
  • the reactor being placed in a substantially vertical position. Exothermic reactions take place mainly in the lower part of the reactor while endothermic reactions take place essentially in the upper part of the reactor, the heat accumulated in the upper part of the reactor due to natural convection can thus directly benefit these endothermic reactions .
  • the process according to the invention for developing a heat treatment atmosphere, by catalytic reaction, between a first gas mixture comprising oxygen and a second gas mixture comprising a hydrocarbon, in a catalytic reactor, is then characterized by that the catalytic reactor is in a substantially vertical position and that the gas mixtures are brought into the catalytic reactor from the bottom of the reactor, to recover the heat treatment atmosphere resulting from the reaction from the top of the catalytic reactor .
  • the catalytic reactor contains a catalyst based on a precious metal such as platinum or palladium, and the reaction is carried out at a temperature between 400 ° C and 900 ° vs.
  • the catalytic reactor contains a catalyst based on a non-noble metal such as nickel, and the reaction is carried out at a temperature between 800 and 1200 ° C.
  • the first mixture comprising oxygen may for example consist of an impure nitrogen produced on site by air separation by membrane or by adsorption, the residual oxygen content of such a first gas mixture is then advantageously understood between 0.5 and 7%, preferably between 2 and 7% by volume.
  • the first gaseous mixture comprising oxygen may also consist of a mixture of air and nitrogen of cryogenic origin.
  • the second gas mixture comprising a hydrocarbon may for example consist of natural gas, or of propane, or of a mixture of hydrocarbons.
  • the second gaseous mixture is a by-product from the recovery of an industrial site, mainly comprising CO, hydrogen, and a hydrocarbon (most often methane), the overall content of the second mixture of these three components being at least 50% by volume.
  • These recovery mixtures traditionally comprise, in addition to CO, hydrogen, and hydrocarbon, heavy hydrocarbons (typically a few%), CO 2 (typically a few% also), but also traces of nitrogen and sulfide.
  • Such a heat exchange could for example be carried out in a gas / gas exchanger of the plate exchanger type.
  • the catalytic reactor is arranged in the installation in a substantially vertical position, and in that the incoming pipe is connected in its downstream part with the bottom of the reactor, the outgoing pipe being connected in its upstream part with the top of the reactor.
  • the first source of gaseous mixture comprising oxygen may for example consist of an air separator by permeation or adsorption, or alternatively consist of a mixture of air and nitrogen of cryogenic origin.
  • the installation also comprises a gas / gas exchanger having at least a first channel and a second channel, the gas inlet of the first channel being connected to the gas outlet of the catalytic reactor, the gas inlet of the second path being connected to the source of the first gas mixture, the gas outlet of the second path being connected to the low point of the catalytic reactor.
  • the first gas mixture is conveyed via line 4, to the inlet of one of the channels of a plate exchanger 5, from which it emerges via line 6 to join the upper inlet 7 of the catalytic reactor 1. added to the first gas mixture, before its arrival in the catalytic reactor, the second gas mixture 3 via the connection line 9.
  • the atmosphere resulting from the reaction inside the catalytic reactor between the two gas mixtures is evacuated, via the low point 8 of the catalytic reactor, via line 10, to another of the paths of the exchanger 5, where it exchanges calories with the first gas mixture 2 comprising oxygen.
  • the heat treatment atmosphere is directed, via the gas line 11, to a user station 14.
  • the gaseous mixture 12 which comprises oxygen is, after having passed through one of the channels of an exchanger with plates 23, directed, via a pipe 21, towards the low point 19 of a catalytic reactor 16.
  • the second gas mixture 26 which comprises a hydrocarbon.
  • the heat treatment atmosphere resulting from the reaction between the two mixtures inside the reactor 16 is evacuated, via the high point 20 of the catalytic reactor, by a gas line 22, connected to another channel of the exchanger 23 , from which it emerges through a pipe 24 to be directed to the user station 14.
  • the heating resistors surrounding the catalytic reactor have been symbolized by the reference 17, and by the reference 18 thermal insulation surrounding the reactor.
  • the number 28 symbolizes an advantageous arrangement of the upper part allowing the supply of this reactor with catalyst, and which will be detailed below in the context of FIGS. 3 and 4.
  • FIGS. 3 and 4 illustrate precisely a particularly advantageous configuration of the upper part of the reactor allowing the supply of fresh catalyst to the reactor, under good conditions of safety and ease of handling (in conditions where, as already mentioned, there is a convection of hot gases towards the top of the reactor).
  • a bifurcation 22 allows to evacuate the heat treatment atmosphere resulting from the reaction carried out inside the catalytic reactor .
  • FIG. 4 makes it possible to better visualize the rod structure 29 integral with the upper part of the flange 31 and located inside the pipe 30, and which in a way makes it possible to decapsulate this part of the installation: the rod 29 is integral with the upper part of the flange 31, as well as with the seal 33, and carries with it, when it is pulled upwards, the succession of an insulator 34, a refractory brick 35, and a mesh screen 36, the functionality of which will be detailed later.
  • the temperature to which it is subjected is relatively low (generally close to 100 ° C.). It therefore works relatively little and is therefore compatible with obtaining a good seal.
  • the structure of insulator 34 and of refractory brick 35 to which it is integral makes it possible to further improve these insulation performances ensuring a low temperature at the level of the flange and the seal.
  • the screen mesh 36 When the system 28 is in place, the screen mesh 36 is located, within the pipe 30, opposite the point 38 where the bypass 22 connects to this same pipe 30.
  • the presence of this screen mesh 36 offers the advantage of intercepting in passing the grains of catalyst which could potentially be entrained with the atmosphere produced in the reactor in its ascent from the bottom to the top of the reactor and its evacuation via line 22.
  • Figures 5 and 6 illustrate the comparative results of thermal profiles measured within the catalyst cartridge according to whether the injection of the reactive gases is carried out from the top of the reactor ( Figure 5) or from the bottom of the reactor ( Figure 6 ).
  • the distance inside the catalyst cartridge is shown on the abscissa, the end of the abscissa scale ("100%) representing the end of the cartridge.
  • the heat treatment atmosphere resulting from such operating conditions in the case of injection of the reactive gases from above was characterized by a residual CO 2 concentration of the order of 0.2%, and a dew point close to -20 ° C, therefore oxidative species conditions clearly degraded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP97400801A 1996-04-23 1997-04-08 Verfahren und Anlage zum Herstellen einer Wärmebehandlungsatmosphäre Ceased EP0803580A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9605106 1996-04-23
FR9605106A FR2747594B1 (fr) 1996-04-23 1996-04-23 Procede et installation d'elaboration d'une atmosphere de traitement thermique

Publications (1)

Publication Number Publication Date
EP0803580A1 true EP0803580A1 (de) 1997-10-29

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EP97400801A Ceased EP0803580A1 (de) 1996-04-23 1997-04-08 Verfahren und Anlage zum Herstellen einer Wärmebehandlungsatmosphäre

Country Status (5)

Country Link
EP (1) EP0803580A1 (de)
JP (1) JPH1046235A (de)
CA (1) CA2203342A1 (de)
FR (1) FR2747594B1 (de)
ZA (1) ZA973067B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004063401A1 (en) * 2003-01-13 2004-07-29 Ati Properties Inc. Hydrogen reclamation apparatus and method from a treatment furnace exhaust

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2286789A1 (fr) * 1974-10-04 1976-04-30 Cms A Vanzo Et C Cornue pour generateurs endothermiques d'atmospheres controlees
JPS624439A (ja) * 1985-07-01 1987-01-10 Ngk Insulators Ltd 雰囲気ガス製造装置
EP0482992A1 (de) * 1990-10-26 1992-04-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren zur Herstellung einer Atmosphäre für thermische Behandlungen
WO1993021350A1 (de) * 1992-04-13 1993-10-28 Messer Griesheim Gmbh Verfahren zur herstellung eines schutz- oder reaktionsgases für die wärmebehandlung von metallen
EP0598384A1 (de) * 1992-11-17 1994-05-25 Praxair Technology, Inc. Verfahren zur Beseitigung von Sauerstoff aus teilweise gereinigtem Stickstoff

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2286789A1 (fr) * 1974-10-04 1976-04-30 Cms A Vanzo Et C Cornue pour generateurs endothermiques d'atmospheres controlees
JPS624439A (ja) * 1985-07-01 1987-01-10 Ngk Insulators Ltd 雰囲気ガス製造装置
EP0482992A1 (de) * 1990-10-26 1992-04-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren zur Herstellung einer Atmosphäre für thermische Behandlungen
EP0692545A1 (de) * 1990-10-26 1996-01-17 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Wärmebehandlungsanlage
WO1993021350A1 (de) * 1992-04-13 1993-10-28 Messer Griesheim Gmbh Verfahren zur herstellung eines schutz- oder reaktionsgases für die wärmebehandlung von metallen
EP0598384A1 (de) * 1992-11-17 1994-05-25 Praxair Technology, Inc. Verfahren zur Beseitigung von Sauerstoff aus teilweise gereinigtem Stickstoff

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 176 (C - 426) 5 June 1987 (1987-06-05) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004063401A1 (en) * 2003-01-13 2004-07-29 Ati Properties Inc. Hydrogen reclamation apparatus and method from a treatment furnace exhaust

Also Published As

Publication number Publication date
FR2747594A1 (fr) 1997-10-24
CA2203342A1 (fr) 1997-10-23
FR2747594B1 (fr) 1998-05-29
ZA973067B (en) 1997-11-05
JPH1046235A (ja) 1998-02-17

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