KR20190068173A - SCR Catalyst Added Carbon Supported Active Catalytic Materials and Preparation Method Thereof - Google Patents
SCR Catalyst Added Carbon Supported Active Catalytic Materials and Preparation Method Thereof Download PDFInfo
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- KR20190068173A KR20190068173A KR1020170168300A KR20170168300A KR20190068173A KR 20190068173 A KR20190068173 A KR 20190068173A KR 1020170168300 A KR1020170168300 A KR 1020170168300A KR 20170168300 A KR20170168300 A KR 20170168300A KR 20190068173 A KR20190068173 A KR 20190068173A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 69
- 239000000463 material Substances 0.000 title claims description 21
- 230000003197 catalytic effect Effects 0.000 title description 6
- 229910052799 carbon Inorganic materials 0.000 title 1
- 238000002360 preparation method Methods 0.000 title 1
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 41
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 34
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 26
- 239000010937 tungsten Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims description 71
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- 239000007864 aqueous solution Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
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- 239000002184 metal Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
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- 239000010936 titanium Substances 0.000 claims description 18
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- 239000000243 solution Substances 0.000 claims description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 7
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- 229910010413 TiO 2 Inorganic materials 0.000 description 2
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- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
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- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
- B01J21/18—Carbon
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- 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
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- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J35/0006—
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- 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
- B01J35/19—Catalysts containing parts with different compositions
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
본 발명은 탄소 재료에 촉매 활성물질이 담지된 선택적 촉매환원반응용 탈질촉매 및 그 제조방법에 관한 것으로, 보다 상세하게는 적은 바나듐 담지량에도 불구하고 질소산화물 제거 성능이 우수하고, 제조가 용이하여 상용화에 기여할 수 있는, 탄소 재료에 촉매 활성물질이 담지된 선택적 촉매환원반응용 탈질촉매 및 그 제조방법에 관한 것이다.The present invention relates to a denitration catalyst for selective catalytic reduction reaction in which a catalytic active material is supported on a carbon material and a method for preparing the same. More particularly, the present invention relates to a denitration catalyst for removing NOx, To a NO x removal catalyst for a selective catalytic reduction reaction in which a catalytic active material is supported on a carbon material, and a production method thereof.
화학공장, 발전소, 보일러, 쓰레기소각장 등과 같은 고정원과 자동차, 선박 등의 이동원으로부터 배출되는 배기가스 중 질소산화물(NOX)은 황산화물(SOX), 분진, 다이옥신, 중금속, 휘발성 유기화합물(Volatile Organic Compounds)과 함께 환경오염을 일으키는 물질로서 잘 알려져 있다.Nitrogen oxides (NO X ) in exhaust gas from fixed sources such as chemical plants, power plants, boilers, and incinerators, and from sources such as automobiles and ships, contain sulfur oxides (SO x ), dusts, dioxins, heavy metals and volatile organic compounds Volatile Organic Compounds) are well known as substances causing environmental pollution.
질소산화물은 주로 고온의 연소설비에서 과잉공기의 존재하에 질소 및 산소의 반응으로 생성되는데, 일산화질소(NO), 이산화질소(NO2), 일산화이질소(N2O), 삼산화이질소(N2O3), 사산화이질소(N2O4), 오산화이질소(N2O5) 등으로 구분되고, 이들 중 일산화질소는 인체에 매우 유해한 발암성 물질로 심각한 대기오염을 일으킬 뿐만 아니라, 황산화물과 함께 산성비와 스모그(smog) 생성의 원인이 되어 지구환경을 파괴하는 오염원들이므로, 이의 발생을 억제하기 위하여 저산소 연소, 배기가스 순환 등 연소조건개선에 대한 발생억제기술과 함께 이들을 효율적으로 제거하는 기술개발노력이 진행되고 있다.NOx is mainly produced by the reaction of nitrogen and oxygen in the presence of excess air in the combustion equipment of a high temperature, the nitrogen monoxide (NO), nitrogen dioxide (NO 2), dinitrogen oxide (N 2 O), diantimony nitrogen (N 2 O 3 ), Nitrous oxide (N 2 O 4 ), and dinitrogen monoxide (N 2 O 5 ). Of these, nitrogen monoxide is a very harmful carcinogenic substance and causes serious air pollution. It is a pollution source that causes acid rain and smog generation and destroys the global environment. Therefore, in order to suppress the occurrence of this phenomenon, it is necessary to develop technologies to suppress the occurrence of combustion conditions such as hypoxic combustion and exhaust gas circulation, Efforts are underway.
그러나 질소산화물은 다른 대기오염물질과는 달리 고온의 연소과정에서 불가피하게 발생하고, 또한 매우 안정한 화합물질이기 때문에 연소기술의 개선만으로는 충분히 질소산화물을 제거할 수 없으므로, 배기가스를 여러 가지 방법으로 처리하는 후처리 기술이 주목받고 있다.However, unlike other air pollutants, nitrogen oxides are inevitably generated in a high temperature combustion process, and since they are highly stable compounds, improvements in combustion technology can not sufficiently remove nitrogen oxides. Therefore, Has attracted attention.
이러한 후처리 기술에는 크게 수용액의 사용 여부에 따라 습식법과 건식법으로 나눌 수 있고, 이 중에서도 건식법인 제거효율 및 경제성 면에서 우수한 선택적 촉매 환원(SCR : Selective Catalytic Reduction) 공정이 상업적으로 널리 사용되고 있다.This post-treatment technique can be roughly classified into a wet process and a dry process depending on whether an aqueous solution is used. Among them, a selective catalytic reduction (SCR) process which is superior in terms of removal efficiency and economical efficiency as a dry process is widely used commercially.
선택적 촉매 환원 공정은 NOX 제거를 위해 NH3, urea, hydrocarbon 등과 같은 환원제가 사용되고 있으며, 촉매 상에서 상기 환원제를 이용하여 NOx를 인체에 무해한 N2나 H2O와 같은 기체로 환원시키게 된다. 환원제 중 암모니아를 사용한 경우 암모니아의 악취 및 유독성 외에도 배기가스 내 성분 중 SO2가 산화되어 SO3가 되면서 배기가스 내 미반응 암모니아와 반응하여 생성되는 황산암모늄(ammonium sulfate)은 설비를 부식시켜 사용 수명을 단축시키는 주요한 원인이다. 따라서 촉매를 제조할 때 SOX 전환율이 고려되어야 한다.In the selective catalytic reduction process, a reducing agent such as NH 3 , urea, hydrocarbon and the like is used for removing NO x , and the reducing agent is used to reduce NO x to a harmless gas such as N 2 or H 2 O on the catalyst. In the case of using ammonia in the reducing agent, in addition to the odor and toxicity of ammonia, the ammonium sulfate produced by reacting unreacted ammonia in the exhaust gas with the SO 3 in the exhaust gas as a result of oxidation of SO 2 in the exhaust gas, Is a major cause to shorten the time. Therefore, the conversion of SO x should be considered when preparing the catalyst.
최근 상용화되어 가장 널리 사용되고 있는 V2O5-WO3-TiO2계 촉매는 반응활성이 높고 현장 적응력이 강하기 때문에 발전소와 소각로 등의 배기가스에 존재하는 NOX 처리를 위해 가장 널리 사용되는 촉매이다. 이 중 촉매 활성 성분인 V2O5과 WO3는 redox cycle에 의해 NOX를 N2로 전환시키는 촉매작용을 함으로써 촉매의 활성을 증가시키는 역할을 하지만, 과량이 첨가될 경우에는 고온영역에서 NH3를 N2O로 산화시키는 반응을 일으키고, SOx 전환율이 높은 값을 가지며 중금속으로 환경 중에 방출되면 인체나 환경에 막대한 영향을 주기 때문에 촉매에 함유되는 V2O5과 WO3의 함량을 제한하고 있다. 그리고 최근 지속적인 수요 및 가격 증가로 V2O5과 WO3 가격이 급격하게 증가되고 있는 것으로 보고되고 있다. 따라서 바나듐과 텅스텐 사용량의 절감이 요구되고 있는 실정이다.Recently, V 2 O 5 -WO 3 -TiO 2 catalyst, which is widely used and widely used, is the most widely used catalyst for NO x treatment in exhaust gas of power plants and incinerators because of its high reactivity and strong field adaptability . Among these catalysts, V 2 O 5 and WO 3 catalyzes the conversion of NO x to N 2 by the redox cycle, thereby increasing the activity of the catalyst. However, when excess amount is added, the reaction of oxidizing NH 3 to N 2 O occurs in the high temperature region , The SOx conversion rate is high, and when it is released into the environment as heavy metals, it greatly affects the human body and the environment. Therefore, V 2 O 5 The content of WO 3 is limited. Recently, demand and prices have increased and V 2 O 5 WO 3 prices are reported to be increasing rapidly. Therefore, it is required to reduce the use amount of vanadium and tungsten.
이에, 한국등록특허 제1434936호에는 균질한 세륨-지르코늄 혼합 옥사이드를 크롬, 몰리브덴, 텅스텐 또는 이들의 혼합물 수용액에 함침시켜 산화세륨이 10 ~ 90 중량% 함유된 세륨-지르코늄 혼합 옥사이드를 활성화한 바나듐 비함유 촉매에 관한 내용을 개시하고 있으나, 상기 바나듐 비함유 촉매는 바나듐을 함유하지 않으므로 환경에 무해하며 열수 조건하에서 노화안정성이 우수한 장점이 있지만, 고온에서 운전해야 하므로 운전비용이 높고 과잉의 산소 존재하에서는 낮은 비표면적으로 인해 비활성화 현상을 보이는 문제점이 있었다.Korean Patent No. 1434936 discloses a process for producing a cerium-zirconium mixed oxide by impregnating a homogeneous cerium-zirconium mixed oxide with an aqueous solution of chromium, molybdenum, tungsten or a mixture thereof to form a cerium- However, since the vanadium-free catalyst is free from vanadium, it is harmless to the environment and has an advantage of excellent aging stability under hydrothermal conditions. However, since it is required to operate at a high temperature, the operation cost is high, and in the presence of excess oxygen There is a problem that the inactivating phenomenon is caused by the low specific surface area.
또한, 한국등록특허 제1565982호에서는 바나듐의 양을 감소시키기 위하여 적은 양의 바나듐을 그래핀 위에 분산 담지시킨 바나듐 담지체에 이산화티타늄 및 산화텅스텐을 혼합시킨 SCR 촉매 및 그 제조방법을 개시하고 있으나, 그래핀 지지체에 담지되어 있는 물질이 바나듐으로 한정되어 있으며, 바나듐과 더불어 고가인 텅스텐의 담지량을 그대로 유지하고 있고, 바나듐 담지 과정을 거친 물질들을 이산화티타늄에 재담지하는 공정을 더함으로써 경제적인 측면에서 효율성이 떨어지는 문제점이 있었다.Korean Patent No. 1565982 discloses a SCR catalyst in which titanium dioxide and tungsten oxide are mixed with a vanadium support in which a small amount of vanadium is dispersed and supported on graphene in order to reduce the amount of vanadium, The substance supported on the graphene support is limited to vanadium, and the amount of tungsten that is expensive as well as vanadium is maintained. Further, by adding a process of treating the vanadium-loaded materials with titanium dioxide, There is a problem that efficiency is low.
본 발명의 주된 목적은 상술한 문제점을 해결하기 위한 것으로서, 적은 바나듐과 텅스텐의 담지량에도 불구하고 배기가스 중의 질소산화물 제거효율이 우수하고, 처리된 가스가 2차 환경오염을 유발하지 않으며, 내마모성과 강도가 우수하여 장기간 운전에도 질소산화물 제거효율이 저하되지 않는 동시에 제조가 용이하여 상용화에 기여할 수 있는, 탄소 재료에 촉매 활성물질이 담지된 선택적 촉매환원반응용 탈질촉매 및 그 제조방법을 제공하는데 있다.The main object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide an exhaust gas purifying apparatus which is excellent in nitrogen oxide removal efficiency in exhaust gas despite small amount of vanadium and tungsten to be loaded, An NO x removal catalyst for a selective catalytic reduction reaction in which a catalytic active material is supported on a carbon material, which is excellent in strength and does not deteriorate the NO x removal efficiency even during long-term operation, and can be easily produced and contributes to commercialization .
상기와 같은 목적을 달성하기 위하여, 본 발명의 일 구현예는 (a) 바나듐 전구체 수용액, 텅스텐 전구체 수용액 및 티타늄 전구체 수용액을 혼합하여 금속 전구체 수용액을 준비하는 단계; (b) 상기 금속 전구체 수용액을 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 함침시켜 함침물을 수득하는 단계; 및 (c) 상기 함침물을 건조시킨 후, 소성하는 단계를 포함하는 선택적 촉매환원반응용 탈질촉매의 제조방법을 제공한다.According to an aspect of the present invention, there is provided a method for preparing a metal precursor solution, comprising the steps of: (a) preparing an aqueous metal precursor solution by mixing a vanadium precursor aqueous solution, a tungsten precursor aqueous solution, and a titanium precursor aqueous solution; (b) impregnating the metal precursor aqueous solution with graphene oxide or reduced graphene oxide to obtain an impregnated product; And (c) drying the impregnated material and then calcining the impregnated material.
본 발명의 바람직한 일 구현예에서, 상기 (a) 단계의 금속 전구체 수용액은 티타늄 전구체 100 중량부에 대하여, 바나듐 전구체 0.1 중량부 ~ 3 중량부 및 텅스텐 전구체 1 중량부 ~ 10 중량부를 함유하는 것을 특징으로 할 수 있다. In one preferred embodiment of the present invention, the aqueous metal precursor solution of step (a) comprises 0.1 to 3 parts by weight of the vanadium precursor and 1 to 10 parts by weight of the tungsten precursor, based on 100 parts by weight of the titanium precursor. .
본 발명의 바람직한 일 구현예에서, 상기 (b) 단계의 그래핀 옥사이드 또는 환원 그래핀 옥사이드 함량은 티타늄 전구체 100 중량부에 대하여, 5 중량부 ~ 15 중량부인 것을 특징으로 할 수 있다.In one preferred embodiment of the present invention, the content of graphene oxide or reduced graphene oxide in the step (b) is 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of the titanium precursor.
본 발명의 다른 구현예는, 촉매 지지체인 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 촉매 활성물질인 바나듐 산화물, 텅스텐 산화물 및 티타늄 산화물이 담지되어 있는 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매를 제공한다.Another embodiment of the present invention provides an NO x removal catalyst for selective catalytic reduction characterized in that catalytically active vanadium oxide, tungsten oxide and titanium oxide are supported on graphene oxide or reduced graphene oxide as a catalyst support .
본 발명의 바람직한 다른 구현예에서, 상기 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 바나듐 산화물 0.1 중량부 ~ 3 중량부 및 텅스텐 산화물 1.0 중량부 ~ 10 중량부를 함유하는 것을 특징으로 할 수 있다.In another preferred embodiment of the present invention, the denitration catalyst for the selective catalytic reduction reaction comprises 0.1 to 3 parts by weight of vanadium oxide and 1.0 to 10 parts by weight of tungsten oxide per 100 parts by weight of titanium oxide can do.
본 발명의 바람직한 다른 구현예에서, 상기 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 그래핀 옥사이드 또는 환원 그래핀 옥사이드 5 중량부 ~ 15 중량부를 함유하는 것을 특징으로 할 수 있다.In another preferred embodiment of the present invention, the denitration catalyst for the selective catalytic reduction reaction may include 5 to 15 parts by weight of graphene oxide or reduced graphene oxide per 100 parts by weight of the titanium oxide.
본 발명에 따른 선택적 촉매환원반응용 탈질촉매는 촉매 지지체에 담지되는 바나듐 및 텅스텐의 감소에도 불구하고 배기가스 중의 질소산화물 제거효율이 우수하며, 처리된 가스가 2차 환경오염을 유발하지 않고, 내마모성과 강도가 우수하여 장기간 운전에도 질소산화물 제거효율이 저하되지 않는 동시에 제조가 용이하여 상용화에 기여할 수 있는 효과가 있다.The NO x removal catalyst for selective catalytic reduction according to the present invention is excellent in the removal efficiency of nitrogen oxides in the exhaust gas despite the reduction of vanadium and tungsten carried on the catalyst support and the treated gas does not cause secondary environmental pollution, And strength, so that the nitrogen oxide removal efficiency is not lowered even in a long-term operation, and the production is easy and contributes to commercialization.
도 1은 본 발명에 따른 선택적 촉매환원반응용 탈질촉매의 제조방법의 공정도이다.
도 2는 반응 온도에 따른 질소산화물의 제거효율을 나타낸 그래프이다.
도 3은 선택적 촉매환원반응용 탈질촉매의 TEM 이미지로, (a)는 실시예 1에서 제조된 촉매환원반응용 탈질촉매의 TEM 이미지이고, (b)는 비교예 1에서 제조된 촉매환원반응용 탈질촉매의 TEM 이미지이다.
도 4는 실시예 1 및 비교예 1에서 제조된 촉매환원반응용 탈질촉매의 온도에 대한 암모니아 승온탈착(NH3-TPD)을 측정한 그래프이다.1 is a process diagram of a method for preparing a NO x removal catalyst for selective catalytic reduction according to the present invention.
2 is a graph showing the removal efficiency of nitrogen oxide according to the reaction temperature.
3 is a TEM image of an NO x removal catalyst for selective catalytic reduction reaction, wherein (a) is a TEM image of an NO x removal catalyst prepared in Example 1, (b) is a TEM image of a NO x reduction catalyst prepared in Comparative Example 1 TEM image of the denitration catalyst.
FIG. 4 is a graph showing ammonia temperature desorption (NH 3 -TPD) measured with respect to the temperature of the NO x removal catalyst prepared in Example 1 and Comparative Example 1.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법 은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.
본 명세서에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.
본 명세서에서 "그래핀(graphene)"은 복수개의 탄소원자들이 서로 공유결합으로 연결되어 형성된 폴리시클릭 방향족 분자를 의미하며, 상기 공유결합으로 연결된 탄소원자들은 기본 반복단위로서 6원환을 형성하나, 5원환 및/또는 7원환을 더 포함하는 것도 가능하다. 따라서 상기 그래핀은 서로 공유결합된 탄소원자들(통상 sp2 결합)의 단일층으로서 보이게 된다. 상기 그래핀은 다양한 구조를 가질 수 있으며, 이와 같은 구조는 그래핀 내에 포함될 수 있는 5원환 및/또는 7원환의 함량에 따라 달라질 수 있다. As used herein, the term "graphene" refers to a polycyclic aromatic molecule formed by covalent bonding of a plurality of carbon atoms, wherein the carbon atoms linked by the covalent bond form a 6-membered ring as the basic repeating unit, It is also possible to further include a toric ring and / or a 7-membered ring. The graphene thus appears as a single layer of covalently bonded carbon atoms (usually sp2 bonds). The graphene may have various structures, and such a structure may vary depending on the content of the 5-membered ring and / or the 7-membered ring which may be contained in the graphene.
본 발명은 일 관점에서, (a) 바나듐 전구체 수용액, 텅스텐 전구체 수용액 및 티타늄 전구체 수용액을 혼합하여 금속 전구체 수용액을 준비하는 단계; (b) 상기 금속 전구체 수용액을 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 함침시켜 함침물을 수득하는 단계; 및 (c) 상기 함침물을 건조시킨 후, 소성하는 단계를 포함하는 선택적 촉매환원반응용 탈질촉매의 제조방법에 관한 것이다.In one aspect, the present invention provides a method for preparing a metal precursor solution, comprising: (a) preparing a metal precursor aqueous solution by mixing a vanadium precursor aqueous solution, a tungsten precursor aqueous solution, and a titanium precursor aqueous solution; (b) impregnating the metal precursor aqueous solution with graphene oxide or reduced graphene oxide to obtain an impregnated product; And (c) drying the impregnated material and then calcining the impregnated material.
보다 구체적으로, 본 발명에 따른 선택적 촉매환원반응용 탈질촉매의 제조방법은 고가이면서 환경적인 문제가 발생할 수 있는 바나듐 및 텅스텐의 원료 사용량을 줄이기 위해 촉매 지지체로 그래핀을 사용하였으며, 함침법을 이용하여 그래핀 촉매 지지체에 응집 없이 촉매 활성물질을 균일하게 분산시킴으로써, 배기가스 중의 질소산화물 제거효율이 우수하며, 장기간 운전에도 질소산화물 제거효율이 저하되지 않는 선택적 촉매환원반응용 탈질촉매를 제조할 수 있다.More specifically, in the method for preparing a NO x removal catalyst for selective catalytic reduction according to the present invention, graphene is used as a catalyst support to reduce the amount of raw materials of vanadium and tungsten which are expensive and cause environmental problems. , It is possible to produce a denitration catalyst for selective catalytic reduction reaction which is excellent in nitrogen oxide removal efficiency in the exhaust gas and does not deteriorate the nitrogen oxide removal efficiency even in long-term operation by uniformly dispersing the catalytically active substance in the graphene catalyst support have.
이하, 본 발명을 단계별로 도면을 참조하여 더욱 상세히 설명한다. 도 1은 본 발명에 따른 선택적 촉매환원반응용 탈질촉매의 제조방법의 공정도이다.Hereinafter, the present invention will be described in more detail with reference to the drawings. 1 is a process diagram of a method for preparing a NO x removal catalyst for selective catalytic reduction according to the present invention.
먼저, 본 발명에 따른 상기 (a) 단계는 바나듐 전구체 수용액, 텅스텐 전구체 수용액 및 티타늄 전구체 수용액을 혼합하여 금속 전구체 수용액을 준비하는 단계이다.The step (a) according to the present invention is a step of preparing an aqueous metal precursor solution by mixing a vanadium precursor aqueous solution, a tungsten precursor aqueous solution and a titanium precursor aqueous solution.
상기 금속 전구체 수용액은 탈염수에 바나듐 전구체, 텅스텐 전구체 및 티타늄 전구체가 각각 용해되어 있는, 바나듐 전구체 수용액, 텅스텐 전구체 수용액 및 티타늄 전구체 수용액을 혼합하여 수득된다. 이때, 탈염수의 함량은 각각의 전구체들이 충분히 용해될 수 있는 함량이면 제한 없이 사용 가능하나, 바람직하게는 탈염수 100 중량부에 대하여 각각의 전구체 5 중량부 ~ 10 중량부를 첨가하여 용해시킬 수 있다.The metal precursor aqueous solution is obtained by mixing a vanadium precursor aqueous solution, a tungsten precursor aqueous solution and a titanium precursor aqueous solution in which a vanadium precursor, a tungsten precursor and a titanium precursor are respectively dissolved in demineralized water. In this case, the amount of demineralized water can be used without limitation as long as the amount of each precursor can be sufficiently dissolved. Preferably, 5 to 10 parts by weight of each precursor may be dissolved in 100 parts by weight of demineralized water.
상기 바나듐 전구체는 촉매 활성물질 제조를 위해 사용하는 것으로, 선택적 촉매환원반응용 탈질 촉매제조 분야에서 통상적으로 사용되는 화합물이면 제한 없이 사용 가능하고, 바람직하게는 암모늄메타바나데이트(NH4VO3), 바나듐옥시트리클로라이드(VOCl3), 바나듐 옥사이드(V2O5) 등을 사용할 수 있으며, 더욱 바람직하게는 암모늄메타바나데이트(NH4VO3)이다. 상기 암모늄메타바나데이트(NH4VO3)는 타 종류의 촉매에 비하여 환경 친화적이며 열분해되면 오산화바나듐(V2O5)이 되는데, 오산화바나듐은 배기가스에서 질소산화물을 환원시키는 촉매작용뿐만 아니라, 황산화물에 대한 내성이 우수하면서 이산화황(SO2)을 삼산화황(SO3)으로 산화시키는 촉매역할을 하여 삼산화황이 배기가스 중의 수증기와 결합하여 황산(H2SO4)으로 전환되므로 배기가스 중의 이산화황을 제거하는 효과도 있다.The vanadium precursor is used for the production of a catalytically active substance. The vanadium precursor can be used without limitation as long as it is a compound commonly used in the field of selective catalytic reduction catalysts. Preferred examples thereof include ammonium metavanadate (NH 4 VO 3 ) Vanadium oxytrichloride (VOCl 3 ), vanadium oxide (V 2 O 5 ) and the like can be used, and ammonium metavanadate (NH 4 VO 3 ) is more preferable. The ammonium metavanadate (NH 4 VO 3 ) is environmentally friendly compared to other types of catalysts. When pyrolyzed, vanadium pentoxide (V 2 O 5 ) is formed. Vanadium pentoxide not only catalyzes the reduction of nitrogen oxides in the exhaust gas, (SO 2 ) to sulfur trioxide (SO 3 ) while sulfur trioxide (SO 3 ) is converted into sulfuric acid (H 2 SO 4 ) by combining sulfur trioxide with water vapor in the exhaust gas. There is also an effect to remove.
상기 바나듐 전구체로 암모늄메타바나데이트를 사용할 경우에는 암모늄메타바나데이트의 용해도가 매우 작기 때문에 용해도를 증가시키기 위해 암모늄메타바나데이트 수용액에 옥살산(oxalic acid)를 조금씩 저어가며 혼합하는 바람직하다.When ammonium metavanadate is used as the vanadium precursor, it is preferable to add oxalic acid to the aqueous solution of ammonium metavanadate by slightly stirring to increase the solubility of ammonium metavanadate because the solubility of ammonium metavanadate is very small.
상기 바나듐 전구체는 티타늄 전구체 100 중량부에 대하여, 0.1 ~ 3 중량부, 바람직하게는 0.5 중량부 ~ 2 중량부, 더욱 바람직하게는 0.6 중량부 ~ 2 중량부로 함유될 수 있다. 상기 바나듐 전구체의 함량이 0.1 중량부 미만이면 질소산화물 제거 효과가 미흡할 수 있고, 3 중량부를 초과하면 높은 함량에 의해 분말의 응집 현상이 생기고, 함량 증가 대비 효율이 만족스럽지 않을 수 있으며, 경제적인 면과 환경적인 면에서 바람직하지 않다.The vanadium precursor may be contained in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 0.6 to 2 parts by weight, based on 100 parts by weight of the titanium precursor. If the content of the vanadium precursor is less than 0.1 parts by weight, the nitrogen oxide removal effect may be insufficient. If the vanadium precursor content is more than 3 parts by weight, aggregation of the powder may occur due to a high content, It is not preferable in terms of surface and environment.
또한, 텅스텐 전구체는 촉매 활성물질 제조를 위해 사용하는 것으로, 선택적 촉매환원반응용 탈질촉매제조 분야에서 통상적으로 사용되는 화합물이면 제한 없이 사용 가능하고, 바람직하게는 암모늄메타텅스테이트[(NH4)6W12O39·XH2O], 암모늄파라텅스테이트[(NH4)10W12O41], 암모늄텅스테이트(H8N2O4W), 암모늄황화텅스테이트(H8N2S4W), 산화텅스텐(WO3) 등을 사용할 수 있다.The tungsten precursor is used for the production of a catalytically active substance. The tungsten precursor can be used without limitation as long as it is a compound commonly used in the field of selective catalytic reduction catalysts, and preferably ammonium metatungstate [(NH 4 ) 6 W 12 O 39 XH 2 O], ammonium paratungstate [(NH 4 ) 10 W 12 O 41 ], ammonium tungstate (H 8 N 2 O 4 W), ammonium sulfur tungstate (H 8 N 2 S 4 W), tungsten oxide (WO 3 ), or the like can be used.
상기 텅스텐 전구체의 함량은 티타늄 전구체 100 중량부에 대하여, 1 중량부 ~ 10 중량부, 바람직하게는 2 중량부 ~ 10 중량부, 더욱 바람직하게는 2 중량부 ~ 8 중량부로 함유될 수 있다. 만일, 상기 텅스텐 전구체의 함량이 1 중량부 미만이면 티타늄 산화물의 구조적인 안정화나 넓은 온도범위의 온도, 특히 고온에서의 촉매 효율이 미흡할 수 있고, 10 중량부를 초과하면 높은 함량에 의해 분말이 응집 현상이 발생되고, 함량 증가 대비 효율이 만족스럽지 않을 수 있으며, 경제적인 면과 환경적인 면에서 바람직하지 않다.The content of the tungsten precursor may be 1 part by weight to 10 parts by weight, preferably 2 parts by weight to 10 parts by weight, more preferably 2 parts by weight to 8 parts by weight, based on 100 parts by weight of the titanium precursor. If the content of the tungsten precursor is less than 1 part by weight, structural stability of titanium oxide or temperature at a wide temperature range, especially at high temperature, may be insufficient. If it exceeds 10 parts by weight, And the efficiency relative to an increase in the content may not be satisfactory, which is not desirable from the viewpoints of economy and environment.
상기 바나듐 전구체의 바나듐과 텅스텐 전구체의 텅스텐은 전이금속으로, 내부의 전자궤도를 차지하는 전자의 수가 불완전하여 전자를 쉽게 잃어서 양이온 상태로 되고, 이에 따라 후술되는 티타늄 전구체와 화합물을 형성하여 탈질촉매의 선택적 촉매환원반응의 활성화와 더불어 내충격성, 내열성 및 내부식성을 향상시키며, 또한, 산소와 쉽게 반응하여 산화물 부동화 보호 피막을 만들기 때문에 잘 산화되지 않고 알칼리, 황산, 염산 등에 대해서 안정하다.The vanadium of the vanadium precursor and tungsten of the tungsten precursor are transition metals, and the number of electrons occupying the electron orbital inside is incomplete, so that the electrons are easily lost and become a cationic state, thereby forming a compound with a titanium precursor, It improves impact resistance, heat resistance and corrosion resistance along with activation of catalytic reduction reaction. It is also not oxidized well and is stable against alkali, sulfuric acid, hydrochloric acid etc. because it easily reacts with oxygen to form oxide passivation protection film.
상기 티타늄 전구체는 이산화티타늄(TiO2), 비결정상의 티타닌산 등을 사용할 수 있으며, 이들은 높은 비표면적으로 인해 주촉매와 조촉매로 사용되는 바나듐과 텅스텐의 지지체로서 작용하고, 탈질촉매의 물리적인 강도를 높이거나, 내열성을 향상시켜 촉매의 수명을 증가시킨다. The titanium precursor may be titanium dioxide (TiO 2 ), amorphous titanic acid or the like. These titanium precursors act as a support for vanadium and tungsten used as a main catalyst and a cocatalyst due to their high specific surface area, The strength is increased, the heat resistance is improved, and the lifetime of the catalyst is increased.
다음으로, 본 발명에 따른 (b) 단계는 상기 금속 전구체 수용액을 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 함침시켜 함침물을 수득한다. Next, in the step (b) according to the present invention, the aqueous metal precursor solution is impregnated with graphene oxide or reduced graphene oxide to obtain an impregnated product.
상기 그래핀 옥사이드(graphene oxide; GO)는 일반적으로 흑연 결정의 산화와 초음파 처리를 이용한 분쇄를 통해 제조할 수 있고, 환원 그래핀 옥사이드(reduced graphene oxide; RGO)는 그래핀 옥사이드를 하이드라진(hydrazine) 등의 환원제를 이용해 그래핀으로 환원시켜 제조할 수 있으나, 상용화된 그래핀 옥사이드 및 환원 그래핀 옥사이드를 구매해서 사용할 수도 있다.The graphene oxide (GO) is generally produced by the oxidation of graphite crystals and pulverization using ultrasonic treatment, and the reduced graphene oxide (RGO) is produced by hydrazine graphene oxide, Or the like. However, commercially available graphene oxide and reduced graphene oxide may be purchased and used.
상기 그래핀 옥사이드 또는 환원 그래핀 옥사이드는 금속 전구체 수용액에 혼합시켜 함침하거나, 또는 탈염수에 그래핀 옥사이드 또는 환원 그래핀 옥사이드를 용해시킨 다음, 그래핀 옥사이드 수용액 또는 환원 그래핀 옥사이드 수용액으로 금속 전구체 수용액에 혼합하여 함침할 수 있다. 이때, 상기 탈염수의 함량은 그래핀 옥사이드 또는 환원 그래핀 옥사이드가 충분히 용해될 수 있는 함량이면 제한 없이 사용 가능하나, 바람직하게는 탈염수 100 중량부에 대하여 그래핀 옥사이드 또는 환원 그래핀 옥사이드 1 중량부 ~ 3 중량부를 첨가하여 용해시킬 수 있다.The graphene oxide or the reduced graphene oxide may be mixed with an aqueous solution of the metal precursor or impregnated with the aqueous solution of the metal precursor by dissolving the graphene oxide or the reduced graphene oxide in the demineralized water or the aqueous solution of the graphene oxide or the reduced graphene oxide Mixed and impregnated. The amount of the desalted water may be any amount as long as the amount of the graphene oxide or the reduced graphene oxide is sufficiently dissolved. Preferably, the amount of the desalted water is 1 part by weight or less of graphene oxide or reduced graphene oxide per 100 parts by weight of the desalted water, 3 parts by weight may be added and dissolved.
상기 그래핀 옥사이드 또는 환원 그래핀 옥사이드는 티타늄 전구체 100 중량부에 대하여, 5 중량부 ~ 15 중량부, 바람직하게는 7 중량부 ~ 12 중량부로 함유될 수 있다. 만일, 상기 그래핀 옥사이드 또는 환원 그래핀 옥사이드의 함량이 5 중량부 미만이면 높은 함량의 활성물질로 인해 그래핀 표면에 골고루 균일하게 분산되지 못하고 응집현상이 발생될 수 있으며, 15 중량부를 초과할 경우에는 그래핀 옥사이드 또는 환원 그래핀 옥사이드 상에 촉매 활성물질의 담지량이 적어 촉매 활성 물질의 지지체 역할을 충분히 수행할 수 없는 문제점이 있다.The graphene oxide or the reduced graphene oxide may be contained in an amount of 5 parts by weight to 15 parts by weight, preferably 7 parts by weight to 12 parts by weight, based on 100 parts by weight of the titanium precursor. If the content of the graphene oxide or the reduced graphene oxide is less than 5 parts by weight, the particles may not uniformly disperse uniformly on the surface of the graphene due to a high content of the active material, There is a problem that the amount of the catalytically active substance supported on the graphene oxide or the reduced graphene oxide is insufficient and thus it can not sufficiently serve as a support for the catalytically active substance.
상기 그래핀 옥사이드 또는 환원 그래핀 옥사이드는 전술된 금속 전구체 수용액에 교반하에 함침시켜 금속 전구체들의 금속이 그래핀 상에 담지되도록 한다. 상기 함침은 30 ℃ ~ 70 ℃에서 1시간 ~ 15시간 동안 수행할 수 있다. 만일 상기 함침이 30 ℃ 또는 1시간 미만으로 수행할 경우에는 충분한 함침이 이루어지지 않아 수율이 저하될 수 있고, 70 ℃ 또는 15시간을 초과할 경우에는 바나듐의 입성장으로 인해 전구체들이 응집되고 고른 분산을 방해하여 촉매의 활성저하를 가져올 수 있다. The graphene oxide or the reduced graphene oxide is impregnated with the above-described metal precursor aqueous solution under agitation so that the metal of the metal precursors is supported on the graphene. The impregnation may be performed at 30 ° C to 70 ° C for 1 hour to 15 hours. If the impregnation is carried out at 30 ° C or less for 1 hour or less, the impregnation may not be performed sufficiently and the yield may be lowered. If the impregnation is carried out at 70 ° C or for more than 15 hours, Which may lead to catalyst deactivation.
이후, 본 발명에 따른 (c) 단계는 상기 함침물을 건조시킨 후, 소성하여 선택적 촉매환원반응용 탈질촉매를 제조한다. Thereafter, in the step (c) according to the present invention, the impregnated material is dried and then fired to produce a denitration catalyst for selective catalytic reduction.
상기 함침 단계 후, 수득된 함침물의 수분은 회전 진공증발기 등을 이용하여 제거한 다음, 함침물 내 미세기공에 포함된 잔여 수분은 건조기 등으로 충분히 건조하여 제조한다. After the impregnation step, the moisture of the obtained impregnated material is removed by using a rotary vacuum evaporator or the like, and the residual moisture contained in the micropores in the impregnated material is sufficiently dried by a dryer or the like.
상기 건조는 건조온도가 너무 낮거나 건조시간이 너무 짧은 경우, 완전히 건조되지 않아 촉매 미세 기공내에 수분을 함유하고 있어 활성 저하가 일어날 수 있으며, 건조온도가 너무 높거나 건조시간이 너무 길어질 경우에는 소결현상으로 인한 주촉매 물질인 바나듐의 입성장으로 인해 촉매의 활성 저하가 발생될 수 있어, 상기 함침물의 건조는 40 ℃ ~ 50 ℃에서 수행할 수 있다.If the drying temperature is too low or the drying time is too short, it may not be completely dried and may contain moisture in the catalyst micropores, which may result in degradation of the activity. If the drying temperature is too high or the drying time is too long, The activity of the catalyst may be lowered due to the grain growth of vanadium as the main catalyst material due to the development, and the impregnation may be performed at 40 ° C to 50 ° C.
상기 건조가 완료된 건조물은 열처리를 통한 활성 성분의 크기 및 분산도를 제어하기 위해 소성 과정을 거쳐 선택적 촉매환원반응용 탈질촉매를 제조한다. 상기 소성은 촉매의 선택적 촉매 환원 능력을 고려할 때 바람직하게는 불활성 분위기하에 400 ℃ ~ 800 ℃에서 1시간 ~ 3시간 동안 수행할 수 있다. 만일 소성하는 동안 불활성 분위기를 유지시키지 못할 경우에는 촉매 지지체 물질인 그래핀이 산화로 인해 공공(vacancy) 등과 같은 촉매의 결함이 발생되어 촉매 활성물질을 지지하지 못하거나 고른 분산을 유도할 수 없는 문제점이 발생될 수 있다. 상기 불활성 분위기를 유지하기 위하여 질소, 아르콘, 헬륨 등을 소성 과정 동안 주입 및 함유할 수 있다.The dried product after the drying is subjected to a calcination process to control the size and the degree of dispersion of the active ingredient through heat treatment to produce a denitration catalyst for selective catalytic reduction reaction. The firing may be carried out at 400 ° C to 800 ° C for 1 hour to 3 hours, preferably in an inert atmosphere, considering the selective catalytic reduction capability of the catalyst. If the inert atmosphere can not be maintained during the firing, the graphene, which is the catalyst support material, is oxidized to cause defects of the catalyst such as vacancy and the like, May occur. In order to maintain the inert atmosphere, nitrogen, argon, helium, etc. may be injected and contained during the firing process.
또한, 소성 조건이 400 ℃ 미만 또는 1시간 미만일 경우에는 전구체로 사용된 물질이 제대로 제거되지 않고, 선택적 촉매환원반응용 탈질촉매 입자 및 기공이 불균일하게 분포되어 질소산화물의 제거효율이 저하될 수 있으며, 800 ℃ 또는 3시간을 초과할 경우에는 촉매활성물질 및 촉매 지지체로 사용된 물질의 물성 변화로 내구성이 저하되거나, 질소산화물의 제거효율이 저하될 수 있다.In addition, when the calcination condition is less than 400 ° C or less than 1 hour, the precursor is not properly removed and the removal efficiency of the NO x removal catalyst may be reduced due to non-uniform distribution of NO x removal catalyst particles and pores , 800 ° C. or 3 hours, the durability may be lowered or the removal efficiency of nitrogen oxides may be lowered due to changes in physical properties of the catalyst active material and the material used as the catalyst support.
이러한 소성 공정은 튜브(tube)형 로, 컨벡션(convection)형 로, 화격자형 로 등 공지된 다양한 형태의 로에서 이루어질 수 있으며, 특별히 제한되지 않는다.The firing process may be performed in various types of furnaces, such as a tube type, a convection type, and a grate type, and is not particularly limited.
상술한 바와 같이 제조되는 선택적 촉매환원반응용 탈질촉매는 촉매 지지체 물질인 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 촉매 활성물질인 바나듐, 텅스텐 및 티타늄이 담지되어 있어 SCR 공정에서 배가스 내 포함된 질소산화물을 제거하는 활성을 안정적으로 유지할 수 있게 된다.The NO x removal catalyst for selective catalytic reduction reaction as described above contains vanadium, tungsten, and titanium, which are catalytically active materials, on graphene oxide or reduced graphene oxide, which is a catalyst support material, so that nitrogen oxides contained in the exhaust gas in the SCR process It is possible to stably maintain the removing activity.
본 발명은 다른 관점에서, 촉매 지지체인 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 촉매 활성물질인 바나듐 산화물, 텅스텐 산화물 및 티타늄 산화물이 담지되어 있는 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매에 관한 것이다.In another aspect, the present invention relates to a NO x removal catalyst for selective catalytic reduction, characterized in that catalytically active vanadium oxide, tungsten oxide and titanium oxide are supported on graphene oxide or reduced graphene oxide as a catalyst support.
본 발명에 따른 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 그래핀 옥사이드 또는 환원 그래핀 옥사이드 5 중량부 ~ 15 중량부를 함유한다. 상기 그래핀 옥사이드 또는 환원 그래핀 옥사이드가 전술된 함량비 범위를 벗어날 경우에는 촉매 활성물질의 담지량이 적어 촉매 활성물질의 역할을 제대로 수행할 수 없거나, 또는 높은 함량에 의해 활성물질이 촉매 지지체 표면에 골고루 균일하게 분산되지 못하고 응집현상이 생기게 되며, 과량의 활성물질로 인한 산화력 증대로 이어져 환원제인 암모니아를 산화시켜 질소산화물 제거성능의 저하를 초래하고, SO2를 SO3로 산화시켜 황산암모늄염(NH4HSO4)과 같은 부반응을 초래할 수 있다.The NO x removal catalyst for selective catalytic reduction according to the present invention contains 5 to 15 parts by weight of graphene oxide or reduced graphene oxide per 100 parts by weight of titanium oxide. If the content of the graphene oxide or the reduced graphene oxide is out of the above range, the amount of the catalytically active material to be loaded is insufficient and the catalytically active material can not be properly performed. Alternatively, It is not uniformly dispersed evenly, and coagulation phenomenon occurs. This leads to an increase in oxidizing power due to an excessive amount of active material, thereby oxidizing ammonia, which is a reducing agent, resulting in deterioration of nitrogen oxide removal performance and oxidation of SO 2 to SO 3 , 4 HSO 4 ).
또한, 상기 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 바나듐 산화물 0.1 중량부 ~ 3 중량부 및 텅스텐 산화물 1.0 중량부 ~ 10 중량부를 함유한다. 상기 조성비의 선택적 촉매환원반응용 탈질촉매는 적은 바나듐과 텅스텐의 담지량에도 불구하고, 배기가스 중의 질소산화물 제거효율이 우수하고, 처리된 가스가 2차 환경오염을 유발하지 않으며, 내마모성과 강도가 우수하여 고온 운전에 의한 촉매의 활성 저하와 수명단축을 억제할 수 있다.The denitration catalyst for the selective catalytic reduction reaction contains 0.1 to 3 parts by weight of vanadium oxide and 1.0 to 10 parts by weight of tungsten oxide per 100 parts by weight of titanium oxide. The denitration catalyst for the selective catalytic reduction reaction of the composition ratio is excellent in the removal efficiency of nitrogen oxide in the exhaust gas despite the small amount of vanadium and tungsten supported thereon and the processed gas does not cause secondary environmental pollution and has excellent abrasion resistance and strength So that it is possible to suppress the reduction of the catalyst activity and the life span due to the high temperature operation.
본 발명에 따른 선택적 촉매환원반응용 탈질촉매는 금속판, 금속섬유, 세라믹 필터, 허니컴(honeycomb)과 같은 구조체나 공기정화기, 실내장식물, 내외장재, 벽지 등에 코팅하여 사용되거나, 소량의 바인더와 함께 입자형 또는 모노리스(monolith) 형태로 압출 가공되거나, 슬레이트, 플레이트, 펠릿 등의 다양한 형태로 제조하여 사용될 수 있다.The NO x removal catalyst for selective catalytic reduction according to the present invention can be used as a coating on a structure such as a metal plate, a metal fiber, a ceramic filter, a honeycomb, an air purifier, an interior decoration, an interior / exterior material, a wallpaper, Or monolith, or may be prepared in various forms such as slate, plate, and pellet.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
<< 실시예Example 1> 1>
암모늄메타바나데이트(AMV) 0.1 g, 암모늄메타텅스테이트(AMT) 0.6 g 및 이산화티탄 10.0 g을 증류수 200 g에 각각 혼합하여 바나듐 전구체 수용액, 텅스텐 전구체 수용액 및 티타늄 전구체 수용액을 준비하고, 이들을 혼합하여 금속 전구체 수용액을 수득하였다. 이어 환원 그래핀 옥사이드(RGO) 1.0 g을 증류수 100 g에 분산시킨 다음, 상기 환원 그래핀 옥사이드 수용액에 금속 전구체 수용액을 60 ℃에서 7 시간 동안 교반하여 함침시켰다. 함침 완료 후, 수득된 함침물은 회전감압증발장치를 이용하여 함침물의 수분을 제거하고, 60 ℃의 오븐에서 건조시킨 다음, 질소 분위기 하에서 500 ℃로 2 시간 동안 소성하여 선택적 촉매환원반응용 탈질촉매를 제조하였다.A vanadium precursor aqueous solution, a tungsten precursor aqueous solution and a titanium precursor aqueous solution were prepared by mixing 0.1 g of ammonium metavanadate (AMV), 0.6 g of ammonium metatungstate (AMT) and 10.0 g of titanium dioxide in 200 g of distilled water, To obtain an aqueous metal precursor solution. Then 1.0 g of reduced graphene oxide (RGO) was dispersed in 100 g of distilled water, and then the aqueous solution of the metal precursor was impregnated with the aqueous solution of the reduced precursor oxide by stirring at 60 ° C for 7 hours. After the completion of the impregnation, the impregnated material obtained was dried in an oven at 60 ° C. by removing the moisture from the impregnated material by using a rotary evaporation apparatus, and then calcined at 500 ° C. for 2 hours in a nitrogen atmosphere to obtain a denitration catalyst for selective catalytic reduction .
<< 실시예Example 2 내지 4 및 2 to 4 and 비교예Comparative Example 1> 1>
실시예 2 내지 4와 비교예 1에 대한 함량 조건을 표 1로 나타내었으며, 각 조건을 제외한 제조방법은 실시예 1과 동일하게 수행하여 선택적 촉매환원반응용 탈질촉매를 제조하였다.The content conditions for Examples 2 to 4 and Comparative Example 1 are shown in Table 1, and a denitration catalyst for the selective catalytic reduction reaction was prepared in the same manner as in Example 1 except for the respective conditions.
(g)Distilled water content
(g)
(g) AMV content
(g)
(g) AMT content
(g)
함량 (g)Titanium dioxide
Content (g)
[[ 실험예Experimental Example 1]: 선택적 촉매환원반응용 1]: for selective catalytic reduction reaction 탈질촉매의Of the denitration catalyst 성분 측정 Component measurement
XRF(X-ray fluorescence, Zetium, PAN’alytical)를 통해 실시예 1 내지 4 및 비교예 1에서 제조된 선택적 촉매환원반응용 탈질촉매의 성분을 측정하여 표 2에 나타내었다.The components of the NO x removal catalysts prepared in Examples 1 to 4 and Comparative Example 1 were measured through X-ray fluorescence (X-ray fluorescence, Zetium, PAN'alytical)
division
표 2에 나타난 바와 같이, 합성시 각기 다른 첨가한 함량에 맞는 분석 결과를 나타남을 확인할 수 있었다. 상기 기타물질은 Al2O3, SiO2 등으로, 전구체로 사용된 물질 또는 측정장비에 존재하는 잔여물인 것으로 파악된다.As shown in Table 2, it was confirmed that the results of analysis corresponding to the different added contents in the synthesis were obtained. The other material is Al 2 O 3 , SiO 2, etc., and is considered to be a residue existing in the material or measurement equipment used as the precursor.
[[ 실험예Experimental Example 2]: 선택적 촉매환원반응용 2]: for selective catalytic reduction reaction 탈질촉매의Of the denitration catalyst 탈질성능Denitrification performance 측정 Measure
NOx 전환반응 실험 장비는 촉매가 장착되고 반응이 일어나는 촉매 반응부, 촉매 반응부의 온도를 조절하는 Heater, 주입 가스를 예열하는 Pre-Heater, 온도와 주입가스 양을 조절하는 온도 control 판넬과 MFC(Mass Flow Controller), Water Pump 등으로 구성되어 있다. 반응기의 온도는 250 ℃ ~ 500 ℃의 범위로 조절하였고, 분석할 촉매는 실시예 및 비교예에서 수득된 파우더 타입의 0.3g을 준비하였다. 2005년부터 유럽, 일본, 미국 등에서 탈질 촉매성능평가의 기준에 의하여 계산된 공간 속도(SV, Surface Velocity) 60,000 ml gcat -1h- 1를 산정하였으며, 반응기에 공급되는 전체 가스 양을 300 sccm으로 흘려주었다. NO gas(1% mol/mol)는 300 ppm (v/v)을 정량적으로 흘려주었으며, NH3 gas는 360ppm (v/v)로 흘려주었다. O2(1% mol/mol)의 농도는 5 % (v/v), N2(고순도 액화질소)로 총 유량을 유지하도록 하였다. 정확한 활성실험을 수행하기 위하여 해당 반응조건에서 일정 시간동안 안정화를 수행한 후 반응실험을 수행하였고, O2를 제외한 반응가스의 분석은 CLD analyzer (Chemi-luminescence detector, T200H, Teledyne)을 사용하여 분석하였으며, O2 가스는 O2 분석기(OXITEC-5000, ENOTEC)을 사용하여 분석하였다. 상기 분석장비를 통해 가스 inlet과 촉매 반응부를 지나온 가스 outlet의 NOx 농도 변화를 통해 측정한 후, 하기 식을 통해 NOx 제거 효율을 계산하여 도 2에 나타내었다.The NOx conversion test system consists of a catalytic reactor where the catalyst is loaded and reacted, a heater that controls the temperature of the catalytic reactor, a preheater that preheats the feed gas, a temperature control panel that controls the amount of the temperature and the feed gas, Flow Controller, and Water Pump. The temperature of the reactor was controlled in the range of 250 ° C to 500 ° C, and 0.3g of the powder type obtained in the Examples and Comparative Examples was prepared as the catalyst to be analyzed. Since 2005, the gas velocity (SV) of 60,000 ml g cat -1 h - 1 calculated by the criteria for the performance evaluation of NO x removal catalysts in Europe, Japan and the United States was calculated, and the total amount of gas supplied to the reactor was 300 sccm Respectively. NO gas (1% mol / mol) was flowed quantitatively at 300 ppm (v / v) and NH 3 gas was flowed at 360 ppm (v / v). The concentration of O 2 (1% mol / mol) was maintained at 5% (v / v) and N 2 (high purity liquid nitrogen). In order to carry out the precise activation experiment, the reaction was performed after stabilization for a certain period of time under the corresponding reaction conditions. The analysis of the reaction gas excluding O 2 was performed using a CLD analyzer (Chemi-luminescence detector, T200H, Teledyne) And O 2 gas was analyzed using an O 2 analyzer (OXITEC-5000, ENOTEC). The NOx removal efficiency was calculated by the following equation after measuring the NOx concentration change of the gas outlet passed through the gas inlet and the catalytic reaction part through the above analyzer, and is shown in FIG.
[식][expression]
NOx conversion (%) = 100 × ((inlet-outlet NOx concentration)/inlet NOx concentration) NO x conversion (%) = 100 × ((inlet-outlet NO x concentration) / inlet NO x concentration)
도 2에 나타난 바와 같이, 실시예 1 내지 3의 촉매는 비교예 1의 촉매에 비해 탈질 성능이 우수한 것으로 나타났고, 특히 실시예 1의 촉매가 다른 촉매에 비해 탈질 성능이 월등히 우수한 것으로 나타났다. 또한, 실시예 4의 촉매 경우에는 비교예 1의 촉매 대비 바나듐과 텅스텐의 절반의 담지량에도 불구하고 비교예 1의 촉매와 유사한 탈질 성능을 보임을 확인할 수 있었다. As shown in FIG. 2, the catalysts of Examples 1 to 3 showed better denitrification performance than the catalyst of Comparative Example 1, and the catalyst of Example 1 was superior to other catalysts in terms of denitrification performance. In addition, it was confirmed that the catalyst of Example 4 exhibited similar denitrification performance to the catalyst of Comparative Example 1, despite the amount of vanadium and tungsten supported by half of the catalyst of Comparative Example 1.
[[ 실험예Experimental Example 3]: 선택적 촉매환원반응용 3]: For Selective Catalytic Reduction Reaction 탈질촉매의Of the denitration catalyst 비표면적Specific surface area 측정 Measure
실시예 1 내지 4 및 비교예 1에서 제조된 선택적 촉매환원반응용 탈질촉매의 비표면적(SBET), 평균 기공크기(average pore size) 및 기공부피(pore volume)을 ASAP 2010(Micrometritics Co., USA)를 통해 측정하여 표 3에 나타내었다. The specific surface area (S BET ), average pore size and pore volume of the NO x removal catalysts prepared in Examples 1 to 4 and Comparative Example 1 were measured by ASAP 2010 (Micrometritics Co., USA). The results are shown in Table 3.
표 3에 기재된 바와 같이, 비교예 1의 촉매에 비해 실시예 1 내지 4의 촉매가 비표면적이 넓은 것으로 나타났다. 이는 비표면적이 넓은 그래핀을 촉매 활성물질의 지지체로 적용되었기 때문인 것으로 파악된다.As shown in Table 3, the catalysts of Examples 1 to 4 showed larger specific surface area than the catalyst of Comparative Example 1. This is because graphene having a large specific surface area is used as a support for a catalytically active substance.
[[ 실험예Experimental Example 4]: 선택적 촉매환원반응용 4]: for selective catalytic reduction reaction 탈질촉매의Of the denitration catalyst TEMTEM 측정 Measure
제조된 선택적 촉매환원반응용 탈질촉매의 응집 여부를 확인하기 위해 TEM(Transmission electron microscope, JEM-2100F, JEOL)을 통하여 실시예 1과 비교예 1에서 제조된 선택적 촉매환원반응용 탈질촉매를 측정하여 도 3에 나타내었다.The denitration catalysts for the selective catalytic reduction reaction prepared in Example 1 and Comparative Example 1 were measured through a TEM (transmission electron microscope, JEM-2100F, JEOL) 3.
도 3에 나타난 바와 같이, 비교예 1[도 3(b)]에서 제조된 촉매의 경우, 응집이 되어 있는 것을 확인할 수 있는 반면, 실시예 1[도 3(a)]에서 제조된 촉매의 경우에는 그래핀 표면에 고르게 분산되어 있는 것을 확인할 수 있었다.As shown in Fig. 3, it was confirmed that the catalyst prepared in Comparative Example 1 (Fig. 3 (b)) was in the state of aggregation, whereas in the case of the catalyst prepared in Example 1 (Fig. 3 Was uniformly dispersed on the surface of the graphene.
촉매는 주로 표면 반응으로 반응에 필요한 활성화 에너지를 낮추며 화학반응에서 반응속도를 조절해주는 역할을 한다. 선택적 촉매환원반응용 탈질촉매에서도, 촉매 표면에 존재하는 활성 성분에 의해 반응속도가 제어되므로 높은 비표면적 특성 및 촉매 활성물질의 분산성이 중요하다. 이에, 본 발명에 따른 선택적 촉매환원반응용 탈질촉매의 경우, 높은 비표면적과 분산성의 특성으로 그래핀에 활성물질이 담지된 촉매의 향상된 활성에 영향을 준 것으로 파악된다.Catalysts are mainly surface reactions that lower the activation energy required for the reaction and control the reaction rate in the chemical reaction. In the NO x removal catalyst for selective catalytic reduction, the reaction rate is controlled by the active component present on the surface of the catalyst, so that high specific surface area and dispersibility of the catalytically active substance are important. Thus, it is understood that the denitration catalyst for the selective catalytic reduction reaction according to the present invention has an effect on the enhanced activity of the catalyst having the active material on the graphene due to its high specific surface area and dispersibility.
[[ 실험예Experimental Example 5]: 선택적 촉매환원반응용 5]: for selective catalytic reduction reaction 탈질촉매의Of the denitration catalyst 암모니아 ammonia 승온탈착법Temperature desorption method 활성 산점 측정 Active acid point measurement
NH 3 -TPD (NH 3 -Temperature Programmed Desorption) 반응기에 실시예 1 및 비교예 1에서 제조된 촉매를 각각 장입하고, 상온에서 한 시간 동안 NH3 가스를 주입하여 촉매의 표면에 NH3를 흡착시킨 후 촉매를 퍼지(purge)하여 온도에 따른 NH3 탈착량을 Mass 분석기(AutochemⅡ 2920, Micromeritics)로 분석하였으며, 그 결과를 도 4에 나타내었다. NH 3 -TPD ( NH 3 - Temperature Programmed Desorption) reactor was charged with the catalyst prepared in Example 1 and Comparative Example 1, NH 3 gas was introduced at room temperature for one hour to adsorb NH 3 on the surface of the catalyst The post catalyst was purged, and NH 3 desorption amount according to the temperature was analyzed by a mass analyzer (Autochem II 2920, Micromeritics). The results are shown in FIG.
도 4에 나타난 바와 같이 분석 온도 전 구간에서 실시예 1의 선택적 촉매환원반응용 탈질촉매가 비교예 1의 촉매보다 NH3의 탈착량이 높은 것을 알 수 있다. 이것은 비교예 1의 촉매보다 실시예 2의 촉매에 산점이 증가하여 NH3가 더 많이 흡착되었음을 의미하며, 이러한 NH3의 흡착량 증가는 결과적으로 탈질율 향상 효과를 가져오게 된다.As shown in FIG. 4, it can be seen that the denitration catalyst for the selective catalytic reduction reaction of Example 1 has a higher desorption amount of NH 3 than the catalyst of Comparative Example 1 in the whole analysis temperature range. This means that the acid value of the catalyst of Example 2 is higher than that of the catalyst of Comparative Example 1, so that NH 3 is more adsorbed. As a result, an increase in the adsorption amount of NH 3 results in an effect of improving the denitration rate.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
(b) 상기 금속 전구체 수용액을 그래핀 옥사이드 또는 환원 그래핀 옥사이드에 함침시켜 함침물을 수득하는 단계; 및
(c) 상기 함침물을 건조시킨 후, 소성하는 단계를 포함하는 선택적 촉매환원반응용 탈질촉매의 제조방법.
(a) preparing an aqueous metal precursor solution by mixing a vanadium precursor aqueous solution, a tungsten precursor aqueous solution, and a titanium precursor aqueous solution;
(b) impregnating the metal precursor aqueous solution with graphene oxide or reduced graphene oxide to obtain an impregnated product; And
(c) drying the impregnated material and then calcining the impregnated material.
상기 (a) 단계의 금속 전구체 수용액은 티타늄 전구체 100 중량부에 대하여, 바나듐 전구체 0.1 중량부 ~ 3 중량부 및 텅스텐 전구체 1 중량부 ~ 10 중량부를 함유하는 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매의 제조방법.
The method according to claim 1,
Wherein the metal precursor aqueous solution of step (a) comprises 0.1 to 3 parts by weight of a vanadium precursor and 1 to 10 parts by weight of a tungsten precursor based on 100 parts by weight of the titanium precursor. ≪ / RTI >
상기 (b) 단계의 그래핀 옥사이드 또는 환원 그래핀 옥사이드 함량은 티타늄 전구체 100 중량부에 대하여, 5 중량부 ~ 15 중량부인 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매의 제조방법.
The method according to claim 1,
Wherein the content of graphene oxide or reduced graphene oxide in step (b) is 5 parts by weight to 15 parts by weight based on 100 parts by weight of the titanium precursor.
Wherein the catalytically active vanadium oxide, tungsten oxide, and titanium oxide are supported on graphene oxide or reduced graphene oxide as a catalyst support.
상기 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 바나듐 산화물 0.1 중량부 ~ 3 중량부 및 텅스텐 산화물 1.0 중량부 ~ 10 중량부를 함유하는 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매.
5. The method of claim 4,
Wherein the denitration catalyst for selective catalytic reduction comprises 0.1 to 3 parts by weight of vanadium oxide and 1.0 to 10 parts by weight of tungsten oxide per 100 parts by weight of titanium oxide.
상기 선택적 촉매환원반응용 탈질촉매는 티타늄 산화물 100 중량부에 대하여, 그래핀 옥사이드 또는 환원 그래핀 옥사이드 5 중량부 ~ 15 중량부를 함유하는 것을 특징으로 하는 선택적 촉매환원반응용 탈질촉매.
5. The method of claim 4,
Wherein the denitration catalyst for selective catalytic reduction reaction comprises 5 to 15 parts by weight of graphene oxide or reduced graphene oxide per 100 parts by weight of titanium oxide.
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