AU595405B2 - Process and apparatus for producing hydrogen - Google Patents

Process and apparatus for producing hydrogen Download PDF

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Publication number
AU595405B2
AU595405B2 AU82007/87A AU8200787A AU595405B2 AU 595405 B2 AU595405 B2 AU 595405B2 AU 82007/87 A AU82007/87 A AU 82007/87A AU 8200787 A AU8200787 A AU 8200787A AU 595405 B2 AU595405 B2 AU 595405B2
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AU
Australia
Prior art keywords
gas
hydrogen
zone
pressure
combustion zone
Prior art date
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Ceased
Application number
AU82007/87A
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AU8200787A (en
Inventor
Johannes Berends
Johannes Didericus De Graaf
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Shell Internationale Research Maatschappij BV
Original Assignee
SHELL INT RESEARCH
Shell Internationale Research Maatschappij BV
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Publication of AU8200787A publication Critical patent/AU8200787A/en
Application granted granted Critical
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Anticipated expiration legal-status Critical
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Separation Of Gases By Adsorption (AREA)

Description

0 it S F Ref: 43418 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICA1 iON
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'9 9J Complete Specification Lodged: Accepted: Published: Priority: FOR OFFICE USE: Class Int Class Related Art: Name and Address of Applicant: .9 Shell Internationale Research Maatschappij B.V.
Carel van Bylandtlaan 2596 HR The Hague THE NETHERLANDS Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Address for Service: .9* Complete Specification for the invention entitled: Process and Apparatus for Producing Hydrogen The following statement is a full description of this best method of performing it known to me/us
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invention, including the 5845/5 5845/4 IA PROCESS AND APPARATUS FOR PRODUCING 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-containing 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 hydrogen-containing product gas e.g. by means of pressure swing adsorption, thus obtaining substantially pure hydrogen and in addition hydrogen-depleted off gas.
It has now been found that said hydrogen-preparation and -separation steps can be efficiently integrated by employing energy produced by combusting in a combustion zone hydrogen-depleted off gas obtained from the latter step in at least one of the steps of the integrated process itself, e.g. for the compression of oxygen-containing gas required in at least the former step of the process.
The invention therefore relates to a process for producing hydrogen which comprises the following steps: 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, removing hydrogen from product gas obtained from step and applying the hydrogen-depleted off gas obtained from step as fuel for convective heating in step and/or for a gas-turbine driving a feed gas and/or air compressor.
The process according to the present invention will be elucidated hereinafter with the use of the Figures in which various preferred options ,30 of the process have been incorporated without having the 9*
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AUSTRALIA
2 -2intent of limiting said process to those particular embodiments as depicted in the Figures.
Figure 1 relates to a preferred embodimtent of the present process wherein hydrogen-depleted off gas is heat-exchanged with flue gas, before use as fuel gas in a convective reforming zone.
Figure 2 relates to another preferred embodiment 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 and are S carried out in reforming zone of convective reformer in pressure swing adsorption unit and in ccbustion zone 15 respectively.
A hydrocarbonaceous feed, preferably containing normally liquid and/or gaseous hydrocarbons, in particular C1-C, hydrocarbons such as those present in natural gas, is introduced via line into reforming zone together with steam introduced via line In zone step of the present process is suitably carried out 20 at a temperature from 600 to 1600 0 C and a pressure from 2 to 200 bar. The reforming zone preferably comprises catalyst in order to operate said zone at a relatively low temperature from 600 to 1100 IC and at a pressure from 5-50 bar.
The reactor which contains said reforming zone and optionally combustion zone (which may also be spaced apart from the reforming zone and be located outside the reactor) preferably contains internals in order to improve heat exchange between said zones and ensure optimal use of catalyst, if any.
The reactor internals suitably comprise double concentric 'A 30 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- -3containing product gas is subsequently passed, are suitably connected to a product outlet manifold. Avantageously, the combustion gas (having a tenperature of e.g. 900-1200 IC) 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 500-BOO IC) upper part of the reactor. When the concentric tubes are mounted 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 remocved from reforming zone through line In order to produce additional hydrogen, at least part and preferably all of OGG.9 said gas mixture is preferably directed to carbon monoxide 1 conversion zone in which at least part of the carbon monoxide GO 15 present in the gas mixture is catalytically converted in the GO presence of steam at the appropriate carbonmonoxide conversion conditions in one or more steps into carbon dioxide. Conversion zone is suitably maintained at a temperature from 180 to 450 OC a On and a pressure fromn 2 to 200 bar.
Hydrogen-containing product gas obtained from conversion zone and/or reforming zone is directed via line to pressure swing adsorption unit from which a substantially pure 9 hydrogen gas stream is withdrawn via line Unit preferably ccaprises a plurality of vessels containing monlecular 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) j* or a hydrogen-permeable mambrane unit for pressure swing adsorption unit (3 in order to recover hydrogen from the product gas obtained via line 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 employed) obtained from unit is -4-I 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 streamn (13) from combustion zone which gas stream generally has a higher temperature (e.g.
from 150 to 1000 OC) than the off gas. Accordingly, the energy efficiency of the process according to the invention is substantially improved, thus enabling optimnal use of the hydrogen-depleted off-gas in one or more process steps.
The heat exchanged off-gas is directed via line (16) to combustion zonie As the energy-content of the off-gas is in many cases not sufficient to employ said gas as the only fuel source for a combustion zone, additional fuel is preferably provided via line (18).
15In a preferred embodiment of the process according to the invention as depicted in Figure 1 the combustion zone as 000 applied in step provides thermal energy for the reforming reaction zone of step by mrans of convective heat transfer.
A main advantage of such an arrangemrent is that the reaction zone .**will as a result be heated substantially uniformly instead of 20 risking local overheating by a number of burners located in the reaction zone, as ~n previous reforming proc-esses.
00Effluent gas from combustion zone applied in steps and 0 as discussed hereinbefore is suitably (after heat exchange) directed via line (19) to a separate combustion zone (20) to be used as mroderator gas together with fuel gas supplied via line Optionially, part of the heat-exchanged effluent gas is recycled via line (17) to combustion zone Effluent gas emanating from the latter combustion zone (20) is preferably directed via line (30) to turbo-expander (22) wherein the gas is expanded to provide mrechanical energy to com-press oxygen-containing gas air) supplied via line (23) to comnpressor In sm cases sufficient oxygen is present in the expanded effluent gas obtained via. line (27) from turbo-xpander (22) to enable the use of said gas as oxygen-containing gas for the combustion zone (not depicted in Figure 1).
i Turbo-expander compressor (24) and generator (33) are preferably coupled by means of axis and optionally combined with one or more other comarpressors Compressed oxygen-containing gas the gas provided via line is preferably employed in at least one of the steps (a) and of the present process, in particular in combustion zone (4) (via line and via line (29) in combustion zone The use of compressed, and thereby preheated, oxygen-containing gas is preferred in the process according to the invention in order to improve the thermal efficiency of the combustion zone(s) and thus of the entire process.
too.The process and apparatus which are schematically depicted in Figure 2 will be described hereinafter only in so far as features :different from those depicted in Figure 1 are included.
S 15 A significant difference is the use of a catalytic or noncatalytic partial oxidation zone (31) in the embodiment depicted in Figure 2. Such a zone is generally operated at a temperature from 600 to 1600 'C and preferably at a temperature from 1000 to 1500 IC, 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 as well as a combustion zone as employed in step of the process according to the invention.
S" 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 through line (11) is used as fuel gas in combustion zone (20) of a gas turbine instead of in a combustion zone of a reforming apparatus. Expanded effluent gas from turbo-expander (22) is optionally at least partly used in a combustion zone (not depicted in Figure 2).
Oxygen-containing gas is advantageously provided by compressor (24) via line (26) to combustion zone Substantially pure oxygen gas is supplied via line (34) to compressor (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 -6 means and product outlet me~ans communicating with heat exchanger reactor internals, a combustor which is in heat exchange relation with said internals, a pressure swing adsorption unit commtunicating with the product outlet means and having separate hydrogen- and off-gas outlet me~ans, and a gasturbine which is in commmuication with the comb~ustor and/or the off-gas outlet means.
The process according to the invention is illustrated by way of the following Exaple.
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 temiperature of 50 0 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 i introduced via line (35) at a temperature, of 100 OC and a pressure of 48 bar.
The hydrogen-containing synthesis gas obtained via line at 380 0 C and 30 bar is subjected in carbon monnoxide conversion zone to a catalytic steam shift together with steam having a 20 temperature of 380 0 C and a pressure of 61 bar. 2160 tons/day of mainly hydrogen- and carbon dioxide-containing product gas from :zone is led to Pressure Swing Adsorption unit at a temrperature of 40 0 C and a pressure of 26 bar; from unit 200 tons/day of substantially pure hydrogen is obtained at 40 IC and bar in addition to 1960 tons/day offgas containing carbon dioxide and hydrogen as major com~ponents at 40 IC and 1.6 bar. Said offgas is led via line (11) to compressor (15) fran which an outlet gas stream (14) is obtained at a temrperature of 310 0 C and a pressure of 17 bar and combined with 344 tons/day of me-thane-containing gas at a pressure of 51 bar and a temnperature, of 50 IC having a similar compsition as the feed gas to zone (31).
The combined gas stream (16) is directed to a gas turbine comprising ccariustion zone comrpressor (24) and turbo expander In said gas turbine 76 Megawatt electric power is generated by generator (33) of w-hich 18 Megawatt is required for operating
U
-7ccitpressors (15) and leaving 58 Megawatt nett pc~er export, excluding additional electricity generation by neans of waste heat recovery fran the expanded effluent gas stream (27).
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Claims (11)

1. A process for producing hydrogen which comprises the following steps: 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, removing hydrogen from product gas obtained from step and applying the hydrogen-depleted off gas obtained from step as fuel for convective heating in step and/or for a gas-turbine driving a feed gas and/or air compressor.
2. The process as claimed in claim 1 wherein energy produced in step is employed to compress oxygen-containing gas.
3. The process as claimed in claim 2 wherein compressed oxygen- containing gas is employed in at least one of steps and procesc,
4. The as claimed in any one of the preceding claims wherein step is carried out in the presence of steam at a temperature from 600 to 1600 0 C and a pressure from 2 to 200 bar.
The process as claimed in any one of the preceding claims wherein at least part of the carbon monoxide present in the gas mixture obtained from step is catalytically converted in the presence of steam at carbon monoxide conversion conditions into carbon dioxide and hydrogen.
6. The process as claimed in any one of the preceding claims wherein step is carried out by passing hydrogen-containing gas to a pressure swing adsorption zone. 0**e
7. The process as claimed in claim 6 wherein hydrogen-depleted gas obtained from the pressure swing adsorption zone is heat exchanged with effluent gas from a combustion zone.
8. The process as claimed in any one of the preceding claims S wherein effluent gas from the combustion zone applied in step is used as moderator gas for the combustion zone employed in step
9. An apparatus suitable for carrying out the process as claimed in ~any one of claims 1-8 comprising a reactor having a feed inlet means and product outlet means communicating with heat exchanger reactor internals, a combustor which is in heat exchange relation with said internals, a pressure swing adsorption unit communicating with the product outlet means and having separate hydrogen- and off-gas outlet means, and a gas turbine which is in communication with the combustor and/or the off-gas outlet means.
JLH/3664U 'I 9 A process for producing hydrogen, substantially as hereinbefore described with reference to any one of the Examples and/or the accompanying drawings.
11. An apparatus suitable for carrying out the process as claimed in claim 10 and as substantially as hereinbefore described with reference to Figure 1 or Figure 2. DATED this TWENTY-FIRST day of NOVEMBER 1989 Shell Internationale Research Maatschappij B.V. Patent Attorneys for the Applicant SPRUSON FERGUSON 0 @0 9 *00 *i 3LH/3664U
AU82007/87A 1986-12-04 1987-12-02 Process and apparatus for producing hydrogen Ceased AU595405B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8629031 1986-12-04
GB868629031A GB8629031D0 (en) 1986-12-04 1986-12-04 Producing hydrogen

Publications (2)

Publication Number Publication Date
AU8200787A AU8200787A (en) 1988-06-09
AU595405B2 true AU595405B2 (en) 1990-03-29

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AU82007/87A Ceased AU595405B2 (en) 1986-12-04 1987-12-02 Process and apparatus for producing hydrogen

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AU (1) AU595405B2 (en)
CA (1) CA1334124C (en)
DE (1) DE3740865A1 (en)
GB (2) GB8629031D0 (en)
MY (1) MY102725A (en)
NL (1) NL8702706A (en)
NZ (1) NZ222775A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
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
GB2307008A (en) * 1995-11-13 1997-05-14 Fred Moseley Gas turbine engine with two stage combustion
DE10122016A1 (en) * 2001-05-07 2002-11-28 Viessmann Werke Kg Apparatus for generating hydrogen and method for allothermic steam reforming
EP1944268A1 (en) 2006-12-18 2008-07-16 BP Alternative Energy Holdings Limited Process
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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.
ES8300304A1 (en) * 1980-12-09 1982-11-01 Linde Ag Adsorption process and installation for carrying out the process.
EP0115752B1 (en) * 1981-08-07 1986-12-10 Union Carbide Corporation Improved process and apparatus for the production of ammonia
DE3310902A1 (en) * 1983-03-25 1984-09-27 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR HEATING HYDROGEN PRESSURE FROM 200 TO 400 BAR
GB8520892D0 (en) * 1985-08-21 1985-09-25 Ici Plc Ammonia synthesis gas
EP0157480B1 (en) * 1984-03-02 1989-07-26 Imperial Chemical Industries Plc Process for producing ammonia synthesis gas
GB8513997D0 (en) * 1985-06-04 1985-07-10 Ici Plc Technical hydrogen
US4919844A (en) * 1984-08-16 1990-04-24 Air Products And Chemicals, Inc. Enhanced heat transfer reformer and method
WO1986005769A1 (en) * 1985-03-25 1986-10-09 Josef Hubert Schick Process for the production of heat energy from synthetic gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
NZ222775A (en) 1989-07-27
CA1334124C (en) 1995-01-31
GB2198429A (en) 1988-06-15
MY102725A (en) 1992-09-30
GB2198429B (en) 1990-12-19
AU8200787A (en) 1988-06-09
DE3740865A1 (en) 1988-06-16
NL8702706A (en) 1988-07-01
GB8629031D0 (en) 1987-01-14
GB8728276D0 (en) 1988-01-06

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