• Title/Summary/Keyword: 촉매 비활성화

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Catalytic Hydrogenation of Unsaturated Organic Compounds by Rutheniumhydridonitrosyl Complexes (Rutheniumhydridonitrosyl 착물을 이용한 불포화 유기화합물의 수소화 반응)

  • Park, Mi Young;Kim, Young Joong;Cho, Ook Jae;Lee, Ik Mo
    • Journal of the Korean Chemical Society
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    • v.40 no.6
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    • pp.445-452
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    • 1996
  • Catalytic hydrogenation of ketones and aldehydes by RuH(NO)$L_3$ ($L_3$: $PPh_3$, PhP($CH_2CH_2PPh_2$)$_2$(etp)) was investigated to examine the reaction mechanism and the competence of hydridonitrosyl complexes as catalysts for organic synthesis. RuH(NO)$L_3$ showed catalytic activity for the hydrogenation and the activities of catalysts were dependent on the steric and electronic factors. The less the steric demands of the substrates become, the more activity the catalysts show. For the electronic effect, the more the partial positive charge on the carbonyl carbon atom in ketones becomes and the more the double bond character of carbonyl group in aldehydes becomes, the more active the catalysts are. These results reflect the difference of reaction mechanisms of two substrates, ketones and aldehydes. Catalytic activities of RuH(NO)(etp) and RuH(NO)($PPh_3$)$_3$ in the presence of extra $PPh_3$ toward hydrogenation showed the existence of a reaction pathway accompanied with the change of the bonding modes of NO ligand. The roles of excess $PPh_3$ change with increase of the mole ratio of $PPh_3$ to catalysts; prevention of ligand dissociation from comlexes → bases → ligands. The activity of RuH(NO)(etp) was lower than that of RuH(NO)($PPh_3$)$_3$ toward the hydrogenation of the same substrates mainly due to the structural difference. These catalysts showed the selectivity toward olefin hydrogenation over carbonyl groups in the competitive reaction.

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Selective Epoxidation of Di-cyclopentadiene Using Ti Containing Zeolite Catalyst (Ti 함유 제올라이트 촉매를 이용한 디시클로펜타디엔의 선택적 에폭시화 반응)

  • Lee, GiBbum;Ko, MoonKyu;Kim, YoungWun;Chung, KeunWo;Yoon, ByungTae;Kim, SeongBo
    • Applied Chemistry for Engineering
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    • v.23 no.6
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    • pp.614-617
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    • 2012
  • Ti-containing zeolite was synthesised and used in the epoxidation of di-cyclopentadiene (DCPD). Among various Ti-zeolite catalysts, Y contained Ti-zeolite showed the highest yield in the epoxidation of DCPD. The study was also investigated in terms of the Ti content in the catalysts, $H_2O_2$/substrate ratio, reaction temperature and applied time. The reaction conditions significantly influenced on both the catalytic activity and selectivity. In addition, Ti structure in the zeolite was analyzed using IR and UV-vis spectroscopy.

Promoter Effect on Ni/YSZ Anode Catalyst of Solid Oxide Fuel Cell for Suppressing Coke Formation in the Methane Internal Reforming (고체산화물 연료전지용 Ni/YSZ 음극 촉매에서의 메탄 내부개질 반응 시 탄소 침적 억제를 위한 첨가제 영향)

  • Kim, Hye-Roung;Choi, Ji-Eun;Youn, Hyun-Ki;Chung, Jong-Shik
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.813-818
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    • 2008
  • Various additives were added in small amounts on Ni/YSZ anode of SOFC (solid oxide fuel cell) in order to improve reactivity and to inhibit deactivation due to coke deposition during methane reforming using a low mole ratio steam ($H_2O/CH_4=1.5$) at $800^{\circ}C$. Ni/YSZ catalysts added with various perovskites did not show any improvement but exhibited a gradual decrease in the methane conversion. K-doped Ni/YSZ showed a steady increase and maintenance of the conversion up to 42 hours, after which there was an abrupt deactivation of catalyst owing to potassium loss by volatilization. Addition of 5% of $K_2Ti_2O_5$ on Ni/YSZ showed a stable maintenance of the conversion without K loss, and was able to prevent coke formation during a long time operation. Deactivation of catalyst during the reaction was mainly caused by the accumulation of graphidic carbon on the catalyst surface.

Highly dispersed $Ru/{\alpha}-Al_2O_3$ Catalyst development for selective CO oxidation reaction (선택적 CO 산화반응을 위한 고분산된 $Ru/{\alpha}-Al_2O_3$ 촉매개발)

  • Eom, HyunJi;Koo, KeeYoung;Jung, UnHo;Rhee, YoungWoo;Yoon, WangLai
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.228.1-228.1
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    • 2010
  • 선택적 CO 산화반응(PrOx)을 위한 Ru이 고분산 담지된 $Ru/{\alpha}-Al_2O_3$ 촉매를 증착-침전법(deposition-precipitation)으로 제조하였다. 용액의 pH와 aging 시간에 따른 Ru 입자의 크기 변화와 분산도의 영향을 살펴보았으며 함침법(impregnation)으로 비교 촉매를 제조하였다. 촉매의 특성분석은 BET, TPR, CO-Chemisorption분석을 수행하여 촉매의 비표면적, 환원특성, 분산도를 알 수 있었다. 특성분석결과, 증착-침전법으로 제조한 $Ru/{\alpha}-Al_2O_3$ 촉매가 함침법으로 제조한 촉매에 비해 분산도가 높았으며, pH별 촉매 제조에서는 pH6.5로 제조한 촉매가 22.06%로 가장 높은 분산도를 보였다. 또한, 담체의 비표면적 영향에 따른 Ru 입자의 분산도를 살펴보기 위해 ${\gamma}-Al_2O_3$${\alpha}-Al_2O_3$ 담체를 적용한 결과, 비표면적이 작은 ${\alpha}-Al_2O_3$ 담체 표면에서 Ru 분산도가 ${\gamma}-Al_2O_3$ 담체에 비해 높았다. 이는 기공이 발달하여 비표면적이 넓은 ${\gamma}-Al_2O_3$ 담체는 소량의 Ru을 고분산 담지 시 담체 표면보다는 기공 내에 담지 되는 양이 많아 실제 반응 시 반응에 참여하는 표면 활성 금속양이 적음을 알 수 있다. 특히, 선택적 산화반응과 같이 표면에서 빠른 반응이 일어나는 경우, 기공 내부의 활성금속이 반응에 참여하기 어려워 반응 활성이 낮음을 PrOx 반응실험을 통해 확인할 수 있었다. PrOx test 조건은 GHSV 250000~60000, 온도는 80~200도, 람다값은 2~4로 성능 비교하여 실험 하였다. PrOx의 성능평가 결과 담체를 ${\alpha}-Al_2O_3$를 사용하여 deposition-precipitation방법으로 제조한 pH6.5 촉매에서 $100{\sim}160^{\circ}C$에서 90%의 가장 높은 CO conversion을 가지고 18%의 선택도를 가졌다.

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Hydrotreating for Stabilization of Bio-oil Mixture over Ni-based Bimetallic Catalysts (Ni계 이원금속 촉매에 의한 혼합 바이오오일의 안정화를 위한 수소첨가 반응)

  • Lee, Seong Chan;Zuo, Hao;Woo, Hee Chul
    • Clean Technology
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    • v.27 no.1
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    • pp.69-78
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    • 2021
  • Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.

Effect of reaction temperature on synthesis of heptafluoropropane over activated carbon (활성탄상의 heptafluoropropane 합성에서 반응온도의 효과)

  • 김재덕;이윤우;임종성;이경환;이윤용
    • Fire Science and Engineering
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    • v.12 no.1
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    • pp.9-14
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    • 1998
  • The hepatfluoropropane(HFC-227ea) synthesis by fluorinatino of hepafluoroproylene(HFP) over activated carbon has been studied. The reaction temperature was varied from 5$0^{\circ}C$ to 40$0^{\circ}C$ at a constant feed mole ration and a residence time. The optimized reaction temperature was found to be about 20$0^{\circ}C$ at 2.5HF/HFP mole ratio and 238 sec. residence time. From these reaction conditions, the yield of HFC-227ea was obtained above 99% and the deactivation of activated carbon was not appeared. Accordingly, the activated carbon showed good performance to obtain heptafluoropropane by fluorinatin of hexafluoropropylene.

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Regeneration of TS-1 Catalyst During Phenol Hydroxylation(Calcination temperature dependence) (페놀의 수산화 반응에 사용한 TS-1 촉매의 효과적인 재생 방법(소성 온도 의존성))

  • Kwon, Song Yi;Yoon, Songhun;Um, Kyung Sub;Lee, Jae Wook;Lee, Chul Wee
    • Korean Chemical Engineering Research
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    • v.48 no.6
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    • pp.679-683
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    • 2010
  • In this study, calcination temperature dependence of TS-1 catalyst was investigated in the hydroxylation of phenol with hydrogen peroxide during the regeneration of catalyst. Catalyst was regenerated 5 times by calcining at $550^{\circ}C$ and $700^{\circ}C$, respectively. When the catalyst was regenerated at $550^{\circ}C$ after 5th regeneration phenol conversion was decreased from 22.9% to 15.1% and at $700^{\circ}C$ after 5th regeneration phenol conversion was decreased from 22.9% to 18.8%. For formation ratio of catechol/hydroquinone was increased from 1.28 to 1.45 after 5th regeneration at $550^{\circ}C$, and from 1.28 to 1.20 after 5th regeneration at $700^{\circ}C$. The main reasons for deactivation of the catalyst were suggested by analyzing chemical/physical properties with XRD, UV-vis spectra, $N_2$ adsorption/desorption and TGA, and evaluating the catalytic activity such as phenol conversion and product selectivity.

Thermal Deactivation of Plate-type V2O5-WO3/TiO2 SCR Catalyst (Plate-type V2O5-WO3/TiO2 SCR 촉매의 열적 비활성화 특성)

  • Cha, Jin-Sun;Park, Jin-Woo;Jeong, Bora;Kim, Hong-Dae;Park, Sam-Sik;Shin, Min-Chul
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.576-580
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    • 2017
  • In the present paper, the thermal deactivation characteristics of plate-type commercial $V_2O_5-WO_3/TiO_2$ SCR catalyst were investigated. For this purpose, the plate-type catalyst was calcined at different temperatures ranging from $500^{\circ}C$ to $800^{\circ}C$ for 3 hours. Structural and morphological changes were characterized byXRD, specific surface area, porosity, SEM-EDS and also NOx conversion with ammonia according to the calcine temperature. The NOx conversion decreased with increasing calcine temperature, especially when the catalysts were calcined at temperatures above $700^{\circ}C$. This is because the crystal phase of $TiO_2$ changed from anatase to rutile, and the $TiO_2$ grain growth and $CaWO_4$ crystal phase were formed, which reduced the specific surface area and pore volume. In addition, $V_2O_5$, which is a catalytically active material, was sublimated or vaporized over $700^{\circ}C$, and a metal mesh used as a support of the catalyst occurred intergranular corrosion and oxidation due to the formation of Cr carbide.

Development of hydrogen production process using combined steam and $CO_2$ reforming of natural gas (천연가스의 수증기 및 이산화탄소 복합 개질을 이용한 수소 생산 공정 개발)

  • Seo, Yu-Taek;Seo, Dong-Ju;Roh, Hyun-Seog;Jeong, Un-Ho;Koo, Kee-Young;Jang, Won-Jin;Yoon, Wang-Lai
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.11a
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    • pp.75-78
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    • 2007
  • 천연가스의 수증기 및 이산화탄소 복합 개질은 탄화수소화합물과 이산화탄소를 원료로 사용하여 수소를 생산하는 공정으로, 온실가스로 지목되고 있는 주요 화합물을 수소와 일산화탄소 혼합 가스로 전환시켜 합성 반응 또는 연료전지에 사용할 수 있도록 해준다. 본 연구에서는 $MgAl_2O_4$를 지지체로 하는 니켈계 촉매를 제조하여 수증기 및 이산화탄소 복합 개질 반응에 사용하였으며, 기존의 수증기 개질촉매 적용 시 문제가 되었던 탄소 침적에 의한 촉매 비활성화를 피할 수 있었다. 개발된 촉매 레시피를 바탕으로 펠릿 촉매를 제조하여 0.1 bpd규모의 Fischer-Tropsch 합성 반응에 적용 가능한 튜브형 반응기에 적용하여 수증기 및 이산화탄소 복합 개질 반응을 실시하였으며, 반응기의 온도 구배, 가스 조성 변화를 관찰하였다. 반응 조건에 따른 촉매 및 반응기의 성능 최적화를 실시하여 최적 촉매 및 반응기 성능을 모색하고자 하였다.

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Preparation of Water-based Magnetic Fluids with Spent Iron Oxide Catalyst (산화철 폐촉매로부터 수상 자성유체 제조방법)

  • Lee, Hyo-Sook;Shao, Hui-Ping;Kim, Chong-Oh
    • Journal of the Korean Magnetics Society
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    • v.15 no.1
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    • pp.37-41
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    • 2005
  • We prepared water-based magnetic fluids with the spent iron oxide catalysts which were used in the styrene monomer production process. The catalyst was composed with 70% magnetite and alkali metals. The water-based magnetic fluids were prepared by mechanical grinding with olecic acid as a surfactant and water in an attritor. The magnetization of the water-based magnetic fluids was 22 emu/g in the 10 kOe.