• Title/Summary/Keyword: heterogeneous chemical reaction

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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.

Catalytic Activity of Metal-phthalocyanine Bonded on Polymer for Decomposition of Hydrogen Peroxide (고분자에 결합된 금속-프탈로시아닌의 과산화수소수 분해반응에 대한 촉매활성)

  • KimKong Soo 김공수;Yong Chul Chun;Young Woo Lee;Sang Ho Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.662-668
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    • 1989
  • The decomposition reaction of hydrogen peroxide was carried out by using metal-4,4',4",4"'-tetraaminophthalocyanine [Mt-$PcNH_2$, Mt = Fe(III), Co(II)] supported on poly (styrene-co-methacrylic acid), in heterogeneous aqueous system. These catalysts showed a catalse-like activity and Fe(III)-$PcNH_2$ supported on the copolymer was particularly effective for the decomposition of hydrogen peroxide. It was found that the rate of decomposition increased smoothly in the higher pH region and catalytic reaction was interfered by adding $CN^-,\;CNS^-,\;{C_2O_4}^{-2},\;I^-$ ions. The kinetics of the catalytic reaction was also investigated and the reaction proceeds according to the Michaelis-Menten type mechanism.

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Knoevenagel Reaction in Water Catalyzed by Mesoporous Silica Materials Synthesized from Industrial Waste Coal Fly Ash (석탄회 산업폐기물로부터 제조한 메조다공성 실리카소재를 촉매로 사용하는 Knoevenagel 수용액 반응)

  • Dhokte, Aashish O.;Khillare, Santosh L.;Lande, Machhindra K.;Arbad, Balasaheb R.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.430-435
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    • 2011
  • Coal fly ash of thermal power plants converted into mesoporous materials MCM-41. The synthesized material was characterized by XRD, FT-IR, SEM, and EDS techniques. The catalytic activity of prepared material was studied for the synthesis of 5-arylindene malononitriles via Knoevenagel condensation of aromatic aldehydes and malonontrile is described. The features of present method are easy handling, stability, reusability, and eco-friendliness of catalyst, high yields, short reaction time, simple experimental and work up procedure.

Synthesis of Iron-loaded Zeolites for Removal of Ammonium and Phosphate from Aqueous Solutions

  • Kim, Kwang Soo;Park, Jung O;Nam, Sang Chul
    • Environmental Engineering Research
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    • v.18 no.4
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    • pp.267-276
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    • 2013
  • This study presents a comparison of different protocols for the synthesis of iron-loaded zeolites, and the results of their application, as well as that of zeolite-A (Z-A), to the removal of ammonium and phosphate from aqueous media. Zeolites prepared by three methods were evaluated: iron-incorporated zeolites (IIZ), iron-exchanged zeolites (IEZ), and iron-calcined zeolites (ICZ). The optimal iron content for preparing of IIZ, as determined via scanning electron microscopy and X-ray photoelectron spectroscopy analyses, expressed as molar ratio of $SiO_2:Al_2O_3:Fe$, was below 0.05. Ammonia removal revealed that the iron-loaded zeolites have a higher removal capacity than that of Z-A due, not only to ion-exchange phenomena, but also via adsorption. Greater phosphate removal was achieved with IEZ than with ICZ; additionally, no sludge production was observed in this heterogeneous reaction, even though the coagulation process is generally accompanied by the production of a large amount of undesired chemical sludge. This study demonstrates that the developed synthetic iron-loaded zeolites can be applied as a heterogeneous nutrient-removal materials with no sludge production.

Quantitative Analysis of Grafted Methacrylate Groups by Michael Addition Reaction between Primary and Secondary Amino Groups on the Silica Nanoparticle Surface with 3-(Acryloyloxy)-2-Hydroxypropyl Methacrylate (실리카 나노 입자 표면에 결합된 1차 및 2차 아미노기와 3-(Acryloyloxy)-2-hydroxypropyl Methacrylate의 마이클 부가 반응에 의해 도입되는 메타크릴레이트기의 정량적 분석)

  • Lee, Sangmi;Ha, KiRyong
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.300-310
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    • 2015
  • In this study, we modified silica nanoparticles with N-[3-(trimethoxysilyl)propyl]ethylenediamine (TPED) silane coupling agent, which has one primary and one secondary amino groups in a molecule, to introduce amino groups on the silica surface. After modification of silica, we used 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) to introduce methacrylate groups by Michael addition reaction. We found about 30% of N-H groups on the TPED modified silica surface reacted with acrylate groups of AHM compared to about 85% of reaction between N-H groups of pure TPED with acrylate groups of pure AHM. This lower degree of Michael addition reaction for heterogeneous reaction between N-H groups on the solid TPED modified silica and liquid AHM compared to homogeneous reaction between pure liquid TPED and pure liquid AHM may be caused by lower mobility of grafted amino groups of TPED moiety and higher steric hindrance caused by solid silica particles.

Carbon bead-supported copper-dispersed carbon nanofibers: An efficient catalyst for wet air oxidation of industrial wastewater in a recycle flow reactor

  • Yadav, Ashish;Verma, Nishith
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.448-460
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    • 2018
  • Copper nanoparticle-doped and graphitic carbon nanofibers-covered porous carbon beads were used as an efficient catalyst for treating synthetic phenolic water by catalytic wet air oxidation (CWAO) in a packed bed reactor over 10-30 bar and $180-230^{\circ}C$, with air and water flowing co-currently. A mathematical model based on reaction kinetics assuming degradation in both heterogeneous and homogeneous phases was developed to predict reduction in chemical oxygen demand (COD) under a continuous operation with recycle. The catalyst and process also showed complete COD reduction (>99%) without leaching of Cu against a high COD (~120,000 mg/L) containing industrial wastewater.

Scale-up Study of Heterogeneous Catalysts for Biodiesel Production from Nepalese Jatropha Oil (네팔산 자트로파 오일로부터 바이오디젤 제조를 위한 불균일계 촉매 Scale-up 연구)

  • Sim, Minseok;Lee, Seunghee;Kim, Youngbin;Ku, Huiji;Woo, Jaegyu;Joshi, Rajendra;Jeon, Jong-Ki
    • Clean Technology
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    • v.27 no.2
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    • pp.198-204
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    • 2021
  • This study focused on a two-step process using heterogeneous catalysts to produce biodiesel using Nepalese jatropha oil as a raw material. As a first step, the effect of the repetitive regeneration number of Amberlyst-15 on the esterification reaction of FFA in jatropha oil was investigated. Second, the possibility of a transesterification reaction scale-up using a dolomite bead catalyst was tested. Using 120 kg of jatropha seeds from Nepal, 30 L (27 kg) of jatropha oil was obtained, and the jatropha oil yield from the seeds was about 25.0 wt%. The acid value and FFA content of jatropha oil were measured to be 11.3 mgKOH g-1 and 5.65%, respectively. As a result of the esterification reaction of jatropha oil using the Amberlyst-15 catalyst in the form of beads, the acid value of the reaction product could be lowered to 0.26 mgKOH g-1 when the fresh Amberlyst-15 catalyst was used. As the regeneration of the Amberlyst-15 catalyst is repeated, the catalyst has been deactivated, and the esterification reaction performance has deteriorated. The cause of the deactivation seems to be due to the catalyst being broken and impurities being deposited. It was confirmed that the Amberlyst-15 catalyst could be reused up to 5 times for the esterification reaction of jatropha oil. In the second step, the transesterification reaction, a dolomite catalyst, was mass-produced and used in the form of beads. By transesterifying the pretreated jatropha oil in a spinning catalyst basket reactor equipped with 90 g of dolomite bead catalyst, 89.1 wt% of biodiesel yield was obtained in 2 hours after the start of the reaction, which was similar to the transesterification of soybean oil under the same conditions.

A Trial for Improvement of Energy Efficiency of Plasma Reactor by Superposing Two Heterogeneous Discharges - Characteristics of Surface and Corona Discharge Combined Plasma Reactor - (이종방전 중첩에 의한 방전 플라스마반응기의 효율개선의 시도 - 연면.직류코로나 방전 중첩형 반응기의 특성 -)

  • ;Mizuki Yamaguma
    • Journal of the Korean Society of Safety
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    • v.15 no.3
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    • pp.66-70
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    • 2000
  • In order to cope with environmental problems caused by harmful gases emitted from various industrial sources, a new technology which employs discharge plasma formed in ordinary atmospheric pressure has been intensively investigated in many industrialized nations. Although a plenty of useful outcomes and suggestions have been made public by scientists in this field, few commercial products which effectively decompose pollutant gases have appeared as yet. This is partly because that the energy efficiency of a most effective plasma reactor has not reached a satisfactory level in comparison with those of devices using conventional technologies. In an attempt to solve the problem mentioned above, we noticed to combine heterogeneous electrical discharges. This concepts is based on that each plasma reactor has its specific spatial region in which chemical reaction are active and by electrically affected with another reactor of different type, the activated region would increase - which may lead to cutting down the energy consumption. To prove this concept experimentally, two different discharge equipments, a plane ceramic-based surface discharge electrode and a corona electrode with tungsten needle may, are selected and combined to fabricate a hybrid plasma reactor. The results are summarized as follows; (1) Ozone concentration generated in the plasma region drastically increases when the positive corona discharge is added to the surface discharge. The rate of increase of ozone depends on the frequency of the surface discharge. The negative corona, however, does not contribute to the improvement of the ozone generation. (2) NO(nitrogen monoxide) decomposition rate also improves by simultaneously applying the surface and the positive corona discharges. The effect of the corona superposition is more evident when the level of the surface discharge is moderate. (3) By adjusting the corona level, the net energy efficiency during NO decomposition improves in comparison with the simple surface discharge reactor.

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Phase Transfer Catalytic Effects for Thiocyanate Displacement on Benzyl Chloride (티오시안산 염에 의한 염화벤질의 치환반응에 미치는 상이동 촉매효과)

  • Seung Hyun Chang;Mu Hong Yoon;Chang Su Kim;Kwang Bo Chung;Jae Hu Shim
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.651-656
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    • 1989
  • The catalytic effects of several phase-transfer catalysts (PTC) on the liquid-liquid heterogeneous nucleophilic displacement reaction of thiocyanate on benzyl chloride have been determined. Reactions followed a pseudo-first order dependency on the benzyl chloride concentration and the observed rate constant $(k_{obsd})$ were linearly related to the concentration of catalyst and varied with variables such as reaction temperature and solvent. The sequences of catalytic activity of the displacement were $NH_4Cl$ < BTMAC < 18-crown-6 < BTEAC < PEG < TBAC < CTMAB. Enthalpies and entropies of activation associated with the displacement were 15∼20 Kcal$mo^{l-1}$, -12∼-29 eu. respectively and the reaction occurs in the interphase comprising of microemulsion.

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New Materials Based Lab-on-a-Chip Microreactors: New Device for Chemical Process

  • Kim, Dong-Pyo
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.51-51
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    • 2012
  • There is a growing interest in innovative chemical synthesis in microreactors owing to high efficiency, selectivity, and yield. In microfluidic systems, the low-volume spatial and temporal control of reactants and products offers a novel method for chemical manipulation and product generation. Glass, silicon, poly(dimethylsiloxane) (PDMS), and plastics have been used for the fabrication of miniaturized devices. However, these materials are not the best due to either of low chemical durability or expensive fabrication costs. In our group, we have recently addressed the demand for economical resistant materials that can be used for easy fabrication of microfluidic systems with reliable durability. We have suggested the use of various specialty polymers such as silicon-based inorganic polymers and fluoropolymer, flexible polyimide (PI) films that have not been used for microfluidic devices, although they have been used for other areas. And inexpensive lithography techniques were used to fabricate Lab-on-a-Chip type of microreactors with differently devised microchannel design. These microreactors were demonstrated for various synthetic reactions: liquid, liquid-gas organic chemical reactions in heterogeneous catalytic processes, syntheses of polymer and non-trivial inorganic materials. The microreactors were inert, and withstand even harsh conditions, including hydrothermal reaction. In addition, various built-in microstructures inside the microchannels, for example Pd decorated peptide nanowires, definitely enhance the uniqueness and performance of microreactors. These user-friendly Lab-on-a-Chip devices are useful alternatives for chemist and chemical engineer to conventional chemical tools such as glass.

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