WO2020076008A1 - Complexe de catalyseur pour traiter des gaz d'échappement d'un moteur diesel de grande taille à l'aide d'un carburant diesel à haute teneur en soufre - Google Patents

Complexe de catalyseur pour traiter des gaz d'échappement d'un moteur diesel de grande taille à l'aide d'un carburant diesel à haute teneur en soufre Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
catalyst
exhaust gas
lower layer
vanadium
catalyst complex
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PCT/KR2019/012993
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English (en)
Korean (ko)
Inventor
이대호
박건면
안능균
이태우
나승철
한현식
Original Assignee
희성촉매 주식회사
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Publication of WO2020076008A1 publication Critical patent/WO2020076008A1/fr

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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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

La présente invention concerne un complexe de catalyseur multifonctionnel pour traiter un gaz d'échappement qui réduit, par réduction, de l'oxyde d'azote (NOx) se produisant dans un moteur de grande taille pour un navire à l'aide d'un carburant diesel à haute teneur en soufre et qui, en même temps, a la fonction d'un catalyseur d'oxydation d'ammoniac (AOC) pour empêcher une fuite de NH3 utilisé en tant qu'agent réducteur, le complexe de catalyseur comprenant une partie de fonction SCR dans une couche supérieure et une partie de fonction AOC dans une couche inférieure, la couche supérieure contenant du vanadium et du sulfate de cérium (sulfate de Ce) sur un premier oxyde métallique résistant au feu et la couche inférieure contenant un métal de platine et du vanadium sur un second oxyde métallique résistant au feu.
PCT/KR2019/012993 2018-10-11 2019-10-04 Complexe de catalyseur pour traiter des gaz d'échappement d'un moteur diesel de grande taille à l'aide d'un carburant diesel à haute teneur en soufre WO2020076008A1 (fr)

Applications Claiming Priority (2)

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KR20180121006 2018-10-11
KR10-2018-0121006 2018-10-11

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WO2020076008A1 true WO2020076008A1 (fr) 2020-04-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115532250A (zh) * 2022-06-27 2022-12-30 国能龙源催化剂江苏有限公司 脱硝脱VOCs催化剂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070112201A (ko) * 2005-02-16 2007-11-22 바스프 카탈리스트 엘엘씨 석탄 연소 설비용 암모니아 산화 촉매
KR20150111979A (ko) * 2013-01-29 2015-10-06 존슨 맛쎄이 퍼블릭 리미티드 컴파니 암모니아 산화 촉매
KR20160025005A (ko) * 2013-07-10 2016-03-07 가부시키가이샤 캬타라 배기 가스 정화용 촉매
KR20160095929A (ko) * 2015-02-04 2016-08-12 대영씨엔이(주) 암모니아 제거용 백금/바나듐/티타니아 촉매의 제조방법

Patent Citations (4)

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KR20070112201A (ko) * 2005-02-16 2007-11-22 바스프 카탈리스트 엘엘씨 석탄 연소 설비용 암모니아 산화 촉매
KR20150111979A (ko) * 2013-01-29 2015-10-06 존슨 맛쎄이 퍼블릭 리미티드 컴파니 암모니아 산화 촉매
KR20160025005A (ko) * 2013-07-10 2016-03-07 가부시키가이샤 캬타라 배기 가스 정화용 촉매
KR20160095929A (ko) * 2015-02-04 2016-08-12 대영씨엔이(주) 암모니아 제거용 백금/바나듐/티타니아 촉매의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HU , WENSHUO ET AL.: "Mechanistic investigation of NH3 oxidation over V-0.5Ce(S04)2Ti NH3-SCR catalyst", CATALYSIS COMMUNICATIONS, vol. 112, 2018, pages 1 - 4, XP055701625, [retrieved on 20180412] *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115532250A (zh) * 2022-06-27 2022-12-30 国能龙源催化剂江苏有限公司 脱硝脱VOCs催化剂及其制备方法与应用
CN115532250B (zh) * 2022-06-27 2023-09-22 国能龙源催化剂江苏有限公司 脱硝脱VOCs催化剂及其制备方法与应用

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