WO2014142046A1 - Method for reducing and removing nitrogen oxides in exhaust gas - Google Patents

Method for reducing and removing nitrogen oxides in exhaust gas Download PDF

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WO2014142046A1
WO2014142046A1 PCT/JP2014/056104 JP2014056104W WO2014142046A1 WO 2014142046 A1 WO2014142046 A1 WO 2014142046A1 JP 2014056104 W JP2014056104 W JP 2014056104W WO 2014142046 A1 WO2014142046 A1 WO 2014142046A1
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catalyst
exhaust gas
alcohol
nitrogen oxides
concentration
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French (fr)
Japanese (ja)
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香奈 清水
日数谷　進
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日立造船株式会社
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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
    • B01D53/92—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
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • 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
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • F01N3/20—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 specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
    • 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
    • F01N3/24—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 constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/208—Hydrocarbons
    • 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
    • B01D2255/2073—Manganese
    • 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
    • B01D2255/20746—Cobalt
    • 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
    • B01D2257/402—Dinitrogen oxide
    • 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
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/06—Adding substances to exhaust gases the substance being in the gaseous form
    • 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
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/10—Adding substances to exhaust gases the substance being heated, e.g. by heating tank or supply line of the added substance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a method for reducing and removing nitrogen oxides contained in various combustion exhaust gases from boilers, diesel generators, diesel engine automobiles, etc. and exhaust gases from industrial facilities.
  • oxygen, sulfur oxide, and the like are contained in addition to nitrogen oxides, which have been a cause of impairing the performance of the denitration catalyst.
  • a temperature of about 300 to 400 ° C. is used with a specific deNOx catalyst using ethanol or isopropyl alcohol as a reducing agent.
  • Patent Documents 1 and 2 JP 2004-261754 A JP 2004-358454 A
  • the reducing agent is introduced in one stage upstream of the one-layer catalyst bed filled with the specific denitration catalyst, so that the reducing agent can reach the entire catalyst.
  • the denitration catalyst used in the above method is a proton-type ⁇ zeolite (Patent Document 1) or a ⁇ -zeolite that carries a predetermined metal (Patent Document 2).
  • Patent Document 1 a proton-type ⁇ zeolite
  • Patent Document 2 a ⁇ -zeolite that carries a predetermined metal
  • side reactions such as dehydration condensation reaction of alcohol also occur.
  • the denitration performance of the catalyst was lowered.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for removing nitrogen oxides in exhaust gas by efficiently denitrating the catalyst as a whole and causing no deterioration in catalyst performance.
  • the present invention provides an exhaust gas containing nitrogen oxides in contact with a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent.
  • a method for reducing and removing nitrogen oxides wherein a plurality of catalyst layers are arranged along the flow path of the exhaust gas so that the exhaust gas contacts the catalyst a plurality of times before being introduced into each catalyst layer.
  • the catalyst is supplied to the exhaust gas, and the concentration of the alcohol in contact with the catalyst layer is less than a limit concentration at which coke that causes deterioration of the catalyst is not formed on the catalyst.
  • a plurality of catalyst layers are arranged along the exhaust gas flow path so that the exhaust gas contacts the catalyst a plurality of times, and alcohol is supplied to the exhaust gas before being introduced into each catalyst layer.
  • the concentration of the alcohol in contact with the catalyst layer is adjusted upstream of each catalyst layer so that the coke that causes deterioration of the catalyst is less than the limit concentration at which the catalyst is not formed on the catalyst. It is possible to provide a method for removing nitrogen oxides in exhaust gas, which can efficiently perform denitration and does not cause deterioration in catalyst performance.
  • the exhaust gas containing nitrogen oxides is brought into contact with a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent.
  • a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent.
  • Zeolite is not particularly limited as long as it can exhibit denitration performance, but an advantageous one is MFI zeolite.
  • the supported metal is not particularly limited as long as it can exhibit denitration performance, but an advantageous one is at least one of Co, Mn and Fe, and a more advantageous one is Co.
  • the alcohol as the reducing agent is not particularly limited as long as it has a reducing power at the temperature during the reduction treatment of the exhaust gas.
  • alcohol having 1 to 3 carbon atoms specifically, Examples include methanol, ethanol, isopropyl alcohol, and the like.
  • the exhaust gas containing nitrogen oxides to be treated in the method according to the present invention is an exhaust gas generated by burning hydrocarbon fuel such as petroleum and coal. For example, from a boiler, a diesel generator, a diesel engine automobile, etc. These are exhaust gases from various combustion exhaust gases and industrial equipment. Since these hydrocarbon fuels are derived from nitrogen compounds, the exhaust gas after combustion contains nitrogen oxides such as NO, NO 2 , and N 2 O.
  • the catalyst used for reducing and removing nitrogen oxides in the method of the present invention is a catalyst in which a predetermined metal is supported on zeolite.
  • the metal supported on the zeolite is not particularly limited as long as it can exhibit the denitration performance, but an advantageous one is at least one of Co, Mn and Fe, and a more advantageous one is Co.
  • the amount of Co supported is not particularly limited as long as the denitration performance can be exhibited, but is preferably 2 to 4% by weight based on the weight of the zeolite.
  • the catalyst in the method of the present invention can reduce nitrogen oxides in exhaust gas at a temperature of 180 to 300 ° C., and particularly exhibits denitration performance even in a low temperature range where the temperature of the exhaust gas is about 250 ° C. This is advantageous in that it can.
  • a plurality of catalyst layers are arranged along the exhaust gas flow path so that the exhaust gas contacts the catalyst a plurality of times.
  • the catalyst layer may have any form conventionally known for reducing and removing nitrogen oxides, and examples thereof include pellets and honeycombs.
  • the number of catalyst layers arranged along the exhaust gas flow path is usually two so that the entire arranged catalyst can be used for denitration.
  • the number may be three or more as long as efficiency of denitration treatment and improvement of catalyst deterioration prevention can be improved depending on various conditions such as concentration, duration of exhaust gas treatment, and type of reducing agent.
  • the alcohol is supplied to the exhaust gas before introducing the exhaust gas to each of the plurality of catalyst layers arranged in this way.
  • the alcohol concentration at that time is adjusted so as to be not more than a limit concentration at which coke which causes catalyst deterioration is not formed on the catalyst.
  • the limit concentration at which coke is not formed on the catalyst varies depending on the type of alcohol used. As a result of investigations by the inventors, about 6,000 ppm for methanol, about 700 ppm for ethanol, isopropyl alcohol (Hereinafter referred to as IPA) has been found to be about 500 ppm.
  • alcohol is supplied to each catalyst layer after adjusting the alcohol concentration to be below the limit concentration determined for each alcohol as described above.
  • Example 10 -Catalyst preparation 10 g of commercially available MFI zeolite was suspended in an aqueous solution in which 194.18 g of ion-exchanged water and 5.82 g of Co (NO 3 ) 2 .H 2 O were mixed, stirred at 80 ° C. overnight, and filtered. , Washed, and dried at 100 ° C. for 3 hours to obtain a Co / MFI zeolite.
  • Fig. 1 shows a flow chart of an apparatus for evaluating the above catalyst.
  • the NO-containing gas to be treated is passed in this order through the denitration reactors (1) and (2) filled with the denitration catalyst prepared above for denitrating NO.
  • An aqueous solution of methanol, ethanol, or IPA, which is a reducing agent, is pumped out from the alcohol aqueous solution tank (3) by the first metering pump (4a) and injected into the first evaporator (5).
  • the first evaporator (5) is also supplied with NO gas in nitrogen (NO / N 2 ) containing NO to be processed and air.
  • Valves are provided in the line for supplying NO gas in nitrogen (NO / N 2 ) and the line for supplying air. Is done.
  • first evaporator (5) methanol, ethanol or IPA as a reducing agent is evaporated by heating.
  • the NO-containing gas discharged from the first evaporator (5) and the mixed gas containing methanol, ethanol or IPA as the reducing agent are supplied to the upstream first denitration reactor (1).
  • a thermocouple (6) for measuring the internal heating state is inserted in the catalyst layer of the first denitration reactor (1).
  • the first denitrated exhaust discharged from the outlet of the first denitration reactor (1) is supplied to the second evaporator (7).
  • the second evaporator (7) is injected with an aqueous solution of methanol, ethanol, or IPA pumped from the alcohol aqueous solution tank (3) by the second quantitative liquid feeding pump (4b).
  • methanol, ethanol or IPA as a reducing agent is evaporated by heating.
  • the exhaust gas discharged from the second evaporator (7) and the exhaust gas treated in the first denitration reactor (1) and the mixed gas containing methanol, ethanol or IPA as the reducing agent are used as the downstream second denitration reaction.
  • a thermocouple (8) for measuring the internal heating state is inserted into the catalyst layer of the second denitration reactor (2).
  • a part of the discharge discharged from the second denitration reactor (2) is supplied to the gas analysis, and the other part is discharged as exhaust gas or waste water.
  • the gas analysis of the final discharge discharged from the second denitration reactor (2) was measured as the outlet NOx concentration by using a NOx meter.
  • the NOx removal rate which is the NOx removal performance of the catalyst was calculated by the following mathematical formula (1).
  • Example 1 In the above performance evaluation method, durability was evaluated using methanol as the reducing agent.
  • the concentration of methanol was 5800 ppm.
  • Example 1 As shown in Table 2, in Comparative Example 1 where the methanol concentration is 7200 ppm, the performance is reduced to about 80% of the initial denitration rate after 164 hours. On the other hand, in Example 1 where the methanol concentration is 5800 ppm, it can be seen that the performance equivalent to the initial value is maintained even after 164 hours.
  • Example 2 In the same manner as in Example 1, durability was evaluated using ethanol (700 ppm) as the reducing agent. Here, the NO concentration of NO supplied to the first denitration reactor was 200 ppm (Comparative Example 2). Durability was evaluated in the same manner as in Example 2 except that the ethanol concentration was 1000 ppm.
  • Example 2 where the ethanol concentration is 1000 ppm, the performance decreases to 10% or less of the initial denitration rate after 110 hours.
  • Example 2 where the ethanol concentration is 700 ppm, the performance equivalent to the initial value is maintained even after 110 hours. From this result, when ethanol is used as the reducing agent, it is considered that performance degradation due to coke deposition can be suppressed by introducing each catalyst layer with about 700 ppm as a guide.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
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Abstract

Provided is a method for removing nitrogen oxides in an exhaust gas, wherein a catalyst as a whole efficiently performs denitration without suffering from deterioration of the catalyst performance. The present invention is a method for reducing and removing nitrogen oxides in an exhaust gas by bringing an exhaust gas containing nitrogen oxides into contact with a catalyst, which is obtained by having zeolite support a predetermined metal, in the presence of an alcohol that serves as a reducing agent. In this method, a plurality of catalyst layers are arranged along the flow path of the exhaust gas so that the exhaust gas comes into contact with the catalyst a plurality of times; the alcohol is supplied to the exhaust gas before the exhaust gas is introduced into each catalyst layer; and the concentration of the alcohol that comes into contact with each catalyst layer is controlled in the upstream of each catalyst layer so that the concentration is not more than the limit concentration at which coke is not formed on the catalyst, said coke causing deterioration of the catalyst.

Description

排ガス中の窒素酸化物の還元除去方法Method for reducing and removing nitrogen oxides in exhaust gas
　本発明は、ボイラー、ディーゼル発電機、ディーゼルエンジン自動車等からの各種燃焼排ガスや産業設備からの排ガスに含まれる窒素酸化物を還元除去する方法に関する。 The present invention relates to a method for reducing and removing nitrogen oxides contained in various combustion exhaust gases from boilers, diesel generators, diesel engine automobiles, etc. and exhaust gases from industrial facilities.
　ボイラー、ディーゼル発電機、ディーゼルエンジン自動車等からの各種燃焼排ガスや産業設備からの排ガスに含まれる窒素酸化物を還元除去する方法として、各種の方法が知られている。 Various methods are known as methods for reducing and removing nitrogen oxides contained in various combustion exhaust gases from boilers, diesel generators, diesel engine automobiles, etc. and exhaust gases from industrial facilities.
　上記のような排ガス中には、窒素酸化物の他、酸素、硫黄酸化物等が含まれており、これらが脱硝触媒の性能を損なう原因となっていた。 In the exhaust gas as described above, oxygen, sulfur oxide, and the like are contained in addition to nitrogen oxides, which have been a cause of impairing the performance of the denitration catalyst.
　このような多量の酸素および硫黄酸化物を含む排ガスにおいても窒素酸化物を除去する脱硝性能が低下しない方法として、還元剤としてエタノールまたはイソプロピルアルコールを用い特定の脱硝触媒により３００～４００℃程度の温度で排ガスの脱硝を行う方法が提案されている（特許文献１、２）。
特開２００４－２６１７５４号公報 特開２００４－３５８４５４号公報 As a method for eliminating the NOx removal performance even in such exhaust gas containing a large amount of oxygen and sulfur oxides, a temperature of about 300 to 400 ° C. is used with a specific deNOx catalyst using ethanol or isopropyl alcohol as a reducing agent. Have proposed a method for denitrating exhaust gas (Patent Documents 1 and 2).
JP 2004-261754 A JP 2004-358454 A
　上記の方法では、特定の脱硝触媒が充填された１層の触媒床の上流側に１段階で還元剤を投入するようになっているため、触媒全体に還元剤が行きわたるようにするために多量の還元剤、すなわち高い濃度の還元剤を触媒床の上流側に投入する必要がある。 In the above method, the reducing agent is introduced in one stage upstream of the one-layer catalyst bed filled with the specific denitration catalyst, so that the reducing agent can reach the entire catalyst. A large amount of reducing agent, that is, a high concentration of reducing agent, needs to be introduced upstream of the catalyst bed.
　しかしながら、上記方法に用いられる脱硝触媒は、プロトン型βゼオライト（特許文献１）やβゼオライトに所定金属を担持させたもの（特許文献２）であり、このようなゼオライト系の触媒にアルコールを接触させると、目的の脱硝反応以外にアルコールの脱水縮合反応等の副反応も起こり、還元剤としてアルコールを用いる場合に触媒床に投入する還元剤の濃度が高すぎると、触媒表面にコークが析出し触媒の脱硝性能が低下するという問題があった。 However, the denitration catalyst used in the above method is a proton-type β zeolite (Patent Document 1) or a β-zeolite that carries a predetermined metal (Patent Document 2). In addition to the target denitration reaction, side reactions such as dehydration condensation reaction of alcohol also occur. There was a problem that the denitration performance of the catalyst was lowered.
　本発明は、上記事情に鑑みてなされたものであり、触媒全体として効率的に脱硝を行い触媒性能の低下が生じない、排ガス中の窒素酸化物の除去方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for removing nitrogen oxides in exhaust gas by efficiently denitrating the catalyst as a whole and causing no deterioration in catalyst performance.
　上記課題を解決するため、本発明は、還元剤であるアルコールの存在下に、窒素酸化物を含有する排ガスを、ゼオライトに所定の金属を担持させてなる触媒と接触させることにより、排ガス中の窒素酸化物を還元除去する方法であって、該排ガスの流通経路に沿って、該排ガスが複数回にわたって該触媒と接触するように複数の触媒層を配置し、各触媒層に導入される前に該排ガスに該アルコールを供給することとし、該触媒層と接触するアルコールの濃度が、該触媒の劣化の原因となるコークが該触媒上に形成されない限界濃度以下であるように、各触媒層の上流に該アルコールを供給する、方法を提供する。 In order to solve the above-mentioned problems, the present invention provides an exhaust gas containing nitrogen oxides in contact with a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent. A method for reducing and removing nitrogen oxides, wherein a plurality of catalyst layers are arranged along the flow path of the exhaust gas so that the exhaust gas contacts the catalyst a plurality of times before being introduced into each catalyst layer. The catalyst is supplied to the exhaust gas, and the concentration of the alcohol in contact with the catalyst layer is less than a limit concentration at which coke that causes deterioration of the catalyst is not formed on the catalyst. A method of supplying the alcohol upstream of
　本発明では、排ガスの流通経路に沿って、該排ガスが複数回にわたって触媒と接触するように複数の触媒層を配置し、各触媒層に導入される前に該排ガスにアルコールを供給することとし、該触媒層と接触するアルコールの濃度は、該触媒の劣化の原因となるコークが該触媒上に形成されない限界濃度以下であるように、各触媒層の上流において調整されるので、触媒全体として効率的に脱硝を行うことができ、触媒性能の低下が生じない、排ガス中の窒素酸化物の除去方法を提供することができる。 In the present invention, a plurality of catalyst layers are arranged along the exhaust gas flow path so that the exhaust gas contacts the catalyst a plurality of times, and alcohol is supplied to the exhaust gas before being introduced into each catalyst layer. The concentration of the alcohol in contact with the catalyst layer is adjusted upstream of each catalyst layer so that the coke that causes deterioration of the catalyst is less than the limit concentration at which the catalyst is not formed on the catalyst. It is possible to provide a method for removing nitrogen oxides in exhaust gas, which can efficiently perform denitration and does not cause deterioration in catalyst performance.
実施例における触媒評価を行うために使用される装置のフロー図である。It is a flowchart of the apparatus used in order to perform catalyst evaluation in an Example.
　以下、本発明による排ガス中の窒素酸化物の還元除去方法について詳細に説明する。 Hereinafter, the method for reducing and removing nitrogen oxides in exhaust gas according to the present invention will be described in detail.
　本発明の排ガス中の窒素酸化物の還元除去方法においては、還元剤であるアルコールの存在下に、窒素酸化物を含有する排ガスを、ゼオライトに所定の金属を担持させてなる触媒と接触させることにより、排ガス中の窒素酸化物が還元除去される。 In the method for reducing and removing nitrogen oxides in exhaust gas of the present invention, the exhaust gas containing nitrogen oxides is brought into contact with a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent. Thus, nitrogen oxides in the exhaust gas are reduced and removed.
　ゼオライトは、脱硝性能が発揮できれば特に制限はないが、有利なものはＭＦＩゼオライトである。担持金属も脱硝性能が発揮できれば特に制限はないが、有利なものはＣｏ、ＭｎおよびＦｅのうち少なくとも一種であり、より有利なものはＣｏである。 Zeolite is not particularly limited as long as it can exhibit denitration performance, but an advantageous one is MFI zeolite. The supported metal is not particularly limited as long as it can exhibit denitration performance, but an advantageous one is at least one of Co, Mn and Fe, and a more advantageous one is Co.
　還元剤であるアルコールは、排ガスの還元処理時の温度において還元力を有するものであれば特に限定されるものではないが、例えば、１～３個の炭素原子を有するアルコール、具体的には、メタノール、エタノール、イソプロピルアルコール等が挙げられる。 The alcohol as the reducing agent is not particularly limited as long as it has a reducing power at the temperature during the reduction treatment of the exhaust gas. For example, alcohol having 1 to 3 carbon atoms, specifically, Examples include methanol, ethanol, isopropyl alcohol, and the like.
　本発明による方法における処理対象となる、窒素酸化物を含有する排ガスは、石油、石炭等の炭化水素燃料を燃焼させることにより生じる排ガスであり、例えば、ボイラー、ディーゼル発電機、ディーゼルエンジン自動車等からの各種燃焼排ガスや産業設備からの排ガスである。これらは、由来となる炭化水素燃料に窒素化合物が含まれていることにより、燃焼後の排ガスに窒素酸化物、例えば、ＮＯ、ＮＯ２、Ｎ２Ｏが含有されることになる。 The exhaust gas containing nitrogen oxides to be treated in the method according to the present invention is an exhaust gas generated by burning hydrocarbon fuel such as petroleum and coal. For example, from a boiler, a diesel generator, a diesel engine automobile, etc. These are exhaust gases from various combustion exhaust gases and industrial equipment. Since these hydrocarbon fuels are derived from nitrogen compounds, the exhaust gas after combustion contains nitrogen oxides such as NO, NO 2 , and N 2 O.
　本発明方法において窒素酸化物を還元除去するために使用される触媒は、ゼオライトに所定の金属を担持させてなるものである。ゼオライトに担持される金属は、脱硝性能が発揮できれば特に制限はないが、有利なものはＣｏ、ＭｎおよびＦｅのうち少なくとも一種であり、より有利なものはＣｏである。またＣｏの担持量は、脱硝性能が発揮できれば特に制限はないが、有利には、ゼオライト重量に対して２～４重量％である。 The catalyst used for reducing and removing nitrogen oxides in the method of the present invention is a catalyst in which a predetermined metal is supported on zeolite. The metal supported on the zeolite is not particularly limited as long as it can exhibit the denitration performance, but an advantageous one is at least one of Co, Mn and Fe, and a more advantageous one is Co. The amount of Co supported is not particularly limited as long as the denitration performance can be exhibited, but is preferably 2 to 4% by weight based on the weight of the zeolite.
　本発明の方法における上記触媒は、１８０～３００℃の温度において排ガス中の窒素酸化物を還元処理することができ、特に、排ガスの温度が２５０℃程度の低温度域においても脱硝性能を発揮することができる点で有利である。 The catalyst in the method of the present invention can reduce nitrogen oxides in exhaust gas at a temperature of 180 to 300 ° C., and particularly exhibits denitration performance even in a low temperature range where the temperature of the exhaust gas is about 250 ° C. This is advantageous in that it can.
　本発明による方法では、排ガスの流通経路に沿って、この排ガスが複数回にわたって上記の触媒と接触するように複数の触媒層が配置される。 In the method according to the present invention, a plurality of catalyst layers are arranged along the exhaust gas flow path so that the exhaust gas contacts the catalyst a plurality of times.
　触媒層は、窒素酸化物を還元除去するために従来から知られている如何なる形態であってもよく、例えば、ペレット、ハニカムが挙げられる。 The catalyst layer may have any form conventionally known for reducing and removing nitrogen oxides, and examples thereof include pellets and honeycombs.
　また、排ガスの流通経路に沿って配置される触媒層は、配置された触媒の全体を脱硝に用いることができるように通常は２個であることが想定されるが、排ガス中の窒素酸化物濃度、排ガス処理の継続時間、還元剤の種類等の諸状況により脱硝処理の効率化および触媒劣化防止の向上が図れるのであれば３個以上であってもよい。 In addition, it is assumed that the number of catalyst layers arranged along the exhaust gas flow path is usually two so that the entire arranged catalyst can be used for denitration. The number may be three or more as long as efficiency of denitration treatment and improvement of catalyst deterioration prevention can be improved depending on various conditions such as concentration, duration of exhaust gas treatment, and type of reducing agent.
　本発明の方法では、このように複数配置された各触媒層に排ガスを導入する前に、排ガスに該アルコールが供給される。 In the method of the present invention, the alcohol is supplied to the exhaust gas before introducing the exhaust gas to each of the plurality of catalyst layers arranged in this way.
　その際のアルコールの濃度は、触媒の劣化の原因となるコークが触媒上に形成されない限界濃度以下であるように調整される。 The alcohol concentration at that time is adjusted so as to be not more than a limit concentration at which coke which causes catalyst deterioration is not formed on the catalyst.
　コークが触媒上に形成されない限界濃度（ｄｒｙガス基準）は、用いられるアルコールの種類によって異なっており、発明者らが検討した結果、メタノールでは、６，０００ｐｐｍ程度、エタノールでは、７００ｐｐｍ程度、イソプロピルアルコール（以下ＩＰＡと称する）では、５００ｐｐｍ程度であることが分かっている。 The limit concentration at which coke is not formed on the catalyst (based on the dry gas) varies depending on the type of alcohol used. As a result of investigations by the inventors, about 6,000 ppm for methanol, about 700 ppm for ethanol, isopropyl alcohol (Hereinafter referred to as IPA) has been found to be about 500 ppm.
　したがって、上記のようなアルコール毎に決められる限界濃度以下になるようにアルコール濃度を調整した上で、各触媒層にアルコールを供給する。 Therefore, alcohol is supplied to each catalyst layer after adjusting the alcohol concentration to be below the limit concentration determined for each alcohol as described above.
　以上に説明した方法を実施することにより、排ガス中の窒素酸化物が還元除去されることとなるが、本発明の方法では、少量の還元剤を投入することにより触媒の劣化を防止することができ、設置される触媒を全体的に効率良く窒素酸化物の還元除去に利用することができる。 By carrying out the method described above, nitrogen oxides in the exhaust gas are reduced and removed. However, in the method of the present invention, deterioration of the catalyst can be prevented by introducing a small amount of reducing agent. In addition, the installed catalyst can be efficiently used for reducing and removing nitrogen oxides as a whole.
　（実施例）
・　触媒調製
　イオン交換水１９４．１８ｇとＣｏ（ＮＯ３）２・Ｈ２Ｏ　５．８２ｇとを混ぜた水溶液に市販のＭＦＩ型ゼオライト１０ｇを懸濁させ、８０℃で一晩攪拌した後、濾過、洗浄し、１００℃で３時間乾燥させることでＣｏ／ＭＦＩゼオライトを得た。 (Example)
-Catalyst preparation 10 g of commercially available MFI zeolite was suspended in an aqueous solution in which 194.18 g of ion-exchanged water and 5.82 g of Co (NO 3 ) 2 .H 2 O were mixed, stirred at 80 ° C. overnight, and filtered. , Washed, and dried at 100 ° C. for 3 hours to obtain a Co / MFI zeolite.
・　触媒性能評価
　上記で得られた触媒をプレス成形後、メッシュサイズ２８から１４に整粒して、内径１０．６ｍｍのステンレス製反応管に充填し、表１に示す条件で触媒の性能評価を行った。 ・ Catalyst performance evaluation After press molding the catalyst obtained above, it is sized to a mesh size of 28 to 14, filled into a stainless steel reaction tube having an inner diameter of 10.6 mm, and the performance of the catalyst is evaluated under the conditions shown in Table 1. went.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　ここで、表１中、「Ｂａｌａｎｃｅ」は、ＮＯが所定濃度となる量を意味する。 Here, in Table 1, “Balance” means the amount of NO at a predetermined concentration.
　図１に上記触媒の評価を行うための装置のフロー図を示す。 Fig. 1 shows a flow chart of an apparatus for evaluating the above catalyst.
　図１において、処理されるべきＮＯ含有ガスは、ＮＯを脱硝するための上記で調製された脱硝触媒が充填された脱硝反応器（１）および（２）をこの順に通過させられる。アルコール水溶液槽（３）から還元剤であるメタノール、エタノールまたはＩＰＡの水溶液が第１の定量送液ポンプ（４ａ）により汲み出されて第１蒸発器（５）に注入される。第１蒸発器（５）には、処理対象のＮＯを含む窒素中ＮＯガス（ＮＯ／Ｎ２）および空気も供給される。窒素中ＮＯガス（ＮＯ／Ｎ２）を供給するラインおよび空気を供給するラインにはそれぞれバルブが設けられており、各ガスが上記表１に示される割合になるように各ガスの流量が調整される。第１蒸発器（５）では加熱により還元剤であるメタノール、エタノールまたはＩＰＡが蒸発させられる。第１蒸発器（５）から排出される、ＮＯ含有ガスおよび還元剤であるメタノール、エタノールまたはＩＰＡを含む混合ガスは、上流側の第１脱硝反応器（１）に供給されるようになっており、第１脱硝反応器（１）の触媒層中には、内部の加熱状態を測定するための熱電対（６）が差し込まれている。第１脱硝反応器（１）の出口から出る１回目の脱硝処理された排出物は、第２蒸発器（７）に供給される。第２蒸発器（７）には、アルコール水溶液槽（３）から第２の定量送液ポンプ（４ｂ）により汲み出されたメタノール、エタノールまたはＩＰＡの水溶液が注入される。第２蒸発器（７）では、加熱により還元剤であるメタノール、エタノールまたはＩＰＡが蒸発させられる。第２蒸発器（７）から排出される、第１脱硝反応器（１）で処理された排出物、および還元剤であるメタノール、エタノールまたはＩＰＡを含む混合ガスは、下流側の第２脱硝反応器（２）に供給されるようになっている。第２脱硝反応器（２）の触媒層中には、内部の加熱状態を測定するための熱電対（８）が差し込まれている。第２脱硝反応器（２）から排出された排出物は、その一部がガス分析に供給され、他の部分は、排ガスまたは排水として排出される。なお、ガス分析の結果によりＮＯ含有量が多い場合は、さらなるＮＯ処理を行った後に排出されることとなる。 In FIG. 1, the NO-containing gas to be treated is passed in this order through the denitration reactors (1) and (2) filled with the denitration catalyst prepared above for denitrating NO. An aqueous solution of methanol, ethanol, or IPA, which is a reducing agent, is pumped out from the alcohol aqueous solution tank (3) by the first metering pump (4a) and injected into the first evaporator (5). The first evaporator (5) is also supplied with NO gas in nitrogen (NO / N 2 ) containing NO to be processed and air. Valves are provided in the line for supplying NO gas in nitrogen (NO / N 2 ) and the line for supplying air. Is done. In the first evaporator (5), methanol, ethanol or IPA as a reducing agent is evaporated by heating. The NO-containing gas discharged from the first evaporator (5) and the mixed gas containing methanol, ethanol or IPA as the reducing agent are supplied to the upstream first denitration reactor (1). A thermocouple (6) for measuring the internal heating state is inserted in the catalyst layer of the first denitration reactor (1). The first denitrated exhaust discharged from the outlet of the first denitration reactor (1) is supplied to the second evaporator (7). The second evaporator (7) is injected with an aqueous solution of methanol, ethanol, or IPA pumped from the alcohol aqueous solution tank (3) by the second quantitative liquid feeding pump (4b). In the second evaporator (7), methanol, ethanol or IPA as a reducing agent is evaporated by heating. The exhaust gas discharged from the second evaporator (7) and the exhaust gas treated in the first denitration reactor (1) and the mixed gas containing methanol, ethanol or IPA as the reducing agent are used as the downstream second denitration reaction. Is supplied to the container (2). A thermocouple (8) for measuring the internal heating state is inserted into the catalyst layer of the second denitration reactor (2). A part of the discharge discharged from the second denitration reactor (2) is supplied to the gas analysis, and the other part is discharged as exhaust gas or waste water. In addition, when there is much NO content by the result of a gas analysis, after performing further NO process, it will discharge | emit.
　第２脱硝反応器（２）から排出された最終排出物のガス分析については、ＮＯｘ計を用いることにより出口ＮＯｘ濃度として測定した。 The gas analysis of the final discharge discharged from the second denitration reactor (2) was measured as the outlet NOx concentration by using a NOx meter.
　ＮＯｘ計での測定値から、下記の数式（１）によって触媒のＮＯｘ除去性能である脱硝率を算出した。 From the measured value with the NOx meter, the NOx removal rate which is the NOx removal performance of the catalyst was calculated by the following mathematical formula (1).
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　（実施例１）
　上記の性能評価方法で、還元剤にメタノールを用い、耐久性評価を実施した。メタノールの濃度は５８００ｐｐｍとした。 (Example 1)
In the above performance evaluation method, durability was evaluated using methanol as the reducing agent. The concentration of methanol was 5800 ppm.
　（比較例１）
　メタノール濃度を７２００ｐｐｍに変更した他は、実施例１と同様にして耐久性評価を実施した。 (Comparative Example 1)
Durability evaluation was performed in the same manner as in Example 1 except that the methanol concentration was changed to 7200 ppm.
　評価結果を下記の表２に示す。 Evaluation results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示すように、メタノール濃度が７２００ｐｐｍである比較例１では、１６４時間後に初期脱硝率の８割程度まで性能が低下している。それに対し、メタノール濃度が５８００ｐｐｍである実施例１では、１６４時間後にも初期と同等の性能を維持していることが分かる。 As shown in Table 2, in Comparative Example 1 where the methanol concentration is 7200 ppm, the performance is reduced to about 80% of the initial denitration rate after 164 hours. On the other hand, in Example 1 where the methanol concentration is 5800 ppm, it can be seen that the performance equivalent to the initial value is maintained even after 164 hours.
　この結果から、メタノールを用いる場合には、６０００ｐｐｍ程度を目安に触媒層ごとに導入することで、コーク析出による性能低下を抑制できると考えられる。 From this result, when methanol is used, it is considered that performance deterioration due to coke deposition can be suppressed by introducing each catalyst layer with about 6000 ppm as a guide.
　（実施例２）
　実施例１と同様の方法で、還元剤にエタノール（７００ｐｐｍ）を用いて耐久性の評価を実施した。ここで、第１脱硝反応器に供給されるＮＯのＮＯ濃度は２００ｐｐｍとした
　（比較例２）
　エタノールの濃度を１０００ｐｐｍとした他は、実施例２と同様の方法で耐久性の評価を実施した。 (Example 2)
In the same manner as in Example 1, durability was evaluated using ethanol (700 ppm) as the reducing agent. Here, the NO concentration of NO supplied to the first denitration reactor was 200 ppm (Comparative Example 2).
Durability was evaluated in the same manner as in Example 2 except that the ethanol concentration was 1000 ppm.
　評価結果を下記表３に示す。 Evaluation results are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　エタノール濃度が１０００ｐｐｍである比較例２では、１１０時間後には、初期脱硝率の１割以下まで性能が低下している。それに対し、エタノール濃度が７００ｐｐｍである実施例２では、１１０時間後にも初期と同等程度の性能を維持している。この結果から、還元剤としてエタノールを用いる場合には、７００ｐｐｍ程度を目安に触媒層ごとに導入することで、コーク析出による性能低下を抑制できると考えられる。 In Comparative Example 2 where the ethanol concentration is 1000 ppm, the performance decreases to 10% or less of the initial denitration rate after 110 hours. On the other hand, in Example 2 where the ethanol concentration is 700 ppm, the performance equivalent to the initial value is maintained even after 110 hours. From this result, when ethanol is used as the reducing agent, it is considered that performance degradation due to coke deposition can be suppressed by introducing each catalyst layer with about 700 ppm as a guide.
（１）：第１脱硝反応器
（２）：第２脱硝反応器
（３）：アルコール水溶液槽
（４ａ）：第１の定量送液ポンプ
（４ｂ）：第２の定量送液ポンプ
（５）：第１蒸発器
（６）：熱電対
（７）：第２蒸発器
（８）：熱電対 (1): First denitration reactor (2): Second denitration reactor (3): Alcohol aqueous solution tank (4a): First metering pump (4b): Second metering pump (5) : First evaporator (6): Thermocouple (7): Second evaporator (8): Thermocouple

Claims (4)

  1. 　還元剤であるアルコールの存在下に、窒素酸化物を含有する排ガスを、ゼオライトに所定の金属を担持させてなる触媒と接触させることにより、排ガス中の窒素酸化物を還元除去する方法であって、
    　該排ガスの流通経路に沿って、該排ガスが複数回にわたって該触媒と接触するように複数の触媒層を配置し、各触媒層に導入される前に該排ガスに該アルコールを供給することとし、該触媒層と接触するアルコールの濃度は、該触媒の劣化の原因となるコークが該触媒上に形成されない限界濃度以下であるように、各触媒層の上流において調整される、方法。     A method for reducing and removing nitrogen oxides in exhaust gas by contacting exhaust gas containing nitrogen oxide with a catalyst in which a predetermined metal is supported on zeolite in the presence of alcohol as a reducing agent. ,
    A plurality of catalyst layers are arranged so that the exhaust gas contacts the catalyst a plurality of times along the flow path of the exhaust gas, and the alcohol is supplied to the exhaust gas before being introduced into each catalyst layer, A method wherein the concentration of alcohol in contact with the catalyst layer is adjusted upstream of each catalyst layer such that the coke causing degradation of the catalyst is below a limit concentration at which coke is not formed on the catalyst.
  2. 　アルコールの前記限界濃度は、メタノール　６０００ｐｐｍ、エタノール　７００ｐｐｍ、ＩＰＡ　５００ｐｐｍである、請求項１に記載の方法。 The method according to claim 1, wherein the limit concentration of alcohol is 6000 ppm of methanol, 700 ppm of ethanol, and 500 ppm of IPA.
  3. 　前記ゼオライトがＭＦＩ型ゼオライトである、請求項１または２に記載の方法。 The method according to claim 1 or 2, wherein the zeolite is MFI type zeolite.
  4. 　前記金属がＣｏである、請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein the metal is Co.
PCT/JP2014/056104 2013-03-12 2014-03-10 Method for reducing and removing nitrogen oxides in exhaust gas WO2014142046A1 (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH11210447A (en) * 1998-01-22 1999-08-03 Toyota Motor Corp Exhaust emission control device of internal combustion engine
JP2004261754A (en) * 2003-03-04 2004-09-24 Sumitomo Metal Mining Co Ltd Exhaust gas purifying catalyst and purifying method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11210447A (en) * 1998-01-22 1999-08-03 Toyota Motor Corp Exhaust emission control device of internal combustion engine
JP2004261754A (en) * 2003-03-04 2004-09-24 Sumitomo Metal Mining Co Ltd Exhaust gas purifying catalyst and purifying method

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