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    • 专利摘要:
    Method for cracking hydrocarbon gases, the hydrocarbon gas being passed through a flow channel of an absorptive receiver reactor (1,30,40), characterized in that the cracking takes place while it is being passed through the receiver reactor (1,30,40) , while the hydrocarbon gases are heated to their cracking temperature in a first area (21) of the flow channel (2), heated above the cracking temperature in a subsequent second, downstream flow area (22) and in a third, further downstream area (23) of the Flow channel is heated even further and is brought into physical contact with a reaction accelerator via its cross section, after which the flow of products behind the reaction accelerator is released from the receiver reactor (1,30,40), and the heating of the hydrocarbon gas up to over its cracking temperature through absorption of black body ray treatment (20) takes place, which is released by the reaction accelerator heated by incident solar radiation (7) to the hydrocarbon gas flowing towards it, in such a way that the hydrocarbon gas in the flow channel (2) up to the reaction accelerator extends across the flow channel (2), disc-shaped temperature zones (60 to 67) staggered one behind the other, each with increasing temperature.
    公开号:CH716081A2
    申请号:CH01407/19
    申请日:2019-11-07
    公开日:2020-10-15
    发明作者:Ambrosetti Gianluca；Good Philipp
    申请人:Synhelion Sa；
    IPC主号:
    专利说明:

    The present invention relates to a method for cracking hydrocarbon gases, in particular methane, according to the preamble of claim 1 and receiver reactors for carrying out this method according to the preamble of claims 8 and 10.
    The cracking of hydrocarbon gases such as e.g. Methane, ethane, propane or butane is generally used on an industrial scale, with the cracking of methane in particular being regarded as a possible technology of the future, since the reaction CH4-> C + 2 H2 takes place in the absence of oxygen, i.e. it does not release any CO2 emissions. The hydrogen produced serves as an energy carrier, while the carbon is used industrially for the manufacture of products such as carbon black, graphite, diamonds, carbon fibers, conductive plastics and tires.
    Industrially applicable, economical processes for cracking methane with the aid of solar energy have not yet become known. The high temperatures required in the range from approx. 500 ° C. to approx. 1200 ° C. at ambient pressure are problematic. At 500 ° C (hereinafter referred to as the cracking temperature) almost 50% of the methane is dissociated in the equilibrium state, at 1200 ° C the dissociation is complete, but the equilibrium state is only reached after a long (theoretically infinite) time. At increased operating pressure, for the same equilibrium state, i.e. higher temperatures are required for a comparable percentage conversion of methane. Overall, the reaction is energy-intensive, sluggish and difficult to control, with the carbon in the form of free nanoparticles, i.e. Soot, is released.
    In WO 2018/205043 a solar receiver is disclosed in which a heat-transporting fluid for the use of the heat in a downstream industrial process can be heated absorptively by infrared radiation, with CO2, water vapor, SO2, SO3, NO, NO2 and HCl also methane in its property as an infrared-absorptive gas is considered as a suitable heat carrier for the transport of heat to a consumer.
    In US 7 140 181 it is proposed to use solar reactors for endothermic reactions such as the cracking of gases, the production of CO as a syngas component from CO 2 with the help of a specially designed receiver reactor is described. A ceramic pin is provided in a tunnel in this receiver reactor to generate the high temperatures required. Another embodiment of a receiver reactor is generally described as an ellipsoidal “holraum reactor”, in which a gas to be dissociated should also be heated by absorption in addition to contact with the hot reactor walls for high thermal efficiency.
    Accordingly, it is the object of the present invention to provide a solar process for cracking methane and a receiver reactor for cracking methane.
    [0007] This object is achieved by the method with the characterizing features of claim 1 and by receiver reactors with the characterizing features of claims 9, 11 and 13.
    Because the methane transversely to the flow path, disc-shaped temperature zones, thus a predetermined, defined temperature stratification with the same temperature level in the respective layers, there is a steady heating of the methane towards the reaction accelerator, without the degree of dissociation impairing cold zones or Forming or maintaining overheated zones so that the entire methane flow is gradually heated to the desired reaction temperature. Because the methane is brought into contact with a physical reaction accelerator, the reaction speed increases in such a way that a predominantly complete reaction is achieved in the receiver reactor through which there is a flow. The fact that the methane is brought above and beyond its cracking temperature by absorption results in a thermochemically particularly efficient process, with the cracking reaction then being triggered comparatively suddenly at the reaction accelerator up to an equilibrium temperature for complete dissociation (and above), All these advantages are realized in a structurally simple and low-maintenance receiver reactor.
    Because the receiver reactor can be operated alternately with a reducible gas, there is even maintenance of the receiver reactor with regard to carbon deposits with the production of syngas, which can also be used industrially for the synthetic production of fuels.
    Because the receiver reactor has a device for generating germs in the absorber area, a permanently installed absorber can be replaced by a cloud of germs, with the advantage that carbon deposits settle on the germs, thus over the germs with the flow of the products carbon and hydrogen are removed directly from the receiver reactor, so that maintenance related to carbon deposits is omitted and the maintenance requirement is reduced accordingly overall.
    Because the receiver reactor is provided with replaceable absorber elements, an element with limited functionality due to carbon deposits can also be exchanged and cleaned or replaced separately during operation, for example on the fly or with only a short operational interruption.
    [0012] Further preferred embodiments have the features of the dependent claims.
    The invention is described in more detail below with reference to the figures.
    It shows:<tb> <SEP> FIG. 1 schematically shows a longitudinal section through a receiver reactor designed according to the invention according to a first exemplary embodiment,<tb> <SEP> Figure 2 schematically shows a longitudinal section through a receiver reactor designed according to the invention according to a second embodiment,<tb> <SEP> Figure 3a schematically shows a longitudinal section through a receiver reactor designed according to the invention according to a third embodiment,<tb> <SEP> Figure 3b schematically shows a longitudinal section through the receiver reactor of Figure 3a, the cross-section being offset by ninety degrees,<tb> <SEP> Figure 4 shows schematically the longitudinal section of Figure 3b together with a diagram of the temperature distribution during operation of the receiver reactor,<tb> <SEP> Figure 5 schematically shows another embodiment of the receiver reactor with modified supply channels,<tb> <SEP> Fig. 6 schematically an embodiment of the receiver reactor according to FIG. 5,<tb> <SEP> Fig. 7 shows a view of an embodiment of the receiver reactor according to FIG. 5 in the horizontal operating position,<tb> <SEP> Fig. 8 shows a section through the annular space of the receiver from FIG. 7,<tb> <SEP> Fig. 9 an enlarged section from FIG. 8, and<tb> <SEP> Fig. 10 shows the temperature distribution in the receiver according to FIGS. 6 to 9 according to a simulation.
    Figure 1 shows a longitudinal section through an absorptive receiver reactor 1 according to a first embodiment with a flow channel 2 passing through it for a process gas symbolized by the arrows 3, 4, which is from an opening 6 closed by a window 5 for the rays 7 of the sun leads to an outlet 8 from the receiver reactor 1. The rays 7 of the sun fall through the opening 6 into an absorber area 9 of the receiver reactor 1, which is thus in the path of the incident radiation from the sun (with any radiation reflected from the side walls 13 also reaching the absorber area 9) in which in the embodiment shown, an absorber 10 is arranged. Individual absorber plates 11 are connected to one another by struts 12 and suspended in the flow channel 2, thus forming the absorber 10. The absorber plates 11 are arranged in such a way that they are opposite the opening 6 and thus the absorber 10 over its entire extent directly onto it during operation incident solar radiation 7 is illuminated. Furthermore, the plates 11 are arranged offset to one another so that the process gas and the process products can easily flow through between the absorber plates 11 - the absorber area 9 and the absorber 10 can be flowed through by the process gas. Another configuration of the absorber 10, for example one or two perforated plates one behind the other and then offset from one another, is also conceivable.
    In operation, the receiver reactor 1 is supplied with a hydrocarbon gas such as methane as a process gas via a feed line 15, preferably (but not necessarily) preheated in a heat exchanger 16 and fed via a transport line 17 into a ring line 18 provided at the opening 6, from which it is emitted, symbolized by the arrow 4, into the flow channel 2 via supply channels 19. The absorber 10 heated by the solar radiation 7 emits black-body radiation in the infrared range, symbolized by the arrows 20. The process gas flowing in the flow channel according to the arrows 3, here methane, is highly transparent for the solar radiation 7, but absorbs the black-body radiation 20 and thus heats up absorptively. It should be noted at this point that in the following, for the sake of simplicity, the invention is only described on the basis of methane, but other hydrocarbon gases can also be cracked according to the invention and thus methane is only an (at least very important) example of these hydrocarbon gases. A person skilled in the art can now coordinate the flow velocity of the methane together with the dimensions of the flow channel 2 and the radiation intensity of the absorber 10 in such a way that the methane is heated to its cracking temperature on its way to the absorber 10 in a first area 21 of the flow channel 2, in a subsequent area second, downstream flow area 22 is heated beyond the cracking temperature and is heated even further in a third, further downstream flow area 23 of flow channel 2, third flow area 23 corresponding to absorber area 9. For the definition of the cracking temperature used here, see. above and also the description of FIG. 4.
    In the third flow area 23, or in the absorber area 9, the methane passes through the cross-section of the flow channel 2 in physical contact with the absorber 10, which acts as a reaction accelerator for the dissociation of the methane through physical contact, ie is a reaction accelerator that at the same time has the function of an absorber in a receiver. A possible convective heat transfer from the reaction accelerator, which is thus designed as an absorber 10, is irrelevant for the dissociation of the methane. As a result, the methane dissociates comparatively suddenly as a result of physical contact, so that in the fourth area 24, behind the absorber area 9, a flow of products is formed which has nanoparticles of carbon and hydrogen, i.e. soot and hydrogen. This stream is output from the receiver reactor 1 through the outlet 8 after heat has been withdrawn from it in the heat exchanger 16.
    Since the formation of the carbon nanoparticles (soot) begins in the first area and slowly builds up in the second area, a proportion of the nanoparticles can be deposited on the absorber 10, here on the absorber plates 11, and as Fix soot layer. This is harmless for the continuous cracking of the freshly fed methane, since carbon or soot has the preferred properties of the absorber material: it is black, i.e. highly absorptive for the incident solar radiation 7, emits the desired (infrared) black body radiation after heating and is temperature-resistant in the range up to well over 2000 ° C. With increasing deposits, however, the geometry of the absorber 10 also changes with regard to its flow properties to a degree at which the cracking is impaired. The deposit must then be removed accordingly by means of a (cyclical) maintenance step.
    In the embodiment shown, this is done in that a second process gas is entered into the reactor receiver 1 via a second supply line 15 via the second transport line 25, guided to a second ring line 26 and from this via second supply channels 27 into the flow channel 2 is output, as is indicated by the arrows 4. The second process gas is preferably a reducible or oxidizing gas, particularly preferably water vapor, which heats up absorptively in the first 21 and second area 22 and then chemically reacts in the absorber zone 9 with the carbon deposited on the absorber 10, according to the equation H2O + C -> CO + H2. In other words, the receiver reactor is then also productive during maintenance and produces syngas as a raw material for synthetic fuel. In any case, the hydrogen production is not interrupted, with the unchanged use of hydrogen (compared to cracking) the carbon monoxide for example for the production of methanol or other liquid hydrocarbons, for example by means of Fischer-Tropsch synthesis.
    There is a receiver reactor for cracking a hydrogen gas, in particular methane, which has an opening 6 for the radiation 7 from the sun, and a flow channel 2 for methane to be cracked through the receiver reactor 1 and one in the path of the incident radiation 7 of the sun, designed for its absorption, which emits black body radiation upstream into the flow path during operation, the absorber area 9 being arranged and designed in such a way that it is opposite the opening for the radiation 7 from the sun and above during operation its entire extent is illuminated by radiation 7 from the sun incident directly on it, and that methane can flow through it, supply sections (14, 15) being provided for a hydrocarbon gas and a carbon oxidizing gas (preferably water vapor), which can be switched in this way are that the receiver reactor (1,30,40) alternately with the coal hydrogen gas and can be operated with the reducible gas. The person skilled in the art can of course also design the transport lines 17 or 25 in such a way that the respective transport line 17.25 can be operated sequentially with both process gases and the other transport line is thus superfluous. PA 10 According to FIG. 1, two line arrangements (18, 19 and 25, 26) opening into flow channel 2 independently of one another are preferably provided.
    It also emerges that instead of methane, a reducible gas is cyclically passed through the receiver reactor in such a way that soot deposited in the flow channel 2, in particular in the absorber region 9, is removed by chemical reaction with the reducible gas. Steam is preferably used as the reducible gas, in such a way that the receiver reactor produces syngas in the steam cycle and soot and hydrogen in the methane cycle. FIG. 2 schematically shows a longitudinal section through a receiver reactor 30 according to a second embodiment of the invention. In contrast to the receiver reactor according to FIG. 1, the absorber area 9 does not have an absorber, but a device 31 for generating a cloud of germs 32 which, in physical contact with the methane as germ cells for cracking, trigger its cracking. These germs preferably consist of soot particles 32 which are sprayed via nozzles 33 from a feed line 34 for a gas-germ particle mixture into the methane flowing through the flow channel 2 according to the arrows 3, so that in the absorber area 9 (or in the third area 23) a constant cloud of germs or soot particles 32 forms, which is absorptively heated by the incident solar radiation 7, so that blackbody radiation 20 itself emits and thus heats the flowing methane in the first area 21 to its cracking temperature and in the second area 22 beyond this. The cloud of germs extends over the cross section of the flow channel 2 and acts in the third area 23 as a reaction accelerator for cracking (see also the description of FIG. 4), with the carbon that forms during cracking being deposited on the germs or soot particles 32 and is discharged from the reactor receiver 30 via the outlet 8. In the event that undesired deposits are to be removed on the section of the supply line 34 protruding into the flow channel 2, a person skilled in the art can for example provide a steam circuit according to the embodiment described in FIG. In the specific case, it is also possible to align the nozzles 33 with the opening 6 so that the germs or soot particles 32 are sprayed out against the flow of methane (arrows 3). This can be advantageous with regard to carbon deposits, since soot that has already formed is less deposited than soot that was formed during cracking as a result of physical contact with the line 34.
    There is a receiver reactor 30 for the cracking of methane, which has an opening 6 for the radiation 7 of the sun, and a flow channel 2 for methane to be cracked through the receiver reactor and one in the path of the incident radiation 7 of the Arranged sun, has absorber area 9 designed for its absorption, which during operation emits black body radiation upstream into the flow channel 2, in which the absorber area 9 is arranged and designed in such a way that it is opposite the opening 6 for the radiation 7 of the sun and during operation via its The entire extent of radiation 7 from the sun incident directly on it is illuminated, the absorber area 9 also having a device 31 for generating a cloud of germs (preferably soot particles 32). The device for generating germs preferably has at least one spray nozzle 33 for germs, preferably soot particles 32.
    There is also a method according to which preferably with the receiver reactor 30 shown in Figure 2 in the third flow region 23 a cloud of germs 32 is injected into the flowing methane, such that the cracking is triggered over the cross section of the flow and wherein the cloud is formed in such a way that it lies in the path of the incident sunlight 7, absorbs it, warms it up and also emits black body radiation 20 upstream into the flowing methane.
    FIG. 3a schematically shows a longitudinal section through a receiver reactor 40 according to a further embodiment. In the absorber area, an absorber 41 is provided, which has a number of here rod-shaped absorber elements 42, which in turn are moved into an operating position in the absorber area 9 of the flow channel 2 via a only schematically indicated movement device 43 in the direction of the double arrow 44 and into a rest position outside the absorber area 9 can be extended. A person skilled in the art can suitably design the movement device 43 in a specific case. Absorber elements 42 whose functionality is impaired by deposits can be removed from the absorber area by the movement device 43 and replaced by absorber elements 42 without harmful deposits. This can be done during the operation of the reactor receiver 40 by replacing the individual absorber elements gradually or in accordance with the detection of deposits or, for example, at night, all at once.
    Figure 3b shows schematically a longitudinal section through the receiver reactor 40 which is placed perpendicular to the length of the absorber elements 42 of Figure 3a. The two rows of absorber elements 42 staggered one behind the other can be seen, although only one or more than two rows can of course also be provided.
    The result is a receiver reactor for cracking a hydrocarbon gas, in particular methane, which has an opening for the radiation of the sun, and a flow channel for methane to be cracked through the receiver reactor and one arranged in the path of the incident radiation from the sun , has absorber area designed for the absorption of which, during operation, emits black body radiation upstream into the flow channel, in which the absorber area is arranged and designed in such a way that it is opposite the opening for the radiation of the sun and, during operation, directly incident on it over its entire extent Radiation from the sun is illuminated, and that methane can flow through it, with an absorber also being provided in the absorber area, the absorber elements movable independently of one another between an operating position in the absorber area and an exchange position outside the absorber area and a moving part has rrichtung for the absorber elements.
    Preferably, the movement device is designed to change a current operating position of the absorber elements in their operating position in a predetermined manner.
    [0028] The movement device is more preferably designed to replace used absorber elements with fresh absorber elements in the rest position.
    In this case, an absorber or parts of the absorber are preferably replaced or cleaned from deposits after a specified threshold has been reached during operation.
    In a further, preferred embodiment, the flow channel 2 is tubular with a straight axis, with the window 5 at one end and transversely to its axis and the absorber region 9 at its other end, which is also transversely to the axis and extends over the entire cross section of the flow channel 2 there.
    Figure 4 shows schematically the longitudinal section through the receiver reactor 40 according to Figure 3b together with a diagram 50 for the temperature distribution in the first 21 to third area 23 of the flow channel 2 during operation of the receiver reactor 40. On the horizontal axis is Distance A from window 5 to the end of absorption area 9 is plotted, temperature T on the vertical axis. Arrow 3 again symbolizes the flow direction of the methane. The relationships shown by diagram 50 also apply analogously to every embodiment of the receiver reactor according to the invention or with regard to the method according to the invention for cracking a hydrocarbon gas.
    The curve 51 shows the temperature profile on an axis 52 of the flow channel 2, the curve 53 that in the vicinity of the side walls 13 and the curve 54 the average temperature profile of the methane flowing from the window 5 through the absorber 41 (or, in cyclic operation according to the description of FIG. 2, also of the oxidizing gas or the water vapor.
    The curves are only given qualitatively in the figure, but are based on a mathematical modeling of an absorptive receiver from the applicant which, according to FIGS. 1 to 4, is designed with a straight, tubular flow channel 2. The system has been modeled with today's most accurate method, namely "Spectral line-by-line (LBL) photon Monte Carlo raytracing", whereby the absorption coefficients come from the HITEMP 2010 Spectroscopic Database. A receiver is modeled whose absorption space (areas 21 to 23) has a diameter of 15.96 m and a height of 15.96 and the opening 6 has a diameter of 11.28 m. This results in a directly illuminated area of the absorption space 9 of 200 m 2 and an area of the opening 6 of 100 m 2. Water vapor was assumed to be the heat-transporting medium (although there were no qualitatively relevant changes in the case of methane) at a pressure of 1 bar, without a window in the opening 6. The radiation flux at the opening 6 is 1,200 kW / m <2 > and in the absorbent absorbent area (9) 600 kW / m <2> (which has twice the area of the opening 6). This modeling can be transferred with regard to the temperature conditions and the average temperature with the deviations to the center or the walls of the flow channel 2, in particular also with regard to the inlet temperature of the methane entering the flow channel 2, which is comparatively low for cracking. In particular, these curves illustrate the steady rise in temperature in the flow channel 2 due to the absorptive heating as well as the temperature deviations from the respective average value to the area close to the wall or the axial area of the flowing methane, which are relevant with regard to cracking.
    The methane is output through the ring line 18 (preferably preheated by the heat exchanger 16) into the flow channel 2, the distance A in the diagram 50 is zero. Because of the side walls 13 heated by the black body radiation 20, the methane in the area near the wall warms up to the cracking temperature Tc early on. As mentioned above, the term cracking temperature is used here for the temperature at which in the equilibrium state, i.e. after an infinitely long time, 50% of the methane is dissociated.
    In the first area 21 of the flow channel 2, however, because of the progressive flow (arrows 3) and because of the sluggish reaction, there is no equilibrium state, the percentage of dissociated methane is much lower than the average temperature (curve 54). Thus, at the end of the first region 22 (distance A22), in which the average temperature reaches the cracking temperature Tc, cracking has only just started. With regard to cracking, there are moderately overheated zones near the wall, i.e. Zones in which the (sluggish) cracking progresses and in the middle of the flow channel 2 moderately supercooled zones in which the cracking does not yet take place. In other words, there is an inhomogeneously beginning dissociation in area 21.
    At the end of the second region 22 (distance A23) the average temperature (curve 54) is well above the cracking temperature Tc, the deviation of the near-wall or central temperatures (curves 53 and 51) has become smaller - the cracking is above initialized the entire cross section of the flow channel 2. But here, too, the dissociation is not as far advanced and not yet as homogeneous as it would correspond to the equilibrium state at the average temperature (curve 54). In terms of temperature and time (equilibrium state) there is still a very small proportion of cracked methane, which would not be sufficient for an economically sensible operation of the receiver reactor.
    In the third area 23, i. the absorber zone 9, the methane comes into physical contact with the reaction accelerator, which is designed as an absorber, be it a permanently installed absorber 10, 42 according to FIGS. 1 or 3a, b or a cloud of germs 32 according to FIG. 2. During the passage Through the absorber zone 9, the temperature of the methane increases sharply, the temperature deviations from the average temperature to the wall 13 or axis of the flow channel 2 decrease further and cannot affect the homogeneity of the dissociation reaction over the cross section of the absorber area 9, so they are for the cracking itself not relevant anymore.
    In detail, when passing through the third area 23 or the absorber zone 9, two effects result: firstly, shortly before physical contact, the methane molecules heat up very strongly due to the intense infrared radiation, they dissociate or overheat (with regard to the cracking temperature) very much strong. Second, physical contact acts as a nucleus for dissociation, which then takes place quickly and almost completely due to the overheating of the methane. As mentioned above, a certain deposit of soot on a permanently installed absorber 10, 42 is unavoidable, but these deposits, which do not interfere with cracking, can be removed, for example, during the night or by solar operation with an oxidizing gas. It should be noted that a reaction accelerator designed as an absorbing germ cloud according to FIG. 2 is particularly favorable with regard to deposits, since the deposits form on the germs 32, which are released with the flow (of now soot particles and hydrogen gas) via the outlet 8 from the receiver reactor 30 can be submitted.
    As a result, temperature zones that are staggered one behind the other are formed in the flow channel (which are roughly divided into the three areas 21 to 23 in the description), see FIG. the dashed lines in FIG. 4 for the zones 60 to 67 assumed here. These zones 60 to 67 naturally extend through the flow channel 2, but the dashed lines are only drawn as far as the side wall 13 of the flow channel 2 to relieve the figure.
    Regardless of where the zone boundaries are exactly placed, it can be stated that they extend transversely to the flow channel 2, are disc-shaped and the temperature rises from temperature zone to temperature zone, although of course no completely homogeneous temperature distribution can exist in each temperature zone , but there is a slightly inhomogeneous temperature distribution (each temperature zone 60 to 67 has its respective higher temperature level), the temperature limits of which, however, at least from the second flow area 22 onwards, are closer and closer together (at the beginning of the first flow area, see zone 60, this is nature according to the matter not yet). This results in practically complete heating of the methane after the second flow region 22, which is uniform with regard to the cracking, so that the cracking can be carried out with a very high degree of dissociation which meets industrial requirements. In addition, the receiver reactor 1, 30, 40 is suitable for continuous operation, with carbon deposits being able to be removed continuously or at night (see the description for FIGS. 1, 3a and 3b) or essentially not occurring (see the description to Figure 2).
    In general, according to the invention there is a method for cracking hydrocarbon gases, preferably methane, wherein the hydrocarbon gas is passed through a flow channel of an absorptive receiver reactor, characterized in that the cracking takes place during the passage through the receiver reactor Methane is heated to its cracking temperature in a first area of the flow channel, heated in a subsequent, second, downstream flow area above the cracking temperature and further heated in a third, further downstream area of the flow channel and in this area in physical contact with a Reaction accelerator is brought, after which the stream of products behind the reaction accelerator is released from the receiver reactor, and wherein the heating of the hydrocarbon gas to above its cracking temperature by absorption of black bodies Radiation takes place, which is released by the reaction accelerator heated by incident solar radiation to the flowing hydrocarbon gas, in such a way that the methane in the flow channel up to the reaction accelerator forms disk-shaped, successively staggered temperature zones with increasing temperature in each case.
    Preferably, an absorber of the receiver reactor is used as the reaction accelerator, through which the medium passed through the receiver reactor flows.
    It should be noted that the embodiments shown in the present description can be combined, so in a specific case the person skilled in the art can combine exchangeable absorber elements according to FIGS. 3a and 3b together with a cloud of germs 32 according to FIG. 2, or additionally the removal provide for carbon deposits with the aid of an oxidizing gas according to FIG.
    In a solar tower power plant, designs are also used in which the receiver (here a receiver-reactor according to the present invention) is arranged at the top of the tower and is oriented obliquely downwards in order to directly absorb the radiation from the heliostat field. The inclined alignment can result in correspondingly inclined temperature zones 60 to 67, which can generate a convection flow in the heat-transporting fluid, which in turn increases the temperature stratification given by the temperature zones and thus also the desired, as homogeneous as possible, temperature distribution in the third area 23 or in the absorber zone 9 can disturb.
    In other designs, for example in a solar tower power plant, the receiver-reactor according to the invention can be aligned vertically, in which case the radiation of a heliostat field is directed vertically downwards onto the receiver 100 located near the ground via mirrors arranged in the solar tower, such an arrangement is the Known as “beam-down” by experts. (Conversely, the radiation from the heliostat field can also be directed vertically upwards via mirrors or by the heliostats themselves, with the receiver 100 then being on top of the solar tower.)
    In particular in a receiver 100 oriented vertically downwards in such a way that the flow of the fluid transported through the absorber space 28 is formed quite evenly and thus a clear temperature stratification over the height of the absorber space 28 results. In the case of a “beam-down” arrangement, it can be useful in the specific case to provide a swirl in the fluid in accordance with FIGS. 5 to 10 described below in addition to a sufficiently high flow velocity of the heat-transporting fluid towards the absorber
    According to the invention, therefore, according to a further embodiment of the receiver reactor 1, process gas, at least the hydrocarbon gas to be cracked or also the reducible gas, according to FIG. 5, is fed tangentially into the flow channel 2 via the correspondingly modified supply channels 19 'and 27', in such a way that the gas flowing in the direction of the arrows 3 additionally rotates about the axis 52. The outlet 8 can also be displaced somewhat from the center of the flow channel 2 so that, for example, in the specific case, i.e. when the receiver 60 is inclined, is close to its upper side.
    For this purpose, the supply channels 19 'and 27' are preferably designed in such a way that they open tangentially into the flow channel 2 and generate an additional swirl according to the arrows 61 and 62 in the flow of the respective process gas. As a result, the temperature zones 60 to 67 according to diagram 50 of FIG. 4 are retained even when the receiver reactor 60 is in an inclined position.
    In the event that the outlet 8 is arranged eccentrically to the disturbance channel 2, the process gas can rotate about an axis corresponding to the axis 52 parallel.
    As a result, the receiver reactor 60 is designed such that the supply channels are tangential to a longitudinal axis (52) of the flow path 2, such that the process gas in the flow path 2 on its way to the The absorber area (9) has a twist about this axis 52.
    It should be noted at this point that the rotation of the flow or the swirl can also be generated by baffles in the flow space 2, which, thanks to the defined temperature stratification, is preferably implemented in its first area 21 and thus the effort for the receiver according to the invention Reactor 60 increased only insignificantly.
    Figure 6 shows schematically a view of an obliquely arranged receiver 110 on the side of its opening 3 for the radiation of the sun, supply lines 104 arranged tangentially to the axis 103 for the heat-transporting medium can be seen, which a rotation of the medium or generate a swirl in the medium flowing against the absorber 27. The absorber 27 can be seen through the opening or the quartz window 3 in the figure, the flow path of the medium through the absorber (or past it) not being drawn in to relieve the figure, but only an outlet connection 106 from which the medium is drawn in dashed lines the receiver 110 leaves. The outlet connector is preferably arranged slightly eccentrically offset upwards, which in combination with the swirl of the flowing medium results in a stable temperature in the heat-transporting medium at the location of the outlet connector 106.
    As a result, the receiver reactor is preferably designed in such a way that, during operation, the process gas has at least partially a twist around an axis 52 of the absorber chamber parallel to the transport direction while the process gas is being traversed in the transport direction, the receiver reactor preferably at the Flow chamber 2 has provided inlet openings for the medium, which are aligned tangentially with respect to its axis 52 in the same swirl direction.
    It should be noted at this point that the rotation of the flow or the swirl can also be generated by baffles in the flow channel 2, which, thanks to the defined temperature stratification, is preferably implemented in its cold area and thus only the effort for the receiver according to the invention marginally increased.
    Figures 7 to 10 show details of a receiver reactor 120, which is designed for high efficiency even with oblique or horizontal positioning. FIG. 7 shows a view of the receiver reactor 120 from the outside, FIGS. 8 and 9 show a cross section through this, and FIG. 10 shows the layered temperature distribution in its flow channel 2 according to a simulation by the applicant. To relieve the figures, the insulation of the receiver reactor 120 and its supporting, external structure, which the person skilled in the art can easily design in a specific case, has been omitted.
    FIG. 7 shows the receiver reactor 120, with its flow channel 2, a collecting space 33 and an outlet connection 121 (see also the illustration in FIGS. 1 and 5). A supply arrangement 122 for cold (Tin) process gas can also be seen. The supply arrangement 122 has an annular space 123 into which supply lines 124 for process gas open, see FIG. the arrows 125, whereby process gas that has flown into the receiver 120 via the annular space 123 traverses the flow channel 2 in a main flow direction parallel to the axis 127, heats up in the process and finally, after the cracking, the receiver 120 with the temperature Tout again via the collecting space 33 and outlet connection 121 leaves (arrows 126). Sun rays 4 pass through an opening covered by the annular space 123 in the figure or through a window 3 into the flow channel 2 as far as the inside of the collecting space 33, the inner wall of which is designed as an absorber for the solar radiation in the embodiment shown. As mentioned in the description of FIG. 6, in the embodiment shown, the outlet connection 121 is also arranged offset upwards.
    FIG. 8 shows the annular space 123 in section, the sectional plane in turn passing through an axis 127 running longitudinally through the flow channel 2 and the supply lines 124 (see also FIG. 10). The annular space 123 is shown to scale, as is the adjoining area of the flow channel 2 and the position of the opening 3 or a window 3 for the radiation of the sun. As mentioned above, however, the insulation and the load-bearing structure are omitted, here in particular that for the window 3 and the annular space 123. The supply lines 124 for the heat-transporting fluid arranged upstream or on the inlet side are also shown. Downstream or on the outlet side, the annular space 123 divides into an outer annular channel 132 with an annular outlet slot 130 and an inner annular channel 133 with an annular outlet slot 131. The outer channel 132 runs coaxially to the axis 127 of the flow channel 2 and adjacent to its wall 138, the inner channel 133 has a frustoconical configuration and is directed obliquely towards the interior of the absorption space 28. As a result, in the area of the wall 138, zones with reduced flow towards the absorber are only formed to a reduced extent or to an extent that is no longer relevant, and despite the somewhat hotter walls (see diagram 50 of FIG. 5) finally in front of the absorber via the Cross-section of the flow channel 2 results in a homogeneous temperature layer (see also FIG. 10). A flow component from the outer channel 132 therefore particularly preferably runs parallel to the wall 138; its angle to the wall 130 is preferably less than or equal to 15 degrees, particularly preferably less than or equal to 10 degrees and especially preferably less than or equal to 5 degrees. A positive effect can still be achieved at an angle less than or equal to 10 degrees or 15 degrees.
    The annular channels 132, 133 are provided with baffles 134, 135 (see FIG. 11 b), so that openings for the process gas are formed in the outlet slots 130, 131 and also give this a flow component tangential to the axis 127. It thus enters the flow channel 2 in a directed flow and, in addition to the main flow direction parallel to the axis 127, has a flow direction tangential (swirl) to the axis 127. This creates the spiral flow lines 136 and 137 shown by way of example in the figure. As a result, a disturbance of the temperature stratification in the receiver 120 by, for example, temperature-related convection currents can be suppressed, especially in the case of inclined or horizontal alignment.
    FIG. 9 shows an enlarged detail from FIG. 8 to illustrate the relationships. The guide plates 134 'to 134 "' and the components of the directed flow 136, namely that in the direction of the main flow 141 and the tangential component 142, can be seen in particular.
    The result is a receiver reactor which has openings for the heat-transporting medium leading into the flow channel 2, which openings are arranged adjacent to a wall 138 of the flow channel 2 and which in the main flow direction have a flow component of the process gas flowing into the flow channel 2 an inclination with respect to the wall 138 of less than 15 degrees, preferably equal to or less than 5 degrees. According to the applicant's findings, such small angles are necessary in order to avoid zones of reduced flow velocity towards the absorber that are relevant for the efficiency of the absorber in the area of the wall 138.
    There is also a receiver reactor in which the transport arrangement has openings for the heat-transporting medium leading into the flow channel 2, which openings generate a flow component of the process gas flowing into the absorption chamber 28 that is tangential to an axis 127 of the flow channel 2.
    Finally, there is a method for operating a receiver reactor, in which the process gas is set in rotation in a flow channel 2, so that it swirls in the flow channel 2 about an axis (127) running in the transport direction or the main flow direction ) having.
    FIG. 10 shows the temperature distribution according to a CFD simulation by the applicant in the flow channel 2 of the receiver reactor 120 with the following boundary conditions:<tb> <SEP> • Diameter of the absorption space 0.8 m, pressure in the flow channel = 1 bar<tb> <SEP> • Tin = 800 ° K, mass flow of the process gas = 0.045 kg / s<tb> <SEP> • Solar radiation output through the transparent opening 3 = 250 kW, diameter of the opening: 0.6 m<tb> <SEP> • Process gas: water vapor<tb> <SEP> • Spectral radiation behavior of water vapor modeled with the weighted sum of gray gases (WSGG) model and radiation solved with the discrete ordinates (DO) method<tb> <SEP> • Black walls, Ewall = 1<tb> <SEP> • Gravity pointing vertically downwards (horizontal receiver)<tb> <SEP> • Angle of the fluid flowing into the absorption space: 45 degrees
    The angle of the inflowing fluid in the annular channel 132 is the angle between the directed flow 136 and the direction of the main flow 141 from FIG. 11b. The annular channel 133, as mentioned above, has a frustoconical configuration, i. its downstream end is circular. The angle of the fluid flowing out of it into the absorption space is analogous to the angle of its flow direction to a tangent to this circle.
    A simplified geometry in the area between the optical opening 3 and the walls 138 of the flow channel 2 was assumed for the simulation: the space between the outlet slots 130 and 131 (FIGS. 8 and 9) is replaced by a frustoconical wall area 150.
    The simulation results in an outlet temperature Tout of 1,862 ° K and the temperature stratification shown in the figure, which is shown by the temperature curves 140 to 145. The temperature curve 140 corresponds to the temperature 1420 ° K, the curve 141 the temperature 1533 ° K, the curve 142 1589 ° K, the curve 143 1645 ° K, the curve 144 1702 ° K, and the curves 145 1870 ° K.
    It turns out that despite the complex thermodynamic conditions, even at very high temperatures, inter alia, by the hot wall 138 heated by the radiation from the absorber 27 and the complex fluidic conditions, among other things by the temperature differences and gravitation Convection flow, there is a temperature stratification in the process gas (here water vapor) at which the temperature from the opening 3 to the outlet connection 121 continuously increases, with the result that, for example, the efficiency-reducing reflection through the opening 3 can be minimized. It should also be noted that the person skilled in the art can suitably set the direction of the inflow or the swirl or the rotation of the fluid in the absorption space around an axis running through this, as well as the location of the outlet connection (centrically according to FIGS. 2 and 3) to 6 or offset according to FIGS. 9 and 10). Can e.g. If, for example, an optimal swirl is generated in the context of the other parameters (for example those of the simulation above), the outlet nozzle can also be arranged centrally in a horizontal orientation. Conversely, the combination of a comparatively weak or non-optimal swirl with an offset position of the outlet connection can produce the desired temperature stratification.
    权利要求:
    Claims (22)
    [1]
    1. A method for cracking hydrocarbon gases, wherein the hydrocarbon gas is passed through a flow channel (2) of an absorptive receiver reactor (1,30,40), characterized in that the cracking occurs during the passage through the receiver reactor (1, 30.40) takes place, while the hydrocarbon gases are heated to their cracking temperature in a first area (21) of the flow channel (2), heated above the cracking temperature in a subsequent, second, downstream flow area (22) and in a third, further downstream Area (23) of the flow channel is heated even further and is brought into physical contact with a reaction accelerator via its cross-section, after which the flow of products is released from the receiver reactor (1,30,40) behind the reaction accelerator, and the The hydrocarbon gas is heated to above its cracking temperature by absorbing black bodies radiation (20) takes place, which is released by the reaction accelerator heated by incident solar radiation (7) to the hydrocarbon gas flowing towards it, in such a way that the hydrocarbon gas in the flow channel (2) up to the reaction accelerator extends transversely to the flow channel (2), disc-shaped temperature zones (60 to 67) staggered one behind the other, each with increasing temperature.
    [2]
    2. The method according to claim 1, wherein an absorber (10,41) of the receiver reactor (1,30,40) is used as the reaction accelerator, through which the medium passed through the receiver reactor (1,30,40) flows.
    [3]
    3. The method of claim 1, wherein in the third flow region (23) a cloud of germs (32) is injected into the flowing hydrocarbon gas, such that the cracking is triggered over the cross section of the flow, and wherein the cloud is formed such that it lies in the path (7) of the incident sunlight, absorbs it, warms up and emits blackbody radiation (20) also upstream into the flowing methane.
    [4]
    4. The method according to claim 3, wherein soot particles are used as seeds (32).
    [5]
    5. The method according to claim 1, wherein a reducible gas is cyclically passed through the receiver reactor (1,30,40) in place of a carbon hydrogen gas, in such a way that soot deposited in the flow path (2) is dissolved by chemical reaction with the reducible gas.
    [6]
    6. The method according to claim 5, wherein water vapor is used as the reducible gas, preferably such that the receiver reactor (1,30,40) produces syngas in the steam cycle and soot and hydrogen in the methane cycle.
    [7]
    7. The method according to claim 1, wherein an absorber (10,41) or parts of the absorber (10,41) are replaced or cleaned after reaching a specified threshold of deposits during operation.
    [8]
    8. The method of claim 1, wherein the hydrocarbon gas is methane.
    [9]
    9. The method according to claim 1, wherein at least the hydrocarbon gas is supplied tangentially to a longitudinal axis (52) of the flow channel (2) in such a way that the gas guided against the third region (23) of the flow channel (2) is additionally guided around a longitudinal axis (52) parallel axis rotates.
    [10]
    10. The method according to claim 1, wherein at least one of the gases hydrocarbon gas or the reducible gas is set in rotation in at least the areas (21) and (22) of the areas (21) to (24) of the flow channel (2), such that that it has a twist around an axis (52) parallel to the transport direction (3) in the flow channel (2).
    [11]
    11. Receiver reactor for cracking a hydrogen gas, in particular methane, which has an opening (6) for the radiation (7) from the sun, and a flow channel (2) for methane to be cracked through the receiver reactor (1,30,40 ) through and an absorber area (9) arranged in the path of the incident radiation (7) of the sun and designed for its absorption, which during operation emits black body radiation (20) upstream into the flow channel (2), characterized in that the absorber area (9 ) is arranged and designed in such a way that it is opposite the opening (6) for the radiation (7) from the sun and, during operation, is illuminated over its entire extent by radiation (7) from the sun incident directly on it, with feed line sections (14) for a hydrocarbon gas and feed line sections (15) for a carbon oxidizing gas are provided, which can be switched such that the receiver reactor (1,30,40) alternates with the hydrocarbon gas s and can be operated with the reducible gas.
    [12]
    12. Receiver reactor according to claim 11, wherein two line arrangements (18, 19 and 25, 26) opening independently of one another into the flow channel 2 are provided.
    [13]
    13. Receiver reactor according to claim 11, wherein the reducible gas is water vapor.
    [14]
    14. Receiver reactor for cracking a hydrogen gas, especially methane, which has an opening (6) for the radiation (7) from the sun, and a flow channel (2) for methane to be cracked through the receiver reactor (1,30,40) and an absorber area (9) which is arranged in the path of the incident radiation (7) of the sun and is designed for its absorption, which during operation emits black body radiation (20) upstream into the flow channel (2), characterized in that the absorber area (9) is arranged and designed in such a way that it is opposite the opening (6) for the radiation (7) from the sun and, during operation, is illuminated over its entire extent by radiation (7) from the sun directly incident on it, the absorber area (9) also a device (31) for generating a cloud of germs (32).
    [15]
    15. Receiver reactor according to claim 14, wherein the device (31) for generating germs (32) has at least one spray nozzle (33) for germs (32), preferably soot particles.
    [16]
    16. Receiver reactor for cracking a hydrogen gas, in particular methane, which has an opening (6) for the radiation (7) from the sun, and a flow channel (2) for methane to be cracked through the receiver reactor (1,30,40) and an absorber area (9) which is arranged in the path of the incident radiation (7) of the sun and is designed for its absorption, which during operation emits black body radiation (20) upstream into the flow channel (2), characterized in that the absorber area (9) is arranged and designed in such a way that it is opposite the opening (6) for the radiation (7) of the sun and, during operation, is illuminated over its entire extent by radiation (7) of the sun incident directly on it, and that it is from through the flow path 2 flowing hydrocarbon gas is designed to be able to flow through, wherein an absorber (41) is also provided in the absorber area (9), which is independent of one another between an operating position in the absorber area (9) and an exchange position outside the absorber area (9) has movable absorber elements and a movement device (43) for the absorber elements (42).
    [17]
    17. Receiver reactor according to claim 16, wherein the movement device (43) is designed to change a current operating position of the absorber elements (42) in their operating position in a predetermined manner.
    [18]
    18. Reciever reactor according to claim 16, wherein the movement device (43) is designed to replace used absorber elements (42) with fresh absorber elements (42) in the rest position.
    [19]
    19. Receiver reactor according to one of claims 11, 14 or 16, wherein the supply channels 17 ', 27' are formed tangentially to a longitudinal axis (52) of the flow path 2, such that when the receiver reactor 60 is in operation, the process gas in the flow path 2 has a twist about this axis 52 on its way to the absorber area (9).
    [20]
    20. Receiver (25,50,100,120) according to one of claims 11,14 or 16, wherein the side walls (13) of the flow channel (2) and / or the absorber area (9) are free of coolants, in particular cooling channels, for the intended operation of the Receivers (1,30,40,60).
    [21]
    21. Receiver (25,50,100,120) according to any one of claims 11,14 or 16, wherein the transport arrangement in the absorber space (28,57) has openings for the heat-transporting medium which are adjacent to a wall 138 of the absorption space (28,57 ) are arranged and which in the main flow direction generates a flow component of the fluid flowing into the Absprotionsraum (28,57) with an inclination relative to the wall 138 of less than 15 degrees, preferably equal to or less than 10 degrees, particularly preferably equal to or less than 5 degrees.
    [22]
    22. Receiver (25,50,100,120) according to one of claims 11,14 or 16, wherein the transport arrangement in the absorber chamber (28,57) has openings for the heat-transporting medium which have an axis 127 of the absorption chamber (28,57) tangential flow component of the fluid flowing into the absorption space (28,57) is generated.
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    同族专利:
    公开号 | 公开日
    AU2020256644A1|2021-11-11|
    CH716069A2|2020-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH00506/19A|CH716069A2|2019-04-12|2019-04-12|Method and apparatus for cracking hydrocarbon gases.|CN202080042759.XA| CN114174218A|2019-04-12|2020-04-10|Method and apparatus for cracking hydrocarbon gas|
    EP20719925.8A| EP3953301A1|2019-04-12|2020-04-10|Process and apparatus for cracking hydrocarbon gases|
    PCT/CH2020/050003| WO2020206561A1|2019-04-12|2020-04-10|Process and apparatus for cracking hydrocarbon gases|
    AU2020256644A| AU2020256644A1|2019-04-12|2020-04-10|Process and apparatus for cracking hydrocarbon gases|
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