• Title/Summary/Keyword: Oxidation Catalyst

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Saturated- and Unsaturated-Azamacrocyclic Complexes $(M = Co^{3+}, Fe^{3+}$ or $Mn^{3+})$ Catalyzed Oxidation of Hindered Phenols by Molecular Oxygen under Sodium Borohydride (Sodium Borohydride 하에서 산소에 의한 포화- 및 불포화-질소주게 거대고리 착물 $(M=Co^{3+},\;Fe^{3+}$$Mn^{3+})$을 촉매로 한 Hindered Phenols의 산화반응)

  • Yu-Chul Park;Seong-Su Kim;Hun-Gil Na
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.648-654
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    • 1993
  • $[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

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The Effect of Pre-Treatment Methods for the Life Time of the Insoluble Electrodes (불용성 전극의 전처리 방법이 전극의 수명에 미치는 영향)

  • Park, Mi-Jung;Lee, Taek-Soon;Kang, Meea;Han, Chi-Bok
    • Journal of Korean Society of Environmental Engineers
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    • v.38 no.6
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    • pp.291-298
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    • 2016
  • Electrochemical water treatment process as a useful treatment method for the removal of non-degradable matter has been consistently studied for several decades. Key process of electrochemical water treatment are oxidation reaction from an anode and reduction from a cathode. In this study, the effect of pre-treatment methods in the insoluble electrode manufacturing process for the water treatment has been evaluated for the life time of electrode The results of this study showed that pre-treatment methods of a base metal such as surface roughness, clean method and interlayer formation influenced to life time of electrode when the same condition (catalyst electrode layer coating method and material system) was applied for pre-treatment methods. This study was conducted by using $IrO_2/Ti$ electrode In the test of sand-blasting process, an electrode manufactured by using sanding media of different sizes resulted in the most effective electrode life time when the size of alumina was used for $212{\sim}180{\mu}m$ praticle size (#80). The most effective method was considered using arc plasma in the additional roughness control and cleaning process, sputtering method to form Ta type interlayer formation process.

New Bleaching Method for KP with Permanganate(III) -Evaluation of Role of Oxalic Acid as a Acid Catalyst and a Reductant on the Permanganate Oxidation with Phenolic Model Compounds- (과망간산칼륨을 이용한 KP의 새로운 표백법(제3보) -모델화합물 실험에서 Oxalic acid 첨가의 평가-)

  • Yasuo Kojima
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.33 no.1
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    • pp.73-79
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    • 2001
  • Stricter environmental demands have increased the need to replace conventional C/D bleaching sequence by chlorine-free sequence. Permanganate is well known as a powerful oxidant and have been used industrially in variable fields. However, it has considered to be difficult to use permanganate as a bleaching reagent because of its strong oxidative effect decreasing the viscosity of pulps extremely. We have tried to use permanganate as a bleaching reagent for KP under the mild condition and it was clear that pernanganate oxidized lignin remained in pulps selectively and increased pulp brightness decreasing K number of pulps with small degradation of cellulose. We have employed the neutral condition in the permanganate bleaching process in this study. In this case, permanganate was converted to manganese dioxide after bleaching reaction. The manganese dioxide is remained in the treated pulp fibers because of its insolublity in water. So it was required to reduction the manganese oxide to manganese ion by using reductants with acid. In this paper, we proposed to use oxalic acid as a reducing reagent converting manganese oxide to manganese ion after bleaching reaction. Oxalic acid plays the role as a reductant and a acid, so post-treatment after bleaching became to be easy by using oxalic acid. On the study using lignin model compounds, it was clear that permaganate react with phenols firstly, after that oxalic acid reduce the manganese oxide to manganese ion in the mixture of permanganate, phenols and oxalic acid. Several lignin model compounds ($\textit{p}$-hydroxybenzaldehyde, vanillin, syringaldehyde, veratraldehyde) are selected to elucidate the effect of substituents on reaction rate and its mechanism with permanganate including oxalic acid in this study. Except for veratraldehyde, the rate of oxidative degradation of phenolic compounds by permanganate with oxalic acid are higher than neutral condition. Especially, the degradation rate of $\textit{p}$-hydroxybenzaldehyde are strongly dependent on pH of reaction mixture. On the other hand, the degradation rate of veratraldehyde are decreased with decreasing pH and main degradation product is veratric acid. This result indicate that pH of bleaching liquor should be kept over 2 to degrade of non-phenolic lignin in the pulps effectively in permanganate bleaching.

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A Study on the Formation of OH Radical by Metal-supported Catalyst in Ozone-catalytic Oxidation Process (오존촉매산화공정에서 금속 담지촉매에 의한 수산화라디칼 생성연구)

  • Lee, Sun Hee;Choi, Jae Won;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.29 no.4
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    • pp.432-439
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    • 2018
  • Metal catalysts such as Fe, Co, Mn, and Pd supported on the activated carbon (AC) were prepared to improve functional groups for the chemical adsorption and catalytic ozonation. Following ascending orders of the phenol decomposition rate, dissolved ozone decomposition ratio and TOC (total organic carbon) removal from experimental results of advanced oxidation process (AOP) were observed: Fe-AC < AC < Co-AC < Mn-AC < Pd-AC. BET analysis results showed that the physical properties of the metal impregnated activated carbon had no effect on the catalytic ozonation, and the catalytic effect was dependent on the kind of impregnated metal. The ratio of the formed concentration of OH radical to that of ozone (RCT) was measured by using the decomposition outcome of p-chlorobenzoic acid, a probe compound that reacts rapidly with OH radical but slowly with ozone. The measured values of RCT were $5.48{\times}10^{-9}$ and $1.47{\times}10^{-8}$ for the ozone alone and activated carbon processes, respectively, and $2.13{\times}10^{-9}$, $1.51{\times}10^{-8}$, $4.77{\times}10^{-8}$, and $5.58{\times}10^{-8}$ for Fe-AC, Co-AC, Mn-AC, and Pd-AC processes, respectively.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols using Cr(VI)-Heterocyclic Complex(Cr(VI)-Isoquinoline) (Cr(VI)-헤테로고리 착물(Cr(VI)-Isoquinoline)를 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구)

  • Park, Young-Cho;Kim, Young-Sik
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.14 no.11
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    • pp.6000-6007
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    • 2013
  • Cr(VI)-heterocyclic complex[Cr(VI)-isoquinoline] was synthesized by the reaction between of heterocyclic compound(isoquinoline) and chromium trioxide, and characterized by IR and ICP analysis. The oxidation of benzyl alcohol using Cr(VI)-isoquinoline in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order : cyclohexene$CH_3$, m-Br, m-$NO_2$). Electron- donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.69(308K). The observed experimental data have been ratiolized. The hydride ion transfer causes the prior formation of a chromate ester in the rate-determining step.

Study of Particle Emission Contour Construction & Characteristics and Reduction Efficiency of Exhaust-Treatment System of Diesel Engine (승용 디젤 엔진의 후처리 시스템 적용에 따른 나노입자 배출 맵 구축 및 저감특성에 관한 연구)

  • Ko, A-Hyun;Hwang, In-Goo;Myung, Cha-Lee;Park, Sim-Soo;Choi, Hoi-Myung
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.34 no.8
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    • pp.755-760
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    • 2010
  • In this study, we mainly focused on the PM (Particulate Matter) emission characteristics of a diesel engine. To analyze particle behavior in the tail-pipe, particle emission was measured on the engine-out (downstream of turbocharger), each upstream and downstream both of DOC (Diesel Oxidation Catalyst) and DPF (Diesel Particulate Filter). Moreover, particle emission contours on each sampling point were constructed. The reduction efficiency of particle number concentration and mass through the DOC and DPF was studied. Parameters such as EGR (Exhaust Gas Recirculation) and the main injection timing were varied in part load conditions and evaluated using the engine-out emissions. The DMS500 (Differential Mobility Spectrometer) was used as a particle measurement instrument that can measure particle concentrations from 5 nm to 1000 nm. Nano-particles of sizes less than 30 nm were reduced by oxidation or coagulated with solid particles in the tail-pipe and DOC. The DPF has a very high filtration efficiency over all operating conditions except during natural regeneration of DPF.

Catalytic Oxidation of Volatile Organic Compounds Over Spent Three-Way Catalysts (배기가스 정화용 폐 자동차 촉매를 이용한 휘발성 유기화합물의 제거)

  • Shim, Wang Geun;Kim, Sang Chai
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.574-581
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    • 2008
  • The optimum regeneration conditions for the regeneration of three way spent catalysts (TWCs), which were taken from automobiles with different driving conditions, were investigated to evaluate the suitability as alternative catalysts for removing VOCs. The spent catalysts were washed with five different acids ($HNO_3$, $H_2SO_4$, $C_2H_2O_4$, $C_6H_8O_7$, and $H_3PO_4$) to remove contaminants and examine the optimum conditions for recovering the catalytic activity. The physicochemical properties of spent and its regenerated TWCs were evaluated by using nitrogen adsorption-desorption isotherms, XRD, and ICP. The relative atomic ratios of contaminants and platinum group metals (PGMs) of the spent TWCs were greatly dependent on the placed positions. The main contaminants formed were lubricant oil additives and metallic components. Also, the regeneration treatment increased the PGMs ratio, BET surface area, and average pore diameter of TWCs. The catalytic activity results indicated that the spent TWCs have the possibility for removing VOCs. Moreover, the employed acid treatments greatly enhanced the catalytic activity of the spent TWCs. Especially, nitric and oxalic acids provided the most improvement in the catalytic behavior. The catalytic activities of the regenerated TWCs were significantly influenced by the containing platinum ratios rather than the removal ratios of contaminants and the changes in the structural properties offered by the acid treatments.

Removal Characteristics of Phenol at Advanced Oxidation Process with Ozone/Activated Carbon Impregnated Metals (오존/촉매 산화공정에서 금속담지 활성탄을 이용한 페놀의 분해 특성)

  • Choi, Jae Won;Yoon, Ji Young;Park, Jin Do;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.23 no.3
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    • pp.302-307
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    • 2012
  • Advanced oxidation processes (AOP) such as O3/activated carbon process and O3/catalysts process were used to compare the decomposition of phenol. Catalysts such as Pd/activated carbon (Pd/AC), Mn/activated carbon (Mn/AC), Co/activated carbon (Co/AC) and Fe/activated carbon (Fe/AC) were prepared by impregnation of Pd, Mn, Co and Fe into the activated carbon of pellet form, respectively. Based on an hour of reactions, the following descending order for the decomposition ratios of dissolved O3 to the 1.48 mg/L of saturated dissolved O3 was observed: Mn/AC (45%) > Pd/AC (42%) > Co/AC (33%) > AC (31%) > Fe/AC (27%). The removal efficiencies of phenol were also arranged in the descending order of AOP as follows: Mn/AC (89%) > Pd/AC (85%) > Co/AC (77%) > AC (76%) > Fe/AC (71%). The remaining ratios (C/Co) of TOC (total organic carbon) after an hour of experiments were arranged in the ascending order of AOP as follows : Pd/AC (0.29) < Mn/AC (0.36) < AC (0.40) < Co/AC (0.49) < Fe/AC (0.51). However, the catalytic effects in the Co/AC and the Fe/AC processes were little in comparison with O3/AC process. The maximum concentrations of intermediates such as hydroquinone and catechol formed from the decomposition of phenol were arranged in the ascending order of AOP as follows: Pd/AC < Fe/AC < Co/AC < AC < Mn/AC. In the case of Pd/AC process, these intermediates were almost disappeared after an one hour of reaction.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Park, Young Cho;Kim, Young Sik;Kim, Soo Jong
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.597-600
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    • 2017
  • $(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl (C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘)

  • Park, Young-Cho;Kim, Young-Sik;Kim, Soo-Jong
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.8
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    • pp.378-384
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    • 2018
  • $C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.