WO2020230638A1 - System control method - Google Patents

System control method Download PDF

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WO2020230638A1
WO2020230638A1 PCT/JP2020/018210 JP2020018210W WO2020230638A1 WO 2020230638 A1 WO2020230638 A1 WO 2020230638A1 JP 2020018210 W JP2020018210 W JP 2020018210W WO 2020230638 A1 WO2020230638 A1 WO 2020230638A1
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ammonia
exhaust gas
nox
catalyst
zeolite
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PCT/JP2020/018210
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French (fr)
Japanese (ja)
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北村　武昭
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株式会社 Ａｃｒ
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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
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • 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
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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 NOx purification system control of an exhaust gas aftertreatment device corresponding to automobile load driving.
  • One embodiment of the present invention relates to a copper zeolite catalyst and its control in an exhaust gas system designed to reduce nitrogen oxides (NOx).
  • certain embodiments relate to controlling the supply of urea and ammonia as NOx selective reducing agents.
  • the NOx purification catalyst for diesel vehicles uses ammonia obtained by spraying urea water with an exhaust gas aftertreatment device and hydrolyzing the urea water as a reducing agent (selective catalytic reduction, generally referred to as an SCR catalyst).
  • SCR catalyst selective catalytic reduction
  • synthetic zeolite is known because it has a high ability to adsorb ammonia at the solid acid point.
  • reaction formula (1) In the exhaust gas aftertreatment device, several chemical reactions occur, all of which reduce NOx to nitrogen.
  • the dominant reaction is represented by the reaction formula (1) in which NO and NH 3 proceed in equal amounts.
  • Patent Document 1 The CuCHA catalyst represented by Patent Document 1 is SSZ-13 in which copper is ion-exchanged.
  • Patent Document 2 As an SCR catalyst other than the above, it is disclosed that an iron and / or copper ion-exchange zeolite of SAPO-34 having a CHA-type crystal structure containing phosphor oxide, alumina and silica as main components is used (Patent Document). 2).
  • the catalyst represented by Patent Document 2 is SAPO-34 in which copper is ion-exchanged.
  • the CuCHA catalyst has excellent low temperature activity from an exhaust gas temperature of 200 ° C. to 350 ° C. and durability activity after aging in hot water.
  • the NOx purification rate decreases as the exhaust gas temperature rises from 350 ° C. to 500 ° C.
  • the temperature of the exhaust gas cooling system such as EGR of the internal combustion engine is adjusted so that the exhaust gas temperature at the inlet of the SCR catalyst is 500 ° C or less. Need to control.
  • the exhaust gas becomes 500 ° C or higher, but since the oxygen concentration is low and the atmosphere is reduced, NOx is reduced without spraying urea, so the SCR system is controlled at 500 ° C or lower. , Not limited to this.
  • the present invention is an SCR system control method capable of uniformly maintaining the NOx reduction purification of urea water at 93% or more from a low temperature of 200 ° C. to a high temperature of 500 ° C. at the exhaust gas temperature under a vehicle running load.
  • urea and / or ammonia are used to select NOx.
  • the catalyst is a zeolite containing copper, and the consumption of ammonia due to partial oxidation is equal to that of NOx in the exhaust gas. It is a system control method characterized in that the amount of ammonia is controlled and supplied.
  • the present invention is to control the amount of ammonia supplied by taking into account the amount of ammonia consumed by the reaction formulas (2) and (3) regardless of NOx purification. Shown in (Equation 1).
  • the catalyst carrier used in the present invention is not particularly limited, but a zeolite having a CHA type and / or AEI type and AFX type crystal structure is preferable because of the characteristics peculiar to the material having high durability due to hot water.
  • the catalyst metal is preferably copper from the viewpoint of low temperature activity, and the copper is preferably contained in an amount of 2.0% by mass to 5.0% by mass in terms of CuO.
  • the present invention is a known exhaust gas aftertreatment system used in a general vehicle as shown in FIG. 3, wherein the exhaust gas temperature of (Equation 1) uses the measured value of the temperature sensor (9) of the SCR catalyst inlet.
  • (Equation 1) catalyst upstream NOx volume concentration uses the measured value of (2) upstream NOx sensor at the engine outlet to control the system.
  • the constant C (Equation 1) of the present invention is an eigenvalue that differs depending on the acidity of various zeolites in the Cu zeolite catalyst.
  • the constant C in the exhaust gas temperature is determined by the model gas performance test shown in the embodiment of the present invention, the exhaust gas temperature is measured by the (9) temperature sensor at the inlet of the SCR catalyst, and the system of the present invention is controlled.
  • the constant C is the catalyst inlet concentration of NO, NH 3 , NO 2 , N 2 O and NO, NH 3 , NO, NH 3 , at each exhaust gas temperature. Obtain the concentrations of the catalyst outlets of NO 2 and N 2 O from the measured values.
  • ion-exchanged water and pseudo-boehmite (Pural SB) are added to a glass container while stirring, and the mixture is stirred at room temperature for 20 minutes. Then, adamantyltrimethylammonium hydroxide (TMadaOH) is slowly added with stirring, and the mixture is kept at room temperature for 1 hour. Then, colloidal silica (Ludox AS40) was added, and stirring was continued for 5 minutes, and the suspension had a pH of 8.4, and the following composition was prepared.
  • TMadaOH adamantyltrimethylammonium hydroxide
  • colloidal silica Lidox AS40
  • the obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 150 ° C. for 72 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature.
  • the gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 10.6.
  • An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
  • CHA type synthetic zeolite The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net. Based on the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensities (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society for Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of CHA-type SSZ-13 having a maximum oxygen ring number of 8 and a three-dimensional structure.
  • a CuCHA powder catalyst was produced by mixing 100 g of the CHA-type SSZ-13 synthetic zeolite with NH 4 + -like CHA in 400 mL of a 1.0 M copper (II) nitrate solution. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form CHA and the copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
  • the obtained CuCHA product was baked at 700 ° C. for 2 hours.
  • the obtained CuCHA catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
  • the obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 170 ° C. for 72 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature.
  • the gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 10.2.
  • An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
  • CHA type synthetic zeolite The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net. From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of CHA-type SAPO-34 having a maximum oxygen ring number of 8 and a three-dimensional structure.
  • the composition of the obtained CHA-type synthetic SAPO-34 zeolite was 44.50 wt% for P 2 O 5 , 9.60 wt% for SiO 2 , 45.90 wt% for Al 2 O 3 , and SiO 2
  • the mol ratio (SAR) of / Al 2 O 3 was 0.355.
  • a CuCHA powder catalyst was produced by mixing 100 g of the CHA-type SAPO-34 synthetic zeolite with NH 4 + -like CHA with 400 mL of a 1.0 M copper (II) nitrate solution. .. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form CHA and the copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
  • the obtained CuCHA product was baked at 700 ° C. for 2 hours.
  • the obtained CuCHA catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
  • zeolite raw material ion-exchanged water is placed in a glass container, and a predetermined amount of 1N NaOH and N, N-diethyl-cis-2,6-dimethylpiperadinium cation hydroxide (DEDMPOH) are added to the glass container while stirring. Stir at room temperature for 20 minutes. Then, NH 4 + form Y-type zeolite and colloidal silica (Ludox AS40) with a predetermined amount was added, stirring was continued for 5 minutes, the suspension is at a pH of 9.2, were prepared following composition.
  • DEDMPOH N-diethyl-cis-2,6-dimethylpiperadinium cation hydroxide
  • the obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 140 ° C. for 7 days while stirring at a speed of 50 rpm, and then slowly cooled to room temperature.
  • the gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 11.3.
  • An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
  • AEI type synthetic zeolite The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net. From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of AEI type SSZ-39 having a maximum oxygen ring number of 8 and a three-dimensional structure.
  • the obtained CuAEI product was baked at 700 ° C. for 2 hours.
  • the obtained CuAEI catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
  • Reference Example 4 a CuAEI catalyst in which copper was ion-exchanged was produced in the same manner as in Reference Example 1 except that the synthetic zeolite of the catalyst carrier was replaced with AEI type SAPO-18 synthetic zeolite.
  • the obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 215 ° C. for 120 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature.
  • the gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 9.2.
  • An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
  • AEI type synthetic zeolite The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net. From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of AEI-type SAPO-18 having a maximum oxygen ring number of 8 and a three-dimensional structure.
  • the composition of the obtained AEI type SAPO-18 zeolite was 61.00 wt% for P 2 O 5 , 1.80 wt% for SiO 2 , and 37.20 wt% for Al 2 O 3 , and SiO 2 /.
  • the mol ratio (SAR) of Al 2 O 3 was 0.082.
  • the pH was adjusted to 3.5 with acetic acid.
  • Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form AEI and copper ions.
  • the resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless.
  • the washed sample was then dried to 90 ° C.
  • the obtained CuAEI product was baked at 700 ° C. for 2 hours.
  • the obtained CuAEI catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
  • the copper-containing SCR catalyst powders of Reference Examples 1 to 4 were prepared into a colloidal silica binder (solid content 20% by mass) and a slurry liquid, and deposited on a known cordierite honeycomb flow-through type substrate.
  • the slurry liquid was dispersed by a ball mill and deposited at 200 g / L per volume of the honeycomb base material. Then, it was dried at 80 ° C. and calcinated at 500 ° C., and an exhaust gas purification performance test using the system control of the present invention was performed.
  • Table 1 shows the relationship between the NOx exhaust gas concentration and the NH 3 supply control concentration in Examples 1 to 4 and Comparative Examples 1 to 4 as ANR (NH 3 / NOx).
  • Table 2 shows the results of NOx purification performance in Examples 1 to 4 and Comparative Examples 1 to 4.
  • Table 3 shows the results of the NH 3 slip (SCR catalyst downstream leakage) concentration in Examples 1 to 4 and Comparative Examples 1 to 4.

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Abstract

In SCR exhaust gas post-treatment systems, there has been a problem in that, regardless of NOx selective reduction, NOx purification is decreased due to partial oxidation of ammonia at an exhaust gas high-temperature range of 350-500ºC. This system control method according to the present invention is characterized by, in a selective catalytic reduction system purifying NOx by using urea and/or ammonia, controlling the amount of ammonia equal to a molar quantity of NOx in exhaust gas and supplying the ammonia, with the consumption amount due to the partial oxidation of ammonia taken into account, wherein a zeolite containing copper is used as a catalyst.

Description

システム制御方法System control method
　本発明は、自動車負荷走行に対応する排気ガス後処理装置のＮＯｘ浄化システム制御に関する。 The present invention relates to NOx purification system control of an exhaust gas aftertreatment device corresponding to automobile load driving.
　本発明の一実施の形態は、銅ゼオライト触媒および酸化窒素（ＮＯｘ）を還元するために設計された排ガスシステムにおける、その制御に関する。さらに、特定の実施形態は、ＮＯｘ選択還元剤としての尿素およびアンモニアの供給量を制御に関する。 One embodiment of the present invention relates to a copper zeolite catalyst and its control in an exhaust gas system designed to reduce nitrogen oxides (NOx). In addition, certain embodiments relate to controlling the supply of urea and ammonia as NOx selective reducing agents.
　ディーゼル自動車のＮＯｘ浄化触媒は、排気ガス後処理装置で尿素水を噴霧し、その尿素水が加水分解して得られるアンモニアを還元剤として用いる（一般にＳＣＲ触媒といわれる選択的接触還元“Ｓｅｌｅｃｔｉｖｅ　ｃａｔａｌｙｔｉｃ　ｒｅｄｕｃｔｉｏｎ”の略）触媒担体として、固体酸点にアンモニア吸着能が高い点で合成ゼオライトが知られている。 The NOx purification catalyst for diesel vehicles uses ammonia obtained by spraying urea water with an exhaust gas aftertreatment device and hydrolyzing the urea water as a reducing agent (selective catalytic reduction, generally referred to as an SCR catalyst). As a catalyst carrier, synthetic zeolite is known because it has a high ability to adsorb ammonia at the solid acid point.
　前記排気ガス後処理装置では、幾つかの化学反応が起こり、それらの全てが、ＮＯｘを窒素に還元する。支配的な反応は、ＮＯとＮＨ3とが等量モルで進行する、反応式（１）に代表される。 In the exhaust gas aftertreatment device, several chemical reactions occur, all of which reduce NOx to nitrogen. The dominant reaction is represented by the reaction formula (1) in which NO and NH 3 proceed in equal amounts.
［化１］
　　　　4NO　＋　4NH3　＋　O2　→　4N2　＋　6H2O　・・・（１） [Chemical 1]
4NO ＋ 4NH 3 ＋ O 2 → 4N 2 ＋ 6H 2 O ・ ・ ・ (1)
　ＳＣＲ触媒として、シリカとアルミナを主成分とするＣＨＡ型結晶構造を有し、シリカのアルミナに対するモル割合が約１５以上、及び銅のアルミニウムに対する原子割合が約０．２５以上のような銅イオン交換ゼオライトを使用することが開示されている。（特許文献１）
　この特許文献１に代表されるＣｕＣＨＡ触媒は、銅がイオン交換されたＳＳＺ－１３である。 As an SCR catalyst, copper ion exchange has a CHA-type crystal structure containing silica and alumina as main components, and the molar ratio of silica to alumina is about 15 or more, and the atomic ratio of copper to aluminum is about 0.25 or more. The use of zeolite is disclosed. (Patent Document 1)
The CuCHA catalyst represented by Patent Document 1 is SSZ-13 in which copper is ion-exchanged.
　前記以外のＳＣＲ触媒として、リン酸化物、アルミナおよびシリカを主成分とするＣＨＡ型結晶構造を有するＳＡＰＯ－３４の鉄および／または銅のイオン交換ゼオライトを使用することが開示されている（特許文献２）。この特許文献２に代表される触媒は、銅がイオン交換されたＳＡＰＯ－３４である。 As an SCR catalyst other than the above, it is disclosed that an iron and / or copper ion-exchange zeolite of SAPO-34 having a CHA-type crystal structure containing phosphor oxide, alumina and silica as main components is used (Patent Document). 2). The catalyst represented by Patent Document 2 is SAPO-34 in which copper is ion-exchanged.
国際公開第２００８／１０６５１９号International Publication No. 2008/106519 国際公開第２００８／１１８４３４号International Publication No. 2008/118434
　前記ＣｕＣＨＡ触媒は、排ガス温度が２００℃から３５０℃まで低温活性および熱水における熟成後の耐久活性は優れている。しかしながら、排ガス温度が３５０℃から５００℃に至るにつれてＮＯｘ浄化率が低下しまう課題があった。 The CuCHA catalyst has excellent low temperature activity from an exhaust gas temperature of 200 ° C. to 350 ° C. and durability activity after aging in hot water. However, there is a problem that the NOx purification rate decreases as the exhaust gas temperature rises from 350 ° C. to 500 ° C.
　競争する、酸素との非選択的反応は、ＳＣＲ触媒入り口の排ガス温度が３５０℃から５００℃までの高温になるに従い、アンモニアの部分酸化反応が進行して、Ｎ2またはＮ2Ｏ（地球温暖化ガス）の生成が増加する。このように非選択的反応は、アンモニアがＮＯｘの還元に使用されずアンモニアを消費する。その反応式（２）および反応式（３）に示す。 In the competing non-selective reaction with oxygen, as the exhaust gas temperature at the inlet of the SCR catalyst rises from 350 ° C to 500 ° C, the partial oxidation reaction of ammonia proceeds and N 2 or N 2 O (global warming). Chemical gas) production increases. Thus, the non-selective reaction consumes ammonia without using it for the reduction of NOx. It is shown in the reaction formula (2) and the reaction formula (3).
［化２］
　　　　　4NH3 ＋3O2　→　2N2　＋　6H2O　・・・（２）
 
　　　　　2NH3 ＋2O2　→　N2O　＋　6H2O　・・・（３）
  [Chemical 2]
4NH 3 ＋ 3O 2 → 2N 2 ＋ 6H 2 O ・ ・ ・ (2)

2NH 3 ＋ 2O 2 → N 2 O ＋ 6H 2 O ・ ・ ・ (3)
　一方、ＳＣＲ触媒入り口の排ガス温度が５００℃を超えると、アンモニアの完全酸化反応が進行する。アンモニアがＮＯｘの還元に使用されずアンモニアから直接ＮＯｘを生成する。高度の排ガス規制を満足するために、Ｃｕゼオライト触媒を用いて高活性のＮＯｘ浄化を行う場合において、ＳＣＲ触媒入り口排ガス温度が５００℃以下になるよう、内燃機関のＥＧＲ等の排ガス冷却システムで温度制御する必要がある。ただし、ＰＭ燃焼を行う場合は、５００℃以上の排ガスとなるが、酸素濃度が少なく還元雰囲気になるため、尿素噴霧を行うことなくＮＯｘが還元されるため、５００℃以下でＳＣＲシステムを制御する、この限りでない。 On the other hand, when the exhaust gas temperature at the inlet of the SCR catalyst exceeds 500 ° C., the complete oxidation reaction of ammonia proceeds. Ammonia is not used to reduce NOx and produces NOx directly from ammonia. When performing highly active NOx purification using a Cu zeolite catalyst in order to satisfy high exhaust gas regulations, the temperature of the exhaust gas cooling system such as EGR of the internal combustion engine is adjusted so that the exhaust gas temperature at the inlet of the SCR catalyst is 500 ° C or less. Need to control. However, when PM combustion is performed, the exhaust gas becomes 500 ° C or higher, but since the oxygen concentration is low and the atmosphere is reduced, NOx is reduced without spraying urea, so the SCR system is controlled at 500 ° C or lower. , Not limited to this.
［化３］
　　　　4NH3 ＋5O2　→　4NO　＋　6H2O　・・・（４） [Chemical 3]
4NH 3 ＋ 5O 2 → 4NO ＋ 6H 2 O ・ ・ ・ (4)
　本発明は、車両走行負荷時の排ガス温度において、尿素水のＮＯｘ還元の浄化が、２００℃低温から５００℃高温に至るまで、一様にして９３％以上を維持できるＳＣＲシステム制御方法にある。 The present invention is an SCR system control method capable of uniformly maintaining the NOx reduction purification of urea water at 93% or more from a low temperature of 200 ° C. to a high temperature of 500 ° C. at the exhaust gas temperature under a vehicle running load.
本発明は、尿素および／またはアンモニアを用い、ＮＯｘを選択触媒還元システムにおいて、触媒が、銅を含むゼオライトであって、アンモニアの部分酸化による消費量を、排ガス中のＮＯｘと等モル量となるアンモニア量を制御して供給することを特徴とする、システム制御方法である。 In the present invention, urea and / or ammonia are used to select NOx. In a catalytic reduction system, the catalyst is a zeolite containing copper, and the consumption of ammonia due to partial oxidation is equal to that of NOx in the exhaust gas. It is a system control method characterized in that the amount of ammonia is controlled and supplied.
　本発明は、ＮＯｘ浄化に係わらず、前記反応式（２）および反応式（３）によるアンモニアの消費量を加味し、アンモニア供給量を制御することにある。（数１）に示す。 The present invention is to control the amount of ammonia supplied by taking into account the amount of ammonia consumed by the reaction formulas (2) and (3) regardless of NOx purification. Shown in (Equation 1).
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　本発明に用いる触媒担体として、特に限定されるものでないが、熱水による耐久性が高い材料固有の特性から、ＣＨＡ型および／またはＡＥＩ型、ＡＦＸ型の結晶構造からなるゼオライトが好ましい。 The catalyst carrier used in the present invention is not particularly limited, but a zeolite having a CHA type and / or AEI type and AFX type crystal structure is preferable because of the characteristics peculiar to the material having high durability due to hot water.
　さらに、触媒金属は、低温活性の観点で銅が好ましく、その銅が、ＣｕＯ換算で２．０質量％～５．０質量％を含まれることが好ましい。 Further, the catalyst metal is preferably copper from the viewpoint of low temperature activity, and the copper is preferably contained in an amount of 2.0% by mass to 5.0% by mass in terms of CuO.
本発明の排ガス温度におけるＮＯｘ浄化率について、実施例１、実施例２、比較例１および比較例２とを比較したグラフである。It is a graph which compared Example 1, Example 2, Comparative Example 1 and Comparative Example 2 about the NOx purification rate at the exhaust gas temperature of this invention. 本発明の排ガス温度におけるＮＯｘ浄化率について、実施例３、実施例４、比較例３および比較例４とを比較したグラフである。It is a graph which compared Example 3, Example 4, Comparative Example 3 and Comparative Example 4 about the NOx purification rate at the exhaust gas temperature of this invention. 本発明の排ガス後処理装置のシステム図の一例である。This is an example of a system diagram of the exhaust gas aftertreatment device of the present invention.
　本発明は、図３に示す、一般的な車両に用いられる公知の排ガス後処理装置システムであって、（数１）の排ガス温度が、ＳＣＲ触媒入口の（９）温度センサーの測定値を用い、（数１）の触媒上流ＮＯｘ体積濃度が、エンジン出口の（２）上流ＮＯｘセンサーの測定値を用いて、システム制御をおこなう。 The present invention is a known exhaust gas aftertreatment system used in a general vehicle as shown in FIG. 3, wherein the exhaust gas temperature of (Equation 1) uses the measured value of the temperature sensor (9) of the SCR catalyst inlet. , (Equation 1) catalyst upstream NOx volume concentration uses the measured value of (2) upstream NOx sensor at the engine outlet to control the system.
　本発明の（数１）定数Ｃは、Ｃｕゼオライト触媒において種々ゼオライトの酸性度で異なる固有値である。排ガス温度における定数Ｃは、本発明の実施例が示すモデルガス性能試験によって定めて、排ガス温度をＳＣＲ触媒入口の（９）温度センサーの測定し、本発明のシステム制御をおこなう。 The constant C (Equation 1) of the present invention is an eigenvalue that differs depending on the acidity of various zeolites in the Cu zeolite catalyst. The constant C in the exhaust gas temperature is determined by the model gas performance test shown in the embodiment of the present invention, the exhaust gas temperature is measured by the (9) temperature sensor at the inlet of the SCR catalyst, and the system of the present invention is controlled.
　本発明の前記モデルガス評価試験において、前記定数Ｃは、比較例１及び２が示すように、各排ガス温度においてＮＯ、ＮＨ3、ＮＯ2、Ｎ2Ｏの触媒入口濃度およびＮＯ、ＮＨ3、ＮＯ2、Ｎ2Ｏの触媒出口の濃度を測定値から求める。 In the model gas evaluation test of the present invention, as shown in Comparative Examples 1 and 2, the constant C is the catalyst inlet concentration of NO, NH 3 , NO 2 , N 2 O and NO, NH 3 , NO, NH 3 , at each exhaust gas temperature. Obtain the concentrations of the catalyst outlets of NO 2 and N 2 O from the measured values.
　まず、各排ガス温度において、ＮＯｘ浄化率を（数２）に従い求める。
　（数２）
　　ＮＯｘ浄化率＝｛１－（[ＮＯ]出口＋[ＮＯ2]出口／[ＮＯ]入口＋[ＮＯ2]入口)｝×１００
  First, at each exhaust gas temperature, the NOx purification rate is obtained according to (Equation 2).
(Number 2)
NOx purification rate = {1-([NO] outlet + [NO 2 ] outlet / [NO] inlet + [NO 2 ] inlet)} x 100
　次に、各排ガス温度において、定数Ｃを（数３）に従い求める。
　（数３）
定数Ｃ＝｛[ＮＨ3] 出口＋（[ＮＯx]入口×[ＮＯx浄化率] ×２) ＋ [ＮＯx]出口＋２＊[Ｎ2Ｏ] 出口｝／（[ＮＯx]入口＋２＊[Ｎ2Ｏ]）
　但し、[ＮＯx]＝[ＮＯ]＋[ＮＯ2] として表す。
 
　本発明は、（数３）から求めた前記定数Ｃを、（数１）に当て嵌めて、実際の自動車負荷走行に対応する排気ガス後処理装置のＮＯｘ浄化システム制御において、図３に示すエンジン出口の（２）上流ＮＯｘセンサーの測定値とＳＣＲ触媒入口の（９）温度センサーの測定値とを演算して、表１に示すＡＮＲ（ＮＨ3／ＮＯx）でシステム制御をおこなう。 Next, at each exhaust gas temperature, the constant C is obtained according to (Equation 3).
(Number 3)
Constant C = {[NH 3 ] Exit + ([NO x ] inlet x [NO x purification rate] x 2) + [NO x ] exit + 2 * [N 2 O] Exit} / ([NOx] entrance + 2 * [N 2 O])
However, it is expressed as [NOx] = [NO] + [NO 2 ].

According to the present invention, the constant C obtained from (Equation 3) is applied to (Equation 1) to control the NOx purification system of the exhaust gas aftertreatment device corresponding to the actual vehicle load driving, the engine shown in FIG. The measured value of the (2) upstream NOx sensor at the outlet and the measured value of the (9) temperature sensor at the inlet of the SCR catalyst are calculated, and the system is controlled by the ANR (NH 3 / NO x ) shown in Table 1.
　以下、本発明の実施例および比較例によって、本発明をさらに詳細に説明するが、本発明は、これらの実施例によって何ら限定されることはない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples.
（参考例１）
　参考例１は、ＣＨＡ型ＳＳＺ－１３ゼオライトを合成し、銅がイオン交換されたＣｕＣＨＡ触媒を作製した。 (Reference example 1)
In Reference Example 1, CHA-type SSZ-13 zeolite was synthesized to prepare a CuCHA catalyst in which copper was ion-exchanged.
（ゼオライト原料の調整）
　まず、ガラス容器にイオン交換水と、攪拌しながら、擬ベーマイト（Ｐｕｒａｌ　ＳＢ）を加え、室温で２０分間攪拌する。次いで、攪拌しながらアダマンチルトリメチルアンモニウムヒドロキシド（ＴＭＡｄａＯＨ）をゆっくり加え、１時間室温になるまで保持する。その後、コロイダルシリカ（Ｌｕｄｏｘ　ＡＳ４０）を加え、５分間攪拌を継続し、懸濁液がｐＨが８．４で、次の組成物を調製した。 (Adjustment of zeolite raw material)
First, ion-exchanged water and pseudo-boehmite (Pural SB) are added to a glass container while stirring, and the mixture is stirred at room temperature for 20 minutes. Then, adamantyltrimethylammonium hydroxide (TMadaOH) is slowly added with stirring, and the mixture is kept at room temperature for 1 hour. Then, colloidal silica (Ludox AS40) was added, and stirring was continued for 5 minutes, and the suspension had a pH of 8.4, and the following composition was prepared.
　　　　０．０３３（Ａｌ2Ｏ3）：１．０（ＳｉＯ2）：０．１９（ＴＭＡｄａＯＨ）：４６（Ｈ2Ｏ） 0.033 (Al 2 O 3 ): 1.0 (SiO 2 ): 0.19 (TMadaOH): 46 (H 2 O)
（水熱合成）
　得られた懸濁液を攪拌付きオートクレーブ（加圧滅菌器）に移し、密閉して、５０ｒｐｍ速度で攪拌しながら７２時間１５０℃で加熱後、室温まで徐冷した。オートクレーブから得られたゲル組成物を取り出し、その上澄み液取り分け、上澄み液のｐＨは１０．６であった。上澄み液を取り除いたゲル組成物に、等体積量のイオン交換水を加え、振り混ぜて、遠心分離機にて、洗浄、固液分離を、繰り返し行った。 (Hydrothermal synthesis)
The obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 150 ° C. for 72 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature. The gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 10.6. An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
（ＣＨＡ型合成ゼオライト）
　耐熱容器に、得られたゲル組成物を移し、乾燥を１２０℃で１２時間後、２０メッシュの篩網を通して粒度調整をおこなった。
　得られた合成ゼオライトをＸ線回折(Ｘ-ｒａｙ　Ｄｉｆｆｒａｃｔｉｏｎ)分析の結果から、主な回折ピークの相対強度（Ｉ）と格子面間隔（ｄ）とを、国際合成ゼオライト学会のＸ線回折パターン・データベースおよびＩＣＤＤのＰＤＦと照らして、最大酸素環員数が８と、３次元構造を有するＣＨＡ型ＳＳＺ－１３からなるゼオライトと同定した。 (CHA type synthetic zeolite)
The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net.
Based on the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensities (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society for Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of CHA-type SSZ-13 having a maximum oxygen ring number of 8 and a three-dimensional structure.
　得られたＣＨＡ型ＳＳＺ－１３合成ゼオライトの組成は、ＩＣＰ分析した結果、ＳｉＯ2が９４．６５ｗｔ％、Ａｌ2Ｏ3が５．３５ｗｔ％で、ＳｉＯ2／Ａｌ2Ｏ3のｍｏｌ比（ＳＡＲ）は、３０．００であった。 The resulting composition of the CHA type SSZ-13 synthetic zeolite, as a result of ICP analysis, SiO 2 is 94.65wt%, Al 2 O 3 is at 5.35wt%, mol ratio of SiO 2 / Al 2 O 3 ( SAR ) Was 30.00.
　次いで、前記ＣＨＡ型ＳＳＺ－１３合成ゼオライト１００ｇのＮＨ4 +状ＣＨＡを４００ｍＬの１．０Ｍの硝酸銅（ＩＩ）溶液と混合することにより、ＣｕＣＨＡ粉末触媒を製造した。酢酸で、ｐＨを３．５に調節した。スラリーを８０℃で１時間攪拌させて、ＮＨ4 +状ＣＨＡと銅イオンとの間のイオン交換反応を行った。得られた混合物を次にろ過し、８００ｍＬの脱イオン水で、ろ液が透明で無色になるまで洗浄した。そして洗浄したサンプルを９０℃に乾燥した。 Next, a CuCHA powder catalyst was produced by mixing 100 g of the CHA-type SSZ-13 synthetic zeolite with NH 4 + -like CHA in 400 mL of a 1.0 M copper (II) nitrate solution. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form CHA and the copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
　次に得られたＣｕＣＨＡ生成物を、７００℃で２時間か焼した。得られたＣｕＣＨＡ触媒は、ＩＣＰ分析で測定して、ＣｕＯを２．８質量％含んでいた。 Next, the obtained CuCHA product was baked at 700 ° C. for 2 hours. The obtained CuCHA catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
（参考例２）
　参考例２は、触媒担体の合成ゼオライトをＣＨＡ型ＳＡＰＯ－３４合成ゼオライトに代えた以外は、参考例１と同様にして、銅がイオン交換されたＣｕＣＨＡ触媒を作製した。 (Reference example 2)
In Reference Example 2, a CuCHA catalyst in which copper was ion-exchanged was prepared in the same manner as in Reference Example 1 except that the synthetic zeolite of the catalyst carrier was replaced with CHA-type SAPO-34 synthetic zeolite.
（ゼオライト原料の調整）
　まず、ガラス容器にイオン交換水と、８５質量％オルトリン酸とを攪拌しながら混合する。そこに、擬ベーマイト（Ｐｕｒａｌ　ＳＢ）を加え、室温で２０分間攪拌する。次いで、攪拌しながらテトラエチルアンモニウムヒドロキシド（ＴＥＡＯＨ）をゆっくり加え、１時間室温になるまで保持する。その後、コロイダルシリカ（Ｌｕｄｏｘ　ＡＳ４０）を加え、５分間攪拌を継続し、懸濁液がｐＨが８．１で、次の組成物を調製した。 (Adjustment of zeolite raw material)
First, ion-exchanged water and 85% by mass orthophosphoric acid are mixed in a glass container with stirring. Pseudo-boehmite (Pural SB) is added thereto, and the mixture is stirred at room temperature for 20 minutes. Then, tetraethylammonium hydroxide (TEAOH) is slowly added with stirring, and the mixture is kept at room temperature for 1 hour. Then, colloidal silica (Ludox AS40) was added, and stirring was continued for 5 minutes, and the suspension had a pH of 8.1 to prepare the following composition.
　　　　１．０（Ａｌ2Ｏ3）：１．０（Ｐ2Ｏ5）：０．３（ＳｉＯ2）：１．０（ＴＥＡＯＨ）：６４（Ｈ2Ｏ） 1.0 (Al 2 O 3 ): 1.0 (P 2 O 5 ): 0.3 (SiO 2 ): 1.0 (TEAOH): 64 (H 2 O)
（水熱合成）
　得られた懸濁液を攪拌付きオートクレーブ（加圧滅菌器）に移し、密閉して、５０ｒｐｍ速度で攪拌しながら７２時間１７０℃で加熱後、室温まで徐冷した。オートクレーブから得られたゲル組成物を取り出し、その上澄み液取り分け、上澄み液のｐＨは１０．２であった。上澄み液を取り除いたゲル組成物に、等体積量のイオン交換水を加え、振り混ぜて、遠心分離機にて、洗浄、固液分離を、繰り返し行った。 (Hydrothermal synthesis)
The obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 170 ° C. for 72 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature. The gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 10.2. An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
（ＣＨＡ型合成ゼオライト）
　耐熱容器に、得られたゲル組成物を移し、乾燥を１２０℃で１２時間後、２０メッシュの篩網を通して粒度調整をおこなった。
　得られた合成ゼオライトをＸ線回折(Ｘ-ｒａｙ　Ｄｉｆｆｒａｃｔｉｏｎ)分析の結果から、主な回折ピークの相対強度（Ｉ）と格子面間隔（ｄ）とを、国際合成ゼオライト学会のＸ線回折パターン・データベースおよびＩＣＤＤのＰＤＦと照らして、最大酸素環員数が８と、３次元構造を有するＣＨＡ型ＳＡＰＯ―３４からなるゼオライトと同定した。 (CHA type synthetic zeolite)
The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net.
From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of CHA-type SAPO-34 having a maximum oxygen ring number of 8 and a three-dimensional structure.
　得られたＣＨＡ型合成ＳＡＰＯ－３４ゼオライトの組成は、ＩＣＰ分析した結果、Ｐ2Ｏ5が４４．５０ｗｔ％、ＳｉＯ2が９．６０ｗｔ％、Ａｌ2Ｏ3が４５．９０ｗｔ％で、ＳｉＯ2／Ａｌ2Ｏ3のｍｏｌ比（ＳＡＲ）は、０．３５５であった。 As a result of ICP analysis, the composition of the obtained CHA-type synthetic SAPO-34 zeolite was 44.50 wt% for P 2 O 5 , 9.60 wt% for SiO 2 , 45.90 wt% for Al 2 O 3 , and SiO 2 The mol ratio (SAR) of / Al 2 O 3 was 0.355.
　次いで、参考例１と同様にして、前記ＣＨＡ型ＳＡＰＯ－３４合成ゼオライト１００ｇのＮＨ4 +状ＣＨＡを４００ｍＬの１．０Ｍの硝酸銅（ＩＩ）溶液と混合することにより、ＣｕＣＨＡ粉末触媒を製造した。酢酸で、ｐＨを３．５に調節した。スラリーを８０℃で１時間攪拌させて、ＮＨ4 +状ＣＨＡと銅イオンとの間のイオン交換反応を行った。得られた混合物を次にろ過し、８００ｍＬの脱イオン水で、ろ液が透明で無色になるまで洗浄した。そして洗浄したサンプルを９０℃に乾燥した。 Next, in the same manner as in Reference Example 1, a CuCHA powder catalyst was produced by mixing 100 g of the CHA-type SAPO-34 synthetic zeolite with NH 4 + -like CHA with 400 mL of a 1.0 M copper (II) nitrate solution. .. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form CHA and the copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
　次に得られたＣｕＣＨＡ生成物を、７００℃で２時間か焼した。得られたＣｕＣＨＡ触媒は、ＩＣＰ分析で測定して、ＣｕＯを２．８質量％含んでいた。 Next, the obtained CuCHA product was baked at 700 ° C. for 2 hours. The obtained CuCHA catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
（参考例３）
　参考例３は、触媒担体の合成ゼオライトをＡＥＩ型ＳＳＺ－３９合成ゼオライトに代えた以外は、参考例１と同様にして、銅がイオン交換されたＣｕＡＥＩ触媒を作製した。 (Reference example 3)
In Reference Example 3, a CuAEI catalyst in which copper was ion-exchanged was prepared in the same manner as in Reference Example 1 except that the synthetic zeolite of the catalyst carrier was replaced with AEI type SSZ-39 synthetic zeolite.
（ゼオライト原料の調整）
　まず、ガラス容器にイオン交換水を入れ、そこへ攪拌しながら、１ＮのＮａＯＨと、Ｎ，Ｎ－ジエチル－シス－２，６－ジメチルピペラジニウムカチオンヒドロキシド(ＤＥＤＭＰＯＨ）とを所定量加えて室温で２０分間攪拌する。次に、ＮＨ4 +状のＹ型ゼオライトとコロイダルシリカ（Ｌｕｄｏｘ　ＡＳ４０）をと所定量加え、５分間攪拌を継続し、懸濁液がｐＨが９．２で、次の組成物を調製した。 (Adjustment of zeolite raw material)
First, ion-exchanged water is placed in a glass container, and a predetermined amount of 1N NaOH and N, N-diethyl-cis-2,6-dimethylpiperadinium cation hydroxide (DEDMPOH) are added to the glass container while stirring. Stir at room temperature for 20 minutes. Then, NH 4 + form Y-type zeolite and colloidal silica (Ludox AS40) with a predetermined amount was added, stirring was continued for 5 minutes, the suspension is at a pH of 9.2, were prepared following composition.
０．０６（Ａｌ2Ｏ3）：１．０（ＳｉＯ2）：０．３５（ＤＥＤＭＰＯＨ）：４３（Ｈ2Ｏ） 0.06 (Al 2 O 3 ): 1.0 (SiO 2 ): 0.35 (DEDMPOH): 43 (H 2 O)
（水熱合成）
　得られた懸濁液を攪拌付きオートクレーブ（加圧滅菌器）に移し、密閉して、５０ｒｐｍ速度で攪拌しながら７日間１４０℃で加熱後、室温まで徐冷した。オートクレーブから得られたゲル組成物を取り出し、その上澄み液取り分け、上澄み液のｐＨは１１．３であった。上澄み液を取り除いたゲル組成物に、等体積量のイオン交換水を加え、振り混ぜて、遠心分離機にて、洗浄、固液分離を、繰り返し行った。 (Hydrothermal synthesis)
The obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 140 ° C. for 7 days while stirring at a speed of 50 rpm, and then slowly cooled to room temperature. The gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 11.3. An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
（ＡＥＩ型合成ゼオライト）
　耐熱容器に、得られたゲル組成物を移し、乾燥を１２０℃で１２時間後、２０メッシュの篩網を通して粒度調整をおこなった。
　得られた合成ゼオライトをＸ線回折(Ｘ-ｒａｙ　Ｄｉｆｆｒａｃｔｉｏｎ)分析の結果から、主な回折ピークの相対強度（Ｉ）と格子面間隔（ｄ）とを、国際合成ゼオライト学会のＸ線回折パターン・データベースおよびＩＣＤＤのＰＤＦと照らして、最大酸素環員数が８と、３次元構造を有するＡＥＩ型ＳＳＺ－３９からなるゼオライトと同定した。 (AEI type synthetic zeolite)
The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net.
From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of AEI type SSZ-39 having a maximum oxygen ring number of 8 and a three-dimensional structure.
　得られたＡＥＩ型ＳＳＺ－３９ゼオライトの組成は、ＩＣＰ分析した結果、ＳｉＯ2が８９．６５ｗｔ％、Ａｌ2Ｏ3が１０．３５ｗｔ％で、ＳｉＯ2／Ａｌ2Ｏ3のｍｏｌ比（ＳＡＲ）は、１４．７であった。 The composition of the obtained AEI type SSZ-39 zeolites, as a result of ICP analysis, SiO 2 is 89.65wt%, Al 2 O 3 is at 10.35wt%, mol ratio of SiO 2 / Al 2 O 3 ( SAR) Was 14.7.
　次いで、実施例１と同様にして、前記ＡＥＩ型ＳＳＺ－３９合成ゼオライト１００ｇのＮＨ4 +状ＡＥＩを４００ｍＬの１．０Ｍの硝酸銅（ＩＩ）溶液と混合することにより、ＣｕＡＥＩ粉末触媒を製造した。酢酸で、ｐＨを３．５に調節した。スラリーを８０℃で１時間攪拌させて、ＮＨ4 +状ＡＥＩと銅イオンとの間のイオン交換反応を行った。得られた混合物を次にろ過し、８００ｍＬの脱イオン水で、ろ液が透明で無色になるまで洗浄した。そして洗浄したサンプルを９０℃に乾燥した。 Then, in the same manner as in Example 1, the NH 4 + form AEI of said AEI type SSZ-39 synthesized zeolite 100g by mixing copper (II) nitrate solution of 1.0M of 400 mL, to prepare a CuAEI powder catalyst .. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form AEI and copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
　次に得られたＣｕＡＥＩ生成物を、７００℃で２時間か焼した。得られたＣｕＡＥＩ触媒は、ＩＣＰ分析で測定して、ＣｕＯを２．８質量％含んでいた。 Next, the obtained CuAEI product was baked at 700 ° C. for 2 hours. The obtained CuAEI catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
（参考例４）
　参考例４は、触媒担体の合成ゼオライトをＡＥＩ型ＳＡＰＯ－１８合成ゼオライトに代えた以外は、参考例１と同様にして、銅がイオン交換されたＣｕＡＥＩ触媒を作製した。 (Reference example 4)
In Reference Example 4, a CuAEI catalyst in which copper was ion-exchanged was produced in the same manner as in Reference Example 1 except that the synthetic zeolite of the catalyst carrier was replaced with AEI type SAPO-18 synthetic zeolite.
（ゼオライト原料の調整）
　まず、ガラス容器にイオン交換水と、８５質量％オルトリン酸とを攪拌しながら混合する。そこに、擬ベーマイト（Ｐｕｒａｌ　ＳＢ）を加え、室温で２０分間攪拌する。次いで、攪拌しながらテトラエチルアンモニウムヒドロキシド（ＴＥＡＯＨ）をゆっくり加え、１時間室温になるまで保持する。その後、コロイダルシリカ（Ｌｕｄｏｘ　ＡＳ４０）を加え、５分間攪拌を継続し、懸濁液がｐＨが７．８で、次の組成物を調製した。 (Adjustment of zeolite raw material)
First, ion-exchanged water and 85% by mass orthophosphoric acid are mixed in a glass container with stirring. Pseudo-boehmite (Pural SB) is added thereto, and the mixture is stirred at room temperature for 20 minutes. Then, tetraethylammonium hydroxide (TEAOH) is slowly added with stirring, and the mixture is kept at room temperature for 1 hour. Then, colloidal silica (Ludox AS40) was added, and stirring was continued for 5 minutes, and the suspension had a pH of 7.8, and the following composition was prepared.
１．０（Ａｌ2Ｏ3）：０．９８（Ｐ2Ｏ5）：０．０７５（ＳｉＯ2）：１．０（ＴＥＡＯＨ）：６４（Ｈ2Ｏ） 1.0 (Al 2 O 3 ): 0.98 (P 2 O 5 ): 0.075 (SiO 2 ): 1.0 (TEAOH): 64 (H 2 O)
（水熱合成）
　得られた懸濁液を攪拌付きオートクレーブ（加圧滅菌器）に移し、密閉して、５０ｒｐｍ速度で攪拌しながら１２０時間２１５℃で加熱後、室温まで徐冷した。オートクレーブから得られたゲル組成物を取り出し、その上澄み液取り分け、上澄み液のｐＨは９．２であった。上澄み液を取り除いたゲル組成物に、等体積量のイオン交換水を加え、振り混ぜて、遠心分離機にて、洗浄、固液分離を、繰り返し行った。 (Hydrothermal synthesis)
The obtained suspension was transferred to an autoclave with stirring (pressure sterilizer), sealed, heated at 215 ° C. for 120 hours while stirring at a speed of 50 rpm, and then slowly cooled to room temperature. The gel composition obtained from the autoclave was taken out and the supernatant was set aside, and the pH of the supernatant was 9.2. An equal volume of ion-exchanged water was added to the gel composition from which the supernatant had been removed, the mixture was shaken, and washing and solid-liquid separation were repeated with a centrifuge.
（ＡＥＩ型合成ゼオライト）
　耐熱容器に、得られたゲル組成物を移し、乾燥を１２０℃で１２時間後、２０メッシュの篩網を通して粒度調整をおこなった。
　得られた合成ゼオライトをＸ線回折(Ｘ-ｒａｙ　Ｄｉｆｆｒａｃｔｉｏｎ)分析の結果から、主な回折ピークの相対強度（Ｉ）と格子面間隔（ｄ）とを、国際合成ゼオライト学会のＸ線回折パターン・データベースおよびＩＣＤＤのＰＤＦと照らして、最大酸素環員数が８と、３次元構造を有するＡＥＩ型ＳＡＰＯ－１８からなるゼオライトと同定した。 (AEI type synthetic zeolite)
The obtained gel composition was transferred to a heat-resistant container, dried at 120 ° C. for 12 hours, and then the particle size was adjusted through a 20-mesh sieve net.
From the results of X-ray diffraction analysis of the obtained synthetic zeolite, the relative intensity (I) and lattice plane spacing (d) of the main diffraction peaks were determined by the X-ray diffraction pattern of the International Society of Synthetic Zeolite. In light of the database and the PDF of the ICDD, it was identified as a zeolite consisting of AEI-type SAPO-18 having a maximum oxygen ring number of 8 and a three-dimensional structure.
　得られたＡＥI型ＳＡＰＯ－１８ゼオライトの組成は、ＩＣＰ分析した結果、Ｐ2Ｏ5が６１．００ｗｔ％、ＳｉＯ2が１．８０ｗｔ％、Ａｌ2Ｏ3が３７．２０ｗｔ％で、ＳｉＯ2／Ａｌ2Ｏ3のｍｏｌ比（ＳＡＲ）は、０．０８２であった。 As a result of ICP analysis, the composition of the obtained AEI type SAPO-18 zeolite was 61.00 wt% for P 2 O 5 , 1.80 wt% for SiO 2 , and 37.20 wt% for Al 2 O 3 , and SiO 2 /. The mol ratio (SAR) of Al 2 O 3 was 0.082.
　次いで、実施例１と同様にして、前記ＡＥＩ型ＳＡＰＯ－１８合成ゼオライト１００ｇのＮＨ4 +状ＡＥＩを４００ｍＬの１．０Ｍの硝酸銅（ＩＩ）溶液と混合することにより、ＣｕＡＥＩ粉末触媒を製造した。酢酸で、ｐＨを３．５に調節した。スラリーを８０℃で１時間攪拌させて、ＮＨ4 +状ＡＥＩと銅イオンとの間のイオン交換反応を行った。得られた混合物を次にろ過し、８００ｍＬの脱イオン水で、ろ液が透明で無色になるまで洗浄した。そして洗浄したサンプルを９０℃に乾燥した。 Then, in the same manner as in Example 1, the NH 4 + form AEI of the AEI-type SAPO-18 synthesized zeolite 100g by mixing copper (II) nitrate solution of 1.0M of 400 mL, to prepare a CuAEI powder catalyst .. The pH was adjusted to 3.5 with acetic acid. Slurry was stirred for 1 hour at 80 ° C., it was subjected to ion exchange reaction between the NH 4 + form AEI and copper ions. The resulting mixture was then filtered and washed with 800 mL of deionized water until the filtrate was clear and colorless. The washed sample was then dried to 90 ° C.
　次に得られたＣｕＡＥＩ生成物を、７００℃で２時間か焼した。得られたＣｕＡＥＩ触媒は、ＩＣＰ分析で測定して、ＣｕＯを２．８質量％含んでいた。 Next, the obtained CuAEI product was baked at 700 ° C. for 2 hours. The obtained CuAEI catalyst contained 2.8% by mass of CuO as measured by ICP analysis.
　参考例１～参考例４の銅を含むＳＣＲ触媒粉を、コロイド状シリカバインダー（固形分２０質量％）とスラリー液を作製し、公知のコージェライト製ハニカムフロースルー型基材に堆積させた。 The copper-containing SCR catalyst powders of Reference Examples 1 to 4 were prepared into a colloidal silica binder (solid content 20% by mass) and a slurry liquid, and deposited on a known cordierite honeycomb flow-through type substrate.
（スラリー配合）
　イオン交換水：　　　　　　　　　　　　　３０ｇ
　ＳＣＲ触媒粉：　　　　　　　　　　　　　３０ｇ
　コロイド状シリカバインダー：　　　　　　１５ｇ (Slurry combination)
Ion-exchanged water: 30 g
SCR catalyst powder: 30 g
Colloidal silica binder: 15g
　前記スラリー液をボールミルにて分散させ、前記ハニカム基材の容積当たり２００ｇ／Ｌに堆積させた。その後、８０℃で乾燥、５００℃でか焼させて、本発明のシステム制御を用いた排ガス浄化性能試験を行った。 The slurry liquid was dispersed by a ball mill and deposited at 200 g / L per volume of the honeycomb base material. Then, it was dried at 80 ° C. and calcinated at 500 ° C., and an exhaust gas purification performance test using the system control of the present invention was performed.
（排ガス浄化性能試験）
　触媒入口温度：２００℃、２５０℃、３００℃、３５０℃、４００℃、４５０℃、５００℃
空間速度（ＳＶ）：５００００／ｈ
ＮＯ：５００ｐｐｍ
ＮＨ3：実施例１～実施例４は、本発明の指数で供給
　　　　比較例１～比較例４は、５００ｐｐｍで一定
ＣＯ2：１０％
Ｏ2：１０％
Ｈ2Ｏ：１０％
Ｎ2：ＢＡＬＡＮＣＥ
排ガス濃度検出器：ＦＴ－ＩＲ
触媒入口及び出口の検出濃度ガス成分：ＮＯ、ＮＨ3、ＮＯ2、Ｎ2Ｏ、ＣＯ2、Ｈ2Ｏ
但し、Ｏ2は計算上での濃度調整。 (Exhaust gas purification performance test)
Catalyst inlet temperature: 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C
Space velocity (SV): 50,000 / h
NO: 500ppm
NH 3 : Examples 1 to 4 are supplied by the index of the present invention Comparative Examples 1 to 4 are constant CO 2 : 10% at 500 ppm.
O 2 : 10%
H 2 O: 10%
N 2 : BALANCE
Exhaust gas concentration detector: FT-IR
Detected concentration gas components at catalyst inlet and outlet: NO, NH 3 , NO 2 , N 2 O, CO 2 , H 2 O
However, O 2 is a calculated concentration adjustment.
　表１に、実施例１～実施例４および比較例１～比較例４におけるＮＯｘ排ガス濃度とＮＨ3供給制御濃度との関係を、ＡＮＲ（ＮＨ3／ＮＯｘ）として示す。 Table 1 shows the relationship between the NOx exhaust gas concentration and the NH 3 supply control concentration in Examples 1 to 4 and Comparative Examples 1 to 4 as ANR (NH 3 / NOx).
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に、実施例１～実施例４および比較例１～比較例４におけるＮＯｘ浄化性能の結果を示す。 Table 2 shows the results of NOx purification performance in Examples 1 to 4 and Comparative Examples 1 to 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３に、実施例１～実施例４および比較例１～比較例４における前記ＮＨ3スリップ（ＳＣＲ触媒下流漏れ）濃度の結果を示す。 Table 3 shows the results of the NH 3 slip (SCR catalyst downstream leakage) concentration in Examples 1 to 4 and Comparative Examples 1 to 4.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　上記の結果により、ＮＯｘ浄化率において、実施例１～実施例４は、比較例１～比較例４と比較して、３５０℃から５００℃まで範囲で明らかに向上した。 Based on the above results, the NOx purification rate of Examples 1 to 4 was clearly improved in the range of 350 ° C to 500 ° C as compared with Comparative Examples 1 to 4.
　一方、ＮＨ3スリップ（漏洩）において、実施例１～実施例４は、比較例１～比較例４と比較して、排ガス高温域３５０℃から５００℃までの範囲で少量の漏洩が認められるが、本発明の対象ＳＣＲ触媒の下段に設けられるＡＭＯＸ触媒（アンモニア酸化触媒）で、浄化できる十分な範囲である。また、排ガス低高温域では、ＳＣＲ触媒の低温活性に依存するため、実施例１～実施例４は、比較例１～比較例４と比較して、同等のＮＨ3スリップ（漏洩）量であった。 On the other hand, in the NH 3 slip (leakage), in Examples 1 to 4, a small amount of leakage is observed in the exhaust gas high temperature range of 350 ° C. to 500 ° C. as compared with Comparative Examples 1 to 4. The AMOX catalyst (ammonia oxidation catalyst) provided below the target SCR catalyst of the present invention is in a sufficient range for purification. Further, in the low and high temperature region of the exhaust gas, since it depends on the low temperature activity of the SCR catalyst, Examples 1 to 4 have the same amount of NH 3 slip (leakage) as those of Comparative Examples 1 to 4. It was.

Claims (4)

  1. 　尿素および／またはアンモニアを用い、ＮＯｘを選択触媒還元システムにおいて、
    　触媒が、銅を含むゼオライトであって、
    　アンモニアの部分酸化による消費量を、排ガス中のＮＯｘと等モル量となるアンモニア量を制御して供給することを特徴とする、システム制御方法。     NOx with urea and / or ammonia in a selective catalytic reduction system
    The catalyst is a copper-containing zeolite,
    A system control method characterized in that the amount of ammonia consumed by partial oxidation is supplied by controlling the amount of ammonia that is equivalent to the amount of NOx in the exhaust gas.
  2. 　前記触媒の入口排ガス温度と、前記尿素の加水分解からなるアンモニアガスおよび／またはアンモニアガスの供給量との関係式が、以下を満たすことを特徴とする、請求項１に記載のシステム制御方法。
    Figure JPOXMLDOC01-appb-M000001
         The system control method according to claim 1, wherein the relational expression between the inlet exhaust gas temperature of the catalyst and the supply amount of ammonia gas and / or ammonia gas composed of hydrolysis of urea satisfies the following.
    Figure JPOXMLDOC01-appb-M000001
  3. 　前記ゼオライトが、ＣＨＡ型、ＡＥＩ型およびＡＦＸ型の結晶構造からなる、請求項１または請求項２に記載のシステム制御方法。 The system control method according to claim 1 or 2, wherein the zeolite has a CHA-type, AEI-type, and AFX-type crystal structure.
  4. 　前記ゼオライトが、２．０質量％～５．０質量％のＣｕＯを含むことを特徴とする、請求項１から請求項３のいずれか１項に記載のシステム制御方法。 The system control method according to any one of claims 1 to 3, wherein the zeolite contains 2.0% by mass to 5.0% by mass of CuO.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009517210A (en) * 2005-11-30 2009-04-30 キャタピラー インコーポレイテッド Multi-stage system for selective catalytic reduction
JP2009293605A (en) * 2008-06-09 2009-12-17 Hino Motors Ltd Control device for exhaust treatment device
JP2015196115A (en) * 2014-03-31 2015-11-09 株式会社キャタラー Scr catalyst and exhaust gas purification catalyst system
JP2017524520A (en) * 2014-08-13 2017-08-31 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ Catalyst system for reducing nitrogen oxides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009517210A (en) * 2005-11-30 2009-04-30 キャタピラー インコーポレイテッド Multi-stage system for selective catalytic reduction
JP2009293605A (en) * 2008-06-09 2009-12-17 Hino Motors Ltd Control device for exhaust treatment device
JP2015196115A (en) * 2014-03-31 2015-11-09 株式会社キャタラー Scr catalyst and exhaust gas purification catalyst system
JP2017524520A (en) * 2014-08-13 2017-08-31 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ Catalyst system for reducing nitrogen oxides

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