WO2022229838A1 - Procédé de production d'hydrogène à partir d'une charge d'hydrocarbures - Google Patents
Procédé de production d'hydrogène à partir d'une charge d'hydrocarbures Download PDFInfo
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- WO2022229838A1 WO2022229838A1 PCT/IB2022/053855 IB2022053855W WO2022229838A1 WO 2022229838 A1 WO2022229838 A1 WO 2022229838A1 IB 2022053855 W IB2022053855 W IB 2022053855W WO 2022229838 A1 WO2022229838 A1 WO 2022229838A1
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 41
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 41
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000007789 gas Substances 0.000 claims abstract description 85
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 64
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 56
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003345 natural gas Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 238000006057 reforming reaction Methods 0.000 claims abstract description 6
- 230000009919 sequestration Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002407 reforming Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 9
- 230000006835 compression Effects 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 4
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000001473 noxious effect Effects 0.000 claims description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229940112112 capex Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- FEBLZLNTKCEFIT-VSXGLTOVSA-N fluocinolone acetonide Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O FEBLZLNTKCEFIT-VSXGLTOVSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
- F25J3/04533—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the direct combustion of fuels in a power plant, so-called "oxyfuel combustion"
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
- F25J3/04521—Coupling of the air fractionation unit to an air gas-consuming unit, so-called integrated processes
- F25J3/04527—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general
- F25J3/04539—Integration with an oxygen consuming unit, e.g. glass facility, waste incineration or oxygen based processes in general for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/80—Integration in an installation using carbon dioxide, e.g. for EOR, sequestration, refrigeration etc.
Definitions
- the present invention relates to a process for producing hydrogen from a hydrocarbon feedstock, such feedstock deriving from fossil sources (solid, liquid or gas) or from bacterial fermentation (biogas).
- Hydrogen (3 ⁇ 4) is an attractive alternative to fossil fuels as a non-polluting source of energy, and it is also a valuable commodity for energy transition media and for industrial uses, for example in product upgrading such as hydrocracking and hydroisomerizing liquid hydrocarbons to produce desirable products.
- Hydrogen is usually produced by reforming or partial oxidation of natural gas or liquid hydrocarbons, which yields synthesis gas (syngas), i.e. a mixture of hydrogen and carbon monoxide (CO) and possibly minor amounts of carbon dioxide (CO2).
- synthesis gas syngas
- CO carbon monoxide
- CO2 carbon dioxide
- the relative amounts of CO/CO2 and 3 ⁇ 4 in a synthesis gas product varies depending upon the way it is generated.
- PSA pressure swing adsorption
- membrane separation or chemical reaction on solid iron oxide and calcium oxide beds, with regeneration of the solids.
- WO 00/03126 relates to a process for the production of electric energy, steam, and carbon dioxide in concentrated form from a hydrocarbon feedstock, comprising formation of synthesis gas in an air driven autothermal reactor unit (ATR); heat exchanging the formed synthesis gas and thereby producing steam, treating at least a portion of the synthesis gas in a CO-shift reactor unit and carbon dioxide separator unit for formation of concentrated carbon dioxide and a hydrogen containing gas which at least partly is combusted in a combined cycle gas turbine for the production of electric energy; and where air from said turbine unit is supplied to the ATR unit, that the exhaust from the gas turbine is heat exchanged for production of steam which together with steam generated upstream is utilized in a steam turbine for production of substantially CO2 -free electric energy.
- ATR air driven autothermal reactor unit
- the Applicant has faced the technical problem of providing a process for producing hydrogen from a hydrocarbon feedstock (the so called "Blue Hydrogen"), especially from natural gas, by means of a reforming reactor, which does not need an external power source, which consumes reduced volumes of fresh water and which does not disperse pollutants, such as nitrogen oxides and particulate, and carbon dioxide in the atmosphere, with a carbon dioxide capture efficiency greater than 99%.
- a hydrocarbon feedstock the so called "Blue Hydrogen”
- pollutants such as nitrogen oxides and particulate
- carbon dioxide capture efficiency greater than 99%.
- the Applicant has found that the above technical problem, and others that are apparent from the present description, can be solved by a process wherein the hydrocarbon feedstock is subjected to a reforming reaction to produce a synthesis gas stream comprising hydrogen (3 ⁇ 4), carbon monoxide (CO) and carbon dioxide (CO2), and the produced synthesis gas stream is then improved in terms of 3 ⁇ 4 yield by a water gas shift (WGS) step. Then, a H2-rich stream and an off-gas stream are produced by a pressure swing adsorption (PSA) step.
- PSA pressure swing adsorption
- the H2-rich stream is ready for subsequent uses, whereas the off-gas stream is subjected to an oxycombustion step, preferably a pressurized oxycombustion step, to generate power and to produce a C0 2 -rich stream, which is then sequestered by water condensation for further use or disposal, e.g. by injection into a geological formation (reservoir).
- oxycombustion step preferably a pressurized oxycombustion step
- water condensation for further use or disposal, e.g. by injection into a geological formation (reservoir).
- the process can be applied in multiple configurations, including the reservoir to operate as recipient when hydrocarbons are taken from the oil&gas field under production.
- the process is especially suitable for small scale plants.
- the present invention relates to a process for producing hydrogen from a hydrocarbon feedstock, comprising the steps of:
- the hydrocarbon feedstock can be natural gas, refinery off-gas, pre-reformed gas, Fischer-Tropsch tail-gas, Liquefied Petroleum Gas (LPG), naphtha, or biogas.
- Biogas is usually obtained by anaerobic bacterial fermentation of organic substrates of vegetal or animal origin, including urban and agriculture wastes.
- the hydrocarbon feedstock is preferably a desulfurized hydrocarbon feedstock, so as to avoid catalyst poisoning in the subsequent steps, especially in the WGS reactor unit.
- the hydrocarbon feedstock is natural gas, which essentially consists of methane.
- the hydrocarbon feedstock is a biogas.
- the process according to the present invention has a negative carbon footprint, because the biogenic carbon is extracted from the atmosphere by means of direct air capture (DAC) technologies.
- the biogas is a desulfurized biogas, i.e. a biogas that has been treated only to eliminate compounds, such as sulfur containing compounds, which may cause catalyst poisoning.
- the reforming reactor unit is usually a refractory-lined pressure-vessel, which operates as an auto-thermal reformer (ATR) or a partial oxidation unit (POX).
- ATR auto-thermal reformer
- POX partial oxidation unit
- the reforming reactor unit comprises:
- the hydrocarbon feedstock is preheated, mixed with steam and fed into the combustion section of the reforming reactor unit, where the gas reaction mixture is heated to a temperature of at least 1200°C.
- the hot gas reaction mixture then enters the reaction section, where the endothermic reforming reaction occurs and reduces the reactor temperature.
- the endothermic reforming reaction may occur in the presence of a catalyst (usually a nickel-based catalyst) or in the absence of a catalyst.
- the reaction pressure is usually maintained at a value of from 20 to 50 barg. If a POX unit is employed, the combustion and reaction sections are usually combined in a single unit.
- the synthesis gas stream exiting from the reforming reactor unit is mainly composed of 3 ⁇ 4, CO and CO2, besides reaction steam in excess and low amounts of unreacted methane and unreacted inert impurities, such as traces of argon and/or nitrogen.
- the reaction steam may be recycled to the reforming reactor unit after the cooling step (ii).
- the synthesis gas stream is subjected to a water gas shift (WGS) reaction, in which CO reacts with steam to form additional 3 ⁇ 4 and CO2.
- WGS water gas shift
- the WGS reaction is subdivided into two steps carried out at different temperatures to achieve high CO conversion and fast reaction rates.
- the high temperature step is usually carried out at a temperature of from 310°C to 450°C, whereas the low temperature step is carried out at a temperature of from 210°C to 240°C.
- the pressure is usually maintained at a value of from 20 and 50 barg.
- the pressure in the WGS reactor unit is substantially the same maintained in the reforming reactor unit, apart a small reduction due to hydraulic loss of the plant.
- the WGS reaction is carried out in the presence of a catalyst.
- a catalyst Generally, an iron/chromium-based catalyst is used in the high temperature step, while a copper/zinc -based catalyst is used in the low temperature step.
- the gas mixture produced in the WGS reactor which is enriched in 3 ⁇ 4 and CO2 by the WGS reaction, is cooled down and fed to a pressure swing adsorption (PSA) unit, which is aimed to separate 3 ⁇ 4 from CO2 and other gases present in the mixture.
- PSA unit is based on adsorption of gases at high pressure by a plurality of adsorbent beds, and their desorption at lower pressure (regeneration). While the adsorption step is usually carried out at the same pressure of the WGS reactor unit (i.e. from 20 barg to 50 barg), the regeneration step is carried out at reduced pressure, usually from 0.2 barg to 1 barg, to maximize the hydrogen recovery yield.
- higher regeneration pressures e.g. from 1 to 5 barg
- a high regeneration pressure increases the overall energy efficiency so as to target the PSA off-gas energy recovery, and also the pressure that can be advantageously used for the subsequent oxycombustion step and the final pressure of the captured CO2, as described below.
- the adsorbent beds usually contain zeolites or activated carbons.
- the PSA unit generally operates at room temperature.
- the off-gas stream obtained from the PSA unit which is produced by desorbing the gaseous products captured by the adsorbent beds, is mainly composed of CO2 and combustible gases, i.e. 3 ⁇ 4, CO and CH4.
- the PSA unit has a yield of high purity 3 ⁇ 4 usually from 80% to 90% of the initial amount of 3 ⁇ 4 present in the gas mixture withdrawn from the WGS reactor.
- the off-gas stream obtained from the PSA unit is fed to an oxycombustion unit.
- the fuel in the present case the fuel is the off-gas stream from the PSA unit
- the exhaust of the oxycombustion process is a C0 2 -rich stream which mainly contains CO2 and steam, with low amounts of gaseous impurities.
- the oxycombustion unit is also fed with an additional fuel stream, which can be natural gas or any hydrocarbon waste or also a portion of the hydrocarbon feedstock employed for the fuel feed stream of the reforming step (i).
- the oxycombustion unit may be operated at atmospheric pressure. However, it is preferred to use a pressurized oxycombustion unit, operating at a pressure of from 12 barg to 35 barg, more preferably from 15 barg to 25 barg. The pressure value is optimized depending on the intended application of the CC -rich stream and on the plant boundary conditions (e.g. the pressure of the feed gases, especially of the oxygen feed stream).
- a pressurized oxycombustion unit allows to minimize the additional fuel stream and to have an overall process independent from external energy sources.
- the pressurized oxycombustion unit may be coupled with a PSA unity employing a higher regeneration pressure, e.g. from 1 to 5 barg, as disclosed above.
- the CCh-rich stream is preferably subjected to cooling and compression so as to condense the steam and separate it from CO2.
- this step comprises a cascade of cooling/compression cycles, wherein condensed water in a stage is recycled back to the previous stage, to flash the dissolved CO2 so as to achieve a higher CO2 capture efficiency.
- the oxycombustion unit allows to recover water condensation energy at high temperature, which would be otherwise lost if steam in the flue gases is sent to the atmosphere: as already pointed out, this increase the overall process energy efficiency.
- the condensed steam is recycled back as steam feed and requires a very small make-up to compensate the steam that remains in the CC -rich stream or with the immiscible gases that separate from the liquid/dense phase CO2.
- the CC -rich stream may be subjected to sequestering by injection into a geological formation, e.g. a hydrocarbon (oil or gas) reservoir, an aquifer or cavern, where CO2 is entrapped in a stable form so as to avoid dispersion into the atmosphere.
- a geological formation e.g. a hydrocarbon (oil or gas) reservoir, an aquifer or cavern, where CO2 is entrapped in a stable form so as to avoid dispersion into the atmosphere.
- the CC -rich stream may also be utilized in supercritical extraction systems or in processes where a low/medium high pressure CO2 stream is demanded.
- the CC -rich stream may be pumped into a pipeline, or refrigerated and loaded into liquid CO2 vessels which are ready for shipping elsewhere. This last application represents indeed a carbon sequestration plant in alternative to post-combustion on flue gases or pre-combustion capture on syngas when hydrogen is used as fuel.
- the CC -rich stream may be advantageously used for enhanced oil recovery (EOR) to increase production capacity from oil reservoirs.
- EOR enhanced oil recovery
- the compressed CCh-rich stream is pumped in the hydrocarbon reservoir where it displaces the hydrocarbons contained in the porous and permeable reservoir rock towards a production well for enhanced recovery of hydrocarbons therefrom.
- the CCh-rich stream may also be used for the stabilization of the extracted oil, i.e. for the removal of noxious volatile components from the extracted oil for subsequent safe storage.
- the removal of volatile components is achieved by the stripping effect caused by CO2 injection into the oil and by direct heat exchange with water condensation which favours evaporation of the same. This minimizes or avoids the supply of heat from external sources for oil stabilization and the use of cooling media for the CCh-rich stream, thus improving energy balance of the overall process.
- CO2 will be considered at plant design stage and duly managed during operational stage with minimal constrains, having it passing through the process as inert gas and so re-injected into the hydrocarbon reservoir together with the new CO2 formed by the process.
- the compressed CCh-rich stream may be sequestered by injection into a depleted oil or gas reservoir where the production wells have been shut-in or into an aquifer or into a cavern for storage therein.
- the CC -rich stream may be also utilized in a chemical process, e.g. in a urea production plant, according to well known techniques.
- the CC -rich stream may be sent to a carbon capture and sequestration (CCS) plant, through an export unit (e.g. a CO2 pipeline or a CO2 liquid carrier).
- CCS carbon capture and sequestration
- export unit e.g. a CO2 pipeline or a CO2 liquid carrier
- the process according to the present invention can be easily coupled with an ammonia plant, where the nitrogen separated in the air separation unit that supplies oxygen can be used for ammonia synthesis and so obtaining Blue Ammonia.
- the CC -rich stream may be used for food and beverage industry, after proper purification to food grade.
- the process according to the present invention has a CO2 capture efficiency of about 99% and an energy conversion efficiency from the hydrocarbon feedstock to Fh at least equal to 70%.
- the energy conversion efficiency is the energy percentage that is transferred from the hydrocarbon feedstock to Fh, with respect to the energy contained in the hydrocarbon feedstock. This efficiency values are remarkably higher that those that can be obtained in the production of blue-hydrogen, which are at most equal to 65%.
- Cascaded utilization of low enthalpy heat can be achieved in nearby applications, such as in a biogas anaerobic digestor plant or in the oil&gas treatment plant that supplies the hydrocarbon feedstock.
- This heat recovery achieves an energy conversion for the process according to the present invention similar to Grey-Fh while capturing pressurized CO2 with 99% efficiency.
- Figure 1 shows a schematic block diagram of a process according to the present invention.
- the plant for carrying out the process according to the present invention comprises an air separation unit (1), which is aimed to separate pure oxygen (O2 3 95% v/v) from air according to known techniques, usually by fractional distillation.
- the pure oxygen stream is conveyed to a reforming reactor unit (2) where it is mixed with a hydrocarbon feedstock stream, preferably a methane feed stream from a natural gas network or from a reservoir (3), and a steam feed line (4a) which collects steam mainly deriving from water recovery from the subsequent steps of the process through steam feed lines (4b), especially from the cooling and compression steps of the CCh-rich stream (10) obtained from the oxycombustion unit (9).
- a portion of the hydrocarbon feedstock stream may be fed to the oxycombustion unit (9).
- the syngas stream withdrawn from the reforming reactor unit (2) is cooled down by means of a cooling unit (5) and then fed to a WGS reactor unit (6), wherein CO is reacted with steam to form 3 ⁇ 4 and CO2 so as to increase the hydrogen yield.
- the cooling unit (5) allows to recover steam that can be recycled to the reforming reactor unit (2) through the steam feed line (4a).
- the gas mixture produced in the WGS reactor unit (6) is then conveyed into a PSA unit (7) to produce a hydrogen- rich stream and an off-gas stream.
- the hydrogen-rich stream may be fed to a hydrogen compression unit (8), where the 3 ⁇ 4 gas is compressed and bottled for transportation to the final user.
- the CC -rich stream produced in the oxycombustion unit (9) is fed to a cooling and compression unit (10), where the steam contained in the CO2- rich stream is condensed and recycled to the cooler (5) through the condensed steam feed line (4b).
- a portion of the CC -rich stream is fed to the oxycombustion unit (9) to control the oxycombustion temperature.
- the heat obtained during condensation is recovered to increase the overall process energy efficiency.
- the compressed CO2- rich stream is then sequestered and/or used in a chemical process as described hereinabove.
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Abstract
L'invention concerne un procédé de production d'hydrogène à partir d'une charge d'hydrocarbures, la charge d'hydrocarbures, de préférence un courant de gaz naturel, étant soumise à une réaction de reformage pour produire un flux de gaz de synthèse comprenant de l'hydrogène (H2), du monoxyde de carbone (CO) et du dioxyde de carbone (CO2), et le courant de gaz de synthèse produit est ensuite amélioré en termes de rendement en H2 par une étape de conversion de gaz à l'eau (WGS). Ensuite, un courant riche en H2 et un courant de dégagement gazeux sont produits par une étape d'adsorption modulée en pression (PSA). Le courant riche en H2 est prêt pour des utilisations ultérieures, tandis que le courant de dégagement gazeux est soumis à une étape d'oxy-combustion pour générer de l'énergie et pour produire un courant riche en CO2. De préférence, l'étape d'oxycombustion est mise sous pression, à une pression prédéterminée pour maximiser l'efficacité énergétique. Le courant riche en CO2 est ensuite séquestré par condensation d'eau pour une utilisation ultérieure ou une élimination, par exemple par injection dans une formation géologique (réservoir). Le procédé peut être appliqué dans de multiples configurations, y compris un procédé pour fonctionner comme une installation de séquestration CCS et un réservoir pour fonctionner comme un récipient lorsque des hydrocarbures sont prélevés du champ pétrolifère et de gaz en cours de production. Le procédé est particulièrement approprié pour des installations à petite échelle.
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EP22720510.1A EP4330187A1 (fr) | 2021-04-27 | 2022-04-26 | Procédé de production d'hydrogène à partir d'une charge d'hydrocarbures |
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IT102021000010631A IT202100010631A1 (it) | 2021-04-27 | 2021-04-27 | Processo per produrre idrogeno da una materia prima idrocarburica. |
IT102021000010631 | 2021-04-27 |
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EP (1) | EP4330187A1 (fr) |
IT (1) | IT202100010631A1 (fr) |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115853479A (zh) * | 2022-12-29 | 2023-03-28 | 西南石油大学 | 一种基于低渗水侵气藏的制氢方法 |
US11814288B2 (en) | 2021-11-18 | 2023-11-14 | 8 Rivers Capital, Llc | Oxy-fuel heated hydrogen production process |
US11859517B2 (en) | 2019-06-13 | 2024-01-02 | 8 Rivers Capital, Llc | Power production with cogeneration of further products |
US11891950B2 (en) | 2016-11-09 | 2024-02-06 | 8 Rivers Capital, Llc | Systems and methods for power production with integrated production of hydrogen |
US11946001B2 (en) | 2021-04-22 | 2024-04-02 | Iogen Corporation | Process and system for producing fuel |
US12054388B2 (en) | 2017-11-09 | 2024-08-06 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
WO2024172664A1 (fr) * | 2023-02-16 | 2024-08-22 | Zeg Power As | Procédé et installation de production d'ammoniac bleu |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003126A1 (fr) | 1998-07-13 | 2000-01-20 | Norsk Hydro Asa | Procede de production d'energie electrique, de vapeur et de dioxyde de carbone a partir d'une charge d'hydrocarbure |
EP2233433A1 (fr) * | 2009-03-24 | 2010-09-29 | Hydrogen Energy International Limited | Procédé pour la génération d'électricité et pour la séquestration de dioxyde de carbone |
EP2233430A1 (fr) * | 2009-03-24 | 2010-09-29 | Hydrogen Energy International Limited | Procédé de génération d'hydrogène et dioxyde de carbone |
US20170152219A1 (en) * | 2015-12-01 | 2017-06-01 | Rachid Mabrouk | Method for the manufacture of urea |
US20200231435A1 (en) * | 2017-09-29 | 2020-07-23 | Research Triangle Institute | Methods and apparatus for production of hydrogen |
-
2021
- 2021-04-27 IT IT102021000010631A patent/IT202100010631A1/it unknown
-
2022
- 2022-04-26 WO PCT/IB2022/053855 patent/WO2022229838A1/fr active Application Filing
- 2022-04-26 EP EP22720510.1A patent/EP4330187A1/fr active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003126A1 (fr) | 1998-07-13 | 2000-01-20 | Norsk Hydro Asa | Procede de production d'energie electrique, de vapeur et de dioxyde de carbone a partir d'une charge d'hydrocarbure |
EP2233433A1 (fr) * | 2009-03-24 | 2010-09-29 | Hydrogen Energy International Limited | Procédé pour la génération d'électricité et pour la séquestration de dioxyde de carbone |
EP2233430A1 (fr) * | 2009-03-24 | 2010-09-29 | Hydrogen Energy International Limited | Procédé de génération d'hydrogène et dioxyde de carbone |
US20170152219A1 (en) * | 2015-12-01 | 2017-06-01 | Rachid Mabrouk | Method for the manufacture of urea |
US20200231435A1 (en) * | 2017-09-29 | 2020-07-23 | Research Triangle Institute | Methods and apparatus for production of hydrogen |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11891950B2 (en) | 2016-11-09 | 2024-02-06 | 8 Rivers Capital, Llc | Systems and methods for power production with integrated production of hydrogen |
US12054388B2 (en) | 2017-11-09 | 2024-08-06 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
US11859517B2 (en) | 2019-06-13 | 2024-01-02 | 8 Rivers Capital, Llc | Power production with cogeneration of further products |
US12098658B2 (en) | 2019-06-13 | 2024-09-24 | 8 Rivers Capital, Llc | Cogeneration of chemical products |
US11946001B2 (en) | 2021-04-22 | 2024-04-02 | Iogen Corporation | Process and system for producing fuel |
US11814288B2 (en) | 2021-11-18 | 2023-11-14 | 8 Rivers Capital, Llc | Oxy-fuel heated hydrogen production process |
CN115853479A (zh) * | 2022-12-29 | 2023-03-28 | 西南石油大学 | 一种基于低渗水侵气藏的制氢方法 |
WO2024172664A1 (fr) * | 2023-02-16 | 2024-08-22 | Zeg Power As | Procédé et installation de production d'ammoniac bleu |
Also Published As
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EP4330187A1 (fr) | 2024-03-06 |
IT202100010631A1 (it) | 2022-10-27 |
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