STEAM REFORMING HEATED BY RESISTANCE HEATING
20210171344 · 2021-06-10
Assignee
Inventors
- Peter Mølgaard Mortensen (Roskilde, DK)
- Robert KLEIN (Roskilde, DK)
- Kim Aasberg-Petersen (Alleroed, DK)
Cpc classification
B01J2219/00155
PERFORMING OPERATIONS; TRANSPORTING
C01B2203/1023
CHEMISTRY; METALLURGY
Y02P20/52
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
C01B2203/141
CHEMISTRY; METALLURGY
C01B2203/0233
CHEMISTRY; METALLURGY
B01J2208/00389
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/2416
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/2428
PERFORMING OPERATIONS; TRANSPORTING
B01J15/005
PERFORMING OPERATIONS; TRANSPORTING
B01J2219/00135
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J15/00
PERFORMING OPERATIONS; TRANSPORTING
B01J19/24
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A reactor system for carrying out steam reforming of a feed gas comprising hydrocarbons, including: a structured catalyst arranged for catalyzing steam reforming of a feed gas including hydrocarbons, the structured catalyst including a macroscopic structure of electrically conductive material, the macroscopic structure supporting a ceramic coating, wherein the ceramic coating supports a catalytically active material; a pressure shell housing the structured catalyst; heat insulation layer between the structured catalyst and the pressure shell; at least two conductors electrically connected to the macroscopic structure and to an electrical power supply placed outside the pressure shell, wherein the electrical power supply is dimensioned to heat at least part of the structured catalyst to a temperature of at least 500° C. by passing an electrical current through the macroscopic structure. Also, a process for steam reforming of a feed gas comprising hydrocarbons.
Claims
1. A reactor system for carrying out steam reforming of a feed gas comprising hydrocarbons, said reactor system comprising: a structured catalyst arranged for catalyzing steam reforming of said feed gas comprising hydrocarbons, said structured catalyst comprising a macroscopic structure of electrically conductive material, said macroscopic structure supporting a ceramic coating, wherein said ceramic coating supports a catalytically active material; a pressure shell housing said structured catalyst, said pressure shell comprising an inlet for letting in said feed gas and an outlet for letting out product gas, wherein said inlet is positioned so that said feed gas enters said structured catalyst in a first end of said structured catalyst and said product gas exits said structured catalyst from a second end of said structured catalyst; a heat insulation layer between said structured catalyst and said pressure shell; and at least two conductors electrically connected to said structured catalyst and to an electrical power supply placed outside said pressure shell, wherein said electrical power supply is dimensioned to heat at least part of said structured catalyst to a temperature of at least 500° C. by passing an electrical current through said macroscopic structure, wherein said at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to said first end of said structured catalyst than to said second end of said structured catalyst, and wherein the structured catalyst is constructed to direct an electrical current to run from one conductor substantially to the second end of the structured catalyst and return to a second of said at least two conductors.
2. A reactor system according to claim 1, wherein the pressure shell has a design pressure of between 5 and 30 bar.
3. A reactor system according to claim 1, wherein the pressure shell has a design pressure of between 30 and 200 bar.
4. A reactor system according to claim 1, wherein the resistivity of the macroscopic structure is between 10.sup.−5 Ω.Math.m and 10.sup.−7 Ω.Math.m.
5. A reactor system according to claim 1, where each of the at least two conductors are led through the pressure shell in a fitting so that the at least two conductors are electrically insulated from the pressure shell.
6. A reactor system according to claim 5, wherein said pressure shell further comprises one or more inlets close to or in combination with at least one fitting in order to allow a cooling gas to flow over, around, close to, or inside at least one conductor within said pressure shell.
7. A reactor system according to claim 1, wherein the reactor system further comprises an inner tube in heat exchange relationship with but electrically insulated from the structured catalyst, said inner tube being adapted to withdraw a product gas from the structured catalyst so that the product gas flowing through the inner tube is in heat exchange relationship with gas flowing through the structured catalyst.
8. A reactor system according to claim 1, wherein the connection between the structured catalyst and said at least two conductors is a mechanical connection, a welded connection, a brazed connection or a combination thereof.
9. A reactor system according to claim 1, wherein the macroscopic structure is an extruded and sintered structure or a 3D printed and sintered structure.
10. A reactor system according to claim 1, wherein the structured catalyst comprises an array of macroscopic structures electrically connected to each other.
11. A reactor system according to claim 1, wherein said structured catalyst has electrically insulating parts arranged to increase the length of a principal current path between said at least two conductors to a length larger than the largest dimension of the structured catalyst.
12. A reactor system according to claim 1, wherein said structured catalyst has at least one electrically insulating part arranged to direct a current through said structured catalyst in order to ensure that for at least 70% of the length of said structured catalyst, a current density vector of the principal current path has a non-zero component value parallel to the length of said structured catalyst.
13. A reactor system according to claim 1, wherein said macroscopic structure has a plurality of parallel channels, a plurality of non-parallel channels and/or a plurality of labyrinthic channels.
14. A reactor system according to claim 1, wherein the reactor system further comprises a bed of a second catalyst material upstream said structured catalyst within said pressure shell.
15. A reactor system according to claim 12, wherein said reactor system further comprises a third catalyst material in the form of catalyst pellets, extrudates or granulates loaded into the channels of said structured catalyst.
16. A reactor system according to claim 1, further comprising a bed of fourth catalyst material placed within the pressure shell and downstream the structured catalyst.
17. A reactor system according to claim 1, wherein the material of the macroscopic structure is chosen as a material arranged to generate a heat flux of 500 to 50000 W/m.sup.2 by resistance heating of the material.
18. A reactor system according to claim 1, wherein the structured catalyst comprises a first part arranged to generate a first heat flux and a second part arranged to generate a second heat flux, where the first heat flux is lower than the second heat flux, and where the first part is upstream the second part.
19. A reactor system according to claim 1, wherein said reactor system further comprises a control system arranged to control the electrical power supply to ensure that the temperature of the gas exiting the pressure shell lies in a predetermined range and/or to ensure that the conversion of hydrocarbons in the feed gas lies in a predetermined range and/or to ensure the dry mole concentration of methane lies in a predetermined range and/or to ensure the approach to equilibrium of the steam reforming reaction lies in a predetermined range.
20. A reactor system according to claim 1, wherein the structured catalyst within said reactor system has a ratio between the area equivalent diameter of a horizontal cross section through the structured catalyst and the height of the structured catalyst in the range from 0.1 to 2.0.
21. A reactor system according to claim 1, wherein the height of the reactor system is between 0.5 and 7 m.
22. A process for carrying out steam reforming of a feed gas comprising hydrocarbons in a reactor system comprising a pressure shell housing a structured catalyst arranged to catalyze steam reforming of a feed gas comprising hydrocarbons, said structured catalyst comprising a macroscopic structure of an electrically conductive material, said macroscopic structure supporting a ceramic coating, where said ceramic coating supports a catalytically active material and wherein said reactor system is provided with heat insulation between said structured catalyst and said pressure shell; said process comprising the following steps: pressurizing a feed gas comprising hydrocarbons to a pressure of at least 5 bar, supplying said pressurized feed gas to said pressure shell through an inlet positioned so that said feed gas enters said structured catalyst in a first end of said structured catalyst; allowing the feed gas to undergo steam reforming reaction over the structured catalyst and outletting a product gas from said pressure shell, wherein said product gas exits said structured catalyst from a second end of said structured catalyst; supplying electrical power via electrical conductors connecting an electrical power supply placed outside said pressure shell to said structured catalyst, allowing an electrical current to run through said macroscopic structure, thereby heating at least part of the structured catalyst to a temperature of at least 500° C., wherein said at least two conductors are connected to the structured catalyst at a position on the structured catalyst closer to said first end of said structured catalyst than to said second end of said structured catalyst, and wherein the structured catalyst is constructed to direct an electrical current to run from one conductor substantially to the second end of the structured catalyst and return to a second of said at least two conductors.
23. A process according to claim 22, further comprising the step of pressurizing the feed gas upstream the pressure shell to a pressure of between 5 and 30 bar.
24. A process according to claim 22, further comprising the step of pressurizing said feed gas upstream said pressure shell to a pressure of between 30 and 200 bar.
25. A process according to claim 22, wherein the temperature of the feed gas let into the reactor system is between 200° C. and 700° C.
26. A process according to claim 22, wherein the macroscopic structure is heated so that the maximum temperature of the macroscopic structure lies between 500° C. and 1300° C.
27. A process according to claim 22, further comprising the step of inletting a cooling gas through an inlet through the pressure shell close to or in combination with at least one fitting in order to allow a cooling gas to flow over, around, close to, or inside at least one conductor within said pressure shell.
28. A process according to claim 22, wherein the space velocity evaluated as flow of gas relative to the geometric surface area of the structured catalyst is between 0.6 and 60 Nm.sup.3/m.sup.3/h or between 700 Nm.sup.3/m.sup.3/h and 70000 Nm.sup.3/m.sup.3/h when evaluated as flow of gas relative to the occupied volume of the structured catalyst.
Description
SHORT DESCRIPTION OF THE FIGURES
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DETAILED DESCRIPTION OF THE FIGURES
[0129] Throughout the Figures, like reference numbers denote like elements.
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[0131] In an embodiment, the electrical power supply supplies a voltage of 70V and a current of 800 A. In another embodiment, the electrical power supply supplies a voltage of 170V and a current of 2000 A. The current is led through electrical conductors 40, 40′ to conductor contact rails 41, and the current runs through the structured catalyst 10 from one conductor contact rail 41, e.g. from the conductor contact rail seen to the left in
[0132] The macroscopic structures 5 are made of electrically conductive material. Especially preferred is the alloy kanthal consisting of aluminum, iron and chrome. The ceramic coating, e.g. an oxide, coated onto the structure catalysts 5 is impregnated with catalytically active material. The conductors 40, 40′ are made in materials like iron, aluminum, nickel, copper, or alloys thereof.
[0133] During operating, a feed gas enters the reactor system 100 from above as indicated by the arrow 11 and exits the reactor system from the bottom thereof as indicated by the arrow 12.
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[0135] In the reactor system shown in
[0136] In the reactor system 100 shown in
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[0138] From
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[0142] The walls 75 of the structured catalyst 10′ are of extruded material coated with a ceramic coating, e.g. an oxide, which has been coated onto the macroscopic structure. In the Figures, the ceramic coating is not shown. The ceramic coating is impregnated with catalytically active material. The ceramic coating and thus the catalytically active material are present on every walls within the structured catalyst 10′ over which the gas flow flows during operation and interacts with the heated surface of the structured catalyst and the catalytically active material.
[0143] Thus, during use in a reactor system for steam reforming, a hydrocarbon feed gas flows through the channels 70 and interacts with the heated surface of the structured catalyst and with the catalytically active material supported by the ceramic coating.
[0144] In the structured catalyst 10′ shown in
[0145] The channels 70 in the structured catalyst 5 are open in both ends. In use of the structured catalyst in a reactor system, a hydrocarbon feed gas flows through the unit, in the direction shown by arrows 11 and 12 in
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[0147] The connectors 7 are e.g. made in materials like iron, aluminum, nickel, copper, or alloys thereof.
[0148] As mentioned, the structured catalyst 10′ is coated with a ceramic coating, such as an oxide, supporting the catalytically active material. However, the parts of the structured catalyst 10′ which are connected to the connectors 7 should not be coated with an oxide. Instead, the macroscopic structure of the structured catalyst should be exposed or connected directly to the connectors 7 in order to obtain a good electrical connection between the macroscopic structure and the connector.
[0149] When the connectors 7 and thus the conductors 40 are connected to the same end of the structured catalyst 5, viz. the upper end as seen in
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[0162] In
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[0168] A general trend in all the curves in the
[0169] It should be noted, that even though the structured catalysts shown in the figures are shown as having channels with a square cross section, as seen perpendicular to the z axis, any appropriate shape of the cross sections of the channels is conceivable. Thus, the channels of the structured catalyst could alternatively be e.g. triangular, hexagonal, octagonal, or circular, where triangular, square, and hexagonal shapes are preferred.
EXAMPLES
[0170] While the invention has been illustrated by a description of various embodiments and examples while these embodiments and examples have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.
[0171] All the examples described below relate to compact reactor systems. This is possible due to the reactor systems comprise compact structured catalysts in the form of compact macroscopic supports having a high thermal flux when powered by a power source. It is moreover to be noted, that the dimensions of the structured catalysts may be chosen relatively freely, so that the structured catalyst may be almost cubic in outer shape or it may be wider than its height.
[0172] The examples all describe operation conditions with high pressure, ranging from 28 bar to 182 bar. Such high pressures are made possible by the configuration of the reactor system since the structured catalyst within the reactor system has high thermal flux upon powering by a power source, is to some extent thermally insulated from the pressure shell, and the pressure drop through the structured catalyst is very low compared to an SMR. The structured catalyst will obtain the highest temperature within the reactor system, while the pressure shell will have a significantly lower temperature due to the thermal insulation between the structured catalyst and the pressure shell. Ideally, the temperature of the pressure shell will not exceed 500° C. When product gas with a high pressure is needed, such as 30 bar or above, the product gas exiting the reactor system can in many cases be used directly, without the use of compressors. This is due to the possibility of pressurizing the feed gas upstream the reactor system of the invention. Pressurizing the feed gas will require less energy than the product gas as the volume of the feed is lower than the product gas as the steam reforming reaction has a net production of molecules. Additionally, one of the feed gas constituents may be pumped which requires significantly less energy compared to gas compression.
[0173] In all the examples described below, the feed gas enters the reactor system and flows through the structured catalyst housed therein. When the heat insulation layer of the reactor system is a heat insulating material, the heat insulating material typically makes up most of the space between the structured catalyst and the pressure shell along the walls of the pressure shell so that the feed gas is forced to flow along walls of the macroscopic structure on its way through the pressure shell.
[0174] The examples below (except for the comparative example) all relate to a reactor system with a structured catalyst. The structured catalysts described in these examples comprise one or more macroscopic structures. The one or more macroscopic structures of the examples below all support a ceramic coating supporting catalytically active material. Advantageously, substantially all the surface of the macroscopic structure supports the ceramic coating supporting the catalytically active material; however, at connections points, e.g. between two adjacent macroscopic structures or between a macroscopic structure and a conductor, the macroscopic structure may be free from ceramic coating in order to facilitate connection between a conductor and the macroscopic structure.
Example 1
[0175] An example calculation of the process of the invention is given in Table 1 below. A feed gas is fed to the reactor system of the invention. The feed gas entering the reactor system is pressurized to a pressure of 28 kg/cm.sup.2.Math.g and has a temperature of 500° C. Inside the reactor system, a structured catalyst with nine macroscopic structures having a square cross section are placed in an array and each macroscopic structure has a size of 0.53 times 0.53 times 2.3 meter. Each macroscopic structure additionally has 17778 channels with a square cross section having a side or edge length of 0.32 cm. Each macroscopic structure has slits parallel to the longitudinal direction thereof, so that clusters of 5 times 5 channels are formed. The clusters are individually insulated from the neighboring cluster, except from the ends, so that the current path through the macroscopic structure is a zigzag path. A current of 200 A and a voltage of ca. 5.5 kV are applied to each macroscopic structure in the reactor system of the invention in order to heat the structured catalyst and thus the gas passing through the structured catalyst, corresponding to a power supplied in the structured catalysts of 9899 kW.
[0176] The reactor system in the current configuration could have an overall internal diameter of the reactor system of 3.2 m and a total internal height of 5.5 m when the reactor system is made as a cylindrical reactor system with spherical heads. In this specific configuration, the macroscopic structures are placed in a square orientation having a diagonal length of 2.3 m. In all the examples described herein, except for the comparative example, inert material is placed around the structured catalyst to close the gap to the insulation material, adjacent to the pressure shell. The insulation material in example 1 has a cylindrical form with an internal diameter of 2.5 m and a thickness of 0.35 m.
[0177] During the passage of the feed gas through the reactor system, the feed gas is heated by the structured catalyst and undergoes steam reforming to a product gas having an exit temperature of 963° C.
TABLE-US-00001 TABLE 1 Size of macroscopic structure: Edge size [m] 0.53 Height [m] 2.3 Number of macroscopic structures 9 Total volume of structured catalyst [L] 5888 Structured catalyst height/diagonal length [—] 1.02 Feed gas Product gas T [° C.] 500 963 P [kg/cm.sup.2 g] 27.97 27.47 CO2 [Nm.sup.3/h] 168 727 N2 [Nm.sup.3/h] 26 26 CH4 [Nm.sup.3/h] 2630 164 H2 [Nm.sup.3/h] 590 8545 CO [Nm.sup.3/h] 1 1907 H2O [Nm.sup.3/h] 8046 5022 Total flow [Nm.sup.3/h] 11461 16391 ΔT.sub.app, SMR [° C.] 10 Power [kW] 9899 Heat flux [kW/m.sup.2] 2.2 Space velocity [Nm.sup.3/m.sup.3/h] 1950
Example 2
[0178] An example calculation of the process of the invention is given in Table 2 below. A feed gas is fed to the reactor system of the invention. The feed gas entering the reactor system is pressurized to a pressure of 28 kg/cm.sup.2.Math.g and has a temperature of 500° C. Inside the reactor system, a structured catalyst in the form of 1 macroscopic structure having a square cross section is placed which has a size of 0.4 times 0.4 times 0.35 meter. The macroscopic structure additionally has 10000 channels with a square cross section having a side or edge length of 0.32 cm. The macroscopic structure has slits parallel to the longitudinal direction thereof, so that clusters of 5 times 5 channels are formed. The clusters are individually insulated from the neighboring cluster, except from the ends, so that the current path through the macroscopic structure is a zigzag path. A current of 200 A and a voltage of ca. 500 V are applied to the macroscopic structure in the reactor system of the invention in order to heat the structured catalyst and thus the gas passing through the structured catalyst, corresponding to a power deposited in the structured catalyst of 99 kW.
[0179] The reactor system in the current configuration could have an overall internal diameter of the reactor system of 1.2 m and a total internal height of 1.5 m when the reactor system is made as a cylindrical reactor system with spherical heads. In this specific configuration, the structured catalyst has a diagonal length of 0.6 m. Inert material is placed around the structured catalysts to close the gap to the insulation material which has an internal diameter of 0.6 m and a thickness of 0.3 m.
[0180] During the passage of the feed gas through the reactor system, the feed gas is heated by the structured catalyst and undergoes steam reforming to a product gas having an exit temperature of 963° C.
TABLE-US-00002 TABLE 2 Size of macroscopic structure: Edge size [m] 0.4 Height [m] 0.35 Number of macroscopic structures 1 Total volume of structured catalyst [L] 55.4 Structured catalyst height/diagonal length [—] 0.61 Feed gas Product gas T [° C.] 500 963 P [kg/cm.sup.2 g] 27.97 27.47 CO2 [Nm.sup.3/h] 1.7 7.3 N2 [Nm.sup.3/h] 0.3 0.3 CH4 [Nm.sup.3/h] 26.3 1.6 H2 [Nm.sup.3/h] 5.9 85.4 CO [Nm.sup.3/h] 0 19.1 H2O [Nm.sup.3/h] 80.5 50.2 Total flow [Nm.sup.3/h] 114.7 163.9 ΔT.sub.app, SMR [° C.] 10 Power [kW] 99 Heat flux [kW/m.sup.2] 2.2 Space velocity [Nm.sup.3/m.sup.3/h] 2071
Example 3
[0181] An example calculation of the process of the invention is given in Table 3 below. A feed gas is fed to the reactor system of the invention. The feed gas entering the reactor system is pressurized to a pressure of 97 bar, viz. 97 kg/cm.sup.2.Math.g and has a temperature of 500° C.
[0182] Inside the reactor system, a structured catalyst comprising nine macroscopic structures having a square cross section are placed in an array and each macroscopic structure has a size of 0.53 times 0.53 times 2.3 meter. Each macroscopic structure additionally has 17778 channels with a square cross section having a side or edge length of 0.32 cm. Each macroscopic structure has slits parallel to the longitudinal direction thereof, so that clusters of 5 times 5 channels are formed. The clusters are individually insulated from the neighboring cluster, except from the ends so that the current path through the macroscopic structure is a zigzag path. A current of 200 A and a voltage of ca. 5.5 kV are applied to each macroscopic structure in the reactor system of the invention in order to heat the structured catalyst and thus the gas passing through the structured catalyst, corresponding to a power deposited in the structured catalyst of 9899 kW.
[0183] The reactor system in the current configuration could have an overall internal diameter of the reactor system of 3.2 m and a total internal height of 5.5 m when the reactor system is made as a cylindrical reactor system with spherical heads. In this specific configuration, the macroscopic structures are placed in a square orientation having a diagonal length of 2.3 m. Inert material is placed around the structured catalyst to close the gap to the insulation material which has an internal diameter of 2.5 m and a thickness of 0.35 m.
[0184] During the passage of the feed gas through the reactor system, the feed gas is heated by the structured catalyst and undergoes steam reforming to a product gas having an exit temperature of 1115° C. It is seen from Table 3 that the total flows of the feed gas and the product gas are lower in Example 3 compared to Example 1.
[0185] Since the product gas exiting the reactor system is pressurized to a pressure of 97 bar, no compressors will be needed downstream the reactor system when a high pressure product gas is requested. This reduces the overall cost of a plant with a reactor system of the invention.
TABLE-US-00003 TABLE 3 Size of macroscopic structure: Edge size [m] 0.53 Height [m] 2.3 Number of macroscopic structures 9 Total volume of structured catalyst [L] 5888 Structured catalyst height/diagonal length [—] 1.01 Feed gas Product gas T [° C.] 500 1115 P [kg/cm.sup.2 g] 96.97 96.47 CO2 [Nm.sup.3/h] 111 510 N2 [Nm.sup.3/h] 23 23 CH4 [Nm.sup.3/h] 2337 143 H2 [Nm.sup.3/h] 372 7354 CO [Nm.sup.3/h] 1 1796 H2O [Nm.sup.3/h] 7111 4518 Total flow [Nm.sup.3/h] 9955 14344 ΔT.sub.app, SMR [° C.] 10 Power [kW] 9899 Heat flux [kW/m.sup.2] 2.2 Space velocity [Nm.sup.3/m.sup.3/h] 1691
Example 4
[0186] An example calculation of the process of the invention is given in Table 3 below. A feed gas is fed to the reactor system of the invention. The feed gas entering the reactor system is pressurized to a pressure of 28 bar, viz. 28 kg/cm.sup.2.Math.g and has a temperature of 500° C.
[0187] Inside the reactor system, a structured catalyst comprising 25 macroscopic structures having a square cross section are placed in an array and each macroscopic structure has a size of 0.24 times 0.24 times 0.9 meter. Each macroscopic structure additionally has 3600 channels with a square cross section having a side or edge length of 0.33 cm in length. Each macroscopic structure has slits parallel to the longitudinal direction thereof, so that clusters of 10 times 10 channels are formed. The clusters are individually insulated from the neighboring cluster, except from the ends, so that the current path through the macroscopic structure is a zigzag path. A current of 1500 A and a voltage of ca. 260 V are applied to each macroscopic structure in the reactor system of the invention in order to heat the structured catalyst and thus the gas passing through the structured catalyst, corresponding to a power deposited in the structured catalyst of 9899 kW.
[0188] The reactor system in the current configuration could have an overall internal diameter of the reactor system of 2.3 m and a total internal height of 3.2 m when the reactor system is made as a cylindrical reactor system with spherical heads. In this specific configuration, the macroscopic structures are placed in a square orientation having a diagonal length of 1.7 m. Inert material is placed around the structured catalyst to close the gap to the insulation material which has an internal diameter of 1.8 m and a thickness of 0.25 m.
[0189] During the passage of the feed gas through the reactor system, the feed gas is heated by the structured catalyst and undergoes steam reforming to a product gas having an exit temperature of 963° C. It is seen from Table 4 that the structured catalyst of Example 4 is somewhat smaller than the one used in Examples 1 and 3 due to the higher current. The total flows of the feed gas and the product gas correspond to the flows of Example 1.
TABLE-US-00004 TABLE 4 Size of macroscopic structure: Edge size [m] 0.24 Height [m] 0.9 Number of macroscopic structures 25 Total volume of structured catalyst [L] 1324 Structured catalyst height/diagonal length [—] 0.54 Feed gas Product gas T [° C.] 500 963 P [kg/cm.sup.2 g] 27.97 27.47 CO2 [Nm.sup.3/h] 168 727 N2 [Nm.sup.3/h] 26 26 CH4 [Nm.sup.3/h] 2630 164 H2 [Nm.sup.3/h] 590 8545 CO [Nm.sup.3/h] 1 1907 H2O [Nm.sup.3/h] 8046 5022 Total flow [Nm.sup.3/h] 11461 16391 ΔT.sub.app, SMR [° C.] 10 Power [kW] 9899 Heat flux [kW/m.sup.2] 9.0 Space velocity [Nm.sup.3/m.sup.3/h] 8653
Example 5
[0190] An example calculation of the process of the invention is given in Table 4 below. A feed gas is fed to the reactor system of the invention. The feed gas entering the reactor system is pressurized to a pressure of 182 bar and has a temperature of 500° C.
[0191] Inside the reactor system, a structured catalyst comprising nine macroscopic structures having a square cross section are placed in an array and each macroscopic structure has a size of 0.53 times 0.53 times 2.3 meter. Each macroscopic structure additionally has 17778 channels with a square cross section having a side or edge length of 0.32 cm. Each macroscopic structure has slits parallel to the longitudinal direction thereof, so that clusters of 5 times 5 channels are formed. The clusters are individually insulated from the neighboring cluster, except from the ends, so that the current path through the macroscopic structure has a zigzag path. A current of 200 A and a voltage of ca. 5.5 kV are applied to each macroscopic structure in the reactor system of the invention in order to heat the structured catalyst and thus the gas passing through the structured catalyst, corresponding to a power deposited in the structured catalyst of 9899 kW.
[0192] The reactor system in the current configuration could have an overall internal diameter of the reactor system of 3.2 m and a total internal height of 5.5 m when the reactor system is made as a cylindrical reactor system with spherical heads. In this specific configuration, the macroscopic structures are placed in a square orientation having a diagonal length of 2.3 m. Inert material is placed around the structured catalyst to close the gap to the insulation material which has an internal diameter of 2.5 m and a thickness of 0.35 m.
[0193] During the passage of the feed gas through the reactor system, the feed gas is heated by the structured catalyst and undergoes steam reforming to a product gas having an exit temperature of 1236° C. The total flows of the feed gas and the product gas are lower than the total flows of the gasses in Examples 1 and 4.
[0194] Since the product gas exiting the reactor system is already pressurized to a pressure of 181 bar, it is suited for being input into e.g. a hydrotreater of a refinery plant without further pressurizing. Thus, no compressors will be needed between the reactor system and the hydrotreater of the refinery plant. This reduces the overall cost of the plant with a reactor system of the invention.
TABLE-US-00005 TABLE 5 Size of macroscopic structure: Edge size [m] 0.53 Height [m] 2.3 Number of macroscopic structures 9 Total volume of structured catalyst [L] 5888 Structured catalyst height/diagonal length [—] 1.01 Feed gas Product gas T [° C.] 500 1236 P [kg/cm.sup.2 g] 181.97 181.47 CO2 [Nm.sup.3/h] 86 395 N2 [Nm.sup.3/h] 21 21 CH4 [Nm.sup.3/h] 2116 96 H2 [Nm.sup.3/h] 278 6648 CO [Nm.sup.3/h] 0 1711 H2O [Nm.sup.3/h] 6425 4096 Total flow [Nm.sup.3/h] 8926 12967 ΔT.sub.app, SMR [° C.] 10 Power [kW] 9899 Heat flux [kW/m.sup.2] 2.2 Space velocity [Nm.sup.3/m.sup.3/h] 1516
Example 6
[0195] Example 6 relates to a reactor system comprising a structured catalyst in the form of a structured catalyst having in total 78540 channels with a total wall length of one channel in the cross section of 0.00628 m each and a length of 2 m, giving a total surface area of 987 m.sup.2 of catalyst surface. For a reactor system with this structured catalyst, a simulation with varying gas flow through the structured catalyst was made where the gas composition in all calculations was 8.8% H.sub.2, 56.8% H.sub.2O, 0.2% N.sub.2, 0.1% CO, 2.3% CO.sub.2, and 31.8% CH.sub.4. In each simulation a kinetic model for steam reforming and water gas shift was used and a variation in the surface flux (Q) of energy from the electrically heated structured catalyst was made to adjust the exit temperature of the product gas from the reactor system housing the structured catalyst to 920° C. The kinetic model used was similar to the approach used by Xu and Froment, (J. Xu and G. F. Froment, Methane steam reforming, methanation and water-gas shift: I. intrinsic kinetics. American Institution of Chemical Engineers Journal, 35:88-96, 1989.).
[0196] The approach to equilibrium from this stage is substantially constant or has a slightly increasing development due to the overall increasing temperature of the reactor system.
Example 7 (Comparative Example)
[0197] An SMR with a number of identical tubes is provided. Each tube has an internal diameter of 10 cm and a length of 13 m. The total heat flux to the SMR tubes is adjusted to an average heat flux (based on the surface area of the inner surface of the tubes) of 90,000 kcal/h/m.sup.2 corresponding to ca. 105 kW/m.sup.2. Each tube is loaded with catalyst pellets. The dimensions of the catalyst pellets are adjusted to give a void fraction of 60%. Such a configuration allows for processing around 410 Nm.sup.3/h of process gas per tube in the SMR, when the feed gas has a composition of 8.8% hydrogen, 56.8% water, 0.2% nitrogen, 0.1% carbon monoxide, 2.3% carbon dioxide, and 31.8% methane.
[0198] This gives: [0199] Total internal tube volume (volume limited by the interior surface of the tube and the height of the tube): 0.1021 m.sup.3 [0200] Internal tube volume occupied by catalyst material: 0.0408 m.sup.3 [0201] Total amount of internal tube volume occupied by catalyst material per unit of internal reactor system volume: 0.4 m.sup.3/m.sup.3 [0202] Total amount of energy supplied to the tube interior: 427.4 kW [0203] Amount of energy supplied to the tube interior per unit of tube interior volume: 4186 kW/m.sup.3. [0204] Gas processed per reactor catalyst volume: 4015 Nm.sup.3/m.sup.3/h.
Example 8
[0205] A reactor system according to the invention is provided. A structured catalyst with a geometric surface area of 800 m.sup.2/m.sup.3 is provided. 95% of the area is covered with a ceramic coating with catalytically active material. The ceramic coating has a thickness of 0.1 mm. A power of 9 kW/m.sup.2 of surface area of the structured catalyst is applied. Such a reactor can process ca. 7700 Nm.sup.3/m.sup.3/h relative to the volume of the structured catalyst, when the feed gas has a composition of 8.8% hydrogen, 56.8% water, 0.2% nitrogen, 0.1% carbon monoxide, 2.3% carbon dioxide, and 31.8% methane.
[0206] This gives: [0207] Amount of energy supplied to the structured catalyst per unit of structured catalyst volume: 7200 kW/m.sup.3. [0208] Total amount of internal reactor system volume occupied by catalyst per unit of internal reactor system volume: 0.076 m.sup.3/m.sup.3. [0209] Gas processed per reactor catalyst volume: 101315 Nm.sup.3/m.sup.3/h
[0210] It is seen by comparing with Example 7, that the internal reactor system volume can be made much more compact. In addition, in the reactor system according to the invention, no furnace is needed thus substantially reducing the reactor size.
[0211] Furthermore, the amount of catalytically active material is reduced considerably compared to the state of the art.