WO2020076008A1 - Catalyst complex for processing exhaust gas of large diesel engine using high-sulfur diesel fuel - Google Patents

Catalyst complex for processing exhaust gas of large diesel engine using high-sulfur diesel fuel Download PDF

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WO2020076008A1
WO2020076008A1 PCT/KR2019/012993 KR2019012993W WO2020076008A1 WO 2020076008 A1 WO2020076008 A1 WO 2020076008A1 KR 2019012993 W KR2019012993 W KR 2019012993W WO 2020076008 A1 WO2020076008 A1 WO 2020076008A1
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catalyst
exhaust gas
lower layer
vanadium
catalyst complex
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French (fr)
Korean (ko)
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이대호
박건면
안능균
이태우
나승철
한현식
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희성촉매 주식회사
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/648—Vanadium, niobium or tantalum or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • 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 SCR catalyst composed of V 2 O 5 -TiO 2 is applied to reduce nitrogen oxides to the form of harmless N 2 and NO.
  • urea (UREA) is used as a reducing agent for the SCR reaction, and urea is decomposed at a high temperature and is introduced into the SCR catalyst as NH 3 .
  • surplus NH 3 (hereinafter referred to as NH 3 slip or leak phenomenon) that is discharged through the catalyst without participating in the SCR reduction reaction is currently regulated to 10 ppm or less in the current regulations due to its effect on the human body.
  • Republic of Korea Patent Publication No. 2015-0111979 relates to an ammonia oxidation catalyst, (a) alumina, titania, zirconia, ceria, silica, and a top layer comprising vanadium on a first refractory metal oxide support selected from mixtures thereof 1 catalyst layer; (b) a second catalyst layer as a lower layer comprising one or more precious metals disposed on the second refractory metal oxide support; And (c) a substrate, the oxidation catalyst for treating a combustion exhaust gas, in particular for reducing ammonia slip associated with a selective catalytic reduction process.
  • the present inventors surprisingly suppress the formation of N 2 O from ammonia used as a reducing agent and the generation of SO 3 from high sulfur fuels, when vanadium oxide is added as a cocatalyst to the lower layer in the catalyst complex having SCR function and ammonia oxidation function, that is, It was confirmed that it is possible to suppress the damage and ABS production due to ammonia slip. Furthermore, it has been found that when the first refractory metal oxide, specifically ceria, in addition to ceria is added to the upper layer, that is, the first catalyst layer, the high-temperature durability of the SCR functional part is improved.
  • An object of the present invention is to provide a catalyst complex in which AOC function for oxidizing and purifying NH 3 slipped as a reducing agent is added in addition to the function of a conventional SCR catalyst.
  • AOC function for oxidizing and purifying NH 3 slipped as a reducing agent is added in addition to the function of a conventional SCR catalyst.
  • the harmfulness caused by leakage of ammonia, a reducing agent participating in the SCR reaction is eliminated, thereby reducing the volume of the catalyst by improving the SCR activity by increasing the injection amount of NH3, ultimately reducing the size of the reactor, reducing the catalyst installation cost, and reducing the back pressure. Effect, the oxidation effect of carbon monoxide in the exhaust gas can be additionally achieved.
  • the catalyst composite according to the present invention although not limited, has the following technical features.
  • the catalyst composite according to the present invention is composed of an SCR function part in the upper layer and an AOC function part in the lower layer.
  • the component V 2 O 5 of the SCR functional part and the Pt of the AOC functional part are completely separated so that there is no mutual performance interference, that is, composed of a double layer, and in the AOC functional part, NH 3 and CO oxidation occurs by the platinum component, and furthermore, the AOC of the lower layer.
  • V 2 O 5 is included as a co-catalyst to suppress N 2 O and SO 3 generation.
  • Example 3 is a comparison of the durability performance between the catalyst composite of Example 1 and a comparative catalyst.
  • Figure 4 shows the CO-NH3 oxidation relationship for the catalyst complex of Example 1.
  • the present invention is to reduce and reduce nitrogen oxides (NOx) generated in a large-sized marine engine using high-sulfur diesel fuel, and at the same time, to a multifunctional catalyst composite that combines ammonia oxidation catalyst function to prevent leakage of NH 3 used as a reducing agent. It is about.
  • the present invention particularly relates to a catalyst complex for improving harmful exhaust gas of high sulfur diesel fuel used in ship operation. According to the present invention, the generation of ABS is prevented while the NH 3 and / or NOx concentration is reduced in the exhaust gas of the marine diesel engine.
  • the catalyst composite according to the present invention is composed of an SCR function part in the upper layer and an AOC function part in the lower layer.
  • the exhaust gas first contacts the upper layer before contacting the lower layer.
  • the lower layer is applied to a substrate called a carrier, and the upper layer is applied on the lower layer.
  • the upper layer may be composed of multiple layers.
  • the exhaust gas contacts the upper layer, penetrates the upper layer, and then contacts the lower layer, and continues to exit again into the upper layer.
  • the upper layer is the first zone disposed on the upstream portion of the substrate, the lower layer is disposed on the substrate as the second zone, and can be downstream of the first zone.
  • V 2 O 5 of the SCR functional part and the Pt of the AOC functional part are completely separated so that there is no mutual performance interference, that is, composed of a double layer, and in the AOC functional part, NH 3 and CO oxidation occurs by the platinum component, and furthermore, the AOC of the lower layer.
  • V 2 O 5 is included as a co-catalyst to suppress N 2 O and SO 3 generation.
  • the upper layer contains vanadium and cerium sulfide (Ce-sulfate) on the first support, preferably the first refractory metal oxide, titania and / or ceria.
  • the form of vanadium is vanadia (V 2 O 5 ), and may include tungsten oxide and / or molybdenum oxide in addition to vanadium oxide.
  • cerium sulfate in the upper layer may be contained in an amount of 0.1 to 20% by weight.
  • the support for the vanadium component and cerium sulfate is titania alone or a mixture of titania and ceria or silica, or a titania combination in combination with other components such as silica.
  • Vanadia and cerium sulfide are in close contact with the support particles and are present in relatively thin layers or coatings, and thus, vanadia and titania are not present in the hybrid oxide state.
  • the lower layer is an AOC function, and NH 3 and CO oxidation proceeds by the platinum component, and furthermore, V 2 O 5 is included as a co-catalyst to suppress the reaction of slip NH 3 to N 2 O and suppress the occurrence of SO 3. It prevents the formation of ABS, which acts as a poisonous substance.
  • the lower layer contains a platinum group and vanadium on a second support, preferably a second refractory metal oxide, titania and / or ceria.
  • the form of vanadium is vanadia (V 2 O 5 ), and it is understood that vanadium oxide prevents ABS formation and enhances durability against sulfur.
  • cerium sulfide may be included similarly to the upper layer.
  • the platinum mentioned above is representative of a noble metal in the lower layer, and examples of suitable noble metals may include ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold, and combinations thereof.
  • the washcoat comprising the vanadium component and the platinum component is a slurry, in the lower layer vanadia is contained at about 0.1-5 weight percent based on the weight of the titania support, and platinum is about 0.1-10 weight based on the weight of the titania support. Contained in percent.
  • cerium sulfide may be included, and the washcoat may include other additives such as non-catalytic components, such as fillers, binders, stabilizers, and the like.
  • the first catalyst layer was prepared as follows. Deionized water and titania washcoat were mixed using a high shear mixer, platinum precursor and vanadium solutions were added, and the resulting mixture was stirred to apply the final washcoat to a 200cpsi cordierite substrate and then calcined at 500 ° C. .
  • the second catalyst layer was prepared as follows.
  • the titania slurry was mixed with a vanadium / cerium sulfate solution.
  • the upper layer washcoat was coated on a lower layer containing platinum, dried, and calcined at 500 ° C. Based on the total weight of the wash coating layer before drying / calcining, Ce-sulfate in the upper layer is 0.1 to 20 wt.%, Vanadia (V2O5): 0.1 to 10 wt.%, The rest is made of titania support, and the lower layer is platinum. This 0.1 to 10 wt.%, V2O5: 0.1 to 5 wt.%, The rest consisted of titania support.
  • the present inventors have found that when vanadium is included in the lower layer of the platinum-containing complex, not only ammonia and carbon monoxide oxidation but also SO3 formation can be prevented, ultimately reducing the occurrence of poisoning substances.
  • the CO oxidation temperature was increased by 50 ° C. based on the purification rate of 50% of carbon monoxide, but was satisfied in the range of 370 to 440 ° C., which is the operating condition of the application field, and the risk of SO2 oxidation was reduced to less than half. Therefore, when the AOC functional unit is disposed under the SCR functional unit, the presence of the cocatalyst vanadium in the AOC functional unit confirms that SO2 oxidation is reduced and ultimately ABS production is reduced.
  • the CO oxidation power should be 90% or higher and 440 ° C, so that the SO2 oxidation level is 5%.
  • cerium sulfide Ce-sulfate
  • the durability improvement effect for SO 2 When observing the slope over time for the presence or absence of cerium sulfide, it can be seen that the durability is improved as the activity is not reduced when the catalyst is used for a long time.
  • the catalyst composite according to the present invention can be applied as a sintering furnace oxidation catalyst. That is, as a result of conducting the NH3 and CO oxidation tests in the double-layer catalyst complex, respectively, it was confirmed that the oxidation temperature was similar, and thus, in addition to the ship in which a large amount of SO 2 is present in the exhaust gas, it is applied to CO oxidation in the sintering furnace of the catalyst according to the present invention I think I can do it.

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Abstract

The present invention relates to a multi-functional catalyst complex for processing an exhaust gas, which reduces, via reduction, nitrogen oxide (NOx) occurring in a large engine for a vessel using a high-sulfur diesel fuel, and which, at the same time, has the function of an ammonia oxidation catalyst (AOC) for preventing a leakage of NH3 used as a reducing agent, the catalyst complex comprising an SCR function part in an upper layer, and an AOC function part in a lower layer, wherein the upper layer contains vanadium and cerium sulfate (Ce sulfate) on a first fire resistant metal oxide, and the lower layer contains a platinum metal and vanadium on a second fire resistant metal oxide.

Description

고유황 경유를 사용하는 대형 디젤 엔진의 배기가스 처리용 촉매복합체Catalyst complex for exhaust gas treatment of large diesel engines using high sulfur gas
본 발명은 고유황 디젤 연료를 사용하는 선박용 대형엔진에서 발생하는 질소산화물 (NOx)을 환원시켜 저감함과 동시에 환원제로써 사용되는 NH 3 누출을 방지하는 암모니아 산화촉매 (AOC, ammonia oxidation catalyst)의 기능을 합친 다기능성 촉매 복합체에 관한 것이다.The present invention is a function of ammonia oxidation catalyst (AOC) that prevents leakage of NH 3 used as a reducing agent while reducing and reducing nitrogen oxide (NOx) generated in a large marine engine using high sulfur diesel fuel. It relates to a multifunctional catalyst composite.
고유황 디젤연료를 사용하는 대형 엔진은 유해한 질소산화물 (NOX)을 배출하므로, V 2O 5-TiO 2로 구성되는 SCR 촉매를 적용하여 질소산화물을 무해한 N 2 및 NO의 형태로 환원한다. 이때 SCR반응의 환원제로써 요소 (UREA)가 사용되며 요소는 고온에서 분해되어 NH 3로 SCR 촉매에 투입된다. 그러나 SCR 환원반응에 참여하지 못하고 촉매를 통과하여 배출되는 잉여 NH 3 (이하 NH 3 슬립 또는 누출 현상이라 칭함)는 인체에 미치는 영향 때문에 현재 법규에서 10ppm 이하로 규제하고 있다. 뿐만 아니라, 누출되는 NH 3는 고유황 디젤연료 중에 함유되는 황 성분과 결합하여 NH 4HSO 4 (이하 ABS) 화합물을 생성하는데, 이는 SCR 촉매에서 피독물질로 작용하여 SCR 환원 활성은 급격하게 저하된다.Since large engines using high sulfur diesel fuel emit harmful nitrogen oxides (NOX), the SCR catalyst composed of V 2 O 5 -TiO 2 is applied to reduce nitrogen oxides to the form of harmless N 2 and NO. At this time, urea (UREA) is used as a reducing agent for the SCR reaction, and urea is decomposed at a high temperature and is introduced into the SCR catalyst as NH 3 . However, surplus NH 3 (hereinafter referred to as NH 3 slip or leak phenomenon) that is discharged through the catalyst without participating in the SCR reduction reaction is currently regulated to 10 ppm or less in the current regulations due to its effect on the human body. In addition, the leaked NH 3 combines with the sulfur component contained in the high sulfur diesel fuel to produce the NH 4 HSO 4 (hereinafter ABS) compound, which acts as a poison in the SCR catalyst, resulting in a rapid reduction in SCR reduction activity. .
배기가스에서 과잉의 암모니아를 산화시키기 위한 촉매가 알려져 있다. 예를들면, 미국특허번호 제7,393,511호는 티타니아, 알루미나, 실리카, 지르코니아 등의 지지체 상에 백금, 팔라듐, 로듐, 또는 금과 같은 귀금속을 함유하는 암모니아 산화 촉매를 개시한다. 다른 암모니아 산화 촉매로는 티타니아 지지체 상의 산화바나듐, 산화텅스텐, 및 산화몰리브덴의 제1 층, 및 티타니아 지지체 상의 백금의 제2 층을 함유한다 (미국특허번호 제8,202,481호 및 제7,410,626호 참조). 그러나, 이들 촉매는 고유황 디젤 연료에서는 ABS 생성을 억제할 수 없으므로 고유황 디젤 연료를 사용하는 선박용으로는 적합하지 않다.Catalysts for oxidizing excess ammonia in exhaust gases are known. For example, U.S. Patent No. 7,393,511 discloses ammonia oxidation catalysts containing precious metals such as platinum, palladium, rhodium, or gold on supports such as titania, alumina, silica, zirconia, and the like. Other ammonia oxidation catalysts include a first layer of vanadium oxide, tungsten oxide, and molybdenum oxide on the titania support, and a second layer of platinum on the titania support (see US Pat. Nos. 8,202,481 and 7,410,626). However, these catalysts are not suitable for ships using high sulfur diesel fuel because ABS production cannot be suppressed in high sulfur diesel fuel.
대한민국 특허공개공보 제2015-0111979호는 암모니아 산화촉매에 관한 것이고, (a) 알루미나, 티타니아, 지르코니아, 세리아, 실리카, 및 이들의 혼합물로부터 선택된 제1 내화성 금속 산화물 지지체 상의 바나듐을 포함하는 상층으로서 제1 촉매층; (b) 제2 내화성 금속 산화물 지지체 상에 배치된 하나 이상의 귀금속을 포함하는 하층으로서 제2 촉매층; 및 (c) 기판을 포함하는, 연소 배기 가스를 처리하기 위한, 특히 선택적 촉매 환원 과정과 관련된 암모니아 슬립을 감소시키기 위한 산화촉매가 개시된다. 그러나 상기 선행기술에 따르면, 하층, 즉 제2 촉매층에 귀금속이 포함되나, 고유황 연료로부터 SO 3 발생을 억제하기 위한 어떠한 기술적 구성이 없으므로, 궁극적으로 SCR 촉매 피독물질인 ABS 생성을 억제할 수 없고, 또한, 상층은 고유황 연료에서 발생되는 황화물에 노출되어 내구성이 약해지는 문제점이 있다.Republic of Korea Patent Publication No. 2015-0111979 relates to an ammonia oxidation catalyst, (a) alumina, titania, zirconia, ceria, silica, and a top layer comprising vanadium on a first refractory metal oxide support selected from mixtures thereof 1 catalyst layer; (b) a second catalyst layer as a lower layer comprising one or more precious metals disposed on the second refractory metal oxide support; And (c) a substrate, the oxidation catalyst for treating a combustion exhaust gas, in particular for reducing ammonia slip associated with a selective catalytic reduction process. However, according to the prior art, the lower layer, that is, the second catalyst layer contains a noble metal, but since there is no technical configuration to suppress the generation of SO 3 from high sulfur fuel, ultimately it is not possible to suppress the production of ABS, a catalyst poisoning to SCR. In addition, the upper layer is exposed to sulfides generated from high sulfur fuels, and thus there is a problem that durability is weakened.
본 발명자들은 SCR 기능 및 암모니아 산화 기능을 하는 촉매복합체에서 하층에 조촉매로서 바나듐 산화물이 첨가되는 경우 놀랍게도 환원제로 사용되는 암모니아로부터 N 2O의 형성 및 고유황 연료로부터 SO 3 발생을 억제하여 즉, 암모니아 슬립으로 인한 폐해 및 ABS 생성을 억제할 수 있다는 것을 확인하였다. 더 나아가, 상층, 즉 제1 촉매층에 제1 내화성 금속 산화물, 구체적으로 세리아 외에도 황화세륨이 부가되는 경우 SCR 기능부의 고온 내구성이 개선된다는 것을 알았다.The present inventors surprisingly suppress the formation of N 2 O from ammonia used as a reducing agent and the generation of SO 3 from high sulfur fuels, when vanadium oxide is added as a cocatalyst to the lower layer in the catalyst complex having SCR function and ammonia oxidation function, that is, It was confirmed that it is possible to suppress the damage and ABS production due to ammonia slip. Furthermore, it has been found that when the first refractory metal oxide, specifically ceria, in addition to ceria is added to the upper layer, that is, the first catalyst layer, the high-temperature durability of the SCR functional part is improved.
본 발명의 목적은 종래 SCR촉매의 기능에 더하여 환원제로써 slip되는 NH 3를 산화시켜 정화하는 AOC 기능이 부가되는 촉매복합체를 제공하는 것이다. 본 발명에 의하면, SCR 반응에 참가하는 환원제인 암모니아 누출에 의한 유해성이 해소됨으로써 NH3 분사량 증가를 통한 SCR 활성 향상으로 촉매의 부피를 감소시켜 궁극적으로 반응기 크기의 소형화 및 촉매 설치비용 절감, 배압 감소의 효과, 배기가스 중 일산화탄소의 산화효과를 부수적으로 달성할 수 있다.An object of the present invention is to provide a catalyst complex in which AOC function for oxidizing and purifying NH 3 slipped as a reducing agent is added in addition to the function of a conventional SCR catalyst. According to the present invention, the harmfulness caused by leakage of ammonia, a reducing agent participating in the SCR reaction, is eliminated, thereby reducing the volume of the catalyst by improving the SCR activity by increasing the injection amount of NH3, ultimately reducing the size of the reactor, reducing the catalyst installation cost, and reducing the back pressure. Effect, the oxidation effect of carbon monoxide in the exhaust gas can be additionally achieved.
따라서, 본 발명에 의한 촉매복합체는, 제한적이지는 않지만, 다음과 같은 기술적 특징부를 가진다. 본 발명에 의한 촉매복합체는 상층의 SCR 기능부 및 하층의 AOC 기능부로 구성된다. SCR 기능부의 성분 V 2O 5와 AOC 기능부의 Pt는 상호 성능간섭이 없도록 완전 분리되되, 즉 이중층으로 구성되며, AOC 기능부에서는 백금 성분에 의해 NH 3 및 CO 산화가 일어나고, 더 나아가 하층의 AOC 기능부에서는 조촉매로써 V 2O 5가 포함되어 N 2O및 SO3 발생을 억제한다.Therefore, the catalyst composite according to the present invention, although not limited, has the following technical features. The catalyst composite according to the present invention is composed of an SCR function part in the upper layer and an AOC function part in the lower layer. The component V 2 O 5 of the SCR functional part and the Pt of the AOC functional part are completely separated so that there is no mutual performance interference, that is, composed of a double layer, and in the AOC functional part, NH 3 and CO oxidation occurs by the platinum component, and furthermore, the AOC of the lower layer. In the functional part, V 2 O 5 is included as a co-catalyst to suppress N 2 O and SO 3 generation.
이론에 구속되지 않지만, 구체적으로는, 하층에 함유되는 바나듐 성분은, 슬립 NH 3를 NO로 산화시키는 과정에서 밀집된 백금들의 배열에 의한 연속반응으로 NO 2가 생성되되 이러한 NO 2가 N 2O로 전환되는 반응을 억제하기 위함과 동시에 ABS형성의 주 원인 중 하나이자, 촉매반응기 시스템의 부식, 입자상 물질 배출 증가의 원인이 되는 SO 3 발생을 억제하는 것으로 이해된다. 본 발명자들은 암모니아 산화촉매에 첨가되는 바나듐은 백금에 이산화황이 흡착 및 탈착을 방해하여 산화반응을 억제하는 것으로 판단하고 있다. 또한, 본 발명에 의한 촉매복합체의 상층에는 세리아 외에도 세륨황화물이 첨가되어 SCR 기능부의 고온 내구성이 개선된다.Without being bound by theory, specifically, the vanadium component contained in the lower layer generates NO 2 in a continuous reaction due to the arrangement of dense platinum in the process of oxidizing slip NH 3 to NO, but these NO 2 are converted into N 2 O. It is understood to suppress the conversion reaction and at the same time suppress the occurrence of SO 3 , which is one of the main causes of ABS formation, and causes corrosion of the catalytic reactor system and increased emission of particulate matter. The present inventors believe that vanadium added to the ammonia oxidation catalyst inhibits the oxidation reaction by preventing the adsorption and desorption of sulfur dioxide on platinum. In addition, cerium sulfide is added to the upper layer of the catalyst composite according to the present invention in addition to ceria to improve the high-temperature durability of the SCR functional unit.
도 1 및 2는 실시예 1의 촉매복합체에 대한 CO-SO2 산화력을 측정한 것이다.1 and 2 is a measurement of the CO-SO2 oxidizing power for the catalyst complex of Example 1.
도 3은 실시예 1의 촉매복합체 및 비교 촉매 간의 내구성능을 비교한 것이다.3 is a comparison of the durability performance between the catalyst composite of Example 1 and a comparative catalyst.
도 4는 실시예 1의 촉매복합체에 대한 CO-NH3 산화 관계를 도시한 것이다.Figure 4 shows the CO-NH3 oxidation relationship for the catalyst complex of Example 1.
본 발명은 고유황 디젤 연료를 사용하는 선박용 대형엔진에서 발생하는 질소산화물 (NOx)을 환원시켜 저감함과 동시에 환원제로써 사용되는 NH 3의 누출을 방지하는 암모니아 산화촉매 기능을 합친 다기능성 촉매 복합체에 관한 것이다. 본 발명은 특히 선박 운행에 사용되는 고유황 디젤 연료의 유해 배기가스를 개선하기 위한 촉매복합체에 관한 것이다. 본 발명에 의하면 선박 디젤 엔진의 배기가스에서 NH 3 및/또는 NOx 농도가 저감되면서도 ABS 생성이 방지된다.The present invention is to reduce and reduce nitrogen oxides (NOx) generated in a large-sized marine engine using high-sulfur diesel fuel, and at the same time, to a multifunctional catalyst composite that combines ammonia oxidation catalyst function to prevent leakage of NH 3 used as a reducing agent. It is about. The present invention particularly relates to a catalyst complex for improving harmful exhaust gas of high sulfur diesel fuel used in ship operation. According to the present invention, the generation of ABS is prevented while the NH 3 and / or NOx concentration is reduced in the exhaust gas of the marine diesel engine.
본 발명에 의한 촉매복합체는 상층의 SCR 기능부 및 하층의 AOC 기능부로 구성된다. 배기가스 흐름 상태에서, 배기가스는 하층과 접촉하기 전에 상층과 먼저 접촉한다. 구체적으로는, 하층은 담체로 불리는 기재 (substrate)에 도포되고, 상층은 상기 하층 상에 도포된다. 이때 상층은 다중 층으로 구성될 수 있다. 이러한 구체예에서, 배기가스는 상층에 접촉하여 상층을 침투하고, 이어 하층과 접촉하며, 계속해서 상층으로 다시 빠져나간다. 다른 구체예에서, 상층은 기재의 상류 부분 상에 배치된 제1 구역이고, 하층은 제2 구역으로서 기재 상에 배치되며, 제1 구역의 하류일 수 있다.The catalyst composite according to the present invention is composed of an SCR function part in the upper layer and an AOC function part in the lower layer. In the exhaust gas flow state, the exhaust gas first contacts the upper layer before contacting the lower layer. Specifically, the lower layer is applied to a substrate called a carrier, and the upper layer is applied on the lower layer. At this time, the upper layer may be composed of multiple layers. In this embodiment, the exhaust gas contacts the upper layer, penetrates the upper layer, and then contacts the lower layer, and continues to exit again into the upper layer. In other embodiments, the upper layer is the first zone disposed on the upstream portion of the substrate, the lower layer is disposed on the substrate as the second zone, and can be downstream of the first zone.
SCR 기능부의 성분 V 2O 5와 AOC 기능부의 Pt는 상호 성능간섭이 없도록 완전 분리되되, 즉 이중층으로 구성되며, AOC 기능부에서는 백금 성분에 의해 NH 3 및 CO 산화가 일어나고, 더 나아가 하층의 AOC 기능부에서는 조촉매로써 V 2O 5가 포함되어 N 2O및 SO3 발생을 억제한다.The component V 2 O 5 of the SCR functional part and the Pt of the AOC functional part are completely separated so that there is no mutual performance interference, that is, composed of a double layer, and in the AOC functional part, NH 3 and CO oxidation occurs by the platinum component, and furthermore, the AOC of the lower layer. In the functional part, V 2 O 5 is included as a co-catalyst to suppress N 2 O and SO 3 generation.
상층은 제1 지지체, 바람직하게 제1 내화성 금속 산화물인 티타니아 및/또는 세리아 상에 바나듐 및 황화세륨 (Ce-sulfate)을 함유한다. 구체예에서, 바나듐의 형태는 바나디아(V 2O 5)이고, 바나듐 산화물 이외에 텅스텐 산화물 및/또는 몰리브덴 산화물을 포함할 수 있다. 본 발명자들은, 지지체 상에 바나디아 및 황화세륨을 함께 침적하면 고유황 디젤연료의 배기가스 중에 노출될 때 SCR 기능부에서 SO 2에 대한 내구성이 개선된다는 것을 확인하였다. 본 발명에 따르면, 상층에서 세륨 설페이트는 0.1 중량% 내지 20중량%로 함유될 수 있다. 바나듐 성분 및 세륨 설페이트를 위한 지지체는 티타니아 단독 또는 티타니아 및 세리아 또는 실리카의 혼합물, 또는 실리카와 같은 다른 성분과 조합된 티타니아 조합물이다. 바나디아 및 황화세륨은 지지체 입자에 밀착되어 상대적으로 얇은 층이나 코팅 상태에 존재하며, 따라서, 바나디아 및 티타니아는 혼성 산화물 상태로는 존재하지 않는다.The upper layer contains vanadium and cerium sulfide (Ce-sulfate) on the first support, preferably the first refractory metal oxide, titania and / or ceria. In an embodiment, the form of vanadium is vanadia (V 2 O 5 ), and may include tungsten oxide and / or molybdenum oxide in addition to vanadium oxide. The present inventors have confirmed that deposition of vanadia and cerium sulfide together on a support improves the durability of SO 2 in the SCR function when exposed to the exhaust gas of high sulfur diesel fuel. According to the present invention, cerium sulfate in the upper layer may be contained in an amount of 0.1 to 20% by weight. The support for the vanadium component and cerium sulfate is titania alone or a mixture of titania and ceria or silica, or a titania combination in combination with other components such as silica. Vanadia and cerium sulfide are in close contact with the support particles and are present in relatively thin layers or coatings, and thus, vanadia and titania are not present in the hybrid oxide state.
하층은 AOC 기능부로서 백금 성분에 의해 NH 3 및 CO 산화가 진행되고, 더 나아가 조촉매로써 V 2O 5가 포함되어 슬립 NH 3가 N 2O로 전환되는 반응을 억제하고 SO 3 발생을 억제하여 피독물질로 작용하는 ABS형성을 방지한다. 상세하게, 하층은 제2 지지체, 바람직하게 제2 내화성 금속 산화물인 티타니아 및/또는 세리아 상에 백금족 및 바나듐을 함유한다. 구체예에서, 바나듐의 형태는 바나디아(V 2O 5)이고, 바나듐 산화물은 ABS 형성 방지 및 유황에 대한 내구성을 증진시키는 것으로 이해된다. 또한, 선택적으로, 상층과 유사하게 황화세륨이 포함될 수 있다. 상기 언급된 백금은 하층에서 귀금속을 대표하는 것으로, 적합한 귀금속의 예들은 루테늄, 로듐, 팔라듐, 은, 오스뮴, 이리듐, 백금, 및 금, 및 이들의 조합을 포함할 수 있다. 바나듐 성분 및 백금 성분을 포함하는 워시코트는 슬러리로서, 하층에서 바나디아는 티타니아 지지체의 중량을 기준으로 약 0.1-5 중량 퍼센트로 함유되고, 백금은 티타니아 지지체의 중량을 기준으로 약 0.1-10 중량 퍼센트로 함유된다. 선택적으로 세륨황화물이 포함될 수 있고, 워시코트는 비-촉매 성분, 예컨대 필러, 바인더, 안정제 등 다른 첨가제를 포함할 수 있다.The lower layer is an AOC function, and NH 3 and CO oxidation proceeds by the platinum component, and furthermore, V 2 O 5 is included as a co-catalyst to suppress the reaction of slip NH 3 to N 2 O and suppress the occurrence of SO 3. It prevents the formation of ABS, which acts as a poisonous substance. Specifically, the lower layer contains a platinum group and vanadium on a second support, preferably a second refractory metal oxide, titania and / or ceria. In an embodiment, the form of vanadium is vanadia (V 2 O 5 ), and it is understood that vanadium oxide prevents ABS formation and enhances durability against sulfur. Also, optionally, cerium sulfide may be included similarly to the upper layer. The platinum mentioned above is representative of a noble metal in the lower layer, and examples of suitable noble metals may include ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold, and combinations thereof. The washcoat comprising the vanadium component and the platinum component is a slurry, in the lower layer vanadia is contained at about 0.1-5 weight percent based on the weight of the titania support, and platinum is about 0.1-10 weight based on the weight of the titania support. Contained in percent. Optionally cerium sulfide may be included, and the washcoat may include other additives such as non-catalytic components, such as fillers, binders, stabilizers, and the like.
실시예Example
실시예 1: 촉매복합체 제조Example 1: Preparation of catalyst complex
제1 촉매층을 다음과 같이 제조했다. 탈이온수와 티타니아 워시코트를 고전단 혼합기를 사용하여 혼합하고, 백금 전구체 및 바나듐 용액을 가하고, 결과의 혼합물을 교반하여, 최종 워시코트를 200cpsi 코디어라이트 기재에 적용하고, 이후 500℃에서 하소하였다.The first catalyst layer was prepared as follows. Deionized water and titania washcoat were mixed using a high shear mixer, platinum precursor and vanadium solutions were added, and the resulting mixture was stirred to apply the final washcoat to a 200cpsi cordierite substrate and then calcined at 500 ° C. .
제2 촉매층을 다음과 같이 제조했다. 티타니아 슬러리에 바나듐/황산세륨 용액을 혼합했다. 다음, 상층 워시코트를 백금이 포함되는 하층에 코팅하고 건조시킨 다음 500℃에서 하소하였다. 건조/하소 전 워시코팅 층의 총 중량을 기준으로 상층에는 Ce-sulfate가 0.1 ~ 20 wt.%, 바나디아 (V2O5): 0.1 ~ 10 wt.%, 나머지는 티타니아 지지체로 구성되며, 하층은 백금이 0.1 ~ 10 wt.%, V2O5: 0.1 ~5 wt.%, 나머지는 티타니아 지지체로 구성된다.The second catalyst layer was prepared as follows. The titania slurry was mixed with a vanadium / cerium sulfate solution. Next, the upper layer washcoat was coated on a lower layer containing platinum, dried, and calcined at 500 ° C. Based on the total weight of the wash coating layer before drying / calcining, Ce-sulfate in the upper layer is 0.1 to 20 wt.%, Vanadia (V2O5): 0.1 to 10 wt.%, The rest is made of titania support, and the lower layer is platinum. This 0.1 to 10 wt.%, V2O5: 0.1 to 5 wt.%, The rest consisted of titania support.
실험예 1 (하층에서 Pt 존재 하에 바나듐 유무에 따른 SO2산화력 측정)Experimental Example 1 (Measurement of SO2 oxidation with and without vanadium in the presence of Pt in the lower layer)
본 발명자들은 백금이 함유된 복합체 하층에 바나듐이 포함되면 암모니아 및 일산화탄소 산화뿐 아니라 SO3 형성을 저지시켜 궁극적으로 피독물질 발생을 크게 줄일 수 있다는 것을 알았다. 도 1을 참고하면, 일산화탄소의 정화률 50%를 기준으로 CO 산화 온도는 50℃ 상승하였으나, 적용 분야 운전조건인 370~440℃ 범위에서 만족하고 SO2 산화의 위험은 절반 이하로 저감되었다. 따라서 SCR 기능부 아래에 AOC 기능부를 배치하는 경우에 AOC 기능부에 조촉매 바나듐이 존재하면 SO2 산화가 감소되어 궁극적으로 ABS 생성이 감소된다는 것을 확인한다.The present inventors have found that when vanadium is included in the lower layer of the platinum-containing complex, not only ammonia and carbon monoxide oxidation but also SO3 formation can be prevented, ultimately reducing the occurrence of poisoning substances. Referring to FIG. 1, the CO oxidation temperature was increased by 50 ° C. based on the purification rate of 50% of carbon monoxide, but was satisfied in the range of 370 to 440 ° C., which is the operating condition of the application field, and the risk of SO2 oxidation was reduced to less than half. Therefore, when the AOC functional unit is disposed under the SCR functional unit, the presence of the cocatalyst vanadium in the AOC functional unit confirms that SO2 oxidation is reduced and ultimately ABS production is reduced.
상기의 시험을 steady-state조건으로 재시험하여 하층에서 바나듐의 기능을 최종 확인하였다.The above test was re-tested under steady-state conditions to finally confirm the function of vanadium in the lower layer.
도 2에서 보여지듯 운전조건인 370~440℃ 범위에서 CO산화력은 90%이상, 440℃ 가 되어야 SO2 산화는 5% 수준이 되는 것을 확인하였다.As shown in FIG. 2, it was confirmed that in the range of 370 to 440 ° C, which is the operating condition, the CO oxidation power should be 90% or higher and 440 ° C, so that the SO2 oxidation level is 5%.
실험예 2Experimental Example 2
한편, 상층인 SCR 기능부의 V 2O 5/TiO2 성분에 황화세륨 (Ce-sulfate)를 추가해 SO 2에 대한 내구성 향상 효과를 확인하였다. 황화세륨 유무에 대한 시간에 따른 기울기를 관찰할 때, 촉매를 장시간 사용할 때 활성이 감소되지 않는 것으로 내구성이 개선된 것을 확인할 수 있다.On the other hand, by adding cerium sulfide (Ce-sulfate) to the V 2 O 5 / TiO 2 component of the upper SCR functional part, it was confirmed the durability improvement effect for SO 2 . When observing the slope over time for the presence or absence of cerium sulfide, it can be seen that the durability is improved as the activity is not reduced when the catalyst is used for a long time.
한편, 본 발명에 의한 촉매복합체를 소결로 산화촉매로 적용할 수 있는지를 확인하였다. 즉, 이중층 촉매복합체에서 NH3및 CO 산화시험을 각각 진행한 결과 산화 온도가 유사한 것을 확인하였으며, 이에 배기가스 내에서 SO 2가 다량 존재하는 선박 외에도 본 발명에 의한 촉매의 소결로에서 CO산화에 적용할 수 있다고 판단된다.On the other hand, it was confirmed that the catalyst composite according to the present invention can be applied as a sintering furnace oxidation catalyst. That is, as a result of conducting the NH3 and CO oxidation tests in the double-layer catalyst complex, respectively, it was confirmed that the oxidation temperature was similar, and thus, in addition to the ship in which a large amount of SO 2 is present in the exhaust gas, it is applied to CO oxidation in the sintering furnace of the catalyst according to the present invention I think I can do it.

Claims (4)

  1. 고유황 경유를 사용하는 디젤엔진의 배기가스 처리용 촉매복합체로서, 상층의 SCR 기능부 및 하층의 AOC 기능부로 구성되고, 상기 상층은 제1 내화성 금속 산화물 상에 바나듐 및 황화세륨 (Ce-sulfate)을 함유하고, 상기 하층은 제2 내화성 금속 산화물 상에 백금족 및 바나듐을 함유하는 것을 특징으로 하는, 배기가스 처리용 촉매복합체.As a catalyst complex for exhaust gas treatment of diesel engines using high-grade sulfur oil, it is composed of SCR functional part in the upper layer and AOC functional part in the lower layer, and the upper layer is vanadium and cerium sulfide (Ce-sulfate) on the first refractory metal oxide. And, the lower layer is characterized in that it contains a platinum group and vanadium on the second refractory metal oxide, catalyst complex for exhaust gas treatment.
  2. 제1항에 있어서, 제1 내화성 금속 산화물 및 제2 내화성 금속 산화물은 티타니아인 것을 특징으로 하는, 배기가스 처리용 촉매복합체.The catalyst composite for exhaust gas treatment according to claim 1, wherein the first refractory metal oxide and the second refractory metal oxide are titania.
  3. 제1항에 있어서, 상기 상층에서 세륨 설페이트는 상층 총 중량 기준으로 0.1 중량% 내지 20중량%로 함유될 수 있는, 배기가스 처리용 촉매복합체.According to claim 1, The cerium sulfate in the upper layer may be contained in an amount of 0.1 to 20% by weight based on the total weight of the upper layer, the catalyst complex for exhaust gas treatment.
  4. 제1항에 있어서, 상기 하층에서 바나듐은 바나디아 형태로서 하층 총 중량 기준으로 0.1 ~5 wt.% 함유될 수 있는, 배기가스 처리용 촉매복합체.According to claim 1, The vanadium in the lower layer is a vanadia form that can be contained in an amount of 0.1 to 5 wt.% Based on the total weight of the lower layer, the catalyst complex for exhaust gas treatment.
PCT/KR2019/012993 2018-10-11 2019-10-04 Catalyst complex for processing exhaust gas of large diesel engine using high-sulfur diesel fuel WO2020076008A1 (en)

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