Steam or Dry Reforming of Hydrocarbons

Abstract

A process for steam or dry reforming of hydrocarbons in a reforming reactor, comprising the steps of: (a) passing a feedstock, comprising one or more hydrocarbons together with steam and/or CO.sub.2, through a first catalytic zone at an elevated temperature, to form a partly reformed process gas, wherein the first catalytic zone comprises one or more elongate conduits, each containing reforming catalyst; and (b) passing the partly reformed process gas through a second catalytic zone at an elevated temperature, so as to form a reformed gas stream, wherein the second catalytic zone comprises one or more elongate conduits, each containing reforming catalyst; wherein the process further comprises the combustion of a fluid fuel with a combustion-sustaining medium in an exothermic combustion region, to form a hot combustion products stream, wherein the exothermic combustion region is adjacent to and laterally surrounds each of the second catalytic zone elongate conduits.

Claims

1. A method for preparing a binder precursor, wherein the method comprises the steps of: i) mixing (A) fungi or glucan and (B) starch with an alkaline agent, in the presence of an aqueous solvent system, to form an alkaline composition. ii) mixing the alkaline composition with an acidic agent to form a mixture; and iii) drying the mixture and forming a powder therefrom, so as to form a powdered binder precursor; or wherein the method comprises the steps of: i) mixing (A) fungi or glucan and (B) starch with an acidic agent in the presence of an aqueous solvent system to form an acidic composition; ii) mixing the acidic composition with an alkaline agent to form a mixture; and iii) drying the mixture and forming a powder therefrom, so as to form a powdered binder precursor.

2. The method of claim 1, wherein the aqueous solvent system comprises water and an organic solvent.

3. The method of claim 2, wherein the organic solvent is selected from the group consisting of: acetone, butanone, methanol, ethanol, 1-propanol, 2-propanol, diethyl ether, methyl acetate, ethyl acetate, toluene, 1,4-dioxane, tetrahydrofuran, acetonitrile, and methylene chloride, and mixtures thereof.

4. The method of claim 3, wherein the organic solvent is selected from the group consisting of: acetone, butanone, methanol, ethanol, 1-propanol, 2-propanol, 1,4-dioxane, tetrahydrofuran, and acetonitrile, and mixtures thereof.

5. The method of claim 4, wherein the organic solvent is acetone or methanol or mixtures thereof.

6. The method of claim 1, wherein the aqueous solvent system comprises 10% or more water by volume, such as from 10 to 50% water by volume.

7. The method of claim 1, wherein the (A) fungi or glucan and (B) starch and the aqueous solvent system is provided in the form of an aqueous mixture, the aqueous mixture having a solvent content of from 45 to 90 wt %.

8. The method claim 1, wherein the starch comprises dextrin or is dextrin.

9. (canceled)

10. The method of claim 1, wherein the method is for producing a shaped article, the method comprising: a) providing a binder precursor by carrying out the steps performed in claim 1, and then: b) forming a binder composition by mixing the binder precursor with filler material; c) shaping the binder composition into a three-dimensional shape; and d) curing the binder composition to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the binder composition.

11. The method of claim 10, wherein, in step b) or c), the binder precursor is rehydrated by mixing the binder composition with water, wherein optionally the water is provided in the form of an aqueous solvent system comprising water and an organic solvent.

12. The method of claim 1, wherein the method is for adhering two component parts to produce a composite product, each component part having a contact surface, the method comprising: a) providing a binder precursor by carrying out the steps performed in claim 1, and then: b) applying the binder precursor to the contact surface of the first component part and/or the contact surface of the second component part; c) contacting the contact surface of the first component part with the contact surface of the second component part; and d) curing the binder precursor to provide a composite product.

13. The method of claim 12, wherein the curing by applying heat and/or pressure.

14. The method of claim 1, wherein the method is for producing a shaped article which is an engineered wood product, the method comprising: a) providing a binder precursor by carrying out the steps performed in claim 1, and then: b) forming a three-dimensional shape by combining the binder precursor and a plurality of component parts, with there being three or more component parts in the form of layers, each comprising wood, and with layers of binder being provided between the layers of wood; and c) curing the three-dimensional shape under pressure to form a shaped article having said three-dimensional shape.

15. The method of claim 1, wherein the method is for making a rehydrated binder, the method comprising the steps of: i) providing a binder precursor by carrying out the steps performed in claim 1, and then: ii) mixing the binder precursor with water so as to form a rehydrated binder, wherein optionally the water is provided in the form of an aqueous solvent system comprising water and an organic solvent.

16. (canceled)

17. The method of claim 15, wherein the method is for making a shaped article, the method comprising: a) providing a rehydrated binder by carrying out the steps performed in claim 15, and then: b) forming a binder composition by mixing the rehydrated binder with filler material; c) shaping the binder composition into a three-dimensional shape; and d) curing the binder composition to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the binder composition.

18. The method of claim 10, wherein the filler material comprises wood and the shaped article is an engineered wood product.

19. The method of claim 15, wherein the method is for producing a shaped article which is an engineered wood product, the method comprising: a) providing a rehydrated binder by carrying out the steps performed in claim 15, and then: b) forming a three-dimensional shape by combining the rehydrated binder and a plurality of component parts, with there being three or more component parts in the form of layers, each comprising wood, and with layers of binder being provided between the layers of wood; and c) curing the three-dimensional shape under pressure to form a shaped article having said three-dimensional shape.

20. The method of claim 15, wherein the method is for adhering two component parts to produce a composite product, each component part having a contact surface, the method comprising: a) providing a rehydrated binder by carrying out the steps performed in claim 15, and then: b) applying the rehydrated binder to the contact surface of the first component part and/or the contact surface of the second component part; c) contacting the contact surface of the first component part with the contact surface of the second component part; and d) curing the rehydrated binder to provide the composite product.

21. The method of claim 20, wherein the curing by applying heat and/or pressure.

22. (canceled)

23. The method of claim 15, wherein the method is for preparing a precursor to a composite product or a precursor to a shaped article, the method comprising: a) providing a rehydrated binder by carrying out the steps performed in claim 15, and then: b) applying the rehydrated binder to a surface of a first component part of the composite product or to a surface of filler material for the shaped article; and c) allowing the rehydrated binder to dry.

24. A method of preparing a precursor to a composite product or a precursor to a shaped article, the method comprising: a) providing a mixture, either by: i) mixing (A) fungi or glucan and (B) starch with an alkaline agent in the presence of an aqueous solvent system to form an alkaline composition; and ii) mixing the alkaline composition with an acidic agent to form the mixture; or wherein the method comprises the steps of: i) mixing (A) fungi or glucan and (B) starch with an acidic agent in the presence of an aqueous solvent system to form an acidic composition; and ii) mixing the acidic composition with an alkaline agent to form the mixture; b) applying the mixture to a surface of a first component part of the composite product or to a surface of filler material for the shaped article; and c) allowing the mixture to dry.

25. The method of claim 23, wherein the rehydrated binder or the mixture dries on the surface of the first component part or on the surface of the filler material for the shaped article, so as to form a coating on the surface.

26. The method claim 23, wherein the first component part or the filler material is porous and the rehydrated binder or the mixture partly or fully penetrates pores that are connected to the surface of the first component part or the filler material, and dries in these pores, so as to form an impregnated first component part or an impregnated filler material.

27. (canceled)

28. (canceled)

29. The method of claim 23, wherein the method is for forming a composite product, the method comprising: a) providing a composite product precursor by carrying out the steps performed in claim 23, and then: b) contacting the surface of the first component part with a surface of a second component part of the composite product; and c) applying heat and/or pressure to cure the binder precursor and adhere the first component part of the composite product to the second component part of the composite product so as to provide the composite product.

30. (canceled)

31. The method of claim 23, wherein the method is for producing a shaped article, the method comprising: a) providing a composite product precursor by carrying out the steps performed in claim 23, and then: b) optionally mixing the shaped article precursor with a crosslinker; c) shaping the shaped article precursor into a three-dimensional shape; and d) curing the binder precursor, to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the binder precursor.

32. A method of obtaining a wood-based filler product, the method comprising: I) providing an engineered wood product, wherein the engineered wood product was made by a method comprising: a) providing a binder, wherein the binder has been produced by a process of: i) mixing (A) fungi or glucan and (B) starch with an alkaline agent to form an alkaline composition; and mixing the alkaline composition with an acidic agent to form the binder; or ii) mixing (A) fungi or glucan and (B) starch with an acidic agent to form an acidic composition; and mixing the acidic composition with an alkaline agent to form the binder; b) forming a binder composition by mixing the binder with wood-based filler material; c) shaping the binder composition into a three-dimensional shape; and d) curing the binder composition to form an engineered wood product which is a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the binder composition; and II) breaking up the engineered wood product into a plurality of pieces.

33. A method of obtaining a wood-based filler product, the method comprising: I) providing an engineered wood product, wherein the engineered wood product was made by a method comprising: a) providing a binder, wherein the binder has been produced by a process of: i) mixing (A) fungi or glucan and (B) starch with an alkaline agent to form an alkaline composition; and mixing the alkaline composition with an acidic agent to form the binder; or ii) mixing (A) fungi or glucan and (B) starch with an acidic agent to form an acidic composition; and mixing the acidic composition with an alkaline agent to form the binder; b) forming a three-dimensional shape by combining the binder and a plurality of component parts, with there being three or more component parts in the form of layers, each comprising wood, and with layers of binder being provided between the layers of wood; and c) curing the three-dimensional shape under pressure to form an engineered wood product which is a shaped article having said three-dimensional shape; II) breaking up the engineered wood product into a plurality of pieces.

34. A method of obtaining a wood-based filler product, the method comprising: I) providing an engineered wood product, wherein the engineered wood product was made by a method comprising: a) providing a binder wherein the binder has been produced by a process of: i) mixing (A) fungi or glucan and (B) starch with an alkaline agent to form an alkaline composition; and mixing the alkaline composition with an acidic agent to form the binder; or ii) mixing (A) fungi or glucan and (B) starch with an acidic agent to form an acidic composition; and mixing the acidic composition with an alkaline agent to form the binder; b) applying the binder to the contact surface of the first component part and/or the contact surface of the second component part; c) contacting the contact surface of the first component part with the contact surface of the second component part; and d) curing the binder to provide the composite product; and II) breaking up the engineered wood product into a plurality of pieces.

35. The method of 32, wherein step II) involves forming wood chips and/or sawdust from the engineered wood product.

36. (canceled)

37. A method for producing a shaped article, the method comprising: a) providing a wood-based filler product as defined in claim 36; b) optionally mixing the wood-based filler product with water and/or a crosslinker; c) shaping the wood-based filler product into a three-dimensional shape; and d) curing the binder precursor to form a shaped article having said three-dimensional shape; wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the wood-based filler product.

38-41. (canceled)

42. The method of claim 17, wherein the filler material comprises wood and the shaped article is an engineered wood product.

43. The method of claim 24, wherein the method is for forming a composite product, the method comprising: a) providing a composite product precursor by carrying out the method steps defined in claim 24; and then: b) contacting the surface of the first component part with a surface of a second component part of the composite product; and c) applying heat and/or pressure to cure the binder precursor and adhere the first component part of the composite product to the second component part of the composite product so as to provide the composite product.

44. The method of claim 24, wherein the method is for producing a shaped article, the method comprising: a) providing a shaped article precursor by carrying out the method steps defined in claim 24, and then: b) optionally mixing the shaped article precursor with a crosslinker; c) shaping the shaped article precursor into a three-dimensional shape; and d) curing the binder precursor, to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the binder precursor.

45. The method of claim 33, wherein the method is for producing a shaped article, the method comprising: a) providing a wood-based filler product by carrying out the method steps defined in claim 33; and then: b) optionally mixing the wood-based filler product with water and/or a crosslinker; c) shaping the wood-based filler product into a three-dimensional shape; and d) curing the binder precursor to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the wood-based filler product.

46. The method of claim 34, wherein the method is for producing a shaped article, the method comprising: a) providing a wood-based filler product by carrying out the method steps defined in claim 34; and then: b) optionally mixing the wood-based filler product with water and/or a crosslinker; c) shaping the wood-based filler product into a three-dimensional shape; and d) curing the binder precursor to form a shaped article having said three-dimensional shape, wherein step c) and step d) can be carried out simultaneously or separately, and wherein during one or both of step c) and step d) pressure is applied to the wood-based filler product.

Description

DETAILED DESCRIPTION OF THE INVENTION WITH REFERENCE TO THE DRAWINGS

[0386] FIG. 1 is a diagram that illustrates the process streams and heat flows in the present invention.

[0387] FIG. 2A is a schematic illustration of a first apparatus according to the present invention.

[0388] FIG. 2B is a schematic illustration of a second apparatus according to the present invention.

[0389] FIG. 3A shows a first configuration of apparatus according to the present invention.

[0390] FIG. 3B shows a second configuration of apparatus according to the present invention.

[0391] FIG. 4 is a partial cross section of the apparatus shown in FIGS. 3A and B, taken across the line “A”-“A”. This provides a part cross-sectional view of the heat recovery section of the apparatus.

[0392] FIG. 5 shows the apparatus according to the invention integrated into a suitable steam reforming system.

[0393] FIG. 6A and FIG. 6B show two possible arrangements of burner nozzles and elongate conduits within an apparatus according to the invention.

[0394] FIG. 7 is a schematic drawing illustrating the use of the process tube assembly of the third aspect of the invention without requiring the burner nozzles/combustion region present in the first and second aspects.

[0395] The process and apparatus of the invention can be understood by reference to the non-limiting embodiments shown in FIGS. 1 to 7.

[0396] The apparatus can be operated inverted from the orientation as indicated in the drawings.

[0397] The invention is described in the context of steam reforming, but it will be appreciated that this can be readily modified for use in dry reforming, with some or all of the steam being replaced with CO.sub.2.

[0398] The entire process as described can be undertaken in a single enclosure or housing (104) containing a single elongate reforming assembly or multiple elongate reforming assemblies (100) arranged in parallel. For simplicity this description relates to multiple elongate reforming assemblies (also known as process tubes) (100).

[0399] The elongate reforming assemblies (100) each comprise an outer process tube which forms the second catalytic zone elongate conduit (101) and a first catalytic zone elongate conduit (114).

[0400] In the embodiment shown in FIG. 3A, each second catalytic zone elongate conduit (101) contains and is attached to a first catalytic zone elongate conduit (114) such that these two conduits (101, 114) are in longitudinal alignment.

[0401] In this embodiment shown in FIG. 3A, each first catalytic zone elongate conduit (114) receives feedstock (1) via a separate feedstock inlet. This may suitably be via a header and lateral system.

[0402] In this embodiment shown in FIG. 3A, each hot reformed gas stream (5) loses heat to a first catalytic zone elongate conduit (114) and the resulting separate cooled reformed gas product streams (6) are then collected together (e.g. in a header and lateral system) to form a combined cooled reformed gas product stream. This single cooled reformed gas product stream then exits the apparatus via one or more outlets.

[0403] In this embodiment shown in FIG. 3A, each combustion products stream (13) loses heat to a first catalytic zone elongate conduit (114) and the resulting further-cooled combustion products streams (14) then combine within the housing, towards the top, before exiting the housing via a single outlet.

[0404] The apparatus shown in FIG. 3A can be understood to include a process tube assembly according to the third aspect of the invention. The process tube assembly comprises an inner tube (114) and an outer tube (101) in a concentric arrangement, wherein the inner tube (114) contains a first reforming catalyst portion, with a first reforming catalyst bed, wherein the outer tube (101) contains a second reforming catalyst portion, with a second reforming catalyst bed, whereby the first reforming catalyst bed and the second reforming catalyst bed are arranged in series, whereby the inner tube (114) has an exit through which partially reformed gas can leave the inner tube (114), and whereby an internal conduit (111), through which partially reformed gas can flow, runs from the exit of the inner tube (114) and passes through the second reforming catalyst portion.

[0405] In the embodiment shown in FIG. 3B, each second catalytic zone elongate conduit (101) contains a first catalytic zone elongate conduit (114) and these two conduits (101, 114) are in longitudinal alignment. The location of the first catalytic zone elongate conduit (114) is fixed at a single location, where the first catalytic zone elongate conduit (114) is held in place by plenum unit (16). The location of the second catalytic zone elongate conduit (101) is likewise fixed at a single location, where the second catalytic zone elongate conduit (101) is held in place by plenum unit (16). Thus the second catalytic zone elongate conduit (101) and the first catalytic zone elongate conduit (114) can be considered as being indirectly attached, at just one single location, via the plenum unit.

[0406] The apparatus shown in FIG. 3B can be understood to include a process tube assembly according to the third aspect of the invention. The process tube assembly comprises an inner tube (114) and an outer tube (101) in a concentric arrangement, wherein the inner tube (114) contains a first reforming catalyst portion, with a first reforming catalyst bed, wherein the outer tube (101) contains a second reforming catalyst portion, with a second reforming catalyst bed, whereby the first reforming catalyst bed and the second reforming catalyst bed are arranged in series, whereby the inner tube (114) has an exit through which partially reformed gas can leave the inner tube (114), and whereby an internal conduit (111), through which partially reformed gas can flow, runs from the exit of the inner tube (114) and passes through the second reforming catalyst portion.

[0407] In the embodiment shown in FIG. 3B the plenum unit (16) comprises a cooled reformed gas plenum. The cooled reformed gas plenum has multiple inlets (30), each being an inlet for a cooled reformed gas stream that is obtained after it has heated a given first catalytic zone elongate conduit (114). The multiple inlets (30) merge into a single chamber (31) located inside the apparatus housing. This chamber or plenum has one or more outlet (32) for the combined cooled reformed gas stream (6); the or each outlet runs to a location outside the apparatus housing.

[0408] In this embodiment shown in FIG. 3B the plenum unit (16) also comprises a further-cooled combustion products stream plenum. The further-cooled combustion products stream plenum has multiple inlets (40), each being an inlet for a further-cooled combustion products stream that is obtained after it has heated a given first catalytic zone elongate conduit (114). The multiple inlets (40) merge into a single chamber (41) located inside the apparatus housing. This chamber or plenum has one or more outlet (42) for the combined further-cooled combustion products stream (14); the or each outlet runs to a location outside the apparatus housing.

[0409] It can be seen that in the embodiment shown in FIG. 3B the plenum unit (16) also serves the purpose of holding in place the top of each of the first catalytic zone elongate conduits (114) and the top of each of the second catalytic zone elongate conduits (101). Therefore their position relative to one another is secured, indirectly.

[0410] In this embodiment shown in FIG. 3B, the apparatus comprises a single combined feedstock inlet (20) which runs from outside the apparatus housing to a chamber (21) inside the apparatus housing to provide feedstock (1). The chamber (21) then has multiple outlets (22), each being a feedstock inlet for one of the first catalytic zone elongate conduits (114).

[0411] In all embodiments of the invention, de-sulphurised natural gas (or any other source of hydrocarbon) and steam can provide a feedstock (1) at a temperature in the region of 300-500° C. This is introduced to the top of the first catalytic zone elongate conduits (process tubes) (114). The feedstock (1) then flows downwards as stream (2) through first reforming catalytic zones (112), each comprising a first reforming catalyst bed. In the first reforming catalytic zones some of the contained methane and essentially all higher hydrocarbons are converted to hydrogen and carbon oxides. Therefore a partly reformed process gas (3) is formed. The first reforming catalyst beds in the first reforming catalytic zones (112) may be composed of more than one catalyst type.

[0412] Second reforming catalytic zones (102) are provided in each second catalytic zone elongate conduit (101). The second catalytic zones (102) each comprise a second reforming catalyst bed.

[0413] Partly reformed process gas stream (3) is routed through these second catalytic zones (102) via transfer conduits (111).

[0414] Then the partly reformed process gas stream (4) flows up through second catalytic zones (102).

[0415] Further reforming and methane conversion takes place in the second catalytic zones to produce hydrogen and carbon oxides. This gas stream exits the catalyst beds at a temperature typically between 750° C. and 1100° C., preferably between 900 and 1000° C. Thus a hot reformed gas stream (5) is formed.

[0416] Heat for the endothermic reforming reaction in the first reforming catalytic zones (112) and for further heating of the feedstock and partly reformed process gas (3), up to a temperature in the region of 650-800° C., is provided by counter-current cooling of the hot reformed gas stream (5).

[0417] In the arrangement shown in FIG. 2A, the hot reformed gas stream (5) flows in an annulus between the first catalytic zone elongate conduit (114) and the outer process tube (101). There is also simultaneous heating of the hot reformed gas stream (5) by the combustion products stream (13) flowing outside of the outer process tube (101).

[0418] In the arrangement shown in FIG. 2B, the hot reformed gas stream (5) flows in a passage inside the elongate conduit (114) of the first catalytic zone (112). There is also simultaneous heating of the first catalytic zone (112) by the combustion products stream (13) flowing outside of the outer process tube (101).

[0419] Fins or other devices (115) may be attached to the outside surface of the elongate conduit (114) of the first catalytic zone (112) to increase the associated heat transfer rate from the reformed gas to the feedstock/partly reformed process gas (2).

[0420] Likewise fins or other suitable devices (not shown) may be attached to the inside and/or outside of the outer process tube (101) adjacent to the first catalytic zone to increase local heat transfer rates.

[0421] Suitable spacers are usefully provided to maintain separation distances between each first catalytic zone elongate conduit (114) and each outer process tube (101).

[0422] To prevent significant heating of partly reformed process gas stream (3) inside the transfer conduits (111), suitable heat insulating material may be applied inside or outside for a part or all of their lengths.

[0423] In a preferred embodiment, free movement of the transfer conduits (111) occurs vertically, during start-ups or shutdowns, when there are differential temperatures and degrees of expansion of the outer process tube (101) relative to the inner conduit (114) and transfer conduit (111). This is achieved by provision of an outer tube (119) in contact with the catalyst in second reforming catalytic zone (102). The transfer conduit (111) is able to slide vertically relative to this outer tube (119), thus allowing also free movement of the inner conduit (114) relative to the outer process tube (101). The outer tube (119) is configured to permit this movement. For example, the outer tube (119) may be formed of discreet parts, may be a shape other than cylindrical, or may be corrugated.

[0424] The internal surfaces of the transfer conduits (111) may be plated or coated with a surface of suitable reforming catalyst or the conduit may be provided with catalytic inserts to aid in the overall reforming process.

[0425] To provide support and restraint of catalysts within the catalytic zones, appropriate support or restraint devices (116, 117, 118) are provided. A first device (116) is below the first catalytic zone, a second device (117) is above the second catalytic zone and a third device (118) is below the second catalytic zone.

[0426] The catalyst support device (116) permits free flow of partially reformed gas to conduit (111) whilst preventing loss of catalyst from the first catalytic zone above.

[0427] The restraining device (117) prevents upward flow of catalyst with the reformed gas to the annulus above between (114) and (101). This device may usefully be attached to the bottom of conduit (114), thereby to prevent an increased separation between the two. An increased separation would result in lower local gas velocities at the outer tube wall (101), with correspondingly lower local heat transfer coefficients leading to higher local tube wall temperatures.

[0428] The support device (118) is provided to prevent the catalyst from passing through in a reverse direction when gas flow is low, whilst allowing upward flow of partially reformed gas therethrough. It is designed so as to move upwards in operation so as to support the bottom catalyst and prevent catalyst particulate fluidisation within the second catalytic zone.

[0429] In order to increase the heat flux to the process tubes in the upper part of the combustion zone, radiative inserts (110) or other devices are provided around the process tubes to increase the velocity of the combustion products and to increase the heat transfer rate to the elongate reforming assemblies (process tubes) (100).

[0430] In a preferred embodiment, radiative inserts (110) are provided in the heat recovery region (2000) and extend in part into the exothermic combustion region (1000). These inserts are external to the catalytic zones (102) and (112) respectively, and may be formed of constant or varying shapes. These provide inert volume, to increase the gas velocity and local heat transfer coefficients of the partly cooled combustion products stream (13) flowing up and outside of outer process tube (101), as well as to absorb heat convectively with subsequent heat transfer to the process tubes via direct radiation.

[0431] The hot reformed gas stream (5) exits second catalytic zone (102), passing up the annulus between tubes (101) and first catalytic zone elongate conduits (114), providing reaction heat for the first catalytic zones. It loses heat as a consequence, and thus becomes cooled reformed gas product stream (6).

[0432] The cooled reformed gas product stream (6) is discharged from the top of process tubes (101) and exits the reformer at a temperature of typically 400-500° C., preferably about 475° C. or lower.

[0433] In the embodiment shown in FIG. 2A, the hot reformed gas stream (5) flows counter-currently and in indirect heat exchange contact with the feedstock (1), and simultaneously the combustion products stream (13) flows co-currently in indirect heat exchange contact with the hot reformed gas stream (5), such that heat is transferred from the combustion products stream (13) to the reformed gas stream (5), and heat is transferred from the hot reformed gas stream (5) to the feedstock (1).

[0434] In the embodiment shown in FIG. 2B, the hot reformed gas stream (5) flows through a passage inside the elongate conduit (114) of the first catalytic zone (112), and provides heat to the feedstock (1) from within the elongate conduit (114), and simultaneously the combustion products stream (13) flows outside the elongate conduit (114) of the first catalytic zone (112) and heat is transferred from the combustion products stream (13) to the feedstock (1).

[0435] Heat of reaction for the reforming reaction in the reformer lower section (second catalytic zone) is provided by combustion of an oxidant, such as air, and a fluid fuel.

[0436] Externally preheated and pressurised combustion sustaining medium (e.g. air stream) (7) is introduced at or near to the bottom of enclosure or housing (104) at a temperature whereby the combination of combustion air and fuel are above the fuel auto-ignition temperature and combustion can be sustained via turbulent diffusion flame. Typically the combustion air stream (7) will be heated to a minimum temperature of about 600° C. to 750° C., although higher temperatures may be used. Higher temperatures above the auto-ignition temperature tend to be disadvantageous mechanically. Hot combustion air is distributed into the combustion zone, as stream (9). The auto-ignition temperature can be reduced if desired by the use of suitable catalytic combustion devices.

[0437] Cold or externally partially preheated fuel gas stream (10) is introduced into the air in the combustion zone via burner nozzles (109) where it is combusted (11) to form combustion products stream (12) which imparts heat both convectively and via gas radiation to the process tubes (101) and thence to process gas stream (4) and second catalytic zones (102).

[0438] The internal walls of the enclosure or housing (104) are covered with suitable refractory material (106) to provide protection to the enclosure or housing (104) and to minimise external heat loss.

[0439] In FIG. 5, the following components of a steam reforming system suitable for use with the current invention are shown:

[0440] Equipment Items [0441] 201. Desulphurization Vessel [0442] 202. Feedstock Saturator [0443] 203. Saturator Water Circulation Pump [0444] 204. Feedstock/Reformed Gas Heat Interchanger [0445] 205. Pre-reformer [0446] 206. Double Convective Reformer=apparatus according to the invention [0447] 207. High Temperature CO Shift Reactor (optional—for H.sub.2 production only) [0448] 208. Reformed Gas Saturator Water Heater [0449] 209. Low Temperature CO Shift Reactor (optional—for H.sub.2 production only) [0450] 210. Saturator Water Make-up Heater [0451] 211. Reformed Gas Cooler [0452] 212. Reformed Gas Separator [0453] 213. Combustion Air Compressor [0454] 214. Combustion Products Expander [0455] 215. Combustion Air Heater [0456] 216. Combustion Air Pre-heater [0457] 217. Desulphurization Pre-heater [0458] 218. Combustion Products Saturator Water Heater [0459] 219. Low Grade Heat Recovery Exchanger [0460] 220. Combustion Products Cooler [0461] 221. Combustion Products Separator

[0462] Stream Numbers [0463] 301′ natural gas feedstock [0464] 302 hydrogen recycle [0465] 303 pre-heated feedstock to desulphurization unit [0466] 304 desulphurised feedstock to saturator [0467] 305 desulphurised fuel gas to DCR [0468] 306 desulphurised fuel gas to CA heater [0469] 307 cooled saturator circulation water [0470] 308 hot saturator circulation water [0471] 309 saturated feed gas [0472] 310 heated pre-reformer feed [0473] 311 DCR feed [0474] 312 DCR reformed gas product [0475] 313 partially cooled reformed gas [0476] 314 partially cooled reformed gas [0477] 315 partially cooled reformed gas [0478] 316 cooled separated reformed gas [0479] 317 process condensate [0480] 320 atmospheric combustion air [0481] 321 compressed pre-heated combustion air [0482] 322 heated combustion air to DCR [0483] 323 combustion products from DCR [0484] 324 partially cooled combustion products [0485] 325 cooled separated combustion products [0486] 326 steam condensate [0487] 327 combustion products to expander [0488] 328 combustion products vent to atmosphere

[0489] FIG. 6 shows two different options for arranging the elongate tubes of the second catalytic zone (101) and the burner nozzles (109). Other arrangements are possible, but these are beneficial arrangement in terms of efficiency and even distribution of heat. In these arrangements a triangular or square arrangement of alternating burner nozzles and elongate tubes is used, and an approximately equal number of burner nozzles and elongate tubes is used. FIG. 6a shows a square arrangement whilst FIG. 6b shows a triangular arrangement. Both arrangements permit each burner nozzle to provide heat to multiple elongate conduits.

[0490] Whilst in a preferred embodiment the process tube assembly of the third aspect is used in the process of the first aspect and is present in the apparatus of the second aspect, the process tube assembly of the third aspect can also be used in other processes and apparatus. FIG. 7 illustrates one such embodiment. FIG. 7 is schematic and only shows part of the process tube assembly but it will be understood that the focus of FIG. 7 is the changes made to utilise the process tube assembly in a different environment, where the hot gas that is required to heat the catalyst in the process tube assembly is produced remotely from (upstream from) the assembly.

[0491] The process tube assembly 401 comprises an inner tube and an outer tube 402, provided in a concentric arrangement. The second reforming catalyst bed 403 can be seen within the assembly.

[0492] The internal conduit 404, through which partially reformed gas 405 can flow, passes through the second reforming catalyst portion.

[0493] The hot combustion products 406 are provided to the assembly, having been produced remotely from (upstream from) the assembly.

[0494] The process tube assembly 401 has been adapted by the inclusion of one or more radiant shields 407 and thermal insulation 408 at the end 401a of the process tube assembly 401, to significantly reduce the heat load to the outer tube 402 at this location. It may be that only one out of a radiant shield 407 and thermal insulation 408 is used to achieve this, but in the illustrated embodiment both are present.

[0495] Heat must also be removed from the bottom of the outer tube 402 to maintain a suitable maximum wall temperature. For example, the tube assembly 401 may be configured to create a flow path 409 adjacent to the process tube assembly walls, such that process fluids flow in contact with the process tube assembly walls to remove heat from the outer tube 402 near the end 401a of the process tube assembly 401.

[0496] An example of the data from a process operating in accordance with the present invention, according to the apparatus as shown in FIG. 3B, is set out in Table 1 below. Per the preferred arrangements described previously, the feedstock is assumed to have passed through an adiabatic pre-reformer immediately upstream of the apparatus, whilst the combustion air has been preheated to above the fuel auto-ignition temperature using additional fuel gas (not shown in Table 1).

[0497] The Example is based on a reformed gas pressure exiting the apparatus of 3,410 kPa. This requires a feedstock inlet pressure of 4,110 kPa, indicating a differential pressure of 700 kPa across the apparatus. This relatively high differential pressure results from the need to provide high process gas velocities across relatively small catalyst pellet sizes in order to generate high heat transfer coefficients in the catalyst beds, to ensure adequate reforming, and across the elongate conduit (process tube) walls, in order to minimise tube wall temperatures.

[0498] The space velocity of the flowing gas in the Example, based on Nm.sup.3/hr methane in the feed per m.sup.3 catalyst, is about 1,400 hr.sup.−1, which is within but at the higher end of that typical of reforming catalysts, but at the low end of the range typical of pre-reforming type catalyst. Typical pre-reforming catalyst is similar in characteristic dimension (size) to that required in the catalytic zones.

[0499] Thus in terms of typical catalyst volume and thus surface area and activity it can be seen that the overall catalyst volume of the apparatus of the current invention is sufficient to achieve the requisite amount of reforming.

TABLE-US-00001 TABLE 1 Stream Data Stream No. 1 2 5 6 10 7 13 14 Stream Description Final Combustion Feedstock Part- Hot reformed Fuel gas to air to Hot Final to reformed reformed gas combustion combustion combustion combustion reformer gas gas product region region product product H.sub.2O 5,425.1 4,032.2 3,156.3 3,156.3 0.0 379.5 1,458.7 1,458.7 H 167.3 3,392.1 6,262.8 6,262.8 21.0 0.0 0.0 0.0 CO 0.2 439.4 1,558.4 1,558.4 6.0 0.0 0.0 0.0 CO.sub.2 159.1 635.9 514.4 514.4 22.0 134.2 705.0 705.0 CH.sub.4 2,226.5 1,310.5 313.1 313.1 495.1 0.0 0.0 0.0 C.sub.2H.sub.6 0.0 0.0 0.0 0.0 15.1 0.0 0.0 0.0 C.sub.3H.sub.8 0.0 0.0 0.0 0.0 3.3 0.0 0.0 0.0 C.sub.4H.sub.10 0.0 0.0 0.0 0.0 1.9 0.0 0.0 0.0 N.sub.2 125.2 125.2 125.2 125.2 30.0 5,107.1 5,137.1 5,137.1 A 0.0 0.0 0.0 0.0 0.0 60.7 60.7 60.7 O.sub.2 0.0 0.0 0.0 0.0 0.0 1,122.3 37.0 37.0 kg mol/hr 8,103.5 9,935.4 11,930.3 11,930.3 594.4 6,803.9 7,398.5 7,398.5 kg/hr 144,307 144,307 144,307 144,307 10,671 194,151 204,821 204,821 mol wt. 17.808 14.525 12.096 12.096 17.954 28.535 27.684 27.684 temperature (C.) 352 757 950 469 380 650 1,050 529 pressure (kPa) 4,110 3,700 3,420 3,410 4,310 3,420 3,420 3,410 Zone 1 2 Total Catalyst % volume per zone 53.4% 46.4% 100.0% Methane conversion per zone 41.1% 44.8% 85.9% Heat load per zone 347.7 315.6 663.3 GJ/hr % heat load per zone 52.4% 47.6% 100.0%