• Title/Summary/Keyword: $H_2-TPR$

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Investigation of Coke Formation in Dry Methane Reforming over Nickel-based Monolithic Catalysts

  • Pornruangsakun, Pongsakorn;Tungkamani, Sabaithip;Ratana, Tanakorn;Phongaksorn, Monrudee;Sornchamni, Thana
    • International Journal of Advanced Culture Technology
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    • v.3 no.1
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    • pp.31-38
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    • 2015
  • Coking accumulations via dry methane reforming (DMR) over 10NAM monolithic catalyst and pelletized catalyst was investigated. 10NAM catalyst was synthesized and coated on a wall of monolithic reactor. Pelletized catalyst of 10NAM was also prepared for the comparison. Consequently, catalyst was characterized by BET, $H_2-TPR$ and $H_2-TPD$. The catalytic reaction was undergone at $600^{\circ}C$ under atmospheric pressure and $CH_4$ to $CO_2$ reactant ratio of 1:2. The coking formation over spent catalyst was then carried out in the hydrogen flow using temperature programmed technique (TPH). According to the results, DMR over 10NAM monolithic catalyst exhibits a minimized coking formation comparing to the use of pelletized catalyst. This could be attributed to a prominent heat transfer efficiency of the monolithic catalyst.

Reaction Characteristics of Water Gas Shift Catalysts in Various Operation Conditions of Blue Hydrogen Production Using Petroleum Cokes (석유코크스 활용 블루수소생산을 위한 Water Gas Shift 촉매의 조업조건에 따른 반응특성)

  • Park, Ji Hye;Hong, Min Woo;Yi, Kwang Bok
    • Clean Technology
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    • v.28 no.1
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    • pp.1-8
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    • 2022
  • To confirm the applicability of the water gas shift reaction for the production of high purity hydrogen for petroleum cokes, an unutilized low grade resource, Cu/ZnO/MgO/Al2O3 (CZMA), catalyst was prepared using the co-precipitation method. The prepared catalyst was analyzed using BET and H2-TPR. Catalyst reactivity tests were compared and analyzed in two cases: a single LTS reaction from syngas containing a high concentration of CO, and an LTS reaction immediately after the syngas passed through a HTS reaction without condensation of steam. Reaction characteristics in accordance with steam/CO ratio, flow rate, and temperature were confirmed under both conditions. When the converted low concentration of CO and steam were immediately injected into the LTS, the CO conversion was rather low in most conditions despite the presence of large amounts of steam. In addition, because the influence of the steam/CO ratio, temperature, and flow rate was significant, additional analysis was required to determine the optimal operating conditions. Meanwhile, carbon deposition or activity degradation of the catalyst did not appear under high CO concentration, and high CO conversion was exhibited in most cases. In conclusion, it was confirmed that when the Cu/ZnO/MgO/Al2O3 catalyst and the appropriate operating conditions were applied to the syngas composition containing a high concentration of CO, the high concentration of CO could be converted in sufficient amounts into CO2 by applying a single LTS reaction.

The Importance of the Aging Time to Prepare Cu/ZnO/Al2O3 Catalyst with High Surface Area in Methanol Synthesis

  • Jung, Heon;Yang, Dae-Ryook;Joo, Oh-Shim;Jung, Kwang-Deog
    • Bulletin of the Korean Chemical Society
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    • v.31 no.5
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    • pp.1241-1246
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    • 2010
  • Ternary Cu/ZnO/$Al_2O_3$ catalysts were prepared by a co-precipitation method. The precursor structures were monitored during the aging. The first precipitate structure was amorphous georgeite, which transformed into the unknown crystalline structure. The transition crystalline structure was assigned to the crystalline georgeite, which was suggested with elemental analysis, IR and XRD. The final structure of precursors was malachite. The Cu surface area of the resulting Cu/ZnO/$Al_2O_3$ was maximized to be 30.6 $m^2$/g at the aging time of 36 h. The further aging rapidly decreased Cu surface areas of Cu/ZnO/$Al_2O_3$. ZnO characteristic peaks in oxide samples almost disappeared after 24 h aging, indicating that ZnO was dispersed in around bulk CuO. TOF of the prepared catalysts of the Cu surface area ranges from 13.0 to 30.6 $m^2/g_{cat}$ was to be 2.67 ${\pm}$ 0.27 mmol/$m^2$.h in methanol synthesis at the condition of $250^{\circ}C$, 50 atm and 12,000 mL/$g_{cat}$. h irrespective of the XRD and TPR patterns of CuO and ZnO structure in CuO/ZnO/$Al_2O_3$. The pH of the precipitate solution during the aging time can be maintained at 7 by $CO_2$ bubbling into the precipitate solution. Then, the decrease of Cu surface area by a long aging time can be prevented and minimize the aging time to get the highest Cu surface area.

A Study on the Characteristics of a Pt/TiO2 Catalyst Prepared by Liquid-Phase Ruduction for Formaldehyde Oxidation at Room Temperature (액상환원 기반 Pt/TiO2 촉매 제조를 이용한 포름알데히드 상온 산화 반응 특성 연구)

  • Jae Heon Kim;Younghee Jang;Geo Jong Kim;Sung Chul Kim;Sung Su Kim
    • Applied Chemistry for Engineering
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    • v.34 no.6
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    • pp.612-618
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    • 2023
  • Modern society spends more than 80% of its daily life indoors, emphasizing the need for attention to indoor air pollution due to the improvement in living standards. In this study, the performance and reaction characteristics of the Pt/TiO2 catalysts prepared by liquid-phase reduction for the removal of formaldehyde (HCHO), one of the indoor air pollutants, at room temperature without the need for additional light or heat were investigated. As a result, it showed that catalysts prepared by the same method showed approximately 40~80% various activities depending on the type of TiO2. XRD, BET, and XPS analyses were performed to investigate the particle size, crystal structure, specific surface area, and O/Ti molar ratio of the support material, and it revealed that the correlation between the properties and performance was insignificant. To explore the oxidation reaction pathway of formaldehyde (HCHO), in situ DRIFT analysis using carbon monoxide and H2-TPR was perfomed. The results revealed that the performance was demonstrated by the oxidation state of the active metal and the adsorption-desorption characteristics of the adsorbate species.

A Study on NH3-SCR Vanadium-Based Catalysts according to Tungsten Content for Removing NOx Generated from Biogas Cogeneration (바이오가스 열병합 발전에서 발생하는 NOx 제거를 위한 텅스텐 함량에 따른 NH3-SCR 바나듐계 촉매 연구)

  • Jung, Min Gie;Hong, Sung Chang
    • Clean Technology
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    • v.27 no.4
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    • pp.315-324
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    • 2021
  • In this study, a vanadium catalyst study was conducted on the various characteristics of the exhaust gas in the Selective-Catalytic-Reduction (SCR) method in which nitrogen oxides emitted from cogeneration using biogas are removed by using ammonia as a reducing agent and a catalyst. V/W/TiO2, a commercial catalyst, was used as the catalyst in this study, and the effect was confirmed according to the tungsten content under various operating conditions. As a result of the NH3-SCR experiment, the denitrification performance was confirmed at 380 ~ 450 ℃ more than 95%, and durability to trace amounts of SO2 was confirmed through the SO2 durability experiment and TGA analysis. As a result of H2-TPR analysis, the higher the tungsten content, the better the redox properties. Accordingly, enhanced oxidizing properties were confirmed in the oxidation test for a trace amount of carbon monoxide emitted from the cogeneration. In NH3-DRIFTs analysis, it was confirmed that the higher the tungsten content, the higher both the Bronsted/Lewis acid sites and the better the thermal durability when tungsten is added to the catalyst. Based on the experiments under various operating conditions, it is considered that a catalyst with a high tungsten content is suitable to be applied to cogeneration using biogas.

Promotion effect of Ru in Ni-based catalyst for combined $H_{2}O$ and $CO_{2}$ reforming of methane (메탄의 수증기/이산화탄소 복합 개질 반응용 니켈 촉매의 루테늄 증진 효과)

  • Jang, Won-Jin;Seo, Yu-Taek;Roh, Hyun-Seog;Koo, Kee-Young;Seo, Dong-Joo;Seo, Yong-Seog;Rhee, Young-Woo;Yoon, Wang-Lai
    • 한국신재생에너지학회:학술대회논문집
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    • 2007.06a
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    • pp.53-56
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    • 2007
  • 미량의 Ru을 증진제로 첨가하여 니켈 촉매의 반응 활성을 증진시킴으로써, 저온 환원성과 장시간 반응에 대한 안정성을 확보하고자 하였다. Ni의 담지량은 12 wt%로 고정하였으며 이에 Ru을 각각 0.1, 0.3, 0.5 wt%로 변화시켜 2차 담지하였다. 메탄의 수증기/이산화탄소 복합 개질 반응에 있어 니켈 촉매에 Ru을 2차 담지 한 촉매는 800 $^{\circ}C$, GHSV(gas hourly space velocity) 265,000 $h^{-1}$ 하에서 100 %에 가까운 $CH_{4}$ 전환율을 보였으며, GHSV 1,060,000 $h^{-1}$ 일 때에도 10시간 동안 90 %의 $CH_{4}$ 전환율을 기록하였다. 또한 이 중 0.3 wt%의 Ru를 담지한 경우가 1,060,000 $h^{-1}$의 조건하에서도 95 %이상으로 가장 높은 $CH_{4}$ 전환율로 유지되었다. $H_{2}-TPR$ 분석 결과, Ni(12)/$MgAl_{2}O_{4}$ 와 비교해 볼 때 Ru(0.5)/Ni(12)/$MgAl_{2}O_{4}$와 Ru(0.3)/Ni(12)/$MgAl_{2}O_{4}$ 촉매의 경우 150 $^{\circ}C$에서 저온 환원이 가능한 $RuO_{2}$의 존재를 확인할 수 있었다.

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Effects of Mg Addition to Cu/Al2O3 Catalyst for Low-Temperature Water Gas Shift (LT-WGS) Reaction

  • Zakia Akter Sonia;Ji Hye Park;Wathone Oo;Kwang Bok Yi
    • Clean Technology
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    • v.29 no.1
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    • pp.39-45
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    • 2023
  • To investigate the effects of Mg addition at different aging times and temperatures, Cu/MgO/Al2O3 catalysts were synthesized for the low-temperature water gas shift (LT-WGS) reaction. The co-precipitation method was employed to prepare the catalysts with a fixed Cu amount of 30 mol% and varied amounts of Mg/Al. Synthesized catalysts were characterized using XRD, BET, and H2-TPR analysis. Among the prepared catalysts, the highest CO conversion was achieved by the Cu/MgO/Al2O3 catalyst (30/40/30 mol%) with a 60 ℃ aging temperature and a 24 h aging time under a CO2-rich feed gas. Due to it having the lowest reduction temperature and a good dispersion of CuO, the catalyst exhibited around 65% CO conversion with a gas hourly space velocity (GHSV) of 14,089 h-1 at 300 ℃. However, it has been noted that aging temperatures greater or less than 60 ℃ and aging times longer than 24 h had an adverse impact, resulting in a lower surface area and a higher reduction temperature bulk-CuO phase, leading to lower catalytic activity. The main findings of this study confirmed that one of the main factors determining catalytic activity is the ease of reducibility in the absence of bulk-like CuO species. Finally, the long-term test revealed that the catalytic activity and stability remained constant under a high concentration of CO2 in the feed gas for 19 h with an average CO conversion of 61.83%.

Selective Catalytic Reduction (SCR) of NOx with NH3 on Sb-promoted VWTi Catalysts (Sb 첨가에 따른 VWTi 촉매의 암모니아 선택적 촉매 환원(SCR)을 통한 질소산화물 저감)

  • Kim, Su Bin;Choi, Gyeong Ryun;Shin, Jung Hun;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.32 no.1
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    • pp.35-41
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    • 2021
  • VWTi, which is used as a commercial catalyst in NH3-SCR, exhibits excellent denitrification performance at 300 to 400 ℃, but there is a problem that efficiency decreases at low temperatures below 300 ℃. Research on catalysts containing promoter to increase low-temperature denitrification efficiency is steadily progressing. However, research on the cause of the improvement in low-temperature denitrification efficiency of the catalyst and the catalyst properties is insufficient. In this study, it was confirmed that by adding Sb to VWTi, denitrification performance was improved by more than 10% in NH3-SCR reaction below 300 ℃. At this time, the space velocity and the size of the catalyst particles were controlled to exclude the influence of external/internal diffusion. In addition, the catalytic properties according to the presence or absence of Sb were investigated by performing BET, TEM/EDS, O2-TPD, H2-TPR and DRIFTs analysis. It was judged that the addition of Sb increased the adsorbed oxygen species on the surface of the catalyst, thereby enhancing the redox properties of the catalyst at low temperature and exhibiting excellent denitrification performance.

A Study on Highly Dispersed Pt/$Al2O_3$ Catalyst for Preferential CO Oxidation (고분산 담지된 Pt/$Al2O_3$ 촉매의 선택적 CO 산화반응 특성에 관한 연구)

  • Kim, Ki Hyeok;Koo, Kee Young;Jung, UnHo;Roh, Hyeon Seog;Yoon, Wang Lai
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.157.1-157.1
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    • 2011
  • 선택적 CO 산화반응(PrOx)에 사용되는 촉매 중 Pt, Ru, Rh 등의 귀금속 계 촉매들은 비귀금속 계 촉매에 비해 활성이 좋은 반면 가격이 비싸다는 경제적인 제한점이 있다. 따라서 소량의 귀금속을 사용하여 높은 활성의 촉매를 제조하고자 활성금속의 고분산 담지 방법에 대한 연구가 이루어지고 있다. 본 연구에서는 담체인 ${\gamma}-Al_2O_3$ 표면에 활성금속인 Pt의 고분산 담지를 위해 증착-침전법(Deposition-precipitation)을 적용하였으며 용액의 pH 변화에 따른 Pt 금속 입자의 분산도에 대한 영향을 살펴보았다. Pt의 함량은 1wt%로 고정하였고 침전제로 NaOH를 사용하여 용액의 pH를 pH 7.5 ~ 10.5로 변화시켰다. 제조된 촉매는 세척 후 $400^{\circ}C$, 3시간 소성 하였다. 제조된 1wt% Pt/$Al_2O_3$ 촉매의 특성분석을 위해 BET, TPR, CO-chemisorption을 수행하였다. PrOx 반응 실험은 GHSV=60,000 $ml/g_{cat}{\cdot}h$, $T=100{\sim}200^{\circ}C$, ${\lambda}$=4 조건에서 수행되었으며 반응 전에 촉매는 $400^{\circ}C$, 3시간 환원 후 사용하였다. 촉매의 특성분석과 PrOx 반응 실험 결과를 통해 촉매가 담체 위에 고분산 되는 최적의 pH를 확인할 수 있었으며, 기존의 함침법으로 제조된 촉매와 성능 비교를 통해 제조방법에 따른 영향을 살펴보았다.

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Improvement of $\lambda$--window Range of the Three-Way Catalyst for Natural Gas Vehicles (천연가스 자동차용 삼원촉매의 $\lambda$-윈도우 영역 개선)

  • 최병철;정필수
    • Transactions of the Korean Society of Automotive Engineers
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    • v.8 no.1
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    • pp.92-100
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    • 2000
  • The model gas reaction tests were carried out to investigate the purification characteristics of methane on the exclusive catalyst for NGV. The experiment was conducted with the factors which affect the conversion efficiency of methane, such as Redox ratio, coexistence components of CO, MO, $H_2$O, precious metals and additives. The catalyst loaded with larger amount of pd and with additive La showed lower light-off temperature. In the presence of CO and NO, the conversion efficiency of methane was varied according to the kind of additive loaded. The conversion efficiency of methane was dropped for the catalyst loaded with La under lean air-fuel ratio, while it increased for the one loaded with Ti+Zr for the same condition. It was shown that the water vapor inhibited methane from oxidation by its poisoning on the surface of catalyst.

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