CA2744672A1 - 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
CA2744672A1
CA2744672A1 CA2744672A CA2744672A CA2744672A1 CA 2744672 A1 CA2744672 A1 CA 2744672A1 CA 2744672 A CA2744672 A CA 2744672A CA 2744672 A CA2744672 A CA 2744672A CA 2744672 A1 CA2744672 A1 CA 2744672A1
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Prior art keywords
ethylene
flue gas
gas mixture
adsorption
catalytic oxidation
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Abandoned
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CA2744672A
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French (fr)
Inventor
Theodoor Petrus Knook
Michiel Makkee
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Individual
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Individual
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Publication of CA2744672A1 publication Critical patent/CA2744672A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/869Multiple step processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8637Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8643Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8656Successive elimination of the components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/10Noble metals or compounds thereof
    • B01D2255/102Platinum group metals
    • B01D2255/1021Platinum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/20761Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • B01D2257/404Nitrogen oxides other than dinitrogen oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/70Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702Hydrocarbons
    • B01D2257/7022Aliphatic hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459Removing 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
    • B01D53/9477Removing 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

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  • 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

The invention relates to a process for removing ethylene, and possibly SO2 and NO x, from a flue gas mixture containing inter alia CO2, 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, 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 C02 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 C02. A suitable catalyst has been described, for example, by Wang et at. (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 C02 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 NOR, from a flue gas mixture containing inter alia CO2, 02, SO2, NOR and ethylene, wherein in a first step SO2 is removed from the flue gas mixture through adsorption; then, in a second step NOR 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 NOR 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 S03 and adsorption of S03 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.
For the removal of NO. 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. As 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
and/or H2.
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 500 C.
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 S02 (oxidizing conditions; Pt.Cu.on a titania washcoat) SO2 + 1/202 + Pt + Sorber ----> Sorber-SO: + Pt Desorption (reducing conditions) Sorber-SO, + H2 + CO + Pt -- Sorber + SO2 + H2O + C02 + Pt For the removal of NOR E(NO) a comparable reaction scheme applies, where as adsorbent a Pt/ an alumina washcoat is used 5 2 NO + 3/2 02 + Pt + K2C03 ----4 2KNO3 + Pt + C02 Desorption (reducing conditions) 2 KNO3 + Pt + CO +4H2 4 K2C03 + 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 400 C 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 NOR 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 S02 NOx NOx NOx 1500 -2000 1-3 40,000 130-220 OXI S02 NOx NOx NOx 200 - 300 1-3 40,000 130-220 S02 OXI NOx NOx NOx 200 - 300 1-3 40,000 130-220 S02 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 (10)

1. A process for removing ethylene, and possibly SO2 and NO x, from a flue gas mixture containing inter alia CO2, 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, 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 NO x is done with the aid of a catalytic oxidation of NO x 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 NO x 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 NO x from the flue gas mixture, comprising a catalytic oxidation/adsorption material for NO x; 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 8 in horticultural greenhouses.
10. Use of an apparatus according to claim 8 for the purification of CO2.
CA2744672A 2008-11-26 2009-11-25 Process and apparatus for removing ethylene from a flue gas mixture Abandoned CA2744672A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL2002257A NL2002257C2 (en) 2008-11-26 2008-11-26 METHOD AND DEVICE FOR REMOVING ETHENE FROM A SMOKE GAS MIXTURE
NL2002257 2008-11-26
PCT/NL2009/050716 WO2010080022A1 (en) 2008-11-26 2009-11-25 Process and apparatus for removing ethylene from a flue gas mixture

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CA2744672A1 true CA2744672A1 (en) 2010-07-15

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WO (1) WO2010080022A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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* 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
KR950007916B1 (en) * 1991-05-10 1995-07-21 스미도모킨조구고오상 가부시기가이샤 Method for removing nitrogen exides from exhaust gases
EP0710499A3 (en) * 1994-11-04 1997-05-21 Agency Ind Science Techn 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
JP3523594B2 (en) * 1998-05-26 2004-04-26 株式会社島川製作所 Hazardous gas purification device and purification method
DE10103206A1 (en) * 2001-01-30 2002-08-01 Ruhrgas Ag Method and device for producing a CO¶2¶-containing gas mixture for fertilizing plants in a greenhouse
US8568513B2 (en) * 2004-03-26 2013-10-29 American Air Liquide, Inc. Systems and methods for purifying unsaturated hydrocarbon(s), and compositions resulting therefrom

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Publication number Publication date
WO2010080022A1 (en) 2010-07-15
NL2002257C2 (en) 2010-05-27

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Effective date: 20131126