WO2018189637A1 - Procédé intégré de production d'hydrogène à partir de sulfure d'hydrogène et de dioxyde de carbone - Google Patents

Procédé intégré de production d'hydrogène à partir de sulfure d'hydrogène et de dioxyde de carbone Download PDF

Info

Publication number
WO2018189637A1
WO2018189637A1 PCT/IB2018/052421 IB2018052421W WO2018189637A1 WO 2018189637 A1 WO2018189637 A1 WO 2018189637A1 IB 2018052421 W IB2018052421 W IB 2018052421W WO 2018189637 A1 WO2018189637 A1 WO 2018189637A1
Authority
WO
WIPO (PCT)
Prior art keywords
elemental sulfur
gas
solvent
sulfur
catalyst
Prior art date
Application number
PCT/IB2018/052421
Other languages
English (en)
Inventor
Sivadinarayana Chinta
Vijayanand RAJAGOPALAN
Lawrence D'souza
Original Assignee
Sabic Global Technologies B.V.
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 B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2018189637A1 publication Critical patent/WO2018189637A1/fr

Links

Classifications

    • 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
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/508—Preparation of sulfur dioxide by oxidation of sulfur compounds
    • 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
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C01B17/0434—Catalyst compositions
    • 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
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • 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
    • 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 generally concerns an integrated process for the production hydrogen (H 2 ), carbon monoxide (CO) and sulfur dioxide (S0 2 ) using H 2 S and carbon dioxide (C0 2 ) as feedstocks.
  • Natural gas is a predominant chemical energy source, natural gas is an expensive feedstock. Natural gas as a resource has limited availability in certain parts of the worlds, and which can make the conventional process even less economical.
  • the reaction can be performed at relatively low temperatures, such as 300 °C and below.
  • the produced hydrogen can be used as a reactant in other reactions (e.g., reverse water gas-shift reaction) as shown in equation (2), which can result in a lower costs (e.g., operating and capital costs).
  • Carbonyl sulfide (COS) can also be produced by this reaction as shown in reaction (4).
  • This reaction can be carried out at relatively low temperatures (e.g., at temperatures at which substantial vapor pressure of S exists, e.g., vapor pressure of S is 5 ⁇ 10 "4 atm at 119 °C and 1 atm at 444.6 °C) and without the assistance of water, oxygen, or hydrogen. Therefore, lower energy requirements are needed to run the reaction, and the costs and complexities associated with introducing water, oxygen, or hydrogen into the reaction can be avoided altogether.
  • the integrated process of the present invention can minimize natural gas consumption, can utilize carbon dioxide produced as a byproduct in the production of many petrochemicals, and can economically convert carbon dioxide and elemental sulfur into value added chemical products (e.g., CO, SO2, and COS).
  • feedstocks containing H 2 S and CO2 can be utilized without purification of the H2S prior to decomposition.
  • a method of producing hydrogen (H 2 ) and carbon monoxide gas (CO(g)), and sulfur dioxide gas (S0 2 (g)) from H 2 S is described.
  • a feed stream that includes H 2 S can be contacted with a catalyst in the absence or presence of a solvent stream under reaction conditions to decompose the H2S into hydrogen (H 2 ) and elemental sulfur.
  • Process conditions to effect the production of hydrogen (H2) and elemental sulfur can include a temperature of less than 700 °C, preferably 0 °C to 300 °C, most preferably 30 °C to 100 °C, a pressure of 0.1 MPa to 20. MPa, or both.
  • the feed stream includes H2S and
  • a bulk metal catalyst and/or a supported catalyst can be used to catalyze the decomposition of hydrogen sulfide.
  • the catalyst can include a metal, a metal oxide, a metal sulfide, a lanthanide, a lanthanide oxide, spinel, perovskite, olivine, pyrochlore, or any combination thereof.
  • Non-limiting examples of the metal or metal oxide includes a Column 2, 3, 4, 6, 9-12 (Group IIA, IB, IIB, IIIB, IVB, VIB, or VIII of the U. S. Periodic Table) metal, metal oxide, and/or metal sulfide.
  • Non-limiting examples of lanthanides or lanthanide oxide includes La, Ce, Dy, Tm, Yb, Lu, Ce0 2 , Dy 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , or La 2 0 3 , or any combination thereof.
  • the catalyst can include a supported Ml or M1M2, where Ml and M2 can be Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, Zr.
  • Ml and M2 can be Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, Zr.
  • the catalyst is an alumina or silica supported Co- Mo or Ni-Mo sulfide catalyst.
  • the hydrogen can be isolated and converted into syngas or used in other applications.
  • the method can further include purifying the hydrogen (e.g., passing the H 2 through a pressure swing adsorption system).
  • the H2S is dispersed in a solvent (e.g., toluene, pyridine, monoethanol amine (MEA), aniline, diethanolamine (DEA), methyldiethanolamine (MDEA), or any combination thereof).
  • the solvent may be chosen from suitable solvents that remove sulfur from the reaction space as soon as it is formed in order to increase the conversion of hydrogen sulfide to hydrogen and elemental sulfur.
  • the solubilized elemental sulfur is separated to obtain elemental sulfur gas and the solvent.
  • the solubilized elemental sulfur is separated from the solution by evaporation at temperature of 25 to 300 °C.
  • the elemental sulfur solid powder is converted into sulfur gas.
  • the sulfur is removed from the reactor as a liquid.
  • the isolated elemental sulfur or sulfur allotrope can be vaporized and reacted with CO2 to produce CO and SO2.
  • the CO2 is obtained from the H 2 S feed stream used to produce H 2 .
  • the molar ratio of C0 2 (g): S(g) is 1 : 1, 2: 1, or 4: 1, or 1 : 1 to 6: 1.
  • other products such as carbonyl sulfide (COS(g)) and/or carbon disulfide (CS 2 (g)) can be produced.
  • the CS 2 (g) is not produced.
  • Process conditions to effect the production of CO(g) and S0 2 (g) include a temperature of at least 250 °C or at least 445 °C, or from 250 °C to 3000 °C, 445 °C to 3000 °C, preferably 900 °C to 2000 °C, most preferably 1000 °C to 1600 °C, a pressure of 0.1 MPa to 2.5 MPa, and a gas hourly space velocity (GHSV) of 1,000 to 100,000 h "1 .
  • GHSV gas hourly space velocity
  • the produced S0 2 and CO can be separated using conventional separation methods (e.g., membrane separation system, cryogenic distillation, or the like).
  • the isolated S0 2 (g) can be isolated and converted to S0 3 (g), and the S0 3 (g) can be subsequently converted to sulfuric acid or ammonium sulfate.
  • COS when produced it can be isolated and recycled to the CO2 and S(g) reaction at a temperature of 900 °C or more. At such temperatures, further production of COS from CO and S can be inhibited.
  • a system for producing hydrogen (H 2 ), carbon monoxide (CO), and sulfur dioxide (SO2) is described.
  • the system can include a H 2 (g) and elemental sulfur production unit in fluid communication with a CO(g) and S0 2 (g) production unit.
  • the H 2 (g) and elemental sulfur production unit can include a first reactor (e.g., a trickle- bed reactor or continuous stirred tank reactor (CSTR)) configured to perform a decomposition of hydrogen sulfide (H 2 S) reaction to produce H 2 (g) and elemental sulfur.
  • a first reactor e.g., a trickle- bed reactor or continuous stirred tank reactor (CSTR)
  • the CO(g) and S0 2 (g) production unit can include a second reactor configured to produce CO(g) and S0 2 (g) from a reaction of carbon dioxide gas (C0 2 (g)) with elemental sulfur gas.
  • the reaction zone can further include a catalyst capable of catalyzing the conversion of hydrogen sulfide (H2S) to hydrogen (H 2 ) and elemental sulfur.
  • the system can further include apparatus capable of separating the separating H 2 (g) from unreacted H 2 S and/or a separation unit capable of separating produced elemental sulfur from a solution that includes a solvent.
  • Aspect 1 is a method of producing hydrogen gas (H 2 (g)), carbon monoxide gas (CO(g)), and sulfur dioxide gas (S0 2 (g)), the method comprising: (a) contacting feed stream comprising hydrogen sulfide (H 2 S) with a catalyst in the presence or absence of a solvent under reaction conditions sufficient to decompose H 2 S into H 2 (g) and elemental sulfur; (b) recovering the H 2 (g) and the elemental sulfur; and (c) contacting the elemental sulfur from step (b) with carbon dioxide gas (C0 2 (g)) under reaction conditions sufficient to produce a product stream comprising CO(g) and S0 2 (g).
  • Aspect 2 is the method of aspect 1, wherein the reaction conditions in step (a) include a temperature of 20 °C to 700 °C and/or a pressure of 0.1 MPa to 20 MPa, preferably 20 °C to 30 °C and 0.1 MPa.
  • Aspect 3 is the method of any one of aspects 1 to 2, wherein the H2S feed stream is contacted with a solvent and the elemental sulfur is solubilized by the solvent to form a solution.
  • Aspect 4 is the method of aspect 3, further comprising: separating the solubilized elemental sulfur from the solution to obtain elemental sulfur and the solvent; vaporizing the elemental sulfur to form elemental sulfur gas (S)(g); and contacting the (S)(g) with carbon dioxide gas (C0 2 (g)) under reaction conditions sufficient to produce a product stream comprising CO(g) and S0 2 (g).
  • Aspect 5 is the method of aspect 4, wherein the solubilized elemental sulfur is separating from the solution by evaporation at temperature of 25 to 300 °C.
  • Aspect 6 is the method of any one of aspects 4 to 6, wherein the separated solvent is recycled and used in step (a).
  • Aspect 7 is the method of any one of aspects 3 to 6, wherein the solvent is toluene, pyridine, monoethanolamine (MEA), aniline, diethanolamine (DEA), or methyldiethanolamine (MDEA).
  • Aspect 8 is the method of any one of aspects 1 to 7, wherein the H 2 S is contacted with a catalyst comprising a metal, a metal oxide, a metal sulfide, a lanthanide, a lanthanide oxide, spinel, perovskite, olivine, pyrochlore, or any combination thereof.
  • Aspect 9 is the method of aspect 8, wherein the metal, metal oxide, or metal sulfide includes a Column 2, 3, 4, 6, 9-12 metal or combinations thereof.
  • Aspect 10 is the method of aspect 9, wherein the catalyst is a supported Ml or M1M2 sulfide catalyst, wherein Ml and M2 are Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, or Zr; and preferably an alumina or silica supported Co-Mo, Ni-Mo sulfide catalyst.
  • Aspect 11 is the method of any one of aspects 4 to 10, wherein the H 2 S in step (a) is dispersed in the solvent in step (a).
  • Aspect 12 is the method of any one of aspects 1 to 11, wherein the product stream from step (d) further comprises carbonyl sulfide gas (COS(g)), carbon disulfide gas (CS 2 (g)), C0 2 (g) and/or S(g).
  • Aspect 13 is the method of aspect 12, wherein the product stream from step (d) consists essentially of or consists of CO(g), S0 2 (g), COS(g), C0 2 (g), and S(g) or CO(g), S0 2 (g), COS(g), CS 2 (g), C0 2 (g), and S(g).
  • Aspect 13 is the method of any one of aspects 1 to 13, wherein the reaction mixture comprises a C0 2 (g): S(g) molar ratio of 1 : 1 to 6: 1 or a C0 2 (g): S(g) molar ratio of 1 : 1, 2: 1, 4: 1, or 6: 1, and wherein the reaction mixture optionally does not include CS 2 (g).
  • Aspect 14 is the method of any one of aspects 1 to 14, wherein: the reaction temperature in step (c) is 250 °C to 3000 °C, preferably 900 °C to 2000 °C, most preferably 1000 °C to 1600 °C; the reaction pressure in step (d) is 0.1 MPa to 2.5 MPa; and/or the gas hourly space velocity (GHSV) in step (d) is 100 to 100,000 h "1 .
  • the reaction temperature in step (c) is 250 °C to 3000 °C, preferably 900 °C to 2000 °C, most preferably 1000 °C to 1600 °C
  • the reaction pressure in step (d) is 0.1 MPa to 2.5 MPa
  • the gas hourly space velocity (GHSV) in step (d) is 100 to 100,000 h "1 .
  • step (d) further comprises contacting the elemental sulfur gas from step (c) with C0 2 (g) and a catalyst, preferably a metal, a metal oxide, a metal sulfide, a lanthanide, a lanthanide oxide, or any combination thereof.
  • a catalyst preferably a metal, a metal oxide, a metal sulfide, a lanthanide, a lanthanide oxide, or any combination thereof.
  • Aspect 17 is a system for producing hydrogen gas (H 2 (g)) gas, carbon monoxide gas (CO(g)), and sulfur dioxide gas (S0 2 (g)), the system comprising: a H 2 (g) and elemental sulfur production unit comprising a first reactor that is configured to perform a decomposition of hydrogen sulfide (H 2 S) reaction to produce H 2 (g) and elemental sulfur; and a CO(g) and S0 2 (g) production unit in fluid communication with the H 2 (g) and elemental sulfur production unit, the CO(g) and S0 2 (g) production unit comprising a second reactor that is configured to produce CO(g) and S0 2 (g) from a reaction of carbon dioxide gas (C0 2 (g)) with elemental sulfur gas.
  • H 2 (g) and elemental sulfur production unit comprising a first reactor that is configured to perform a decomposition of hydrogen sulfide (H 2 S) reaction to produce H 2 (g) and elemental sulfur
  • Aspect 18 is the system of aspect 17, wherein the first reactor is coupled to a pressure swing adsorption apparatus capable of separating H 2 (g) from unreacted H 2 S.
  • Aspect 19 is the system of any one of aspects 17 to 18, wherein the first reactor is coupled to a separation unit capable of separating produced elemental sulfur from a solution comprising a solvent.
  • Aspect 20 is the system of aspect 19, wherein the first reactor is a trickle-bed reactor and the separation unit is an evaporation unit that is capable of separating elemental sulfur from the solution.
  • Elemental sulfur includes all allotropes of sulfur (i.e., S « where n is greater than or equal to 1).
  • Non-limiting examples of sulfur allotropes include S, S 2 , S 4 , S 6 , and S 8 , with the most common allotrope being S 8 .
  • Solid sulfur can contain either (a) sulfur rings, which may have 6, 8, 10 or 12 sulfur atoms, with the most common form being S 8 , or (b) chains of sulfur atoms, referred to as catenasulfur having the formula S ⁇ .
  • Liquid sulfur is typically made up of S 8 molecules and other cyclic molecules containing a range of six to twenty atoms.
  • wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the methods of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase “consisting essentially of,” in one non- limiting aspect, a basic and novel characteristic of the methods of the present invention are their abilities to produce H 2 , CO, and S0 2 in an economical manner.
  • FIG. 1 is an illustration of various products that can be produced from syngas.
  • FIGS. 2A and 2B are schematics of methods and systems of the present invention to produce H 2 , CO, and S0 2 from H2S with recovery of elemental sulfur in a solvent.
  • FIG. 3 is a schematic of a method and a system to separate CO, SO2 and optionally COS.
  • FIG. 4 is a schematic of a method and a system to produce H 2 , CO, and SO2 from H 2 S with recovery of elemental sulfur in the absence of a solvent.
  • FIG. 5 depicts argon (Ar) concentration profiles of production of H 2 from solutions of water, solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • FIG. 6 depicts H2S and H 2 concentration profiles from solutions of water, solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • FIG. 7 depicts Ar concentration profiles during the production of H 2 from a solution of alcohol, solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • FIG. 8 depicts H 2 and H2S concentration profiles from a solution of alcohol, solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • FIG. 9 depicts Ar concentration profiles solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • FIG. 10 depicts H 2 and H2S concentration profiles solvent, iron catalyst contacted with a stream containing 4.8 vol.% H 2 S/Ar.
  • the present invention provides a solution to the current problems associated with converting hydrogen sulfide to hydrogen.
  • the solution resides in an integrated process that combines the decomposition of hydrogen sulfide process with the reduction of CO2 process to produce H 2 , CO, and SO2.
  • the integrated process uses economical abundant feed stocks, i.e., H 2 S and CO2.
  • H 2 S is decomposed to produce H 2 and elemental sulfur, which is used with CO2 as the feedstock in the reduction of CO2 process.
  • the reduction of CO2 process can be tuned via the reaction temperature and amounts of reactants used to obtain a particular product stream profile. For instance, other reaction products that can be produced during the reaction include COS(g), S(g), and CS(g).
  • Each of the reaction products can be further processed into desired chemicals.
  • the produced carbon monoxide can be converted to synthesis gas (syngas) by converting part of the carbon monoxide to into hydrogen gas by the water gas shift reaction.
  • Syngas can be used in a variety of processes to produce desired chemicals, examples of which are provided in FIG. 1.
  • the produced SO2 can be converted into SO3 and then sulfuric acid and ultimately ammonium sulfate fertilizers.
  • COS(g) and S(g) can be converted into valuable commercial products or used as reactants to produce more carbon monoxide.
  • the H2S feed stream can include H2S and other components such as CO2 ⁇ e.g., sour gas)
  • the H2S can be obtained from various sources.
  • hydrogen sulfide can be obtained from a waste or recycle stream (for example, from a plant on the same site, or as a product from hydrodesulfurization of petroleum products) or recovery the hydrogen sulfide from a gas stream (for example, separation for a gas stream produced during production of petroleum oil, natural gas, or both).
  • a benefit of using hydrogen sulfide as a starting material is that it is abundant and relatively inexpensive to obtain as compared to hydrogen gas.
  • the H2S feed stream can include at least 50, 60, 70, 80 or 90 vol.% of H2S, with the balance being H2O, CO2 or gases inert to the H2S decomposition process.
  • the solvent can include any solvent suitable to solubilize sulfur.
  • Non-limiting examples of solvents include aromatic hydrocarbons, amines, aromatic amines, alkanolamines or the like.
  • Non-limiting examples of aromatic hydrocarbons include toluene, xylene, benzene, and derivatives thereof.
  • Non-limiting examples of aromatic amines include aniline, pyridine and substituted pyridines.
  • Non-limiting examples of alkanolamines include monoethanol amine (MEA), diethanolamine (DEA), and methyldiethanolamine (MDEA). In instances when aniline is used, the reaction is performed at temperatures less than 170 °C.
  • the solvent can be ethylene diamine, ethanolamine, or mixtures thereof.
  • water and/or alcohol ⁇ e.g., propanol, isopropanol, ethanol, with ethanol being preferred
  • the solvent can include 60 to 95 vol.% water and 5 to 40 vol.% amine, or 33 vol.%) amine and 66 vol.%> water, or 10 vol%> amine and 90 vol.%> water.
  • the solvent can include 50 to 95 vol.% alcohol and 5 to 50 vol.% amine, or 95 vol.% alcohol and 5 vol.% amine.
  • the solvent does not include water or alcohols.
  • Carbon dioxide can be obtained from various sources.
  • the carbon dioxide can be obtained from a waste or recycle gas stream (e.g. from a plant on the same site, like for example from ammonia synthesis) or after recovering the carbon dioxide from a gas stream.
  • a benefit of recycling such carbon dioxide as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site).
  • the CO2 is present in the H2S stream.
  • the molar ratio of CC"2(g) to S(g) can range from 1 : 1 to 6: 1 and any range therein. Ratios lower than 1 : 1 and higher than 6: 1 are also contemplated in the context of the present invention. Ultimately, the ratio can be varied to produce a desired reaction product profile.
  • the reactant gas stream is substantially devoid of other reactant gas such as hydrocarbon gases, oxygen gas, hydrogen gas, water or any combination thereof.
  • Hydrocarbon gases include, but are not limited to, Ci to C5 hydrocarbon gases, such as methane, ethylene, ethane, propane, propylene, butane, butylene, isobutene, pentane and pentene.
  • the gaseous feed contains 0.1 wt.% or less, or 0.0001 wt.%) to 0.1 wt.%) of combined other reactant gas.
  • the products made from the decomposition of hydrogen sulfide in the gas phase can be varied by adjusting the amount of H2S provided to a reactor, the catalyst, the reaction conditions, or a combination thereof.
  • Hydrogen gas and elemental sulfur (S) are the major products produce from the decomposition of H2S as shown in reaction equation (1) above.
  • the products made from the reduction of carbon dioxide with sulfur in the gas phase can be varied by adjusting the molar ratio of C02(g) to gaseous elemental S(g), the reaction conditions, or both.
  • the major products produced from the reaction of carbon dioxide and sulfur are carbon monoxide and sulfur dioxide as shown in reaction equation (3).
  • the other products that can be produced by the reaction include CS2 and COS as shown in equation (5), with 10%) or less of the reaction product being CS2 at any ratio of CO2 to S.
  • the distribution of products in the product stream can be controlled by adjusting the ratio of carbon dioxide to sulfur from 1 : 1 to 2: 1 and up to 6: 1 and the temperature of the reaction.
  • the amount of COS(g) produced can be adjusted by varying the temperature of the reaction.
  • the product stream contains COS and SO2 with a minimal amount of CO.
  • the ratio of COS:S02 can be 2: 1 or 1 : 1.
  • the COS can be separated from the SO2 and CO2 as described throughout this Specification and sold or further processed into other chemical products. 4. CO and SO2 Formation from COS
  • CO and SO2 are produced at temperatures between 700 and 3000 °C, 900 to 2000 °C, or 1500 to 1700 °C, with a preferred temperature of between 1000 and 1600 °C and CO2 to S ratios of 1 : 1 to 2: 1, and up to 6: 1.
  • lower temperatures are also contemplated (e.g., 250 °C or more or certain temperature and pressure conditions can be used to ensure sulfur is in the gaseous phase— e.g., conditions at which substantial vapor pressure of S exists (e.g., vapor pressure of S is 5 ⁇ 10 "4 atm at 1 19 °C and 1 atm at 444.6 °C).
  • the ratio of CO(g) to S02(g) in the product mixture can be 0.1 : 1, 1 :2, 1 : 1, or 2: 1.
  • the temperature of the reaction and/or CO2/S ratio can be adjusted to produce a desired CO/SO2 ratio. For example, if a high CO/SO2 is desired, a temperature of 1200 °C can be used instead of 1500 °C. On the other hand, if a high CO/COS ratio is desired, a CO2/S ratio of 6: 1 and temperature of 1500 °C or 1200 °C can be used.
  • the of equilibrium ratios of CO(g) to S02(g) at 918 °C, 1120 °C and 1500 °C and different temperatures are summarized in Table 1
  • a ratio of CO/COS at about 900 °C is about 120: 1 with a starting CO2 to S ratio 6: 1.
  • Equilibrium ratio of CO2 to the combined CO and SO2 is summarized in Table 2.
  • CS2 can be formed as shown in equation (10).
  • the amount of carbon disulfide produced can be about 10% or less on a molar basis.
  • the oxygen produced can react with sulfur to form sulfur dioxide.
  • the amount of CO2 can be increased in the reaction mixture. Without wishing to be bound by theory, it is believed that the increased CO2 reacts with the CS2 to give CO and SO2 at higher concentrations of CO2.
  • CS2 is formed at temperatures between 400 to 3000 °C. It is believed that at temperatures greater than 1000 °C, any carbon disulfide that is generated decomposes to carbon monosulfide CS(g) and S(g). The generated sulfur can react with excess carbon dioxide to continue production of COS, CO and SO2. Without wishing to be bound by theory, it is believed that the carbon monosulfide can polymerize at reaction temperatures above 1000 °C.
  • Decomposition of hydrogen sulfide can be performed at conditions to produce hydrogen gas and elemental sulfur.
  • the produced sulfur can be reacted with CO2 at conditions to produce CO and SO2, and optionally COS.
  • Non-limiting examples of the integrated process to produce H2, CO and SO2 are illustrated with reference to the Figures.
  • FIGS. 2 A and 2B are schematics of a first reactor system 100 of the present invention for the production of hydrogen (H2) and elemental sulfur from the decomposition of hydrogen sulfide (H2S) in the presence of a solvent.
  • the H2S decomposition reactor used for the present invention can be a reactor suitable for contacting solvent with H2S, or in some alternative aspects, when a solvent is not used, can include fluidized bed reactors, plug-flow reactors, fixed bed reactors.
  • H2S decomposition reactor 102 can be manufactured from material resistant to corrosion from solvents, hydrogen sulfide, sulfur and/or carbon dioxide.
  • FIG. 2A depicts a trickle bed reactor system and FIG. 2B depicts a CSTR system.
  • H2S decomposition reactor 102 includes solvent 104 that is capable of solubilizing elemental sulfur.
  • Gaseous hydrogen sulfide stream 106 can enter H2S decomposition reactor and be dispersed (trapped) in the solvent.
  • gaseous hydrogen sulfide stream 106 can enter H2S decomposition reactor and be dispersed in the solvent.
  • solvent 104 and gaseous hydrogen sulfide stream 106 are being added in a concurrent movement.
  • solvent 104 and gaseous hydrogen sulfide stream 106 can flow in a counter-current direction.
  • Solvent 104 can be heated up to 300 °C, for example above 20 to 100 °C, 20 °C to 50 °C, or 20 to 40 °C.
  • the decomposition of H2S is performed at 20 to 30 °C, or 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, or any value or range there between at 0.08 to 0.2 MPa, or about 0.1 of pressure.
  • the H2S decomposes to H2 and elemental sulfur.
  • the elemental sulfur is solubilized in solvent 104.
  • reactor 102 may include one or more catalysts of the present inventions (for example, catalysts described in Section D) can be positioned in the reaction zone 108.
  • Gaseous H2S feed 106 can contact the catalyst in reaction zone 108 to produce H2 and elemental sulfur.
  • the elemental sulfur that is produced during contact of the H2S with the catalyst is solubilized in solvent 104.
  • Solubilized elemental sulfur solution 1 10 can exit reactor 102 and enter liquid/solid separation unit 1 12.
  • separation unit 1 12 is an evaporation unit capable of separation solid sulfur from the solvent.
  • the sulfur/solvent solution is heated to temperatures sufficient to vaporize the solvent to produce solvent stream 1 14 and solid elemental sulfur.
  • Solvent stream 1 14 can exit evaporation unit 1 12 and be returned to reactor 102 or mixed with a feed stream entering the reactor.
  • additional solvent can be added to reactor 102 to maintain the solvent at a constant level. Elemental sulfur in solid form can be removed from separation unit 1 12 and stored in a sulfur storage unit (not shown).
  • the solid elemental sulfur can be heated to a temperature that is sufficient to allow the sulfur to flow (e.g., liquid or slurry form).
  • Hot elemental sulfur 1 16 can exit separation unit 1 12 and be transported to a CO and SO2 production unit. In some aspects, hot elemental sulfur 1 16 can exit separation unit 1 12 and be transported to sulfur melting unit 120.
  • Product stream 1 18 that includes H2 and any unreacted hydrogen sulfide can exit reactor 102 and enter gas separation unit 122.
  • separation unit is a pressure swing adsorption unit (PSA).
  • PSA pressure swing adsorption unit
  • the H2 is separated from other gases in product stream 1 18 to produce purified H2 stream 124 and recycle gas stream 126.
  • Recycle gas stream 126 which can include H2S and/or CO2 can be recycled to reactor 102.
  • Purified H2 stream 124 can be collected, sold, or transported to other units for processing (e.g., synthesis gas unit).
  • Valves 128 can be used to control the flow of gas and liquid in and out of reactor 102 to maintain the desired gas to solvent ratio. Valves 128 may be two-way or three-way valves.
  • H2S decomposition reactor 102 can include solvent 104 in reaction zone 108.
  • reaction zone 108 includes one or more catalysts of the present invention.
  • Gaseous hydrogen sulfide stream 106 can enter reactor 102 and contact solvent 104 with agitation.
  • Gaseous hydrogen sulfide stream 106 can include H2S and an inert carrier gas.
  • gaseous hydrogen sulfide stream 106 flows through the agitated solution at a constant flow.
  • at least 5 vol.%, at least 50 vol.%, at least 90 vol.% or at least 100% or about 5% to 100% or any range or value there between of the H2S is trapped by the solvent.
  • Catalyst stream 130 can exit decomposition reactor 102 and enter solid/liquid separation recovery unit 132.
  • Catalyst stream 130 can include catalyst, or a mixture of catalyst and solvent, dissolved sulfur, and trapped H2S.
  • the catalyst can be separated from the solvent, sulfur, and optional H2S mixture to produce catalyst stream 134 and solvent stream 136.
  • the catalyst is regenerated in solid/liquid separation recovery unit 132.
  • Catalyst stream 134 can exit solid/liquid separation recovery unit 132 and enter decomposition reactor 102.
  • Separated solvent stream 136 can include sulfur and H2S dissolved in the solvent.
  • Separated solvent stream 136 can enter gas/liquid/solid separator 138.
  • separator 138 the solid sulfur phase can be separated from the liquid and gas phases through evaporation of the solvent and/or gas to from a solid sulfur phase and solvent stream 140.
  • Solvent stream 140 can include solvent 104 and H2S. In some aspects, solvent stream 104 does not include any H2S.
  • Solvent stream 140 can be recycled to reactor 102 and/or be combined with gaseous H2S stream 106 as it enters the reactor 102.
  • Sulfur stream 142 can exit gas/liquid/solid separator 138 and enter sulfur melter 120.
  • sulfur stream 142 is heated to a temperature sufficient to reduce the viscosity of the sulfur to produce molten sulfur so that the sulfur can flow or be pumped from the solid separator 138 to sulfur melter 120.
  • elemental sulfur can be vaporized to elemental sulfur gas (S)(g) 144 in sulfur melter 120.
  • Gaseous sulfur stream 144 can exit sulfur melter 120 and enter CO and SO2 production unit 146.
  • Gaseous CO2 stream 148 can enter CO/SO2 production unit 146.
  • CO2 and S(g) are reacted to produce product stream 150 that includes CO, SO2, and optional COS.
  • a catalyst can be used to promote the reaction of C02(g) and S(g).
  • CO and SO2 production unit 146 can be any type of reactor system that allows for the contact of S(g) and C02(g) in the presence or absence of a catalyst and is manufactured from material resistant to corrosion from sulfur and/or carbon oxides. Such materials include corrosion resistant stainless steels.
  • reactors include fixed-bed reactors, stacked bed reactors, fluidized bed reactors, slurry or ebullating bed reactors, spray reactors, or plug flow reactor. Suitable reactors and reaction conditions for conversion of CO to SO2 are described in International Application Publication No. WO 2016/061205 to D' Souza et al., which is incorporated herein by reference in its entirety.
  • Product stream 150 can exit CO/SO2 production unit 146 and enter quench unit 152 to cool the product stream.
  • Quench unit 152 can be a series of heat exchangers.
  • Cooled product stream 154 can exit quench unit 152 and enter separation unit 156.
  • separation unit 156 SO2, CO, and COS can be separated from cooled product stream 158 and be collected, stored, recycled to CO/SO2 production unit 146, or used in process to produce H2 (e.g., RWGSR).
  • FIG. 3 is a schematic of a separation process to separate cooled product stream 158 into one or more products.
  • Cooled product stream 158 can enter SO2 separation unit 202, in which the SO2 is removed.
  • Separation unit 202 can be any separation unit capable of separating SO2 from CO and COS.
  • separation column can include an adsorption column, permeable to CO and COS (i.e., SO2 adsorbs on the column) to produce CO/COS stream 204.
  • Adsorbed SO2 can be desorbed from the column (i.e., change in pressure of the column) and exit separation unit 202 as SO2 product stream 206.
  • SO2 product stream can be collected, stored or transported to other units for processing.
  • SO2 product stream can be transported to a sulfuric acid production unit.
  • CO/COS product stream 204 can exit separation unit 202 and undergo compression in compressor 208 to produce compressed CO/COS stream 210.
  • Compressed CO/COS 210 stream can be passed through CO2 separation unit 212 to remove any CO2 present in the stream and produce CO2 stream 214 and scrubbed CO/SO2 stream 216.
  • Separation unit 212 can be any separation unit capable of separating CO2 from CO and/or COS (e.g., a membrane unit).
  • Recovered CO2 stream 214 can be recycled to CO/SO2 production unit 146, collected, stored or used in other processing units.
  • CO/COS separation unit 218 can be separation unit capable of separating CO from COS (e.g., membranes, distillation units, and the like) into CO product stream 220 and COS product stream 222.
  • the separated COS can be collected, stored, or transported for further processing.
  • CO product stream can be collected, stored or transported for further processing.
  • CO product stream can be transported to a water- gas shift reactor for conversion to CO2 and H2.
  • H2S is decomposed in the absence of a solvent.
  • FIG. 4 depicts a schematic of the process 300 for the decomposition of H2S in the absence of a solvent.
  • Gaseous hydrogen sulfide stream 106 can enter H2S decomposition reactor 302 and contact catalyst 304 in reaction zone 306. As gaseous H2S stream contacts catalyst 304, the H2S decomposes to H2 and gaseous elemental sulfur.
  • Product stream 310 that includes H2 can exit H2S decomposition reactor 302, and be collected, stored, or transported.
  • H2 product stream 310 can be purified to remove any residual sulfur or unreacted hydrogen sulfide (e.g., the stream can be provided to separation unit 122).
  • Gaseous elemental sulfur stream 312 can exits H2S decomposition reactor 302 and enter CO/SO2 processing reactor 146 to produce CO and SO2.
  • hot elemental sulfur can be collected and stored for future use in CO/SO2 processing reactor 146.
  • gaseous elemental sulfur stream 312 can exits H2S decomposition reactor 302 is provided in sulfur melter 120 and mixed with liquid sulfur.
  • FIGS. 2 through 4 not all conduits and vessel inlets and outlets are described as it should be understood that the units described in the figures have inlets, outlets and conduits that in fluid communication. It should also be understood that the arrangement of the components in the systems can be combined and/or used in a different order.
  • Catalytic material used in the context the H2S decomposition reactor 102 and the CO/SO2 production unit 146 of the present invention may be the same catalysts, different catalysts, or a mixture of catalysts.
  • the catalysts may be supported or unsupported catalysts.
  • the support may be active or inactive.
  • the catalyst support can include refractory oxides, alumina oxides, aluminosilicates, silicon dioxide, metal carbides, metal nitrides, metal sulfides, metal phosphates, or any combination thereof.
  • Non-limiting examples of such compounds includes MgO, AI2O3, S1O2, M02C, TiC, CrC, WC, OsC VC, M02N, TiN, VN, WN, CrN, M02S, ZnS, and any combination thereof.
  • All of the support materials can be purchased or be made by processes known to those of ordinary skill in the art (e.g., precipitation/co-precipitation, sol- gel, templates/surface derivatized metal oxides synthesis, solid-state synthesis, of mixed metal oxides, microemulsion technique, solvothermal, sonochemical, combustion synthesis, etc.).
  • One or more of the catalysts can include one or more metals or metal compounds thereof.
  • the metals that can be used in the context of the present invention to create bulk metal oxides, bulk metal sulfides, or supported catalysts include a metal from Column 2 or compound thereof, a metal from Column 1 1 or compound thereof, a metal from Column 3 or compound thereof, a metal from Column 4 or compound thereof, a metal from Columns 6 or compound thereof, a metal from Columns 8-10 or compound thereof, at least one lanthanide or compound thereof, or any combination thereof.
  • the metals or metal compounds can be purchased from any chemical supplier such as SigmaMillipore ® (USA), Alfa-Aeaser (USA), Strem Chemicals (USA), etc.
  • Non-limiting examples of Column 2 metals (alkaline-earth metals) and metal compounds include Mg, MgO, Ca, CaO, Ba, BaO, or any combinations thereof.
  • Column 1 1 metals and metal compounds can include Cu and CuO.
  • Column 12 metals and metal compounds can include zinc or zinc sulfide.
  • Non-limiting examples, of Column 3 metals and metal compounds can include Sc, SC2O3, the lanthanides or lanthanide compounds, or any combination thereof.
  • Lanthanides that can be used in the context of the present invention to create lanthanide oxides include La, Ce, Dy, Tm, Yb, Lu, or combinations of such lanthanides.
  • Non-limiting examples of lanthanide oxides include Ce0 2 , Dy 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , or La 2 0 3 , or any combination thereof.
  • Lanthanide oxides can be produced by methods known in the art such as by high temperature (e.g., >500 °C) decomposition of lanthanide salts or by precipitation of salts into respective hydroxides followed by calcination to the oxide form.
  • Column 12 metals and compounds include, but are not limited to, Zr and Zr0 2 .
  • Column 6 metals and metal compounds include, but are not limited to, Cr, Cr 2 0 3 , Mo, MoO, Mo 2 0 3 , or any combination thereof.
  • Non-limiting examples of Columns 8-10 metals and metal compounds can include Ru, Ru0 2 , Os, Os0 2 , Co, Co 2 0 3 , Rh, Rh 2 0 3 , Ir, lr 2 0 3 , Ni, Ni 2 0 3 , Pd, Pd 2 0 3 , Pt, Pt 2 0 3 , or combinations thereof.
  • the catalytic material can be subjected to conditions that results in sulfurization of the metal in the catalytic material.
  • Non-limiting examples of metal that can be sulfided prior to use are Co, Mo, Ni and W.
  • the catalyst material can, in some instances include a promoter compound.
  • a non-limiting example of promoter compound is phosphorus.
  • a non-limiting example of a catalyst that includes a promoter compound is catalyst material that includes Mo-Ni-P.
  • the metal oxides described herein can be of spinel (general formula: M304), olivine (general formula: M2Si04), perovskite (general formula: M1M20 3 ), or pyrochlore (general formula: M1M206 or MlM2Cb) classification.
  • the catalyst for H 2 S decomposition can include a supported Ml metal or M1M2 metal, where, without limitation, Ml and M2 can be Cr, Mn, Fe, Co, Ni, CU, Zn, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, Zr.
  • the catalyst can be a Co-Mo, Ni-Mo, Fe-Mo, Mn-Mo, Cu-Mo, or Zn-Mo sulfide catalyst.
  • preferred catalysts for the decomposition of hydrogen sulfide may include an alumina or silica supported Co-Mo or Ni-Mo sulfide catalyst.
  • Process conditions to effect the production of hydrogen (H 2 ) and elemental sulfur can include a temperature and pressure.
  • the temperature can be 0 °C to 300 °C, 20 °C to 100 °C, or about 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 150 °C, 200 °C, 250 °C, 300 °C, or any range or value there between.
  • the pressure can be 0.1 MPa to 20 MPa, 0.5 MPa to 10 MPa, 1 to 5 MPa, or any range or value there between.
  • the catalysts used in the present invention for CO2 reduction is sinter and coke resistant at elevated temperatures, (e.g., 445 °C to 3000 °C, 900 to 2000 °C, or 1000 to 1600 °C). Further, the produced catalysts can be used effectively in reaction of sulfur with carbon dioxide at a pressure of 0.1 MPa to 2.5 MPa, or 0.5 MPa to 2 MPa, or 0.8 MPa to 1.5 MPa, and/or at a gas hourly space velocity (GHSV) range from 1000 to 100,000 h "1 , or any value or range there between.
  • GHSV gas hourly space velocity
  • Non-limiting examples of catalyst for the CO2 reduction can include MoS and/or ZnS.
  • the carbon monoxide produced using the method of the invention can be partially converted into H2 through water gas shift reaction for the production of syngas of desired H2/CO ratio as shown in equation (11).
  • the produced CO2 can be used in the current process to produce more carbon monoxide. This provides an efficient, economic, and novel method to convert a greenhouse gas (CO2) into value added and useful products.
  • SO2 Processing [0067] The sulfur dioxide produced using the method of the invention can be converted to SO3, which can be further processed into sulfuric acid and ammonium sulfate as shown in the equations (12) through (15).
  • the carbonyl sulfide produced using the method of the invention can be used in the production of thiocarbamates.
  • Thiocarbamates can be used in commercial herbicide formulations.
  • the method of the invention provides an advantage over commercially prepared COS, which is synthesized by treatment of potassium thiocyanide and sulfuric acid as shown in equation (16).
  • the conventional treatment produces potassium bisulfate and ammonium bisulfate which needs to be separated, which is a difficult and time consuming process.
  • the method of the invention provides an efficient and economic method solution to the production of COS.
  • Catalyst testing was performed in a reactor system consisting of a two neck 100 ml round bottom flask. In all testing, as stream of 4.8 vol.% FhS/Ar was used as a feed of FhS. The FhS feed (10 ml/min 4.8 Vol.% FhS/Ar) was bubbled through the solution containing solvent mixture and catalysts. Contents of the reactor were continuously stirred using magnetic stirrer at different rates from 100- 400 rpm. All reactions were performed at 22 °C and 1 bar pressure. [0074] Gas analysis performed using a Process Mass Spectrometer (Model: Thermo BT) supplied by Thermo Scientific, UK. All gases were procured from Air Liquide, Saudi Arabia.
  • FIG. 5 and 6 depict gives the profiles for Ar, FhS and Fh over a 72 hour reaction period.
  • FIG. 5 depicts argon concentration profiles of the gaseous FhS/Ar stream during contact with the aqueous amine solvent that includes the iron catalyst.
  • FIG. 6 depicts FhS and Fh concentration profiles of the gaseous FhS/Ar stream during contact with the aqueous amine solvent that includes the iron catalyst.
  • the feed gas was first bypassed to the mass spectrometer (MS) to confirm the concentration of FhS and Ar in the feed gas. After about 5 min., the feed gas was diverted through the reactor where it bubbled through the solution, reacted and left the reactor system. As and when feed gas was passed through the solution containing amine and catalysts, almost 100% FhS was trapped into the amine solution and only pure Ar come out of the solution. After about 20-30 minutes, Fh slowly generated and appeared in the product stream, the concentration of Fh increased with time. After 46 hours, the feed gas was temporarily bypassed from the reactor to check the healthiness of the analysis/analytics and it was found that everything was in order. The experiment was stopped after 72 hours and gasses were bypassed to the mass spectrometer and once again verified the healthiness of the analytics by obtaining the original gas concentration.
  • MS mass spectrometer
  • FIGS. 7 and 8 depict Ar, FhS and Fh profiles obtained for similar reaction in ethanol and ethylene diamine media with Fe as a catalyst over 22 hours.
  • FIG. 7 depicts Ar concentration profiles of the gaseous FhS/Ar stream during contact with the alcohol/amine solvent that includes the iron catalyst.
  • FIG. 8 depicts concentration profiles of the gaseous FhS/Ar stream during contact with the alcohol/amine solvent that includes the iron catalyst.
  • Neat ethanolamine solvent A gaseous FhS/Ar stream (10 mL/min, 4.8 vol.% FhS/Ar) was contacted with an iron metal catalyst (2 g) dispersed in a solvent that included ethanolamine (50 mL).
  • FIG. 9 depicts argon concentration profiles of the gaseous FhS/Ar stream during contact with the ethanolamine solvent that includes the iron catalyst.
  • FIG. 10 depicts Fh and FhS concentration profiles of the gaseous FhS/Ar stream during contact with the ethanolamine solvent that includes the iron catalyst.
  • Post characterization of Fe catalyst was done using powder X-ray diffractometer and found that spent catalyst possessed the same characteristics as the starting material without any chemical/crystallographic changes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'hydrogène gazeux, de monoxyde de carbone gazeux et de dioxyde de soufre gazeux. Le procédé comprend la production d'un mélange d'hydrogène et de soufre élémentaire à partir de sulfure d'hydrogène, la séparation de l'hydrogène du soufre élémentaire et l'utilisation du soufre élémentaire comme réactif dans une réaction de réduction du CO2 pour produire du monoxyde de carbone, du dioxyde de soufre et éventuellement du sulfure de carbonyle.
PCT/IB2018/052421 2017-04-13 2018-04-06 Procédé intégré de production d'hydrogène à partir de sulfure d'hydrogène et de dioxyde de carbone WO2018189637A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762484987P 2017-04-13 2017-04-13
US62/484,987 2017-04-13

Publications (1)

Publication Number Publication Date
WO2018189637A1 true WO2018189637A1 (fr) 2018-10-18

Family

ID=63793166

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2018/052421 WO2018189637A1 (fr) 2017-04-13 2018-04-06 Procédé intégré de production d'hydrogène à partir de sulfure d'hydrogène et de dioxyde de carbone

Country Status (1)

Country Link
WO (1) WO2018189637A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4180386A1 (fr) * 2021-11-16 2023-05-17 TotalEnergies OneTech Procédé de conversion continue de h2s en h2 et en soufre

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611685B2 (en) * 2004-04-01 2009-11-03 Institu Kataliza Imeni G. K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Method for hydrogen sulphide and/or mercaptans decomposition
US20160107893A1 (en) * 2014-10-17 2016-04-21 Sabic Global Technologies B.V. Carbon monoxide production from carbon dioxide reduction by elemental sulfur
JP2017043501A (ja) * 2015-08-24 2017-03-02 昭和シェル石油株式会社 硫化水素の処理方法及び装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611685B2 (en) * 2004-04-01 2009-11-03 Institu Kataliza Imeni G. K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Method for hydrogen sulphide and/or mercaptans decomposition
US20160107893A1 (en) * 2014-10-17 2016-04-21 Sabic Global Technologies B.V. Carbon monoxide production from carbon dioxide reduction by elemental sulfur
JP2017043501A (ja) * 2015-08-24 2017-03-02 昭和シェル石油株式会社 硫化水素の処理方法及び装置

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BANDERMANN, F. ET AL.: "Production of H2 via thermal decomposition of H2S and separation of H2 and H2S by pressure swing adsorption", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 7, no. 6, 1982, pages 471 - 475, XP025591267, Retrieved from the Internet <URL:https://doi.org/10.1016/0360-3199(82)90103-3> *
STARTSEV, A. N. ET AL.: "Low Temperature Catalytic Decomposition of Hydrogen Sulfide into Hydrogen and Diatomic Gaseous Sulfur", TOPICS IN CATALYSIS, vol. 56, no. 11, August 2013 (2013-08-01), pages 969 - 980, XP055552653, Retrieved from the Internet <URL:DOI10.1007/s11244-013-0061-y> *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4180386A1 (fr) * 2021-11-16 2023-05-17 TotalEnergies OneTech Procédé de conversion continue de h2s en h2 et en soufre

Similar Documents

Publication Publication Date Title
US9896339B2 (en) Carbon monoxide production from carbon dioxide reduction by elemental sulfur
CN107250106B (zh) 用于生产甲醛稳定化的尿素的整合方法
CN108368037B (zh) 生产甲醛稳定的脲的整合方法
CN107428650B (zh) 用于生产甲醛的方法
EP3532456B1 (fr) Procédé de production d&#39;urée stabilisée par du formaldéhyde
CN104837555B (zh) 用于同时制造氢的硫回收方法的催化剂、其制造方法以及使用该催化剂的同时制造氢的硫回收方法
JPH0261402B2 (fr)
JPH1143306A (ja) 一酸化炭素および水素を得る方法
ES2882289T3 (es) Proceso para la producción de urea estabilizada con formaldehído
US20190010058A1 (en) Systems and methods for carbon monoxide production by reduction of carbon dioxide with elemental sulfur
WO2018189637A1 (fr) Procédé intégré de production d&#39;hydrogène à partir de sulfure d&#39;hydrogène et de dioxyde de carbone
WO2018127852A1 (fr) Production de monoxyde de carbone, de dioxyde de soufre hydrogéné et de soufre élémentaire à partir de la réduction de dioxyde de carbone par le sulfure d&#39;hydrogène
KR20110076103A (ko) 전로 가스를 이용한 암모니아 제조방법 및 요소 제조방법
RU2782258C2 (ru) Способ получения метанола и аммиака

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: 18783992

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18783992

Country of ref document: EP

Kind code of ref document: A1