EP4551736A1 - Procédé permettant de produire de l'éthylène - Google Patents
Procédé permettant de produire de l'éthylèneInfo
- Publication number
- EP4551736A1 EP4551736A1 EP23738548.9A EP23738548A EP4551736A1 EP 4551736 A1 EP4551736 A1 EP 4551736A1 EP 23738548 A EP23738548 A EP 23738548A EP 4551736 A1 EP4551736 A1 EP 4551736A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stream
- ethanol
- enriched
- ethylene
- enriched stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/046—Alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/023—Measuring, analysing or testing during electrolytic production
- C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
- C25B15/027—Temperature
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/083—Separating products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
Definitions
- the present invention relates to a process for producing ethylene, in particular from a CO-containing stream that has been obtained from CO2 captured from the atmosphere, flue gas or the like.
- Ethylene is an important raw material for multiple end products like ethylene oxide, ethylene glycol, polymers, rubbers, plastics, etc. Processes for producing ethylene are known in the art.
- ethylene has been predominantly produced via steam cracking of hydrocarbons derived from crude oil or via conversion of natural gas.
- One or more of the above or other objects may be achieved according to the present invention by providing a process for producing ethylene, the process at least comprising the steps of:
- step (b) converting the CO-containing stream provided in step (a) in an electrolyzer thereby producing an ethylene-containing vapour stream and an ethanol- containing liquid stream;
- step (c) subjecting at least a part of the ethylenecontaining vapour stream obtained in step (b) to hydration thereby obtaining a first ethanol-enriched stream;
- step (d) separating the first ethanol-enriched stream obtained in step (c) thereby obtaining a second ethanol- enriched stream and a water-enriched stream;
- a further advantage of the process according to the present invention is that ethanol can be easily stored in for example low-cost tanks. This can be of importance in case the electrolyzer is driven by renewable power such as wind, solar and other forms of renewable power that has intermittency issues.
- renewable power such as wind, solar and other forms of renewable power that has intermittency issues.
- the use of relatively expensive batteries to ensure a (n otherwise needed) continuous operation of the electrolyzer can be avoided; this, as in case the electrolyzer is not working because of intermittency issues, the stored ethanol can be used in downstream processes (which often operate continuously) .
- a CO-containing gas stream is provided.
- the CO-containing gas stream is not limited in any way (in terms of composition, temperature, pressure, etc.), as long as it contains CO.
- the CO-containing gas stream may have various origins.
- the CO-containing stream has been obtained from a C02-containing stream, preferably CO2 captured from the atmosphere.
- the CO-containing gas stream may have been obtained by thermochemical or electrochemical CO2 conversion routes; methane conversion routes; gasification of biomass or waste; etc.
- the CO-containing stream provided in step (a) comprises at least 25 mol.% CO, preferably at least 50 mol.% CO.
- H2 is present in the CO-containing stream in an amount of at most 75 mol.%, preferably at most 50 mol.%.
- the CO-containing stream does not contain oxygen (O2) and sulfur compounds such as H2S and SO X .
- the CO-containing stream as provided in step (a) has a temperature in the range of from 0 to 90°C, preferably from 15 to 80°C, more preferably below 65°C.
- the CO-containing gas stream as provided in step (a) typically has a pressure in the range of from 0.5 to 30.0 bara, preferably below 10.0 bara and preferably around 1.0 bara. If appropriate, the CO- containing stream may have been pre-processed to obtain the desired composition and conditions.
- step (b) the CO-containing stream provided in step (a) is converted in an electrolyzer thereby producing an ethylene-containing vapour stream and an ethanol-containing liquid stream.
- the electrolyzer is driven by renewable power.
- Renewable power can be either intermittent or continuous.
- the person skilled in the art will readily understand that the components of the electrolyzer may be constructed from a wide range of materials.
- the cathode as used in the electrolyzer is not particularly limited.
- the cathode of the electrolyzer is selected from copper, silver, gold, platinum, tin, lead, palladium, aluminium, zinc, titania, carbon black, carbon nanotubes, graphene (with or without nitrogen, sulphur, phosphorus doping) or combinations thereof.
- the electrolyzer in step (b) has a cathode that comprises copper (Cu) or a copper-based alloy.
- the anode as used in the electrolyzer is not particularly limited.
- the electrolyzer in step (b) has an anode that comprises a metal selected from the group consisting of nickel (Ni), iron (Fe), iridium (Ir), cobalt (Co), manganese (Mn), ruthenium (Ru) or combinations thereof.
- the anode may comprise an oxide of the above metals.
- the electrolyte is also not particularly limited.
- the electrolyte is an aqueous electrolyte containing a compound selected from the group consisting of carbonates, bicarbonates, hydroxides, halides of Na+, K+, Rb+, Cs+, NH 4 + , deionized water, preferably KOH.
- the temperature at which the electrolyzer is operated is not limited, preferably the electrolyzer in step (b) is operated at a temperature of from 20 to 100°C, preferably from 40 to 90°C. Further, the electrolyzer is preferably operated at a pressure of 0.5- 30 bara, preferably 1.0-10 bara.
- step (b) an ethylenecontaining vapour stream and an ethanol-containing liquid stream are produced.
- the ethylene-containing vapour stream obtained in step (b) comprises at least 0.5 mol.% ethanol, preferably at least 1.0 mol.% ethanol.
- the ethylene-containing vapour stream obtained in step (b) comprises at least 20 mol.% ethylene .
- the ethanol-containing liquid stream obtained in step (b) comprises at most 5.0 mol.% ethylene, preferably at most 1.0 mol.%.
- (b) comprises at least 0.2 mol.% ethanol, preferably at least 1.0 mol.% ethanol.
- the ethanol- containing liquid stream contains some electrolyte, acetate and propanol as well.
- the ethylene-containing vapour stream produced in step (b) is, before subjecting to hydration in step (c), separated thereby obtaining an ethylene-enriched gas stream and a third ethanol-enriched stream, and wherein the ethylene- enriched gas stream is subjected to the hydration in step
- the third ethanol-enriched stream is liquid.
- the ethylene-containing vapour stream is typically separated in a gas/liquid separation vessel, after first being flashed.
- the ethylene-enriched gas stream typically comprises at least 20 mol.% ethylene, preferably at least 30 mol.%.
- the ethylene-enriched gas stream typically contains some CO and H2 as well.
- the third ethanol-enriched liquid stream is typically an aqueous stream and typically comprises at least 10 mol.% ethanol, preferably at least 20 mol.%.
- step (c) at least a part, and preferably all, of the ethylene-containing vapour stream obtained in step (b) is subjected to hydration thereby obtaining a first ethanol-enriched stream.
- a residual CO-containing stream is obtained in addition to the first ethanol-enriched stream.
- This residual CO-containing stream typically also containing some H2 can be recycled.
- the first ethanol-enriched stream typically comprises at least 20 mol.% ethanol, preferably at least 30 mol.% ethanol. It is preferred that the first ethanol-enriched stream (and preferably also the third ethanol-enriched stream) is temporarily stored before separating in step (d).
- the temporary storing can for example take place in a storage tank (hereinafter referred to with a 'first buffer tank').
- a storage tank (hereinafter referred to with a 'first buffer tank').
- An important advantage of the use of such a storage tank (which can be low-cost) is that in case the electrolyzer is driven by renewable power such as wind, solar and other forms of renewable power intermittency issues can be accommodated without the use of expensive batteries. This, as in case the electrolyzer is not working because of intermittency issues, the stored ethanol can be used in downstream processes (which often operate continuously).
- a further advantage of the use of a storage tank is that it can be easily scaled up .
- the third ethanol-enriched stream and the first ethanol-enriched stream formed in step (c) are combined thereby obtaining a combined ethanol stream, and wherein the combined ethanol stream is used in the separation of step (d).
- the combined ethanol stream is temporarily stored before separating in step (d).
- the combined ethanol stream typically comprises at least 20 mol.% ethanol, preferably at least 30 mol.%.
- step (d) the first ethanol-enriched stream obtained in step (c) - or the combined ethanol stream - is separated thereby obtaining a second ethanol-enriched stream and a water-enriched stream.
- step (d) may be performed in many ways, the separation is typically done by distillation. As the person skilled in the art is familiar with such distillation, this is not further discussed here in detail.
- the second ethanol-enriched stream which may be a vapour or liquid, typically comprises at least 85 mol.% ethanol, preferably at least 90 mol.%.
- the second ethanol-enriched stream typically contains some water as well.
- the water-enriched stream typically comprises at least 90 mol.% water and may contain some ethanol, acetate/acetic acid and propanol as well.
- step (e) the second ethanol-enriched stream is subjected to dehydration thereby obtaining ethylene.
- this dehydration step this is not further discussed here in detail.
- the obtained ethylene may be further purified; typically, some water as generated during the dehydration step will be removed.
- the ethanol- containing liquid stream obtained in step (b) is separated thereby obtaining a fourth ethanol-enriched stream and an oxygen-enriched gas stream.
- the ethanol-containing liquid stream is typically separated in a gas/liquid separation vessel, after first being flashed.
- the fourth ethanol-enriched stream is typically liquid and typically comprises at least 0.2 mol.% ethanol, preferably at least 2.0 mol.%.
- the fourth ethanol-enriched stream typically contains some CO and H2 as well.
- the oxygen-enriched gas stream typically comprises at least 90 mol.% oxygen, preferably at least 95 mol.%.
- the remainder is typically water, with some trace amounts of CO2, ethanol and propanol.
- the fourth ethanol-enriched stream is separated thereby obtaining a fifth ethanol-enriched stream and a propanol-enriched stream.
- the separation of the fourth ethanol- enriched stream is via distillation in an alcohol separation unit.
- the fifth ethanol-enriched stream typically comprises at least 70 mol.% ethanol, preferably at least 80 mol.%.
- the fifth ethanol-enriched stream typically contains some water as well.
- the propanol-enriched stream typically comprises at least 0.1 mol.% propanol, preferably at least 0.2 mol.%.
- the propanol-enriched stream will typically obtain some electrolyte, acetate and water as well.
- the fourth ethanol- enriched stream is temporarily stored before being separated (as discussed hereinafter) to obtain the fifth ethanol-enriched stream.
- the temporary storing can for example take place in a storage tank (hereinafter referred to with a 'second buffer tank').
- a storage tank hereinafter referred to with a 'second buffer tank'.
- the fifth ethanol- enriched stream is combined with the combined ethanol stream.
- the propanol-enriched stream is separated thereby obtaining a purified propanol stream and an electrolyte-enriched stream; wherein at least a part of the electrolyte- enriched stream is separated in a further electrolyte- enriched stream and an acetic acid-enriched stream; wherein the acetic acid-enriched stream is hydrogenated thereby obtaining a further ethanol stream; and wherein the further ethanol stream is subjected to dehydration in step (e).
- the present invention provides an apparatus suitable for performing the process for producing ethylene according to the present invention, the apparatus at least comprising:
- a hydration unit for hydrating at least a part of the ethylene-containing vapour stream, thereby obtaining a first ethanol-enriched stream
- a hydration unit for hydrating at least a part of the ethylene-containing vapour stream, thereby obtaining a first ethanol-enriched stream
- an alcohol separation unit for separating the first ethanol-enriched stream, thereby obtaining a second ethanol-enriched stream and a water-enriched stream
- dehydration unit for dehydrating the second ethanol-enriched stream thereby obtaining ethylene.
- Fig. 1 schematically a flow scheme of the process for producing ethylene according to the present invention.
- FIG. 1 The flow scheme of Figure 1 generally referred to with reference number 1, shows an electrolyzer 2, a first g/1 vessel 3, a hydration process unit 4, an ethanol separation (distillation) unit 5, a dehydration unit 6, a first liquid storage tank 7, a mol-sieve unit 8, a second g/1 vessel 9, an alcohol separation (distillation) unit 11, a second liquid storage tank 12, a propanol separation (distillation) unit 13, an acetate/acetic acid separation unit 14 and a hydrogenation unit 15.
- a CO-containing stream 10 is provided.
- the CO-containing stream 10 has preferably been obtained from a C02-containing stream that has been captured from the atmosphere.
- the CO-containing stream 10 is fed, together with an electrolyte 20 to the electrolyzer 2.
- the CO-containing stream 10 is converted thereby producing an ethylene-containing vapour stream 30 and an ethanol-containing liquid stream 40.
- the ethylene-containing vapour stream 30 is subsequently separated - after being flashed in a flash separator (not shown) - in the first g/1 vessel 3, thereby obtaining an ethylene-enriched gas stream 50 and a liquid, third ethanol-enriched stream 60.
- At least a part, but typically all, of the ethylene- enriched gas stream 50 is subjected in the hydration process unit 4 to hydration (enabled by process water stream 70) thereby obtaining a liquid, first ethanol- enriched stream 90 and a residual CO-containing stream 80.
- This residual CO-containing stream 80 (typically also containing some H2) can be recycled to or combined with the output of e.g. a CO-producing unit (not shown) to obtain the CO-containing stream 10.
- the third ethanol-enriched stream 60 and the first ethanol-enriched stream 90 are combined thereby obtaining a combined ethanol stream 100.
- the combining takes place in the first storage tank 7 where the combined stream is temporarily stored, but this may also happen before entering the first storage tank 7.
- the combination may take place somewhere before or in the ethanol separation (distillation) unit 5.
- the combined ethanol stream 100 is separated thereby obtaining a second ethanol-enriched stream 110 and a water-enriched stream 120.
- the second ethanol-enriched stream 110 is then subjected to dehydration in dehydration unit 6, usually in the presence of additional water, thereby obtaining ethylene stream 130 and a further water-enriched stream 135.
- the ethylene stream 130 may be further purified in e.g. a mol-sieve unit 8 to obtain a purified ethylene stream 140 and a water stream 150.
- the ethanol-containing liquid stream 40 is separated - after being flashed in a flash separator (not shown) - in the second g/1 vessel 9, thereby obtaining a liquid, fourth ethanol-enriched stream 160 and an oxygen- enriched gas stream 170.
- the fourth ethanol-enriched stream 160 is temporarily stored in second storage tank 12 and subsequently separated in the alcohol separation (distillation) unit 11 thereby obtaining a fifth ethanol- enriched stream 190 and a propanol-enriched stream 180.
- the fifth ethanol-enriched stream 190 is combined with the combined ethanol stream 100. In the embodiment of Fig. 1, this combination takes places in the ethanol separation (distillation) unit 5, but this can also be done upstream of the ethanol separation (distillation) unit 5.
- the propanol- enriched stream 180 (which also contains electrolyte, acetic acid and acetate) is separated in propanol separation (distillation) unit 13 thereby obtaining a purified propanol stream 200 and an electrolyte-enriched stream 210 which may be recycled to the electrolyzer 2 (not shown).
- FIG. 1 Also shown in Fig. 1 is an optional acetate/acetic acid separation unit 14 for separating (at least a part of) the electrolyte-enriched stream 210 into a further electrolyte-enriched stream 220 (which may be recycled to the electrolyzer 2) and an acetic acid enriched stream 230.
- the acetic acid enriched stream 230 may be treated in the hydrogenation unit 15 to obtain a further ethanol stream 240 which may be fed to the ethanol separation
- Table 1 The values in Table 1 were calculated using a model generated with commercially available Aspen Plus software, whilst using standard thermodynamic packages with setting such that CO2 conversion, alcohol distillation, gas/liquid separation, etc. are simulated.
- electrolyzer block experimental data available from D.S. Ripatti et al., Carbon Monoxide Gas Diffusion Electrolysis that Produces Concentrated C2 Products with High Single-Pass Conversion, Joule, Volume 3, Issue 1, pages 240-256, 2019 (DOI: https://doi.org/10.1016/j.joule.2018.10.007) was used to supplement the Aspen model.
- the process according to the present invention allows for an effective way of producing ethylene from a CO-containing stream.
- An important advantage of the present invention is that by the 'indirect' conversion of carbon monoxide (CO) to ethylene (via the intermediate conversion into ethanol) the separation (via cryogenic distillation) of CO, ethylene and H2 can be avoided.
- CO carbon monoxide
- a further important advantage of the process according to the present invention is that ethanol can be easily stored in for example low-cost tanks. This can be of importance in case the electrolyzer is driven by renewable power such as wind, solar and other forms of renewable power that has intermittency issues.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Analytical Chemistry (AREA)
- Automation & Control Theory (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MA71375A MA71375A (fr) | 2022-07-08 | 2023-07-05 | Procédé permettant de produire de l'éthylène |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263359271P | 2022-07-08 | 2022-07-08 | |
| EP22186030 | 2022-07-20 | ||
| PCT/EP2023/068544 WO2024008793A1 (fr) | 2022-07-08 | 2023-07-05 | Procédé permettant de produire de l'éthylène |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4551736A1 true EP4551736A1 (fr) | 2025-05-14 |
Family
ID=87155606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23738548.9A Pending EP4551736A1 (fr) | 2022-07-08 | 2023-07-05 | Procédé permettant de produire de l'éthylène |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20250369127A1 (fr) |
| EP (1) | EP4551736A1 (fr) |
| CN (1) | CN119546803A (fr) |
| AU (1) | AU2023302583A1 (fr) |
| CA (1) | CA3259750A1 (fr) |
| CL (1) | CL2025000010A1 (fr) |
| MA (1) | MA71375A (fr) |
| WO (1) | WO2024008793A1 (fr) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2978146B1 (fr) * | 2011-07-21 | 2013-08-30 | IFP Energies Nouvelles | Procede de deshydratation de l'ethanol en ethylene a basse consommation energetique |
| US8853468B2 (en) * | 2011-11-18 | 2014-10-07 | Celanese International Corporation | Vapor esterification method to produce ester feed for hydrogenolysis |
| US11920248B2 (en) * | 2018-12-18 | 2024-03-05 | Prometheus Fuels, Inc | Methods and systems for fuel production |
| US20220274094A1 (en) | 2019-07-17 | 2022-09-01 | Sabic Global Technologies B.V. | Selective production of ethylene from methane |
| JP7720057B2 (ja) * | 2020-01-27 | 2025-08-07 | 国立研究開発法人理化学研究所 | カソード電極、カソード電極と基材との複合体及びカソード電極と基材との複合体の製造方法 |
| EP4162099A2 (fr) * | 2020-06-09 | 2023-04-12 | Twelve Benefit Corporation | Système et procédé pour augmenter la concentration de produits à électrons multiples ou de co dans une sortie d'électrolyseur |
| EP4189143A2 (fr) * | 2020-08-03 | 2023-06-07 | Twelve Benefit Corporation | Système et procédé de commande de réacteur à dioxyde de carbone |
-
2023
- 2023-07-05 EP EP23738548.9A patent/EP4551736A1/fr active Pending
- 2023-07-05 AU AU2023302583A patent/AU2023302583A1/en active Pending
- 2023-07-05 CN CN202380052522.3A patent/CN119546803A/zh active Pending
- 2023-07-05 US US18/874,339 patent/US20250369127A1/en active Pending
- 2023-07-05 MA MA71375A patent/MA71375A/fr unknown
- 2023-07-05 CA CA3259750A patent/CA3259750A1/fr active Pending
- 2023-07-05 WO PCT/EP2023/068544 patent/WO2024008793A1/fr not_active Ceased
-
2025
- 2025-01-02 CL CL2025000010A patent/CL2025000010A1/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA3259750A1 (fr) | 2024-01-11 |
| CL2025000010A1 (es) | 2025-04-21 |
| AU2023302583A1 (en) | 2025-01-02 |
| WO2024008793A1 (fr) | 2024-01-11 |
| US20250369127A1 (en) | 2025-12-04 |
| CN119546803A (zh) | 2025-02-28 |
| MA71375A (fr) | 2025-04-30 |
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