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WO2013131916A1 - Process for the production of hydrogen - Google Patents

Process for the production of hydrogen Download PDF

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Publication number
WO2013131916A1
WO2013131916A1 PCT/EP2013/054406 EP2013054406W WO2013131916A1 WO 2013131916 A1 WO2013131916 A1 WO 2013131916A1 EP 2013054406 W EP2013054406 W EP 2013054406W WO 2013131916 A1 WO2013131916 A1 WO 2013131916A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
hydrogen
stream
effluent
steam reforming
Prior art date
Application number
PCT/EP2013/054406
Other languages
French (fr)
Inventor
Chang Jie Guo
Shu SHU
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2013131916A1 publication Critical patent/WO2013131916A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/063—Refinery processes
    • C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/146—At least two purification steps in series
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to a process for the production of hydrogen.
  • Hydrogen is an important industrial gas used in oil refining processes and also in chemical processes. It is to be expected that hydrogen will be increasingly
  • downstream pressure swing absorption unit is usually fed to the furnace.
  • a disadvantage of steam reforming is that a relatively large amount of fuel is needed for fuelling the furnace.
  • the hydrocarbonaceous fuel burnt in the furnace produces a flue gas containing carbon dioxide at a relatively low concentration and pressure. Capture of carbon dioxide at such low concentration and pressure is very costly.
  • the present invention relates to a process for the production of hydrogen, comprising
  • hydrocarbon to an endothermic steam reforming reaction by contacting the feedstock, in a steam reforming unit and in the presence of steam, with a steam reforming catalyst under steam reforming conditions, to obtain a steam reforming effluent comprising carbon monoxide, hydrogen and hydrocarbon, and wherein heat needed for the
  • endothermic reaction is provided by a furnace fueled by a fuel gas
  • step e) supplying the hydrogen-rich gas stream obtained in step e) to the furnace as part of the fuel gas; and g) recycling the hydrocarbon-rich gas stream to the steam reforming unit.
  • the hydrogen-rich gas obtained after separating hydrocarbon from the tail gas of the pressure swing absorption unit i.e. the low purity hydrogen stream obtained in step e) , is not sufficient to fuel the
  • the fuel gas fed to the furnace comprises a further gaseous stream with a low carbon content.
  • a further gaseous stream with a low carbon content may for example be a hydrogen-comprising purge gas from a hydroprocessing unit or from a naphtha reforming process.
  • the further gaseous stream may also be a tail gas of a pressure swing absorption unit for hydrogen purification of the effluent of a hydrocarbon partial oxidation
  • the process according to the invention can be advantageously integrated with a hydroprocessing unit, a partial oxidation unit or a naphtha reforming unit.
  • a feedstock comprising a gaseous hydrocarbon is first subjected to an endothermic steam reforming reaction (step a) ) by
  • a steam reforming effluent comprising carbon monoxide, hydrogen and unconverted hydrocarbon is
  • the effluent may comprise further compounds, such as carbon dioxide or unconverted steam.
  • the steam reforming unit comprises a steam reforming reactor and a furnace. The heat needed for the endothermic reaction carried out in the steam reforming reactor is provided by a furnace fueled by a fuel gas. Steam reforming of
  • hydrocarbons is well-known in the art. Any suitable feedstock, steam-to-feedstock ratio, catalyst,
  • Preferred feedstocks are natural gas, methane, ethane, propane, liquefied propane gas (LPG) , biogas, or
  • Natural gas is a particularly preferred feedstock.
  • step b) carbon monoxide in the effluent is reacted in step b) with steam to be converted into carbon dioxide and additional
  • step b) the steam reforming effluent obtained in step a) is subjected to a water-gas-shift reaction to obtain a water-gas-shift effluent comprising carbon dioxide, hydrogen and
  • step c) carbon dioxide is removed from the water-gas-shift effluent to obtain a carbon-dioxide depleted water-gas-shift effluent.
  • An advantage of removing carbon dioxide at this stage is that the carbon dioxide is present at a relatively high pressure and concentration.
  • Any suitable technique known for carbon dioxide removal may be used, for example acid gas removal (AGR) or pressure swing adsorption.
  • AGR acid gas removal
  • AGR carbon dioxide is removed from a gaseous stream by means of an aqueous solution of one or more alkylamines.
  • step d) the carbon-dioxide depleted water-gas-shift effluent is subjected to pressure swing adsorption to obtain a high purity hydrogen stream and a low purity hydrogen stream comprising hydrocarbon.
  • step e) the low purity hydrogen stream is
  • membranes are known in the art and include polymeric membranes such as for example polyimide membranes.
  • the hydrogen-rich gas stream thus obtained is supplied to the furnace of the steam reforming unit as part of the fuel gas (step f) ) .
  • the hydrocarbon-rich gas stream obtained is recycled to the steam reforming unit as part of the feed (step g) ) .
  • desorption is carried out at a pressure slightly higher than 1 bar (absolute) , usually in the range of from 1.1 to 1.5 bar (absolute) .
  • absolute 1 bar
  • absolute absolute
  • a low purity hydrogen stream is obtained at a pressure of just above 1 bar. If such stream is to be separated by means of membrane separation, the stream first needs to be
  • step d) it is advantageous to operate the pressure swing adsorption in step d) at a somewhat higher
  • desorption pressure preferably in the range of from 3 to 4 bar (absolute) .
  • a low purity hydrogen stream is obtained at a pressure in the range of from 3 to 4 bar.
  • separation step e) a hydrocarbon-rich stream with about the same elevated pressure is obtained and less
  • the fuel gas needs to comprise a further fuel in addition to the hydrogen-rich gas stream obtained in step e) .
  • a further fuel has a low carbon content. More preferably the carbon content of the further fuel is such that the carbon dioxide
  • concentration in flue gas obtained after burning the fuel gas in the furnace is below 10 vol%, even more preferably below 5 vol%.
  • the further gaseous stream comprising less than 10 mole % carbon atoms based on the total moles of atoms in the further gaseous stream, more preferably less than 5 mole %, even more preferably less than 1 mole %.
  • Any low carbon fuel stream may be used, for example low purity hydrogen streams that are produced in a refinery such as a hydrogen-comprising purge gas from a
  • hydroprocessing unit or from a naphtha reforming unit, tail gas of a pressure swing absorption unit, low pressure hydrogen-rich streams from a chloralkali process, from coke ovens, or from methanol, ammonia or ethylene
  • the fuel gas fuelling the furnace Preferably, the fuel gas fuelling the furnace
  • step e essentially consists of the hydrogen-rich gas stream obtained in step e) and a further gaseous stream
  • the further gaseous stream is a hydrogen- comprising purge gas from a hydroprocessing unit.
  • a hydroprocessing process such as hydrodesulphurisation, hydrodenitrification, hydrocracking or hydroisomerisation, a hydrocarbonaceous feedstock is contacted, in the
  • hydroprocessing effluent is separated into a liquid product stream and a hydroprocessing purge gas comprising purge hydrogen and purge hydrocarbons .
  • Such hydroprocessing purge gas may suitably be supplied to the furnace of the steam reforming unit as part of the fuel gas.
  • at least part of the purge hydrocarbons are removed from the purge gas prior to supplying the purge gas to the fuel.
  • Such removal may be done by any suitable means known in the art, preferably by means of membrane separation or pressure swing adsorption. Membrane separation is particularly preferred.
  • a hydrocarbon-rich gas stream is obtained that is preferably supplied to the steam reforming unit as part of the feed.
  • hydrocarbon-rich gas stream comprises
  • the process according to the invention is an integrated steam reforming and hydroprocessing process.
  • the process comprises in addition to steps a) to g) as described hereinabove, the following steps:
  • step d) In order to increase the pressure of the low purity hydrogen stream comprising hydrocarbon obtained in step d) , i.e. the tail gas of the pressure swing absorption downstream of the steam reforming unit, it may be
  • hydroprocessing unit in order to provide part of the hydrogen needed in such unit.
  • at least part of the hydrogen- comprising purge gas is used as fuel in the furnace of the steam reforming unit.
  • part of the high purity hydrogen stream obtained in step d) i.e. the high purity hydrogen stream from the pressure swing adsorption unit, to the hydroprocessing unit.
  • external hydrogen may be supplied to the hydroprocessing unit, preferably high-purity external hydrogen .
  • the process for the production of hydrogen according to the invention may be a process integrating hydrogen production by steam reforming and hydrogen production by partial oxidation of a
  • the process comprises in addition to steps a) to g) as described hereinabove, the following steps:
  • Step k) may be partial oxidation of any suitable hydrocarbonaceous feedstock, for example biomass, coal or a hydrocarbon stream such as for example natural gas, LPG, or naphtha. Any suitable process conditions may be used in step k) . Such process conditions are well-known in the art.
  • an effluent comprising carbon monoxide and hydrogen is obtained. Typically, the effluent will also comprises some carbon dioxide.
  • step 1) the partial oxidation effluent is
  • a water-gas-shift reaction In the water-gas- shift reaction, carbon monoxide in the effluent is reacted with steam in the presence of a suitable water-gas-shift reaction catalyst to form carbon monoxide and further hydrogen.
  • a second water-gas-shift effluent is obtained comprising carbon dioxide and hydrogen.
  • step m) carbon dioxide is removed from the second water-gas shift effluent to obtain a second carbon-dioxide depleted water-gas-shift effluent.
  • This step may be carried out in the same way as described hereinabove for step c) .
  • step n) the second carbon-dioxide depleted water- gas-shift effluent is subjected to pressure swing
  • the second high purity hydrogen stream is supplied to the furnace as the further gaseous stream in step o) .
  • the first and the second high purity hydrogen streams are preferably combined to form a single high purity hydrogen product stream.
  • the further gaseous stream is a
  • purge gas from a naphtha reforming unit also known as catalytic reforming.
  • a naphtha reforming process a high-octane gasoline (reformate) is formed and a significant amount of hydrogen is formed as by-product.
  • the hydrogen is removed from the process as purge gas and may be advantageously used, optionally after removal of any purge hydrocarbons, as further gaseous stream in the process according to the invention. If purge hydrocarbons are removed from the purge gas, such removal may be done by any suitable means known in the art, preferably by means of membrane separation or pressure swing adsorption, more preferably by membrane separation. In case of such removal of purge hydrocarbons, a
  • hydrocarbon-rich gas stream is obtained that is preferably supplied to the steam reforming unit as part of the feed.
  • hydrocarbon-rich gas stream comprises
  • sulphur-containing compounds it is preferably subjected to desulphurisation prior to supplying it to the steam reforming unit.
  • Natural gas is fed via line 1 to desulphurisation unit 2 before it is supplied via line 3 to stream reforming unit 4.
  • Steam reforming unit 4 comprises a steam reforming reactor 5 and a furnace 6 for providing heat for the endothermic steam reforming reaction carried out in reactor 5. Steam is supplied to reactor 5 via line 7.
  • Furnace 6 is fuelled by a fuel gas that is supplied via line 8. Oxidant is fed to the furnace via line 9. Flue gas is withdrawn from the furnace via line 10.
  • natural gas is steam reformed to obtain a steam reforming effluent comprising carbon dioxide, carbon monoxide, hydrogen and unconverted hydrocarbon.
  • the effluent further comprises unconverted steam.
  • the effluent is withdrawn via line 11 and supplied to water-gas-shift reaction zone 12. Additional steam is supplied via line 13.
  • zone 12 carbon monoxide and steam are reacted to form carbon dioxide and additional hydrogen.
  • Water-gas-shift effluent comprising carbon dioxide, hydrogen and unconverted hydrocarbon is supplied via line 14 to amine solvent extraction unit 15 for carbon dioxide removal.
  • Carbon dioxide is removed from the process via line 16 and a carbon-dioxide depleted water-gas-shift effluent is supplied via line 17 to pressure swing absorption unit 18 for hydrogen purification.
  • a high purity hydrogen stream is obtained and withdrawn via line 19.
  • a tail gas is obtained and withdrawn via line 19.
  • hydrocarbon and hydrogen is withdrawn via line 20 and supplied to membrane separation unit 21 wherein it is separated into a hydrocarbon-rich gas stream and a hydrogen-rich gas stream.
  • the hydrogen-rich gas stream is supplied to furnace 6 via line 22 as part of the fuel gas.
  • the hydrocarbon-rich gas stream is recycled to the
  • a hydrocarbonaceous feedstock mainly comprising C5 to Ci5 hydrocarbons and hydrogen are fed to hydrocracking reactor 30 via lines 31 and 32, respectively.
  • Effluent of reactor 30 is fed via line 33 to gas/liquid separator 34, wherein it is separated into a liquid product stream that is withdrawn via line 35 and a purge gas stream comprising purge hydrogen and purge hydrocarbons .
  • the purge gas stream is supplied via line 36 to membrane separation unit
  • Part of the hydrogen-rich purge gas is supplied to furnace 6 via line 40 as part of the fuel gas. Another part is recycled to hydrocracking reactor 30 via line 41.
  • part of the purge gas stream comprising purge hydrogen and purge hydrocarbons that is obtained after gas-liquid separation in separator 34 is mixed with the tail gas of pressure swing absorption unit 18 (dotted line 42 in Figure 1) in order to increase the pressure of the tail gas and thus avoiding the need of a compressor (not shown) in line 20 or the need to operate pressure swing absorption unit 18 at a relatively high desorption pressure in order to provide the driving force for
  • Natural gas and oxygen are fed to partial oxidation unit 50 via lines 51 and 52, respectively.
  • natural gas is converted into synthesis gas, i.e. a gaseous stream comprising carbon monoxide and hydrogen.
  • the synthesis gas may comprise some carbon dioxide, but will comprise no or a negligible amounts of unconverted hydrocarbon.
  • Synthesis gas is supplied via line 53 to water-gas-shift reaction zone 54. Steam is supplied to zone 54 via line 55. In zone 54, carbon monoxide and steam are catalytically converted into carbon dioxide and additional hydrogen.
  • a water-gas-shift effluent is obtained comprising carbon dioxide and
  • the effluent is supplied via line 56 to acid gas removal unit 57 wherein carbon dioxide is removed from the effluent by means of an amine solvent. Carbon dioxide is withdrawn via line 58 and combined with carbon dioxide from acid gas removal unit 15.
  • the carbon-dioxide depleted water-gas-shift effluent thus obtained is supplied via line 59 to pressure swing absorption unit 60 for hydrogen purification.
  • a second high purity hydrogen stream is obtained and withdrawn via line 61 and combined with the first high purity hydrogen stream in line 19 to obtain a combined high purity hydrogen product stream 62.
  • a tail gas comprising hydrogen in low purity is withdrawn from unit 60 via line 63 and supplied to furnace 6 as part of the fuel gas.

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Abstract

The invention relates to process for the production of hydrogen, comprising • a) subjecting a feedstock comprising a gaseous hydrocarbon to an endothermic steam reforming reaction by contacting the feedstock, in a steam reforming unit (4) and in the presence of steam (7), to obtain a steam reforming effluent comprising carbon monoxide, hydrogen and hydrocarbon, and wherein heat needed for the endothermic reaction is provided by a furnace fueled by a fuel gas; • b) subjecting the steam reforming effluent to a water-gas-shift reaction (12) to obtain a water-gas-shift effluent comprising carbon dioxide, hydrogen and hydrocarbon; • c) removing carbon dioxide from the water-gas-shift effluent (15) to obtain a carbon-dioxide depleted water-gas-shift effluent (17); • d) subjecting the carbon-dioxide depleted water-gas-shift effluent to pressure swing adsorption (18) to obtain a high purity hydrogen stream (19) and a low purity hydrogen stream comprising hydrocarbon (20); • e) separating the low purity hydrogen stream in a hydrocarbon-rich gas stream and a hydrogen-rich gas streamn (22) by means of membrane separation (21); • f) supplying the hydrogen-rich gas stream obtained in step e) to the furnace (6) as part of the fuel gas; and • g) recycling the hydrocarbon-rich gas stream to the steam reforming unit.

Description

PROCESS FOR THE PRODUCTION OF HYDROGEN
Field of the invention
The invention relates to a process for the production of hydrogen.
Background to the invention
Hydrogen is an important industrial gas used in oil refining processes and also in chemical processes. It is to be expected that hydrogen will be increasingly
important as energy carrier, in particular in the field of transportation.
Most hydrogen is currently produced via steam
reforming of natural gas due to the relatively low costs of the process. Steam reforming is a strongly endothermic process. The heat needed for the process is typically provided by burning part of the natural gas feed in a furnace. Also recycle methane in tail gas from a
downstream pressure swing absorption unit is usually fed to the furnace. A disadvantage of steam reforming is that a relatively large amount of fuel is needed for fuelling the furnace. Moreover, the hydrocarbonaceous fuel burnt in the furnace produces a flue gas containing carbon dioxide at a relatively low concentration and pressure. Capture of carbon dioxide at such low concentration and pressure is very costly.
Summary of the invention
A novel process has been found that avoids the
disadvantages of the known steam reforming processes, in particular avoids the production of large amounts of carbon dioxide that cannot be captured. In the novel process, carbon dioxide is removed from water-gas shifted steam reforming effluent whilst it is at relatively high pressure and hydrocarbon is removed from the tail gas of a downstream pressure swing absorption unit before such tail gas is fed to the furnace. The hydrocarbon thus removed is recycled as feed to the steam reforming process.
Accordingly, the present invention relates to a process for the production of hydrogen, comprising
a) subjecting a feedstock comprising a gaseous
hydrocarbon to an endothermic steam reforming reaction by contacting the feedstock, in a steam reforming unit and in the presence of steam, with a steam reforming catalyst under steam reforming conditions, to obtain a steam reforming effluent comprising carbon monoxide, hydrogen and hydrocarbon, and wherein heat needed for the
endothermic reaction is provided by a furnace fueled by a fuel gas;
b) subjecting the steam reforming effluent to a water- gas-shift reaction to obtain a water-gas-shift effluent comprising carbon dioxide, hydrogen and hydrocarbon;
c) removing carbon dioxide from the water-gas-shift effluent to obtain a carbon-dioxide depleted water-gas- shift effluent;
d) subjecting the carbon-dioxide depleted water-gas-shift effluent to pressure swing adsorption to obtain a high purity hydrogen stream and a low purity hydrogen stream comprising hydrocarbon;
e) separating the low purity hydrogen stream in a
hydrocarbon-rich gas stream and a hydrogen-rich gas stream by means of membrane separation;
f) supplying the hydrogen-rich gas stream obtained in step e) to the furnace as part of the fuel gas; and g) recycling the hydrocarbon-rich gas stream to the steam reforming unit. An important advantage of the process according to the invention is that fuel that is low in carbon is fed to the furnace. Further, the carbon dioxide can be captured at a point in the process where it is at a relatively high pressure, thus significantly reducing costs for carbon capture .
The hydrogen-rich gas obtained after separating hydrocarbon from the tail gas of the pressure swing absorption unit, i.e. the low purity hydrogen stream obtained in step e) , is not sufficient to fuel the
furnace. Preferably, in order to increase the benefit of the process according to the invention, the fuel gas fed to the furnace comprises a further gaseous stream with a low carbon content. Such low carbon further gaseous stream may for example be a hydrogen-comprising purge gas from a hydroprocessing unit or from a naphtha reforming process. The further gaseous stream may also be a tail gas of a pressure swing absorption unit for hydrogen purification of the effluent of a hydrocarbon partial oxidation
effluent, such as a gasifier for hydrocarbons, biomass or coal. Thus, the process according to the invention can be advantageously integrated with a hydroprocessing unit, a partial oxidation unit or a naphtha reforming unit.
Brief description of the drawings
In Figure 1, a process according to the invention integrating a hydrocracking process and a steam reforming process is schematically shown.
In Figure 2, a process according to the invention integrating a natural gas partial oxidation process and a steam reforming process is schematically shown.
Detailed description of the invention
In the process according to the invention, a feedstock comprising a gaseous hydrocarbon is first subjected to an endothermic steam reforming reaction (step a) ) by
contacting the feedstock and steam in a steam reforming unit with a steam reforming catalyst under steam reforming conditions. A steam reforming effluent comprising carbon monoxide, hydrogen and unconverted hydrocarbon is
obtained. The effluent may comprise further compounds, such as carbon dioxide or unconverted steam. The steam reforming unit comprises a steam reforming reactor and a furnace. The heat needed for the endothermic reaction carried out in the steam reforming reactor is provided by a furnace fueled by a fuel gas. Steam reforming of
hydrocarbons is well-known in the art. Any suitable feedstock, steam-to-feedstock ratio, catalyst,
temperature, pressure and reactor configuration may be used.
Preferred feedstocks are natural gas, methane, ethane, propane, liquefied propane gas (LPG) , biogas, or
combinations of two or more thereof. Natural gas is a particularly preferred feedstock.
In order to increase the hydrogen yield, carbon monoxide in the effluent is reacted in step b) with steam to be converted into carbon dioxide and additional
hydrogen (water-gas-shift reaction) . The steam is
preferably a combination of excess steam present in the steam reforming effluent and additional steam added to the steam reforming effluent. Thus, in step b) the steam reforming effluent obtained in step a) is subjected to a water-gas-shift reaction to obtain a water-gas-shift effluent comprising carbon dioxide, hydrogen and
hydrocarbon. The water-gas-shift reaction is well known in the art. Any suitable reaction conditions and catalysts known in the art may be applied. In subsequent step c) , carbon dioxide is removed from the water-gas-shift effluent to obtain a carbon-dioxide depleted water-gas-shift effluent. An advantage of removing carbon dioxide at this stage is that the carbon dioxide is present at a relatively high pressure and concentration. Any suitable technique known for carbon dioxide removal may be used, for example acid gas removal (AGR) or pressure swing adsorption. In AGR, carbon dioxide is removed from a gaseous stream by means of an aqueous solution of one or more alkylamines.
In subsequent step d) , the carbon-dioxide depleted water-gas-shift effluent is subjected to pressure swing adsorption to obtain a high purity hydrogen stream and a low purity hydrogen stream comprising hydrocarbon.
Pressure swing adsorption for hydrogen purification is well-known in the art.
In step e) , the low purity hydrogen stream is
separated into a hydrocarbon-rich gas stream and a
hydrogen-rich gas stream by means of membrane separation. Any membrane known to selectively permeate hydrogen whilst retaining hydrocarbons may be suitably used. Such
membranes are known in the art and include polymeric membranes such as for example polyimide membranes.
The hydrogen-rich gas stream thus obtained is supplied to the furnace of the steam reforming unit as part of the fuel gas (step f) ) . The hydrocarbon-rich gas stream obtained is recycled to the steam reforming unit as part of the feed (step g) ) .
Typically, in a pressure swing adsorption unit for hydrogen purification, desorption is carried out at a pressure slightly higher than 1 bar (absolute) , usually in the range of from 1.1 to 1.5 bar (absolute) . Thus, a low purity hydrogen stream is obtained at a pressure of just above 1 bar. If such stream is to be separated by means of membrane separation, the stream first needs to be
compressed in order to provide a driving force for the membrane separation. In the process according to the invention, it is advantageous to operate the pressure swing adsorption in step d) at a somewhat higher
desorption pressure, preferably in the range of from 3 to 4 bar (absolute) . Thus, a low purity hydrogen stream is obtained at a pressure in the range of from 3 to 4 bar. In separation step e) , a hydrocarbon-rich stream with about the same elevated pressure is obtained and less
compression is needed prior to recycling this stream to the steam reforming unit.
In order to provide sufficient fuel to the furnace of the steam reforming unit for providing the heat needed for the endothermic reaction, the fuel gas needs to comprise a further fuel in addition to the hydrogen-rich gas stream obtained in step e) . Preferably, such further fuel has a low carbon content. More preferably the carbon content of the further fuel is such that the carbon dioxide
concentration in flue gas obtained after burning the fuel gas in the furnace is below 10 vol%, even more preferably below 5 vol%.
Preferably, the further gaseous stream comprising less than 10 mole % carbon atoms based on the total moles of atoms in the further gaseous stream, more preferably less than 5 mole %, even more preferably less than 1 mole %. Any low carbon fuel stream may be used, for example low purity hydrogen streams that are produced in a refinery such as a hydrogen-comprising purge gas from a
hydroprocessing unit or from a naphtha reforming unit, tail gas of a pressure swing absorption unit, low pressure hydrogen-rich streams from a chloralkali process, from coke ovens, or from methanol, ammonia or ethylene
manufacturing facilities.
Preferably, the fuel gas fuelling the furnace
essentially consists of the hydrogen-rich gas stream obtained in step e) and a further gaseous stream
comprising less than 10 mole % carbon atoms.
Preferably, the further gaseous stream is a hydrogen- comprising purge gas from a hydroprocessing unit. In a hydroprocessing process, such as hydrodesulphurisation, hydrodenitrification, hydrocracking or hydroisomerisation, a hydrocarbonaceous feedstock is contacted, in the
presence of hydrogen with a hydroprocessing catalyst under hydroprocessing conditions to obtain a hydroprocessing effluent. The effluent is separated into a liquid product stream and a hydroprocessing purge gas comprising purge hydrogen and purge hydrocarbons .
Such hydroprocessing purge gas, optionally after removal of at least part of the purge hydrocarbons, may suitably be supplied to the furnace of the steam reforming unit as part of the fuel gas. Preferably, at least part of the purge hydrocarbons are removed from the purge gas prior to supplying the purge gas to the fuel. Such removal may be done by any suitable means known in the art, preferably by means of membrane separation or pressure swing adsorption. Membrane separation is particularly preferred. In case of such removal of hydrocarbons, a hydrocarbon-rich gas stream is obtained that is preferably supplied to the steam reforming unit as part of the feed. In case such hydrocarbon-rich gas stream comprises
sulphur-containing compounds, it is preferably subjected to desulphurisation prior to supplying it to the steam reforming unit. Preferably, the process according to the invention is an integrated steam reforming and hydroprocessing process. In such integrated process, the process comprises in addition to steps a) to g) as described hereinabove, the following steps:
h) contacting, in a hydroprocessing unit, a
hydrocarbonaceous stream in the presence of hydrogen with a hydroprocessing catalyst under hydroprocessing
conditions to obtain a hydroprocessing effluent;
i) separating the hydroprocessing effluent into a liquid product stream and a hydroprocessing purge gas comprising purge hydrogen and purged hydrocarbons; and
j) supplying at least part of the hydroprocessing purge gas, optionally after removal of at least part of the purge hydrocarbons, to the furnace as part of the fuel gas .
In order to increase the pressure of the low purity hydrogen stream comprising hydrocarbon obtained in step d) , i.e. the tail gas of the pressure swing absorption downstream of the steam reforming unit, it may be
advantageous to mix part of the hydroprocessing purge gas comprising purge hydrogen and purge hydrocarbons, i.e. prior to any removal of hydrocarbon, with the low purity hydrogen stream. In this way, the pressure of the low purity hydrogen stream is increased, thus providing driving force for membrane separation step e) without the need for compression.
In prior art hydroprocessing processes, hydrogen- comprising purge gas is typically recycled to the
hydroprocessing unit in order to provide part of the hydrogen needed in such unit. In the integrated process according to the invention, at least part of the hydrogen- comprising purge gas is used as fuel in the furnace of the steam reforming unit. In order to supply sufficient hydrogen to the hydroprocessing unit, it is preferred to supply part of the high purity hydrogen stream obtained in step d) , i.e. the high purity hydrogen stream from the pressure swing adsorption unit, to the hydroprocessing unit. Alternatively, external hydrogen may be supplied to the hydroprocessing unit, preferably high-purity external hydrogen .
Alternatively, the process for the production of hydrogen according to the invention may be a process integrating hydrogen production by steam reforming and hydrogen production by partial oxidation of a
hydrocarbonaceous feedstock. In such integrated process, the process comprises in addition to steps a) to g) as described hereinabove, the following steps:
k) subjecting a hydrocarbonaceous feedstock to partial oxidation to obtain a partial oxidation effluent
comprising carbon monoxide and hydrogen;
1) subjecting the partial oxidation effluent to a water- gas-shift reaction to obtain a second water-gas-shift effluent comprising carbon dioxide and hydrogen;
m) removing carbon dioxide from the second water-gas- shift effluent to obtain a second carbon-dioxide depleted water-gas shift effluent;
n) subjecting the second carbon-dioxide depleted water- gas-shift effluent to pressure swing adsorption to obtain a second high purity hydrogen stream and a second low purity hydrogen stream; and
o) supplying the second high purity hydrogen stream to the furnace as the further gaseous stream.
Step k) may be partial oxidation of any suitable hydrocarbonaceous feedstock, for example biomass, coal or a hydrocarbon stream such as for example natural gas, LPG, or naphtha. Any suitable process conditions may be used in step k) . Such process conditions are well-known in the art. In step k) , an effluent comprising carbon monoxide and hydrogen is obtained. Typically, the effluent will also comprises some carbon dioxide.
In step 1) , the partial oxidation effluent is
subjected to a water-gas-shift reaction. In the water-gas- shift reaction, carbon monoxide in the effluent is reacted with steam in the presence of a suitable water-gas-shift reaction catalyst to form carbon monoxide and further hydrogen. Thus, a second water-gas-shift effluent is obtained comprising carbon dioxide and hydrogen.
In step m) , carbon dioxide is removed from the second water-gas shift effluent to obtain a second carbon-dioxide depleted water-gas-shift effluent. This step may be carried out in the same way as described hereinabove for step c) .
In step n) , the second carbon-dioxide depleted water- gas-shift effluent is subjected to pressure swing
adsorption to obtain a second high purity hydrogen stream and a second low purity hydrogen stream. The second high purity hydrogen stream is supplied to the furnace as the further gaseous stream in step o) .
The first and the second high purity hydrogen streams are preferably combined to form a single high purity hydrogen product stream.
In an alternative embodiment of the process according to the invention, the further gaseous stream is a
hydrogen-comprising purge gas from a naphtha reforming unit also known as catalytic reforming. In a naphtha reforming process, a high-octane gasoline (reformate) is formed and a significant amount of hydrogen is formed as by-product. The hydrogen is removed from the process as purge gas and may be advantageously used, optionally after removal of any purge hydrocarbons, as further gaseous stream in the process according to the invention. If purge hydrocarbons are removed from the purge gas, such removal may be done by any suitable means known in the art, preferably by means of membrane separation or pressure swing adsorption, more preferably by membrane separation. In case of such removal of purge hydrocarbons, a
hydrocarbon-rich gas stream is obtained that is preferably supplied to the steam reforming unit as part of the feed.
In case such hydrocarbon-rich gas stream comprises
sulphur-containing compounds, it is preferably subjected to desulphurisation prior to supplying it to the steam reforming unit.
Detailed description of the drawings
In Figure 1, a process according to the invention integrating a hydrocracking process and a steam reforming process is schematically shown.
Natural gas is fed via line 1 to desulphurisation unit 2 before it is supplied via line 3 to stream reforming unit 4. Steam reforming unit 4 comprises a steam reforming reactor 5 and a furnace 6 for providing heat for the endothermic steam reforming reaction carried out in reactor 5. Steam is supplied to reactor 5 via line 7.
Furnace 6 is fuelled by a fuel gas that is supplied via line 8. Oxidant is fed to the furnace via line 9. Flue gas is withdrawn from the furnace via line 10. In reactor 5, natural gas is steam reformed to obtain a steam reforming effluent comprising carbon dioxide, carbon monoxide, hydrogen and unconverted hydrocarbon. The effluent further comprises unconverted steam. The effluent is withdrawn via line 11 and supplied to water-gas-shift reaction zone 12. Additional steam is supplied via line 13. In zone 12, carbon monoxide and steam are reacted to form carbon dioxide and additional hydrogen. Water-gas-shift effluent comprising carbon dioxide, hydrogen and unconverted hydrocarbon is supplied via line 14 to amine solvent extraction unit 15 for carbon dioxide removal. Carbon dioxide is removed from the process via line 16 and a carbon-dioxide depleted water-gas-shift effluent is supplied via line 17 to pressure swing absorption unit 18 for hydrogen purification. A high purity hydrogen stream is obtained and withdrawn via line 19. A tail gas
comprising hydrocarbon and hydrogen is withdrawn via line 20 and supplied to membrane separation unit 21 wherein it is separated into a hydrocarbon-rich gas stream and a hydrogen-rich gas stream. The hydrogen-rich gas stream is supplied to furnace 6 via line 22 as part of the fuel gas.
The hydrocarbon-rich gas stream is recycled to the
reaction zone 5 of steam reforming unit 4.
A hydrocarbonaceous feedstock mainly comprising C5 to Ci5 hydrocarbons and hydrogen are fed to hydrocracking reactor 30 via lines 31 and 32, respectively. Effluent of reactor 30 is fed via line 33 to gas/liquid separator 34, wherein it is separated into a liquid product stream that is withdrawn via line 35 and a purge gas stream comprising purge hydrogen and purge hydrocarbons . The purge gas stream is supplied via line 36 to membrane separation unit
37 and separated into a hydrogen-rich purge gas that is withdrawn via line 38 and a hydrocarbon-rich purge gas that is withdrawn via line 39. The hydrogen-rich purge is recycled, after compression (not shown) to steam reforming reactor 5 via desulphurization unit 2.
Part of the hydrogen-rich purge gas is supplied to furnace 6 via line 40 as part of the fuel gas. Another part is recycled to hydrocracking reactor 30 via line 41. Optionally, part of the purge gas stream comprising purge hydrogen and purge hydrocarbons that is obtained after gas-liquid separation in separator 34 is mixed with the tail gas of pressure swing absorption unit 18 (dotted line 42 in Figure 1) in order to increase the pressure of the tail gas and thus avoiding the need of a compressor (not shown) in line 20 or the need to operate pressure swing absorption unit 18 at a relatively high desorption pressure in order to provide the driving force for
membrane separation unit 21.
In Figure 2, a process according to the invention integrating a natural gas partial oxidation process and a steam reforming process is schematically shown. Reference numbers in Figure 2 corresponding to reference numbers in Figure 1, have the same meaning as in Figure 1.
Natural gas and oxygen are fed to partial oxidation unit 50 via lines 51 and 52, respectively. In partial oxidation unit 50, natural gas is converted into synthesis gas, i.e. a gaseous stream comprising carbon monoxide and hydrogen. The synthesis gas may comprise some carbon dioxide, but will comprise no or a negligible amounts of unconverted hydrocarbon. Synthesis gas is supplied via line 53 to water-gas-shift reaction zone 54. Steam is supplied to zone 54 via line 55. In zone 54, carbon monoxide and steam are catalytically converted into carbon dioxide and additional hydrogen. Thus, a water-gas-shift effluent is obtained comprising carbon dioxide and
hydrogen. The effluent is supplied via line 56 to acid gas removal unit 57 wherein carbon dioxide is removed from the effluent by means of an amine solvent. Carbon dioxide is withdrawn via line 58 and combined with carbon dioxide from acid gas removal unit 15. The carbon-dioxide depleted water-gas-shift effluent thus obtained is supplied via line 59 to pressure swing absorption unit 60 for hydrogen purification. A second high purity hydrogen stream is obtained and withdrawn via line 61 and combined with the first high purity hydrogen stream in line 19 to obtain a combined high purity hydrogen product stream 62. A tail gas comprising hydrogen in low purity is withdrawn from unit 60 via line 63 and supplied to furnace 6 as part of the fuel gas.

Claims

C L A I M S
1. A process for the production of hydrogen, comprising a) subjecting a feedstock comprising a gaseous
hydrocarbon to an endothermic steam reforming reaction by contacting the feedstock, in a steam reforming unit and in the presence of steam, with a steam reforming catalyst under steam reforming conditions, to obtain a steam reforming effluent comprising carbon monoxide, hydrogen and hydrocarbon, and wherein heat needed for the
endothermic reaction is provided by a furnace fueled by a fuel gas;
b) subjecting the steam reforming effluent to a water-gas shift reaction to obtain a water-gas-shift effluent comprising carbon dioxide, hydrogen and hydrocarbon;
c) removing carbon dioxide from the water-gas-shift effluent to obtain a carbon-dioxide depleted water-gas- shift effluent;
d) subjecting the carbon-dioxide depleted water-gas-shift effluent to pressure swing adsorption to obtain a high purity hydrogen stream and a low purity hydrogen stream comprising hydrocarbon;
e) separating the low purity hydrogen stream in a
hydrocarbon-rich gas stream and a hydrogen-rich gas stream by means of membrane separation;
f) supplying the hydrogen-rich gas stream obtained in step e) to the furnace as part of the fuel gas; and g) recycling the hydrocarbon-rich gas stream to the steam reforming unit.
2. A process according to claim 1, wherein in step d) pressure swing adsorption is operated at a desorption pressure in the range of from 3 to 4 bar (absolute) .
3. A process according to claim 1 or 2, wherein the fuel gas comprises the hydrogen-rich gas stream obtained in step e) and a further gaseous stream comprising less than 10 mole % carbon atoms based on the total moles of atoms in the further gaseous stream.
4. A process according to claim 3, wherein the fuel gas comprises the hydrogen-rich gas stream obtained in step e) and a further gaseous stream comprising less than 5 mole % carbon atoms based on the total moles of atoms in the further gaseous stream.
5. A process according to claim 3 or 4, wherein the fuel gas essentially consists of the hydrogen-rich gas stream obtained in step e) and the further gaseous stream.
6. A process according to any one of claims 3 to 5, wherein the further gaseous stream is a hydrogen- comprising purge gas from a hydroprocessing unit.
7. A process according to claim 6, wherein the process is an integrated steam reforming and hydroprocessing process, the process further comprising:
h) contacting, in a hydroprocessing unit, a
hydrocarbonaceous stream in the presence of hydrogen with a hydroprocessing catalyst under hydroprocessing
conditions to obtain a hydroprocessing effluent;
i) separating the hydroprocessing effluent into a liquid product stream and a hydroprocessing purge gas comprising purge hydrogen and purge hydrocarbons; and
j) supplying at least part of the hydroprocessing purge gas, optionally after removal of at least part of the purge hydrocarbons, to the furnace as part of the fuel gas .
8. A process according to claim 7, wherein at least part of the purge hydrocarbons are removed from the
hydroprocessing purge gas and the purge hydrocarbons thus removed are recycled to the steam reforming unit.
9. A process according to claim 7 or 8, wherein part of the hydroprocessing purge gas comprising purge hydrogen and purge hydrocarbons is mixed with the low purity hydrogen stream comprising hydrocarbon obtained in step d) .
10. A process according to any one of claims 6 to 9, wherein the hydroprocessing unit is selected from the group consisting of a hydrodesulphurisation unit, a hydrodenitrification unit, a hydrocracking unit, and a hydroisomerisation unit.
11. A process according to any one of claims 6 to 10, wherein part of the high purity hydrogen stream obtained in step d) is recycled to the hydroprocessing unit.
12. A process according to any one of claims 3 to 5, wherein the process further comprises:
k) subjecting a hydrocarbonaceous feedstock to partial oxidation to obtain a partial oxidation effluent
comprising carbon monoxide and hydrogen;
1) subjecting the partial oxidation effluent to a water- gas-shift reaction to obtain a second water-gas-shift effluent comprising carbon dioxide and hydrogen;
m) removing carbon dioxide from the second water-gas- shift effluent to obtain a second carbon-dioxide depleted water-gas-shift effluent;
n) subjecting the second carbon-dioxide depleted water- gas-shift effluent to pressure swing adsorption to obtain a second high purity hydrogen stream and a second low purity hydrogen stream; and o) supplying the second high purity hydrogen stream the furnace as the further gaseous stream.
13. A process according to any one of claims 3 to 5, wherein the further gaseous stream is a hydrogen- comprising purge gas from a naphtha reforming unit.
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