• Title/Summary/Keyword: Catalyst-free

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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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Carbon Dioxide Reforming of Methane over a Ni/KIT-1 Catalyst (Ni/KIT-1 촉매를 이용한 메탄의 이산화탄소 개질반응 연구)

  • Ryn, Seong-Yun;Ahn, Wha-Seung;Park, Sang-Eon
    • Applied Chemistry for Engineering
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    • v.9 no.7
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    • pp.1070-1078
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    • 1998
  • Thermodynamic analysis on carbon dioxide reforming of methane was performed using a computer program which can handle condensed species in the products, and the reforming experiments were conducted over $Al_2O_3$, $La_2O_3$, ZSM-5, MCM-41, KIT-1 supported nickel catalysts, and a commercial ICI 46-1. It was estabished that a system which consists of $CH_4$, $CO_2$, CO, $H_2$, $H_2O$, and C is appropriate for theoretical equilibrium calculations and addition of water vapor or oxygen was found to diminish the contribution of carbon dioxide in reforming. Silicate molecular sieve-supported catalysts such as Ni/ZSM-5, Ni/MCM-41, Ni/KIT-1 were effective for high $CH_4$ and $CO_2$ conversions as well as for high CO yield. Coke formation was suppressed when CaO was added as a promoter. Ni/Ca/KIT-1 which contains 10% Ni with 3% Ca showed conversion approaching equilibrium levels above $650^{\circ}C$ and maintained constant activity over 20 h. Despite increased space velocity, relatively high conversion and CO yield were observed.

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Simple one-step synthesis of carbon nanoparticles from aliphatic alcohols and n-hexane by stable solution plasma process

  • Park, Choon-Sang;Kum, Dae Sub;Kim, Jong Cheol;Shin, Jun-Goo;Kim, Hyun-Jin;Jung, Eun Young;Kim, Dong Ha;Kim, Daseulbi;Bae, Gyu Tae;Kim, Jae Young;Shin, Bhum Jae;Tae, Heung-Sik
    • Carbon letters
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    • v.28
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    • pp.31-37
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    • 2018
  • This paper examines a simple one-step and catalyst-free method for synthesizing carbon nanoparticles from aliphatic alcohols and n-hexane with linear molecule formations by using a stable solution plasma process with a bipolar pulse and an external resistor. When the external resistor is adopted, it is observed that the current spikes are dramatically decreased, which induced production of a more stable discharge. Six aliphatic linear alcohols (methanol-hexanol) containing carbon with oxygen sources are studied as possible precursors for the massive production of carbon nanoparticles. Additional study is also carried out with the use of n-hexane containing many carbons without an oxygen source in order to enhance the formation of carbon nanoparticles and to eliminate unwanted oxygen effects. The obtained carbon nanoparticles are characterized with field emission-scanning electron microscopy, energy dispersive X-ray spectroscopy, and Raman spectroscopy. The results show that with increasing carbon ratios in alcohol content, the synthesis rate of carbon nanoparticles is increased, whereas the size of the carbon nanoparticles is decreased. Moreover, the degree of graphitization of the carbon nanoparticles synthesized from 1-hexanol and n-hexane with a high carbon (C)/oxygen (O) ratio and low or no oxygen is observed to be greater than that of the carbon nanoparticles synthesized from the corresponding materials with a low C/O ratio.

Effects of Fume silica on synthesis of New Austria Tunnel Method Resin for new material in space aviation (우주항공의 신소재를 위한 New Austria Tunnel Method 수지합성에 대한 Fume silica의 영향)

  • Kim, Kijun;Lee, Jooho;Park, Taesul;Lee, Joo-Youb
    • Journal of the Korean Applied Science and Technology
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    • v.31 no.4
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    • pp.595-601
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    • 2014
  • The microstructures of NATM were examined by SEM, FT-IR spectra, tensile properties, mole % of [NCO/OH], and particle size analyzer. Growing concerns in the environment-friendly industries have led to the development of solvent-free formulations that can be cured. We had synthesized NATM(New Austria Tunnel Method) resin having the ability to protect stainless steel against corrosion. Comparing with general NATM resin and coatings, this resin that synthesized with polyurethane and epoxy was highly stronger in intensity and longer durability. Hybrid resin was composed of polyols, MDI, epoxy, silicone surfactant, catalyst and crosslink agent, and fillers. Moreover, fillers such as fume silica not only accelerated the curing rate but also improved the physical property as thermal barriers. The rigid segments of synthetic resin in mechanical properties were due to fume silica and the increase the mole% of [NCO/OH] for corrosion protection. In conclusion, the hybrid resin microstructure with crosslink agent and fume silica are good material for thermosetting coating of metal substrates such as stainless steel.

Wet Co-Oxidation of Quinoline and Phenol (퀴놀린-페놀 혼합용액의 습식산화)

  • Ryu, Sung Hun;Yoon, Wang-Lai;Suh, Il-Soon
    • Applied Chemistry for Engineering
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    • v.20 no.5
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    • pp.486-492
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    • 2009
  • Wet oxidations (WO) of quinoline in aqueous solution were carried out at $225^{\circ}C$ and $250^{\circ}C$. In the WO at $250^{\circ}C$, quinoline was degraded completely within 30 min and the reduction in total organic carbon (TOC) of 63% was achieved during 120 min. However, the rate of the reduction in TOC was only 13% within 240 min during the WO at $225^{\circ}C$. Nicotinic and acetic acid were found to be main intermediates formed during the oxidation of quinoline. With the addition of the homogeneous catalyst $CuSO_4$ or more easily oxidizable phenol, WOs of quinoline were also carried out under moderate conditions at $200^{\circ}C$. The catalytic WO with $CuSO_4$ of 0.20 g/L showed the destruction rates of quinoline and TOC comparable to those in the WO at $250^{\circ}C$. The WOs of quinoline-phenol mixture exhibited induction periods to degrade quinoline and phenol during which free radicals were produced to initiate WOs. With increasing initial concentrations of phenol at a given initial concentration of quinoline, the induction periods in the destructions of quinoline and phenol became shorter and the reduction in TOC increased from 60% to 75% during 180 min of the WOs. The reduction rate of an induction period decreased as increasing the initial concentration ratio of phenol to quinoline. On the other hand, phenol degradation in the WOs of quinoline-phenol mixtures required a longer induction period and proceeded slower compared to the case of the WO of phenol.

The Studies on The Tetrazotization of Aromatic Diamines (I). Tetrazotization of p-Phenylenediamine in Hydrochloric Acid and Perchloric Acid (방향족 디아민의 Tetrazo 화에 관한 연구 (제1보). 염산 및과염소산 중에서 p-Phenylenediamine의 Tetrazo 화)

  • Woo Young Lee;Youn Young Lee;Sae Hee Chang
    • Journal of the Korean Chemical Society
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    • v.17 no.4
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    • pp.262-268
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    • 1973
  • p-Phenylenediamine was tetrazotized with sodium nitrite in an excess amount of concentrated hydrochloric acid media at -10$^{\circ}$C. It was also tetrazotized almost completely in 45% perchloric acid media. The two diazo groups in the tetrazonium salt were substituted by halogen, and the degree of tetrazotization reaction was observed by dihalobenzene yielded. The result of the tetrazotization was dependent upon the stability of the tetrazonium salt, and the stability was determined by concentration and quantity of the acid media. In dilute acid media the tetrazonium salt was unstable and completely decomposed. In concentrated acid media, though the tetrazonium salt was stable, tetrazotization reaction was retarded. To harmonize the two opposing tendencies it was advisable to find the optimum acidity of media at which the salt was fairly stable. About $40{\sim}45$% of the acid media was suitable. The fact that the $H^+$ ion behaved as a negative catalyst supported the assumption that the diazotization reaction is primarily a reaction between the free amine and a nitroso group. The reaction of tetrazotization is expressed with respect to the kinetics and mechanism of diazotization.

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Synthesis of vertically aligned thin multi-walled carbon nanotubes on silicon substrates using catalytic chemical vapor deposition and their field emission properties (촉매 화학 기상 증착법을 사용하여 실리콘 기판위에 수직 정렬된 직경이 얇은 다중층 탄소나노튜브의 합성과 그들의 전계방출 특성)

  • Jung, S.I.;Choi, S.K.;Lee, S.B.
    • Journal of the Korean Vacuum Society
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    • v.17 no.4
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    • pp.365-373
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    • 2008
  • We have succeeded in synthesizing vertically aligned thin multi-walled carbon nanotubes (VA thin-MWCNTs) by a catalytic chemical vapor deposition (CCVD) method onto Fe/Al thin film deposited on a Si wafers using an optimum amount of hydrogen sulfide ($H_2S$) additive. Scanning electron microscope (SEM) images revealed that the as-synthesized CNT arrays were vertically well-oriented perpendicular to the substrate with relatively uniform length. Transmission electron microscope (TEM) observations indicated that the as-grown CNTs were nearly catalyst-free thin-MWCNTs with small outer diameters of less than 10nm. The average wall number is about 5. We suggested a possible growth mechanism of the VA thin-MWCNT arrays. The VA thin-MWCNTs showed a low turn-on electric field of about $1.1\;V/{\mu}m$ at a current density of $0.1\;{\mu}A/cm^2$ and a high emission current density about $2.5\;mA/cm^2$ at a bias field of $2.7\;V/{\mu}m$. Moreover, the VA thin-MWCNTs presented better field emission stability without degradation over 20 hours (h) at the emission current density of about $1\;mA/cm^2$.

Investigation of the luminescence properties of ZnO nanostructures (ZnO 나노 구조의 형상에 따른 발광 특성에 관한 연구)

  • Jung, Mi-Na;Ha, Seon-Yeo;Park, Seung-Hwan;Yang, Min;Kim, Hong-Seung;Lee, Uk-Hyeon;Yao, Takafumi;Chang, Ji-Ho
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • v.9 no.1
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    • pp.1013-1016
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    • 2005
  • ZnO nanostructure was fabricated by catalyst-free method using Zn powder in air. The growth temperature was controlled from 450$^{\circ}$C to 600$^{\circ}$C, and the structural and optical properties were investigated by scanning electron microscopy (SEM), photoluminescence (PL), energy dispersive X-ray spectroscopy (EDX) and cathodoluminescence (CL). From all samples both ZnO tetrapods and clusters were observed. No significant dispersion was observed from the ZnO tetrapods, however, ZnO clusters show considerable change in density and size. From the EDX results, atomic composition difference was found. The clusters have O-deficiencies, while tetrapods have stoichiometric composition. Strong luminescence was observed at room temperature. From room temperature PL, UV emission at 380 nm and green emission at 500 nm were observed, and the intensity ratio ($I_{uv}/I_{green}$) increased as growth temperature increases. CL measurements show that the UV emission is closely related with tetrapods and the green emission is dominated from the clusters.

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Preparation and Properties of Crosslinked Thermo-responsive Poly(N-isopropylacrylamide) Gel Materials For Smart Windows - Effect of Glycerol Content in Water/Glycerol Solvent - (스마트 윈도우용 가교 열감응성 폴리(N-이소프로필아마이드) 겔 소재의 제조 및 특성 - 물/글리세롤 혼합용매 중의 글리세롤 함량의 영향 -)

  • Park, Jae-Hyong;Kim, Il-Jin;Lee, Dong-Jin;Sim, Jae-Hak;Song, Min-Seop;Lee, Young-Hee;Yoo, Jung-Whan;Kim, Han-Do
    • Clean Technology
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    • v.24 no.2
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    • pp.112-118
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    • 2018
  • Thermo-responsive polymers that exhibit phase transition in response to temperature change can be used as materials for smart windows because they can control solar light transmission depending on the outside temperature. The development of thermo-responsive polymers for smart windows that can be used over a wide temperature range is desirable. To obtain high performance smart windows materials, three-dimensional thermo-responsive poly(N-isopropylacrylamide) (PNIPAm) gels were prepared by free radical polymerization from monomer N-isopropylacrylamide, N, N'-methylenebis acrylamide (MBAm) as a crosslinking agent, ammonium persulfate (APS) as a strong oxidizing agent/tetramethylene diamine as a catalyst, and a mixture of two solvents (water/glycerol). This study examined the effect of glycerol content on the lower critical solution temperature (LCST), freezing temperature and the solar light transmittance of crosslinked PNIPAm gel films. The LCST and freezing temperature of PNIPAm gel films were found to be significantly decreased from 34.3 and $6.3^{\circ}C$ to 28.2 and $-6.5^{\circ}C$ with increasing glycerol content from 0 wt% to 10 wt%, respectively. It was found that the transparent PNIPAm gel films at $25^{\circ}C$ (temperature < LCST) were converted to translucent gels at higher temperature ($45^{\circ}C$) (temperature > LCST). These results suggested that the crosslinked PNIPAm gel materials prepared in this study could have high potential for application in smart glass materials.