GB2198429A - Process and apparatus for producing hydrogen - Google Patents

Process and apparatus for producing hydrogen Download PDF

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Publication number
GB2198429A
GB2198429A GB08728276A GB8728276A GB2198429A GB 2198429 A GB2198429 A GB 2198429A GB 08728276 A GB08728276 A GB 08728276A GB 8728276 A GB8728276 A GB 8728276A GB 2198429 A GB2198429 A GB 2198429A
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United Kingdom
Prior art keywords
gas
zone
hydrogen
pressure
combustion zone
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GB08728276A
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GB2198429B (en
GB8728276D0 (en
Inventor
Johannes Berends
Johannes Didericus De Graaf
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of GB8728276D0 publication Critical patent/GB8728276D0/en
Publication of GB2198429A publication Critical patent/GB2198429A/en
Application granted granted Critical
Publication of GB2198429B publication Critical patent/GB2198429B/en
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Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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

Description

1 1 2198429 PROCESS AND APPARATUS FOR PRODUCM HYDROGEN The invention
relates to a process for producing hydrogen and to an apparatus suitable for carrying out such a process.
It is well known to prepare a hydrogen-oontaining gas such as synthesis gas (which mainly contains hydrogen and carbon monoxide, and in addition carbon dioxide, nitrogen and (unconverted) hydrocarbons and steam) by means of steam reforming or (non) catalytic partial oxidation of a hydrocarbonaceous; feed.
It is furthermore known to remove hydrogen from a hydrogencontaining product gas e.g. by means of pressure swing adsorption, thus obtaining substantially pure hydrogen and in addition hydrogendepleted off gas.
It has now been found that said hydrogen-preparation and -separation steps can be efficiently integrated by employing energy produced by ccinbusting in a ocabustion zone hydrogen-depleted off gas cbtained_frcir the latter step in at least one of the steps of the integrated process itself, e.g. for the ompression of oxygencontaining gas required in at least the former step of the process.
The invention therefore relates to a process for producing hydrogen which conprises the following steps: (a) converting a hydrocarbonaceous; feed in a reaction zone at elevated temperature and pressure at least partly into a gas mixture containing hydrogen and carbon monoxide, (b) removing hydrogen from product gas obtained from step (a), and (c) ccirbusting hydrogen- depleted off gas obtained from step (b) with an oxygen-containing gas in a carbustion zone and employing energy thus produced in at least one step of the process.
The process according to the present invention will be elucidated hereinafter with the use of the Figures in which various preferred options of the process have been incorporated without having the intent of limiting said process to those particular embodiments as depicted in the Figures.
Figure 1 relates to a preferred embodiment of the present process wherein hydrogen-depleted off gas is heat-exchanged with flue gas, before use as fuel gQis in a convective reforming zone.
Figure 2 relates to another preferred entodiment of the process according to the invention in which off gas is used as fuel gas in a gas turbine.
Reference numerals relating to similar process steps and/or equipment are the same in the two Figures.
In Figure 1 the essential process steps (a), (b) and (c) are carried out in reforming zone (1) of convective reformer (2), in pressure swing adsorption unit (3), and in combustion zone (4), respectively.
A hydrocarbonaceous feed, preferably containing normally liquid and/or gaseous hydrocarbons, in particular C 1 -c 4 hydrocarbons such as those present in natural gas, is introduced via line (5) into reforming zone (1) together with steam introduced via line (6). In zone M_step (a) of the present process is suitably carried out at a trature from 600 to 1600 "C and a pressure from 2 to 200 bar. The reforming zone preferably cmprises catalyst in order to operate said zone at a relatively low temperature from 600 to 1100 C and at a pressure from 5-50 bar.
The reactor which contains said reforming zone (1) and optionally combustion zone (4) (Which may also be spaced apart from the reforming zone and be located outside the reactor) preferably contains internals in order to inprove heat exchange between said zones and ensure optimal use of catalyst, if any.
The reactor internals suitably conprise double concentric tubes with catalyst in the annular space between the tubes. The outer tubes are suitably mounted substantially vertically in a horizontal inlet manifold for hydrocarbon/steam feed distribution. The lower ends of the outer tubes are preferably closed in order to reverse the flow of gas having passed downwardly through the annular catalyst bed. The inner tubes into which the hydrogen- tl 1 containing product gas is subsequently passed, are suitably cormected to a product outlet manifold. Advantageously, the corrbustion gas (having a teaperature of e.g. 900-1200 OC) enters the reforming reactor below or near the lower ends of the tubular reaction zone and leaves the reactor below the horizontal inlet manifold, situated at the relatively cold (e.g. 500-800 OC) upper part of the reactor. When the concentric tubes are nnunted in the above-described manner, their hot lower ends can expand freely and thermal expansion in the manifolds is kept to a minimum.
A gas mixture containing hydrogen and carbon monoxide is removed from reforming zone (1) through Line (7). In order to produce additional hydrogen, at least part and preferably all of said gas mixture is preferably directed to carbon monoxide conversion zone (8) in which at least part of the carbon monoxide present in the gas mixture is catalytically converted in the presence of steam at the appropriate carbonmonoxide conversion conditions in one or more steps into carbon dioxide. Conversion zone (8) is suitably maintained at a teuperature from 180 to 450 IC and a pressure from 2 to 200 bar.
Hydrogen-containing product gas obtained from conversion zone (8) and/or reforming zone (1) is directed via line (9) to pressure swing adsorption unit (3) from which a substantially pure hydrogen gas stream is withdrawn via line (10). Unit (3) preferably ccnprises a plurality of vessels containing molecular sieve beds which are sequentially in the adsorption-, desorption- and purgestage. However, it is also possible to substitute a liquid absorption unit (wherein carbon monoxide and/or carbon dioxide are selectively absorbed by a liquid which is subsequently regenerated) or a hydrogen-permeable maTbrane unit for pressure swing adsorption unit (3) in order to recover hydrogen from the product gas obtained via line (9).
Hydrogen-depleted off gas (which may still contain up to 5 or even up to 30% by volume of hydrogen, depending on the type of adsorption unit and pressure eniployed) obtained from unit (3) is preferably directed via line (11) to compressor (15) and subsequently via line (14) to heat exchanger (12) wherein heat is exchanged with the effluent gas stream (13) f7CIL coabustion zone (4) which gas stream generally has a higher terperature (e.g. from 150 to 1000 OC) than the gff gas. Accordingly, the energy efficiency of the process according to the invention is substantially irrproved, thus enabling optimal use of the hydrogen-depleted off-gas in one or more process steps.
The heat exchanged off-gas is directed via line (16) to ecuibustion zone (4). As the energy-content of the off-gas is in many cases not sufficient to "lay said gas as the only fuel source for a ocinbustion zone, additional fuel is preferably provided via line (18).
In a preferred embodin-ent of the process according to the invention as depicted in Figure 1 the combustion zone (4) as applied in step (c) provides thermal energy for the reforming reaction zone (1) of step (a) by means of convective heat transfer. A main advantage of such an arrangenent is that the reaction zone will as a result be heated substantially uniformly instead of risking local overheating by a number of burners located in the reaction zone, as in previous reforming processes.
Effluent gas from combustion zone (4) applied in steps (a) and (c) as discussed hereinbefore is suitably (after heat exchange) directed via line (19) to a separate ocabustion zone (20) to be used as moderator gas together with fuel gas lied via line (21). optionally, part of the heatexchanged effluent gas is recycled via line (17) to combustion zone (4). Effluent gas emanating from the latter caTibustion zone (20) is preferably directed via line (30) to turbo-expander (22) wherein the gas is expanded to provide mechanical energy to compress oxygen-containing gas (e.g. air) supplied via line (23) to =pressor (24). In some cases sufficient oxygen is present in the expanded effluent gas obtained via line (27) frorn turbo-expander (22) to enable the use of said gas as oxygen-containing gas for the contustion zone (not depicted in Figure 1).
Turbo-expander (22), compressor (24) and generator (33) are preferably coupled (e.g. by means of axis (25)) and optionally combined with one or more other compressors (15).
Compressed oxygen-containing gas (e.g. the gas provided via line (26)) is preferably emplQyed in at least one of the steps (a) and (c) of the present process, in particular in cmbustion zone (4) (via line (28)) and via line (29) in combustion zone (20). The use of compressed, and thereby preheated, o)Wgen--containing gas is preferred in the process according to the invention in order to improve the thermal efficiency of the cmibustion zone(s) and thus of the entire process.
The process and apparatus which are schematically depicted in Figure 2 will be described hereinafter only in so far as features different frat those depicted in Figure 1 are included.
A significant difference is the use of a catalytic or noncatalytic partial oxidation zone (31) in the drbodiment depicted in Figure 2. Such a zone is generally operated at a teq:)erature from 600 to 1600 IC and preferably at a tenperature from 1000 to 1500 'C, whereas the pressure in said zone is generally from 1 to 250 bar and preferably from 10 to 100 bar. Zone (31) constitutes the reaction zone employed in step (a) as well as a ocubustion zone as employed in step (c) of the process according to the invention.
A further difference with the process and apparatus as depicted in Figure 1 is that in Figure 2 the hydrogen-depleted off gas obtained from hydrogen separation unit (3) through line (11) is used as fuel gas in combustion zone (20) of a gas turbine instead of in a coubustion zone (4) of a reforming apparatus. 5q)anded effluent gas from turbo-expander (22) is optionally at least partly used in a combustion zone (not depicted in Figure 2). Cxygen-containing gas is advantageously provided by compressor (24) via line (26) to combustion zone (20). Substantially pure oxygen gas is supplied via line (34) to cmpressor (32) and subsequently directed via line (35) to partial oxidation zone (31).
The invention further relates to an apparatus suitable for producing hydrogen which comprises a reactor having feed inlet ineans and product outlet means connunicating with heat exchanger reactor internals, a ustor which is in heat exchange relation with said internals, a pressure swing adsorption unit comamicating with the product outlet neans and having separate hydrogen- and off-gas outlet means, and a ga!gturbine which is in ccmnmication with the combustor and/or the off- gas outlet neans.
The process according to the invention is illustrated by way of the following Ele. EXAMPLE The process substantially as depicted in Figure 2 is carried out by introducing 872 tons/day of feed gas (containing substantially methane) at a trature of 50 'C and a pressure of 51 bar in catalytic partial oxidation zone (31) and reacting the feed gas with 2490 tons/day of substantially pure oxygen gas introduced via line (35) at a trature of 100 OC and a pressure of 48 bar.
The hydrogen-containing synthesis gas obtained via line (7) at 380 'C and 30 bar is subjected in carbon monoxide conversion zone (8) to a catalytic steam shift together with steam having a temperature of 380 OC and a pressure of 61 bar. 2160 tons/day of nainly hydrogen- and carbon dioxidecontaining product gas from zone (8) is led to Pressure Swing Adsorption unit (3) at a tenperature of 40 OC and a pressure of 26 bar; from unit (3) 200 tons/day of substantially pure hydrogen is obtained at 40 c1C and 25 bar in addition to 1960 tons/day offgas containing carbon dioxide and hydrogen as major cnents at 40 OC and 1.6 bar. Said offgas is led via line (11) to ccopressor (15) from which an outlet gas stream (14) is obtained at a trature of 310 OC and a pressure of 17 bar and cc[rbined with 344 tons/day of rethane-containing gas at a pressure of 51 bar and a trature of 50 C having a similar carrposition as the feed gas to zone (31).
The corrbined gas stream (16) is directed to a gas turbine ccuprising combustion zone (20), ressor (24) and turbo expander (22). In said gas turbine 76 Megawatt electric power is generated by generator (33) of which 18 Megawatt is required for operating ccnpressors (15) and (32), leaving 58 Megawatt nett r export, excluding additional electricity generation by n-eans of waste heat recovery from the expanded effluent gas stream (27).
1

Claims (13)

1. A process for producing hydrogen which comprises the following steps: (a) converting a hydrocarbonaceous feed in a reaction zone at elevated tenperature and pressure at least partly into a gas mixture containing hydrogen and carbon monoxide, (b) removing hydrogen from product gas obtained from step (a), and (c) combusting hydrogen-depleted off gas obtained frcr step (b) with an oxygen-containing gas in a ceirbustion zone and employing energy thus produced in at least one step of the process.
2. A process according to claim 1 wherein energy produced in step (c) is enplayed to compress oxygen-containing gas.
3. A process according to claim 2 wherein compressed oxygen containing gas is enployed in at least one of steps (a) and (c).
4. A process according to any one of the preceding claims wherein step (a) is carried out in the presence of steam at a trature from 600 to 1600 OC and a pressure from 2 to 200 bar.
5. A process according to any one of the preceding claims wherein at least part of the carbon monoxide present in the gas mixture obtained from step (a) is catalytically converted in the presence of steam at carbon monoxide conversion conditions into carbon dioxide and hydrogen.
6. A process according to any one of the preceding claims wherein step b) is carried out by passing hydrogen-containing gas to a pressure swing adsorption zone.
7. A process according to claim 6 wherein hydrogen-depleted gas obtained from the pressure swing adsorption zone is heat exchanged with effluent gas from a combustion zone.
8. A process according to any one of the preceding claim wherein effluent gas from the combustion zone applied in step (c) is used as moderator gas for the combustion zone eiTployed in step (a).
1
9. A process according to claim 1 wherein the ustion zone applied in step (c) provides thermal energy for the reaction zone of step_(a) by means of convective heat transfer.
10. A process according to claim 9 wherein effluent gas from the combustion zone applied in steRs (a) and (c) is used as moderator gas for a different combustion zone and effluent gas en- e nating from the latter zone is expanded to provide mechanical energy.
11. An apparatus suitable for producing hydrogen which rises a reactor having feed inlet means and product outlet means commanicating with heat exchanger reactor internals, a c"ustor which is in heat exchange relation with said internals, a pressure swing adsorption unit communicating with the product. outlet means and having separate hydrogenand off-gas outlet means, and a gasturbine which is in communication with the combustor and/or the off-gas outlet mans.
12. A process for producing hydrogen according to claim 1 substantially as hereinbefore described with reference to the accompanying drawings.
13. An apparatus according to claim 11 substantially as hereinbefore described with reference to the accompanying drawings.
1 J EJRH04 Published 1988 at The Patent Office, State House, 66,71 High Holoom, London WClR 4TP. Further copies may be obtained 1rom The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1/87.
GB8728276A 1986-12-04 1987-12-03 Process and apparatus for producing hydrogen Expired - Fee Related GB2198429B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB868629031A GB8629031D0 (en) 1986-12-04 1986-12-04 Producing hydrogen

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GB8728276D0 GB8728276D0 (en) 1988-01-06
GB2198429A true GB2198429A (en) 1988-06-15
GB2198429B GB2198429B (en) 1990-12-19

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GB868629031A Pending GB8629031D0 (en) 1986-12-04 1986-12-04 Producing hydrogen
GB8728276A Expired - Fee Related GB2198429B (en) 1986-12-04 1987-12-03 Process and apparatus for producing hydrogen

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GB868629031A Pending GB8629031D0 (en) 1986-12-04 1986-12-04 Producing hydrogen

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AU (1) AU595405B2 (en)
CA (1) CA1334124C (en)
DE (1) DE3740865A1 (en)
GB (2) GB8629031D0 (en)
NL (1) NL8702706A (en)
NZ (1) NZ222775A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2307008A (en) * 1995-11-13 1997-05-14 Fred Moseley Gas turbine engine with two stage combustion
US8567200B2 (en) 2006-12-18 2013-10-29 Peter Holroyd Brook Process

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Publication number Priority date Publication date Assignee Title
DE4003210A1 (en) * 1990-02-01 1991-08-14 Mannesmann Ag METHOD AND APPARATUS FOR GENERATING MECHANICAL ENERGY
DE10122016A1 (en) * 2001-05-07 2002-11-28 Viessmann Werke Kg Apparatus for generating hydrogen and method for allothermic steam reforming
RU2599407C1 (en) * 2015-06-09 2016-10-10 Федеральное государственное унитарное предприятие "Центральный институт авиационного моторостроения имени П.И. Баранова" Method of continuous operation gas turbine plant action

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EP0053837A1 (en) * 1980-12-09 1982-06-16 Linde Aktiengesellschaft Adsorption process and installation for carrying out the process
EP0115752A1 (en) * 1981-08-07 1984-08-15 Union Carbide Corporation Improved process and apparatus for the production of ammonia
GB2136788A (en) * 1983-03-25 1984-09-26 Metallgesellschaft Ag Process for heating hydrogen under pressure
GB2154566A (en) * 1984-02-07 1985-09-11 Union Carbide Corp Process and apparatus for ammonia synthesis gas production
EP0167300A1 (en) * 1984-06-06 1986-01-08 Humphreys & Glasgow Limited Process for the production of alcohols
EP0183358A2 (en) * 1984-10-18 1986-06-04 Imperial Chemical Industries Plc Production of ammonia synthesis gas

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JPS4930915B1 (en) * 1967-07-15 1974-08-16
US4132065A (en) * 1977-03-28 1979-01-02 Texaco Inc. Production of H2 and co-containing gas stream and power
DE2911669A1 (en) * 1979-03-24 1980-10-02 Linde Ag Hydrogen mfr. from hydrocarbon(s) by steam reforming and adsorption - with combustion and/or recirculation of purging gas after carbon di:oxide sepn.
DE3571797D1 (en) * 1984-03-02 1989-08-31 Ici Plc Process for producing ammonia synthesis gas
US4919844A (en) * 1984-08-16 1990-04-24 Air Products And Chemicals, Inc. Enhanced heat transfer reformer and method
EP0215930B1 (en) * 1985-03-25 1990-06-27 SCHICK, Josef Hubert Process for the production of heat energy from synthetic gas
GB8513997D0 (en) * 1985-06-04 1985-07-10 Ici Plc Technical hydrogen
GB8520892D0 (en) * 1985-08-21 1985-09-25 Ici Plc Ammonia synthesis gas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0053837A1 (en) * 1980-12-09 1982-06-16 Linde Aktiengesellschaft Adsorption process and installation for carrying out the process
EP0115752A1 (en) * 1981-08-07 1984-08-15 Union Carbide Corporation Improved process and apparatus for the production of ammonia
GB2136788A (en) * 1983-03-25 1984-09-26 Metallgesellschaft Ag Process for heating hydrogen under pressure
GB2154566A (en) * 1984-02-07 1985-09-11 Union Carbide Corp Process and apparatus for ammonia synthesis gas production
EP0167300A1 (en) * 1984-06-06 1986-01-08 Humphreys & Glasgow Limited Process for the production of alcohols
EP0183358A2 (en) * 1984-10-18 1986-06-04 Imperial Chemical Industries Plc Production of ammonia synthesis gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2307008A (en) * 1995-11-13 1997-05-14 Fred Moseley Gas turbine engine with two stage combustion
US8567200B2 (en) 2006-12-18 2013-10-29 Peter Holroyd Brook Process

Also Published As

Publication number Publication date
NL8702706A (en) 1988-07-01
AU8200787A (en) 1988-06-09
DE3740865A1 (en) 1988-06-16
AU595405B2 (en) 1990-03-29
CA1334124C (en) 1995-01-31
GB8629031D0 (en) 1987-01-14
GB2198429B (en) 1990-12-19
GB8728276D0 (en) 1988-01-06
NZ222775A (en) 1989-07-27

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