• Advances in Energy Research
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• 제1권1호
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• pp.1-12
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• 2013

In this work, we present the catalytic dehydrogenation of hydrazine borane $N_2H_4BH_3$ (HB) using supported nickel catalysts at $50^{\circ}C$. In the presence of monometallic nickel catalysts, the dehydrogenation of HB is a one-step reaction consisting of the hydrolysis of the $BH_3$ group only. The challenge is to activate nickel to make it reactive towards the $N_2H_4$ moiety of HB. A set of 52 catalysts were prepared by using 2 supports ($Al_2O_3$ and $TiO_2$), 5 nickel precursors and 3 preparation methods. For the first time, we show that the supported nickel catalysts are able to dehydrogenate the $NH_3$ moiety of HB. In our experimental conditions, the best results were obtained with 20 wt% Ni-$Al_2O_3$ and 20 wt% Ni-$TiO_2$, with ca. 190 mL $H_2+N_2$ generated over a total theoretical volume of 283 mL, suggesting $H_2$ selectivity of 37 and 32%, respectively. Both catalysts were then characterized by EDX, XPS, and XRD. Our achievement is the first step forward and opens new perspectives for developing catalysts for the total dehydrogenation of HB.

• Korean Chemical Engineering Research
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• 제59권2호
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• pp.269-275
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• 2021

메탄의 부분 산화반응을 위해 규칙적인 메조기공을 갖는 실리카를 지지체로 한 니켈 촉매를 제조하였다. 니켈 플레이팅(Nickel plating) 방법을 이용하여 촉매 제조 시 기존 함침 촉매 제조법과 달리 니켈이 실리카 표면에 도포된다. 이때 니켈이 고분산 되어 안정적인 니켈입자를 형성하게 된다. 니켈 플레이팅 촉매의 경우, TEM-EDS 분석에서 니켈이 매우 고분산 된 것을 확인할 수 있었다. 이러한 고분산된 촉매로 메탄 부분산화 반응 시 기존 함침촉매와는 달리 니켈의 소결과 탄소침적이 상대적으로 적어 촉매의 비활성화가 매우 낮았다. 팔라듐은 환원 조촉매로서의 역할을 하여, 메탄 전환율과 생성된 합성가스의 H2/CO 비 관점에서 우수한 반응 성능을 보이는 것을 확인 할 수 있었다.

• 공업화학
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• 제7권5호
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• pp.913-924
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• 1996

본 연구에서는 소량의 네오디뮴이 첨가된 니켈 촉매에 대하여 티오펜 탈황 반응을 조사하였으며, 촉매 제조 방법에 따라, 공침법으로 제조된 비담지 NdNi 촉매, 비담지 금속간 화합물 $NdNi_5$ 촉매, 활성탄에 담지된 NdNi 촉매 등이 연구되었다. 공침법으로 제조된 비담지 NdNi 촉매의 경우 소량의 네오디뮴이 첨가되면 티오펜 탈황 반응성이 급격히 증가하여 니켈 촉매에서 네오디뮴의 역할이 아주 큼을 알 수 있다. 비담지 금속간 화합물 $NdNi_5$ 촉매는 소성, 황화 처리의 과정을 거치면서 금속간 화합물이 파괴되고 산화물, 황화물로 각각 변하였다. 비담지 촉매의 경우 티오펜 탈황 반응성은 촉매의 표면적으로 설명이 가능하고 네오디뮴의 역할은 니켈 촉매의 표면적을 높게 유지시키는 구조 촉진제(structural promoter)로 작용한다. 니켈의 분산도가 다른, 금속간 화합물 $NdNi_5$ 촉매, 공침법으로 제조된 NdNi 촉매, 활성탄에 담지 된 NdNi 촉매 순으로 니켈을 기준으로 할 때 티오펜 탈황 반응활성이 각각 10배씩 증가하였다.

• Environmental Engineering Research
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• 제10권3호
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• pp.131-137
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• 2005

The catalytic activity of precious metals(Rh, Pd, Pt) and nickel catalysts supported on ${\gamma}-Al_2O_3\;and\;CeO_2$ in the partial combustion of methane(PCM) to syngas was investigated based on the product distribution in a fixed bed now reactor under atmospheric condition and also on analysis results by SEM, XPS, TPD, BET, and XRD. The activity of the catalysts based on the syngas yield increased in the sequence $Rh(5)/CeO_2{\geq}Ni(5)/CeO_2>>Rh(5)/Al_2O_3>Pd(5)/Al_2O_3>Ni(5)/Al_2O_3$. Compared to the precious catalysts, the syngas yield and stability of the $Ni(5)/CeO_2$ catalyst were almost similar to $(5)/CeO_2$ catalyst, and superior to these of any other catalysts. The syngas yield of $Ni(5)/CeO_2$ catalyst was 90.66% at 1023 K. It could be suggested to be the redox cycle of the successive reaction and formation of active site, $Ni^{2-}$ and the lattice oxygen, $O^{2-}$ produced due to reduction of $Ce^{4-}$ to $Ce^{3-}$.

• Bulletin of the Korean Chemical Society
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• 제19권8호
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• pp.809-812
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• 1998

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2288-2292
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• 2007

The catalytic activities of nickel-based catalysts were estimated for oxidizing acetaldehyde of VOCs exhausted from industrial facilities. The catalysts were prepared by sol-gel methods of SiO2 and SiO2-TiO2 as a xerogel followed by impregnating Al2O3 powder with the nickel nitrate precursor. The crystalline structure and catalytic properties for the catalysts were investigated by use of BET surface area, X-ray diffraction (XRD), Xray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) techniques. These results show that nickel oxide is transformed to NiAl2O4 spinel structure at the calcination temperature of 400 °C in response to the steps with after- and co-impregnation of Al2O3 powder in sol-gel process. The NiAl2O4 could suppress the oxidation reaction of acetaldehyde by catalysts. The NiO is better dispersed on SiO2-TiO2/Al2O3 support than SiO2/Al2O3 and SiO2-TiO2-Al2O3 supports. From the testing results of catalytic activities for oxidation of acetaldehyde, Catalysts showed a big difference in conversion efficiencies with the way of the preparation of catalysts and the loading weight of nickel. The catalyst of 8 wt.% Ni/TiO2-SiO2/Al2O3 showed the best conversion efficiency on acetaldehyde oxidation with 100% conversion efficiency at 350 °C.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1273-1279
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• 2007

The NiSO4 supported on Fe2O3 catalysts were prepared by the impregnation method. No diffraction line of nickel sulfate was observed up to 30 wt %, indicating good dispersion of nickel sulfate on the surface of Fe2O3. The addition of nickel sulfate to Fe2O3 shifted the phase transition of Fe2O3 (from amorphous to hematite) to higher temperatures because of the interaction between nickel sulfate and Fe2O3. 20-NiSO4/Fe2O3 containing 20 wt % of NiSO4 and calcined at 500 oC exhibited a maximum catalytic activity for ethylene dimerization. The initial product of ethylene dimerization was found to be 1-butene and the initially produced 1-butene was also isomerized to 2-butene during the reaction. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method.

• Bulletin of the Korean Chemical Society
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• 제22권12호
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• pp.1303-1308
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• 2001

A series of catalysts, NiSO4/TiO2, for ethylene dimerization was prepared by the impregnation method using aqueous solution of nickel sulfate. On the basis of the results obtained from X-ray diffraction, the addition of NiSO4 shifted the transition of TiO2 from the anatase to the rutile phase toward higher temperatures due to the interaction between NiSO4 and TiO2. Nickel sulfate supported on titania was found to be very active even at room temperature. The high catalytic activity of NiSO4/TiO2 closely correlated with the increase of acidity and acid strength due to the addition of NiSO4. It is suggested that the active sites responsible for ethylene dimerization consist of low valent nickel, Ni+, with an acid.

• 한국대기환경학회지
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• 제3권1호
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• pp.1-12
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• 1987

A series of supported sulfided Ni-W/$\gamma-Al_2O_3$ and Co-W/$\gamma-Al_2O_3$ catalysts with different nickel and cobalt contents were studied in the hydrodenitrogenation of pyridine dissolved in n-heptane. The ranges of experimental conditions were at the temperatures between 453 and 753 K, and the pressures between 30 and 50 Bar. The catalytic activities with different nickel and cobalt contents were shown to be maximum at Ni/Ni+W = 0.2 - 0.3, Co/Co+W = 0.3 - 0.4. Pyridine conversion increased with pressure and temperature and the step of piperidine formation was found to be irreversible. The reaction orders in Ni-W/$\gamma-Al_2O_3$ and Co-W/$\gamma-Al_2O_3$ catalysts were the first with respect to pyridine and reaction rate constants decreased with increase of initial pyridine concentration and their activation energies were 12.98 and 9.23 kcal/mol, respectively.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1512-1514
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• 2005

Catalytic properties of Ni-Zr$O_2$ catalysts prepared by coprecipitation have been studied for the gas-phase hydrogenation of 1,3-butadiene to butenes. The coprecipitation method led to the solid solution of Ni-Zr$O_2$, which contains highly resistant Ni species to thermal reduction with H2. Nickel species of the solid solution were highly dispersed in the ZrO2 lattice, so that the reduced catalysts were selective for hydrogenation of 1,3-butadiene to butenes (99.9%) even in the presence of 1-butene.