• Title/Summary/Keyword: Homogeneous catalyst

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Heterogeneous SnCl2/SiO2 versus Homogeneous SnCl2 Acid Catalysis in the Benzo[N,N]-heterocyclic Condensation

  • Darabi, Hossein Reza;Aghapoor, Kioumars;Mohsenzadeh, Farshid;Jalali, Mohammad Reza;Talebian, Shiva;Ebadi-Nia, Leila;Khatamifar, Ehsan;Aghaee, Ali
    • Bulletin of the Korean Chemical Society
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    • v.32 no.1
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    • pp.213-218
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    • 2011
  • The scope of homogeneous Lewis acid-catalyzed benzo[N,N]-heterocyclic condensation was expanded to include the use of various metal salts not reported in the literature and $SnCl_2{\cdot}2H_2O$ was finally selected. Among various solid supports activated with $SnCl_2$, heterogeneous $SnCl_2/SiO_2$ proved to be the most effective and significantly higher conversions were achieved compared to $SnCl_2{\cdot}2H_2O$ itself. The results of TG-DTA and BET indicated that dispersed $SnCl_2$ coordinates with surface hydroxyl groups of silica leading to formation of stable Lewis acid sites. Low catalyst loading, operational simplicity, practicability and applicability to various substrates render this eco-friendly approach as an interesting alternative to previously applied procedures.

Synthesis of Cyclododecatriene from 1,3-Butadiene by Trimerization over Amine-Titanium Complex Catalyst (아민-티타늄착체 촉매상에서 1,3-부타디엔의 삼량화반응에 의한 싸이클로도데카트리엔의 합성)

  • Park, Da Min;Kim, Gye-Ryeong;Lee, Ju Hyun;Cho, Deuk Hee;Kim, Geon-Joong
    • Korean Chemical Engineering Research
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    • v.51 no.3
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    • pp.394-402
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    • 2013
  • The new complex catalysts were synthesized by the reaction of titanium compounds (titanium chloride or titanium butoxide) and diamines in this work, and they showed very high catalytic activities for the cyclododecatriene (CDT) synthesis from 1,3-butadiene through trimerization. CDT synthetic reaction was performed in an autoclave reactor, and the effects of reaction temperature, type of catalyst, catalyst amount added into the system, the mole ratio of Al/Ti and immobilization method were investigated on the yield of product CDT. The titanium complex catalyst combined to diamine with 1:1 ratio showed high selectivity to CDT more than 90%. The ratio of TTT-CDT/TTC-CDT isomers in the product revealed as different values, depending on the type of diamine combined to titanium and Ti/diamine ratios. Those homogeneous complexes could be used as a heterogenized catalyst after anchoring on the supports, and the immobilized titanium catalyst retained the catalytic activities for several times in the recycled reactions without leaching. The carbon support containing titanium has exhibited superior activity to the silica support. Especially, when the titanium complex was anchored on the support which was fabricated by the hydrolysis of tripropylaminosilane itself, the resulting titanium catalyst showed the highest BD conversion and CDT selectivity.

Direct Preparation of Dichloropropanol from Glycerol over Acetin Catalyst (아세틴 촉매상에서 글리세롤로부터 디클로로프로판올의 직접 제조)

  • Song, Sun-Ho;Park, Dong-Ryul;Woo, Sung-Yul;Song, Won-Seob;Kwon, Myong-Suk;Song, In-Kyu
    • Clean Technology
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    • v.15 no.1
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    • pp.42-46
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    • 2009
  • Solvent-free direct preparation of dichloropropanol (DCP) from glycerol (by-product of bio-diesel production) and hydrochloric acid gas was carried out over acetin catalyst in a gas-liquid batch reactor. For this purpose, acetin mixture and triacetin were used as a homogeneous acetin catalyst. Performance in the acetin-catalyzed reaction was compared to that in the non-catalytic reaction under the same reaction conditions ($110^{\circ}C$, 3 bar, 3 h). Conversion of glycerol in the acetin-catalyzed reactions was ca. 3% higher than that in the non-catalytic reaction, and selectivity for dichloropropanol in the acetin-catalyzed reactions was ca. 50% higher than that in the non-catalytic reaction. It was also revealed that the catalytic performance of triacetin was ca. 2% higher than that of acetic mixture.

Controlling the Growth of Few-layer Graphene Dependent on Composition Ratio of Cu/Ni Homogeneous Solid Solution

  • Lim, Yeongjin;Choi, Hyonkwang;Gong, Jaeseok;Park, Yunjae;Jeon, Minhyon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.273.1-273.1
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    • 2014
  • Graphene, a two dimensional plane structure of $sp^2$ bonding, has been promised for a new material in many scientific fields such as physics, chemistry, and so on due to the unique properties. Chemical vapor deposition (CVD) method using transitional metals as a catalyst can synthesize large scale graphene with high quality and transfer on other substrates. However, it is difficult to control the number of graphene layers. Therefore, it is important to manipulate the number of graphene layers. In this work, homogeneous solid solution of Cu and Ni was used to control the number of graphene layers. Each films with different thickness ratio of Cu and Ni were deposited on $SiO_2/Si$ substrate. After annealing, it was confirmed that the thickness ratio accords with the composition ratio by X-ray diffraction (XRD). The synthesized graphene from CVD was analyzed via raman spectroscopy, UV-vis spectroscopy, and 4-point probe to evaluate the properties. Therefore, the number of graphene layers at the same growth condition was controlled, and the correlation between mole fraction of Ni and the number of graphene layers was investigated.

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Development of Internal Reforming Catalysts using Homogeneous Precipitation (균일용액 침전법을 이용한 내부개질촉매 개발에 대한 연구)

  • Jung, You-Shick;Rhee, Young-Woo;Koo, Kee-Young;Jung, Un-Ho;Youn, Wang-Lai;Seo, Yong-Seog
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.11a
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    • pp.199-202
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    • 2009
  • 본 연구에서는 내부 개질반응에서 사용되는 고함량의 니켈촉매(Ni/Al2O3계열 촉매)제조를 위해, 요소(urea)를 이용한 균일용액 침전법을 이용하여 니켈이 고분산된 52wt% Ni/$Al_2O_3$ 촉매를 제조하였다. 제조 촉매는 BET 표면적, 니켈분산도, 니켈표면적 등 물리.화학적 물성 모두 우수하였으며, 환원 패턴은 상용촉매와 비슷하게 나타났다. 실제 반응온도인 $650^{\circ}C$에서 소성하여 화학흡착을 비교한 결과,상용촉매는 니켈분산도 및 니켈표면적이 감소한 반면 균일용액 침전법으로 제조한 촉매는 거의 변화가 없었다. 개질 성능 또한 상용촉매보다 우수하였는데, 이것은 균일용액 침전법으로 제조한 촉매는 활성점(니켈)이 지지체에 나노사이즈로 고르게 잘 분산되었기 때문이라고 판단하였다. 또한 합성온도 조절을 통해, $650^{\circ}C$ 소성 후에 물성변화를 살펴보았고 합성온도 $85^{\circ}C$에서 고분산 니켈 촉매 제조가 가능하였다.

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Characteristics of Transesterification Reaction of Soy Bean Oil by Acid Catalysts (산촉매에 의한 대두유의 전이에스테르화 반응 특성)

  • Shin, Yong-Seop
    • Journal of Environmental Science International
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    • v.18 no.2
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    • pp.231-238
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    • 2009
  • Characteristics of the transesterification reaction between triglycerides in soy bean oil and methanol were investigated in the presence of acid catalysts. such as sulfuric acid and PTS (p-toluene sulfonic acid). Concentrations of diglyceride and monoglyceride which were intermediates in the reaction mixtures, were far below 10% of triglyceride under any reaction conditions. Thus, conversion of the reaction could be determined from the concentration of triglyceride. Dried PTS had more superior catalytic power than sulfuric acid for transesterification reaction between soy bean oil and methanol. When transesterification reaction of soy bean oil was catalyzed by 1 wt% of PTS at methanol stoichiometric mole ratio of 2 and $65^{\circ}C$, final conversion reached 95% within 48 hours. If FAME (fatty acid methyl ester) was added into reaction mixture of soy bean oil, methanol and PTS catalyst, it converted reaction mixture into homogeneous phase, and substantially increased reaction rate. When reaction mixture was freely boiling which had equal volumetric amount of FAME to soy bean oil, methanol stoichiometric mole ratio of 2 and 1 wt% of PTS, final conversion achieved value of 94% and temperature approached to $110^{\circ}C$ within 2 hours.

Effect of Water and Aluminum Sulfate Mole Ratio on Pore Characteristics in Synthesis of AlO(OH) Nano Gel by Homogeneous Precipitation (균일침전에 의한 AlO(OH) 나노 겔 합성에서 물/황산알루미늄의 몰 비가 세공특성에 미치는 영향)

  • Choe, Dong-Uk;Park, Byung-Ki;Lee, Jung-Min
    • Journal of the Korean Ceramic Society
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    • v.43 no.9 s.292
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    • pp.564-568
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    • 2006
  • AlO(OH) nano gel is used in precursor of ceramic material, coating material and catalyst. For use of these, not only physiochemical control for particle morphology, pore characteristic and peptization but also studies of synthetic method for preparation of advanced application products were required. In this study, AlO(OH) nano gel was prepared through the aging and drying process of aluminum hydroxides gel precipitated by the hydrolysis reaction of dilute NaOH solution and aluminum sulfate solution. In this process, optimum synthetic condition of AlO(OH) nano gel having excellent pore volume as studying the effect of water and aluminum sulfate mole ratio on gel precipitates has been studied. Water and aluminum sulfate mole ratio brought about numerous changes on crystal morphology, surface area, pore volume and pore size. Physiochemical properties were investigated as using XRD, TEM, TG/DTA, FT-IR, and $N_2$ BET method.

Inhibition of Side Reactions Forming Dimers of Diols in the Selective Hydrogenation of Methacryl Aldehyde (메타아크릴 알데히드의 선택적 수소화에서 2가 알코올의 이합체 형성 부반응 억제효과)

  • Kook-Seung Shin;Mi-Sun Cha;Kyoung-Ku Kang;Chang-Soo Lee
    • Clean Technology
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    • v.29 no.2
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    • pp.79-86
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    • 2023
  • The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

Operation characteristics of partial oxidation reformer for transportation fuels (수송 연료용 부분산화 개질기의 운전특성)

  • Lee, Sangho;Bae, Joongmyeon
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.159.1-159.1
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    • 2011
  • Partial oxidation reformer was fabricated and operated using commercial transportation fuels. Fuel injector and heating coil were used for fuel atomization and startup, respectively. The reformer was designed to produce syngas for $150{\sim}200W_e$ class solid oxide fuel cell. The reformer was operated in the $O_2$/C range between 0.6 and 0.8 while the capacity was fixed at $150W_e$. The temperature range in catalyst bed was between $500^{\circ}C$ and $900^{\circ}C$. Only 83% fuel was converted to $H_2$, CO, $CO_2$ and $CH_4$ at the operating conditions. The lowest temperature increase to $700^{\circ}C$ when the reformer was operated at $200W_e$, Although the temperature profiles was improved, fuel conversion was 88%. On the other hand, fuel was completely converted when micro-reactor operated at the same condition. This difference maybe due to aromatic compounds formation at homogeneous region. In addition, a significant amount of coke deposition was observed at vent line. Homogeneous reaction depends on the degree of mixing. For this purpose, two fluid nozzle and Ultra sonic injector were compared to investigate the effect of atomization. Sauter mean diameter(SMD) of Ultra sonic injector was lower than two-fluid nozzle at test condition. However, conversion efficiency and fuel conversion were not improved by using two-fluid nozzle. these results imply that the temperature of homogeneous reaction region should be controlled to prevent coke formation.

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Effects of Concentration of Precipitants and Aging Time on Synthesis of Mn-Substituted Barium Hexaaluminates by Homogeneous Precipitation (균일용액침전법을 이용한 침전제의 농도와 합성 시간에 따른 Mn이 대체된 바륨 헥사알루미네이트의 합성의 영향)

  • Park, Ji Yun;Jung, You Shick;Rhee, Young Woo
    • Korean Chemical Engineering Research
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    • v.56 no.3
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    • pp.349-355
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    • 2018
  • $BaMnAl_{11}O_{19}$ was prepared by urea-induced homogeneous precipitation and characterized by X-ray diffraction and scanning electron microscopy. At increased precipitant concentrations, AlOOH replaced $Al(OH)_3$ as an Al precursor. $BaMnAl_{11}O_{19}$ exhibited enhanced catalytic combustion performance and inhibited CO generation. Catalytic performance was also enhanced by the presence of $BaAl_2O_4$ and $BaMnAl_{11}O_{19}$. Compared to $BaAl_2O_4$, $BaMnAl_{11}O_{19}$ exhibited superior catalytic combustion activity.