• 공업화학
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• 제29권4호
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• pp.376-381
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• 2018

본 연구는 무수말레인산의 수소화 반응 공정에서 발생한 palladium (Pd)/C 폐촉매에서 Pd를 회수하고 이 회수용액을 이용한 Pd/C 재제조 특성에 대해서 연구하였다. 폐촉매 내 담지체로 사용된 탄소(carbon)의 탄화를 위해 $600-900^{\circ}C$에서 열처리를 진행하였고, 탄화된 촉매의 Pd의 함량을 XRF 및 ICP를 통하여 분석하였다. Pd의 함량이 가장 높게 나타난 탄화조건에서 탄화된 촉매를 이용하여 다양한 농도의 침출 용액을 사용하여 Pd를 침출하였으며, 이때 가장 높은 침출률을 나타나는 용액을 별도의 전처리 없이 Pd/C 촉매제조에서 전구체로 사용하였다. Pd용해를 위해 1,2 및 4 M HCl 용액을 침출용액으로 사용하여 가장 높은 회수율을 가지는 조건을 최적화하고자 하였다. 그 결과, 4 M HCl을 사용하였을 때 92.4%의 가장 높은 Pd 침출률을 확인하였다. 이후, (1) 회수 용액을 전구체 용액으로 사용한 경우 (2) 시약급 $H_2PdCl_4$ 용액을 전구체 용액으로 사용한 경우, 두 가지 각기 다른 전구체 용액을 사용하여 각각 5 wt% Pd/C를 이온교환법으로 제조하였고, 전구체 용액에 따른 특성을 CO-chemisorption 및 FE-TEM으로 확인하였다. 그 결과 회수용액을 사용하여 촉매를 제조하였을 경우 2-5 nm의 균일한 입자크기와 34.6%의 분산도를 나타내어 기존 폐촉매가 가지는 약 5.02% 분산도보다 월등히 높은 것을 확인하였고, 시약급 전구체 용액을 사용한 경우와 비교하여도 동등수준의 분산도를 가지는 것을 확인하였다.

• 한국수소및신에너지학회논문집
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• 제26권3호
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• pp.227-233
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• 2015

In this study, we evaluate catalytic activity of Pd/C catalyst that is synthesized by modified polyol method. With such formed Pd/C is used as anodic catalyst for direct formic acid fuel cell (DFAFC) and performances of the DFAFC are measured to verify whether the new catalyst is effective for enhancing DFAFC performance and to determine optimal loadings of the Pd/C needed for obtaining best DFAFC performance. Pd particle distribution of the Pd/C catalyst is analyzed by TEM, while its catalytic activity is estimated by using cyclic voltammogram (CV) as measuring formic acid oxidation reaction and active surface area. As a result of that, the Pd/C catalyst synthesized by modified polyol shows better catalytic activity and DFAFC performance with small loading amount of Pd/C. When loading amount of Pd/C is $1.5mgcm^{-2}$, maximum power density of DFAFC adopting the catalyst is $122mWcm^{-2}$.

• 한국수소및신에너지학회논문집
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• 제27권3호
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• pp.283-289
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• 2016

In this study, electrochemical characterizations of PdCu/C catalysts that are synthesized by modified polyol method are investigated. Most of all, amount of ethylene glycol (EG) that is used as main component for catalyst synthesis is mainly modulated to optimize synthetic condition of the PdCu/C catalyst, For evaluations about catalytic activity and performance of direct formic acid fuel cell (DFAFC), half cell and full cell tests are implemented. As a result, when amount of EG is 4M, catalytic activities of the PdCu/C catalyst such as peak current of formic acid oxidation and active surface area are best, while maximum power density of DFAFC using the optimized PdCu/C catalyst is better than that using commercial Pd/C (30 wt%) by 6%. Based on that, PdCu/C catalyst synthesized by modified polyol method plays a critical role in improving (i) catalytic activity for formic acid oxidation and (ii) DFAFC performance by employing as anodic catalyst.

• Bulletin of the Korean Chemical Society
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• 제23권12호
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• pp.1785-1789
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• 2002

2,2'-Dichlorohydroazobenzene was prepared by selective hydrogenation of o-nitrochlorobenzene with hydrogen in the presence of 0.8% and 5% Pd/C catalyst. O-Chloroaniline was a minor product in the catalytic hydrogenation of o-nitrochlorobenzene. The effects of base, Pd/C catalyst, and co-catalyst were discussed on catalytic hydrogenation. 2,2'-Dichlorohydroazobenzene, as an intermediate, was rearranged to 3,3'-dichlorobenzidine after reacting with HCl. It was shown that selectivity of catalytic hydrogenation of o-nitro-chlorobenzene is affected strongly by concentration of base, Pd/C catalyst, and co-catalyst. $^1Hand^{13}C$NMR spectroscopy confirmed the chemical structures of 2,2'-dichlorohydrazobenzene and 3,3'-dichlorobenzidine.

• 한국대기환경학회지
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• 제20권5호
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• pp.663-670
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• 2004

The catalytic oxidation of benzene, toluene and xylene over a spent industrial catalyst (Pd-based) was investigated in a fixed bed flow reactor system. According to the priming condition, the properties of a spent Pd-based catalyst were characterized by XRD(X-ray diffraction). BET(Brunauer-Emmett-Teller) and ICP(Inductively coupled plasma). When air was used as a primer, optimum priming temperature was found to be 200$^{\circ}C$, and the catalytic activity decreased as the priming temperature increased. When a spent Pd-based catalyst primed with air at 200$^{\circ}C$ was re-treated with hydrogen at 200$^{\circ}C$, 300$^{\circ}C$ or 400$^{\circ}C$, respectively, the catalytic activity increased and thermal effect were negligible. $HNO_3$ aqueous solution priming resulted in slight decrease of the catalytic activity, with little effects on $HNO_3$ concentrations. The activity of a spent Pd-based catalyst with respect to VOC molecule was observed to follow sequence: xylene> toluene> benzene. Benzene. toluene and xylene could be removed to almost 100% by a spent Pd-based catalyst primed with hydrogen.

• 에너지공학
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• 제6권1호
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• pp.34-40
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• 1997

자동차 촉매인 Pd/cordierite 촉매상에서 메탄의 연소시험을 통하여 천연가스 이용기술 활용가능성에 대해서 고찰하였다. 중고온 연소에서 알맞은 비표면적 18.7$m^2$/g 을 갖으며 안정한 구조를 확인하였다. 메탄 연소 반응시 활성화에너지는 19.2 kcal/mol로써 비교적 우수한 활성을 보여주었으며, 메탄 연소 반응의 승온과 온도를 내리면서 촉매의 비활성 특성을 보여주는 활성 히스테리시스 현상을 관찰하였다. Pd/cordierite 촉매상에서 반응온도 $700^{\circ}C$이하에서 공간속도와 공연비를 변화시키면서 메탄 연소특성을 수행하였다.

• Bulletin of the Korean Chemical Society
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• 제29권2호
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• pp.328-334
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• 2008

The effects of catalyst preparation on the reaction route and the mechanism of biphenol (BP) hydrogenation, which consists of a long series-reaction, were studied. Pd/C catalysts were prepared by incipient wetness method and precipitation and deposition method. The reaction behaviors of the prepared catalysts and a commercial catalyst along with the final product distributions were very different. The choice of the catalyst preparation conditions during precipitation and deposition including the temperature, pH, precursor addition rate, and reducing agent also had significant effects. The reaction behaviors of the catalysts were interpreted in terms of catalyst particle size, metal distribution, and support acidities.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2099-2104
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• 2013

We present here an efficient and simple method for preparation of highly active Pd heterogeneous catalyst (CNT-Pd), specifically by reaction of dichlorobis(triphenylphosphine)palladium ($Pd(PPh_3)_2Cl_2$) with thiolated carbon nanotubes (CNTs). The as-prepared CNT-Pd catalysts demonstrated an excellent catalytic activity for the carbon-carbon (C-C) cross-coupling reactions (i.e. Suzuki, Stille, and decarboxylative coupling reactions) under mild conditions. The CNT-Pd catalyst could easily be removed from the reaction mixture; additionally, in the decarboxylative coupling of iodobenzene and phenylpropiolic acid, it showed a six-times recyclability, with no loss of activity. Moreover, once its activity had decreased by repeated recycling, it could easily be reactivated by the addition of phosphine ligands. The remarkable recyclability of the decarboxylative coupling reaction is attributable to the high degree of dispersion of Pd catalysts in CNTs. Aggregation of the Pd catalysts is inhibited by their strong adhesion to the thiolated CNTs during the chemical reactions, thereby permitting their recycling.

• 한국응용과학기술학회지
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• 제31권4호
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• pp.541-548
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• 2014

This study was performed to obtain high conversion efficiency of $C_7H_8$ using non-thermal plasma and metal-supported catalyst. Adsorption-desorption characteristics of toluene was performed using 4A type (Zeolite) filled in a concentration reactor. Through this test, it was found that the concentration reactor has 0.020 g/g of adsorption capacity (at ambient temperature and pressure) and 3,600 ppm of desorption property at $150^{\circ}C$ (with in 20 min). In case of developed catalyst, toluene decomposition rate of Pd-AO (Pd coated catalyst) was better than Pd/Cu-AO and Pd/Ag-AO (Pd/Ag composite metal catalyst). Developed non-thermal plasma system was obtained flame amplification effect using injection process of desorbed tolune, and 98% of removal efficiency.

• 대한화학회지
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• 제46권1호
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• pp.57-63
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• 2002

CTA(crude terephthalic acid)의 수소화 정제 반응이 고온의 회분식반응기에서 PdRu/CCM(carbon-carbonaceous composite material) 촉매 상에서 수행되었다. 반응 시간에 따른 In(4-CBA; 4-carboxybenzaldehyde)의 의존도가 선형성을 보임에서 수소화 정제는 1차 속도론을 따름을 알 수 있었다. 촉매량에 따른 반응 속도의 선형성에서 조사된 반응 조건은 정제 반응을 잘 대변할 수 있음을 알 수 있었다. 반응 전환율이 증가하면(4-CBA가 감소하면) 고체 및 액체의 p-toluic acid(p-tol)의 농도는 증가하였으나 벤조산(BA)의 농도는 크게 변하지 않았다. 4-CBA 농도가 대략 0.15% 이하일 때에는 PTA의 AT(alkalitransmittance)는 4-CBA농도에 반비례하며 이는 4-CBA의 수소화에 따라 발색물질도 제거 됨을 보여 준다. 4-CBA농도가 약 0.2% 이상이면 AT는 일정하였는데 이는 4-CBA 자체는 발색 효과를 가지지 않음을 보여준다. (0.3%Pd-0.2%Ru)/CCM 촉매는 0.5%Pd/C 상업 촉매에 비해 초기 활성은 낮으나, 상업 공장 반응기에서 사용한 후에는 오히려 큰 잔존 활성을 보였고 PdRu/CCM 촉매는 루테늄 함량이 약 $0.2{\sim}0.35%$ 일 때 활성의 상승효과를 보였다. PdRu/CCM 촉매는 0.5%Pd/C 상업 촉매를 대체할 가능성이 높음을 알 수 있다.