• Title/Summary/Keyword: Heterogeneous Reaction

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Simulation for Possible Coke-Free Operation of a Packed Catalyst Bed Reactor in the Steam-CO2 Reforming of Natural Gas (천연가스의 수증기-이산화탄소 복합개질용 촉매 충진 반응기의 코킹 회피 운전을 위한 모사)

  • LEE, DEUK KI;LEE, SANG SOO;SEO, DONG JOO;YOON, WANG LAI
    • Transactions of the Korean hydrogen and new energy society
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    • v.26 no.5
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    • pp.445-452
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    • 2015
  • A tubular packed bed reactor for the steam-$CO_2$ combined reforming of natural gas to produce the synthesis gas of a target $H_2/CO$ ratio 2.0 was simulated. The effects of the reactor dimension, the feed gas composition, and the gas feeding temperature upon the possibility of coke formation across the catalyst bed were investigated. For this purpose, 2-dimensional heterogeneous reactor model was used to determine the local gas concentrations and temperatures over the catalyst bed. The thermodynamic potential distribution of coke formation was determined by comparing the extent of reaction with the equilibrium constant given by the reaction, $CH_4+2CO{\Leftrightarrow}3C+2H_2O$. The simulation showed that catalysts packed in the central region nearer the entrance of the reactor were more prone to coking because of the regional characteristics of lower temperature, lower concentration of $H_2O$, and higher concentration of CO. With the higher feeding temperature, the feed gas composition of the increased $H_2O$ and correspondingly decreased $CO_2$, or the decrease in the reactor diameter, the volume fraction of the catalyst bed subsequent to coking could be diminished. Throughout the simulation, reactor dimension and reaction condition for coking-free operation were suggested.

Gas hold-up variation with sparging direction in bubble column (기포탑 반응기에서 기체 분사 방향에 따른 gas hold-up 변화)

  • Yang, Jung Hoon;Yang, Jung-Il;Kim, Hak-Joo;Chun, Dong Hyun;Lee, Ho-Tae;Jung, Heon
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.112.2-112.2
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    • 2010
  • 슬러리 기포탑 반응기는 열 및 물질 전달의 용이성, 낮은 운전비용 및 장치의 간단성의 장점을 가지고 있어서 Fischer-Tropsch 반응, bio-reaction 등에 많이 응용되고 있다. 그러나 기포탑 반응기 내의 물질 거동은 매우 복잡하기 때문에 많은 연구가 이루어지고 있음에도 불구하고 그 현상에 대한 명확한 이해는 어려운 상황이다. 특히 기포탑반응기내에 기체의 포집율(gas hold-up)을 증가시키는 것을 목적으로 하는 연구들이 활발히 진행되고 있다. 본 연구에서는 기체의 분사 방향에 따른 기체 포집율의 변화를 관찰하였다. 기체 분사는 0.6 mm의 pore가 66개로 구성된 perforated plate를 통해서 이루어졌고, 수직방향, 수평방향, 45도 그리고 수직/수평 조합의 네 가지 분사방향에 대해서 실험을 수행하였다. 반응기는 내경이 0.15 m이고 높이 2.0 m 아크릴 반응기를 이용하였다. 사용된 연속상은 수돗물을 사용하였고 분산상 기체로는 압축 공기를 이용하였다. 전체적인 기체 포집율은 수직방향의 분사방향에서 가장 높게 측정되었다. 그리고 수직/수평의 조합 분사방향의 경우, 기체 포집율이 가장 낮게 관찰되었다. 이것은 분사방향이 수직/수평으로 서로 엇갈릴 경우, 기포간의 충돌 가능성이 높아지고 bubble coalescence가 증가하였기 때문인 것으로 보인다. 실제로 homogeneous flow regime에서 heterogeneous flow regime으로 전환되는 기체선속도는 분사방향이 수직, 45도, 수평, 수직/수평 조합의 순서로 감소하였다. 즉 이 순서로 기체흐름의 와류가 증가하는 것을 알 수 있었다. 또한 Dynamic Gas Disengagement(DGD) 분석을 통하여 큰 기포가 발생하기 시작하는 기체 선속도의 변화를 관찰하였다. 이 경우, 예상되듯이 수직/수평 조합에서는 1.5 cm/sec 기체 선속도에서 큰 기포가 발생하기 시작한 반면 수직 방향 분사의 경우에는 2.5 cm/sec의 보다 높은 기체 선속도에서 관찰되기 시작하였다. 이러한 현상들을 종합하였을 때, 기체 분사방향을 수직으로 일정하게 했을 때, 기포간 출동을 최소화하고 와류발생을 최대한 지연시키며 전체 기체 포집율을 증가시킬 수 있음을 알 수 있다.

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Synthesis of Flake Ag Powder by Polyol Process (폴리올법에 의한 편상의 은 분말 합성)

  • Kim Dong-Jin;Liang Huanzhen;Ahn Jong-Gwan;Lee Jae-Ryeong;Chung Hun-Saeng
    • Journal of Powder Materials
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    • v.11 no.6 s.47
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    • pp.477-485
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    • 2004
  • Monodispersed flaky silver powder was obtained by controlling the ratios of $H_{2}O_{2}/NH_{3}$ and Agin in a mixed solution of ethylene glycol and ammonia with an addition of PVP. The effects of $NH_{3}/Ag,\; H_{2}O_{2}/Ag\;and\;H_{2}PtCl_{6}/Ag$ on its morphology and size were investigated. In $H_{2}O_{2}-NH_{3}-AgNO_{3}\;system,\;NH_{3}/Ag$ molar ratio was found to be an important reaction factor for the nucleation and crystal growth of Ag powder. The synthesis of flaky powder was optimized at over 6 of $NH_{3}/Ag \;and\;5\;of\;H_{2}O_{2}/Ag\;under\;1.0{\times}10^{-3}\;of\;Pt/Ag.\;Moreover,\;as\;the\; NH_{3}/Ag$ molar ratio increased, the size of precipitates was increased regardless of the amount of Pt. In the absence of $H_{2}PtCI$, the morphology and size of reduced Ag powder were found to be irregular in shape $2-4{\mu}m$ in diameter. However, homogenized fine Ag powder was obtained due to heterogeneous nucleation when $H_{2}PtCI$ used as a cat-alyst, and flaky one was synthesized with the addition of Pt over $1.0{\times}10^{-3}$ of Pt/Ag.

Fabrication of Meso/Macroporous Carbon Monolith and its Application as a Support for Adsorptive Separation of D-Amino Acid from Racemates

  • Park, Da-Min;Jeon, Sang Kwon;Yang, Jin Yong;Choi, Sung Dae;Kim, Geon Joong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1720-1726
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    • 2014
  • (S)-Alanine Racemase Chiral Analogue ((S)-ARCA) was used as an efficient adsorbent for the selective separation of D-amino acids (D-AAs), which are industrially important as chiral building blocks for the synthesis of pharmaceutical intermediates. The organic phase, containing (S)-ARCA adsorbent and phase transfer reagents, such as ionic liquid type molecules (Tetraphenylphosphonium chloride (TPPC), Octyltriphenylphosponium bromide (OTPPBr)), were coated on the surfaces of mesoporous carbon supports. For the immobilization of chiral adsorbents, meso/macroporous monolithic carbon (MMC), having bimodal pore structures with high surface areas and pore volumes, were fabricated. The separation of chiral AAs by adsorption onto the heterogeneous (S)-ARCA was performed using a continuous flow type packed bed reactor system. The effects of loading amount of ARCA on the support, the molar ratio of AA to ARCA, flow rates, and the type of phase transfer reagent (PTR) on the isolation yields and the optical purity of product D-AAs were investigated. D-AAs were selectively combined to (S)-ARCA through imine formation reaction in an aqueous basic solution of racemic D/L-AA. The (S)-ARCA coated MMC support showed a high selectivity, up to 95 ee%, for the separation of D-type phenylalanine, serine and tryptophan from racemic mixtures. The ionic liquids TPPC and OTPPBr exhibited superior properties to those of the ionic surfactant Cetyltrimethyl ammonium bromide (CTAB), as a PTR, showing constant optical purities of 95 ee%, with high isolation yields for five repeated reuses. The unique separation properties in this heterogeneous adsorption system should provide for an expansion of the applications of porous materials for commercial processes.

A Study on Prediction of Moment Developed in Bottom of Foundations between Pile and Heterogeneous Soils (말뚝기초와 이질지반 경계부 기초저판에서의 발생모멘트 예측에 관한 연구)

  • Lim, Hae-Sik;Park, Yong-Boo
    • Land and Housing Review
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    • v.2 no.3
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    • pp.277-285
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    • 2011
  • To reinforce bearing capacity-changed section or different foundation in the same building, empirical or simple tools have been used. To solve this problem, an analytical solution which can evaluate and reinforce the stability of foundation is introduced. To suggest a clue for the problems, current foundation reinforcing method is studied through recent literature studies and the structural analyses of foundation slab are performed on the pile foundation of 49$m^2$, 59$m^2$ and 84$m^2$ I type apartments in 15 story building. The analyses are conducted with SAP 2000, a computer program for ordinary structural analysis. To predict the moments of slab by ground non-uniformity, the structural analysis results for the foundation slab of 3 types 15 story apartment buildings in 49$m^2$, 59$m^2$ and 84$m^2$ I type on non-uniformity ground are shown in the diagrams.

Decomposition of Sulfamethoxazole by Catalytic Wet Peroxide Oxidation (촉매습식과산화(CWPO)를 이용한 설파메톡사졸의 분해)

  • Kim, Dul Sun;Lee, Dong-Keun;Kim, Jin Sol
    • Clean Technology
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    • v.24 no.4
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    • pp.293-300
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    • 2018
  • Sulfamethoxazole (SMX) is sulfaamide-based synthetic antibiotics, which are widely prescribed pharmaceutical compound to treat bacterial infections in both human and animals. Most of them are not completely decomposed as refractory substances. The environmental impact of pharmaceuticals as emerging contaminants has generated severe concerns. In this study, catalytic wet peroxide oxidation (CWPO) of SMX was carried out with $Cu/Al_2O_3$ catalyst and investigated the optimum reaction conditions of temperature, dosage of catalyst and concentration of $H_2O_2$ to completely decompose the SMX. It was observed that SMX was completely decomposed within 20 min using 0.79 mM $H_2O_2$ and 6 g $Cu/Al_2O_3$ catalyst at 1 atm and $40^{\circ}C$, but SMX was not fully mineralized and converted to intermediates as hydroylated-SMX, sulfanilic acid, 4-aminobenzenesulfinic acid and nitrobenzene. After that these are completely mineralized through organic acid. We proposed the decomposition reaction path ways of SMX by analyzing the behavior of these intermediates. To investigate the durability of heterogeneous catalyst, decomposition of SMX was observed by continuously recycling catalysts. When the heterogeneous catalyst of 10 wt% $Cu/Al_2O_3$ was continuously reused 5 times, decomposition of SMX was a little lowered, but the activity of catalyst was overall very stable.

Genesis of Bonanza-style Ores in Uichang Area, Changwon City: Geochemical Interpretation by Reaction Path Modeling (창원시 의창지역 보난자형 금광상 성인 : 반응경로 모델링에 의한 지구화학적 해석)

  • Lee, Seung-han;No, Sang-gun;Park, Maeng-Eon
    • Economic and Environmental Geology
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    • v.50 no.2
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    • pp.85-96
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    • 2017
  • Gold mineralization of Samjeong and Yongjang gold mines in Uichang area shows characteristics of Bonanza-type gold deposits. Ores are mainly developed along the contact parts between quartz vein and arkosic sandstone beds(Fe-rich bed) in sedimentary rock. Electrum, silver sulfide and sulfate minerals are mainly in the ores. On the other hand, gold mineralization is less developed in cherty rock and andesitic rock than arkosic sandstone. The study highlights characteristics of gold precipitation in the deposit on the basis of numerical modelling of the reactions between the assumed hydrothermal ore fluids with multicomponent heterogeneous equilibrium calculations. Aqueous species, gases and minerals, containing electrum are included in the calculations. The reaction result between hydrothermal ore fluids and arkosic sandstone show that pH increasing in the ore-forming fluid would trigger precipitation of quartz, chlorite, sericite, chalcopyrite, galena, pyrite, electrum, actinolite and feldspar. The numerical modelling also illustrates the drastic increase of pH and desulfidation lead to precipitation of electrum. Ag/Au ratios in the ore vary with pH conditions and subsequently precipitation of silver-bearing sulfides such as acanthite and polybasite. The modelling of the reaction between andesitic rock and ore-forming fluid shows that mineral assemblages of the case are analogous to ones of the reaction between arkosic sandstone and fluid except the latter has little portion of electrum. The abovementioned modelling results suggest that gold-silver mineralization is bounded by host rocks at the study area.

Oxidative Coupling Reaction of Purified Aldrich Humic Acid by Horseradish Peroxidase (산화환원효소에 의한 휴믹산의 산화중합반응)

  • Jee, Sang-Hyun;Kim, Do-Gun;Kim, Jeong-Hyun;Ko, Seok-Oh
    • Journal of Korean Society of Environmental Engineers
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    • v.32 no.11
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    • pp.1054-1062
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    • 2010
  • Oxidative coupling reactions of humic substances (HS) can be catalyzed by a variety of natural extracellular enzymes and metal oxides. In this study, property changes of HS induced by a natural enzyme, horseradish peroxidase (HRP), and the effect of it to microfiltration (MF) were investigated. PAHA was transformed by oxidative coupling reaction with HRP and hydrogen peroxide ($H_2O_2$), verifying the catalytic effects of the HRP. Size exclusion chromatography (SEC) revealed that weight-average molecular weight (MWw) of PAHA was proportionally increased with the dosages of HRP and $H_2O_2$, indicating the transform action of HS into larger and complex molecules. An increase in the conformational stability of HS was achieved through the promotion of intermolecular covalent bondings between heterogeneous humic molecules. Spectroscopic analysis (fluorescence and infrared spectroscopy) proved that functional groups were transformed by the reaction. Additionally, HS and transformed products were undergone microfiltration (MF) to examine the treatment potential of them in a water treatment facility. Original HS could not be removed by MF but larger molecules of transformed products could be removed. Meanwhile, transformed products caused more fouling on the filtration than original HS. This results proved that natural organic matter (NOM) can be removed by MF after its increase in molecular size by oxidative coupling reaction.

Dynamic Modeling of Gasification Reactions in Entrained Coal Gasifier (석탄 가스화 반응의 동적 거동 전산 모사)

  • Chi, Jun-Hwa;Oh, Min;Kim, Si-Moon;Kim, Mi-Young;Lee, Joong-Won;Kim, Ui-Sik
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.3
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    • pp.386-401
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    • 2011
  • Mathematical models for various steps in coal gasification reactions were developed and applied to investigate the effects of operation parameters on dynamic behavior of gasification process. Chemical reactions considered in these models were pyrolysis, volatile combustion, water shift reaction, steam-methane reformation, and char gasification. Kinetics of heterogeneous reactions between char and gaseous agents was based on Random pore model. Momentum balance and Stokes' law were used to estimate the residence time of solid particles (char) in an up-flow reactor. The effects of operation parameters on syngas composition, reaction temperature, carbon conversion were verified. Parameters considered here for this purpose were $O_2$-to-coal mass ratio, pressure of reactor, composition of coal, diameter of char particle. On the basis of these parametric studies some quantitative parameter-response relationships were established from both dynamic and steady-state point of view. Without depending on steady state approximation, the present model can describe both transient and long-time limit behavior of the gasification system and accordingly serve as a proto-type dynamic simulator of coal gasification process. Incorporation of heat transfer through heterogenous boundaries, slag formation and steam generation is under progress and additional refinement of mathematical models to reflect the actual design of commercial gasifiers will be made in the near futureK.

A novel Fabry-Perot fiber optic temperature sensor for early age hydration heat study in Portland cement concrete

  • Zou, Xiaotian;Chao, Alice;Wu, Nan;Tian, Ye;Yu, Tzu-Yang;Wang, Xingwei
    • Smart Structures and Systems
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    • v.12 no.1
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    • pp.41-54
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    • 2013
  • Concrete is known as a heterogeneous product which is composed of complex chemical composition and reaction. The development of concrete thermal effect during early age is critical on its future structural health and long term durability. When cement is mixed with water, the exothermic chemical reaction generates hydration heat, which raises the temperature within the concrete. Consequently, cracking may occur if the concrete temperature rises too high or if there is a large temperature difference between the interior and the exterior of concrete structures during early age hydration. This paper describes the contribution of novel Fabry-Perot (FP) fiber optic temperature sensors to investigate the thermal effects of concrete hydration process. Concrete specimens were manufactured under various water-to-cement (w/c) ratios from 0.40 to 0.60. During the first 24 hours of concreting, two FP fiber optic temperature sensors were inserted into concrete specimens with the protection of copper tubing to monitor the surface and core temperature change. The experimental results revealed effects of w/c ratios on surface and core temperature developments during early age hydration, as well as demonstrating that FP fiber optic sensors are capable of capturing temperature variation in the concrete with reliable performance. Temperature profiles are used for calculating the apparent activation energy ($E_a$) and the heat of hydration (H(t)) of concrete, which can help us to better understand cement hydration.