Process and apparatus for producing hydrogen by thermocatalytic decomposition of hydrocarbons

[0009] (i) Field of the Invention

[0010] The present invention relates to the field of the production of hydrogen by the thermocatalytic decomposition (cracking) of hydrocarbons.

[0011] (ii) Description of the Related Art

[0012] It is known that hydrogen production, in particular on-site, is a major field, especially because of a growing demand in the industrial market for hydrogen, for example for heat-treatment applications.

[0013] Many studies have been published in recent years on this subject, particularly studies using catalysts consisting of nickel powder supported on silica (SiO₂).

[0014] In particular, the following documents may therefore be referred to:

[0015] the article by Zhang et al., published in “Applied Catalysis A,” 1998, vol. 167, pp. 161-172;

[0016] the article by Muradov, published in “energy and Fuels,” 1998, vol. 12, pp. 41-48;

[0017] the article by Chen et al., published in the journal “carbon,” 1997, vol. 35, pp. 1495-1501;

[0018] the article by Poirier et al., published in “International Journal of Hydrogen Energy,” 1997, vol. 22. pp. 429-433; or

[0019] the article by Steinberg, published in “International Journal of Hydrogen Energy,” 1998, vol. 23, pages 419-425.

[0020] The mechanism for hydrogen production under such conditions, which is most commonly accepted in the literature, thus seems to be the adsorption of the hydrocarbon molecule on the surface of a catalyst particle (for example a nickel particle supported on porous silica) followed by the successive dehydrogenation of the hydrocarbon (for example going from CH₄to CH₃, then CH₂, then CH), in order to end in a carbon atom adsorbed on the surface of the catalyst. This carbon then travels, by thermal diffusion, through the catalyst particle in order to form what are called carbon “nanotubes” or “nanofilaments,” a phenomenon allowing the catalyst to be active for a much longer time (the metal surface remains free, accessible and active for a longer time).

[0021] It is known that the phenomenon of nanotube formation depends especially on the size of the catalyst particles, on the metal content of the catalyst and on the porosity of the material serving as support for the metal.

[0022] This literature can therefore be rapidly summarized by the fact that it has demonstrated the feasibility of the cracking reaction on such catalysts and the activation of the reaction between approximately 550 and 800° C., the fact that maintaining the activity of the catalyst depends essentially on forming these carbon nonofilaments, and that specifically this reaction becomes deactivated when there is so not enough space for these filaments to grow, therefore resulting in the need to regenerate the catalyst, for example by an air flush.

[0023] Thus, although all this literature presents the direct catalytic cracking of hydrocarbons as a very promising avenue to explore for the purpose of producing hydrogen (especially on-site), developments undeniably remain to be carried out in order to provide a really industrial process based on this concept, especially when considering the fact that the prior art has obtained all these feasibility results with low gas flow rates and small amounts of catalysts (typically a few milliliters).

[0024] Extensive studies by the Applicant have also demonstrated that certain key technical questions still need to be addressed:

[0025] the problem of carbon deposition after cracking: occurring immediately from the start of cracking, and entailing a significant risk of the reactor becoming blocked (only the first portion of the catalyst is then used);

[0026] the difficulties encountered during regeneration of the catalyst: which regeneration is a source of CO and CO₂, therefore of soot deposition;

[0027] the regeneration is, moreover, an exothermic process: the increase in temperature and thus the thermocycling resulting therefrom may throw doubt on the integrity of the material;

[0028] short regeneration times have to be obtained, especially when it is hoped to achieve truly industrial conditions.

[0029] One of the objectives of the present invention is therefore to propose a response to the technical questions mentioned above.

[0030] The process according to the invention, for producing a production gas mixture comprising hydrogen, by thermocatalytic decomposition of an initial mixture which comprises a hydrocarbon or a mixture of hydrocarbons, the decomposition taking place over a catalyst which is capable, on contact with the hydrocarbon, of forming carbon nanotubes, is characterized in that:

[0031] at least one succession, which comprises at least one first and one second catalytic reaction zone, these zones being separate within at least two different consecutive reactors or else being consecutive reactors or else being consecutive within the same reactor, is used;

[0032] the at least one first and one second consecutive catalytic reaction zone are subjected to an increasing temperature gradient and/or have an increasing metal concentration gradient in the catalyst;

[0033] the initial mixture is made to flow into the first catalytic reaction zone so as to form therein a first intermediate mixture which is directed toward the second catalytic reaction zone of the succession, in order to form the required production mixture.

[0034] As will have been understood on reading the foregoing, the notion according to the invention of “first zone” and “second zone” of the succession should be understood by considering the direction of flow of gas to be cracked in the succession.

[0035] The process according to the invention may also adopt one or more of the following technical characteristics:

[0036] the succession comprises at least two catalytic reaction zones, each zone being located in a separate reactor;

[0037] the succession comprises at least two catalytic reaction zones positioned consecutively in the same reactor;

[0038] after a phase in which the production mixture is produced, the process continues with a phase in which the catalytic reaction zones of the succession are regenerated in the following manner: each of the catalytic reaction zones of the succession are independently and simultaneously flushed with the aid of a regeneration gas (for example an oxidizing gas);

[0039] after a phase in which the production mixture is produced, the process continues with a phase in which the catalytic reaction zones of the succession are regenerated in the following manner: each of the catalytic reaction zones of the succession are independently and simultaneously flushed with the aid of an oxidizing regeneration gas, the regeneration gas used differing from one zone to another by the fact that it has a different residual oxygen concentration;

[0040] after a phase in which the production mixture is produced, the process continues with a regeneration of the catalytic reaction zones of the succession by independently and simultaneously flushing each of the catalytic reaction zones with the aid of a regeneration gas, each of the reaction zones following the first zone of the succession being regenerated in the following manner: a pipe for feeding a regeneration gas is used for each of the catalytic reaction zones which follow the first zone of the succession, each feed pipe being connected to the line used for directing, toward the zone to be regenerated in question, the intermediate mixture produced by the zone preceding it in the succession (the “first zone” and “the following zones” of the succession will be defined by considering the direction of flow of the gas to be cracked in the succession—the regeneration configuration thus described therefore corresponds to concurrent regeneration with respect to the direction of flow of the gas to be cracked in the succession);

[0041] after a phase in which the production mixture is produced, the process continues with a regeneration of the catalytic reaction zones of the succession by independently and simultaneously flushing each of the catalytic reaction zones with the aid of a regeneration gas, each of the reaction zones which precede the last zone of the succession being regenerated in the following manner, a pipe for feeding a regeneration gas is used for each of the catalytic reaction zones which precede the last zone of the succession, each of the feed pipes being connected to the line used for extracting, from the zone to be regenerated in question, the intermediate mixture produced by the zone in question (and for directing the intermediate mixture toward the next zone in the succession) (the “last zone” and “the preceding zones” of the succession will be defined by considering the direction of flow of the gas to be cracked in the succession—the regeneration configuration thus described therefore corresponds to a countercurrent regeneration with respect to the direction of flow of the gas to be cracked in the succession);

[0042] the phase of regenerating each reaction zone is carried out in the following manner: the flow rate of regeneration gas flushing a given catalytic reaction zone is less than the flow rate of regeneration gas flushing the zone which precedes this given zone in the succession;

[0043] the phase of regenerating each reaction zone is carried out in two successive steps of flushing each of thee reaction zones with the aid of the regeneration gas, the regeneration-gas flow rate in the second step being greater than the gas flow rate used for the first step;

[0044] before the phase of regenerating each reaction zone, each zone of the succession is purged with the aid of an inert gas;

[0045] after the phase of regenerating each reaction zone and before a production phase is started, each zone of the succession is purged with the aid of an inert gas and then each sone of the succession is flushed with the aid of a hydrogen gas;

[0046] the regeneration gas coming from one of the zones of the succession is quenched before it flows into the next zone;

[0047] the regeneration gas is an oxidizing gas chosen from air, oxygen, CO₂, water vapor and mixtures of these gases;

[0048] each of the catalytic reaction zones of the succession is maintained at a temperature lying within the range going from 500 to 1000° C.;

[0049] each of the catalytic reaction zones of the succession uses a catalyst based on nickel, cobalt, chromium, iron, platinum, palladium or rhodium;

[0050] each of the catalytic reaction zones of the succession uses a catalyst based on supported nickel;

[0051] the production gas mixture thus obtained as output from the succession of catalytic reaction zones undergoes one or more purification post-treatments for the purpose of increasing the hydrogen concentration in the mixture, for example by employing a preferential adsorption technique;

[0052] at least two successions of catalytic reactions are used, one of the successions being used in production phase while another succession is in regeneration phase, and so on.

[0053] Further characteristics and advantages of the invention will emerge from the following description, given solely by way of example, and with reference to the appended drawings.

[0054] FIG. 1 is a partial schematic representation of a plant suitable for implementing the process according to the invention;

[0055] FIG. 2 is a partial schematic representation of another plant suitable for implementing the process according to the invention; and

[0056] FIG. 3 is a detailed partial schematic view of one of the reaction zones of FIG. 1, in particular of its line for discharging the intermediate cracking mixture which is produced therein and of a regeneration-gas feed pipe which is connected to this line according to the invention.

[0057] FIG. 1 shows a succession of four consecutive catalytic reaction zones R₁, R₂, R₃, and R₄located within four different catalytic reactors.

[0058] Shown symbolically by the reference 1 is the influx of an initial gas mixture which comprises the hydrocarbon (for example, natural gas) at the bottom of the reactor R₁.

[0059] As shown very clearly in FIG. 1, the first intermediate gas mixture resulting from the catalytic cracking of the initial mixture in the reactor R₁is transferred (line 2) into the bottom of the reactor R₂, where it undergoes catalytic cracking, the resulting intermediate mixture then being transferred (line 3) to the bottom of the reactor R₃and so on.

[0060] The final gas mixture coming from the reactor R₄, that is to say the required production gas mixture which comprises hydrogen, is then withdrawn from the plant via the line 10 and, for example, directed toward the user point, or else toward one or more purification post-treatment points for the purpose of increasing the hydrogen concentration in the mixture, for example by employing a preferential adsorption technique. It will therefore be advantageous here to recycle the desorption mixture, rich in hydrogen and in hydrocarbon, into the inlet for the process (initial mixture).

[0061] Depending in particular on the nature of the subsequent uses of the production mixture and depending on whether or not post-treatment steps for purifying the mixture are carried out, the initial mixture may be made to flow into the first zone of the succession at a pressure close to atmospheric pressure or, on the contrary, it may be chosen to flow thereinto under pressure, typically with an initial pressure of 5 to 15 or even 20 bars (which may, for example, make it easier to carry out a subsequent purification step by preferential adsorption, which typically requires pressure).

[0062] The production gas mixture therefore typically comprises hydrogen, an uncracked residue of hydrocarbon(s) and usually nitrogen, nitrogen being constantly present in the sources of hydrocarbon available.

[0063] The references X₁to X₄depict the inflows of regeneration gas (here an oxidizing gas) into the plant, allowing each of the catalytic reaction zones of the plant to be regenerated in parallel, simultaneously and independently: in this case, the regeneration-gas feed pipe X₁(for regenerating R₁) being connected to the bottom of the reactor R₁, the oxidizing regeneration-gas feed pipe X₂(for the reactor R₂) being connected to the pipe 2 for transferring the first intermediate mixture from the reactor R₁to the reactor R₂, and so on.

[0064] As will be clearly apparent to those skilled in the art upon examining this figure, such inflows X_iof regeneration gas into the bottom of the first reactor of the succession, and between two reaction zones with regard to the following reactors, make it possible, on the one hand, to regenerate the reactor following the point of connection of a given feed pipe, but also to flush the lines, preventing any soot being deposited.

[0065] As will also have been understood on reading the foregoing, the feed pipes X_iserve not only to supply the oxidizing regeneration gas but also may serve, if required, depending on the chosen mode of implementing the invention, to supply an inert purge gas prior to the regeneration phase or to supply an inert purge gas and a hydrogen flushing gas after the regeneration phase.

[0066] Although FIG. 1 illustrates one mode of implementing the invention, in which the regeneration is carried out as a cocurrently with respect to the direction of flow of the gas to be cracked in the succession, it is conceivable, as already mentioned earlier, and without departing from the scope of the present invention, for there to be a countercurrent regeneration with respect to the direction of flow of the gas to be cracked in the succession, by slightly modifying the plant shown in FIG. 1:

[0067] elimination of the inflow X₁;

[0068] the inflow X₂serves to regenerate R₁, the inflow X₃serves to regenerate R₂and the inflow X₄serves to regenerate R₃;

[0069] an inflow X₅of the gas for regenerating the reactor R₄then has to be provided, this being connected downstream of this reactor near the line 10.

[0070] According to the invention, the four reaction zones in FIG. 1 are subjected to an increasing temperature gradient (that is to say conditions under which the temperature of R₁is less than the temperature of R₂, which in turn is less than the temperature of R₃, etc.) and/or have an increasing metal concentration gradient in the catalyst (metal concentration in R₁less than the metal concentration in R₂, which in turn is less than the metal concentration in R₃, etc.).

[0071] By way of illustration, the plant in FIG. 1 may be used under the following conditions, each catalytic reaction zone employing a nickel catalyst on silica (specific surface area of about 500 m²/g, particle size of less than 800 μm and typically between 100 and 600 μm, porosity of the order of 50 to 100 Å):

[0072] reactor R₁: maintained at a temperature of 600° C. to 700° C., the nickel concentration of the catalyst being about 10%;

[0073] reactor R₂: maintained at a temperature of 700° C. to 800° C., the nickel concentration of the catalyst being about 15%;

[0074] reactor R₃: maintained at a temperature of 800° C. to 875° C., the nickel concentration of the catalyst being about 20%;

[0075] reactor R₄: maintained at a temperature of 875° C. to 950° C., the nickel concentration of the catalyst being about 25%;

[0076] Such catalyst characteristics (size, porosity, etc.) favor the production of a fluidized bed (catalyst suspended in the gas, uniformity of distribution in space, better temperature uniformity in the reactor).

[0077] By way of illustration, the use of such a plant for cracking methane gives the following compositions of output mixtures from each reactor.

[0078] output from the first reactor R₁: about 51% H₂and 49% CH₄;

[0079] output from the second reactor R₂; about 76% H₂and 24% CH₄;

[0080] output from the third reactor R₃; about 89% H₂and 11% CH₄;

[0081] output from the fourth reactor R₄, about 98% H₂and 2% CH₄.

[0082] FIG. 2 shows another mode of implementing the invention in which five catalytic reaction zones R₁to R₅are joined together consecutively within the same reactor.

[0083] Here again, the reference 1 denotes the inflow of the initial gas mixture to be cracked in the bottom of the reactor, that is to say in the bottom of the reaction zone R₁, while the reference 10 represents the withdrawal of the final production gas mixture obtained in the top of the reactor, that is to say in the top of the last reaction zone R₅of the succession.

[0084] Once again, starting here with the same regeneration source S (but, as already pointed out, a multiplicity of regeneration gas sources could also be used instead of this single source S), means (X₁to X₅) are used which allow each of the catalytic reaction zones of the succession to be independently and simultaneously in flushed and regenerated.

[0085] As regards FIG. 3, this shows a detailed view of the intermediate part between two successive reactors in FIG. 1 (typically between the reactors R₁and R₂or else between the reactors R₃and R₄).

[0086] This therefore shows, between the reactor R_nand the reactor R_n+1, a line allowing the intermediate gas mixture resulting from the cracking carried out in the reactor R_nto be transferred to the reactor R_n+1, to which line a feed pipe X_n+1, for a gas mixture for regenerating the reactor R_n+1is connected.

[0087] This detailed view makes it possible to show an advantageous method of implementing the invention in which a system 21 (here, a coil through which water, for example, flows) for quenching the regeneration gas mixture coming from the reactor R_nis used over part of the line in question, which quenching is carried out not only to reduce the temperature of the regeneration gas coming from the reactor in question (let us recall that the regeneration is very exothermic) but also to freeze the composition of this mixture (which includes CO and CO₂) and prevent the formation of any particle (especially soot). Moreover, the regeneration-gas feed pipe X_n+1is connected to this quenched portion of the line.

[0088] This mode of implementation also includes a fixture 22 provided with a means 23 for retaining the catalyst powders which possibly might have been entrained upward by gas coming from the reactor R_i. The means 23 may consist of a filter, a porous substance, a frit, etc.

[0089] As already mentioned, although FIG. 1 illustrates a cocurrent regeneration configuration with respect to the direction of flow of the gas to be cracked in the succession, a countercurrent regeneration configuration is also conceivable (the inflow X₄serving to regenerate the reactor R₃, etc.). Just as before, in such a case of countercurrent regeneration, it will also be advantageous to use a system for quenching the regeneration gas mixture coming from a given reactor R_n,similar to the system described in the context of FIG. 3.

[0090] Examining the modes of implementation illustrated in FIGS. 1 and 2, it is apparent that, especially for practical maintenance and material-changing reasons, a mode of implementation such as that illustrated in the context of FIG. 1, in which all the reaction zones are placed in separate and consecutive reactors, is preferred over a mode of implementation in which all the reaction zones are all combined within the same reactor, as is the case of the mode illustrated in the context of FIG. 2.

[0091] Returning to the mode of implementation illustrated in the context of FIG. 1, with its temperature gradient and/or metal concentration gradient in the catalyst, the following characteristics and advantages may also be mentioned:

[0092] a) the use of such a succession of reactors decreases the amount of carbon deposited from one zone to another in the succession: more carbon deposited in the zone R₁and less carbon deposited in the last zone R₄.

[0093] It is known in fact that the degree of conversion of the reaction depends not only on the temperature but also on the concentration of hydrocarbon present in the incoming mixture. Here, because of the succession adopted and therefore of the successive cracking, this hydrocarbon concentration decreases from one zone to another.

[0094] However, the application according to the invention of an increasing temperature gradient in the succession and/or of an increasing metal concentration gradient in the catalyst makes it possible for the amount of carbon deposited in each zone to be precisely controlled;

[0095] b) the independent and simultaneous regeneration of each of the zones makes it possible to obtain a shorter regeneration time compared with the case of a single-reactor structure in which the carbon is deposited immediately at the start of the zone, entailing a significant risk of blockage, and therefore a long subsequent regeneration procedure;

[0096] c) it is known that the regeneration of these reaction zones with the aid of an oxidizing gas, such as air, proves to be an exothermic reaction and that the resulting temperature increase (and thus the thermal cycling) may throw into question the integrity of the materials. In practice, it is preferable to remain, during regeneration, at a temperature not exceeding 1000° C. in each zone.

[0097] According to the mode of implementing the invention involving a temperature gradient, the maximum amount of carbon is deposited in a zone at lower catalyst temperature while the minimum amount of carbon is deposited in the last zone of the succession which is maintained at the highest temperature. It is therefore found that, according to the invention, the regeneration will proceed better and more reliably at a temperature not exceeding 1000° C. in any of the zones of the succession;

[0098] d) as described earlier in the present application, it is then most particularly advantageous at each zone to adapt the necessary regeneration-gas flow rate, in this case by the fact that decreasing amounts of carbon from one zone to another of the succession are obtained, it will be advantageous to use a regeneration-gas flow rate which decreases from the first zone R₁of the succession to the last zone R₄of the succession;

[0099] e) it should be noted that, according to one of the advantageous modes of implementing the invention, the phase of regenerating each reaction zone is carried out in two successive flushing steps, the regeneration-gas flow rate of the second step being greater than the regeneration-gas flow rate employed for the first step. The first flushing step at a lower flow rate is most particularly advantageous so as to firstly reduce the temperature of the catalyst;

[0100] f) likewise, it is advantageous, as mentioned, to purge each zone of the succession with the aid of an inert gas before the phase of regenerating each reaction zone. Such a purge makes it possible, on the one hand, to precool the zone and, on the other hand, to remove any residual traces of hydrogen and therefore prevent the formation of water vapor during the subsequent regeneration;

[0101] g) according to one of the aspects of the invention, after a phase of regenerating each reaction zone and before a production phase is restarted, it is possible to purge each zone of the succession with the aid of an inert gas and then flush each zone of the succession with the aid of a hydrogen gas. This is because the inert purge allows possible traces of oxygen, water vapor or carbon oxides to be removed before the hydrogen flushing that follows, the purpose of which is, depending on the specifications required by user site for the production mixture, to limit the presence of nitrogen in this mixture.