EP1377370A1 - Procede et dispositif de reformage catalytique d'hydrocarbures ou d'alcools - Google Patents

Procede et dispositif de reformage catalytique d'hydrocarbures ou d'alcools

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Publication number
EP1377370A1
EP1377370A1 EP02729840A EP02729840A EP1377370A1 EP 1377370 A1 EP1377370 A1 EP 1377370A1 EP 02729840 A EP02729840 A EP 02729840A EP 02729840 A EP02729840 A EP 02729840A EP 1377370 A1 EP1377370 A1 EP 1377370A1
Authority
EP
European Patent Office
Prior art keywords
microreactors
reactor
microreactor
channels
kmj
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.)
Withdrawn
Application number
EP02729840A
Other languages
German (de)
English (en)
Inventor
Peter Jörg PLATH
Ernst-Christoph Hass
Magnus Buhlert
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.)
Mir-Chem GmbH
Original Assignee
Mir-Chem GmbH
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
Priority claimed from DE10118618A external-priority patent/DE10118618A1/de
Application filed by Mir-Chem GmbH filed Critical Mir-Chem GmbH
Publication of EP1377370A1 publication Critical patent/EP1377370A1/fr
Withdrawn legal-status Critical Current

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    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01BBOILING; BOILING APPARATUS ; EVAPORATION; EVAPORATION APPARATUS
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    • B01B1/005Evaporation for physical or chemical purposes; Evaporation apparatus therefor, e.g. evaporation of liquids for gas phase reactions
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Definitions

  • the invention is in the field of catalytic reforming of hydrocarbons or alcohols.
  • the reforming of higher hydrocarbons or alcohols is an industrially established process for the production of hydrogen.
  • the known units are still quite large today and are therefore not very suitable for use in mobile devices.
  • Another problem of producing hydrogen for the fuel cell with the aid of the reforming of higher hydrocarbons or alcohols arises from the complexity of the chemical processes taking place during the reforming and the associated reaction procedure which is difficult to handle.
  • Known units for reforming the hydrocarbons or alcohols provide complex control devices for handling the complicated reaction processes and are therefore not suitable for use in mobile devices, for example automobiles.
  • the object of the invention is therefore to provide an improved method and an improved device for the reforming of higher hydrocarbons or alcohols, for example gasoline, diesel, methanol or methane, which (facilitates) hydrogen production for a fuel cell in mobile devices, in particular vehicles ,
  • microreactor network is particularly suitable as a device for generating hydrogen for non-industrial applications, since the space requirement has been considerably reduced in comparison with known (industrial) plants.
  • hydrogen generated during the reforming can also be used in fuel cells for the home energy supply, for example.
  • Vmj control valves
  • the transport of the starting materials and / or the reaction products of the plurality of partial reactions Tk is regulated through the at least part of the channels Kmj with the aid of the actuation of the control valves Vmj.
  • At least one further reaction substance and / or a further quantity of one or all starting substances is fed into one or all of the channels Kmj in order to control the process parameters by means of premixing.
  • the course of the reaction in the individual microreactors can be controlled in a targeted manner.
  • the chemical equilibrium of a reaction in one of the microreactors can be shifted by feeding in the further reactant or the further amount of one or all of the starting materials.
  • the selective oxidation of CO to CO creates an H 2 / CO mixture that counteracts the selective oxidation under equilibrium conditions (water balance). If humidified air is fed in via the channels, the water balance can be shifted in the preferred direction.
  • the feed, in which the further reactant for controlling the process parameters is a feed gas, is therefore a preferred embodiment.
  • An expedient embodiment of the invention provides that the process parameters are controlled with the aid of the process control means in order to keep at least part of the partial reactions Tk away run from a reaction equilibrium. In this way, reactions in the microreactors of the microreactor network can be influenced in a targeted manner in order to obtain the desired reaction products.
  • an optimization of the chemical reactions in the reforming of hydrocarbons and alcohols in order to achieve a higher effectiveness is achieved in that in a reactor space RRx (1 ⁇ x ⁇ p) of a microreactor Rx (1 ⁇ x ⁇ n ) generates a supplementary reactant, is transmitted through one or more of the channels Kmj from the reactor space RRx to at least one reactor space RRy (1 ⁇ y p p, x ⁇ y) and is processed in the other reactor space RRy.
  • the feedback of thermal energy between different microreactors in the microreactor network can be used for the advantageous configuration of the chemical reactions taking place.
  • the thermal energy generated in exothermic reactions can be used to stimulate or control endothermic reactions in another microreactor for autothermal reaction control.
  • the additional reactant is steam for steam reforming in the at least one other reactor space RRy.
  • the microreactor network thus allows one of the microreactors to be used in a targeted manner for the production of additional reaction substances which are used in one or more other microreactors to carry out the chemical reactions taking place there.
  • a further development of the invention achieves a further optimization of the efficiency of the chemical reactions taking place during the reforming in that a reaction product is fed back from one of the microreactors Rn to another of the microreactors Rn via at least one of the channels Kmj.
  • a preferred development of the invention can provide that one of the partial reactions Tk is carried out in parallel in several of the microreactors Rn. In this way, the conversion of certain starting materials can be specifically increased.
  • an expedient embodiment of the invention provides that the process Control means comprise a temperature control device, and that the reactor rooms RRp are heated and / or cooled separately from one another with the aid of the temperature control device. In this way, an individual consideration of the temperature properties of the partial reactions in the reactor rooms RRp is made possible.
  • An advantageous development of the invention can provide that the microreactors Rn are formed in a base block and that the base block for heating and / or cooling the microreactors Rn is preheated and / or pre-cooled with the aid of a base block temperature control device. As a result, the effort for setting a predetermined starting temperature for the several microreactors of the microreactor network is minimized.
  • a reaction environment can be created that is adapted to the respective application.
  • FIG. 1 shows a microreactor network for the catalytic purification of a hydrogen stream with carbon monoxide
  • Figure 2 shows a microreactor network with five microreactors for reforming
  • methanol shows the microreactor network according to FIG. 2, a reactor chain for selective CO oxidation being connected downstream;
  • FIG. 4 shows the microreactor network according to FIG. 2, a channel between the microreactors R2 and R4 being closed;
  • FIG. 5 shows the microreactor network according to FIG. 3, a channel between the micro-reactors R2 and R4 being closed;
  • FIG. 6 shows a further microreactor network for the steam reforming of methane
  • FIG. 7 shows a schematic illustration of a microreactor device from the side
  • Figure 8 shows a base plate of the Mil roreal gate device according to Figure 7 in plan view
  • FIG. 9 shows a cooling plate of the microreactor device according to FIG. 7 with a schematic illustration of a heat flow ⁇ ; and 10 shows a heating plate of the microreactor device according to FIG. 7 with a heating cord.
  • FIG. 1 shows a schematic representation of a microreactor network with a plurality of microreactors R1, ..., R4.
  • a highly selective, multi-stage, heterogeneous, catalytic oxidation is carried out for converting the carbon monoxide (CO) contained in a hydrogen gas into carbon dioxide (CO 2 ) without the hydrogen (H 2 ) also being oxidized to any appreciable extent
  • the microreactors of R1-R4 have a respective reactor space RR1, ..., RR4.
  • the reactor rooms RR1-RR4 are connected to one another via channels K12, K23 and K34.
  • the reactants are transported between the reactor spaces RR1-RR4 through channels K12, K23 and K34.
  • the micro-reactors R1-R4 are preferably designed as described in the international patent application PCT / DE 01/02509, so that a catalytic tubular reactor is formed through which an H 2 / CO mixture flows.
  • the microreactors R1-R4 and the channels Kl 2, K23 and K34 are formed in a base block 1, in which the heating wires 2 run, so that the base block 1 can be kept at a predetermined basic temperature.
  • Chemical catalysts are arranged in the reactor rooms RR1-RR4, as is disclosed in the international patent application PCT / DE 01/02509.
  • the reactor rooms RR1-RR4 can each be individually heated so that their temperature can be above the basic temperature of the base block 1.
  • the temperature in the reactor rooms RR1-RR4 is measured with the aid of a respective temperature sensor 4.
  • the data measured here are picked up by the temperature sensors 4, processed with the aid of a control device and used to readjust the temperature via the individual heating of the reactor rooms RR1-RR4.
  • Gas inlets 5, 6 are provided in channels K1, K23 and K34 for feeding in further gases. In this way it is possible to feed gases in front of each reactor space RR1-RR4 to influence the chemical reactions taking place.
  • humidified air and, on the other hand, an H 2 / CO mixture gas are fed in via the gas inlets 5, 6. This corresponds to a controlled forward mixing. Forward mixing is used to bring and keep the entire microreactor network with the microreactors R1-R4 out of equilibrium, which significantly increases the selectivity of the catalytic oxidation of CO to CO in the presence of H 2 .
  • By adding humidified air through the gas inlets 5 and an appropriate choice of flow rate can avoid the establishment of equilibrium conditions in the oxidation of CO to CO 2 .
  • the reactor spaces RR1-RR4 are preferably designed as flat cylinders with a diameter of approximately ⁇ 2 cm and a height of approximately ⁇ 5 mm.
  • the reactor rooms RR1-RR4 are linearly connected to one another via the channels K12, K23 and K34.
  • the channels K12, K23 and K34 preferably have a width of approximately ⁇ 3 mm and a height of approximately ⁇ 3 mm. This results in an overall size of the microreactor network with dimensions of only a few centimeters.
  • the microreactor network shown in FIG. 1 carbon monoxide can be catalytically oxidized from the H 2 / CO gas mixture with high selectivity in the presence of large amounts of the hydrogen.
  • the hydrogen purified in this way is suitable as fuel for fuel cells since the CO content in the remaining gas is below 100 ppm. Maintaining the microreactor temperature required for the reaction is possible with little effort because of the small dimensions of the microreactor network in the basic block 1 with the individual reactor rooms RR1-RR4 and the channels K12, K23, K34.
  • the microreactor network has a very low weight.
  • the compact design of the microreactor network also supports very low energy consumption when carrying out the catalytic oxidation of CO. It can be provided to form the base block 1 from ceramic, in particular as a foamed ceramic. This embodiment has the advantage that ceramic is an electrically non-conductive material, which facilitates the introduction of the heating wires 2.
  • the device shown in FIG. 1 is particularly suitable for use in mobile fuel cell assemblies, for example in vehicles.
  • FIGS. 2 to 6 show microreactor networks for the catalytic reforming of alcohols or higher hydrocarbons (KW).
  • the microreactors R1-R4 are coupled in series as a linear chain
  • microreactors R1,..., R5 form a more complex structure in the microreactor networks according to FIGS. 2 to 6, in which a microreactor is used several other microreactors can be connected and feedback between the microreactors is possible.
  • Figure 2 shows a microreactor network for reforming methanol.
  • the starting material methanol is introduced into the microreactor R1 and evaporated.
  • the evaporated methanol reaches microreactors R2 and R4 via channels Kl 2 and Kl 4.
  • Methanol is catalytically decomposed in the microreactor R2.
  • the microreactor R4 is connected to the microreactor R2 via a channel K24, to the microreactor R1 via a channel K1 and to the microreactor 5 via a channel K54.
  • a water-gas shift reaction with premixing by methanol methanol-steam reforming
  • the evaporated methanol reaches the microreactor R4 via the channel Kl 4.
  • the products of the catalytic decomposition of methanol in the R2, CO and H 2 microreactor reach the microreactor 4 via the channel K24.
  • superheated steam which is generated from water in the microreactor R5 is fed to the microreactor R4 via the channel K54.
  • a water-gas shift reaction also takes place in the microreactor R3, but without premixing in comparison to the microreactor R4.
  • the microreactor R3 is connected to the microreactor R2 via a channel K23 in FIG. 1, so that CO and H can be passed to the microreactor R3.
  • Overheated water vapor enters the microreactor R3 via a channel K53.
  • the starting materials for the microreactors R4 and R3 are CO, CO 2 , H 2 , respectively.
  • the channels between the microreactors R1-R5 are each provided with a control valve VI 2, V13, V14, ..., so that mass transport through the channels can be permitted or blocked.
  • the control valves with an arrow, for example VI 2 and V53, are open, while the other control valves, such as V25 and VI 5, are closed.
  • FIG. 3 shows the microreactor according to FIG. 2, the channel K24 being blocked. This means that in the milk reactor network according to FIG. 3, the methanol-steam refoming and the water-gas shift reaction are carried out without premixing both in the milk reactor R3 and in the microreactor R4.
  • the microreactor networks shown in FIGS. 4 and 5 include the microreactor network from FIG. 2 and the microreactor network from FIG. 3.
  • the microreactor networks in FIGS. 4 and 5 there is a reactor chain with microreactors R6 , R7 and R8 for selective CO oxidation in Presence of hydrogen downstream.
  • These microreactors R6-R8 are a linear reactor chain similar to the microreactor network from FIG. 1, which was added in order to reduce the CO content of the starting gas mixture of the reforming.
  • the starting products of the microreactors R3 and R4, CO, CO 2 and H 2 enter the microreactor 6 via the channels K36 and K46.
  • Both the microreactor 6 and the microreactors R7 and R8 via a channel 100 are discharged from the microreactor with superheated steam R5 and supplied with air that is humidified by the water vapor. In this way, the influence of the H 2 / CO 2 gas mixture formed in the selective oxidation of CO to CO 2 is to be reduced.
  • FIG. 6 shows a microreactor network with microreactors R1-R7 for carrying out steam reforming of methane.
  • the steam reforming of methane is carried out essentially in the part of the microreactor network which comprises the microreactors R1-R5.
  • the microreactors R6 and R7 are connected downstream as a linear reactor chain for cleaning carbon monoxide.
  • the mode of operation of the microreactor network according to FIG. 6 is explained below using the example of methane, but can be adapted for the steam reforming of any hydrocarbons (KW).
  • the methane to be reformed is introduced into the microreactor R1 and preheated.
  • the methane then reaches the microreactor R3 via the channel Kl 3, where it is catalytically mixed with water vapor, which leads to partial reforming.
  • the water vapor is fed to the microreactor R3 via the channel K23 from the microreactor R2.
  • the partially reformed methane is then transported via channel K34 to microreactor R4. Here the reforming is continued at an elevated temperature. Water vapor reaches the microreactor R4 via the channel K24.
  • the reaction products CO and H 2 then pass from the microreactor R4 as a gas mixture to the microreactor R5.
  • humidified air is added here for the catalytic purification of the hydrogen stream.
  • Carbon monoxide purification ie the selective oxidation of CO to CO 2 in the microreactors R5 to R7 is exothermic.
  • the heat generated here is returned to the microreactors R1 to R4, since the processes taking place in these microreactors (in R3 and R4) are endothermic and therefore require an energy supply, in particular the preheating of the methane in the microreactor R1 and the evaporation process of the water in the micro reactor R2 , In this way, a completely autothermal implementation is not ensured, but the heat balance is balanced as far as possible.
  • the microreactors of the microreactor networks in FIGS. 2 to 6 are similar in terms of their individual size and shape to the microreactors from the microreactor network according to FIG. 1.
  • the channels between the microreactors in the microreactor networks according to FIGS. 2 to 6 also correspond in terms of their design the channels of Figure 1.
  • the microreactors in Figures 2 to 6 are preferably formed in a common base block which, as described in connection with Figure 1, can be heated or cooled to a basic temperature.
  • respective heating devices are provided in the base block in the area of the microreactors.
  • the respective heating devices can be connected to control devices which control the heating devices as a function of a temperature measured via a temperature sensor in the associated microreactor.
  • the respective heating devices are a heating wire which is arranged in the base block in the vicinity of the associated microreactor.
  • the area of the microreactors in which a catalyst is arranged can be specifically heated.
  • a microreactor device 70 is shown schematically in a side view in FIG.
  • Microreactors and channels (not shown) which connect the microreactors to one another are formed in two base plates 71 and 72, respectively.
  • Respective cooling plates 73 and 74 are arranged above and below the base plates 71 and 72, respectively.
  • a heating plate 75 or 16 is provided above the cooling plate 73 and below the cooling plate 74 in order to keep the microreactors in the base plates 71, 72 at a predetermined base temperature.
  • Materials with suitable thermal conductivity can be used as the material for the base, heating and cooling plates.
  • Metals are preferably used in the microreactor device 70, namely brass for the heating and cooling plates 75, 16 and 73, 74.
  • the base plate 72 which receives the catalyst material, is made of a chromium-nickel steel, which is expediently coated with the chemical catalysts; the base plate 71 is preferably made of copper in order to achieve optimal conductivity.
  • the base plate 71 comprises a microreactor network with fourteen reactor chambers RK1, ..., RK14, in which a catalytic reforming of methanol and a subsequent CO cleaning are carried out.
  • the base plate 71 has a length of a few centimeters, preferably approximately 25 cm, and a width of a few centimeters, preferably about 7 cm.
  • the distance between the reactor chamber RKl and the reactor chambers RK13 or RK14 is approximately 16 cm.
  • the distance between adjacent reactor chambers, for example between the reactor chambers RK3 and RK4 or the reactor chambers RK7 and RK8, is approximately 4 cm.
  • the base plate 72 is designed in the same way as the base plate 71. The dimensions are exemplary details that can be undercut for further miniaturization of the micro-reactor device 70.
  • the reactor chambers RKl, ..., RK14 are connected via channels 80.
  • Each of the RKl -RKl 4 reactor chambers has its own heating, which is implemented, for example, by means of heating cartridges, and sensors for temperature measurement, which are designed as thermocouples.
  • the microreactor chambers RK1-RK14 and the channels 80 between them correspond to the microreactors and the channels of the microreactor network according to FIG. 1.
  • microreactor device 70 methanol (CH 3 OH) and water (H 2 O) are evaporated, then catalytically converted (reformed) to a mixture of hydrogen (H) and carbon dioxide (CO) in a multi-stage process with premixing with methanol and water. , The proportions of carbon monoxide (CO) contained in this gas mixture are then converted into carbon dioxide in a further multi-stage process by heterogeneous, catalytic oxidation, without the hydrogen also being oxidized to any appreciable extent.
  • Liquid methanol is injected into the RK1 realctor chamber and liquid water is injected into the RK2 realctor chamber. Air is fed into the system of the milk reactor chambers via the gas inlets 81 and passed into the reactor chambers RK9 to RKl 4 via the channels extending from the gas inlets 81.
  • the liquid methanol is evaporated in the reactor chamber RK1 and passed on to the reactor chambers RK3 to RK6 via the channels emanating from the reactor chamber RKl.
  • the liquid water is evaporated in the reactor chamber RK2 and passed into the reactor chambers RK3 to RKl 4 via the channels emanating from the reactor chamber RK2.
  • the first stage of methanol reforming (without premixing) is carried out in each of the Realctor chambers RK3 and RK4.
  • the second stage of methanol reforming takes place in the reactor chambers RK5 and RK6, with methanol and water being premixed with the reaction products from the reactor chambers RK3 and RK4 (H 2 , CO, CO). Therefore, in addition to methanol reforming, the RK5 and RK6 reactor chambers are already being used a partial water-gas shift reaction. This leads to an improved energy balance compared to a single-stage methanol reforming, since the heat released in the exothermic water-gas shift reaction is fed directly to the strongly endothermic reforming process.
  • the reaction products from the reactor chambers RK5 and RK6 are passed through the respective channels into the reactor chambers RK7 and RK8 with the addition of water vapor. This is where the majority of the water-gas shift reaction from CO and HO to CO 2 and H 2 takes place, with a residual proportion of CO remaining.
  • a chain of reactor chambers RK9, RK11 and RKl 3 or the reactor chamber RK8 is followed by a chain of reactor chambers RK10, RK12 and RK14.
  • the two reactor chamber chains RK9-RK11-RK13 and RK10-RK12-RK14 are expediently designed as described in the international patent application PCT / DE 01/02509.
  • cooling plates 73 and 74 are provided above and below the base plates 71 and 72 (see FIG. 7), which are designed in such a way that a heat flow ⁇ from the locations of the exothermic reactions to the locations of endothermic reactions and evaporation processes.
  • FIG. 9 shows an example of a top view of the cooling plate 74 with cooling plate areas KP1,..., KP 14, which are arranged below the microreactor chambers RK1 to RK14 in the base plate 72.
  • the heat flow ⁇ is indicated with the aid of arrows 90.
  • the gases in the channels 80 pass one another in such a way that the energy is transferred by heat exchange from the exothermic to the endothermic reactions. This is achieved, for example, by means of a twisted arrangement of the reactor chambers RKl -RKl 4 in the base plates 71 and 72, respectively.
  • Figure 10 shows the heating plate 16 in plan view.
  • a heating cord 100 is placed around heating plate areas HP1,..., HP14, which are arranged in the heating plate 76 below the microreactor chambers RK1-RK14 in the base plate 72, in such a way that the microreactor chambers RKl -RKl 4 are heated from below.
  • the heating plate 75 is configured like the heating plate 76 and is arranged above the cooling plate 73 for heating the reactor chambers RK1-RK14 in the base plate 71 from above (cf. FIG. 7).
  • each reactor chamber RK1-RK14 can be heated individually, so that the temperature in the respective reactor chamber can be above the base temperature of the base plate 71 or 72.
  • Fourteen heating cartridges are used for this purpose in the microreactor device 70.
  • the temperature in the reactor rooms of the reactors R1 to R14 is measured individually using an additional temperature sensor. The data obtained in this way are tapped by the individual temperature sensors, processed with the aid of a control device (not shown) and used to readjust the temperature via the individual heating of the reactor chambers RKl to RKl 4.
  • heating wires which are coated with a catalyst material can be used instead of the heating cartridges. This saves energy and the base heating of the base plate 71 or 72 can be lowered to a lower temperature. In addition, an even better balance of heat exchange can be expected.

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Abstract

La présente invention concerne un procédé et un dispositif permettant le reformage catalytique d'hydrocarbures ou d'alcools pour donner de l'hydrogène au cours de plusieurs réactions partielles. Les réactions partielles sont mises en oeuvre individuellement et/ou par combinaison d'au moins deux réactions partielles dans un réseau de microréacteurs, et dans des canaux formés entre les microréacteurs, au moins un partie des canaux servant à transporter les substances de sortie et/ou produits réactionnels des réactions partielles entre les compartiments réactionnels des microréacteurs. Le déroulement des réactions partielles dans le réseau de microréacteurs est commandé par des éléments de commande de processus servant à réguler des paramètres de processus.
EP02729840A 2001-04-12 2002-04-02 Procede et dispositif de reformage catalytique d'hydrocarbures ou d'alcools Withdrawn EP1377370A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10118618A DE10118618A1 (de) 2001-04-12 2001-04-12 Katalytische Reinigung eines Wasserstoffstromes von Kohlenmonoxid in einer Mini-Reaktor-Anlage mit Vorvermischung
DE10118618 2001-04-12
DE10137188 2001-07-31
DE10137188 2001-07-31
PCT/DE2002/001184 WO2002083291A1 (fr) 2001-04-12 2002-04-02 Procede et dispositif de reformage catalytique d'hydrocarbures ou d'alcools

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CN1289181C (zh) 2006-12-13
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WO2002083291A1 (fr) 2002-10-24
US20040136902A1 (en) 2004-07-15
DE10291574D2 (de) 2004-04-15
CA2444201A1 (fr) 2002-10-24

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