KR100527963B1 - Manufacturing method of hydrothermally stable Fe/ZSM-5 zeolite catalyst - Google Patents

Manufacturing method of hydrothermally stable Fe/ZSM-5 zeolite catalyst Download PDF

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KR100527963B1
KR100527963B1 KR10-1999-0067646A KR19990067646A KR100527963B1 KR 100527963 B1 KR100527963 B1 KR 100527963B1 KR 19990067646 A KR19990067646 A KR 19990067646A KR 100527963 B1 KR100527963 B1 KR 100527963B1
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catalyst
thermal stability
zeolite catalyst
iron
sublimation
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KR10-1999-0067646A
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KR20010066064A (en
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이호택
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현대자동차주식회사
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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
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/06—Washing
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

본 발명은 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법에 관한 것으로서, 더욱 상세하게는 종래의 승화법에 의해 촉매를 제조하는 공정을 다시 반복하여 수행함으로써, 열적 안정성이 향상된 촉매를 얻을 수 있어 희박연소 배기가스 정화에 적용시 높은 NOx 정화율이 안정적으로 유지되는 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법에 관한 것이다.The present invention relates to a method for preparing an iron / G.S.M-5 zeolite catalyst having improved thermal stability, and more particularly, by repeating the process of preparing a catalyst by a conventional sublimation method, thermal stability is improved. The present invention relates to a method for preparing an iron / G.S-5M zeolite catalyst having improved thermal stability in which a high NOx purification rate is stably maintained when applied to lean burn exhaust gas purification.

Description

열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법{Manufacturing method of hydrothermally stable Fe/ZSM-5 zeolite catalyst} Manufacturing method of iron / G.S.M-5 zeolite catalyst with improved thermal stability {Manufacturing method of hydrothermally stable Fe / ZSM-5 zeolite catalyst}

본 발명은 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법에 관한 것으로서, 더욱 상세하게는 종래의 승화법에 의해 촉매를 제조하는 공정을 다시 반복하여 수행함으로써, 열적 안정성이 향상된 촉매를 얻을 수 있어 희박연소 배기가스 정화에 적용시 높은 NOx 정화율이 안정적으로 유지되는 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법에 관한 것이다.The present invention relates to a method for preparing an iron / G.S.M-5 zeolite catalyst having improved thermal stability, and more particularly, by repeating the process of preparing a catalyst by a conventional sublimation method, thermal stability is improved. The present invention relates to a method for preparing an iron / G.S-5M zeolite catalyst having improved thermal stability in which a high NOx purification rate is stably maintained when applied to lean burn exhaust gas purification.

일반적으로 자동차로부터 배출되는 배기가스로는 수증기(H2O), 이산화탄소(CO2), 일산화탄소(CO), 탄화수소(HC), 질화산화물(NOx) 등이 있다In general, exhaust gases emitted from automobiles include water vapor (H 2 O), carbon dioxide (CO 2 ), carbon monoxide (CO), hydrocarbons (HC), and nitride oxides (NOx).

이 중에서 H2O, CO2는 인체에 무해하지만, CO, HC, NOx는 인체에 치명적인 요소로서 이를 사전에 제거하는 것이 중요하다.Of these, H 2 O, CO 2 is harmless to the human body, CO, HC, NOx is a fatal factor to the human body it is important to remove it in advance.

여기서, 특히 NOx는 강한 태양 광선을 받아 광화학 반응을 일으켜 광화학 스모그 현상을 일으킨다.Here, in particular, NOx receives photovoltaic reactions under strong sunlight, causing photochemical smog.

더군다나, 문제가 되는 것은 상기 NOx가 대기를 오염시킬 뿐만 아니라 대기속의 자외선의 영향을 받아 광화학 반응이 반복하여 일어나기 때문에 사람의 눈과 호흡기 계통에 자극을 주는 물질이 2차적으로 형성된다는 점이다.Furthermore, the problem is that the NOx not only pollutes the atmosphere, but also because the photochemical reactions occur repeatedly under the influence of ultraviolet rays in the atmosphere, substances that irritate human eyes and the respiratory system are formed secondarily.

따라서, 상기 NOx을 제거하기 위한 연구가 활발이 이루어지고 있고 이 중 하나가 탄화수소를 환원제로 NOx를 환원·제거시키는 촉매환원공정이다.Therefore, studies to remove the NOx have been actively conducted, and one of them is a catalytic reduction process for reducing and removing NOx with a hydrocarbon as a reducing agent.

특히, 철이 이온교환된 제올라이트 촉매는 다른 촉매보다 NOx 환원반응을 보다 활성화하는데, 이것의 제조방법에는 통상 두가지, 즉 NaZSM-5에 옥살레이트 철(Ferrous Oxalate)용액을 넣어 공정을 수행하여 촉매를 제조하는 옥살레이트 법과, 에치.지.에스.엠-5에 염화철 증기를 승화시킨 다음 세정 및 소성 공정을 하여 촉매를 제조하는 승화법이 있다.In particular, iron-ionized zeolite catalysts activate NOx reduction reactions more than other catalysts, and there are two methods for preparing the catalyst, in which a oxalate solution is added to NaZSM-5 to prepare a catalyst. Oxalate method and sublimation method in which the iron chloride vapor is sublimed to E.G.S.M-5 and then washed and calcined to produce a catalyst.

그러나, 상기 옥살레이트 법은 일시적으로 내구성이 우수한 촉매재료를 제조할 수는 있으나 재현성에 문제가 있고, 반면에 승화법은 열적 안정성과 내구성이 다른 촉매 재료에 비해 떨어지는 문제가 있다.However, the oxalate method can produce a catalyst material having excellent durability temporarily, but there is a problem in reproducibility, while the sublimation method has a problem that thermal stability and durability are inferior to other catalyst materials.

일예로 배기가스 조건에서 내구실험을 한 결과, 600℃에서 10시간 내구실험후의 촉매 활성이 초기활성의 40%이하로 감소했다.For example, as a result of the endurance test under the exhaust gas condition, the catalytic activity after 10 hours endurance test at 600 ℃ was reduced to less than 40% of the initial activity.

그러므로, 상기의 제조법의 문제점을 개선하여 열적 안정성이 향상된 촉매재료를 개발하는 것은 NOx 제거 효율을 높이는데 중요하게 된다.Therefore, it is important to improve the NOx removal efficiency to develop a catalyst material having improved thermal stability by improving the problems of the above manufacturing method.

따라서, 본 발명은 상기와 같은 문제점을 감안하여 안출한 것으로서, 종래의 승화법에 의해 촉매를 제조하는 공정을 다시 반복하여 수행함으로써, 열적 안정성이 향상된 촉매를 얻을 수 있어 높은 NOx 정화율을 안정적으로 유지시키는데 그 목적이 있다. Accordingly, the present invention has been made in view of the above problems, and by repeatedly performing a process of preparing a catalyst by a conventional sublimation method, a catalyst having improved thermal stability can be obtained, resulting in a stable NOx purification rate. The purpose is to maintain.

이하, 본 발명을 설명하면 다음과 같다.Hereinafter, the present invention will be described.

본 발명은 염화철을 질소 분위기 350℃ 상압에서 증기로 승화시켜 준 다음 질소 블로잉으로 승화된 염화철을 에치.지.에스.엠-5와 반응시키고(ⅰ) 세정(ⅱ) 및 소성(ⅲ) 공정을 하여 촉매를 제조하는 제올라이트 촉매의 제조방법에 있어서, 상기에서 (ⅰ), (ⅱ) 및 (ⅲ) 공정을 한번 더 반복하여 수행하는 것을 특징으로 한다.The present invention sublimates iron chloride into steam at 350 ° C. under a nitrogen atmosphere, and then reacts the iron chloride sublimed with nitrogen blowing with etch.S.M-5 (iii) and the washing (ii) and calcining processes. In the method for producing a zeolite catalyst for producing a catalyst, it characterized in that the above (iv), (ii) and (iii) are repeated once more.

이하, 첨부도면을 참조하여 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

본 발명은 열적 안정성이 향상된 철/지.에스.엠(ZSM)-5 제올라이트 촉매의 제조방법에 관한 것으로서, 종래의 공정 중에서 승화, 세정 및 소성 공정을 한번 더 반복하여 수행하여 열적 성능을 향상시킨 것이다.The present invention relates to a method for preparing an iron / G.S.M (ZSM) -5 zeolite catalyst with improved thermal stability, and to improve thermal performance by repeatedly performing a sublimation, washing and firing process in a conventional process. will be.

통상적으로 열적 안정성에 가장 밀접한 관계를 갖는 인자는 지.에스.엠-5의 이온 교환위치에 존재하는 양성자의 양이다.Typically, the factor most closely related to thermal stability is the amount of protons present at the ion exchange site of G.S.M-5.

따라서, 양성자의 양이 증가하면 촉매재의 성질이 친수성이 되게 되어 열적안정성이 바람직하지 않게 된다.Therefore, when the amount of protons is increased, the property of the catalyst material becomes hydrophilic, and thermal stability becomes undesirable.

철/지.에스.엠-5 제올라이트 촉매의 제조방법을 살펴보면 도 1에 도시된 바와 같이, 승화 반응로에서 승화 공정을 수행한다.Looking at the manufacturing method of the iron / G. S. M-5 zeolite catalyst, as shown in Figure 1, the sublimation reaction is performed in a sublimation reactor.

상기 승화 반응로(10)는 'U'자 형상으로 이루어지고, 입구에는 글로브 박스 또는 진공장치에 연결하기 위한 컨넥터 단자(1a,1b)가 설치되고, 상기 컨넥터 단자(1a,1b)와 용기(3,6) 사이 또는 용기(3)와 용기(6) 사이에 튜브(2a,2b,2c)가 연결되고, 상기 튜브(2a,2b,2c)보다 직경이 큰 용기(3,6)에 각각의 재료(5,7)를 담아주고 각각의 재료(5,7)를 담아주는 지지대(4a,4b)에는 통공이 뚫려 있는 것을 포함한 용기(3,6)로 이루어진다.The sublimation reactor 10 is formed in a 'U' shape, and a connector terminal (1a, 1b) for connecting to a glove box or a vacuum device is provided at the inlet, the connector terminal (1a, 1b) and the container ( Tubes 2a, 2b, 2c are connected between 3, 6 or between the container 3 and the container 6, respectively in a container 3, 6 having a larger diameter than the tubes 2a, 2b, 2c. The support 4a, 4b for holding the material (5,7) of each of the material (5,7) consists of a container (3,6) including a through hole.

(ⅰ) 승화 공정(Iii) sublimation process

다음, 글로브 박스에 있는 염화철(FeCl3)(5)을 상기 승화반응로(10)의 컨넥터 단자(1a)에 연결하여 염화철 용기(3)에 넣는다.Next, iron chloride (FeCl 3 ) 5 in the glove box is connected to the connector terminal 1a of the sublimation reactor 10 and placed in the iron chloride container 3.

먼저, 에치.지.에스.엠(HZSM)-5(7) 재료를 상기 승화반응로(10)의 컨넥터 단자(1b)에 연결하여 에치.지.에스.엠-5 용기(6)에 넣고 수분을 없애주기 위해 550℃의 진공상태에서 5시간 정도 건조시켜준다.First, the HZSM-5 (7) material is connected to the connector terminal 1b of the sublimation reactor 10 and placed in the H.SM-5 container 6. To remove moisture, dry for about 5 hours in a vacuum of 550 ℃.

그리고, 질소 분위기 350℃ 상압에서 승화 공정을 수행한다. 즉, 상기 온도에서 염화철(5)은 증기로 변환되고 이 때 질소를 흘려주면 증기가 질소에 실려 상기 지지대(4a)에 형성된 통공을 통해 배출되어 튜브(2c)를 경유하여 에치.지.에스.엠-5 용기(6)의 지지대(4b)의 통공을 통해 에치.지.에스.엠-5(7)와 반응을 하게 된다.Then, the sublimation process is carried out in a nitrogen atmosphere 350 ℃ atmospheric pressure. That is, at this temperature, the iron chloride (5) is converted to steam, and when nitrogen is flowed at this time, steam is carried in the nitrogen and discharged through the through hole formed in the support (4a) to pass through the tube (2c). Reaction with the etch S. M-5 (7) through the through hole of the support (4b) of the M-5 vessel (6).

이 때의 반응식을 보면,If you look at the reaction at this time,

FeCl3+ HZSM-5 →FeCl2ZSM-5 + HCl↑FeCl 3 + HZSM-5 → FeCl 2 ZSM-5 + HCl ↑

(ⅱ) 세정 공정(Ii) washing process

상기 식에서 염소성분을 제거하기 위해 세정 공정을 수행한다.In the above formula, a cleaning process is performed to remove the chlorine component.

상기 승화 반응로(10)에서 시료를 꺼내 비이커에 넣고 증류수(H2O)로 상온에서 4회 반복하여 세정을 하고 다시 상온에서 건조시킨다.The sample is removed from the sublimation reactor 10, placed in a beaker, and washed four times at room temperature with distilled water (H 2 O), followed by drying at room temperature.

(ⅲ) 소성 공정(Iii) firing process

세정 공정을 끝낸 시료는 500℃에서 질소를 흘려주면서 대략 2시간정도 소성을 하는 것으로 고정을 마친다.After the cleaning process, the sample is fixed by baking for about 2 hours while flowing nitrogen at 500 ° C.

그러나, 본 발명에서는 이와 별도로 상기 승화(ⅰ), 세정(ⅱ) 및 소성(ⅲ) 공정을 한번 더 반복 수행하게 되며, 이 때, 모든 조건은 전과 동일하다.However, in the present invention, the sublimation, washing and firing processes are repeated one more time, and all the conditions are the same as before.

비교예 1Comparative Example 1

도 2는 에치.지.에스.엠-5인 원재료, 종래 촉매제조방법 즉, 승화, 세정 및 소성 공정를 모두 거친 시료 1와 종래 촉매 제조방법을 한번 더 반복하여 수행한 경우의 시료 2의 양성자의 량을 나타낸 것이다.FIG. 2 shows the protons of the raw material of H.G.S.M-5, the conventional catalyst production method, that is, the sample 1 which has been subjected to the sublimation, washing, and calcining processes once more and the conventional catalyst production method is repeated once more. The amount is shown.

도 2에 도시된 바와 같이, 원재료보다는 시료 1이, 시료 1보다는 시료 2가 양성자의 양이 현저히 줄어듬을 알 수 있다.As shown in Figure 2, it can be seen that the amount of protons is significantly reduced in sample 1 than the raw material, sample 2 than the sample 1.

이로써, 시료 2가 열적 안정성이 가장 좋음을 알 수 있다.As a result, it can be seen that Sample 2 has the best thermal stability.

비교예 2Comparative Example 2

도 3은 본 발명에 따라 제조된 촉매 그리고 그 촉매를 내구시험을 거친후의 촉매를 NOx 정화율에 대해 실험한 것이다.Figure 3 is a catalyst prepared according to the present invention and the catalyst after the endurance test is tested for the NOx purification rate.

이 때, 내구시험 조건은 NOx 500ppm, HC 2000ppmC(부탄), 산소 5%, 물 10%, 공간속도 30,000h-1, 600℃에서 10시간 노출로 한다.At this time, the endurance test conditions were 10 hours exposure at NOx 500ppm, HC 2000ppmC (butane), oxygen 5%, water 10%, space velocity 30,000h -1 , 600 ℃.

도 3에 도시된 바와 같이, 내구성은 다소 떨어지지만, 내구시험후 종래의 촉매(시료 1)와 본 발명에 따른 촉매(시료 2)에 있어서는, NOx 정화율이 350℃ 기준으로 시료 1은 30%이고 시료 2는 50%로 시료 2가 20%정도 향상됨을 알 수 있다.As shown in FIG. 3, the durability is somewhat reduced, but in the conventional catalyst (Sample 1) and the catalyst (Sample 2) according to the present invention after the endurance test, the NOx purification rate is 30% in Sample 1 at 350 ° C. And sample 2 is 50% it can be seen that sample 2 is improved by about 20%.

상기와 같은 본 발명에 의한 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법은 종래의 승화법에 의해 촉매를 제조하는 공정을 다시 반복하여 수행함으로써, 열적 안정성이 향상된 촉매를 얻을 수 있어 높은 NOx 정화율이 안정적을 안정성으로 유지시키는 효과가 있다. The method for preparing the iron / G.S.M-5 zeolite catalyst having improved thermal stability according to the present invention is performed by repeating the process of preparing the catalyst by a conventional sublimation method, thereby improving the catalyst having thermal stability. It is possible to obtain a high NOx purification rate, thereby keeping the stability stable.

도 1은 본 발명에 따른 승화반응로의 개략 단면도.1 is a schematic cross-sectional view of a sublimation reactor according to the present invention.

<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>

1a, 1b : 커넥터 단자 2a, 2b, 2c : 튜브1a, 1b: Connector terminals 2a, 2b, 2c: Tube

3 : 염화철 용기 4a, 4b : 지지대3: iron chloride container 4a, 4b: support stand

5 : 염화철 6 : 에치. 지.에스. 엠-5 용기5: iron chloride 6: etch. G.S. M-5 container

7 : 에치. 지.에스. 엠-5 10 : 승화 반응로7: etch. G.S. M-5 10: Sublimation Reactor

Claims (1)

염화철을 질소 분위기 350℃ 상압에서 증기로 승화시켜 준 다음 질소 블로잉으로 승화된 염화철을 에치.지.에스.엠-5와 반응시키고(ⅰ) 세정(ⅱ) 및 소성(ⅲ) 공정으로 구성된 촉매의 제조방법에 있어서, 상기에서 (ⅰ), (ⅱ) 및 (ⅲ) 공정을 한번 더 반복하여 수행하는 것을 특징으로 하는 열적 안정성이 향상된 철/지.에스.엠-5 제올라이트 촉매의 제조방법.Subsequently, the iron chloride was sublimed to steam in a nitrogen atmosphere at 350 ° C. at atmospheric pressure, and then the sublimed iron chloride was reacted with etch.G.S.M-5 (iii) and the cleaning (ii) and calcining processes were carried out. A process for producing an iron / G.S.M-5 zeolite catalyst with improved thermal stability, characterized in that the steps (iii), (ii) and (iii) are repeated once more.
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Citations (5)

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JPH05269386A (en) * 1991-06-13 1993-10-19 Tosoh Corp Catalyst for reduction removing nitrogen oxide and method for reduction removing
JPH06165919A (en) * 1992-11-30 1994-06-14 Ishikawajima Harima Heavy Ind Co Ltd Method for removing nitrous oxide
JPH06199707A (en) * 1992-12-28 1994-07-19 Asahi Chem Ind Co Ltd Catalytic cracking of light hydrocarbon
JPH07213864A (en) * 1994-01-31 1995-08-15 Ishikawajima Harima Heavy Ind Co Ltd Removing method of nitrous oxide
JPH10192706A (en) * 1996-12-29 1998-07-28 Agency Of Ind Science & Technol Catalyst for catalytically reducing and removing nox

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05269386A (en) * 1991-06-13 1993-10-19 Tosoh Corp Catalyst for reduction removing nitrogen oxide and method for reduction removing
JPH06165919A (en) * 1992-11-30 1994-06-14 Ishikawajima Harima Heavy Ind Co Ltd Method for removing nitrous oxide
JPH06199707A (en) * 1992-12-28 1994-07-19 Asahi Chem Ind Co Ltd Catalytic cracking of light hydrocarbon
JPH07213864A (en) * 1994-01-31 1995-08-15 Ishikawajima Harima Heavy Ind Co Ltd Removing method of nitrous oxide
JPH10192706A (en) * 1996-12-29 1998-07-28 Agency Of Ind Science & Technol Catalyst for catalytically reducing and removing nox

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