AU2014204520C1 - A Reaction Method and Reactor - Google Patents
A Reaction Method and Reactor Download PDFInfo
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- AU2014204520C1 AU2014204520C1 AU2014204520A AU2014204520A AU2014204520C1 AU 2014204520 C1 AU2014204520 C1 AU 2014204520C1 AU 2014204520 A AU2014204520 A AU 2014204520A AU 2014204520 A AU2014204520 A AU 2014204520A AU 2014204520 C1 AU2014204520 C1 AU 2014204520C1
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Abstract
A method of producing hydrogen from methane including the steps of: 5 (a) purging a reactor of oxygen; (b) supplying a feed stream containing methane into the reactor while maintaining oxygen-free conditions in the reactor; (c) dissociating the methane into carbon and hydrogen in the reactor at a temperature ranging from 700-1400*C and under 10 oxygen-free conditions in the reactor; and (d) discharging hydrogen from the reactor. 5591520_1 (GHMatters) P94375.AU. 1 PCABRAL 21/07/14
Description
74) Agent / Attorney
Griffith Hack, GPO Box 1285, Melbourne, VIC, 3001, AU (56) Related Art
US 2004/0118047 A1 WO 2012/118730 A2 US 2002/0007594 A1 US 5650132 A US 2005/0063900 A1
DE JESLIS, J. C. et al., ‘Preparation of nickel nanoparticles and their catalytic activity in the cracking of methane’, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, 2008, Vol. 26(4), pp. 913-918
2014204520 21 Jul 2014
ABSTRACT
A method of producing hydrogen from methane including the steps of:
(a) purging a reactor of oxygen;
(b) supplying a feed stream containing methane into the reactor while maintaining oxygen-free conditions in the reactor;
(c) dissociating the methane into carbon and hydrogen in the reactor at a temperature ranging from 700-1400°C and under oxygen-free conditions in the reactor; and (d) discharging hydrogen from the reactor.
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A REACTION METHOD AND REACTOR
FIELD OF INVENTION
The present invention relates to a reactor and a method for producing hydrogen.
The present invention also relates to a reactor system and a method for co-producing hydrogen and carbon monoxide.
BACKGROUND OF THE INVENTION
Syngas or synthesis gas (i.e. hydrogen and carbon monoxide) is important for a variety of uses including power generation and as feed material for Gas-to-Liquids (GTL) or Gas-to-Olefins (GTO) and other chemical processes. GTL and GTO processes produce long-chained hydrocarbons such as diesel fuel and gasoline and short-chain hydrocarbons such as the olefins ethylene and propylene that are essential for a range of modern day applications including powering vehicles and manufacture of a wide range of plastic household goods.
The manufacture of syngas from natural gas or other light hydrocarbon gases is typically carried out in a single reactor which dissociates methane into hydrogen and carbon monoxide according to the following overall reaction:
CH4(g)+ |o2(g)^2H2 + CO(g)
However, this process also produces carbon dioxide due to overall system heat requirements and the difficulty in controlling the partial oxidation of carbon (formed as an intermediary product during the reaction). Other side products such as short-chained hydrocarbons may also form during the reaction. As a result, the product gas stream has to undergo costly purification to remove carbon dioxide and other
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It is desirable to provide a reactor, reactor system and method that can produce hydrogen and/or a mixture of hydrogen and carbon monoxide (for example in the form of syngas) that minimises the production of carbon dioxide. It is also desirable to provide a reactor, reactor system and method that can produce synthesised gas(es) that is(are) suitable for downstream processing with minimum purification.
The above discussion should not taken to be an admission of the common general knowledge in Australia or elsewhere.
SUMMARY OF THE INVENTION
In this specification, the term dissociation refers generally to the splitting or decomposition of a substance into its elemental components, with the reaction occurring with or without the presence of an oxygen-containing gas. In this specification, the term pyrolysis refers to thermal decomposition of a substance in the absence of an oxygen25 containing gas. The term pyrolysis is understood herein to be a sub-set of the broader term dissociation.
The invention provides a method of producing hydrogen from methane including the steps of:
(a) purging a reactor of oxygen;
(b) supplying a feed stream containing methane into the reactor while maintaining oxygen-free conditions in the reactor;
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2014204520 21 Jul 2014 (c) dissociating the methane into carbon and hydrogen in the reactor at a temperature ranging from 700-1400°C and under oxygen-free conditions in the reactor; and (d) discharging hydrogen from the reactor.
As indicated above, the dissociation of methane into hydrogen and carbon can be described by the following reaction:
CH4(g) -> 2H2(g) + C(s)
The dissociation of methane under oxygen-free conditions (i.e. pyrolysis) in the reactor makes it possible to prevent or at least minimise the production of carbon dioxide and is beneficial on this basis.
Step (b) may involve continuously supplying feed stream containing methane into the reactor.
The method may include supplying a catalyst for dissociating methane into the reactor. The catalyst may be in the form of particulate carbon.
The method may include a step of supplying a particle support into the reactor for absorbing carbon produced in the reactor and forming a carbon-loaded particle support.
The particle support may include a catalyst for dissociating methane. The particle support may include carbon as the catalyst. The particle support may include any other suitable catalyst, including rare earth and noble metals such as Ni (Nickel) and V (Vanadium) .
The method may include a step of removing carbon from the reactor and returning at least some of the carbon to the reactor.
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The invention also provides a method of producing separate streams of hydrogen and carbon monoxide from methane including the steps of:
(a) supplying a feed stream containing methane into a first reactor which is substantially free of oxygen;
(b) dissociating the methane into carbon and hydrogen in the first reactor at a temperature ranging from 700-1400°C;
(c) discharging hydrogen from the first reactor;
(d) transferring carbon from the first reactor to a second reactor;
(e) partially oxidising at least some of the carbon to carbon monoxide at a temperature from 700—l,600°C in the second reactor;
(f) discharging carbon monoxide from the second reactor;
(g) transferring heat from the second reactor to the first reactor.
The dissociation of methane into hydrogen and the subsequent partial oxidation of carbon to carbon monoxide can be described by the following two reactions:
CH4(g)-> 2Hz(g) + C(s) (1)
C(s)+|o2(g)^CO(g) (2)
The invention makes it possible to minimize the production of carbon dioxide during the production of syngas and other downstream products by carrying out reactions (1) and (2) separately. The production of hydrogen and carbon monoxide in separate reactors makes it possible to optimize the reaction conditions for producing these gases from methane. The separation makes it possible to partially oxidize carbon into carbon monoxide while minimizing the production of carbon
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The method may include a step of transferring carbon from the 5 second reactor to the first reactor.
The method may include controlling the heat balance of the reactions in the first and second reactors. In general, the reactor system may use heat obtained from exothermic reaction (2) in the second reactor to satisfy the heat requirements of endothermic reaction (1) in the first reactor. Any shortfall in heat may be supplemented by external heat sources.
The method may include supplying a catalyst for reaction (1) 15 into the first reactor. The catalyst may be in the form of particulate carbon.
The method may include into the first reactor reactor and forming a particle support is a produced via reaction a step of supplying a particle support for adsorbing carbon formed in the first carbon-loaded particle support. The convenient option for removing carbon (1) from the first reactor.
The particle support may include the catalyst for reaction (1). 25 The catalyst may be carbon. The particle support may include any other suitable catalyst, including rare earth and noble metals such as Ni (Nickel) and V (Vanadium).
The method may include a step of transferring carbon-loaded 30 particle support from the first reactor to the second reactor to remove carbon from the particle support and thereby regenerate the particulate support. More specifically, step (e) partially oxidises carbon into carbon monoxide, thereby regenerating the particle support for further use in the first reactor.
The method may include a step of transferring regenerated particle support from the second reactor to the first reactor.
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In situations where there is direct transfer of the regenerated particle support from the second reactor to the first reactor, the regenerated particle support provides heat for the first reactor. This transfer (recycle) of regenerated particle support is an option for controlling the heat balance.
Step (b) may include dissociating methane into carbon and hydrogen in the first reactor at a temperature of about 850°C.
Step (e) may include partially oxidising carbon to carbon monoxide at a temperature of about 900°C.
Step (e) may be carried out without forming any or any appreciable amount of carbon dioxide. This may be achieved by controlling the amount of oxygen supplied to the second reactor.
The method may include a step of purging the first reactor of oxygen before step (a) of dissociating methane in the first reactor. This prevents altogether or at least minimizes oxidation of carbon generated during the dissociation of the methane.
Step (a) may include supplying methane into the first reactor so that the methane has a velocity greater than a fluidisation velocity of the particle support.
The residence time of the reactants in the second reactor may be less than 30 seconds. Typically, the residence time is less than 15 seconds and more typically less than 5 seconds.
The invention also provides a reactor for producing hydrogen and carbon by pyrolysis of methane, with the reactor including an inlet for supplying a methane-containing feed stream to the reactor, an outlet for discharging hydrogen from the reactor, and an outlet for discharging carbon from the reactor.
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The reactor may include an inlet for supplying a catalyst for pyrolysing methane in the reactor.
The reactor may include an inlet for supplying a particle 5 support for absorbing carbon into the reactor. The particle support may include the catalyst for pyrolysing methane.
The reactor may include a conduit for recycling a part of the carbon generated in and discharged from the reactor back to the reactor. The conduit may have a valve such as a slide valve to control the flow of carbon.
The residence time of the reactants in the reactor may be less than 30 seconds. Typically, the residence time is less than 15 seconds and more typically less than 5 seconds.
The reactor may be used in a system as described below for producing separate streams of hydrogen and carbon monoxide from methane .
The invention also provides a reactor system for producing separate streams of hydrogen and carbon monoxide from methane, the system including a first reactor, which is substantially free of oxygen, for dissociating methane into carbon and hydrogen, a second reactor for partially oxidising carbon from the first reactor into carbon monoxide, with the first reactor being connected to the second reactor by a first conduit for transferring carbon generated in the first reactor to the second reactor, and by a second conduit for transferring heat from the second reactor to the first reactor.
The reaction system may be adapted to provide syngas with a desirable 2:1 ratio of hydrogen to carbon monoxide, for use in the Fischer—Tropsch process to produce long chain hydrocarbons from syngas and/or for the synthesis of methanol, by separating reactions (1) and (2) and allowing each reaction to run to or get close to completion. This is often not possible when the dissociation of methane is carried out in a single reactor
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2014204520 21 Jul2014 because the oxidation of carbon into carbon dioxide often prevents both reactions from running to completion.
The feed stream for the first reactor may be methane only. The 5 feed stream may also include longer chain hydrocarbon gases, such as light hydrocarbon gases. These longer chain hydrocarbon gases may break down to methane in the first reactor.
Alternatively, the feed stream for the first reactor may only 10 include longer chain hydrocarbon gases, such as light hydrocarbon gases, that break down to methane in the first reactor.
The first reactor may include an outlet for hydrogen.
The second reactor may include an outlet for carbon monoxide.
The first and the second reactors may include outlets for carbon.
The first reactor may be adapted to pyrolyse methane into carbon and hydrogen. More particularly, the first reactor may be adapted to operate as an oxygen-free reactor to prevent altogether or at least minimize the production of carbon monoxide and/or carbon dioxide from the carbon generated in the first reactor during the dissociation of the methane.
The first reactor may be oriented in a vertical, horizontal or inclined direction. Typically, the first reactor is vertically oriented.
The gases (e.g. methane and hydrogen in the first reactor and the oxygen/air and carbon monoxide in the second reactor) and carbon may flow upwardly or downwardly along the axial direction of the reactors. Typically, the gases and carbon flow upwardly along the axial direction of the reactors.
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The first and the second reactors may have separate external heat and/or internal ignition sources for heating reactants in each of the reactors. This allows reactions (1) and (2) to be brought up to, and controlled at if required, the relevant reaction temperatures. This reduces the likelihood of side products forming during the reaction.
Reaction (1) may be a catalytically promoted reaction using carbon generated from and during the dissociation of methane.
The catalyst may be in the form of particulate carbon (e.g. soot) or as carbon adsorbed onto a particle support (i.e. carbon-loaded particle support). In the absence of a particle support, particulate carbon (e.g. soot) may agglomerate and adhere to the reactor walls which may reduce the catalytic efficiency of the carbon. The particle support may be a silicazeolite particle support. The particle support may include commercially available fluid catalytic cracking (FCC) catalysts or spent FCC Equilibrium Catalysts.
The first reactor may include an inlet for feeding carbon-loaded particle support or particulate carbon as catalyst into the first reactor.
At least one of the reactors may be a fluidised or transport bed reactor. At least one of the reactors may be a fluidized or transport bed riser reactor. The use of riser reactors allow the residence time of the reactants within each reactor to be controlled. Both reactors may be a fluidised or transport bed reactor.
The first and second reactors may be connected by a first conduit for transferring carbon from the first reactor directly to the second reactor. The first conduit may also be used to transfer carbon-loaded particle support directly to the second reactor. The first conduit may have a valve such as a slide valve to control the flow of carbon.
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Alternatively, the first reactor may include an outlet for withdrawing carbon and/or carbon-loaded particle support for later use in the second reactor. The second reactor may include an inlet for receiving carbon-loaded particle support from the first reactor.
In use, the carbon fed to the second reactor undergoes reaction (2) which produces carbon monoxide and regenerates the particle support by reducing its carbon content for further use in the first reactor. The reactor system may include a second conduit for returning (recycling) the regenerated particle support from the second reactor directly to the first reactor.
Alternatively, the second reactor may have an outlet for withdrawing the regenerated particle support for later use in the first reactor.
Reaction (2) is an exothermic reaction and generates heat in the second reactor. The heat is at least partly transferred to the carbon and/or particle support. Reaction (1) is an endothermic reaction and requires heat. Transferring the remaining carbon and/or regenerated particle support directly from the second reactor to the first reactor makes it possible to provide heat (by way of recycling carbon and/or particle support) to the first reactor.
At least one of the reactors may be connected to a separator for gas-solid separation. The separator may be a reaction termination device such as an impingement plate. For example, the separator may be used for removing carbon and/or particle support entrained in the hydrogen stream in the first reactor and removing carbon and/or particle support entrained in the carbon monoxide stream in the second reactor.
At least one of the reactors may be further connected to a cyclonic separator (cyclone) or set of cyclones for improving the gas-solid separation. At least one of the reactors may be
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2014204520 21 Jul2014 connected to two or more sequential sets of cyclones. At least one of the reactors may be connected to three or more sequential sets of cyclones.
One of the reactors may include a recycle loop for returning unreacted reactants to the reactor. For example, a recycle loop in the first reactor returns unreacted methane to the first reactor. By way of further example, a recycle loop in the second reactor returns unreacted carbon to the second reactor.
The reactor system may include a methane preheater for controlling the temperature of methane entering the first reactor. The methane may be preheated to a temperature ranging from 0-1,500°C before being fed into the first reactor.
The reactor system may include a stripper for separating any remnant gas from the solid particles (carbon with/without catalyst support). The stripping of remnant gas from solid particles maximises hydrogen and undissociated or partly undissociated methane recovery in the first reactor and minimizes hydrogen and methane flow into the second reactor.
The stripper may include a solid/gas flow separation device, such as for example, orifice plates arranged in a disk and doughnut fashion one above the other, or blocks of corrugated stainless steel or ceramic or ceramic coated metal plates stacked and joined together to form a lattice structure with large voids. Typically, the blocks of corrugated plates are stacked and joined together at 90° orientation to each other, and the blocks cut to fit the stripper dimensions.
The internal surfaces may be lined with a refractory material such as a refractory cement to protect the metal surfaces from abrasion and the effects of heat. The refractory material may be any suitable thickness.
BRIEF DESCRIPTION OF DRAWINGS
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Embodiments of the present invention are hereinafter described by way of example only with reference to the accompanying drawings, wherein:
Figure 1 is an isometric view of a reaction system according to one embodiment of the present invention; and
Figure 2 is a schematic view of a reaction system according to another, although not the only other, embodiment of the present invention.
DETAILED DESCRIPTION
The reaction system 10 shown in Figure 1 includes a first reactor 12 for pyrolysing methane into carbon and hydrogen and a second reactor 14 for partially oxidising carbon from the first reactor 12 into carbon monoxide. The reactors 12, 14 are in the form of vertically-oriented fluidised bed riser reactors. It is noted that the invention is not confined to reactors of this type.
The first reactor 12 is connected to the second reactor via a first conduit 20 to feed carbon from the first reactor to the second reactor. The first and second reactors also have separate ignition sources, 22 and 24 respectively, for controlling the temperatures in each of the reactors.
The first reactor includes an inlet 26 for feeding a particle support or carbon catalyst into the first reactor. The particle support is used to adsorb carbon generated in the first reactor to improve the catalytic efficiency of the carbon.
Alternatively, catalyst comprising carbon-loaded particle support (e.g. carbon adsorbed onto a particle support) may be added into inlet 26.
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The first reactor further includes a feed stream inlet 28 for feeding methane into the reactor. This methane serves as a fluidisation gas and is fed into the reactor with a velocity greater than the fluidisation velocity of the catalyst.
The first reactor 12 includes a hydrogen outlet 16 for hydrogen obtained from the pyrolysis of methane and the second reactor 14 includes a carbon monoxide outlet 18 for carbon monoxide obtained from the partial oxidation of carbon.
The first reactor is operated under oxygen-free conditions to prevent altogether or to at least minimize oxidation of carbon generated during the pyrolysis of methane to avoid the production of carbon monoxide and/or dioxide in the first reactor.
The first reactor 12 has an outlet 30 for withdrawing carbonloaded particle support for regenerating the particle support in the second reactor 14. The withdrawn carbon-loaded particle support is added to the second reactor via inlet 32 while a second conduit 34 returns the regenerated particle support to the first reactor.
The first and second reactors may also include ash outlets 36 and 38, respectively, for removing ash formed within the reaction system, as well as to remove any surplus catalyst particle support.
The first reactor 12 may be used in isolation to produce carbon and hydrogen only. In this embodiment, the first conduit 20 is connected directly to the second conduit 34 to form a conduit for circulating unreacted feedstock and/or catalyst within the reactor.
In operation, a feed stream comprising methane is fed into a first reactor 12 via feed stream inlet 28. The feed stream may be natural gas or other light hydrocarbon gases. A silica5591520 1 (GHMatters) P94375.AU.1 PC ABRAL 21/07/14
2014204520 21 Jul2014 alumina zeolite particle support is also fed into the first reactor for adsorbing the carbon via inlet 26. The particle support adsorbs carbon formed in the first reactor and reduces agglomeration of carbon. The particle support also cleans the first reactor by removing carbon adhering onto the reactor wall.
The first reactor 12 is purged of oxygen before the methane is introduced and the methane temperature is increased to about 850°C via an external heat source (e.g. a feed heater).
Alternatively, ignition source 22 is ignited to heat the first reactor 12 to a temperature of about 850°C. Methane pyrolysis into hydrogen and carbon according to the following reaction in which carbon acts as a catalyst (auto-catalyst):
CH4(g) -> 2H2(g) + C(s) (1)
The reaction products generated in the first reactor flow upwardly along the axial direction of the first reactor towards the hydrogen outlet 16, where the hydrogen is discharged for downstream processing or use, while carbon falls downwardly along the first conduit 20 into the second reactor 14. An impingement plate or other reaction termination device or cyclonic separation device (cyclone or set(s) of cyclones) may be present near the hydrogen outlet 16 (as shown in Figure 2 by the numeral 118) to prevent altogether or at least minimize carbon exiting through the outlet 16.
The carbon-loaded particle support (i.e. catalyst) is withdrawn from catalyst outlet 30 and introduced into the bottom of the second reactor 14. Air or oxygen is introduced into the second reactor via inlet 32. Ignition source 24 is ignited to initialise the heating of the reactants in the second reactor to a temperature of about 900°C to partially oxidise carbon into carbon monoxide according to the following reaction and regenerate the particle support:
C(s) + |o2(g)^CO(g) (2)
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The oxidation process is controlled to prevent altogether or at least minimize the production of carbon dioxide. Carbon monoxide formed in the second reactor flows flow upwardly along the axial direction of the reactor and exits through the carbon monoxide outlet 18 for downstream processing.
Once the temperature in the second reactor reaches around 900°C, the partial oxidation of carbon to carbon monoxide becomes self10 sustaining and the ignition source 24 no longer needs to be operated. The ignition source 24 consists of a standard industrial burner, with its exposed parts made from hardened (stellited) steel. The ignition source 24 is connected to separate supplies of air and methane and is lit by a piezo15 electronic igniter ignited by human intervention.
Regenerated particle support travels towards the carbon monoxide outlet 18 with the carbon monoxide, however, an impingement plate or other reaction termination device or cyclonic separation device (cyclone or set(s) of cyclones) located near outlet 18 (as shown in Figure 2 by the numeral 120) prevents altogether or at least minimizes the particle support from exiting with the carbon monoxide. Instead, the regenerated particle support falls downwardly along the second conduit 34 and returns to the first reactor 12 for further use.
Reaction (2) is an exothermic reaction and generates heat in the second reactor which is at least partly transferred to the particle support. Reaction (1) is an endothermic reaction and requires heat. Transferring (recycling) the regenerated particle support directly from the second reactor to the first reactor makes it possible to provide heat to the first reactor. As such, the first reactor requires less or no energy to heat the reactants and the regenerated particle support up to the reaction temperature once reactions (1) and (2) have been initiated.
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Each of the first and second reactors may include recycle loops to improve the conversion of reactions (1) and (2). This allows hydrogen and carbon monoxide to be produced close to a stoichiometric ratio of 2:1. This is desirable for a variety of 5 downstream processes such as the Fischer-Tropsch process and the synthesis of methanol. The production of side products is also minimised due to the controlled nature of reactions (1) and (2).
In the reactor system 100 illustrated in Figure 2, each of the riser reactors are connected to a separation vessel, in the form of vessel 112, 114, for gas-solid separation. In particular, to separate hydrogen from particulate carbon and/or catalysts in the first reactor and to separate carbon monoxide from the regenerated particle support in the second reactor. Separation is initially achieved by a riser termination device, e.g. an impingement plate or more complex termination device, mounted at the end of the riser. Gas flow in each separation vessel issues further to a set of cyclones (118, 120) or two or more sets of cyclones in series for improving the gas-solid separation.
Alternatively, the riser can be coupled directly (closecoupled) to the inlet horn(s) of the first (set of) cyclone(s).
The vessel 112 is further connected to a stripper 116 (or itself contains such a stripper) for separating any remnant hydrogen from the carbon and/or particle support. The stripper 116 may include a solid/gas flow separation device, such as for example, orifice plates arranged in a disk and doughnut fashion one above the other, or blocks of corrugated stainless steel plates stacked and joined together at 90° orientation to each other to form a lattice structure with large voids.
The reactor system may include a methane preheater (not shown) for controlling the temperature of methane entering the first reactor, preferably at a temperature from 30-300°C. The heat to the methane preheater may be supplied from heat exchange with the hot gas streams leaving the reactor and/or regenerator. Heat
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It is evident from the above description of the embodiments that 5 is the invention provides a reactor system and a method for producing hydrogen and carbon monoxide that minimises the generation of carbon dioxide. The reactor system also produces hydrogen and carbon monoxide suitable for downstream processing with minimal purification.
Many modifications may be made to the embodiments of the invention described in relation to the drawings without departing from the spirit and scope of the invention.
By way of example, whilst the embodiments include fluidized bed reactors in the form of risers, it is note that the invention is not limited to this form of reactor.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word comprise or variations such as comprises or comprising is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
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Claims (5)
1/2
5 Figure 1:
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1. A method of producing separate streams of hydrogen and carbon monoxide from methane including the steps of:
(a) supplying a feed stream containing methane into a first reactor which is substantially free of oxygen;
(b) dissociating the methane into carbon and hydrogen in the 10 first reactor at a temperature ranging from 700-1,400°C;
(c) discharging hydrogen from the first reactor;
(d) transferring carbon from the first reactor to a second 15 reactor;
(e) partially oxidising at least some of the carbon to carbon monoxide at a temperature from 700—l,600°C in the second reactor;
(f) discharging carbon monoxide from the second reactor; and (g) transferring heat from the second reactor to the first reactor.
2/2
2. The method according to claim 1 including a step of transferring carbon from the second reactor to the first reactor.
30
3. The method according to any one of the preceding claims including a step of supplying a catalyst into the first reactor.
4. The method according to any one of the preceding claims including a step of supplying a particle support into the first
35 reactor.
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5. The method according to any one of the preceding claims including a step of transferring carbon-loaded particle support from the first reactor to the second reactor to regenerate the particulate support.
6. The method according to claim 5 including a step of transferring the regenerated particle support from the second reactor to the first reactor.
10
7. The method according to any one of claims 4 to 6, wherein step (a) includes supplying methane into the first reactor so that the methane has a velocity greater than a fluidisation velocity of the particle support.
15
8. The method according to any one of the preceding claims, wherein step (b) includes dissociating methane into carbon and hydrogen in the first reactor at a temperature of about 850°C.
9. The method according to any one of the preceding claims,
20 wherein step (e) includes partially oxidising carbon to carbon monoxide at a temperature of about 900°C.
10. The method according to any one of the preceding claims, wherein the residence time of reactants in the second reactor is
25 less than 30 seconds.
11. The method according to claim 3, wherein the catalyst is particulate carbon.
30
12. The method according to claim 4, wherein the particle support includes a catalyst for dissociating methane.
13. The method according to claim 12, wherein the catalyst is selected from any one or a combination of carbon or rare earth
35 and noble metals such as Ni (Nickel) and V (Vanadium).
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14. A reactor system for producing separate streams of hydrogen and carbon monoxide from methane, the system including a first reactor, which is substantially free of oxygen, for dissociating methane into carbon and hydrogen, a second reactor
5 for partially oxidising carbon from the first reactor into carbon monoxide, with the first reactor being connected to the second reactor by a first conduit for transferring carbon generated in the first reactor to the second reactor, and by a second conduit for transferring heat from the second reactor to
10 the first reactor.
15. The reactor system according to claim 14, wherein at least one of the reactors is a fluidised or transport bed reactor.
15 16. The reactor system according to either claim 14 or 15, wherein the first reactor includes an outlet for withdrawing carbon and/or carbon-loaded particle support for use in the second reactor, and the second reactor includes an inlet for receiving the carbon-loaded particle support from the first
20 reactor.
17. The reactor system according to any one of claims 14 to
16. wherein the first reactor includes an inlet for feeding carbon-loaded particle support or particulate carbon as catalyst
25 into the first reactor.
18. The reactor system according to any one of claims 14 to 17 wherein the second conduit returns (recycles) regenerated particle support from the second reactor directly to the first
30 reactor.
19. The reactor system according to any one of claims 14 to 18, wherein one of the reactors includes a recycle loop for returning unreacted reactants to the reactor.
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5 Figure 2:
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2014204520A AU2014204520C1 (en) | 2013-07-25 | 2014-07-21 | A Reaction Method and Reactor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2013902755A AU2013902755A0 (en) | 2013-07-25 | A Reaction Method and Reactor | |
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|---|---|---|---|---|
| US5650132A (en) * | 1994-12-14 | 1997-07-22 | Director-General Of Agency Of Industrial Science And Technology | Process for producing hydrogen from hydrocarbon |
| US20020007594A1 (en) * | 2000-04-05 | 2002-01-24 | Muradov Nazim Z. | Thermocatalytic process for CO2-free production of hydrogen and carbon from hydrocarbons |
| US20040118047A1 (en) * | 2002-12-18 | 2004-06-24 | Choudhary Vasant Ramchandra | Process for the continuous production of carbon monoxide-free hydrogen from methane or methane-rich hydrocarbons |
| US20050063900A1 (en) * | 2003-09-23 | 2005-03-24 | Haiyou Wang | CO-free hydrogen from decomposition of methane |
| WO2012118730A2 (en) * | 2011-02-28 | 2012-09-07 | The Trustees Of Columbia University In The City Of New York | Methods and systems for converting gaseous hydrocarbons to synthetic gas |
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|---|---|---|---|---|
| US5650132A (en) * | 1994-12-14 | 1997-07-22 | Director-General Of Agency Of Industrial Science And Technology | Process for producing hydrogen from hydrocarbon |
| US20020007594A1 (en) * | 2000-04-05 | 2002-01-24 | Muradov Nazim Z. | Thermocatalytic process for CO2-free production of hydrogen and carbon from hydrocarbons |
| US20040118047A1 (en) * | 2002-12-18 | 2004-06-24 | Choudhary Vasant Ramchandra | Process for the continuous production of carbon monoxide-free hydrogen from methane or methane-rich hydrocarbons |
| US20050063900A1 (en) * | 2003-09-23 | 2005-03-24 | Haiyou Wang | CO-free hydrogen from decomposition of methane |
| WO2012118730A2 (en) * | 2011-02-28 | 2012-09-07 | The Trustees Of Columbia University In The City Of New York | Methods and systems for converting gaseous hydrocarbons to synthetic gas |
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| AU2014204520B2 (en) | 2017-11-23 |
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