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Optimization of Catalytic Reaction for Synthesis of 2-Methyl-4-methoxydiphenylamine (2-Methyl-4-methoxydiphenylamine 합성을 위한 촉매반응의 최적화)

  • Cho, Jeong-Woo;Kim, Eun-Seok;Kim, Kiseok;Kim, Seong-Hoon
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.293-298
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    • 1999
  • Reaction mechanism was elucidated and reaction condition were optimized for the catalytic reaction synthesizing 2-methyl-4-methoxy-diphenylamine (MMDPA) which is an intermediate of Fluoran heat-sensitive dyestuff. Reactants consisted of 2-methyl-4-methoxyaniline (MMA), 3-methyl-4-nitroanisole (MNA), and cyclohexanone, and 5 wt % Pd/C was used as a catalyst. Experiments were run in an open slurry reactor equipped with reflux condenser, and products were analyzed by means of GC/MS and NMR. MMDPA yield of 90 mole % could be obtained after reaction time of 8~10 hours under the optimal reaction conditions comprising the reaction mass composition of MMA : MNA : cyclohexanone = 1 : 2 : 150 based on MMA input of 0.01 gmoles in xylene solvent, reaction temperature of $160^{\circ}C$, and catalyst amount of 0.5 g. It was found that the rate-determining step of overall reaction was dehydrogenation of the intermediate product obtained from condensation of MMA and cyclohexanone. Overall reaction rate and MMDPA yield were enhanced owing to hydrogen transfer reaction by introducing MNA together with MMA in the reaction mass. Excess cyclohexanone in the reaction mass played an important role of promoting the condensation of MMA and cyclohexanone.

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The Catalytic Reduction of Sulfur Dioxide to Elemental Sulfur over Supported Cobalt Catalysts (담지 코발트 촉매를 이용한 SO2의 원소황으로의 환원반응 특성)

  • Park, Joon Hyo;Han, Jong Dae
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1129-1135
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    • 1999
  • The reduction of $SO_2$ by CO over supported cobalt catalysts was investigated within the temperature range of $350{\sim}550^{\circ}C$, initial $SO_2$ concentration of 1000~10000 ppm, $CO/SO_2$ molar ratio of 1.0~3.0 and space velocity of $5000{\sim}15000h^{-1}$. Several types of supports such as ${\gamma}-Al_2O_3$, $TiO_2$ were tested. The $SO_2$ conversion and selectivity to elemental sulfur were investigated using a differential fixed bed reactor at atmospheric pressure. The catalyst prepared by wet impregration of 5 wt % cobalt on ${\gamma}-Al_2O_3$ showed $SO_2$ conversion higher than 90% and COS yield lower than 6% at temperature above $400^{\circ}C$. The optimum $CO/SO_2$ molar ratio was investigated as 2.0. At higher $CO/SO_2$ molar ratio, the $SO_2$ conversion became higher but the main product was COS. The effect of $SO_2$ concentration and space velocity over $SO_2$ conversion and COS yield was not appreciable in the experimental range. The activated cobalt phase was detected as $CoS_2$ and the $CoS_2$ phase unchanged even after reaction.

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A Kinetic Study on the Oxidation of Diphenylmethane under Aliquat 336 Phase Transfer Catalyst (Aliquat 336 상이동 촉매하에서 디페닐메탄의 산화반응에 관한 속도론적 연구)

  • Lee, Hwa-Soo;Moon, Jeong-Yeol;Na, Suk-En;Park, Dae-Won
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.373-377
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    • 1994
  • A mechanism for the synthesis of benzophenone from oxidation of diphenylmethane under Aliquit 336 phase transfer catalyst is investigated in this study. The production rate of benzophenone increased with the increasing amount of Allquat 336 and potassium tert-butoxide. At low concentrations of diphenylmethane and oxygen, the reaction order was first with the concentrations of diphenylmethane and oxygen respectively, but it approached to zero order at high concentrations. Tert-butyl alcohol, by-product of the reaction, inhibited the formation of benzophenone. Experimental results fit fairly well to the following initial reaction rate equation derived from reaction mechanism. $$({\gamma}_{BP})_0={\frac{k_1k_3k_5[QCI]_0[DPM]_0[PTB]_0[O_2]_0}{k_2k_4[TBA]_0+k_2k_5[O_2]_0+k_3k_5[O_2]_0[DPM]_0}}$$

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Evaluation of Chemical Pre-treatment for the Optimization of CO2 Fixatiom Using by Carbonation Reaction with Serpentine (이산화탄소 광물고정화 효율 증가를 위한 사문석의 화학적 전처리에 관한 연구)

  • Jang, Na Hyung;Shim, Hyun Min;Hua, Xu Li;Kim, Hyung Teak
    • Applied Chemistry for Engineering
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    • v.19 no.5
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    • pp.526-532
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    • 2008
  • The proposed $CO_2$ storage technology in the present study is a one-step sequestration process that stabilizes $CO_2$ in a reactor with Serpentine. The advantage of this technology is associated with its high stability of final product so that the entire system is recognized as permanent environment-friendly $CO_2$ removal method. Since the sequestration reaction mechanisms are generally understood that carbonation reaction proceeds with very slow rate, so that pretreatment method to increases reaction rate of $CO_2$ carbonation reaction should be developed. To increase the reactivity of Serpentine with $CO_2$, two different methods of pretreatment are carried out in the present investigation. One is heat-treatment, the other is chemical pretreatment. In this study, only chemical pretreatment is considered leaching method of magnesium from Serpentine using sulfuric acid at the various reaction temperatures, times, and acid concentrations. Experimental results illustrated that pretreatment by sulfuric acid increases surface area of serpentine from $11.1209m^2/g$ to $98.7903m^2/g$ and extracts magnesium compounds. Single variable experiment demonstrated the enhancements of magnesium extraction with increased reaction temperature and time. Amount of magnesium extraction is obtained by using the data of ICP-AES as maximum extraction condition of magnesium is 2 M acid solution, $75^{\circ}C$ and 1hr. After performing chemical pretreatment, carbonation yield increased from 23.24% to 46.30% of weight.

Removal of Radioactive Ions from Contaminated Water by Ion Exchange Resin (오염된 물로부터 이온교환수지를 이용한 방사성이온 제거)

  • Shin, Do Hyoung;Ju, Ko Woon;Cheong, Seong Ihl;Rhim, Ji Won
    • Applied Chemistry for Engineering
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    • v.27 no.6
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    • pp.633-638
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    • 2016
  • In this study, we used three kinds of commercially available cation, anion, and mixed-ion exchange resins to separate radioactive ions from a polluted water containing Cs, I, and other radioactive ions. The experiment was conducted at a room temperature with a batch method, and a comparative analysis on the decontamination ability of each resin for the removal of Cs and I was performed by using different quantities of resins. The concentration was analyzed using ion chromatography and the ion exchange resin product from company D showed an overall high ion exchange ability. However, for most of the experiments when the amount of ion exchange resin was decreased, the decontamination ability of the resins against mass increased. When the mass of company D's cation exchange resin was small, the ion exchange ability against Cs and I ions were measured as 0.199 and 0.344 meq/g, respectively. When the mixed ion exchange resin was used, the ion exchange ability against I ions was measured as 0.33 meq/g. All in all, company D's ion exchange resins exhibited a relatively higher ion exchange ability particularly against I ions than that of other companies' exchange ions.

Synthesis of High Purity Al2O3 from Low Grade Bauxite Ore(II) (저품위 Bauxite로부터 고순도 Al2O3의 합성(II))

  • Kwon, Kung-Taek;Song, Yon-Ho;Lee, Chul-Tae
    • Applied Chemistry for Engineering
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    • v.5 no.4
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    • pp.597-608
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    • 1994
  • A new process for the production of high purity ${\alpha}-Al_2O_3$ from ammonium aluminium sulfate solution abtained through the sulfation of low grade bauxite ore with $(NH_4)_2SO_4$, and leaching of the sulfated product was investigated. This process is consisted of solvent extraction for Fe component removal from ammonium aluminum sulfate solution and homogeneous precipitation of Al containing precipitate from the refined ammonium aluminium sulfate solution by using urea as precipitator. The optimum conditions of solvent extraction with Alamine 336 as extractant were shaking time of 4min, organic phase ratio to aqueous phase of 0.25. The types of precipitation products from this precipitation were amorphous alumina gel, pseudo-boehmite and crystalline boehmite in the lower temperature of $100^{\circ}C$, in the range from $125^{\circ}C$ to $150^{\circ}C$, and above $150^{\circ}C$, respectively. And also amorphous alumina gel hydrate in $1000^{\circ}C$ and crystalline boehmite in $1250^{\circ}C$ were tranfered to ${\alpha}-Al_2O_3$, respectively. This alumina was identified as ${\alpha}-Al_2O_3$ of purity 99.7%.

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Synthesis of High Purity Al2O3 from Low Grade Bauxite Ore(I) -Extraction of Al Component by the Decomposition of Bauxite Ore with Ammonium Sulfate- (저품위 Bauxite로부터 고순도 Al2O3의 합성(I) -Bauxite의 황산암모늄분해에 의한 Al 성분의 추출-)

  • Kwon, Kung-Taek;Song, Yon-Ho;Lee, Chul-Tae
    • Applied Chemistry for Engineering
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    • v.5 no.4
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    • pp.588-596
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    • 1994
  • A decomposition reaction of bauxite ore with $(NH_4)_2SO_4$ was investigated to prepare Al component pregnant solution for the direct product of high purity $Al_2O_3$ from low grade bauxite ore. Al component in the bauxite was sulfatized to $NH_4Al(SO_4)_2$ or $Al_2(SO_4)_3$ in this decomposition. The optimum conditions of the decomposition for bauxite ore were reaction temperature of $425^{\circ}C$, reaction time of 40min, $(NH_4)_2SO_4$ weight ratio to bauxite of 7.0 and particle size of bauxite ore of -200mesh. The optimum leaching conditions of sulfated bauxite ore were leaching temperature of $100^{\circ}C$, leaching time of 1hr and pulp density of 200ml $H_2O$ to sulfated ore of 1.0g bauxite. Under the above mentioned decomposition and leaching conditions, 94% of Al component in the bauxite ore was extracted.

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Study of Hydrotrope Action and Liquid Crystal Behavior of Concentrated Liquid Detergents (농축세정제의 액정 상거동과 하이드로트로프 작용에 대한 연구)

  • Chi, Gyeong-Yup
    • Applied Chemistry for Engineering
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    • v.27 no.5
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    • pp.516-520
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    • 2016
  • Concentrated liquid detergents have 2~3 times higher surfactant contents [35~45% (w/w)] compared to those of normal type detergents. In general, a single surfactant forms a lyotropic liquid crystal (LC) phase when the concentration is in the region of 30~60% (w/w). Whereas the concentrated liquid detergent at about 40% (w/w) concentration in a mixed surfactant system shows an opaque appearance of gel or LC. In order to meet consumer needs and preference for product appearance, we applied hydrotropes and various surfactants systems in concentrated liquid detergents to obtain an opaque gel-phase and also a clear transparent phase at even below zero $^{\circ}C$ temperature. The more effective hydrotropes for making concentrated liquid detergents are 1,6-hexanediol, adipic acid and dipropylene glycol (DPG) which have two hydrophilic groups in both terminated positions. In order to prepare an excellent concentrated liquid detergent, good hydrotropes alongside secondary type surfactants like LAS and SAS were used. The formation of LC phase of concentrated liquid detergents at about 40% (w/w) concentration could be prevented by the use of both hydrotropes and secondary type surfactants. The result indicate that concentrated detergents having excellent low temperature stability and controlled viscosity can be prepared.

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.

Optimization of the Bone-softening and Fishy Odor-reducing Processing of Mackerel Scomber japonicus Products using Response Surface Methodology (표면반응분석법을 활용한 뼈 연화 및 비린내 저감화 고등어(Scomber japonicus) 가공품의 가공공정 최적화)

  • Park, Sun Young;Kim, Yong Jung;Kang, Sang In;Lee, Jung Suck;Kim, Jin-Soo
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.51 no.5
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    • pp.499-509
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    • 2018
  • This study optimized the bone-softening and fishy odor-reducing process for mackerel Scomber japonicus products using response surface methodology (RSM). The RSM showed that the optimum concentrations of doenjang and citric acid for reducing the fishy odor in bone-softened mackerel were 11.8% and 0.04%, respectively, and the optimum immersion time was 52.2 min. The estimated overall acceptance, salinity, and acidity of the products under these optimum conditions were 7.7 points, 1.1%, and 202.6 mg/100 g, respectively, which were similar to the actual measured values of $7.6{\pm}1.2$ points, $1.0{\pm}0.1%$ and $203.2{\pm}3.8mg/100g$. Moreover, the heating temperature and time for bone-softening based on RSM were $107.3^{\circ}C$ and 4.4 h, respectively. The estimated hardness and proportion of skin removed from the product under the optimal conditions were $161.5g/cm^2$ and 0.09%, respectively, which were also similar to the actual measured values of $171.1{\pm}12.6g/cm^2$ and $0.10{\pm}0.02%$. The optimum bone-softening and fishy odor-reducing process for mackerel consisted of the following steps: thawing (${\leq}10^{\circ}C$, 8 h), filleting, washing/dewatering, immersing in an 11.8% doenjang -0.04% citric acid solution for 52 min, washing/dewatering, heating ($107.3^{\circ}C$, 4.4 h), freezing, depanning, internal and external packaging, and X-ray detection treatment.