WO2014111315A1 - Auto-thermal reforming reactor - Google Patents

Auto-thermal reforming reactor Download PDF

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Publication number
WO2014111315A1
WO2014111315A1 PCT/EP2014/050396 EP2014050396W WO2014111315A1 WO 2014111315 A1 WO2014111315 A1 WO 2014111315A1 EP 2014050396 W EP2014050396 W EP 2014050396W WO 2014111315 A1 WO2014111315 A1 WO 2014111315A1
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WO
WIPO (PCT)
Prior art keywords
gas
methane
furnace body
combustion chamber
reactor
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Application number
PCT/EP2014/050396
Other languages
French (fr)
Inventor
Bin Liu
Yuhan Sun
Zhiyong Tang
Dongfei WANG
Yaning XIAO
Tiejun Zhao
He ZHU
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Shanghai Advanced Research Institute, Chinese Academy Of Sciences
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Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company, Shanghai Advanced Research Institute, Chinese Academy Of Sciences filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2014111315A1 publication Critical patent/WO2014111315A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • C01B2203/1282—Mixing of different feed components using static mixers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention is in the field of CI chemistry and relates to a reactor for the auto-thermal reforming of methane and carbon dioxide and to a process for the preparation of synthesis gas using such reactor.
  • Syngas or synthesis gas is a commonly used term for a gas comprising carbon monoxide (CO) and hydrogen (3 ⁇ 4) and is used in a variety of processes as the starting reaction mixture for producing different chemicals, such as methanol or longer-chain hydrocarbons
  • a catalytic process for converting CO2 at high temperature may turn into a very important direction for CO2 utilization at a large scale. Accordingly, a process for reforming CO2 and CH 4 into syngas not only
  • the CO 2 -CH 4 reforming reaction is a highly endothermic reaction. Based on thermodynamic analysis, it is clear that the temperature has to be increased to at least 600 °C before the CO 2 and CH 4 effectively react into CO and H 2 . Furthermore, the conversion rate, and hence syngas yield, increases with increasing reaction temperature. Providing adequate heat sources which can provide the necessary reaction heat and operate such high
  • Reforming reactors for methane steam reforming i.e. reacting methane with steam to form carbon monoxide and hydrogen, are known. However, no industrial reactors for the CO 2 -CH 4 reforming reaction are available.
  • the conversion rate of methane in the endothermic steam reforming reaction is relatively low.
  • steam methane reforming can be combined with partial oxidation of remaining methane in the steam reforming reaction product gas.
  • partial oxidation needs to take place in a second reactor. In this configuration two separate reactors are required, which is expensive.
  • the reactor should enable the auto-thermal reforming to have a low energy consumption, high
  • the reactor should enable a good conversion rate of the methane and should enable an economically attractive way to produce synthesis gas.
  • the present invention provides a reactor for the auto-thermal reforming of methane and carbon dioxide comprising gas inlet and outlet means, a furnace body, gas nozzle, gas
  • the reactor according to the invention is designed in such a way that, when in use, (i) the feed gases methane and carbon dioxide are introduced into the reactor and mixed before being contacted with oxygen, (ii) the inlet means for oxygen is positioned such that it enables effective injection of oxygen into the reaction space where it reacts with methane, (iii) the heat generated in the exothermic reaction between methane and oxygen is effectively used as the required heat for the endothermic reforming reaction between methane and carbon dioxide and
  • the present invention provides a reactor for the auto-thermal reforming of methane and carbon dioxide comprising a vertically oriented furnace body provided with gas inlet means for an oxygen-containing gas, gas inlet means for a methane-comprising gas and carbon dioxide and gas outlet means, wherein
  • the furnace body comprises from top to bottom mixing means, gas distribution means, a combustion chamber, a reforming reaction chamber and a gas-collecting chamber fluidly connected with the gas outlet means;
  • the gas distribution means is positioned around the outlet end of the gas nozzle.
  • the reactor according to the present invention enables an effective reaction between carbon dioxide and methane on an industrial scale and thereby can contribute to reducing the emission of these greenhouse gases, in particular carbon dioxide.
  • a further advantage is that the reactor does not require the addition of large amounts of steam to ensure the reforming reaction to occur.
  • the reactor is designed such that it realizes the self-supply of heat for the endothermic reforming reaction by using the heat generated in the exothermic oxidation reaction between methane and oxygen.
  • the reactor design allows for a very efficient conversion of methane resulting in a raw synthesis gas product which contains only a small residual amount of methane (typically 0.1-2 mole%) . No second reactor is required to reach an adequate methane conversion rate. This is not only advantageous from a capital investment cost perspective but also from an operation cost perspective.
  • the reactor is designed such that it realizes the self-supply of heat for the endothermic reforming reaction by using the heat generated in the exothermic oxidation reaction between methane and oxygen.
  • the reactor design allows
  • the inner wall of the furnace body is suitably lined with a fire-resistant liner. In this way the furnace body is protected from high
  • Particularly suitable cooling means in this connection is a water jacket surrounding the furnace body which water jacket is provided with water inlet means and water outlet means for cooling water.
  • the gas nozzle which is used to inject oxygen (or an oxygen-containing gas) into the combustion chamber, is also exposed to high temperatures. Therefore, the gas nozzle is suitably provided with cooling means which surround the central gas supply tube inside the nozzle.
  • cooling means comprises a water jacket provided with a water inlet and water outlet.
  • a further insulation layer of heat resistant material is surrounding the outer wall of the water jacket. Suitable nozzles are known in the art and several types which can be used in the present reactor are commercially
  • the mixing means should ensure thorough and efficient mixing of the methane-comprising feed gas and the carbon dioxide feed gas.
  • Known mixing means can be used.
  • a very effective mixing means was found to be in the shape of a cylinder, positioned between the top plate of the furnace body and the gas distribution means and fluidly connected with the gas inlet means for the methane and carbon dioxide feed gases.
  • the dimensions of the mixing means are preferably such that the ratio of height to diameter of the mixing means is in the range of from 2 to 3.
  • the gas distribution means are an important part of the reactor according to the present invention, as it should ensure effective introduction of the mixture of methane and carbon dioxide into the combustion chamber. It was found particularly suitable to use gas
  • distribution means consisting of a round plate with multiple holes unevenly distributed over such plate.
  • the holes in the round plate are arranged in the shape of concentric circles with the density of the holes decreasing from the inner circle of holes towards the outer circle of holes.
  • the combustion chamber is the space where the
  • the combustion space accordingly, is the entire space between the bottom of gas distribution means and the top of the reforming reaction chamber.
  • the combustion chamber can be fully cylindrically shaped, but it was found particularly suitable that the combustion chamber comprises a tapered section with the diameter of such section increasing in downward direction inside the furnace body. The top end of the tapered section is connected to a cylindrically shaped section which, in return, is connected at its top end with the mixing means, has the same diameter as the mixing means and is separated from the mixing means by the gas distribution means.
  • the low end of the tapered section is connected with a cylindrically shaped section which, at its bottom end, is connected with the top part of the reforming reaction chamber.
  • the dimensions of the combustion chamber consisting of the top cylindrical section, tapered section and bottom cylindrical section are such that the ratio of total height of the combustion chamber to diameter of the mixing means is in the range of from 3 to 5.
  • the reactor according to the present invention is further illustrated by Figures 1 to 5.
  • Figure 1 depicts a reactor according to the
  • Figure 2 illustrates a suitable gas nozzle
  • FIG. 3 shows an example of suitable gas
  • FIGS 4 and 5 show different suitable embodiments of the mixing means which forms part of the reactor according to the present invention.
  • the reactor comprises a vertically oriented furnace body (1) provided with gas inlet means (12, 13) and gas outlet means (14) .
  • Gas inlet (12) for the oxygen-containing gas comprises a gas nozzle (11) which extends into combustion chamber (6) along the vertical longitudinal axis (15) of the furnace body (1) through mixing means (5) and gas distribution means (2) .
  • This gas distribution means (2) is positioned around the outlet end of the gas nozzle
  • Gas inlet (13) for the methane and carbon dioxide is fluidly connected with mixing means (5) .
  • Furnace body (1) is provided at the inside with fire-resistant liner (3), whilst at the outside it is surrounded by water jacket
  • Vents (19) in the outer wall of water jacket (4) allow water vapour or steam to be released when the cooling water in water jacket (4) evaporates because of the high temperatures in combustion chamber (6) and reforming reaction chamber (7) .
  • the top plate (18) shields off the top end of the space in mixer (5) where the methane and carbon dioxide are thoroughly mixed and enables the mixer (5) to be fixed to the top end of the furnace body (1) .
  • catalyst beds (22a) and (22b) from the heat generated in combustion chamber (6) and forms the separation between combustion chamber (6) and reforming reaction chamber
  • Reforming reaction chamber (7) contains catalyst beds (22a) and catalyst bed (22b).
  • Catalyst beds (22a) are constituted of a heat resistant catalyst with a lower amount of catalytically active metal to avoid sintering because of the high temperatures. Some reforming of methane and carbon dioxide takes place in these catalyst beds (22a), but most of the reforming reaction takes place in reforming catalyst bed (22b) .
  • This bed (22b) contains the actual and more active reforming catalyst. Temperature in the catalyst beds is monitored by
  • thermocouple thermometers (9) . When the reactor is not in operation catalyst replacement can take place via
  • the catalyst beds (22a) and 22(b) are supported at the bottom end by gas permeable alumina balls (24) and arch (23) of thermostable bricks.
  • the top layer of alumina balls (24) forms the bottom of reforming reaction chamber (7) .
  • the hot raw syngas formed is collected in gas
  • thermocouple thermometer (10) enables cleaning of the gas collection chamber (8) when the reactor is out of operation.
  • Figure 2 depicts a cross-sectional side-view of an example of a suitable gas nozzle (11) with gas inlet
  • a cooling water jacket (29) surrounds the central gas supply tube and is provided with a cooling water inlet (25) and cooling water outlet (26) .
  • the nozzle shown in Figure 2 is also provided with a steam inlet (27) for further protection of the nozzle.
  • the arrows (30) indicate the flow of cooling water when in operation.
  • Ceramic fiber insulation layer (28) provides further protection against the high temperatures in the combustion (6) of the reactor.
  • Figure 3 is a top-view of a preferred embodiment of gas distributor (2) consisting of round metal plate (31) provided with holes (32) which are arranged in concentric circles around central opening (33) in the shape of concentric circles with the density of the holes
  • gas nozzle (11) extends through central opening (33) into combustion zone (6) .
  • Figures 4 and 5 are cross-sectional top-views of preferred embodiments for mixer (5) with a single gas inlet (13) ( Figure 4) or with two gas inlets (13) ( Figure 5) .
  • the arrows indicate the direction of the gas flow.
  • gas nozzle (11) When introduced into gas inlet (13) the feed gas of methane and carbon dioxide swirls around and effective mixing occurs.
  • gas nozzle (11) When mounted inside the reactor, gas nozzle (11) extends through central opening (34) .
  • the diameter of central opening (34) will be identical to the central opening (33) in gas distributor (2) shown in Figure 3, as the top side of the gas distributor (2) will form the bottom end of mixer (5) .
  • the present invention also relates to a process for the preparation of synthesis gas using the reactor as described above and as further illustrated and
  • the process according to the invention comprises the steps of
  • step (d) reacting a second part of the methane in the methane- comprising gas with carbon dioxide in reforming reaction chamber (7) in the presence of a reforming catalyst and using the heat generated in step (c) ;
  • the oxygen-comprising gas used in step (a) suitably is pure oxygen or oxygen having a purity of more than
  • the methane-comprising gas used in step (b) is selected from the group consisting of natural gas, coke oven gas, oil gas, refinery gas and coal bed methane. Such gas needs to be desulphurized before it is mixed with carbon dioxide and is introduced into the reactor. Alternatively, a methane-comprising gas which results from a process and comprises a substantial amount of carbon dioxide is used as the gas mixture in step (b) . In this case a separate carbon dioxide feed gas stream may not be required. Examples of such methane/carbon dioxide comprising gases are methanol synthesis purge gas and Fischer-Tropsch synthesis vent gas.
  • the mixture of methane-comprising gas and carbon dioxide is preheated to a temperature sufficient to initiate the oxidation reaction being introduced into the combustion chamber in step (b) .
  • a temperature sufficient to initiate the oxidation reaction being introduced into the combustion chamber in step (b) .
  • Upon contact with oxygen in the combustion zone the oxidation reaction starts and the temperature will rise to above the auto-ignition point of methane (645 °C) , which will further accelerate the oxidation.
  • Suitable preheating temperatures are in the range of from 400 to 700 °C, preferably from 500 to 600 °C .
  • the hot methane introduced in step (b) will instantaneously react with the oxygen introduced in step (a) .
  • the temperature of the reaction mixture during the oxidation reaction in step (c) will increase.
  • Overall temperature of the gas mixture in the combustion chamber will, however, generally be between 1000 and 1500 °C, more typically between 1100 and 1400 °C. This heat is subsequently used to promote the endothermic reforming reaction between methane and carbon dioxide in step (d) .
  • the temperature of the gas mixture will be lower in the reforming catalyst bed and will typically be in the range of from 700 to 1250 °C, preferably from 900 to 1100 °C.
  • the reforming catalyst used in step (d) and present in the reforming reaction chamber in catalyst bed (22b) can be any catalyst known to catalyze the reforming reaction between methane and carbon dioxide. Examples include nickel-based refractory oxide catalysts and noble metal-based refractory oxide catalysts. Suitable
  • refractory oxide support materials include alumina
  • Ni-based composite catalysts such as Ni-Al 2 C>3, Ni-CaO-Zr0 2 , Ni-CaO-Ce0 2 , Ni-CaO-Al 2 0 3 , Ni-CaO-Al 2 0 3 -Zr0 2 , Ni-MgO-Al 2 0 3 , Ni-MgO-CaO-Al 2 0 3 , Ni-MgO-Cr 2 03-Al 2 03 , Ni-CaO- Ti0 2 -Al 2 0 3 , Ni-MgO-Ti0 2 -Si0 2 .
  • noble metal-based catalysts are Ru, Rh, Pd and/or Pt supported on one of the refractory oxide supports mentioned above.
  • a specific example is a Pt-Al 2 C>3 catalyst. It was, however, found that a catalyst comprising nickel, calcium and zirconium (i.e. nickel (Ni) on a calcium-promoted
  • Ni-CaO-Zr0 2 composite catalyst was particularly suitable for the process of the present invention.
  • the heat-resistant catalyst used in catalyst beds (22a) can have has a similar or the same refractory oxide support as the reforming catalyst used in catalyst bed (22b) , but with a lower amount of catalytically active metal to avoid sintering because of the high
  • step (e) the hot raw syngas formed is collected from gas collecting chamber (8) through gas outlet (14) .
  • the hot syngas will subsequently be cooled, suitably by heat exchange against water to produce steam or against another process stream that needs to be heated, e.g. the gas mixture of methane and carbon dioxide used as the feed gas in step (b) .

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Abstract

The invention relates to a reactor for the auto-thermal reforming of methane and carbon dioxide comprising a vertically oriented furnace body (1) provided with gas inlet means (12, 13) and gas outlet means (14), wherein (a) the furnace body (1) comprises from top to bottom mixing means (5), gas distribution means (2), a combustion chamber (6), a reforming reaction chamber (7) and a gas-collecting chamber (8) fluidly connected with gas outlet means (14); (b) the gas inlet means (12) comprises a gas nozzle (11) positioned at the top of the furnace body (1) and extends into combustion chamber (6) along the vertical longitudinal axis (15) of the furnace body (1) through mixing means (5) and gas distribution means (2); and (c) the gas distribution means (2) is positioned around the outlet end of the gas nozzle (11). The invention also relates to a process for the preparation of synthesis gas using the above reactor. In this process methane-comprising gas (CH4), carbon dioxide (CO2) and an oxygen-containing gas (O2) are fed into the auto-thermal reforming reactor and the heat released by the oxidation reaction between CH4 and O2 is provided as heat source to promote the reforming reaction between CO2 and CH4, thereby forming synthesis gas.

Description

AUTO-THERMAL REFORMING REACTOR
Field of technology
The present invention is in the field of CI chemistry and relates to a reactor for the auto-thermal reforming of methane and carbon dioxide and to a process for the preparation of synthesis gas using such reactor.
Background
Global warming is an important problem facing the world today. People are, therefore, increasingly
interested in finding ways to reduce the emission of greenhouse gases, such as methane (CH4) and carbon dioxide ( CO2 ) · As CO2 is an important resource of carbon and oxygen, its conversion to syngas in a catalytic reforming reaction with CH4 could be an effective and advantageous way of re-using any CH4 and CO2 produced and/or emitted. Syngas or synthesis gas is a commonly used term for a gas comprising carbon monoxide (CO) and hydrogen (¾) and is used in a variety of processes as the starting reaction mixture for producing different chemicals, such as methanol or longer-chain hydrocarbons
(via Fischer-Tropsch synthesis).
A catalytic process for converting CO2 at high temperature may turn into a very important direction for CO2 utilization at a large scale. Accordingly, a process for reforming CO2 and CH4 into syngas not only
effectively uses two greenhouse gases CO2 and CH4 (which, inter alia, come from coal chemical industry and coal bed gas), but also decreases the emission of these gases. This leads to the cyclic utilization of carbon resources into energy and chemicals which could also have enormous economic benefits. Thus, the reaction of C02-CH4 reforming could potentially be one of the key
technologies for the efficient (re) utilization of carbon resources in the coal chemical industry for the future.
At this point in time, however, there is no example of CO2-CH4 reforming to syngas on an industrial scale.
The CO2-CH4 reforming reaction is a highly endothermic reaction. Based on thermodynamic analysis, it is clear that the temperature has to be increased to at least 600 °C before the CO2 and CH4 effectively react into CO and H2. Furthermore, the conversion rate, and hence syngas yield, increases with increasing reaction temperature. Providing adequate heat sources which can provide the necessary reaction heat and operate such high
temperatures would also be a challenge in any industrial CO2-CH4 reforming process.
Reforming reactors for methane steam reforming, i.e. reacting methane with steam to form carbon monoxide and hydrogen, are known. However, no industrial reactors for the CO2-CH4 reforming reaction are available.
Typical steam reforming reactors have several
disadvantages .
Firstly, the conversion rate of methane in the endothermic steam reforming reaction is relatively low. To get up to conversion rates of 30-90% steam methane reforming can be combined with partial oxidation of remaining methane in the steam reforming reaction product gas. Such partial oxidation needs to take place in a second reactor. In this configuration two separate reactors are required, which is expensive.
Secondly, large amounts of steam have to be added to the steam reforming reactor. This is not only necessary for the steam reforming reaction, but also to eliminate carbon deposition during the process. This results in increased operating costs, including costs for the subsequent steam separation.
Summary of the invention
The technical problem to be solved by this invention is to provide a reactor which can be used on an
industrial scale for the preparation of synthesis gas by carbon dioxide-methane auto-thermal reforming.
Furthermore, the reactor should enable the auto-thermal reforming to have a low energy consumption, high
efficiency without needing any external heating. In addition, the reactor should enable a good conversion rate of the methane and should enable an economically attractive way to produce synthesis gas.
To solve this technical problem the present invention provides a reactor for the auto-thermal reforming of methane and carbon dioxide comprising gas inlet and outlet means, a furnace body, gas nozzle, gas
distribution means, mixing means, combustion chamber, a reforming reaction chamber and a gas-collecting chamber.
The reactor according to the invention is designed in such a way that, when in use, (i) the feed gases methane and carbon dioxide are introduced into the reactor and mixed before being contacted with oxygen, (ii) the inlet means for oxygen is positioned such that it enables effective injection of oxygen into the reaction space where it reacts with methane, (iii) the heat generated in the exothermic reaction between methane and oxygen is effectively used as the required heat for the endothermic reforming reaction between methane and carbon dioxide and
(iv) the syngas produced is collected and removed from the reactor through appropriate gas outlet means. Detailed description of the invention
Accordingly, the present invention provides a reactor for the auto-thermal reforming of methane and carbon dioxide comprising a vertically oriented furnace body provided with gas inlet means for an oxygen-containing gas, gas inlet means for a methane-comprising gas and carbon dioxide and gas outlet means, wherein
(a) the furnace body comprises from top to bottom mixing means, gas distribution means, a combustion chamber, a reforming reaction chamber and a gas-collecting chamber fluidly connected with the gas outlet means;
(b) the gas inlet means for an oxygen-containing gas
comprises a gas nozzle positioned at the top of the furnace body and extends into combustion chamber along the vertical longitudinal axis of the furnace body through the mixing means and the gas
distribution means; and
(c) the gas distribution means is positioned around the outlet end of the gas nozzle.
The reactor according to the present invention enables an effective reaction between carbon dioxide and methane on an industrial scale and thereby can contribute to reducing the emission of these greenhouse gases, in particular carbon dioxide. A further advantage is that the reactor does not require the addition of large amounts of steam to ensure the reforming reaction to occur. Yet another advantage is that the reactor is designed such that it realizes the self-supply of heat for the endothermic reforming reaction by using the heat generated in the exothermic oxidation reaction between methane and oxygen. The reactor design allows for a very efficient conversion of methane resulting in a raw synthesis gas product which contains only a small residual amount of methane (typically 0.1-2 mole%) . No second reactor is required to reach an adequate methane conversion rate. This is not only advantageous from a capital investment cost perspective but also from an operation cost perspective. Finally, the reactor
comprises mixing means, gas distribution means and a combustion chamber, where the combustion chamber has enough space to ensure the complete consumption of all oxygen added, thereby ensuring a homogeneous gas
distribution at the entrance of the reforming reaction chamber, which contains one or more reforming catalyst beds .
Because of the high temperatures reached during operation of the reactor, the inner wall of the furnace body is suitably lined with a fire-resistant liner. In this way the furnace body is protected from high
temperatures .
In order to further protect the furnace body against the high temperatures further cooling means are suitably surrounding the outer wall of the furnace body.
Particularly suitable cooling means in this connection is a water jacket surrounding the furnace body which water jacket is provided with water inlet means and water outlet means for cooling water.
The gas nozzle, which is used to inject oxygen (or an oxygen-containing gas) into the combustion chamber, is also exposed to high temperatures. Therefore, the gas nozzle is suitably provided with cooling means which surround the central gas supply tube inside the nozzle. In a preferred embodiment such cooling means comprises a water jacket provided with a water inlet and water outlet. In a further preferred embodiment a further insulation layer of heat resistant material is surrounding the outer wall of the water jacket. Suitable nozzles are known in the art and several types which can be used in the present reactor are commercially
available .
The mixing means should ensure thorough and efficient mixing of the methane-comprising feed gas and the carbon dioxide feed gas. Known mixing means can be used. A very effective mixing means was found to be in the shape of a cylinder, positioned between the top plate of the furnace body and the gas distribution means and fluidly connected with the gas inlet means for the methane and carbon dioxide feed gases. The dimensions of the mixing means are preferably such that the ratio of height to diameter of the mixing means is in the range of from 2 to 3.
The gas distribution means are an important part of the reactor according to the present invention, as it should ensure effective introduction of the mixture of methane and carbon dioxide into the combustion chamber. It was found particularly suitable to use gas
distribution means consisting of a round plate with multiple holes unevenly distributed over such plate.
Preferably the holes in the round plate are arranged in the shape of concentric circles with the density of the holes decreasing from the inner circle of holes towards the outer circle of holes.
The combustion chamber is the space where the
oxidation reaction between oxygen and methane takes place to form syngas and to generate heat for the subsequent endothermic reforming reaction between the remainder of the methane and carbon dioxide. The combustion space, accordingly, is the entire space between the bottom of gas distribution means and the top of the reforming reaction chamber. The combustion chamber can be fully cylindrically shaped, but it was found particularly suitable that the combustion chamber comprises a tapered section with the diameter of such section increasing in downward direction inside the furnace body. The top end of the tapered section is connected to a cylindrically shaped section which, in return, is connected at its top end with the mixing means, has the same diameter as the mixing means and is separated from the mixing means by the gas distribution means. The low end of the tapered section is connected with a cylindrically shaped section which, at its bottom end, is connected with the top part of the reforming reaction chamber. In a preferred embodiment the dimensions of the combustion chamber consisting of the top cylindrical section, tapered section and bottom cylindrical section are such that the ratio of total height of the combustion chamber to diameter of the mixing means is in the range of from 3 to 5.
The reactor according to the present invention is further illustrated by Figures 1 to 5.
Figure 1 depicts a reactor according to the
invention .
Figure 2 illustrates a suitable gas nozzle.
Figure 3 shows an example of suitable gas
distribution means.
Figures 4 and 5 show different suitable embodiments of the mixing means which forms part of the reactor according to the present invention.
In Figure 1 the reactor comprises a vertically oriented furnace body (1) provided with gas inlet means (12, 13) and gas outlet means (14) . The furnace body (1) from top to bottom successively comprises mixing means
(5) , gas distribution means (2), a combustion chamber
(6) , a reforming reaction chamber (7) and a gas- collecting chamber (8) fluidly connected with gas outlet means (14) . Gas inlet (12) for the oxygen-containing gas comprises a gas nozzle (11) which extends into combustion chamber (6) along the vertical longitudinal axis (15) of the furnace body (1) through mixing means (5) and gas distribution means (2) . This gas distribution means (2) is positioned around the outlet end of the gas nozzle
(11) .
Gas inlet (13) for the methane and carbon dioxide is fluidly connected with mixing means (5) . Furnace body (1) is provided at the inside with fire-resistant liner (3), whilst at the outside it is surrounded by water jacket
(4) having a water inlet (16) and water outlet (17) .
Vents (19) in the outer wall of water jacket (4) allow water vapour or steam to be released when the cooling water in water jacket (4) evaporates because of the high temperatures in combustion chamber (6) and reforming reaction chamber (7) .
At the top of furnace body (1) the top plate (18) shields off the top end of the space in mixer (5) where the methane and carbon dioxide are thoroughly mixed and enables the mixer (5) to be fixed to the top end of the furnace body (1) .
When in operation, the oxidation reaction between methane and oxygen takes place in combustion chamber (6) . Alumina ball layer (24) shields off the reforming
catalyst beds (22a) and (22b) from the heat generated in combustion chamber (6) and forms the separation between combustion chamber (6) and reforming reaction chamber
(7) . Reforming reaction chamber (7) contains catalyst beds (22a) and catalyst bed (22b). Catalyst beds (22a) are constituted of a heat resistant catalyst with a lower amount of catalytically active metal to avoid sintering because of the high temperatures. Some reforming of methane and carbon dioxide takes place in these catalyst beds (22a), but most of the reforming reaction takes place in reforming catalyst bed (22b) . This bed (22b) contains the actual and more active reforming catalyst. Temperature in the catalyst beds is monitored by
thermocouple thermometers (9) . When the reactor is not in operation catalyst replacement can take place via
discharge hole (20) . The catalyst beds (22a) and 22(b) are supported at the bottom end by gas permeable alumina balls (24) and arch (23) of thermostable bricks. The top layer of alumina balls (24) forms the bottom of reforming reaction chamber (7) .
The hot raw syngas formed is collected in gas
collection chamber (8) and is recovered from this chamber (8) through gas outlet (14) . The temperature of the hot raw syngas is monitored by thermocouple thermometer (10) . Manhole (21) enables cleaning of the gas collection chamber (8) when the reactor is out of operation.
Figure 2 depicts a cross-sectional side-view of an example of a suitable gas nozzle (11) with gas inlet
(12a) and outlet (12b) forming the start and end of the central gas supply tube. A cooling water jacket (29) surrounds the central gas supply tube and is provided with a cooling water inlet (25) and cooling water outlet (26) . The nozzle shown in Figure 2 is also provided with a steam inlet (27) for further protection of the nozzle. The arrows (30) indicate the flow of cooling water when in operation. Ceramic fiber insulation layer (28) provides further protection against the high temperatures in the combustion (6) of the reactor.
Figure 3 is a top-view of a preferred embodiment of gas distributor (2) consisting of round metal plate (31) provided with holes (32) which are arranged in concentric circles around central opening (33) in the shape of concentric circles with the density of the holes
decreasing from the inner circle of holes towards the outer circle of holes. When the gas distributor (2) is mounted inside the reactor, gas nozzle (11) extends through central opening (33) into combustion zone (6) .
Figures 4 and 5 are cross-sectional top-views of preferred embodiments for mixer (5) with a single gas inlet (13) (Figure 4) or with two gas inlets (13) (Figure 5) . The arrows indicate the direction of the gas flow.
When introduced into gas inlet (13) the feed gas of methane and carbon dioxide swirls around and effective mixing occurs. When mounted inside the reactor, gas nozzle (11) extends through central opening (34) . The diameter of central opening (34) will be identical to the central opening (33) in gas distributor (2) shown in Figure 3, as the top side of the gas distributor (2) will form the bottom end of mixer (5) . The present invention also relates to a process for the preparation of synthesis gas using the reactor as described above and as further illustrated and
exemplified in Figures 1 to 5.
Suitably, the process according to the invention comprises the steps of
(a) feeding an oxygen-containing gas to combustion
chamber (6) through gas nozzle (11); (b) feeding a mixture of a methane-comprising gas and carbon dioxide to combustion chamber (6) through successively gas inlet means (13), mixing means (5) and gas distribution means (2);
(c) reacting a first part of the methane in the methane- comprising gas with oxygen in combustion chamber (6);
(d) reacting a second part of the methane in the methane- comprising gas with carbon dioxide in reforming reaction chamber (7) in the presence of a reforming catalyst and using the heat generated in step (c) ; and
(e) collecting the synthesis gas from gas-collecting
chamber (8) through gas outlet means (14) .
The oxygen-comprising gas used in step (a) suitably is pure oxygen or oxygen having a purity of more than
99%.
The methane-comprising gas used in step (b) is selected from the group consisting of natural gas, coke oven gas, oil gas, refinery gas and coal bed methane. Such gas needs to be desulphurized before it is mixed with carbon dioxide and is introduced into the reactor. Alternatively, a methane-comprising gas which results from a process and comprises a substantial amount of carbon dioxide is used as the gas mixture in step (b) . In this case a separate carbon dioxide feed gas stream may not be required. Examples of such methane/carbon dioxide comprising gases are methanol synthesis purge gas and Fischer-Tropsch synthesis vent gas.
The mixture of methane-comprising gas and carbon dioxide is preheated to a temperature sufficient to initiate the oxidation reaction being introduced into the combustion chamber in step (b) . Upon contact with oxygen in the combustion zone the oxidation reaction starts and the temperature will rise to above the auto-ignition point of methane (645 °C) , which will further accelerate the oxidation. Suitable preheating temperatures are in the range of from 400 to 700 °C, preferably from 500 to 600 °C . When preheated to a temperature above the auto- ignition point of methane, the hot methane introduced in step (b) will instantaneously react with the oxygen introduced in step (a) .
The temperature of the reaction mixture during the oxidation reaction in step (c) will increase. Overall temperature of the gas mixture in the combustion chamber will, however, generally be between 1000 and 1500 °C, more typically between 1100 and 1400 °C. This heat is subsequently used to promote the endothermic reforming reaction between methane and carbon dioxide in step (d) .
Accordingly, the temperature of the gas mixture will be lower in the reforming catalyst bed and will typically be in the range of from 700 to 1250 °C, preferably from 900 to 1100 °C.
The reforming catalyst used in step (d) and present in the reforming reaction chamber in catalyst bed (22b) can be any catalyst known to catalyze the reforming reaction between methane and carbon dioxide. Examples include nickel-based refractory oxide catalysts and noble metal-based refractory oxide catalysts. Suitable
refractory oxide support materials include alumina
(AI2O3) , silica (Si02), titania (Ti02) , zirconia (Zr02), cerium oxide (Ce02) and chromium oxide (Cr2C>3) , optionally in combination with a promoter such as calcium oxide (CaO) and/or magnesium oxide (MgO) resulting in a refractory oxide composite catalyst. Specific examples include Ni-based composite catalysts such as Ni-Al2C>3, Ni-CaO-Zr02, Ni-CaO-Ce02, Ni-CaO-Al203, Ni-CaO-Al203-Zr02, Ni-MgO-Al203, Ni-MgO-CaO-Al203 , Ni-MgO-Cr203-Al203 , Ni-CaO- Ti02-Al203, Ni-MgO-Ti02-Si02. Examples of noble metal- based catalysts are Ru, Rh, Pd and/or Pt supported on one of the refractory oxide supports mentioned above. A specific example is a Pt-Al2C>3 catalyst. It was, however, found that a catalyst comprising nickel, calcium and zirconium (i.e. nickel (Ni) on a calcium-promoted
zirconate (CaO-Zr02) support, also referred to as Ni-CaO- Zr02 composite catalyst) was particularly suitable for the process of the present invention.
Nickel content of the reforming catalyst will
typically be up to 25 wt%, suitable between 5 and 20 wt%, more suitably between 10 and 20 wt%.
The heat-resistant catalyst used in catalyst beds (22a) can have has a similar or the same refractory oxide support as the reforming catalyst used in catalyst bed (22b) , but with a lower amount of catalytically active metal to avoid sintering because of the high
temperatures. A nickel content of between 0.1 and 10 wt%, more suitably between 2 and 6 wt% would be adequate.
In step (e) the hot raw syngas formed is collected from gas collecting chamber (8) through gas outlet (14) . The hot syngas will subsequently be cooled, suitably by heat exchange against water to produce steam or against another process stream that needs to be heated, e.g. the gas mixture of methane and carbon dioxide used as the feed gas in step (b) .

Claims

C L A I M S
1. A reactor for the auto-thermal reforming of methane and carbon dioxide comprising a vertically oriented furnace body provided with gas inlet means for an oxygen- containing gas, gas inlet means for a methane-comprising gas and carbon dioxide and gas outlet means, wherein
(a) the furnace body comprises from top to bottom mixing means, gas distribution means, a combustion chamber, a reforming reaction chamber and a gas-collecting chamber fluidly connected with the gas outlet means;
(b) the gas inlet means for an oxygen-containing gas
comprises a gas nozzle positioned at the top of the furnace body and extends into combustion chamber along the vertical longitudinal axis of the furnace body through the mixing means and the gas
distribution means; and
(c) the gas distribution means is positioned around the outlet end of the gas nozzle.
2. Reactor according to claim 1, wherein the inner wall of the furnace body is lined with a fire-resistant liner.
3. Reactor according to claim 1 or 2 , wherein the gas nozzle is provided with cooling means.
4. Reactor according to claim 3, wherein the cooling means comprises a water jacket provided with a water inlet and water outlet.
5. Reactor according to any one of claims 1-4, wherein the reactor further comprises a water jacket surrounding the furnace body which water jacket is provided with water inlet means and water outlet means.
6. Reactor according to any one of claims 1-5, wherein the mixing means is in the shape of a cylinder, is positioned between a top plate and the gas distribution means and is fluidly connected with the gas inlet means, with the ratio of height to diameter of the mixing means (5) being in the range of from 2 to 3.
7. Reactor according to any one of claims 1-5, wherein the gas distribution means consists of a round plate with multiple holes unevenly distributed over such plate.
8. Reactor according to claim 6, wherein the holes in the plate are arranged in the shape of concentric circles with the density of the holes decreasing from the inner circle of holes towards the outer circle of holes.
9. Reactor according to any one of claims 1-8, wherein the combustion chamber comprises a tapered section with the ratio of height of the combustion chamber to diameter of the mixing means being in the range of from 3 to 5.
10. Process for the preparation of synthesis gas using the reactor according to any one of claims 1-9.
11. Process according to claim 10 comprising the steps of (a) feeding an oxygen-containing gas to the combustion chamber through the gas nozzle;
(b) feeding a mixture of a methane-comprising gas and
carbon dioxide to the combustion chamber through successively the gas inlet means for the methane- comprising gas and carbon dioxide, the mixing means and the gas distribution means;
(c) reacting a first part of the methane in the methane- comprising gas with oxygen in the combustion chamber;
(d) reacting a second part of the methane in the methane- comprising gas with carbon dioxide in the reforming reaction chamber in the presence of a reforming catalyst and using the heat generated in step (c) ; and
(e) collecting the synthesis gas from the gas-collecting chamber through the gas outlet means.
12. Process according to claim 11, wherein the reforming catalyst used in step (d) is a Ni-CaO-ZrC>2 composite catalyst .
PCT/EP2014/050396 2013-01-17 2014-01-10 Auto-thermal reforming reactor WO2014111315A1 (en)

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