EP2069275A1 - A method and an arrangement for making methanol - Google Patents

A method and an arrangement for making methanol

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Publication number
EP2069275A1
EP2069275A1 EP07808874A EP07808874A EP2069275A1 EP 2069275 A1 EP2069275 A1 EP 2069275A1 EP 07808874 A EP07808874 A EP 07808874A EP 07808874 A EP07808874 A EP 07808874A EP 2069275 A1 EP2069275 A1 EP 2069275A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
methanol
wall
rotor blade
carbonic anhydrase
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.)
Withdrawn
Application number
EP07808874A
Other languages
German (de)
French (fr)
Inventor
Dan Borgström
Alf Larsson
Olof Dahlberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Morphic Technologies AB
Original Assignee
Morphic Technologies AB
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 Morphic Technologies AB filed Critical Morphic Technologies AB
Publication of EP2069275A1 publication Critical patent/EP2069275A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D9/00—Adaptations of wind motors for special use; Combinations of wind motors with apparatus driven thereby; Wind motors specially adapted for installation in particular locations
    • F03D9/20—Wind motors characterised by the driven apparatus
    • F03D9/25—Wind motors characterised by the driven apparatus the apparatus being an electrical generator
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
    • F03D1/06—Rotors
    • F03D1/065—Rotors characterised by their construction elements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D9/00—Adaptations of wind motors for special use; Combinations of wind motors with apparatus driven thereby; Wind motors specially adapted for installation in particular locations
    • F03D9/10—Combinations of wind motors with apparatus storing energy
    • F03D9/19—Combinations of wind motors with apparatus storing energy storing chemical energy, e.g. using electrolysis
    • 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
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction
    • 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
    • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
    • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
    • 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
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method and an arrangement for making methanol.
  • methanol can be used as a source of energy.
  • methanol can be used in a fuel cell in a process where electricity is generated.
  • Methanol can also be used to produce energy by combustion. Therefore, it is an object of the present invention to provide a method and a suitable arrangement for producing methanol. It is a further object of the invention to provide a method for storing energy at such times when energy is easily available or the need for energy is small such that the stored energy may be used when energy is scarce or large amounts of energy are needed.
  • the invention relates to a method of making methanol.
  • the inventive method comprises the steps of providing a wall having a surface on which a carbonic anhydrase is placed, e.g. immobilized, exposing the wall to a stream of gas, in particular air, and using the carbonic anhydrase to remove carbon dioxide from the stream of gas. The carbon dioxide so obtained may then be used to subsequently produce methanol.
  • the carbon dioxide is used to produce methanol in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol.
  • the wall may be formed by, for example, a rotor blade of a wind power plant. Electrical energy from the wind power plant may then be used to transform water and carbon dioxide into methanol. Of course, even if the wall is formed by a rotor blade of a wind power plant, electrical energy used for the production of methanol may come from another source than the wind power plant.
  • the rotor blade may be divided into a plurality of cells separated from each other in the radial direction of the rotor blade. Each cell may then have a wall on which carbonic anhydrase is arranged, e.g. immobilized, such that each cell can extract carbon dioxide.
  • the methanol obtained may be subsequently used to produce electrical energy in for example a fuel cell.
  • the invention also relates to an arrangement for making methanol.
  • the arrangement comprises a wall having a surface upon which carbonic anhydrase is arranged (e.g. immobilized) such that carbon dioxide can be extracted from a gas, in particular air.
  • the arrangement further comprises a fuel cell connected to the wall and a source of electrical energy connected to the fuel cell.
  • the wall may be formed by, for example, a rotor blade of a wind power plant.
  • the rotor blade can be divided into a plurality of cells separated from each other in the radial direction of the rotor blade. At least some of the cells and possibly each cell has a wall on which carbonic anhydrase is arranged/immobilized such that some cells (or each cell) can extract carbon dioxide.
  • Figure 1 is a schematic representation of the invention.
  • Figure 2 shows an embodiment of the invention where the invention is applied to a rotor blade.
  • Figure 3 shows schematically how the invention may be applied to a wind power plant.
  • Figure 4 is a cross-sectional schematic representation similar to Fig. 1 but showing more clearly the path of evacuation of carbon dioxide.
  • Figure 5 is a side view of the cell shown in Fig. 4.
  • Figure 6 shows schematically a process in a fuel cell.
  • Figure 7 is a schematic representation of a process run in reverse in relation to the process of Fig. 6.
  • the inventive method for making methanol comprises providing a wall 1 having a surface 2 on which a carbonic anhydrase 3 is arranged (e.g. immobilized).
  • Carbonic anhydrase is an enzyme that has the capacity to remove carbon dioxide from a stream of gas (for example a stream of air).
  • a process where carbon dioxide is removed from air is disclosed in, for example, US patent No. 6143556 and reference is made to that document for further detail about carbonic anhydrase and the process by which carbonic anhydrase removes carbon dioxide from air.
  • the surface 2 of the wall 1 is exposed to a stream of gas such as air.
  • the carbonic anhydrase 3 is thereby put to use to remove carbon dioxide from the stream of gas.
  • the carbon dioxide so obtained is then used to produce methanol.
  • the wall 1 on the surface of which the carbonic anhydrase 3 is placed constitutes an outer surface of a cell 8 having an extraction chamber 19 for extraction of carbon dioxide.
  • the chamber 19 may be divided into a front compartment 20 and a rear compartment 21 and where the front compartment 20 serves as an extraction compartment.
  • the chamber 19 is filled with liquid.
  • the liquid in the chamber 19 can be pumped around by a pump 22 that keeps the liquid circulating between the front compartment 20 and the rear compartment 21.
  • the liquid pressure in the rear compartment should preferably be higher than the pressure in the front compartment 20.
  • a flow restriction 23 may be formed between the rear and front compartment 20, 21. To enter the front compartment, the liquid must pass the flow restriction 23.
  • the liquid in the chamber 19 is an aqueous phosphate buffer system, i.e. it is based on water.
  • the liquid may contain an anti-freezing agent.
  • a rear wall 4 of the cell 8 is in contact with a primary evacuation conduit 24.
  • Extraction of carbon dioxide functions as follows.
  • a gas such as air passes over the surface of the wall 1.
  • Carbon dioxide is absorbed by the carbonic anhydrase and passes through the wall 1 into the liquid in the front compartment 20 of the cell 8.
  • the part of the wall 1 where the carbonic anhydrase 3 is placed is formed by a permeable or semipermeable membrane, for example a semipermeable plastic membrane or a lipid membrane.
  • the membrane may be doped with ionophores to provide ion conducting channels.
  • the liquid is circulated by pump 22 into the rear compartment 21. From the rear compartment 21 , carbon dioxide passes through the rear wall 4 into the primary evacuation conduit 24.
  • the rear wall 4 is also formed by a permeable or semipermeable membrane, for example a lipid membrane.
  • the atmospheric pressure Pi is larger than the pressure P 2 in the front compartment 20, i.e. Pi > P 2 .
  • the pressure P 3 in the rear compartment 21 is also higher than the pressure P 2 in the front compartment 20, i.e. P 3 > P 2 .
  • the pressure P 3 in the rear compartment 21 is also higher than the pressure P 4 in the primary evacuation conduit 24.
  • 1 gram carbonic anhydrase can process 10 moles of carbon dioxide which equals 440 grams of carbon dioxide. In normal air, there is about 340 ml carbon dioxide per m 3 which equals 0.61 grams of carbon dioxide per m 3 . Consequently, 1 gram of carbonic anhydrase can process the carbon dioxide in 70 m 3 air per second.
  • the pH in the front compartment 20 should preferably exceed 7.0.
  • a suitable pH level for the front compartment 20 may be, for example, 7.4. When pH is above 7, the carbon dioxide is more easily solved in the water phase in the front compartment 20 (the extraction compartment).
  • the carbonic anhydrase here works to transform the carbon dioxide into hydrocarbonate that is immediately solved in the liquid.
  • the wall 1 may be formed by a rotor blade 5 and be a part of the rotor blade 5.
  • the rotor blade 5 may be the rotor blade 5 of as wind power plant 6.
  • the wall 1 could be formed by something else than a rotor blade 5. It could be part of a stationary structure that is not moved by the wind. For example, it could be formed by a discharge chimney or by any object that can be exposed to a stream of gas such as air.
  • the rotor blade 5 may be the rotor blade 5 of a wind power mill 6.
  • the rotor blade is shown as mounted on a hub 27.
  • the hub is rotatably journalled in a housing 30 that is supported by a pillar 29.
  • the primary evacuation conduit 24 leads to a main evacuation conduit 25 that may be common to several cells 8 for extraction of carbon dioxide.
  • the main evacuation conduit 25 extends along the rotor blade 5 from an outer part of the blade 5 and up through the hub 27 of the rotor blade 5.
  • the main evacuation conduit 25 can be connected to a source 26 of underpressure/vacuum that can be located inside the structure of the wind power plant 6.
  • the source 26 of underpressure may be, for example, a pump or a fan.
  • the carbon dioxide may optionally be sent through a further conduit 28 as schematically indicated in Fig. 3 and finally arrive in a fuel cell 9 where carbon dioxide is used in a process to manufacture methanol.
  • the fuel cell 9 is thus connected to the wall 1 in such a way that carbon dioxide extracted from the air through the wall 1 can be transported from the wall 1 to the fuel cell 9.
  • the wall 1 is connected to the fuel cell 9 through the conduits 24, 25 and 28 and the source of underpressure 26.
  • the connection or communication line from the wall 1 to the fuel cell 9 could be designed in other ways that what has been disclosed above.
  • the source of underpressure 26 does not necessarily have to be located inside the structure of the wind power plant 6.
  • the carbon dioxide extracted from air can be used to produce methanol in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol, i.e.
  • the process may include the formation of intermediate compounds such as O 2 ).
  • the wall 1 is formed by a rotor blade 5 of a wind power plant 6
  • electrical energy obtained from the wind power plant 6 can be used in a process where water and carbon dioxide is transformed into methanol.
  • the electrical energy may come from another source than the wind power plant 6. For example, it could come from the power-mains.
  • a fuel cell 9 may be used. In the process to produce methanol, the fuel cell 9 will be run in reverse compared to its normal mode of operation.
  • Fig. 6 A process for producing methanol will now be explained with reference to Fig. 6.
  • the fuel cell 9 is shown as has an anode 15 and a cathode 16.
  • the anode 15 and the cathode 16 are separated by a membrane 17.
  • An electric circuit is indicated by the numeral 18.
  • carbon dioxide and water are fed into a fuel cell 9 through the opening 11 in the fuel cell 9.
  • An electric current is added at the electric circuit 18.
  • water is added through opening 13 while O 2 exits through opening 14 (it should be understood that Fig. 6 is a schematic representation).
  • methanol (CH 3 OH) leaves the fuel cell through opening 12.
  • Fig. 7 it is indicated how methanol is supplied to the fuel cell 9 through opening 12. In the resulting reaction, an electrical current is generated in the circuit 18.
  • the rotor blade 5 is divided into a plurality of cells 8 separated from each other in the radial direction of the rotor blade 5, each cell 8 has a wall 1 on which carbonic anhydrase is arranged/immobilized such that each cell 8 can extract carbon dioxide. If necessary, steps may be taken to reduce pressure in the cells.
  • the invention can also be described in terms of an arrangement for making methanol which comprises a wall 1 having a surface 2 upon which carbonic anhydrase 3 is immobilized such that carbon dioxide can be extracted from for example air (but possibly also from other gases or from air mixed with other gases).
  • This arrangement comprised a fuel cell 9 connected to the wall 1 and a source of electrical energy connected to the fuel cell 9.
  • the source of electric energy may be, for example, a wind power plant 6 but other sources of electrical energy are also possible.
  • Fig. 4 the circulation of the liquid in chamber 19 is indicated as going in an anti-clockwise direction. In the front chamber adjacent the atmosphere, the liquid will then move in the direction of arrow C.
  • the rotor blade 5 is preferably arranged such that, as the rotor blade 5 moves through the air, the air moves relative to the rotor blade in the direction of arrow A such that the wind assists in pressing the fluid in chamber 19 in the correct direction.
  • the relative direction of movement of the wind in relation to the rotor blade can be determined in advance and the cells 8 oriented such that the wind will assist in the circulation of liquid inside each cell 8.
  • the arrangement according to the invention may include a fuel cell 9 and a tank 10 may be connected to the fuel cell 9 such that methanol produced in the fuel cell 9 can be subsequently stored in the storage tank 10.
  • the function of the arrangement can be as follows. When air passes over the wall 1, carbon dioxide is absorbed and used to manufacture methanol.
  • the rotor 5 of a wind power plant 6 When the wind is blowing, the rotor 5 of a wind power plant 6 is exposed to a stream of air. Electrical energy is generated by the wind power plant and carbon dioxide is simultaneously extracted along the rotor blade 5. From the rotor blade 5, one or several conduits 24, 25, 28 may lead to a fuel cell 9 where the carbon dioxide can be transformed into methanol. A part of the electricity generated by the wind power plant 6 is used for a reaction where the extracted carbon dioxide is used to produce methanol which can then be stored.
  • the need for electrical energy may be monitored.
  • one or several indicators may be monitored in order to determine whether electrical energy is needed somewhere else.
  • One such indicator may be, for example, the price of electricity.
  • An increase in the price of electricity may indicate that the need for electricity has increased.
  • stored methanol may be used to produce electricity such that electricity can be produced when the need for electricity is large.
  • Fig. 2 an embodiment is indicated where the rotor blade 5 is divided into a plurality of cells 8 that are separated from each other in the radial direction of the rotor blade 5.
  • Each cell 8 has a wall 1 on which carbonic anhydrase 3 is arranged/immobilized such that each cell 8 can extract carbon dioxide.
  • the cells 8 contain liquid, the liquid pressure could become undesirably high if one single cell extended along the entire rotor blade - the column of liquid would be high and the centrifugal forces would make the problem even more serious. If a plurality of cells 8 is used, the liquid in each cell can be separated from the liquid in the other cells. In this way, liquid pressure can be kept lower.
  • the invention could be applied on a stationary surface in an environment where the content of carbon dioxide is very high, for example in an exhaust conduit in an industry.
  • a rotor blade placed in such an environment could also be considered.

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Abstract

The invention relates to a method of making methanol. The method comprises the steps of providing a wall (1) formed by a rotor blade (5) of a wind power plant (6), the wall (1) having a surface (2) on which a carbonic anhydrase (3) is immobilized, exposing the surface (29) of the wall (1) to a stream of gas and using the carbonic anhydrase (3) to remove carbon dioxide from the stream of gas. The carbon dioxide so obtained is then used to produce methanol in a fuel cell, in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol. The invention also relates to an arrangement for making methanol.

Description

A METHOD AND AN ARRANGEMENT FOR MAKING METHANOL
FIELD OF THE INVENTION The present invention relates to a method and an arrangement for making methanol.
BACKGROUND OF THE INVENTION
It is known that methanol can be used as a source of energy. For example, methanol can be used in a fuel cell in a process where electricity is generated. Methanol can also be used to produce energy by combustion. Therefore, it is an object of the present invention to provide a method and a suitable arrangement for producing methanol. It is a further object of the invention to provide a method for storing energy at such times when energy is easily available or the need for energy is small such that the stored energy may be used when energy is scarce or large amounts of energy are needed.
DISCLOSURE OF THE INVENTION
The invention relates to a method of making methanol. The inventive method comprises the steps of providing a wall having a surface on which a carbonic anhydrase is placed, e.g. immobilized, exposing the wall to a stream of gas, in particular air, and using the carbonic anhydrase to remove carbon dioxide from the stream of gas. The carbon dioxide so obtained may then be used to subsequently produce methanol.
Preferably, the carbon dioxide is used to produce methanol in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol.
The wall may be formed by, for example, a rotor blade of a wind power plant. Electrical energy from the wind power plant may then be used to transform water and carbon dioxide into methanol. Of course, even if the wall is formed by a rotor blade of a wind power plant, electrical energy used for the production of methanol may come from another source than the wind power plant.
The rotor blade may be divided into a plurality of cells separated from each other in the radial direction of the rotor blade. Each cell may then have a wall on which carbonic anhydrase is arranged, e.g. immobilized, such that each cell can extract carbon dioxide. The methanol obtained may be subsequently used to produce electrical energy in for example a fuel cell.
The invention also relates to an arrangement for making methanol. The arrangement comprises a wall having a surface upon which carbonic anhydrase is arranged (e.g. immobilized) such that carbon dioxide can be extracted from a gas, in particular air. The arrangement further comprises a fuel cell connected to the wall and a source of electrical energy connected to the fuel cell.
The wall may be formed by, for example, a rotor blade of a wind power plant.
In some embodiments, the rotor blade can be divided into a plurality of cells separated from each other in the radial direction of the rotor blade. At least some of the cells and possibly each cell has a wall on which carbonic anhydrase is arranged/immobilized such that some cells (or each cell) can extract carbon dioxide.
DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic representation of the invention.
Figure 2 shows an embodiment of the invention where the invention is applied to a rotor blade.
Figure 3 shows schematically how the invention may be applied to a wind power plant.
Figure 4 is a cross-sectional schematic representation similar to Fig. 1 but showing more clearly the path of evacuation of carbon dioxide.
Figure 5 is a side view of the cell shown in Fig. 4. Figure 6 shows schematically a process in a fuel cell.
Figure 7 is a schematic representation of a process run in reverse in relation to the process of Fig. 6.
DETAILED DESCRIPTION OF THE INVENTION With reference to Fig. 1, the inventive method for making methanol comprises providing a wall 1 having a surface 2 on which a carbonic anhydrase 3 is arranged (e.g. immobilized). Carbonic anhydrase is an enzyme that has the capacity to remove carbon dioxide from a stream of gas (for example a stream of air). A process where carbon dioxide is removed from air is disclosed in, for example, US patent No. 6143556 and reference is made to that document for further detail about carbonic anhydrase and the process by which carbonic anhydrase removes carbon dioxide from air. In the method according to the present invention, the surface 2 of the wall 1 is exposed to a stream of gas such as air. The carbonic anhydrase 3 is thereby put to use to remove carbon dioxide from the stream of gas. The carbon dioxide so obtained is then used to produce methanol.
As indicated in Fig. 1, the wall 1 on the surface of which the carbonic anhydrase 3 is placed constitutes an outer surface of a cell 8 having an extraction chamber 19 for extraction of carbon dioxide. The chamber 19 may be divided into a front compartment 20 and a rear compartment 21 and where the front compartment 20 serves as an extraction compartment. The chamber 19 is filled with liquid. The liquid in the chamber 19 can be pumped around by a pump 22 that keeps the liquid circulating between the front compartment 20 and the rear compartment 21. The liquid pressure in the rear compartment should preferably be higher than the pressure in the front compartment 20. For this purpose, a flow restriction 23 may be formed between the rear and front compartment 20, 21. To enter the front compartment, the liquid must pass the flow restriction 23. The liquid in the chamber 19 is an aqueous phosphate buffer system, i.e. it is based on water. The liquid may contain an anti-freezing agent. A rear wall 4 of the cell 8 is in contact with a primary evacuation conduit 24.
Extraction of carbon dioxide functions as follows. A gas such as air passes over the surface of the wall 1. Carbon dioxide is absorbed by the carbonic anhydrase and passes through the wall 1 into the liquid in the front compartment 20 of the cell 8. The part of the wall 1 where the carbonic anhydrase 3 is placed is formed by a permeable or semipermeable membrane, for example a semipermeable plastic membrane or a lipid membrane. The membrane may be doped with ionophores to provide ion conducting channels. The liquid is circulated by pump 22 into the rear compartment 21. From the rear compartment 21 , carbon dioxide passes through the rear wall 4 into the primary evacuation conduit 24. The rear wall 4 is also formed by a permeable or semipermeable membrane, for example a lipid membrane. During this process, the atmospheric pressure Pi is larger than the pressure P2 in the front compartment 20, i.e. Pi > P2. The pressure P3 in the rear compartment 21 is also higher than the pressure P2 in the front compartment 20, i.e. P3 > P2. The pressure P3 in the rear compartment 21 is also higher than the pressure P4 in the primary evacuation conduit 24.
Per second, 1 gram carbonic anhydrase can process 10 moles of carbon dioxide which equals 440 grams of carbon dioxide. In normal air, there is about 340 ml carbon dioxide per m3 which equals 0.61 grams of carbon dioxide per m3. Consequently, 1 gram of carbonic anhydrase can process the carbon dioxide in 70 m3 air per second. The pH in the front compartment 20 should preferably exceed 7.0. A suitable pH level for the front compartment 20 may be, for example, 7.4. When pH is above 7, the carbon dioxide is more easily solved in the water phase in the front compartment 20 (the extraction compartment). The carbonic anhydrase here works to transform the carbon dioxide into hydrocarbonate that is immediately solved in the liquid.
With reference to Fig. 2, the wall 1 may be formed by a rotor blade 5 and be a part of the rotor blade 5. As indicated schematically in Fig. 3, the rotor blade 5 may be the rotor blade 5 of as wind power plant 6. It should be understood that the wall 1 could be formed by something else than a rotor blade 5. It could be part of a stationary structure that is not moved by the wind. For example, it could be formed by a discharge chimney or by any object that can be exposed to a stream of gas such as air.
As seen in Fig. 3, the rotor blade 5 may be the rotor blade 5 of a wind power mill 6. In Fig, 3, the rotor blade is shown as mounted on a hub 27. The hub is rotatably journalled in a housing 30 that is supported by a pillar 29.
As indicated in Fig. 4 and Fig. 5, the primary evacuation conduit 24 leads to a main evacuation conduit 25 that may be common to several cells 8 for extraction of carbon dioxide. With reference once again to Fig. 2, the main evacuation conduit 25 extends along the rotor blade 5 from an outer part of the blade 5 and up through the hub 27 of the rotor blade 5. The main evacuation conduit 25 can be connected to a source 26 of underpressure/vacuum that can be located inside the structure of the wind power plant 6. The source 26 of underpressure may be, for example, a pump or a fan. From the source 26 of underpressure, the carbon dioxide may optionally be sent through a further conduit 28 as schematically indicated in Fig. 3 and finally arrive in a fuel cell 9 where carbon dioxide is used in a process to manufacture methanol. The fuel cell 9 is thus connected to the wall 1 in such a way that carbon dioxide extracted from the air through the wall 1 can be transported from the wall 1 to the fuel cell 9. In the above disclosed embodiment, the wall 1 is connected to the fuel cell 9 through the conduits 24, 25 and 28 and the source of underpressure 26. However, it should be understood that the connection or communication line from the wall 1 to the fuel cell 9 could be designed in other ways that what has been disclosed above. For example, if a source of underpressure 26 is used, the source of underpressure 26 does not necessarily have to be located inside the structure of the wind power plant 6. The carbon dioxide extracted from air can be used to produce methanol in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol, i.e. electrical current + CO2+H2O → CH3OH (the process is here indicated in a simplified form, in practice the process may include the formation of intermediate compounds such as O2). When the wall 1 is formed by a rotor blade 5 of a wind power plant 6, electrical energy obtained from the wind power plant 6 can be used in a process where water and carbon dioxide is transformed into methanol. Alternatively, the electrical energy may come from another source than the wind power plant 6. For example, it could come from the power-mains.
In order to produce methanol, a fuel cell 9 may be used. In the process to produce methanol, the fuel cell 9 will be run in reverse compared to its normal mode of operation.
A process for producing methanol will now be explained with reference to Fig. 6. In Fig. 6 it can be seen that the fuel cell 9 is shown as has an anode 15 and a cathode 16. The anode 15 and the cathode 16 are separated by a membrane 17. An electric circuit is indicated by the numeral 18. To produce methanol, carbon dioxide and water are fed into a fuel cell 9 through the opening 11 in the fuel cell 9. An electric current is added at the electric circuit 18. On the cathode side, water is added through opening 13 while O2 exits through opening 14 (it should be understood that Fig. 6 is a schematic representation). In Fig. 6 methanol (CH3OH) leaves the fuel cell through opening 12.
It should be understood that the process can also be run in the opposite direction as indicated in Fig. 7. In Fig. 7 it is indicated how methanol is supplied to the fuel cell 9 through opening 12. In the resulting reaction, an electrical current is generated in the circuit 18.
The rotor blade 5 is divided into a plurality of cells 8 separated from each other in the radial direction of the rotor blade 5, each cell 8 has a wall 1 on which carbonic anhydrase is arranged/immobilized such that each cell 8 can extract carbon dioxide. If necessary, steps may be taken to reduce pressure in the cells.
It should be understood that the invention can also be described in terms of an arrangement for making methanol which comprises a wall 1 having a surface 2 upon which carbonic anhydrase 3 is immobilized such that carbon dioxide can be extracted from for example air (but possibly also from other gases or from air mixed with other gases). This arrangement comprised a fuel cell 9 connected to the wall 1 and a source of electrical energy connected to the fuel cell 9. The source of electric energy may be, for example, a wind power plant 6 but other sources of electrical energy are also possible.
One aspect of the invention shall now be explained with reference to Fig. 4. In Fig. 4, the circulation of the liquid in chamber 19 is indicated as going in an anti-clockwise direction. In the front chamber adjacent the atmosphere, the liquid will then move in the direction of arrow C. The rotor blade 5 is preferably arranged such that, as the rotor blade 5 moves through the air, the air moves relative to the rotor blade in the direction of arrow A such that the wind assists in pressing the fluid in chamber 19 in the correct direction. In, for example, a wind power plant, the relative direction of movement of the wind in relation to the rotor blade can be determined in advance and the cells 8 oriented such that the wind will assist in the circulation of liquid inside each cell 8.
With reference to Fig. 3, the arrangement according to the invention may include a fuel cell 9 and a tank 10 may be connected to the fuel cell 9 such that methanol produced in the fuel cell 9 can be subsequently stored in the storage tank 10.
The function of the arrangement can be as follows. When air passes over the wall 1, carbon dioxide is absorbed and used to manufacture methanol. A specific example shall now be explained with reference to an embodiment where the carbonic anhydrase 3 is placed on the rotor blade 5 of a wind power plant 6. When the wind is blowing, the rotor 5 of a wind power plant 6 is exposed to a stream of air. Electrical energy is generated by the wind power plant and carbon dioxide is simultaneously extracted along the rotor blade 5. From the rotor blade 5, one or several conduits 24, 25, 28 may lead to a fuel cell 9 where the carbon dioxide can be transformed into methanol. A part of the electricity generated by the wind power plant 6 is used for a reaction where the extracted carbon dioxide is used to produce methanol which can then be stored.
In some embodiments of the invention, the need for electrical energy may be monitored. For example, one or several indicators may be monitored in order to determine whether electrical energy is needed somewhere else. One such indicator may be, for example, the price of electricity. An increase in the price of electricity may indicate that the need for electricity has increased. At times when a high need for electricity is indicated, stored methanol may be used to produce electricity such that electricity can be produced when the need for electricity is large. With reference to Fig. 2, an embodiment is indicated where the rotor blade 5 is divided into a plurality of cells 8 that are separated from each other in the radial direction of the rotor blade 5. Each cell 8 has a wall 1 on which carbonic anhydrase 3 is arranged/immobilized such that each cell 8 can extract carbon dioxide. Since the cells 8 contain liquid, the liquid pressure could become undesirably high if one single cell extended along the entire rotor blade - the column of liquid would be high and the centrifugal forces would make the problem even more serious. If a plurality of cells 8 is used, the liquid in each cell can be separated from the liquid in the other cells. In this way, liquid pressure can be kept lower.
Possibly, the invention could be applied on a stationary surface in an environment where the content of carbon dioxide is very high, for example in an exhaust conduit in an industry. Of course, a rotor blade placed in such an environment could also be considered.
By the use of carbonic anhydrase to extract carbon dioxide from the air, a source of carbon dioxide for the production of methanol is provided that is practically inexhaustible since the total amount of carbon dioxide in the earth's atmosphere is very large. If the principle of using carbonic anhydrase is combined with a wind power plant, this means that electric energy generated by the wind power plant can be used in the process where carbon dioxide is transformed into methanol. This means that methanol can be produced at a very low cost. The methanol manufactured in such a process can later be used to produce electrical energy at such times when the wind is not blowing. This results in a more reliable supply of electrical energy since the energy obtained from the wind power plant can be more evenly distributed over time.

Claims

1. A method of making methanol comprising the steps of providing a wall (1) formed by a rotor blade (5) of a wind power plant (6), the wall (1) having a surface (2) on which a carbonic anhydrase (3) is arranged, exposing the surface (2) of the wall (1) to a stream of gas and using the carbonic anhydrase (3) to remove carbon dioxide from the stream of gas; and using the carbon dioxide so obtained to produce methanol in a chemical reaction where electrical energy is used to transform water and carbon dioxide to methanol.
2. A method according to claim 1, wherein electrical energy from the wind power plant (6) is used to transform water and carbon dioxide into methanol.
3. A method according to claim 1, wherein the gas is air.
4. A method according to any of claims 1 - 3, wherein electrical energy from a wind power plant is used to transform water and carbon dioxide into methanol.
5. A method according to claim 1, wherein the rotor blade (5) is divided into a plurality of cells (8) separated from each other in the radial direction of the rotor blade (5), each cell (8) has a wall (1) on which carbonic anhydrase is arranged such that each cell (8) can extract carbon dioxide.
6. A method according to any of claims 1 - 5, wherein the methanol obtained is subsequently used to produce electrical energy in a fuel cell.
7. An arrangement for making methanol which comprises a wall (1) that is formed by a rotor blade (5) of a wind power plant (6), the wall (1) having a surface (2) upon which carbonic anhydrase (3) is arranged such that carbon dioxide can be extracted from for example air, a fuel cell (9) in which carbon dioxide can be transformed into methanol, the fuel cell being connected to the wall (1) such that extracted carbon dioxide can be transported to the fuel cell (9); and a source of electrical energy connected to the fuel cell (9).
8. An arrangement according to claim 7, wherein the rotor blade (5) is divided into a plurality of cells (8) separated from each other in the radial direction of the rotor blade (5), each cell (8) has a wall (1) on which carbonic anhydrase (3) is arranged such that each cell (8) can extract carbon dioxide.
EP07808874A 2006-10-06 2007-09-11 A method and an arrangement for making methanol Withdrawn EP2069275A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111425351A (en) * 2020-03-27 2020-07-17 杭州祥博传热科技股份有限公司 Offshore liquid cooling system based on wind driven generator and hydrogen-oxygen fuel cell

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2461723B (en) * 2008-07-10 2013-03-27 Christopher Denham Wall The economic conversion of waste carbon dioxide gas such as that produced by fossil fuel burning power stations, to bulk liquid fuels suitable for automobiles
KR101477335B1 (en) * 2008-07-18 2014-12-30 알렌 존스 Wind powered energy amplification system and method
US20110223650A1 (en) * 2008-07-31 2011-09-15 Novozymes A/S Modular Membrane Reactor and Process for Carbon Dioxide Extraction
GB2464691A (en) * 2008-10-22 2010-04-28 Christopher Denham Wall Manufacture of methanol from agricultural by-product cellulosic/lignitic material
WO2012003299A2 (en) 2010-06-30 2012-01-05 Codexis, Inc. Highly stable beta-class carbonic anhydrases useful in carbon capture systems
AU2011272825A1 (en) 2010-06-30 2013-01-10 Codexis, Inc. Chemically modified carbonic anhydrases useful in carbon capture systems
US8354261B2 (en) 2010-06-30 2013-01-15 Codexis, Inc. Highly stable β-class carbonic anhydrases useful in carbon capture systems
US9694317B2 (en) 2012-05-03 2017-07-04 Altira Technology Fund V L.P. Multi-pollutant abatement device and method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4332789A1 (en) * 1993-09-27 1995-03-30 Abb Research Ltd Process for storing energy
AU6104596A (en) * 1995-06-07 1996-12-30 Michael C. Trachtenberg Enzyme systems for gas processing
JP4413334B2 (en) * 1999-10-20 2010-02-10 アルストム株式会社 Regenerative carbon dioxide separator and carbon dioxide separation system
CA2352626A1 (en) * 2001-07-12 2003-01-12 Co2 Solution Inc. Coupling for linking a hydrogen fuel cell to an enzyme bioreactor for processing and sequestering co2
CA2388423C (en) * 2002-05-31 2005-03-22 Co2 Solution Inc. A ventilation system for an enclosure in which people live and a method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008041921A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111425351A (en) * 2020-03-27 2020-07-17 杭州祥博传热科技股份有限公司 Offshore liquid cooling system based on wind driven generator and hydrogen-oxygen fuel cell

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