WO2010080022A1 - Process and apparatus for removing ethylene from a flue gas mixture - Google Patents

Process and apparatus for removing ethylene from a flue gas mixture Download PDF

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Publication number
WO2010080022A1
WO2010080022A1 PCT/NL2009/050716 NL2009050716W WO2010080022A1 WO 2010080022 A1 WO2010080022 A1 WO 2010080022A1 NL 2009050716 W NL2009050716 W NL 2009050716W WO 2010080022 A1 WO2010080022 A1 WO 2010080022A1
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WO
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Prior art keywords
ethylene
flue gas
gas mixture
adsorption
catalytic oxidation
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PCT/NL2009/050716
Other languages
French (fr)
Inventor
Theodoor Petrus Knook
Michiel Makkee
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Theodoor Petrus Knook
Michiel Makkee
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Filing date
Publication date
Application filed by Theodoor Petrus Knook, Michiel Makkee filed Critical Theodoor Petrus Knook
Priority to CA2744672A priority Critical patent/CA2744672A1/en
Publication of WO2010080022A1 publication Critical patent/WO2010080022A1/en

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    • 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
    • B01D53/86—Catalytic processes
    • B01D53/869—Multiple step processes
    • 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
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8656—Successive elimination of the 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
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems

Definitions

  • the invention relates to a process and apparatus for removing ethylene from a flue gas mixture.
  • flue gases there is an increasing need to purify flue gases from engines, more particularly (bio)gas engines, to a far-reaching extent.
  • these flue gases still contain organic compounds, such as methane and ethylene, as well as inorganic compounds, such as sulfur oxides (SO2), nitrogen oxides (NOx) and carbon monoxide.
  • SO2 sulfur oxides
  • NOx nitrogen oxides
  • carbon monoxide For the further use of flue gases, for example as a CO2 source in greenhouses, it is desired that the flue gases contain as few pollutants as possible, in particular that they contain as few sulfur oxides, nitrogen oxides and ethylene as possible.
  • the emission of the flue gases to the atmosphere it is desired that the content of pollutants be as low as possible.
  • the flue gases are typically treated by passing them over an oxidation catalyst, with or without supply of extra oxygen to the flue gas.
  • the organic compounds and the carbon monoxide in this way can be oxidized to form CO2.
  • a suitable catalyst has been described, for example, bj Wang et al. (Low temperature complete combustion of methane over titania- modified alumina supported palladium, Fuel 81 (2002) 1883-1887). In that publication, the positive effect is described of titania on the activity of a palladium catalyst for the oxidation of ethylene.
  • the removal of the organic compounds and the carbon monoxide is accomplisheded to combine the removal of sulfur oxides and/or nitrogen oxides.
  • a flue gas mixture is passed under oxidative conditions over specific adsorbents for sulfur oxides and nitrogen oxides, also the sulfur oxides and nitrogen oxides can be effectively removed from the stream of the flue gas mixture.
  • Such systems in which on the one hand the carbon-containing compounds are oxidized to CO2 and on the other hand the sulfur oxides and/or nitrogen oxides are adsorbed, utilize, for example, monolithic blocks with platinum catalyst and adsorption material immobilized thereon.
  • CO2 As is well-known, it is desirable to supply CO2 to horticultural greenhouses as a carbon source for the growth of the plants. This can be done via gas pipes, through separate supply with tank trucks and/or storage in containers. Often, it is endeavored to use CO2 from gas engine flue gases that are used for combined heat and power (CHP) cogeneration at the greenhouse.
  • CHP combined heat and power
  • the invention is based on the surprising insight that through the specific choice of the order of the treatment steps in the process leads to a surprisingly good purification of the gases and yields a CO2 gas stream that is so pure that it can be used as a CO2 feed for greenhouses without any problems. Only with the present order is this result obtained, as appears from the examples included herein. Other orders of treatment lead only to a limited and insufficient result.
  • the invention accordingly relates to a process for removing ethylene, and possibly SO2 and NO x , from a flue gas mixture containing inter alia CO ⁇ , O2, SO2, NO x and ethylene, wherein in a first step SO2 is removed from the flue gas mixture through adsorption; then, in a second step NO x is removed through adsorption, and after this, in a third step ethylene is removed through catalytic oxidation.
  • the present invention further relates to an apparatus for removing ethylene from a flue gas mixture, comprising in downstream direction:
  • a compartment for the removal of SO2 from the flue gas mixture comprising a catalytic oxidation/adsorption material for SO2;
  • a compartment for the removal of NO x from the flue gas mixture comprising a catalytic oxidation/adsorption material for NO x ;
  • a compartment for the removal of ethylene from the flue gas mixture comprising an oxidation catalyst, in particular an oxidation catalyst comprising platinum or palladium or the combination of the two.
  • a combination of catalytic oxidation of SO2 into SO ⁇ and adsorption of S ⁇ 3 is used.
  • the oxidation catalyst and the adsorbent are then preferably integrated in the same material, which as such, in turn, may be provided on a monolith.
  • Suitable catalysts are noble metals, while as adsorbent a material that forms sulfates is used.
  • An example of a suitable combination of materials is Pt/Cu on titania.
  • Pt/K salt such as a carbonate
  • alumina washcoat For the removal of NO x a comparable system is used, a preferred material being Pt/K salt, such as a carbonate, on alumina washcoat.
  • Ethylene is most preferably removed using a noble metal on a washcoat.
  • Suitable noble metals are platinum, palladium or combinations thereof.
  • Ae a washcoat, preferably alumina or titania is used.
  • regeneration may be done under reducing conditions, for example through treatment with CO
  • the invention is preferably used for the treatment of flue gases of gas engines.
  • engines with powers of from 1 MWe to 22 MWe, flue gas flow rates in the range of from 5,000 kg/h to 110,000 kg/h, with temperatures of between 300 and 500 0 C.
  • flue gas flow rates in the range of from 5,000 kg/h to 110,000 kg/h, with temperatures of between 300 and 500 0 C.
  • a Pt/KCO3 system for the removal of NOx a Pt/KCO3 system is used for the removal of NOx . Adsorption takes place under oxidizing conditions, the following two reaction schemes being representative of the removal and desorption.
  • Flue gases of a gas engine with a temperature of 400 0 C were treated using a removal system with various configurations.

Abstract

The invention relates to a process for removing ethylene, and possibly SO2 and NOx, from a flue gas mixture containing inter alia CO2, O2, SO2, NOx and ethylene, wherein in a first step SO2 is removed from the flue gas mixture through adsorption; then, in a second step NOx is removed through adsorption; and after this, in a third step ethylene is removed through catalytic oxidation, and to an apparatus suitable therefor.

Description

Title: Process and apparatus for removing ethylene from a flue gas mixture.
The invention relates to a process and apparatus for removing ethylene from a flue gas mixture.
There is an increasing need to purify flue gases from engines, more particularly (bio)gas engines, to a far-reaching extent. Typically, these flue gases still contain organic compounds, such as methane and ethylene, as well as inorganic compounds, such as sulfur oxides (SO2), nitrogen oxides (NOx) and carbon monoxide. For the further use of flue gases, for example as a CO2 source in greenhouses, it is desired that the flue gases contain as few pollutants as possible, in particular that they contain as few sulfur oxides, nitrogen oxides and ethylene as possible. Also for the emission of the flue gases to the atmosphere, it is desired that the content of pollutants be as low as possible.
To be able to effectively remove organic compounds and carbon monoxide, the flue gases are typically treated by passing them over an oxidation catalyst, with or without supply of extra oxygen to the flue gas. The organic compounds and the carbon monoxide in this way can be oxidized to form CO2. A suitable catalyst has been described, for example, bj Wang et al. (Low temperature complete combustion of methane over titania- modified alumina supported palladium, Fuel 81 (2002) 1883-1887). In that publication, the positive effect is described of titania on the activity of a palladium catalyst for the oxidation of ethylene.
Preferably, it is endeavored to combine the removal of the organic compounds and the carbon monoxide with the removal of sulfur oxides and/or nitrogen oxides. If a flue gas mixture is passed under oxidative conditions over specific adsorbents for sulfur oxides and nitrogen oxides, also the sulfur oxides and nitrogen oxides can be effectively removed from the stream of the flue gas mixture. Such systems, in which on the one hand the carbon-containing compounds are oxidized to CO2 and on the other hand the sulfur oxides and/or nitrogen oxides are adsorbed, utilize, for example, monolithic blocks with platinum catalyst and adsorption material immobilized thereon.
As is well-known, it is desirable to supply CO2 to horticultural greenhouses as a carbon source for the growth of the plants. This can be done via gas pipes, through separate supply with tank trucks and/or storage in containers. Often, it is endeavored to use CO2 from gas engine flue gases that are used for combined heat and power (CHP) cogeneration at the greenhouse.
To this end, it is necessary to lower the concentration of nitrogen oxides, sulfur oxides and ethylene. For it is well-known that the first two gases have an adverse effect on crop growth, and that the last gas is a growth hormone for plants. Too much ethylene in (horticultural) greenhouses can lead to soft crops with fruits ripening too soon and too fast. As expected, under oxidative conditions prevailing in the different monolithic blocks, both the concentration of sulfur oxides, or nitrogen oxides, and the concentration of ethylene can be reduced. The ethylene concentration proved to be reduced from 40,000 ppb to 2,000 ppb. Through the use of an extra monolith, specifically for the oxidation of ethylene, it was found that the concentration of ethylene can be reduced to 300 ppb. While this satisfies the current standards for (horticultural) greenhouses, the concentration of ethylene is still too high for future standards.
It is an object of the invention to provide a process by which the ethylene content in the CO2 can be reduced to values in the order of magnitude of a few tens of ppb's at most. It is in particular an object of the invention to find a procedure by which the concentration of ethylene can be reduced to less than 300 ppb, in particular to less than 10 ppb.
The invention is based on the surprising insight that through the specific choice of the order of the treatment steps in the process leads to a surprisingly good purification of the gases and yields a CO2 gas stream that is so pure that it can be used as a CO2 feed for greenhouses without any problems. Only with the present order is this result obtained, as appears from the examples included herein. Other orders of treatment lead only to a limited and insufficient result.
The invention accordingly relates to a process for removing ethylene, and possibly SO2 and NOx, from a flue gas mixture containing inter alia COΪ, O2, SO2, NOx and ethylene, wherein in a first step SO2 is removed from the flue gas mixture through adsorption; then, in a second step NOx is removed through adsorption, and after this, in a third step ethylene is removed through catalytic oxidation.
The present invention further relates to an apparatus for removing ethylene from a flue gas mixture, comprising in downstream direction:
- a compartment for the removal of SO2 from the flue gas mixture, comprising a catalytic oxidation/adsorption material for SO2;
- a compartment for the removal of NOx from the flue gas mixture, comprising a catalytic oxidation/adsorption material for NOx; and
• a compartment for the removal of ethylene from the flue gas mixture, comprising an oxidation catalyst, in particular an oxidation catalyst comprising platinum or palladium or the combination of the two.
According to a preferred embodiment, for the removal of SO2 a combination of catalytic oxidation of SO2 into SOβand adsorption of Sθ3is used. The oxidation catalyst and the adsorbent are then preferably integrated in the same material, which as such, in turn, may be provided on a monolith. Suitable catalysts are noble metals, while as adsorbent a material that forms sulfates is used. An example of a suitable combination of materials is Pt/Cu on titania.
For the removal of NOx a comparable system is used, a preferred material being Pt/K salt, such as a carbonate, on alumina washcoat.
Ethylene is most preferably removed using a noble metal on a washcoat. Suitable noble metals are platinum, palladium or combinations thereof. Ae a washcoat, preferably alumina or titania is used.
Since all process steps preferably utilize oxidation, it is desired that in the gas mixture oxidizing conditions prevail, preferably an excess of oxygen with respect to the components to be oxidized.
As soon as the materials are saturated, regeneration may be done under reducing conditions, for example through treatment with CO
The invention is preferably used for the treatment of flue gases of gas engines. To be considered in this connection are, for instance, engines with powers of from 1 MWe to 22 MWe, flue gas flow rates in the range of from 5,000 kg/h to 110,000 kg/h, with temperatures of between 300 and 5000C. In a representative example, for the removal of NOx a Pt/KCO3 system is used. Adsorption takes place under oxidizing conditions, the following two reaction schemes being representative of the removal and desorption.
Adsorption of SO2 (oxidizing conditions; Pt.Cu on a titania washcoat)
SO2 + I/2O2 + Pt + Sorber — > Sorber-SO, + Pt
Desorption (reducing conditions)
Sorber-SOx + H2 + CO + Pt → Sorber + SO2 + H2O + CO2 + Pt For the removal of NOx ((NO) a comparable reaction scheme applies, where as adsorbent a Pt/ an alumina washcoat is used
2 NO + 3/2 O2 + Pt + K2CO3 ~ -> 2KNO3 + Pt + CO2 Desorption (reducing conditions)
2 KNO3 + Pt + CO +4Hz ■» K2CO3 + N2 + 4 H2O + Pt
In the following examples, under comparable conditions the conversion of ethylene, SO2 and NOx is given with different configurations of the catalysts.
Flue gases of a gas engine with a temperature of 4000C were treated using a removal system with various configurations.
In the table the conversion values of NOx and ethylene are given for different configurations. The NOx and SO2 removal are based on the systems as described above. Ethylene removal is done with the aid of a Pt catalyst on an alumina washcoat.
Average ethylene and NOx values under practical conditions
Inlet concentration configuration Outlet concentration
Ethylene NOx Ethylene NOx
(PPb) (ppm) (PPb) (ppm)
40, 000 130-220 no cleaner 40,000 130-220
40,000 130-220 SO2 NOx NOx NOx 1500 - 2000 1-3
40,000 130-220 OXI SO2 NOx NOx NOx 200 - 300 1-3
40,000 130-220 SO2 OXI NOX NOX NOX 200 - 300 1-3
40,000 130-220 SO2 NOx NOx NOx OXI < 50 1-3
This shows that the ethylene conversion before the SO2 and before the NOx (after the SO2) gives the same conversion of ethylene from approximately 40,000 ppb to approximately 200-300 ppb. This conversion satisfies the current standards for ethylene concentration to the horticultural greenhouse, but for future standards the conversion level is too low. Surprisingly, the placement of the oxidation catalyst after the NOx adsorption gives a much higher degree of conversion of ethylene (40,000 ppb to less than 50 ppb and in most cases below 10 ppb and in some cases below the detection level of 2 ppb).
The reasons of this surprisingly strong reduction of the ethylene content cannot be explained on the basis of the known literature and the patent literature.

Claims

Claims
1. A process for removing ethylene, and possibly SO2 and NOx, from a flue gas mixture containing inter alia CO2, O2, SO2, NOx and ethylene, wherein in a first step SO2 is removed from the flue gas mixture through adsorption; then, in a second step NOx is removed through adsorption; and after this, in a third step ethylene is removed through catalytic oxidation, wherein in each step preferably an excess of oxygen is present.
2. A process according to claim 1, wherein the adsorption of SO2 is done with the aid of a catalytic oxidation of SO2 to SO3 and adsorption of the SO3 formed, preferably with the aid of a Pt/Cu on titania catalyst/adsorbent.
3. A process according to claim 1 or 2, wherein the adsorption of NOx is done with the aid of a catalytic oxidation of NOx to NO3 and adsorption of the NO3 formed, preferably with the aid of a Pt/alkali metal on alumina catalyst/adsorbent.
4. A process according to claims 1-3, wherein the catalytic oxidation of ethylene is done with the aid of a supported noble metal catalyst, preferably a platinum on a metal oxide, such as alumina.
5. A process according to claim 4, wherein the catalytic oxidation of ethylene is done in a monolith, provided with an alumina or titania washcoat with noble metal catalyst.
6. A process according to claims 1 - 5, wherein the concentration of ethylene after the third step is lower than 300 ppb, in particular lower than 50 ppb, and more particularly lower than 10 ppb.
7. A process according to claims 1 - 6, wherein the concentration of NOx after the third step is lower than 10 ppm, preferably lower than 5 ppm, in particular lower than 2 ppm.
8. An apparatus for removing ethylene from a flue gas mixture, comprising in downstream direction - a compartment for the removal of SO2 from the flue gas mixture, comprising a catalytic oxidation/adsorption material for SO2;
- a compartment for the removal of NOx from the flue gas mixture, comprising a catalytic oxidation/adsorption material for NOx; and - a compartment for the removal of ethylene from the flue gas mixture, comprising an oxidation catalyst, in particular an oxidation catalyst comprising platinum.
9. Use of an apparatus according to claim β in horticultural greenhouses.
10. Use of an apparatus according to claim 8 for the purification
Of CO2.
PCT/NL2009/050716 2008-11-26 2009-11-25 Process and apparatus for removing ethylene from a flue gas mixture WO2010080022A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA2744672A CA2744672A1 (en) 2008-11-26 2009-11-25 Process and apparatus for removing ethylene from a flue gas mixture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2002257 2008-11-26
NL2002257A NL2002257C2 (en) 2008-11-26 2008-11-26 METHOD AND DEVICE FOR REMOVING ETHENE FROM A SMOKE GAS MIXTURE

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WO2010080022A1 true WO2010080022A1 (en) 2010-07-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3018999A4 (en) * 2013-07-11 2017-06-07 Royal Institution for the Advancement of Learning/McGill University Apparatus for carbon dioxide enrichment

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2640889A1 (en) * 1988-12-26 1990-06-29 Toulouse Inst Nat Polytech Process and device for catalytic purification of the atmosphere of an enclosure for storing plants
EP0512506A1 (en) * 1991-05-10 1992-11-11 Sumitomo Metal Mining Company Limited Method for removing nitrogen oxides from exhaust gases
EP0799633A1 (en) * 1996-04-04 1997-10-08 Linde Aktiengesellschaft Process and apparatus for eliminating carbon monoxide and/or hydrogen from an air stream
US5780002A (en) * 1994-11-04 1998-07-14 Jiro Hiraishi, Director-General Of Agency Of Industrial Science And Technology Exhaust gas cleaner and method for cleaning exhaust gas
EP1090674A1 (en) * 1998-05-26 2001-04-11 Shimakawa Seisakusyo Co., Ltd. Device and method for cleaning noxious gas
EP1226862A2 (en) * 2001-01-30 2002-07-31 Ruhrgas Aktiengesellschaft Process and device for the production of a gas mixture containing CO2 to fertilize hothouse plants
US20050247196A1 (en) * 2004-03-26 2005-11-10 Robert Benesch Systems and methods for purifying unsaturated hydrocarbon(s), and compositions resulting therefrom

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2640889A1 (en) * 1988-12-26 1990-06-29 Toulouse Inst Nat Polytech Process and device for catalytic purification of the atmosphere of an enclosure for storing plants
EP0512506A1 (en) * 1991-05-10 1992-11-11 Sumitomo Metal Mining Company Limited Method for removing nitrogen oxides from exhaust gases
US5780002A (en) * 1994-11-04 1998-07-14 Jiro Hiraishi, Director-General Of Agency Of Industrial Science And Technology Exhaust gas cleaner and method for cleaning exhaust gas
EP0799633A1 (en) * 1996-04-04 1997-10-08 Linde Aktiengesellschaft Process and apparatus for eliminating carbon monoxide and/or hydrogen from an air stream
EP1090674A1 (en) * 1998-05-26 2001-04-11 Shimakawa Seisakusyo Co., Ltd. Device and method for cleaning noxious gas
EP1226862A2 (en) * 2001-01-30 2002-07-31 Ruhrgas Aktiengesellschaft Process and device for the production of a gas mixture containing CO2 to fertilize hothouse plants
US20050247196A1 (en) * 2004-03-26 2005-11-10 Robert Benesch Systems and methods for purifying unsaturated hydrocarbon(s), and compositions resulting therefrom

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3018999A4 (en) * 2013-07-11 2017-06-07 Royal Institution for the Advancement of Learning/McGill University Apparatus for carbon dioxide enrichment
US9750200B2 (en) 2013-07-11 2017-09-05 Royal Institution For The Advancement Of Learning/Mcgill University Apparatus for carbon dioxide enrichment

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CA2744672A1 (en) 2010-07-15

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