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EP-4739621-A1 - PLANT AND PROCESS FOR PRODUCING HYDROGEN FROM HYDROCARBONS WITH REDUCED CO2 EMISSIONS

EP4739621A1EP 4739621 A1EP4739621 A1EP 4739621A1EP-4739621-A1

Abstract

Hydrogen production plant comprising: - At least one reformer (30) for converting a stream comprising a hydrocarbon feedstock (1) through conversion with steam rich in oxygen (02) into a reformed gas stream (32) comprising hydrogen, carbon monoxide, carbon dioxide and at least one hydrocarbon as impurity, said reformer (30) comprising exothermic, oxygen-based autothermal (ATR) or partial oxidation (POX) reforming and a heat recovery section (40), - A fired heater (90) configured to preheat the stream comprising the hydrocarbon feedstock (1) before entry into the at least one reformer (30), - At least one water gas shift (WGS) reactor (50) for converting the carbon monoxide of the reformed gas stream (32) into a shifted gas stream (51) containing additional carbon dioxide and hydrogen, - A Hydrogen and Carbon Dioxide Recovery Unit (60) located downstream of the WGS reactor (50) and configured to remove carbon dioxide and hydrogen from the shifted gas stream (51), and to produce a first product stream (61) enriched in carbon dioxide and a second product stream (62) enriched in hydrogen, a waste stream (63) depleted in both hydrogen and carbon dioxide, - A compressor (70) for compressing a part (65) of the waste gas stream (63) from hydrogen and carbon dioxide recovery unit (60) into a compressed gas stream (71), - A membrane separation system (80) selective for the permeation of hydrogen configured to be fed with the compressed gas stream (71) and to produce a hydrogen- enriched permeate (82) stream and a hydrocarbon-enriched retentate (81) stream, - A passageway for feeding at least part of the hydrogen-enriched permeate (82) to the fired heater (90) to be used as a low-carbon fuel by the fired heater (90), and - A passageway for recycling the hydrocarbon-enriched retentate (81) to the hydrocarbon feed (1) via a pipeline (83) and/or to the reformer (30) via the pipeline (85) and/or to the inlet to the water gas shift reactor (50) via the pipeline (87).

Inventors

  • ELSEVIERS, WIM FRANS
  • RIEGMAN, Jan-Jaap
  • WILLEM, Hesselink
  • ALAEZ, Sonia Laura Gomez
  • PITCHER, MATTHEW BOWERS

Assignees

  • Technip Energies France

Dates

Publication Date
20260513
Application Date
20240704

Claims (17)

  1. 1. A Hydrogen production plant comprising : At least one reformer (30) for converting a stream comprising a hydrocarbon feedstock (1) through conversion with steam rich in oxygen 02 into a reformed gas stream (32) comprising hydrogen, carbon monoxide, carbon dioxide and at least one hydrocarbon as impurity, said reformer (30) comprising exothermic, oxygen-based autothermal (ATR) or partial oxidation (POX) reforming and a heat recovery section (40), A fired heater (90) configured to preheat the stream comprising the hydrocarbon feedstock (1) before entry into the at least one reformer (30), At least one water gas shift (WGS) reactor (50) for converting the carbon monoxide of the reformed gas stream (32) into a shifted gas stream (51) containing additional carbon dioxide and hydrogen, A Hydrogen and Carbon Dioxide Recovery Unit (60) located downstream of the WGS reactor (50) and configured to remove carbon dioxide and hydrogen from the shifted gas stream (51), and to produce a first product stream (61) enriched in carbon dioxide and a second product stream (62) enriched in hydrogen, a waste stream (63) depleted in both hydrogen and carbon dioxide, A compressor (70) for compressing a part (65) of the waste gas stream (63) from hydrogen and carbon dioxide recovery unit (60) into a compressed gas stream (71), A membrane separation system (80) selective for the permeation of hydrogen configured to be fed with the compressed gas stream (71) and to produce a hydrogen-enriched permeate (82) stream and a hydrocarbon-enriched retentate (81) stream, A passageway for feeding at least part of the hydrogen-enriched permeate (82) to the fired heater (90) to be used as a low-carbon fuel by the fired heater (90), and A passageway for recycling the hydrocarbon-enriched retentate (81) to the hydrocarbon feed (1) via a pipeline (83) and/or to the reformer (30) via the pipeline (85) and/or to the inlet to the water gas shift reactor (50) via the pipeline (87) .
  2. 2. Hydrogen production plant according to claim 1, wherein the plant comprises a passageway for feeding the fired heater (90) with a part (64) of the waste gas stream (63) from hydrogen and carbon dioxide recovery unit (60).
  3. 3. Hydrogen production plant according to claim 1 or claim 2, wherein the Hydrogen and Carbon Dioxide Recovery Unit (60) is configured to produce a flash gas stream (69), and/or a stream (68) depleted in carbon dioxide and rich in hydrogen.
  4. 4. Hydrogen production plant according to claim 3, wherein the fired heater (90) receives its fuel from at least one of the following streams: a) At least a part (64) of the waste gas stream (63) from the hydrogen and carbon dioxide recovery unit (60); b) At least a part of the hydrogen-enriched permeate (82) produced by the hydrogen-permeating membrane separation system (80); c) At least a part of the hydrogen-enriched product (62) from the hydrogen and carbon dioxide recovery unit (60); d) At least a part of the hydrocarbon feedstock stream (1); e) A make-up fuel stream imported from a battery limit; f) At least a part of the flash gas stream (69) and g) At least a part of the stream depleted in carbon dioxide and rich in hydrogen (68).
  5. 5. Hydrogen production plant according to one of claims 1 to 4, wherein the heat recovery section (40) is configured to generate a steam stream (41) and the plant comprises means for routing at least a part of this steam stream (41): a) As process steam (45) to the inlet of the reformer (30) and/or b) As process steam (43) to the inlet of the water gas shift reactor (50) c) As export steam (46) to a battery limit.
  6. 6. Hydrogen production plant according to one of claims 1 to 5, wherein the hydrogen plant comprises a feed purification section (10) upstream of the reformer (30), configured to produce a treated hydrocarbon stream (11).
  7. 7. Hydrogen production plant according to claim 6, wherein the heat recovery section (40) is configured to generate a steam stream (41) and the hydrogen plant comprises: At least one pre-reformer reactor (20) upstream of the reformer (30), configured to produce a pre-reformed syngas stream (21) from at least one or both of the treated hydrocarbon stream (11) and a part of the hydrocarbon-rich stream (81) via means (84) Means for routing at least a part (44) of steam stream (41) to the inlet of the prereformer (20).
  8. 8. Hydrogen plant according to any of the claims 6 or 7, wherein the heat recovery section (40) is configured to generate a steam stream (41) and the plant comprises: a heat exchanger reformer (35) installed in series to the reformer (30) to receive at least one of the hydrocarbon feed (11), the pre-reformer feed (23) or part of the hydrocarbon-rich stream (81) provided via means (86), mixed with steam (42) to the tube side inlet in order to produce a reformed stream (37) from the tube side outlet; means for feeding this reformed stream (37) to the reformer (30) to produce a reformed stream (32), with the reformed stream (32) configured to enter the shell side inlet of heat exchanger reformer (35) and provide the heat of reaction to the tube side of the heat exchanger reformer (35) and to produce a reformate stream (36) from the shell side outlet of the heat exchanger reformer (35), means for sending the reformate stream (36) to the heat recovery section (40). means for mixing at least a part (42) of steam stream (41) to the tube inlet of the heat exchanger reformer (35).
  9. 9. Hydrogen production plant according to claim 6 or 7 , wherein: the heat recovery section (40) is configured to generate a steam stream (41) The plant comprises means for dividing the reformer feed stream (21) into a first part (23) and a second part (22), The reformer (30) is configured to receive the second part (22) and to produce the reformed gas stream (32), The plant comprises a heat-exchanger reformer (35) installed in parallel to the reformer (30) and configured to receive at least one or both of the part (23) of the reformer feed stream (21) and at least part of the hydrocarbon-rich stream (81) through means (86), as well as the reformed gas stream (32), to produce a reformate stream (36), and means for mixing the reformed feed gas stream (32) into the shell side of the heat exchanger-reformer (35) with the outlet of the heat exchanger reformed gas from the tube side of the heat exchanger-reformer (35), inside or outside of the heat exchanger-reformer (35), and means for mixing at least a part (42) of steam stream (41) to the tube inlet of the heat exchanger reformer (35), and the heat recovery section (40) is configured to receive reformate stream (36).
  10. 10. Hydrogen production plant according to any of the claims 8 or 9, comprising multiple heat exchanger reformers (35).
  11. 11. Hydrogen production plant according to any of the claims 1 to 10, wherein the heat recovery section (40) is configured to produce a steam stream (41) and the plant comprises a steam turbine (47) configured to receive at least a part of the steam stream (41) and to produce a lower pressure stream (48).
  12. 12. Hydrogen production plant according to any of the claims 1 to 11, wherein the membrane separation system (80) comprises membrane elements based polysulfone, poly-imid, poly-aramid, cellulose acetate, any combination thereof, or other polymeric material, or Palladium sheets, exhibiting a selectivity to preferentially permeate hydrogen to a lower pressure.
  13. 13. Hydrogen production plant according to any of the claims 1 to 12, wherein the plant comprises a passageway for importing hydrogen and hydrocarbon containing off-gas (72) from a battery limit as feed to the membrane separation system (80), recovering hydrogen from said off-gas to the hydrogen-enriched permeate (82) and hydrocarbons to the hydrocarbon-enriched retentate (81).
  14. 14. Hydrogen production plant according to any of the claims 1 to 13, wherein the plant comprises a passageway to route at least part of the hydrogen-rich permeate stream (82) as fuel to the fired heater (90) and means for recycling the remaining part of the hydrogen-rich permeate stream (82) to the inlet of the hydrogen recovery unit inside the Hydrogen and Carbon Dioxide Recovery Unit (60).
  15. 15. Hydrogen production plant according to any of the claims 1 to 14, in which at least a part (88) of the hydrogen-rich permeate stream (82) from the membrane separation system (80) is sent as a product stream to the plant battery limits.
  16. 16. Hydrogen production plant according to any preceding claim, further comprising a hydrogen recovery unit positioned between the reformer (30) and the water gas shift reactor (50), the hydrogen recovery unit configured to remove hydrogen from the reformed gas stream (32) before entry into the water gas shift reactor (50).
  17. 17. Hydrogen production plant according to any preceding claim, wherein the fired heater (90) is provided as a separate component to the at least one reformer (30).

Description

Title: Plant and process for producing hydrogen from hydrocarbons with reduced CO2 emissions The present invention relates to a hydrogen plant and a process for producing a hydrogen-comprising product gas from a hydrocarbon feedstock with reduced CO2 emissions implementing this plant. In particular, the present invention concerns a plant and process for producing hydrogen from a hydrocarbon feed, in which this hydrocarbon feed is subjected to reforming using a reformer using Autothermal Reforming (ATR) with optional prereforming for generating a synthesis gas, that is subjected to water gas shift conversion to increase the conversion of hydrocarbon feed to hydrogen and carbon dioxide, that are recovered in a hydrogen and carbon dioxide recovery section, producing two products streams, one of which is hydrogen-rich and one of which is carbon dioxide-rich, and a waste stream that is depleted in hydrogen and carbon dioxide, and where all or at least a part of this waste stream are compressed to a membrane separation system selective for hydrogen, such that the hydrogen rich permeate product stream from the membrane separation system is used as low-carbon fuel for a fired heater while the hydrocarbon-enriched retentate stream from the membrane separation system is recycled to at least partly the pre-reformer feed and/or partly to the reformer feed and/or partly to the water gas shift section. Plants for producing hydrogen from hydrocarbons, in particular steam methane reforming (SMR) plants, are widely applied in refinery complexes to supply hydrogen for upgrading of several products, for example in hydrocracking, hydrogenation or hydrodesulphurization. Additionally, hydrogen is used as a component of syngas (a mixture comprising hydrogen and carbon monoxide). Syngas is an essential building block to produce for example ammonia, methanol, synthetic fuels and many different chemicals. Autothermal Reforming (ATR) is widely applied forthe generation of syngas and, in combination with integrated CO2 capture, is developing as an alternative to SMR based processes for the generation of hydrogen as well. Furthermore, there is growing interest in using hydrogen as such as an alternative to petroleum-based fuel in energy sector as a means to provide seasonal energy storage, in industry to provide high quality heat and in mobility mostly for heavy and long hauls transportation means. It is estimated that about 95% of the global hydrogen supply is produced from fossil fuels; as by-product of the technology, CO2 is produced and emitted to the atmosphere. The CO2 is produced not only by combustion of a carbon-based fuel for heating the feedstock to the temperatures needed to carry out the reforming, but CO2 is also formed as a side-product in the hydrogen production: the steam reforming reaction produces carbon monoxide (with methane as a starting compound: CH4 + H2O CO +3 H2), which is subsequently converted to carbon dioxide via the water gas shift reaction (CO + H2O CO2 + H2). The steam reforming reaction is highly endothermic and requires a significant additional heat input. In processes based on exothermic reforming, such as autothermal reforming (ATR) or partial oxidation reforming, are carried out by a partial combustion of the hydrocarbon feedstock (with methane as starting component: 2 CH4 + 02 2C0 +4 H2) , such that a small-size fired heater is required only for preheating the hydrocarbon feedstock to the reactor inlet temperature but not for supplying the heat of reaction for the reforming reaction. Exothermic reforming processes thereby consume oxygen 02 that is an additional feed to the plant. The formed CO is also subsequently converted to C02 through the water gas shift reaction. In recent years an increasing industrial focus on environmental emissions and reduction of the carbon footprint challenges the design of hydrogen production facilities (a.k.a. Hydrogen Production Units: HPU's) to reduce carbon footprint as well. Traditionally, hydrogen plants were integrated with a refinery or industrial complex where the generated excess steam could be used, since the hydrogen plant is considered as an efficient steam producer, in order to recover as much low grade heat as possible, the excess steam generated was optimized to meet the external steam demand, making the excess steam a valuable by-product of the facility. Consequently, the firing and thus C02 emissions were not the main design parameters but this changes with the evolving regulations on greenhouse gas emissions. Many different solutions have been proposed to reduce the steam production of the hydrogen plant by reducing the firing demand. The options include preheating the combustion air (up to typically 600°C) with flue gas or another indirect heat source, preheating fuel and/or tail gas, applying an adiabatic (pre)reforming step. All these solutions reduce the required firing demands and thereby also the export steam flowrate and CO2 emissions.