[go: up one dir, main page]

WO2019229665A1 - Production d'hydrogène à partir d'eau à l'aide de catalyseurs au sulfure métallique - Google Patents

Production d'hydrogène à partir d'eau à l'aide de catalyseurs au sulfure métallique Download PDF

Info

Publication number
WO2019229665A1
WO2019229665A1 PCT/IB2019/054441 IB2019054441W WO2019229665A1 WO 2019229665 A1 WO2019229665 A1 WO 2019229665A1 IB 2019054441 W IB2019054441 W IB 2019054441W WO 2019229665 A1 WO2019229665 A1 WO 2019229665A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
metal sulfide
water
reaction zone
sulfide
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/IB2019/054441
Other languages
English (en)
Inventor
Balamurugan VIDJAYACOUMAR
Ilia KOROBKOV
Khalid Albahily
Sandro Gambarotta
Virginie PENEAU
Nicholas P. ALDERMAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
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 SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of WO2019229665A1 publication Critical patent/WO2019229665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention generally concerns processes for producing hydrogen gas (H 2 ) from water (H2O).
  • the invention concerns a self-sustaining reaction that includes contacting H2O with a metal sulfide catalyst at a reaction temperature of less than 600 °C to convert the metal sulfide to a metal oxide and produce a gaseous product stream that includes H2, optional hydrogen sulfide (H2S), and optional hydrogen sulfide (SO2).
  • H2 can be produced using diverse resources including fossil fuels (e.g ., such as natural gas and coal, nuclear energy, or the like) and renewable energy sources (e.g., biomass, wind, solar, geothermal, and hydroelectric power) through a wide range of technologies.
  • fossil fuels e.g ., such as natural gas and coal, nuclear energy, or the like
  • renewable energy sources e.g., biomass, wind, solar, geothermal, and hydroelectric power
  • a problem with using fossil fuels is their inevitable depletion, which necessitates finding alternative feedstocks to meet the growing demand for hydrogen production globally.
  • Another problem associated with using renewable energy sources is the costs and technical difficulties associated with the storage and/or transportation of the produced H 2 .
  • H2 can be produced from splitting of H2O using photocatalysts or Z-scheme catalysts.
  • these types of technologies suffer from low efficiencies and high economic costs.
  • Other efforts to split H2O include using an inorganic shuttle or carrier.
  • German Patent Application DE2541824 to Kluas describes producing hydrogen from water using a thermochemical cycle to split sulfuric acid into water, elemental sulfur, sulfur dioxide, hydrogen and oxygen.
  • Bhosale et a/. International Journal of Hydrogen Energy , 2015, 40, 1639-1650 describes solar hydrogen production via thermochemical iron oxide-iron sulfate water-splitting.
  • the solution is premised on a self-sustaining process that contacts water with a catalyst that includes a metal sulfide at high temperatures (e.g ., greater than 300 °C, but less than 600 °C) to produce a metal oxide material and a gaseous product stream that includes H2, optional H2S, and optional SO2.
  • the produced metal oxide material can then be converted back to a metal sulfide by contact with a sulfur source (e.g., H2S, elemental sulfur or the like), which can also produce additional water.
  • the generated water can be contacted with the generated metal sulfide to continue the reaction cycle.
  • Reaction conditions can be adjusted to control the amount of elemental sulfur formed during the process.
  • the temperature can be greater than 300 °C, but less than 600 °C during the production of H2 from water to inhibit the production of elemental sulfur.
  • the temperature can be raised to above 600 °C to convert the produced iron oxide to FeS.
  • little to no (e.g, less than 0.001 wt.%) sulfuric acid (H2SO4) and/or SO2 is produced during the reaction when iron-containing catalysts are used, and neither of these compounds are needed to perform or initiate the reaction.
  • a process to produce H2 from H2O can include contacting H2O with a catalyst that can include metal sulfide at a reaction temperature of less than 600 °C (e.g, 350 °C to 575 °C, or 475 °C to 525 °C, or about 500 °C) to produce a product stream that can include H2, optional H2S and optional SO2, or combinations thereof.
  • the product stream can be substantially free of elemental sulfur. Any H2S produced during the reaction can contact the metal oxide material to produce additional H2S.
  • the iron oxide material can be converted to iron sulfide.
  • the metal oxide can be converted to metal sulfide at a reaction temperature of 600 °C to 800 °C.
  • SO2 can be formed by contact of sulfur or metal sulfide with the metal oxide material. Any water produced during the metal oxide conversion can be contacted with the iron sulfide catalyst material to produce H2, optionally H2S, optionally SO2, or combinations thereof.
  • the product stream can include H2 and H2S, and the method can further include isolating the H2S from the product stream and providing the H2S to the metal oxide so as to convert the metal oxide back to the metal sulfide.
  • elemental sulfur can be produced.
  • the metal sulfide catalyst can include iron (Fe), tungsten W), tin (Sn), nickel (Ni), manganese (Mn), cobalt (Co), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), or mixtures thereof and, in some embodiments, be a bulk metal catalyst (i.e. unsupported catalyst).
  • the catalyst can have a general formula of FeSx, where x is 1 or 2, preferably 1.
  • the FeSx catalyst can form a metal oxide material (e.g., Fe30 4 , Fe2Cb, WO3, etc.) during the reaction. When iron sulfide is used the water can be free of sulfur dioxide (SO2).
  • SO2 sulfur dioxide
  • the metal sulfide is not obtained from a thermal hydrocarbon cracking process.
  • a system to produce hydrogen from water can include an inlet for a reactant feed that include water, a reaction zone configured to be in fluid communication with the inlet, and a first outlet configured to be in fluid communication with the reaction zone.
  • the reaction zone can have a temperature of less than 600 °C and can include water and a metal sulfide catalyst.
  • the reaction zone can include the reactant feed and the product stream.
  • the first outlet can remove a gaseous product stream that can include Fh, optional SO2, and optional hydrogen sulfide (FhS) from the reaction zone.
  • the product stream can include FhS, and the metal sulfide catalyst can be at least partially or fully converted to metal oxide material.
  • the system can further include a separation zone in fluid communication (coupled) with first outlet.
  • the separation zone can be configured to separate FhS from Fh in the product stream and provide the FhS to the inlet or to the reaction zone. Contact of the FhS with the iron oxide material can produce iron sulfide catalyst material to sustain the reaction cycle.
  • the terms“about” or“approximately” are defined as being close to the value, term, or phrase that follows, as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
  • the terms“wt.%”,“vol.%”, or“mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight of the material, the total volume of material, or total moles of material, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the processes of the present invention can“comprise,”“consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification.
  • a basic and novel characteristic of the processes of the present invention are their abilities to produce Eh from H 2 0 through the use of a metal sulfide catalyst.
  • Embodiment l is a process for producing hydrogen (Eh) from water.
  • the process includes the steps of contacting water with a metal sulfide at a reaction temperature of less than 600 °C to convert the metal sulfide to a metal oxide, and produce a product stream containing hydrogen (H 2 ), optional sulfur dioxide (SO2), and optional hydrogen sulfide (H2S).
  • Embodiment 2 is the process of embodiment 1, wherein the product stream has less than 0.01 wt.% of elemental sulfur or is preferably free of elemental sulfur.
  • Embodiment 3 is the process of any one of embodiments 1 to 2, wherein the reaction temperature is 350 °C to 575 °C, or 475 °C to 525 °C, or about 500 °C.
  • Embodiment 4 is the process of any one of embodiments 1 to 3, further including contacting EhS with the metal oxide at a temperature of at least 600 °C to convert the metal oxide to the metal sulfide to produce additional Eh.
  • Embodiment 5 is the process of embodiment 4 wherein the reaction temperature for converting the metal oxide to the metal sulfide is 600 °C to 800 °C.
  • Embodiment 6 is the process of any one of embodiments 4 to 5, wherein the product stream includes Eh and EhS, and the method further including isolating the EhS from the product stream and contacting the EhS with the metal oxide.
  • Embodiment 7 is the process of embodiment 6, wherein elemental sulfur is produced.
  • Embodiment 8 is the process of any one of embodiments 1 to 7, wherein less than 0.001 wt.% or no sulfuric acid (H2SO4) is produced during the reaction.
  • Embodiment 9 is the process of any one of embodiments 1 to 8, wherein the metal sulfide contains iron (Fe), tungsten (W), tin (Sn), nickel (Ni), manganese (Mn), cobalt (Co), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), or mixtures thereof.
  • Embodiment 10 is the process of embodiment 9, wherein the metal sulfide is FeSx, where x is 1 or 2, preferably 1, and the metal oxide contains Fe30 4 .
  • Embodiment 11 is the process of embodiment 9, wherein the metal sulfide is WS2 and the metal oxide contains WO3.
  • Embodiment 12 is the process of any one of embodiments 1 to 11, wherein the process is self-sustaining.
  • Embodiment 13 is the process of any one of embodiment 1 to 12, wherein the metal sulfide is not obtained from a thermal hydrocarbon cracking process.
  • Embodiment 14 is the process of any one of embodiments 1 to 13, wherein the metal sulfide is a bulk metal catalyst.
  • Embodiment 15 is a system for producing hydrogen (Eh) from water.
  • the system includes an inlet for a reactant feed comprising water (H2O); a reaction zone that is configured to be in fluid communication with the inlet, wherein the reaction zone has a temperature of less than 600 °C and contains water and a metal sulfide catalyst; a first outlet configured to be in fluid communication with the reaction zone and configured to remove a first product stream comprising Fb and optionally hydrogen sulfide (FhS) from the reaction zone.
  • Embodiment 16 is the system of embodiment 15, wherein the reaction zone further contains the reactant feed and the product stream.
  • Embodiment 17 is the system of any one of embodiments 15 to 16, wherein the reaction zone contains a metal oxide and the system further includes a second inlet in fluid communication with the reaction zone and including a second reactant feed, the second reactant feed containing FES; and a heat source configured to heat the reaction zone to at least 600 °C, wherein the first inlet is configured to remove a second product stream comprising H 2 and gaseous sulfur dioxide (S0 2 ) from the reaction zone.
  • Embodiment 18 is the system of any one of embodiments 15 to 17, further including a separation zone coupled to the first outlet and configured to separate FES from the H 2 in the product stream and provide the FES to the first inlet or reaction zone.
  • Embodiment 19 is the system of any one of embodiments 15 to 18, wherein the metal sulfide catalyst includes a transition metal.
  • Embodiment 20 is the system of embodiment 19, wherein the transition metal is iron or tungsten.
  • FIG. 1 depicts a system to produce H 2 from H 2 0 using a process of the present invention.
  • FIG. 2 shows the gas chromatography (GC) chromatogram of the gas products of the reaction of FeS with water.
  • FIG. 3 shows the formation of FeS from Fe30 4 and elemental sulfur at temperatures from 200 °C and 700 °C.
  • FIG. 4 shows the percentage of Fe30 4 , FeS, and FeS 2 at 400 °C between 5 minutes and 1 hour.
  • FIG. 5 shows the percentage of Fe30 4 , FeS, and FeS 2 at 500 °C between 5 minutes and 1 hour.
  • FIG. 6 shows the X-ray diffraction (XRD) pattern of Fe 2 03 heated with elemental sulfur at 400 °C for 1 hour.
  • FIG. 7 shows the XRD pattern of Fe 2 0 4 heated with elemental sulfur at 400 °C for 1 hour.
  • FIG. 8 shows a graphical representation of continuous evolution of hydrogen from a water/H 2 S mixture using Fe30 4 where the orange bars indicate the hourly rate of hydrogen evolution and the blue line the cumulative production of hydrogen H 2 produced (mmoles).
  • the solution is premised on producing Th from water by contacting the water with a metal sulfide catalyst (e.g ., iron (Fe), tungsten W), tin (Sn), nickel (Ni), manganese (Mn), cobalt (Co), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), or mixtures thereof).
  • a metal sulfide catalyst e.g ., iron (Fe), tungsten W), tin (Sn), nickel (Ni), manganese (Mn), cobalt (Co), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), or mixtures thereof.
  • the metal sulfide catalyst is a bulk catalyst.
  • the metal sulfide can be converted to metal oxides (e.g., Fe 2 0 3 and/or Fe 3 0 4 , WO3).
  • the metal oxide material can be converted back to the metal sulfide catalyst material using hydrogen sulfide produced during the water-splitting reaction and/or addition of a sulfur source (e.g, elemental sulfur or additional FhS) to the reaction mixture.
  • a sulfur source e.g, elemental sulfur or additional FhS
  • Water can be produced during the regeneration of the iron sulfide catalyst material. The produced water can contact the metal sulfide catalyst to continue the H 2 production cycle.
  • the reaction process can be a self-sustaining cycle as shown in reaction scheme I:
  • FIG. 1 can also include various equipment that is not shown and is known to one of skill in the art of chemical processing.
  • controllers, piping, computers, valves, pumps, heaters, thermocouples, and/or pressure indicators may not be shown.
  • FIG. 1 is a schematic of a system using the process of the present invention to produce Fh from FLO.
  • System 100 can include reactor 102, water inlet 104, and product stream outlet 106.
  • Reactor 102 can include reaction zone 108 that can include a catalyst material, a reactant feed stream (water), a product stream, or combinations thereof.
  • water stream 110 can enter reactor via water inlet 104 and enter reaction zone 108.
  • the water can be provided in a continuous manner.
  • water can be added to the reaction zone at 0.5 to 5 mL/hour, 1 to 4 mL/hour, 1 to 3 mL/hour or any range or value there between.
  • Water can be provided as a liquid and be vaporized in reaction zone 108. In other embodiments, water can be added as steam or in vapor form.
  • the source of water can be from potable or non-potable sources (e.g refining operations, chemical reactions, or the like). In a preferred instance, the water contains little, substantially no, or no SO2.
  • the water can contact the catalyst material at reaction conditions sufficient to produce product stream 112 and a metal oxide material.
  • the catalyst material can include a metal sulfide, preferably a bulk metal sulfide (i.e., less than 0.1 wt.% support material or no support material).
  • the metal sulfide catalyst can be a transition metal.
  • Transition metals include Columns 5 to 12 of the Periodic Table.
  • Non-limiting examples of transition metals include iron (Fe), tungsten (W), tin (Sn), nickel (Ni), manganese (Mn), cobalt (Co), zinc (Zn), lead (Pb), copper (Cu), cadmium (Cd), or mixtures thereof.
  • Metal sulfides can be obtained from commercial sources or prepared by contact of metals with a sulfur source e.g ., hydrogen sulfide, elemental sulfur, or both).
  • the catalyst includes greater than, equal to, or between two of 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, 90 wt.% or 100 wt.% of metal sulfide.
  • the catalyst is unsupported and includes 95 wt.% to 100 wt.% of metal sulfide with the balance being metal oxides (e.g., 5 wt.% or less).
  • the metal sulfide containing catalyst can have the general formula of FeSx where x is 1 or 2 (e.g, FeS or FeS2).
  • the catalyst is unsupported and includes 95 wt.% to 100 wt.% of FeSx with the balance being iron oxides (e.g, Fe30 4 and/or Fe2Cb).
  • FeS is used as the catalyst and only Fe30 4 is formed by contact of the FeS with water at the reaction temperatures.
  • FeS2 is used as the catalyst and Fe2Cb and/or Fe30 4 is formed by contact of the FeS2 with water at the reaction temperatures.
  • WS2 can forms WO 3 , NiS forms NiO, SnS forms SnCk, MnS forms MnO.
  • the metal sulfide forms higher sulfides (e.g, CoS forms C09S8) or elemental metals (e.g, CuS form Cu).
  • the reaction conditions in reaction zone 108 can include a temperature less than 600 °C, or 350 °C to 575 °C, or 475 °C to 525 °C, or at least, equal to, or between any two of 350 °C, 375 °C, 400 °C, 425 °C, 450 °C, 475 °C, 500 °C, 525 °C, 575 °C, and 590 °C.
  • the reaction temperature is 475 °C to 525 °C or about 500 °C.
  • a reaction pressure can be 0.101 MPa to 0.5 MPa or about 1 atmosphere of pressure. At these conditions no, or substantially no, elemental sulfur is formed.
  • Product stream 112 can include gaseous hydrogen, optional gaseous hydrogen sulfide, and/or optional gaseous sulfur dioxide, depending on the metal sulfide used.
  • CdS, ZnS, and WS2 can produce Fh and SO2.
  • NiS, SnS, PbS, FeS, MnS, and CoS can produce Fk, FkS, and SO2.
  • CuS can produce Fk.
  • the amounts of Fh, FhS and SO2 can vary depending on the catalyst and amounts of catalyst used.
  • the temperature and pressure of the reaction zone 108 can be adjusted to control the amount of elemental sulfur formed during the reaction.
  • Generated H 2 S can react with any iron oxide present and convert the iron oxide to catalytic iron sulfide, and water can also be produced.
  • the temperature in reaction zone 108 can be greater than 500 °C, but less than 600 °C during the production of H 2 from water. After the H 2 production decreases, the temperature can be raised to above 600 °C to convert the metal oxide to metal sulfide.
  • the temperature in reaction zone 108 can be increased to 500 °C to 800 °C, 600 °C to 700 °C, or greater than, equal to, or between any two of 500 °C, 525 °C, 550 °C, 575 °C, 600 °C, 625 °C, 650 °C, 675 °C, 700 °C, 725 °C, 750 °C, 775 °C, and 800 °C.
  • a reaction pressure can be 0.101 MPa to 0.5 MPa or about 1 atmosphere of pressure.
  • a mixture of FeS and FeS 2 can be produced at temperatures between 500 °C and 600 °C.
  • a supplemental sulfur source can be added to reaction zone 108 to assist in conversion of the metal oxide material back to the catalytic metal sulfide material when the amounts of produced H 2 S and/or elemental sulfur are inadequate to convert the iron oxide material to iron sulfide material.
  • Non-limiting examples of a supplemental sulfur source can include FhS and elemental sulfur.
  • the sulfur source can enter reactor 102 through reactant inlet 104
  • the produced water stream can contact the iron sulfide catalyst and continue the cycle.
  • the produced water can be removed from the reactor. While the invention has been described as starting with the metal sulfide catalyst, it should be understood that the self- sustaining cycle can be started with the metal oxide.
  • a metal sulfide listed in Table 1 was placed in a tubular reactor.
  • the tubular reactor was purged with argon.
  • the argon flow was stopped, and the tubular reactor was heated to between 400 °C and 500 °C.
  • Water was then injected into the tubular reactor at a rate of between 0.5 and 5 mL/h for 1 hour.
  • the produced gasses were analyzed by GC-TCD, which showed the formation of H 2 and FhS.
  • FIG. 2 shows the GC chromatogram of the gas products of the iron sulfide reaction.
  • Fe30 4 (2.32 g, 10 mmoles) was placed in a tubular reactor. Argon was flowed through the tube to purge it for 20 minutes, after which the tubular reactor was heated to between 200 °C and 700 °C. After reaching the desired temperature, H 2 S was flowed at a rate of 0.5 L/hr for between 5 minutes and 1 hour. The produced gasses were analyzed by GC- TCD and showed no gas formation. Powder XRD was used to determine the iron phases (FeS, FeS2). Both FhO and elemental sulfur were formed as reaction products. At temperatures above 600 °C, only FeS was formed. At temperatures from 300 °C to 500 °C, a mixture of FeS and FeS 2 was formed.
  • FIG. 3 shows the formation of FeS at temperatures from 200 °C and 700 °C.
  • FIG. 4 shows the percentage of Fe30 4 , FeS, and FeS 2 at 400 °C between 5 minutes and 1 hour.
  • FIG. 5 shows the percentage of Fe30 4 , FeS, and FeS2 at 500 °C between 5 minutes and 1 hour.
  • Fe2Cb or Fe30 4 (2.3 mmoles) was placed in a tubular reactor sealed at one end.
  • elemental sulfur (18.75 mmoles) was added, and the tubular reactor was purged with argon. The argon flow was stopped, and the tubular reactor was heated to between 200 °C and 500 °C for between 5 minutes and 1 hour.
  • the gasses were analyzed by GC-TCD, which showed the formation of SO2.
  • XRD was used to identify the iron species present. From the XRD pattern, it was determined that FeS2 was formed from Fe203 and Fe30 4 , with traces of Fe(m) in the case of Fe203 only.
  • FIG. 6 shows the XRD pattern of Fe203 heated with elemental sulfur at 400 °C for 1 hour.
  • the XRD showed peaks for FeS2 (peaks designated by stars) and Fe metal (peaks designated by circles).
  • FIG. 7 shows the XRD pattern of Fe20 4 heated with elemental sulfur at 400 °C for 1 hour.
  • the XRD showed peaks for FeS2 (peaks designated by stars) and Fe30 4 (peaks designated by circles).
  • Fe30 4 (14 g, 60 mmoles) was placed in a tube. Argon was flowed through the tube to purge it for 20 minutes after which the mixture was heated to 700 °C. A mixture of FhS and H2O at flow rate of 0.5 L /hr was passed through the tube. A linear evolution of hydrogen was observed as a function of time during a several hours run (See, FIG. 8). After 7 hours, over 27 mmoles of hydrogen had been produced from 3 mmoles of Fe30 4 . Sulfur was also produced (14 mmoles).
  • Fe30 4 (7g, 30 mmoles) was heated to 600 °C and reacted with FhS at a flow rate
  • Example 2 0.5 L /hr for 15 minutes using the protocol described in Example 2. The tube was then purged with inert gas to prevent the presence of FhS, which may result in sulfur formation. Water was injected at the same temperature for 30 minutes. In the first cycle of H2S/H2O, no sulfur was produced. However, in the second cycle of H2S/H2O, in the water step sulfur was formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des systèmes et des procédés de production d'hydrogène gazeux (H2) à partir d'eau (H2O). Un procédé peut consister à mettre en contact H2O avec un catalyseur qui comprend du sulfure de fer à une température de réaction de 500 °C à 800 °C pour produire un flux de produit qui comprend H2 et éventuellement du sulfure d'hydrogène gazeux (H2S).
PCT/IB2019/054441 2018-05-31 2019-05-29 Production d'hydrogène à partir d'eau à l'aide de catalyseurs au sulfure métallique Ceased WO2019229665A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201862678349P 2018-05-31 2018-05-31
US62/678,349 2018-05-31

Publications (1)

Publication Number Publication Date
WO2019229665A1 true WO2019229665A1 (fr) 2019-12-05

Family

ID=67297207

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2019/054441 Ceased WO2019229665A1 (fr) 2018-05-31 2019-05-29 Production d'hydrogène à partir d'eau à l'aide de catalyseurs au sulfure métallique

Country Status (1)

Country Link
WO (1) WO2019229665A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635947A (en) * 1948-07-02 1953-04-21 Union Oil Co Hydrogen process
DE2541824A1 (de) 1975-09-19 1977-03-31 Rheinische Braunkohlenw Ag Thermochemische verfahren zur erzeugung von wasserstoff aus wasser
EP0016644A1 (fr) 1979-03-22 1980-10-01 Nippon Mining Company Limited Procédé de traitement d'huile lourde contenant du soufre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635947A (en) * 1948-07-02 1953-04-21 Union Oil Co Hydrogen process
DE2541824A1 (de) 1975-09-19 1977-03-31 Rheinische Braunkohlenw Ag Thermochemische verfahren zur erzeugung von wasserstoff aus wasser
EP0016644A1 (fr) 1979-03-22 1980-10-01 Nippon Mining Company Limited Procédé de traitement d'huile lourde contenant du soufre

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BHOSALE ET AL., INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 40, 2015, pages 1639 - 1650
KAI ZHANG ET AL: "Metal sulphide semiconductors for photocatalytic hydrogen production", CATALYSIS SCIENCE & TECHNOLOGY, vol. 3, no. 7, 1 January 2013 (2013-01-01), United Kingdom, pages 1672, XP055614422, ISSN: 2044-4753, DOI: 10.1039/c3cy00018d *
SOLIMAN M A ET AL: "Hydrogen production via thermochemical cycles based on sulfur chemistry", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, ELSEVIER SCIENCE PUBLISHERS B.V., BARKING, GB, vol. 1, no. 3, 1 January 1976 (1976-01-01), pages 265 - 270, XP025413880, ISSN: 0360-3199, [retrieved on 19760101], DOI: 10.1016/0360-3199(76)90022-7 *
WU JINXIA ET AL: "Ternary Transitional Metal Chalcogenide Nanosheet with Significantly Enhanced Electrocatalytic Hydrogen-Evolution Activity", CATALYSIS LETTERS, SPRINGER NEW YORK LLC, UNITED STATES, vol. 147, no. 1, 12 November 2016 (2016-11-12), pages 215 - 220, XP036147549, ISSN: 1011-372X, [retrieved on 20161112], DOI: 10.1007/S10562-016-1907-2 *

Similar Documents

Publication Publication Date Title
Chehade et al. Simulation and optimization of hydrogen production by steam reforming of natural gas for refining and petrochemical demands in Lebanon
Moon et al. Molybdenum carbide water–gas shift catalyst for fuel cell-powered vehicles applications
Ausfelder et al. Hydrogen in the chemical industry
Yang et al. Hydrogen production from the steam− iron process with direct reduction of iron oxide by chemical looping combustion of coal char
Zhang et al. Hydrogen generation, storage and utilization
US8287838B2 (en) Thermochemical hydrogen produced from a vanadium decomposition cycle
Sun et al. Hydrogen from steam reforming of ethanol in low and middle temperature range for fuel cell application
CA2900192C (fr) Methodes de conversion de carburant en gaz de synthese comportant des oxydes metalliques composites
Hargus et al. Looped-oxide catalysis: a solar thermal approach to bio-oil deoxygenation
Sheu et al. Redox reforming based, integrated solar-natural gas plants: reforming and thermodynamic cycle efficiency
Lachén et al. Production and purification of hydrogen by biogas combined reforming and steam-iron process
Kambolis et al. CO methanation for synthetic natural gas production
Uchida et al. Hydrogen energy engineering applications and products
US4242104A (en) Cyclic process for producing methane with catalyst regeneration
US20250091976A1 (en) Method of producing formaldehyde
EP2076332A1 (fr) Procédé de fabrication d'hydrogene par décomposition directe de gaz naturel et de gaz de petrole liquefié (lpg)
WO2019229665A1 (fr) Production d'hydrogène à partir d'eau à l'aide de catalyseurs au sulfure métallique
KR102287865B1 (ko) 플라즈마에 의한 메탄의 건식 개질반응을 포함하는 이산화탄소 함유 가스자원으로부터의 메탄올 제조 방법
Minet et al. Cost-effective methods for hydrogen production
Kermode Hydrogen from fossil fuels
AU686189B2 (en) Process to produce methanol
EP0004456B1 (fr) Méthanisation de monoxyde de carbone sans séparation préalable des gaz inertes
Zhao et al. Hydrogen Storage by Reduction of CO₂ to Synthetic Hydrocarbons
KR101487387B1 (ko) 금속 카바이드계 메탄 리포밍 촉매 제조방법 및 그 방법에 의해 제조된 메탄 리포밍 촉매
US11471872B2 (en) Pure phase ε/ε' iron carbide catalyst for Fischer-Tropsch synthesis reaction, preparation method thereof and Fischer-Tropsch synthesis process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19740062

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19740062

Country of ref document: EP

Kind code of ref document: A1