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WO2010080022A1 - Processus et appareil d'extraction d'éthylène dans un mélange de gaz de carneau - Google Patents

Processus et appareil d'extraction d'éthylène dans un mélange de gaz de carneau 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
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
flue gas
gas mixture
adsorption
catalytic oxidation
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
Application number
PCT/NL2009/050716
Other languages
English (en)
Inventor
Theodoor Petrus Knook
Michiel Makkee
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CA2744672A priority Critical patent/CA2744672A1/fr
Publication of WO2010080022A1 publication Critical patent/WO2010080022A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01D53/34—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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

L'invention concerne, outre un appareil approprié, un processus d'extraction de l'éthylène, et éventuellement SO2 et NOx, d'un mélange de gaz de carneau contenant, entre autres, CO2, O2, SO2, NOx et de l'éthylène. Une première opération consiste à extraire SO2 par adsorption, une seconde opération à extraire NOx également par adsorption et une troisième opération à extraire l'éthylène par oxydation catalytique.
PCT/NL2009/050716 2008-11-26 2009-11-25 Processus et appareil d'extraction d'éthylène dans un mélange de gaz de carneau Ceased WO2010080022A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA2744672A CA2744672A1 (fr) 2008-11-26 2009-11-25 Processus et appareil d'extraction d'ethylene dans un melange de gaz de carneau

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2002257A NL2002257C2 (nl) 2008-11-26 2008-11-26 Werkwijze en inrichting voor het verwijderen van etheen uit een rookgasmengsel.
NL2002257 2008-11-26

Publications (1)

Publication Number Publication Date
WO2010080022A1 true WO2010080022A1 (fr) 2010-07-15

Family

ID=40846426

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2009/050716 Ceased WO2010080022A1 (fr) 2008-11-26 2009-11-25 Processus et appareil d'extraction d'éthylène dans un mélange de gaz de carneau

Country Status (3)

Country Link
CA (1) CA2744672A1 (fr)
NL (1) NL2002257C2 (fr)
WO (1) WO2010080022A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3018999A4 (fr) * 2013-07-11 2017-06-07 Royal Institution for the Advancement of Learning/McGill University Appareil d'enrichissement en dioxyde de carbone

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 (fr) * 1991-05-10 1992-11-11 Sumitomo Metal Mining Company Limited Méthode d'élimination d'oxydes d'azote dans les gaz d'échappement
EP0799633A1 (fr) * 1996-04-04 1997-10-08 Linde Aktiengesellschaft Procédé et dispositif pour l'élimination de monoxyde de carbone et/ou d'hydrogène d'un courant d'air
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 (fr) * 1998-05-26 2001-04-11 Shimakawa Seisakusyo Co., Ltd. Procede et dispositif pour purifier un gaz nocif
EP1226862A2 (fr) * 2001-01-30 2002-07-31 Ruhrgas Aktiengesellschaft Procédé et dispositif de production d'un mélange gazeux contenant du CO2 pour pour la fertilisation de plantes dans une serre
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 (fr) * 1991-05-10 1992-11-11 Sumitomo Metal Mining Company Limited Méthode d'élimination d'oxydes d'azote dans les gaz d'échappement
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 (fr) * 1996-04-04 1997-10-08 Linde Aktiengesellschaft Procédé et dispositif pour l'élimination de monoxyde de carbone et/ou d'hydrogène d'un courant d'air
EP1090674A1 (fr) * 1998-05-26 2001-04-11 Shimakawa Seisakusyo Co., Ltd. Procede et dispositif pour purifier un gaz nocif
EP1226862A2 (fr) * 2001-01-30 2002-07-31 Ruhrgas Aktiengesellschaft Procédé et dispositif de production d'un mélange gazeux contenant du CO2 pour pour la fertilisation de plantes dans une serre
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 (fr) * 2013-07-11 2017-06-07 Royal Institution for the Advancement of Learning/McGill University Appareil d'enrichissement en dioxyde de carbone
US9750200B2 (en) 2013-07-11 2017-09-05 Royal Institution For The Advancement Of Learning/Mcgill University Apparatus for carbon dioxide enrichment

Also Published As

Publication number Publication date
CA2744672A1 (fr) 2010-07-15
NL2002257C2 (nl) 2010-05-27

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