KR900004117B1 - Catalyst for preparing methacrolein from isobutylene - Google Patents
Catalyst for preparing methacrolein from isobutylene Download PDFInfo
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- KR900004117B1 KR900004117B1 KR1019880008101A KR880008101A KR900004117B1 KR 900004117 B1 KR900004117 B1 KR 900004117B1 KR 1019880008101 A KR1019880008101 A KR 1019880008101A KR 880008101 A KR880008101 A KR 880008101A KR 900004117 B1 KR900004117 B1 KR 900004117B1
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Abstract
Description
본 발명은 이소부틸렌과 산소 또는 산소를 함유하는 기체를 일반식(Ⅰ)으로 표시하는 고체촉매와 기상 접촉시켜 메타크롤레인을 제조하는 고체촉매 및 그 제조방법에 관한 것이다.The present invention relates to a solid catalyst for producing methacrolein by gas-phase contact with isobutylene and a gas containing oxygen or oxygen with a solid catalyst represented by formula (I).
Mo12Bi1FeaCobNicPbdSieAfDgOx......................(Ⅰ)Mo 12 Bi 1 Fe a Co b Ni c Pb d Si e A f D g O x ... (Ⅰ)
프로필렌이나 이소부틸렌을 산화시켜 아크롤레인이나 메타크롤레인을 제조하는 촉매에 대하여 많은 문헌과 특허들이 알려져 있다. 그러나 프로필렌의 기상산화공정이 일찌기 공업화된데 비하여 공업화에 이용될만 한 이소부틸렌의 산화촉매는 많지 않으며 특히 메타크롤레인 제조촉매는 아크롤레인 제조촉매에 비하여 촉매의 활성과 선택성이 크게 뒤져 있다.Many literatures and patents are known on catalysts for the oxidation of propylene or isobutylene to produce acrolein or methacrolein. However, compared to the early industrialization of propylene gas phase oxidation process, there are not many oxidation catalysts of isobutylene that can be used for industrialization. In particular, the methacrolein preparation catalyst is far behind the activity and selectivity of the catalyst compared to the acrolein preparation catalyst.
프로필렌산화에 우수한 성능을 보이는 MoBi계 촉매를 이용하여 이소부틸렌을 산화시킬 경우, 반응개시 직후에는 프로필렌의 산화때와 같이 높은 활성을 보이지만 반응이 진행될수록 차츰 활성이 떨어진다. 이것은 이소부틸렌의 프로필렌보다 염기성이 강해서 촉매표면에 강흡착하거나 불가역흡착을 하여 부반응을 크게하고 촉매활성점을 감소시키기 때문이다. 따라서 이소부틸렌 산화촉매에 있어서는 촉매의 산화력과 산강도의 조절이 가장 중요하며, 현재까지 특허된 대부분의 촉매들도 위의 개선에 중점을 두고 있다. 대표적인 메타크롤레인 제조촉매로는 MoBiCo계, MoBiSb계, MoBiFe계 및 MoTe계 등의 복합산화물 촉매가 개발되었다. 이들 촉매는 아크롤레인 제조촉매의 개량촉매로서 첨가원소, 조성비, 소성조건 등을 미세하게 조절한 촉매들이다. 이들 촉매중에 촉매의 산강도를 조절하기 위해서는 다음의 방법들이 제시되고 있다.When isobutylene is oxidized using a MoBi-based catalyst which shows excellent performance in propylene oxidation, it shows high activity as in the case of propylene oxidation immediately after the start of the reaction, but gradually decreases as the reaction proceeds. This is because the basicity is stronger than that of isobutylene propylene, which causes strong side adsorption or irreversible adsorption on the surface of the catalyst to increase side reactions and decrease the catalytic activity point. Therefore, in the isobutylene oxidation catalyst, the control of the oxidation power and the acid strength of the catalyst is the most important, and most of the catalysts patented to date focus on the above improvement. As a typical methacrolein production catalyst, complex oxide catalysts such as MoBiCo-based, MoBiSb-based, MoBiFe-based and MoTe-based have been developed. These catalysts are catalysts for improving the acrolein production catalyst and finely controlling the additive element, composition ratio, firing conditions and the like. Among these catalysts, the following methods have been proposed to control the acid strength of the catalyst.
일본특허공보 47-42241 및 일본공개 특허공보 50-30815 등에는 칼륨, 루비듐 및 세슘을 사용하여 산 강도를 조절하였고, 일본특허공보 47-32044 및 일본공개 특허공보 56-161341 등에서는 탈륨 및 텔루륨을 사용하여 촉매의 산화력증가와 함께 촉매의 산강도를 조절하였다.Potassium, rubidium, and cesium were used to control acid strength in Japanese Patent Application Laid-Open No. 47-42241 and Japanese Patent Application Laid-Open No. 50-30815, and the like. Was used to adjust the acid strength of the catalyst with increasing oxidation power of the catalyst.
그러나 본 발명자의 실험에 의하면 칼륨, 루비듐 및 세슘을 사용한 촉매는 이 성분들의 염기성이 강하여 촉매의 활성이 크게 감소되므로 선택성의 향상에는 한계가 있어서 최고 수율을 얻기위해서는 알칼리금속의 사용량을 극히 미세하게 조절해야 하며, 탈륨과 텔루륨을 사용한 촉매는 장기간 반응시킬때 탈륨과 텔루륨이 서서히 승화되어 촉매의 활성이 떨어지는 단점이 있었다.However, according to the experiments of the present inventors, the catalyst using potassium, rubidium, and cesium has strong basicity of these components, which greatly reduces the activity of the catalyst. Therefore, there is a limit in improving the selectivity. In addition, the catalyst using thallium and tellurium has a disadvantage in that the activity of the catalyst is lowered as the thallium and tellurium are gradually sublimed when reacted for a long time.
본 발명에 따른 촉매는 몰리브덴, 비스무스 성분에 철, 코발트, 니켈, 납 구리 및 규소를 필수성분으로 복합화시키는 것이 특징으로 단위표면적당이 활성을 현저히 증가시키므로써 칼륨, 루비듐 및 세슘 등의 알칼리금속 단독이나 알칼리 금속간이나 또는 알칼리금속과 마그네슘, 칼슘 및 바륨 등의 알칼리토금속을 적절한 원소비로 조합 첨가하여도 활성의 감소없이 높은 선택성을 유지하였다. 또한 복합화성분의 조성비와 제조방법을 조절함으로써 촉매의 구조적 열적 안정성이 현저히 향상되어 장기간의 조업에서 높은 활성과 선택성을 유지하는 것이 특징이다.The catalyst according to the present invention is characterized by complexing molybdenum and bismuth with iron, cobalt, nickel, lead copper, and silicon as essential components.Also, the activity per unit surface area significantly increases the activity of alkali metals such as potassium, rubidium, and cesium. Even when alkali metals or alkali metals and alkaline earth metals such as magnesium, calcium, and barium were added in an appropriate element ratio, high selectivity was maintained without decreasing activity. In addition, the structural and thermal stability of the catalyst is remarkably improved by adjusting the composition ratio and the preparation method of the complexed component, so that it is characterized by maintaining high activity and selectivity in long-term operation.
본 발명에 따른 촉매조성은 다음 일반식(Ⅰ)와 같다.Catalyst composition according to the present invention is represented by the following general formula (I).
Mo12Bi1FeaCobNicPbdSieAfDgOx......................(Ⅰ)Mo 12 Bi 1 Fe a Co b Ni c Pb d Si e A f D g O x ... (Ⅰ)
상기 식에서 Mo, Bi, Fe, Co, Ni, Pb, Si 및 O는 몰리브덴, 비스무스, 철, 코발트, 니켈, 납, 규소 및 산소를 나타내고 A는 구리, 바나듐, 인, 텔루륨, 크롬 및 망간 중 적어도 한가지 이상이며, D는 칼륨, 류비듐, 세슘, 칼슘, 마그네슘 및 바륨 중 적어도 한가지 이상이다, a, b, c, d, e, f, g 및 x는 각 원소의 원자비이다. 바람직한 촉매조성은 Mo12Bi1일때, a, b, c 및 d는 0.1-6, e는 2.5-15, f는 0.1-6, g는 0.05-5이다. x는 상기식에서 다른 원소의 원자가 및 원자비에 따라 균형을 이루는데 필요한 산소의 수이다.Wherein Mo, Bi, Fe, Co, Ni, Pb, Si and O represent molybdenum, bismuth, iron, cobalt, nickel, lead, silicon and oxygen and A represents copper, vanadium, phosphorus, tellurium, chromium and manganese At least one, and D is at least one of potassium, rubidium, cesium, calcium, magnesium, and barium. A, b, c, d, e, f, g, and x are the atomic ratios of each element. Preferred catalyst compositions for Mo 12 Bi 1 are a, b, c and d of 0.1-6, e of 2.5-15, f of 0.1-6 and g of 0.05-5. x is the number of oxygen needed to balance with the valence and atomic ratio of the other elements in the formula.
위 촉매조성 중에서 특히 바람직한 촉매는 다음과 같다.Particularly preferred catalysts among the above catalyst compositions are as follows.
A는 구리, 바나듐 및 인 중 적어도 한가지 이상이며 D는 칼륨, 루비듐, 세슘, 바륨 및 마그네슘 중 적어도 한가지 이상이고, a, b, c 및 d는 각각 0.2-5, a+b+c+d+f는 6-12, e는 2.5-8, f는 0.2-4, g는 0.2-3.0이다.A is at least one of copper, vanadium and phosphorus and D is at least one of potassium, rubidium, cesium, barium and magnesium, and a, b, c and d are 0.2-5, a + b + c + d +, respectively. f is 6-12, e is 2.5-8, f is 0.2-4, g is 0.2-3.0.
상기식에서 조성물은 단지 성분들의 물리적 혼합물이 아니라 오히려 각각의 성분들이 서로 화학적 또는 물리적으로 결합되어 있는 복합산화물이며 본 발명 촉매의 고활성과 고선택성은 이러한 복합화에 기인하고, 복합화조건은 촉매제조방법을 결정하는 요소가 된다.Wherein the composition is not just a physical mixture of components, but rather a composite oxide in which each component is chemically or physically bonded to each other, and the high activity and high selectivity of the catalyst of the invention is due to such complexation, and the complexing conditions are dependent on the catalyst preparation method. It is a deciding factor.
또한 촉매의 활성뿐만 아니라 촉매의 열안정성을 증진시키기 위해서 촉매 전체의 전하를 중심에 가깝게 각 성분의 원소비를 조절하는 것이 중요하며 Mo12B1일때 a+b+c+d+e가 6-12이어야 한다는 것이 본 발명 촉매의 제한조건이고 위의 제한조건내에서 촉매조성물은 장기간의 조업에서 안정된 활성을 보여주었다.Also, it is important to control the activity as well as the components of the circle close to the center of the charge on the overall catalyst consumption in order to improve the thermal stability of the catalyst of the catalyst and the Mo 12 B 1 when a + b + c + d + e is 6 It should be 12 which is a limitation of the catalyst of the present invention and within the above constraints, the catalyst composition showed stable activity in long term operation.
본 발명의 고체촉매는 100% 활성형이나, 또는 실리카, 알루미나 및 실리카-알루미나 등의 담체나 지지체를 사용하여 성형물로 제조할 수 있다. 또한 분산제를 사용할 수도 있다. 분산제를 사용하면 촉매성분을 회석시켜 활성점을 분산시키므로 발열반응에서 발생하기 쉬운 촉매소결현상 및 부반응을 억제하게되고 촉매제조원가도 감소시킬 수 있다. 바람직한 분산제로는 실리콘카바이드, 그라파이트, 카올린, 키젤구어, 티타늄 및 실리카 등이 있다. 바람직한 분산제의 사용량은 분산제와 촉매조성물을 합한 중량당 5-50%이다.The solid catalyst of the present invention is 100% active, or may be formed into a molded article using a carrier or a support such as silica, alumina and silica-alumina. It is also possible to use dispersants. When the dispersant is used to disperse the active site by diluting the catalyst component, it is possible to suppress catalyst sintering and side reactions which are likely to occur in the exothermic reaction and to reduce the catalyst manufacturing cost. Preferred dispersants include silicon carbide, graphite, kaolin, kigelgear, titanium and silica and the like. The preferred amount of dispersant is 5-50% by weight of the combined dispersant and catalyst composition.
본 발명 촉매의 성형방법은 타정법이나 압출법등 어느 것이나 모두 사용할 수 있다. 촉매 제조시 성분의 원료로서 사용되는 몰리브덴은 몰리브덴산 염 및 할로겐화물 등이 사용되고 바람직하게는 몰리브덴산 암모늄이 사용된다. 비스무스, 철, 코발트, 납, 크롬, 망간, 니켈, 구리, 알칼리금속 및 알칼리 토금속들은 이들의 각종 산화물 및 수산화물, 질산화물 및 염화물 등이 사용되며 주로 질산화물이 사용된다. 인은 인산 및 포스포 몰리브덴산 등의 이종축합산 및 이들의 염 또는 유기인 화합물이 사용된다.The shaping | molding method of the catalyst of this invention can use all, such as a tableting method and an extrusion method. As the molybdenum used as a raw material for the component in the preparation of the catalyst, molybdate salts and halides are used, and ammonium molybdate is preferably used. Bismuth, iron, cobalt, lead, chromium, manganese, nickel, copper, alkali metals and alkaline earth metals are used for these various oxides and hydroxides, nitrates and chlorides, mainly nitrates. Phosphorus is used for heterocondensed acids such as phosphoric acid and phosphomolybdic acid and salts thereof or organophosphorus compounds.
위의 각 원소의 원료화합물로부터 촉매를 제조할때 바람직한 촉매제조법은 다음과 같다. 각 성분원소의 출발물질들을 복합화 조건에 따라 그룹별로 용해시킨 뒤 혼합 공침시켜 만든다. 첨가순서는 실시예 1에 예시되어 있다. 비스무스 화합물로 질산비스무스를 사용할때는 용액에 질산을 첨가하여 질산 산성수용액으로 사용한다. 물에 불용성인 텔루륨 산화물은 질산과 염산의 비가 1:1인 혼산에 녹인뒤 현탁액에 첨가한다. 현탁액을 균일하게 교반시키면서 60-80℃에서 8-12시간 동안 숙성시키고 슬러리가 될때까지 서서히 물을 증발시킨다. 현탁액의 숙성시 바람직한 산성조건은 pH 3이하이다. 슬러리는 분무건조하거나 100℃이하의 공기중에서 건조한후 촉매 혼합물내에 함유되어 있는 암모니아 및 산화질소 기체가 충분히 분해탈착될 수 있도록 210℃에서 4-5시간 하소된다. 지지체 및 분산제는 현탁액에 첨가시키거나 분무건조된 촉매분말에 첨가한다. 건조된 촉매를 성형한 후 소성하며 통상 소성온도는 300-800℃이며 몰리브덴의 승화성 및 촉매소결 현상을 피하기 위해서는 400-600℃에서 4-6시간 공기하에서 소성하는 것이 바람직하다.Preferred catalyst preparation methods for preparing catalysts from the raw compounds of the above elements are as follows. Starting materials of each component are dissolved by group according to the complexing conditions and mixed coprecipitation is made. The order of addition is illustrated in Example 1. When bismuth nitrate is used as the bismuth compound, nitric acid is added to the solution and used as an acidic nitric acid solution. Tellurium oxide, which is insoluble in water, is dissolved in a mixed acid having a ratio of nitric acid and hydrochloric acid 1: 1 and added to the suspension. The suspension is aged for 8-12 hours at 60-80 ° C. with uniform stirring and water is slowly evaporated until it is a slurry. Preferred acidic conditions upon aging of the suspension are below pH 3. The slurry is calcined at 210 ° C. for 4-5 hours to allow for sufficient decomposition and desorption of the ammonia and nitric oxide gas contained in the catalyst mixture after spray drying or drying in air below 100 ° C. The support and dispersant are added to the suspension or to the spray dried catalyst powder. The dried catalyst is molded and then fired, and the firing temperature is usually 300-800 ° C., and it is preferable to fire at 400-600 ° C. for 4-6 hours under air to avoid the sublimation of the molybdenum and the catalyst sintering phenomenon.
본 발명의 촉매는 비교적 낮고 넓은 반응조건에서 조업이 가능하며, 특히 부산물의 종류와 양이 매우 적으면서 높은 수율로 메타크롤레인을 제조할 수 있다. 본 발명의 촉매로 이소부틸렌을 산화시킬 경우 폐가스중에서 CO와 CO2를 제외한 유기물중의 메카크롤레인 순도는 98.5GC Area% 이상이다.The catalyst of the present invention can be operated under relatively low and wide reaction conditions, and in particular, it is possible to prepare methacrolein with high yields with very few kinds and amounts of by-products. When isobutylene is oxidized by the catalyst of the present invention, the mechacrolein purity in organic matter except CO and CO 2 in the waste gas is 98.5 GC Area% or more.
원료기체인 이소부틸렌은 고순도일 필요가 없으며 질소, 일산화탄소, 이산화탄소 등의 불활성기체 또는 수증기와 함께 공급된다. 산소의 주된 공급원은 공기이다. 이소부틸렌에 대한 산소의 비율은 몰비로 1-5이며 바람직하게는 1-3의 범위이다. 이소부틸렌의 농도는 2.5-12부피%가 적당하다. 반응온도는 통상 250-500℃의 범위이고 바람직하게는 310-420℃범위이다. 원료기체의 공간속도는 800-2500hr-1이고 바람직하게는 1200-2000hr-1의 범위이다. 바람직한 반응압력은 0-100psig의 범위이고 더욱 바람직하게는 0-50psig이다.Isobutylene, a raw material gas, does not need to be of high purity and is supplied with inert gas or water vapor such as nitrogen, carbon monoxide and carbon dioxide. The main source of oxygen is air. The ratio of oxygen to isobutylene is 1-5 in molar ratio, preferably in the range of 1-3. The concentration of isobutylene is suitably 2.5-12% by volume. The reaction temperature is usually in the range of 250-500 ° C. and preferably in the range of 310-420 ° C. The space velocity of the raw material gas is 800-2500hr −1 and preferably in the range of 1200-2000hr −1 . Preferred reaction pressures range from 0-100 psig and more preferably 0-50 psig.
본원서에 촉매의 전환율, 메타크롤레인의 선택도, 메타크롤레인의 수율은 다음식으로 정의된다.In the present application, the conversion of the catalyst, the selectivity of methacrolein, and the yield of methacrolein are defined by the following formula.
메타크롤레인 수율(%)=전환율×선택도/100Methacrolein yield (%) = conversion rate × selectivity / 100
실시예를 들어 설명하면 다음과 같다.An example is described as follows.
[실시예 1]Example 1
Mo12Bi1Fe3Co3Ni1Pb1Si5.5Cu0.5Rb0.65Ox Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 Cu 0.5 Rb 0.65 O x
파라몰리브덴산암모늄 100g과 염화루비듐 3.71g을 60℃에서 500ml의 증류수에 녹이고 여기에 실리카분말 15.6g을 잘 분산시킨다(용액 A). 질산철 57.2g, 질산코발트 41.2g, 질산니켈 13.7g, 질산납 15.6g 및 질산구리 5.5g을 60℃에서 600ml의 증류수에 녹인다(용액 B). 질산비스무스 22.9g을 상온에서 묽은 질산용액에 녹인다(용액 C). 용액의 A에 용액 B를 적하하여 공침시킨후 요액 C를 첨가하고 60-80℃에서 강하게 교반하면서 8-10시간 숙성시킨다. 숙성된 촉매는 슬러리 상태가 될때까지 물을 증발시키고 100℃이하에서 건조시킨후 210℃에서 4시간 하소한다. 하소된 촉매는 성형후 10-20메시 크기로 선별하고 550℃에서 공기 분위기에서 6시간 소성하여 활성화시킨다. 촉매 20ml를 내부직경이 12mm인 스테인레스 튜브반응기에 충진하고 대기압에서 공급기체의 몰비가 이소부틸렌/공기/질소=6/54/40의 조건에서 반응시킨다. 이때 접촉시간은 2.25초로 하였다. 반응결과는 표 1에 나타내었다. 반응경과시간은 400시간이다.100 g of ammonium paramolybdate and 3.71 g of rubidium chloride are dissolved in 500 ml of distilled water at 60 ° C., and 15.6 g of silica powder is dispersed well (solution A). 57.2 g of iron nitrate, 41.2 g of cobalt nitrate, 13.7 g of nickel nitrate, 15.6 g of lead nitrate, and 5.5 g of copper nitrate are dissolved in 600 ml of distilled water at 60 ° C (solution B). 22.9 g of bismuth nitrate is dissolved in dilute nitric acid solution at room temperature (solution C). The solution B was added dropwise to the solution A to coprecipitate. The aged catalyst is evaporated until it is in a slurry state, dried at 100 ° C. or lower, and calcined at 210 ° C. for 4 hours. The calcined catalyst is sorted to a size of 10-20 mesh after molding and activated by firing at 550 ° C. for 6 hours in an air atmosphere. 20 ml of the catalyst is charged into a stainless tube reactor having an internal diameter of 12 mm and reacted at a molar ratio of feed gas at isobutylene / air / nitrogen = 6/54/40 at atmospheric pressure. At this time, the contact time was 2.25 seconds. The reaction results are shown in Table 1. The reaction elapsed time is 400 hours.
[실시예 2-14]Example 2-14
Mo12BiyFeaCobNicPbdSieCu0.5Rb0.65Ox Mo 12 Bi y Fe a Co b Ni c Pb d Si e Cu 0.5 Rb 0.65 O x
실시예 1의 촉매성분 등 필수성분인 비스무스, 철, 코발트, 니켈, 납 및 규소의 조성을 변화시켜 보았다. 실시예 2-14의 촉매성분의 조성비는 표 1에 기재된 바와 같으며 실시예 1과 동일한 방법으로 제조하였다. 반응조건과 반응경과 시간도 실시예 1과 동일하였고 반응결과는 표 1에 기재하였다.The composition of bismuth, iron, cobalt, nickel, lead, and silicon, which are essential components such as the catalyst component of Example 1, was changed. Composition ratios of the catalyst component of Example 2-14 are as described in Table 1 and prepared in the same manner as in Example 1. Reaction conditions and reaction time were also the same as in Example 1, and the reaction results are shown in Table 1.
[표 1]TABLE 1
Mo12BiyFeaCobNicPbdSieCu0.5Rb0.65Ox촉매의 이소부틸렌 산화반응Isobutylene Oxidation of Mo 12 Bi y Fe a Co b Ni c Pb d Si e Cu 0.5 Rb 0.65 O x Catalyst
[실시예 15-24]Example 15-24
Mo12Bi1Fe3Co3Ni1Pb1AfRb0.5Ox Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 A f Rb 0.5 O x
실시예 1의 촉매성분중 구리의 조성을 바꾸고 다른 금속으로 치환시켜 보았다. 실시예 15-24의 촉매성분의 원소비는 표 2에 기재된 바와 같으며 실시예 1과 동일한 방법으로 제조하였다. 반응조건과 반응경과시간도 실시예 1과 동일하다. 반응결과는 표 2에 기재하였다.The composition of copper in the catalyst component of Example 1 was changed and replaced with another metal. The element ratios of the catalyst components of Examples 15-24 were as shown in Table 2 and prepared in the same manner as in Example 1. Reaction conditions and reaction elapsed time are also the same as in Example 1. The reaction results are shown in Table 2.
[표 2]TABLE 2
Mo12Bi1Fe3Co3Ni1Pb1Si5.5AfRb0.65Ox촉매의 이소부틸렌 산화반응Isobutylene Oxidation of Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 A f Rb 0.65 O x Catalyst
[실시예 25-38]Example 25-38
Mo12Bi1Fe3Co3Ni1Pb1Si5.5Cu0.5DgOx Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 Cu 0.5 D g O x
실시예 1의 촉매성분중 루비듐을 다른 알칼리 및 알칼리토금속으로 치환시켜 보았다. 실시예 25-38의 촉매성분의 조성비는 표 3에 기술된 바와 같으며 실시예 1과 동일한 방법으로 제조하였다. 반응조건과 반응경과 시간도 실시예 1과 동일하며 반응결과는 표 3에 기재하였다.In the catalyst component of Example 1, rubidium was replaced with other alkali and alkaline earth metals. Composition ratios of the catalyst components of Examples 25-38 are as described in Table 3 and prepared in the same manner as in Example 1. Reaction conditions and reaction time were also the same as in Example 1, and the reaction results are shown in Table 3.
[표 3]TABLE 3
Mo12Bi1Fe3Co3Ni1Pb1Si5.5Cu0.5Dg5Ox촉매의 이소부틸렌 산화반응Isobutylene Oxidation of Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 Cu 0.5 D g5 O x Catalyst
[실시예 39-44]Example 39-44
실시예 1의 조성을 갖는 촉매의 반응조건중에서 반응온도와 반응압력을 변화시켰다. 반응온도와 반응압력 이외의 반응조건은 실시예 1과 동일하였다. 실시예 39-44의 반응조건과 반응결과는 표 4에 기재되어 있다.In the reaction conditions of the catalyst having the composition of Example 1, the reaction temperature and the reaction pressure were changed. Reaction conditions other than the reaction temperature and the reaction pressure were the same as in Example 1. The reaction conditions and reaction results of Examples 39-44 are shown in Table 4.
[표 4]TABLE 4
Mo12Bi1Fe3Co3Ni1Pb1Si5.5Cu0.5Rb0.65Ox촉매의 이소부틸렌 산화반응Isobutylene Oxidation of Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 Cu 0.5 Rb 0.65 O x Catalyst
[실시예 45]Example 45
실시예 1의 조성을 갖는 촉매를 6000시간 반응시킨 후 반응시작으로부터 반응성을 비교하였다. 반응 결과는 표 5에 기술되어 있다. 반응조건은 실시예 1과 동일하다. 그 결과는 6000시간 동안 반응성의 변화가 거의 없었다.After reacting the catalyst having a composition of Example 1 6000 hours, the reactivity was compared from the start of the reaction. The reaction results are described in Table 5. The reaction conditions are the same as in Example 1. The result showed little change in reactivity over 6000 hours.
[표 5]TABLE 5
Mo12Bi1Fe3Co3Ni1Pb1Si5.5Cu0.5Rb0.5Ox촉매의 수명실험Life Test of Mo 12 Bi 1 Fe 3 Co 3 Ni 1 Pb 1 Si 5.5 Cu 0.5 Rb 0.5 O x Catalyst
[비교 실시예 1-5]Comparative Example 1-5
Mo12Bi1FeaCobNicPbdSieCu0.5Rb0.65Ox Mo 12 Bi 1 Fe a Co b Ni c Pb d Si e Cu 0.5 Rb 0.65 O x
실시예 1의 촉매성분 중 필수성분인 철, 코발트, 니켈, 납 및 규소중 한가지를 제거하였다. 비교실시예 1-5의 촉매성의 조성비는 표 6에 기재된 바와 같으며 실시예 1과 동일한 방법으로 제조하였다. 반응조건은 실시예 1과 동일하며 반응경과시간과 반응결과는 표 6에 기재하였다.One of the essential components of the catalyst component of Example 1, iron, cobalt, nickel, lead and silicon, was removed. The compositional ratio of catalytic properties of Comparative Example 1-5 was as described in Table 6 and prepared in the same manner as in Example 1. The reaction conditions are the same as in Example 1, and the reaction elapsed time and the reaction results are shown in Table 6.
[표 6]TABLE 6
Mo12Bi1FeaCobNicPbdSieCu0.5Rb0.65Ox촉매의 이소부틸렌 산화반응Isobutylene Oxidation of Mo 12 Bi 1 Fe a Co b Ni c Pb d Si e Cu 0.5 Rb 0.65 O x Catalyst
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| KR1019880008101A KR900004117B1 (en) | 1988-06-30 | 1988-06-30 | Catalyst for preparing methacrolein from isobutylene |
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| WO2009044999A1 (en) * | 2007-10-02 | 2009-04-09 | Sk Energy Co., Ltd. | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using said catalysts |
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| WO2009044999A1 (en) * | 2007-10-02 | 2009-04-09 | Sk Energy Co., Ltd. | Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using said catalysts |
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