EP2861326A1 - Procédé pour réduire la concentration de dioxyde d'azote - Google Patents

Procédé pour réduire la concentration de dioxyde d'azote

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Publication number
EP2861326A1
EP2861326A1 EP13735216.7A EP13735216A EP2861326A1 EP 2861326 A1 EP2861326 A1 EP 2861326A1 EP 13735216 A EP13735216 A EP 13735216A EP 2861326 A1 EP2861326 A1 EP 2861326A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
uhc
temperature
red
exhaust gas
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
EP13735216.7A
Other languages
German (de)
English (en)
Inventor
Thomas Hammer
Arno Römpke
Ralf Sigling
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.)
Siemens Energy Global GmbH and Co KG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP2861326A1 publication Critical patent/EP2861326A1/fr
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
    • B01D53/92—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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—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
    • B01D53/92—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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9431—Processes characterised by a specific device
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • 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
    • B01D2255/20707—Titanium
    • 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
    • B01D2255/20723—Vanadium
    • 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
    • B01D2255/20738—Iron
    • 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
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • 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
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Definitions

  • the present invention relates to a process for Minde ⁇ tion of the concentration (reduction of the content) of nitrogen dioxide in an exhaust gas from an incomplete combustion of hydrocarbons or hydrocarbon mixtures using a catalyst for the reduction of
  • Nitrogen dioxide by oxidation of unburned hydrocarbons or hydrocarbon mixtures a device for reducing the concentration of nitrogen dioxide in an exhaust gas from incomplete combustion of hydrocarbons or hydrocarbon mixtures using a catalyst for reducing nitrogen dioxide by oxidation of unburned hydrocarbons or hydrocarbon mixtures, and a plant comprising the same before ⁇ direction.
  • a catalyst for reducing nitrogen dioxide by oxidation of unburned hydrocarbons or hydrocarbon mixtures and a plant comprising the same before ⁇ direction.
  • Gas turbine driven generators provide a clean and efficient way of generating electric power
  • gas turbines can today be operated with mean turbine inlet temperatures of in some cases over 1500 ° C and thus net efficiencies of 40% without heat recovery ⁇ tion and exergetic efficiencies of more than 60% with heat ⁇ recovery by coupling with a steam turbine achieve.
  • the nationa ⁇ len limits on power plant emissions can thus in many developed countries such as Germany still without any further exhaust aftertreatment comply.
  • Gas turbines are characterized not only by low emissions and high efficiency but also by capabilities such as operation at very different loads (load flexibility of 100% up to values of less than 30%) and fast Lastän ⁇ changes up to the quick start (reaching the base load in less than 30 minutes). Because of the increasing proportion of energy from renewable sources (wind, solar, etc.), which are characterized by high temporal fluctuations of the fed into the electrical supply network power is made Ge ⁇ increased consumption of the load flexibility of gas turbines.
  • O 2 has the unpleasant property of absorbing light in the blue and near ultraviolet spectral range, so that even the operation of gas turbines whose pollutant emissions comply with all legal requirements, due to a yellowish color of the plume emanating from the chimney of the power plant in Ta ⁇ Sawed (referred to as "yellow plume”) can lead to acceptance problems.
  • NO 2 can be other causes ha ⁇ ben that other measures to NO 2 may - require emission reduction: As has been the case of gas turbines with heat recovery steam generator and integrated multi-stage exhaust aftertreatment consisting of vorgelagertem CO-
  • a further object of the invention is to provide a retrofittable solution for reducing NO 2 emissions in an exhaust gas from an incomplete combustion of hydrocarbons or hydrocarbon mixtures for installations which do not already have a system for selective catalytic reduction (SCR ) of nitrogen oxides by means of NH 3 as reducing agent, and thereby advantageously to dispense with the storage, dosage, and injection of any reducing agent such as ammonia.
  • SCR selective catalytic reduction
  • the solution proposed here for reducing NO2 - emissions in gas turbine exhaust gases is based on the surprising finding that by a catalytic reaction of O2 with unburned hydrocarbons at sufficiently low elected catalytic activity a Abgaszusammenset ⁇ Zung can be brought about for the oxidation of hydrocarbons with oxygen in the self unchanged nitrogen oxide (NO x) total concentration, the NO2 - concentration can be brought to a value which is far below the given by the thermodynamic Gleichelecommunication Gleichconsistssver ⁇ ratio between O2 and NO value for each catalyst temperature.
  • FIG. 1 shows a conventional turbine power plant without exhaust ⁇ treatment.
  • FIG. 2 shows a gas turbine power plant with catalytic treatment for NO 2 reduction according to an embodiment of the present invention.
  • FIG. 3 shows a gas turbine power plant with waste heat steam generator and catalytic exhaust gas purification according to a further embodiment of the following invention.
  • FIG. 4 shows a device according to an embodiment of the present invention.
  • Figure 5 shows another device according to an embodiment of the present invention.
  • FIG. 6 shows the concentration curve of NO and O 2 in the relative thermal equilibrium in the exhaust gas of a gas turbine and the concentrations of NO and NO 2 according to an NO 2 reduction catalyst according to an embodiment of the present invention.
  • Figure 7 shows the concentrations of NO and NO2 of Example 2 in Figure 7a, the temperature history and the Jardingeschwindig ⁇ ness SV (space velocity) of Example 2 in Figure 7b, and the concentration profile of hydrocarbons of Example 2, as measured by Cl-fraction, in Figure 7c.
  • Nitrogen dioxide is reduced at the catalyst 1 by oxidation of UHC at least to nitrogen monoxide, NO, wherein the catalyst 1
  • Oxidation of UHC with oxygen, O2 begins in the exhaust, wherein the storage temperature T UH ca b s for the storage of UHC is less than the activation temperature T red for the reduction of NO 2, as set forth in equation (I):
  • the inventive apparatus for reducing the concentra ⁇ tion of nitrogen dioxide in an exhaust gas mixtures from the gene from incomplete ⁇ combustion of hydrocarbons or hydrocarbons is characterized in that the device comprises eduction for N02- a catalyst 1, the
  • (i) has a storage temperature T UH ca b s above which it stores unburned hydrocarbons, UHC, as well as partial oxidation products of UHC,
  • an activation temperature T red has, above the he the reduction of O2 to at least nitric oxide, NO, ka ⁇ catalyses oxidation of UHC, and
  • the process according to the invention can be operated at a temperature of less than ox , so that as complete a reduction as possible of the NO 2 -
  • the operating temperature can exceed the operating temperature T ox briefly, for example for a period of less than a STUN de, preferably less than 30 minutes, more preferably Weni ⁇ ger than 20 minutes and most preferably less than 10 minutes.
  • the operating temperature, the operating temperature T ox for a longer period exceed, for example, the exhaust gas-generating Burn ⁇ voltage runs completely and O 2 is not, or formed only in such low concentrations that a reduction is not required.
  • the process according to the invention may be carried out at a temperature greater than or equal to the activation temperature T red so that nitrogen dioxide can be reduced as best as possible.
  • T red activation temperature
  • methods according to the invention it is also possible for methods according to the invention to be used for a short time, for example for a period of time. niger than 30 minutes, preferably less than 20 minutes, more preferably less than 10 minutes and in particular before perform Trains t ⁇ less than 5 minutes at a temperature less than T red, however, it may be preferred, the temperature quickly to a temperature Greater than T red .
  • ⁇ the temperature is increased to a value above or equal to T red when the storage capacity of the memory for storing O 2 is exhausted.
  • a memory for storing O 2 can in this case the catalytic converter 1 or an additional catalyst, for example a catalyst 3 for storing NO 2, or other memory for storing NO 2 may be play an absorption liquid, ⁇ .
  • the concentration of O 2 on the catalyst can be reduced both completely and only partially.
  • the O 2 can be further reduced to nitrogen N 2 , but it is at least reduced to Stickstoffmo ⁇ noxide NO to prevent the occurrence of yellowish Ab ⁇ gas vanes by N0 2 emission.
  • the reduction of O 2 by UHC to NO may be preferred because it requires less activation energy compared to complete reduction to N 2 .
  • a com- plete reduction of O 2 to N 2 from an environmental point of view be preferred in order to prevent the re-formation of O 2 from NO in the at ⁇ gas atmosphere after dispensing of the purified exhaust gas, so long as the required conditions for the erfindungsgemä- SEN catalyst 1 are ensured.
  • the total amount of NO x which comprises NO and NO 2 , to be reduced.
  • the oxidation of the UHC in the process according to the invention can be both partial and complete
  • the oxidation may be a complete oxidation, as a result of which subsequent oxidation of the partial oxidation products of the UHC, such as aldehydes and carbon monoxide, CO, which may be detrimental to the atmosphere and / or the environment, can be avoided.
  • the oxidation may preferably have a complete oxidation to carbon dioxide of UHC, CO 2, take place.
  • UHC unburned hydrocarbons alone as well as mixtures without ⁇ have burned hydrocarbons from incomplete combustion of hydrocarbons or hydrocarbon mixtures.
  • the hydrocarbons and hydrocarbons during combustion as well as the unburned hydrocarbons and hydrocarbon mixtures are not particularly limited.
  • hydrocarbons and hydrocarbon mixtures that are burned, crude oil, natural gas, diesel,
  • hydrocarbons such as methanol or ethanol.
  • the hydrocarbons may in this case comprise any number of carbons, for example 1 to 40 carbon atoms and may be branched or unbranched, saturated or unsaturated ⁇ saturated, substituted, or unsubstituted or substituted aromatic or cyclic. It is not excluded that the hydrocarbon mixtures for combustion and other substances include, such as carbon, sulfur, metals or other impurities, as well as substituted hydrocarbons such as thiols, alcohols, Aldehy ⁇ de, ketones, amines, nitro compounds, etc.
  • Such other substances may be found in certain embodiments in the exhaust gas, but can also in certain embodiments before the catalyst 1 and / or the catalysts 1 and / or 2 and / or 3 are filtered. In certain embodiments it is preferable to use substances which have a negative effect on the catalyst 1 and / or the catalysts 1 and / or 2 and / or 3, for example as catalyst poison, before the catalyst 1 and / or the catalysts 1 and / or 2 and / or or 3 to remove.
  • the hydrocarbons and hydrocarbon mixtures intended for combustion can also be referred to as fuels in the context of the invention, unless otherwise stated in the context.
  • Unburned hydrocarbons for example, Koh ⁇ bons having 1 to 20, preferably 1 to 10, further be ⁇ vorzugt be 1 to 4 carbon atoms, for example Me ⁇ than, ethane, propane, propene, butane, 1-butene, 2-butene, pentane, Pentene, cyclopentane, hexane, benzene, or toluene.
  • ⁇ vorzugt be 1 to 4 carbon atoms, for example Me ⁇ than, ethane, propane, propene, butane, 1-butene, 2-butene, pentane, Pentene, cyclopentane, hexane, benzene, or toluene.
  • ovin- the unburned hydrocarbons and unburned hydrocarbon mixtures NEN partially oxidized
  • Christspro ⁇ -products from the combustion of hydrocarbons and hydrocarbon mixtures to be which are still capable of further oxidation, for example
  • the hydrocarbons may be saturated or unsaturated and branched or unbranched as well as cyclic or aro matic ⁇ here. Also, the hydrocarbons may be substituted in certain embodiments.
  • the catalyst 1 and / or the catalysts 1 and / or 2 and / or 3 are preferred hydrocarbons are fed to the latter and / or non-nega tive ⁇ influence them.
  • High NO.sub.2 emissions in an exhaust gas can be reduced in the process according to the invention, in particular in the operation of gas turbines or systems with natural gas or oil in the range of low partial load ( ⁇ 50%) and at startup or other load changes, preferably by combining at least two measures. that no visible discoloration of the flue gas occurs more and at the same time all legal limits are met.
  • Load changes or low partial loads can occur, for example with other systems of the invention, such as plants, feed electricity into the power grid ⁇ or equipment whose load does not need to be continuously equal to or ships that reduce their VELOCITY ⁇ ness.
  • Low loads can occur, for example, in power plants based on the combustion of hydrocarbons or hydrocarbon mixtures, when a high amount of energy from fluctuating renewable energies, such as wind and / or solar power, are stored in the power grid and thus less energy from such power plants is needed.
  • an exhaust gas such as a gas turbine exhaust
  • a catalyst 1 having the following properties: Above an activation temperature T red , it reacts O 2 with unburned hydrocarbon gasoline UHC emissions and at least reduces it to NO, thereby oxidizing the UHC become. Above an operating temperature T ox > T red , the oxidation of UHC with unused oxygen uses O 2 in the exhaust gas.
  • the reaction rate for oxidation with O 2 may be less than that with NO 2 as long as the NO 2 concentration is above the desired emission limit.
  • the emission limit value for the process according to the invention may be 100 ppm, preferably 50 ppm, more preferably 20 ppm, particularly preferably 10 ppm and in particular 8 ppm, more particularly 6 ppm.
  • the catalyst 1 in the method of this invention can have the property of above a low tempera ⁇ tur TuHcabs ⁇ T reci UHC and the reaction products of partial oxi- dation to store UHC such as aldehydes and preferably above, in particular only considerably above the tem ⁇ temperature for T ox the oxidation at a temperature T UH CCIEs as the release ⁇ as set forth in equation (III).
  • the catalyst 1 can release the UHC and the reaction products of partial Oxi ⁇ dation of UHC at a temperature, preferably 50 ° C and more preferably 100 ° C above T ox is 20 ° C.
  • a temperature preferably 50 ° C and more preferably 100 ° C above T ox is 20 ° C.
  • it can be ensured, in particular, that even at low temperatures there is a supply of UHC in the catalyst 1 for NO 2 reduction, even if, during operation of a plant in the process according to the invention, there is a deficiency of UHC in comparison to O 2.
  • the catalyst 1 may further have the property of above a likewise nied ⁇ membered temperature T N0 2a s / which is smaller than T red, such as in sliding ⁇ chung (IV) above, also O2 store, and this only above the Activation temperature for the reduction at a temperature T N0 2cies re-release / desorb, as set forth in equation (V).
  • (V) ⁇ red ⁇ T N02des In such exemplary embodiments, a further reduction of the NO 2 concentration at low temperatures is possible, such as at the start of combustion of hydrocarbons, for example in a plant according to the invention at ambient temperatures in the range from -40 ° C to + 40 ° C, optionally in FIG Range from 10 to 35 ° C, optionally in the range of 20 to 30 ° C.
  • the temperature T N0 2 it may be preferred that the temperature T N0 2 be lower than T ox to ensure that sufficient UHC for N02 reduction is present in the desorption / release of O2.
  • T In ⁇ be preferred exemplary forms of T is N0 2a s with the smaller the exhaust gas is passed through the catalyst 1 as the Tempe ⁇ temperature.
  • control of the method by the temperature may not be possible, so in such embodiments it may be preferable to generate more UHCs at start-up, which may then be stored to assist them Increase the temperature to the N02 ⁇ reduction available. After achieving a suitable NO 2 reduction, the amount of UHC produced can then be reduced again.
  • the combustion in the method according to the invention can be controlled in such a way that the UHC concentration, for example during the start phase and phases with low partial load, is averaged over the time average of the NO 2 emission by a specific factor .gamma equation (VI) can be calculated from the concentra tions of UHC ⁇ X UHC and O2 NO 2.
  • this factor may in this case for example of a set ⁇ fuel in the combustion of hydrocarbons or hydrocarbon mixtures, for example natural gas or oil, from the catalyst material in relation to beispiels- Its composition, crystal structure and / or specific surface area and / or depend on the catalyst temperature.
  • the factor ⁇ may be, for example, the amount / ratios of materials added to the combustion such as air and hydrocarbons or hydrocarbon mixtures and / or the temperature of addition of, for example, air and / or by controlling the temperature of combustion, for example in a combustor BK, done.
  • the factor ⁇ briefly, for example in the range of 1 minute to 30 minutes, preferably in the range of 5 minutes to 10 minutes, assume a value less than 1, if he then back to a Value greater than 1 is set.
  • the exhaust gas downstream of the catalyst 1 may be passed over a catalyst 2 for the oxidation of UHC, which may oxidize UHC and / or oxidation products of UHC, for example, by oxygen. In this way, the release of UHC or oxidation products of
  • the catalyst 2 may catalyze the oxidation of the UHC and / or oxidation products of UHC at a temperature having the exhaust gas after passing through the catalyst 1. In certain embodiments, the catalyst 2 may perform the oxidation of the UHC and / or oxidation products of UHC at a temperature less than or equal to T red . In certain embodiments, the catalyst 2 is advantageously additionally include carbon monoxide CO can, at least partially, to oxidize to Koh ⁇ dioxide CO2. Suitable catalyst materials for such a catalyst 2 can be suitably used by the person skilled in the art.
  • N02 storage catalyst 3 which, in preferred embodiments, stores nitrogen dioxide at the temperature T N0 2a s at the temperature T N0 releases 2cies.
  • additional N0 2 storage is possible, whereby the concentration of O 2 in the exhaust gas can be further reduced.
  • T N0 2des is less than T ox to ensure that the O 2 is directed to the catalyst 1 at a temperature less than T ox .
  • the exhaust gas upstream of the catalytic converter 1 can also be conducted via one or more further NO 2 storage media in addition to or in place of the catalytic converter 3, for example a N0 2 sorption medium or a solid storage medium, the additional storage media also being used in certain Embodiments may have the temperature characteristics of the catalyst 3 with respect to T N0 2abs and T N0 2 des In preferred embodiments, T N0 2a s is less than the temperature at which the exhaust gas is passed through the catalyst 3 and / or an additional storage medium. In certain embodiments, the catalyst 3 and another N02 storage medium may also be provided. Suitable catalyst materials for the catalyst 3 can be suitably determined by the person skilled in the art on the basis of simple tests, for example in measuring stalls.
  • further storage catalytic converters and / or other catalysts for exhaust gas purification may be provided in certain embodiments.
  • T max the maximum exhaust gas temperatures
  • measures for heat recovery / heat transfer such as steam generators before the catalysts, such as catalytic reactors, taken / used to ensure that the exhaust gas temperature in the catalyst is smaller T max .
  • heat recovery measures can not or may not be provided, in certain embodiments it may be preferable to use less sensitive catalysts that can operate up to the maximum exhaust temperature after combustion of the hydrocarbons or hydrocarbon mixtures, preferably without loss of activity. in which T max is greater than the maximum exhaust temperature ⁇ tur.
  • the measures for increasing the temperature can be carried out in certain embodiments by one or more heat exchangers / heat exchangers.
  • the type of heat exchanger is in this case limited in any way.
  • a device according to the invention comprising a catalyst 1 and / or a catalyst 2 and / or a catalyst 3, it is possible to carry one or more heat exchangers upstream of and / or after the catalyst (1) and / or optionally before and / or after the catalyst Catalyst (2) and / or optionally before / and after the catalyst (3) provide.
  • from 0 to 30, preferably from 4 to 20, and particularly preferably from 10 to 15 heat exchangers may be provided.
  • the temperatures before and / or after the catalysts can also be suitably adjusted in addition or alone by adjusting the pressure before and / or after the catalysts.
  • At least one heat exchanger is present in each case before each catalyst and after the last catalyst, the exhaust gas is passed.
  • the temperature requirements and / or reaction rate requirements in the process of the invention and / or the device according to the invention can be adjusted by suitable choice of material of the catalyst (s). In certain embodiments, the requirements for temperatures and / or reaction rates can be ensured by different choice of materials of the catalysts.
  • the storage of UHC and, if appropriate, O 2 in the catalyst 1 and / or optionally of O 2 in the catalyst 3 for NO 2 storage can be achieved both by absorption and by adsorption on the catalyst according to certain embodiments. which can each be based on chemical and / or physical processes.
  • composition and crystal structure of the catalysts used for the storage 1 and / or 3 can preferably be adjusted so that storage and regeneration by non-reactive or reactive release of the stored substances in the process according to the invention are reversible.
  • the material properties can be adjusted so that the catalyst 1 or other storage catalysts, for example the catalyst 3 for NO 2 storage, in the process according to the invention by the storage and regeneration by non-reactive or reactive release of the stored substances is not damaged.
  • a reference to the catalyst 1 and / or the catalyst 2 and / or the catalyst 3 can also be set forth by reference to the catalysts 1 and / or 2 and / or 3, unless otherwise stated in the illustration ,
  • one or more catalysts 1 and / or one or more catalysts 2 and / or one or more catalysts 3 and / or one or more heat exchangers are provided in the inventive method and / or the device according to the invention ,
  • the catalysts and / or heat transferers may be the same or different.
  • the catalysts 1 and / or 2 and / or 3 are combined on a carrier, for example by a catalyst 1 on one side and / or opposite sides with a solution and / or an emulsion and / or a suspension of the catalyst material 2 and / or 3 is so impregnated and is subsequently treated thermally, that not the whole Ka ⁇ catalyst 1 by the catalyst material of the catalyst 2 and / or the catalyst 3 is covered.
  • a catalyst may then have different zones, each corresponding to a catalyst 1 and / or a catalyst 2 and / or a catalyst 3.
  • the catalyst materials for the catalysts 1 and / or 2 and / or 3 in the process according to the invention and / or the device according to the invention are not particularly limited, as long as they meet the required temperature determinations.
  • Suitable catalyst and storage materials characterized for example by composition, crystal form and / or surface condition, can be determined by the skilled person using known experimental methods such as temperature-programmed reaction, temperature-programmed absorption and temperature-programmed desorption, stress tests and long-term studies. Such tests can be carried out, for example, at measuring stations at which gas mixtures with controlled adjustable composition, controlled adjustable gas flow and controlled adjustable temperature passed through a material samples containing reactor with controlled adjustable temperature and can be analyzed quantitatively with appropriate gas analysis technology to the change in composition.
  • the N0 2 storage properties and / or the UHC storage properties of a catalyst can be influenced by its acidity and / or its pore structure. Also, storage properties can be adjusted via the structure of crystal pores, such as zeolites.
  • titanium dioxide T1O 2 shows good UHC storage, which can also be stabilized by, for example, tungsten trioxide WO 3 in such a way that it can be used in the full exhaust gas temperature range of the gas turbine. At the same time, such a material also shows storage capacity for O 2 . Due to a higher content of WO 3 , it is also possible to obtain catalyst materials for applications at higher temperatures, for example way up to 650 ° C. Further mixed oxides of titanium dioxide with, for example, zirconium dioxide or aluminum trioxide such as T 1 O 2 / ZrC> 2 or T 1 O 2 / Al 2 O 3 are known to the person skilled in the art as the basis for catalyst preparation and can of course likewise be used.
  • Emissions can be achieved more.
  • a content of V 2 0 5 1.7 wt.% Even at higher temperatures, a good N0 2 ⁇ reduction can be ensured, whereas at a content of V 2 0 5 of 3 wt.% At temperatures above 400 ° C in certain embodiments already a reduction of N0 2 ⁇ reduction may occur.
  • zeolites such as, for example, ZSM5 show excellent adsorption capacity for UHC and, with appropriate doping with catalytically active components such as Cu, Fe, Pt, W, In, or Ag (eg by impregnation with appropriate salts), also show good conversion from O2 to NO and sometimes even complete reduction of nitrogen oxides to N 2 .
  • catalytically active components such as Cu, Fe, Pt, W, In, or Ag (eg by impregnation with appropriate salts)
  • H-ZSM5 as a basic component of the NO 2 reduction catalyst, while the more widespread Na-ZSM5 is less advantageous for this application.
  • the zeolites are generally suitable for use at higher temperature, for example above 650 ° C.
  • various catalyst materials can oxidize UHC to various products.
  • the Pt-NH 4 ZMS5 catalyst UHC used in Example 1 can be oxidized to CO 2 . decode, while the used in Example 1 Fe-NaZSM5- catalyst or the Katalysa ⁇ tor UHC employed in Example 2 is oxidized to carbon monoxide.
  • the control of the method according to the invention and / or a device according to the invention and / or a system according to the invention can be in the range of 1 minute to 30 minutes, preferably in the range of 3 minutes to 10 minutes. However, in certain embodiments faster control may also be provided.
  • an apparatus for reducing the concent ration ⁇ of nitrogen dioxide in an exhaust gas from the incomplete combustion of hydrocarbons or hydrocarbons comprises at least one catalyst for 1 NO2 - to reduction,
  • a device according to the invention may in certain embodiments have one or more catalysts 1 and / or one or more catalysts 2 and / or one or more catalysts 3 and / or one or more heat exchangers.
  • a device according to the invention may be inserted in an exhaust gas line of a vehicle
  • Gas turbine integrated catalytic reactor for exhaust gas purification which contains at least one catalyst 1.
  • the catalyst 1 and / or the catalyst 2 and / or the catalyst 3 may be embodied as honeycomb catalyst, plate catalyst, etc., wherein, for example, cell density and catalyst length are selected such that the exhaust gas residence time under the relevant operating conditions in certain embodiments exceeds 30 ms and the catalytic conversion of O 2 with UHC in catalyst 1 is neither transport-limited nor appreciably limited by the turnover frequency of the catalyst, but on the other hand the exhaust gas backpressure under full load is below a tolerable for the efficiency of the gas turbine, typically 5 to 10 mbar.
  • Catalyst 1 or catalysts 1 and / or 2 and / or 3 may, in certain embodiments, be an extruded solid catalyst with thin cell walls or catalyst material coated ceramic or metallic supports of small wall thickness.
  • the device according to the invention can be used in installations in certain embodiments.
  • systems comprising a erfindungsge ⁇ Permitted device.
  • plants may be gas turbine power plants, compressors operated with one or more gas turbines, gas or oil powered boilers, gas engines, or marine diesel powered by the combustion of diesel or heavy oil.
  • one or more heat recovery and / or heat exchange devices may be provided in the exhaust line of the plant.
  • Such heat recovery and / or heat exchange devices may, in certain embodiments, include at least one-piece heat exchangers in contact with the exhaust gas.
  • a heat recovery device may be a heat recovery steam generator.
  • Installations according to the invention may in certain embodiments also be combined heat and power plants with combined heat and power, in which embodiments a careful coordination with the other catalysts and the process may be required.
  • An exemplary system in which an inventive Before ⁇ direction may be provided is a gas turbine power plant, as shown in Figure 1, a generator G, a compressor KP for compressing air L, and a combustor BK, with a fuel B, a Kohlenwas ⁇ serstoff or a mixture of hydrocarbons having for operating a gas turbine G. Exhaust gas from the gas turbine GT is conducted in such a system via a diffuser D in the chimney K.
  • a device comprising a catalytic reactor KR can be introduced into such a plant behind the diffuser D, as shown in FIG.
  • the device with the catalytic reactor KR is not installed in the chimney K or at least not mounted in the chamber K in such a way that the catalyst material can be exposed to rain, since rain causes the catalyst or the catalysts can damage or destroy, for example, as a result of a pressure explosion by evaporating rain. Damage can also occur in certain embodiments due to large temperature fluctuations, since catalysts are sensitive to temperature shocks.
  • a heat recovery steam generator AD which has a catalyst 1 and 4 heat exchanger WT1, WT2, WT3 and WT4.
  • a heat recovery steam generator may also include one or more catalysts, for example, catalysts 1 and / or 2 and / or 3, and one or more heat exchangers, wherein the heat exchangers may be arranged in different ways.
  • FIG. 4 An exemplary embodiment of a device according to the invention is shown in Figure 4, in which the exhaust gas flows from left to right successively through a catalyst 3, a catalyst 1 and a catalyst 2.
  • 5 shows another exemplary embodiment of a device according OF INVENTION ⁇ dung is shown in which in addition heat transfer WTA, WTB, and WTC WTD before, are provided between and after the catalysts 1, 2 and 3.
  • FIG. 5 it is also possible to provide a plurality of catalysts, for example catalysts 1, 2 and 3 and / or several or fewer heat exchangers and / or to dispense with the catalyst 2 and / or the catalyst 3.
  • the device shown in FIG. 5 may, in particular embodiments, have advantages in particular during start-up / start-up or transient operation of a system, since nitrogen dioxide can be stored. Also, the temperature can be be better controlled in the catalysts by the heat exchangers.
  • Pt-NH 4 ZMS5 is a with Platinum-doped ammonium-exchanged ZSM5 zeolite, and Fe-NaZSM5 an iron-doped, sodium ion-exchanged ZSM5 zeolite.
  • the space velocity in all experiments was 50,000 / hour in terms of normal gas density.
  • the total concentration of hydrocarbons HC dead was measured by flame ionization and the specified concentration on a volume basis in ppm Cl fraction.
  • the concentrations of NO and NO 2 were determined by means of electrochemical sensors.
  • deNC> 2 in percent is expressed as deNC> 2 in percent and can be calculated as the difference in N0 2 concentration in the feed gas minus the respective N0 2 concentration after the catalyst, which was determined by
  • the N0 2 concentration downstream of the catalyst compared to the concentration before the catalyst can be significantly reduced by appropriately controlling the gas turbine and the system as well as, for example, by providing ⁇ position a sufficient amount of UHC in the gas turbine exhaust gas, and thus also clearly the Auftre ⁇ th a yellowish color of the discharged exhaust gas can be avoided.
  • the figures also show the storage and emptying processes of UHC in the catalyst, which are used for
  • N0 2 emissions are assumed, which are formed by catalytic oxidation of NO in concentrations up to the temperature-dependent thermodynamic equilibrium ratio between NO and NO 2 .
  • the solution proposed here for reducing NO 2 -, however, emissions, for example in gas turbine exhaust gases, is based on the surprising finding that with suffi ⁇ accordingly low elected catalytic activity for oxidation of hydrocarbons with oxygen an exhaust gas composition can be brought about, in which the NO 2 - concentration can be brought to a value which is far below the given by the thermodynamic GleichThatsver ⁇ ratio between N02 and NO for the respective temperature, as shown in Figure 6 by way of example for a gas-turbine At temperatures below 300 ° C, it would be expected that the nitrogen oxides would predominantly be present as O 2 .
  • the test results in FIG. 7 show that O 2 can be reduced to NO predominantly by catalytic treatment.
  • the solution presented here does not require reductant storage and injection (ammonia or urea) because it is not based on an NH 3 -SCR process.
  • reductant storage and injection ammonia or urea
  • only one catalytic section in the exhaust gas system may be required, which can also be significantly more compact than any of the sections in conventional processes because the gas residence times required for N0 2 reduction are only 25-50% of that for SCR or CO oxidation required gas residence times.
  • the solution provided here can in principle be retrofitted, while a full SCR system can not be retrofitted for reasons of space in some cases.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
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Abstract

L'invention concerne un procédé pour réduire la concentration de dioxyde d'azote dans des gaz brûlés générés par la combustion incomplète d'hydrocarbures ou de mélanges d'hydrocarbures, en utilisant un catalyseur afin de réduire la teneur en dioxyde d'azote par oxydation des hydrocarbures ou des mélanges d'hydrocarbures non brûlés. L'invention concerne également un dispositif pour réduire la concentration de dioxyde d'azote dans des gaz brûlés générés par la combustion incomplète d'hydrocarbures ou de mélanges d'hydrocarbures en utilisant un catalyseur pour réduire la teneur en dioxyde d'azote par oxydation des hydrocarbures ou des mélanges d'hydrocarbures non brûlés, ainsi qu'une installation comprenant ce dispositif.
EP13735216.7A 2012-08-02 2013-06-13 Procédé pour réduire la concentration de dioxyde d'azote Ceased EP2861326A1 (fr)

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DE102012213728 2012-08-02
PCT/EP2013/062244 WO2014019756A1 (fr) 2012-08-02 2013-06-13 Procédé pour réduire la concentration de dioxyde d'azote

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EP (1) EP2861326A1 (fr)
JP (1) JP6174143B2 (fr)
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WO (1) WO2014019756A1 (fr)

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KR102079768B1 (ko) * 2018-05-08 2020-02-20 에스케이가스 주식회사 올레핀 제조 공정 중에 발생하는 배가스 내 이산화질소를 저감하는 방법
KR102445419B1 (ko) * 2020-07-21 2022-09-21 에스케이가스 주식회사 환원제의 주입 없이 고정 배출원의 배가스 내 이산화질소를 저감하는 방법
CN112879126B (zh) * 2021-01-21 2022-05-13 天津大学 一种无催化的双还原剂NOx脱除方法及其装置
KR20230155810A (ko) * 2022-05-04 2023-11-13 에스케이가스 주식회사 고정 배출원의 배가스 내 질소산화물 및 탄화수소를 저감하는 방법

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JP2015531671A (ja) 2015-11-05
CN104519981B (zh) 2017-11-03
US9403124B2 (en) 2016-08-02
JP6174143B2 (ja) 2017-08-02
WO2014019756A1 (fr) 2014-02-06
US20150202570A1 (en) 2015-07-23
KR102083851B1 (ko) 2020-05-27
KR20150039811A (ko) 2015-04-13
CN104519981A (zh) 2015-04-15

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