WO2015014527A1 - Process for producing high purity co by membrane purification of soec-produced co - Google Patents
Process for producing high purity co by membrane purification of soec-produced co Download PDFInfo
- Publication number
- WO2015014527A1 WO2015014527A1 PCT/EP2014/062362 EP2014062362W WO2015014527A1 WO 2015014527 A1 WO2015014527 A1 WO 2015014527A1 EP 2014062362 W EP2014062362 W EP 2014062362W WO 2015014527 A1 WO2015014527 A1 WO 2015014527A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bar
- membrane
- soec
- retentate
- permeate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- 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
- B01D53/22—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 diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- 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
-
- 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
- B01D2256/20—Carbon monoxide
-
- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0208—Other waste gases from fuel cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/25—Recirculation, recycling or bypass, e.g. recirculation of concentrate into the feed
- B01D2311/251—Recirculation of permeate
- B01D2311/2512—Recirculation of permeate to feed side
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates to a process for producing high purity carbon monoxide (CO) by membrane purification of CO produced in a solid oxide electrolysis cell (SOEC) .
- CO carbon monoxide
- a solid oxide electrolysis cell is a solid oxide fuel cell (SOFC) run in reverse mode, which uses a solid oxide or ce- ramie electrolyte to produce e.g. oxygen and hydrogen gas by electrolysis of water. It can also be used to produce CO from carbon dioxide (C0 2 ) , which is led to the fuel side of the SOEC or SOEC stack with an applied current. Excess oxy ⁇ gen is transported to the oxygen side of the SOEC, option- ally using air, nitrogen or CO 2 to flush the oxygen side, and afterwards the product stream from the SOEC, containing CO mixed with CO 2 , is subjected to a separation process.
- SOFC solid oxide fuel cell
- Carbon monoxide of high purity is an important raw material for the synthesis of chemicals. Most reactions for the syn ⁇ thesis of chemicals require high temperatures as well as high pressures, and therefore the CO used should have the lowest possible content of carbon dioxide (C0 2 ) which cor ⁇ rodes the reactor by oxidation. Additionally, CO 2 may limit the equilibrium conversion of the reaction in which the produced CO takes part. CO 2 may also inhibit the kinetics of the reaction where CO is used.
- US 6,787,118 is related to selective removal of CO. More specifically it deals with catalyst compositions useful for destruction of volatile organic carbon compounds (VOCs) in an oxygen-containing gas stream at low temperatures and for selective oxidation of carbon monoxide from a hydrogen- containing gas. This patent is not related to any use of membranes.
- VOCs volatile organic carbon compounds
- EP 0 129 444 and US 4,539,020 concern high- purity CO obtained by pressure swing adsorption (PSA) .
- PSA pressure swing adsorption
- PSA pressure swing adsorption
- SOEC is an attractive alternative to PSA, mainly due to its simplicity, because a membrane separation unit operates without any moving parts, but also due to a reduced capital expenditure (CAPEX) because of its modular nature.
- Gas separation membranes are presently used for the removal of CO2 from natural gas and syngas.
- Such membranes can be based on polymers or zeolites coated on alumina tubes, and they generally have a selectivity towards transporting CO2 through the membrane, whereas hydrocarbons, 3 ⁇ 4 and CO are held back on the retentate side.
- Typical selectivity con ⁇ stants for CO/ CO2 are between 5 and 20, and fluxes may vary from 20 to 200 Nm 3 /h per m 2 membrane area.
- Membrane separation is driven by the difference in partial pressure, and thus it is most suitable for removing the bulk of an impurity, such as CO2 , whereas an extensive mem ⁇ brane area is required to reach a high purity when the driving force for separation decreases.
- the mem ⁇ branes may be of planar or tubular shape, and they may be used in a single membrane unit or in multiple membrane units in series or in parallel.
- the driving force for separation can be boosted by applying a high absolute pressure on the retentate side of the mem- brane and applying an approximate vacuum on the permeate side of the membrane.
- a CAPEX limitation for installing a multi-stage compressor to reach a high pressure and the power required to drive the compressor.
- the maximum pressure difference is also limited by the mechanical strength of the membrane and of the mem ⁇ brane module.
- the present invention relates to a selective separation of CO from a mixture of CO and CO 2 , especially in relation to small scale production of CO by SOEC electrolysis.
- the principle is quite similar to a reflux column within dis ⁇ tillation.
- the invention concerns a process for pro- ducing high purity carbon monoxide (CO) by membrane purifi ⁇ cation of CO produced in a solid oxide electrolysis cell (SOEC), said process comprising the following steps:
- the driving force for CO2 flux through the membrane is increased.
- the driving force for transportation of CO through the membrane is decreased, and thus the yield of CO can be increased when high purities of CO are targeted.
- the outlet permeate stream is fully or partly recycled back to the SOEC as a feed gas together with fresh CO2 in the above step (7), whereby the CO2 yield is increased.
- the moderate pressure on the retentate side of the membrane can be from 250 bar g down to 3 bar g, preferably from 175 bar g down to 3 bar g, more preferably from 40 bar g down to 3 bar g and most preferably from 20 bar g down to 5 bar g.
- the lower pressure on the permeate side of the membrane can be between -0.8 bar g and 50 bar g, preferably between -0.8 bar g and 10 bar g, more preferably between -0.8 bar g and 3 bar g, even more preferably between -0.8 and 2 bar g and most preferably between -0.3 bar g and 0.5 bar g, especial- ly between 0 and 0.3 bar g.
- the splitting of the retentate stream into two separate parts also has analogy to the reflux at the top of a dis- tillation column.
- the SOEC unit has a function similar to the reboiler in a distillation unit; see the appended fig 1.
- the membrane unit is preferably designed with a tubular membrane or multiple planar membranes connected in series where the retentate and permeate streams are operated in counter-current mode. This implies that the enriched CO re ⁇ flux stream from the retentate side enters (after expan ⁇ sion) the permeate side of the membrane unit in the oppo- site end from the feed gas entering the membrane unit from the SOEC unit.
- the process according to the invention can be further outlined with reference to fig. 1, which shows a solid oxide electrolysis cell (SOEC) unit with the oxygen side at the top, the electrolyte in the middle and the fuel side at the bottom.
- SOEC solid oxide electrolysis cell
- CO 2 is led to the fuel side of the SOEC unit with an applied current to convert CO 2 to CO and transport any oxygen surplus to the oxygen side of the SOEC unit.
- CO 2 is also led to the oxygen side to flush this side, but air or nitrogen may also be used for this purpose.
- Flushing the oxygen side of the SOEC unit has two advantages, more spe ⁇ cifically (1) to reduce the oxygen concentration and relat ⁇ ed corrosive effects and (2) to provide means for feeding energy into the SOEC unit, operating it endothermic.
- the product stream from the SOEC contains mixed CO and CO 2 , which is led to a compressor C, which serves to establish a high absolute pressure on the retentate side of the mem ⁇ brane.
- a lower pressure is applied on the permeate side of the membrane by leading part of the CO product stream through a pressure reduction valve P and into the permeate side of the membrane.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2916959A CA2916959A1 (en) | 2013-07-30 | 2014-06-13 | Process for producing high purity co by membrane purification of soec-produced co |
| CN201480043120.8A CN105431221A (en) | 2013-07-30 | 2014-06-13 | Process for producing high-purity CO by membrane purification of CO produced from SOECs |
| US14/903,186 US20160151739A1 (en) | 2013-07-30 | 2014-06-13 | Process for producing high purity co by membrane purification of soec-produced co |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13178475.3 | 2013-07-30 | ||
| EP13178475.3A EP2832421B1 (en) | 2013-07-30 | 2013-07-30 | Process for producing high purity co by membrane purification of soec-produced co |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2015014527A1 true WO2015014527A1 (en) | 2015-02-05 |
Family
ID=48900819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2014/062362 Ceased WO2015014527A1 (en) | 2013-07-30 | 2014-06-13 | Process for producing high purity co by membrane purification of soec-produced co |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20160151739A1 (en) |
| EP (1) | EP2832421B1 (en) |
| CN (1) | CN105431221A (en) |
| AR (1) | AR097092A1 (en) |
| CA (1) | CA2916959A1 (en) |
| ES (1) | ES2583903T3 (en) |
| TW (1) | TW201516184A (en) |
| WO (1) | WO2015014527A1 (en) |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015202789A1 (en) * | 2015-02-17 | 2016-08-18 | Robert Bosch Gmbh | Product gas treatment apparatus and method for processing a product gas |
| WO2018228716A1 (en) | 2017-06-14 | 2018-12-20 | Linde Aktiengesellschaft | Method and system for producing a gas product containing carbon monoxide |
| DE102017005678A1 (en) | 2017-06-14 | 2018-12-20 | Linde Aktiengesellschaft | Process and plant for producing a carbon monoxide-containing gas product |
| DE102017005681A1 (en) | 2017-06-14 | 2018-12-20 | Linde Aktiengesellschaft | Process and plant for producing a carbon monoxide-containing gas product |
| EP3511441A1 (en) | 2018-01-12 | 2019-07-17 | Linde Aktiengesellschaft | Production of a gas product containing carbon monoxide |
| EP3511442A1 (en) | 2018-01-12 | 2019-07-17 | Linde Aktiengesellschaft | Production of a gas product containing carbon monoxide |
| WO2019158308A1 (en) | 2018-02-15 | 2019-08-22 | Siemens Aktiengesellschaft | Method for the electrochemical production of a gas product containing co |
| WO2019158305A1 (en) | 2018-02-15 | 2019-08-22 | Siemens Aktiengesellschaft | Electrochemical production of carbon monoxide and/or syngas |
| DE102018202337A1 (en) | 2018-02-15 | 2019-08-22 | Linde Aktiengesellschaft | Electrochemical production of a gas comprising CO with intercooling of the electrolyte flow |
| DE102018003332A1 (en) | 2018-04-24 | 2019-10-24 | Linde Aktiengesellschaft | Preparation of a synthesis product |
| DE102018003343A1 (en) | 2018-04-24 | 2019-10-24 | Linde Aktiengesellschaft | Process and plant for the production of ethanol |
| DE102018003342A1 (en) | 2018-04-24 | 2019-10-24 | Linde Aktiengesellschaft | Production of a gas product containing at least carbon monoxide |
| WO2021073769A1 (en) | 2019-10-18 | 2021-04-22 | Linde Gmbh | Method and plant for producing a carbon-monoxide-rich gas product |
| DE102020000476A1 (en) | 2020-01-27 | 2021-07-29 | Linde Gmbh | Process and plant for the production of hydrogen |
| DE102020000937A1 (en) | 2020-02-14 | 2021-08-19 | Linde Gmbh | Method and system for providing an industrial product using oxygen |
| WO2022136025A1 (en) | 2020-12-22 | 2022-06-30 | Topsoe A/S | An improved method for operation of a solid oxide electrolysis cell in carbon dioxide electrolysis |
| US11905173B2 (en) | 2018-05-31 | 2024-02-20 | Haldor Topsøe A/S | Steam reforming heated by resistance heating |
| EP4324957A1 (en) | 2022-08-19 | 2024-02-21 | Linde GmbH | Method and installation for the production of a product containing hydrocarbon |
| EP4345086A1 (en) | 2022-09-30 | 2024-04-03 | Linde GmbH | Method and system for producing methanol |
| EP4345191A1 (en) | 2022-09-30 | 2024-04-03 | Linde GmbH | Method and system for producing a hydrogen-containing product using electrolysis |
| US12214327B2 (en) | 2018-05-31 | 2025-02-04 | Haldor Topsøe A/S | Endothermic reactions heated by resistance heating |
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| US12246964B2 (en) | 2019-10-01 | 2025-03-11 | Haldor Topsøe A/S | On demand hydrogen from methanol |
| US12246299B2 (en) | 2019-11-12 | 2025-03-11 | Haldor Topsøe A/S | Electric steam cracker |
| US12410054B2 (en) | 2019-10-01 | 2025-09-09 | Haldor Topsøe A/S | Synthesis gas on demand |
| EP4706782A1 (en) | 2024-09-04 | 2026-03-11 | Linde GmbH | Method for operating a process engineering system and process engineering system |
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|---|---|---|---|---|
| DE102015202117A1 (en) | 2015-02-06 | 2016-08-11 | Siemens Aktiengesellschaft | Process and electrolysis system for carbon dioxide recovery |
| ITUA20163761A1 (en) * | 2016-05-24 | 2017-11-24 | Microprogel S R L | Gas dryer |
| FR3063437B1 (en) * | 2017-03-02 | 2019-03-29 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | APPARATUS AND METHOD FOR MEMBRANE PERMEATION TREATMENT OF A GAS SUPPLY FLOW COMPRISING METHANE AND CARBON DIOXIDE |
| DE102018009198A1 (en) * | 2018-11-22 | 2020-05-28 | Linde Aktiengesellschaft | Process for changing the operating mode of an electrolysis plant and electrolysis plant |
| US20210381116A1 (en) * | 2020-06-09 | 2021-12-09 | Opus 12 Incorporated | System and method for high concentration of multielectron products or co in electrolyzer output |
| CA3240316A1 (en) | 2021-12-08 | 2023-12-14 | Twelve Benefit Corporation | Systems and methods for ethylene production |
| US12305304B2 (en) | 2022-10-13 | 2025-05-20 | Twelve Benefit Corporation | Interface for carbon oxide electrolyzer bipolar membrane |
| US12378685B2 (en) | 2022-12-22 | 2025-08-05 | Twelve Benefit Corporation | Surface modification of metal catalysts with hydrophobic ligands or ionomers |
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| US20110253551A1 (en) * | 2010-04-19 | 2011-10-20 | Jonathan Andrew Lane | Electrochemical carbon monoxide production |
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2013
- 2013-07-30 ES ES13178475.3T patent/ES2583903T3/en active Active
- 2013-07-30 EP EP13178475.3A patent/EP2832421B1/en not_active Not-in-force
-
2014
- 2014-06-13 WO PCT/EP2014/062362 patent/WO2015014527A1/en not_active Ceased
- 2014-06-13 US US14/903,186 patent/US20160151739A1/en not_active Abandoned
- 2014-06-13 CA CA2916959A patent/CA2916959A1/en not_active Abandoned
- 2014-06-13 CN CN201480043120.8A patent/CN105431221A/en active Pending
- 2014-06-17 TW TW103120810A patent/TW201516184A/en unknown
- 2014-07-28 AR ARP140102804A patent/AR097092A1/en unknown
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| US11560633B2 (en) | 2018-02-15 | 2023-01-24 | Siemens Energy Global GmbH & Co. KG | Electrochemical production of carbon monoxide and/or syngas |
| US11105007B2 (en) | 2018-02-15 | 2021-08-31 | Siemens Aktiengesellschaft | Method for the electrochemical production of a gas product containing CO |
| WO2019206450A1 (en) | 2018-04-24 | 2019-10-31 | Linde Aktiengesellschaft | Producing a synthesis product |
| DE102018003343A1 (en) | 2018-04-24 | 2019-10-24 | Linde Aktiengesellschaft | Process and plant for the production of ethanol |
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2583903T3 (en) | 2016-09-22 |
| AR097092A1 (en) | 2016-02-17 |
| TW201516184A (en) | 2015-05-01 |
| CN105431221A (en) | 2016-03-23 |
| EP2832421A1 (en) | 2015-02-04 |
| CA2916959A1 (en) | 2015-02-05 |
| EP2832421B1 (en) | 2016-05-25 |
| US20160151739A1 (en) | 2016-06-02 |
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