• Title/Summary/Keyword: sodium borohydride

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Reduction of N-Arylpyridinium Compounds by Sodium Borohydride and Dithionite: Regioselectivity and Isomerization of Reduction Products

  • Koh, Park, Kwang-Hee;Han, Du-Hee;Shin, Dae-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.201-204
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    • 1986
  • Reduction of N-arylpyridinium compounds by $NaBH_4$ gave mixtures of the corresponding 1,2-dihydropyridine(major) and 1,4-dihydropyridine(minor), whereas similar reduction by $Na_2S_2O_4$ produced 1,4-dihydropyridines regioselectively. The proportion of 1,4-isomer in the product by $NaBH_4$ reduction appeared to increase with the electron-donating ability of N-aryl groups. When the N-aryl group is p-methylphenyl, p-ethylphenyl or p-methoxyphenyl, the 1,2-dihydropyridines in ethanol-water (4:1) solutions isomerized to the corresponding 1,4-dihydropyridines. N-(p-methylphenyl)-1,2-dihydropyridine and N-(p-ethylphenyl)-1,2-dihydropyridine in solid state also isomerized to the corresponding 1,4-dihydropyridines. The different behaviors of reduction among N-arylpyridiniums and isomerization of the reduction products depending on the substituent in N-aryl group were explained in terms of difference in the electronic effects of the substituents.

Characteristics of Hydrolysis Reaction Using Unsupported Catalyst at High Concentration of NaBH4 Solutions (고농도 NaBH4 수용액에서 비담지 촉매의 가수분해 반응 특성)

  • Lee, Hye-Ri;Na, Il-Chai;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.54 no.5
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    • pp.587-592
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    • 2016
  • Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-P-B Co-B, catalyst at high concentration $NaBH_4$ solution were studied. In order to enhance the hydrogen generation yield at high concentration of $NaBH_4$, the effect of catalyst type, $NaBH_4$ concentration and recovery of condensing water on the hydrogen yield were measured. The yield of hydrogen evolution increased as the boron ratio increased in preparation process of Co-P-B catalyst. The hydrogen yield decreased as the concentration increased from 20 wt% to 25 wt% in $NaBH_4$ solution during hydrolysis reaction using 1:5 Co-P-B catalyst. Maximum hydrogen yield of 96.4% obtained by recovery of condensing water and thinning of catalyst pack thickness in reactor using Co-P-B with Co-B catalyst and 25 wt% $NaBH_4$ solution.

Studies on the Synthesis of Cyclitol derivatives -Part 5. Synthesis of O-(p-hydroxybenzoyl)-inositols and their test for food industry- (Cyclitol 유도체(誘導體) 합성(合成)에 관(關)한 연구(硏究) -제(第)5보(報) O-(p-hydroxybenzoyl)-inositol류(類)의 합성(合成)과 식품공업상(食品工業上) 응용(應用)을 위한 시험(試驗)-)

  • Sohn, Joo-Hwan
    • Korean Journal of Food Science and Technology
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    • v.5 no.4
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    • pp.240-248
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    • 1973
  • Reduction of penta-O-acetyl-myo-inosose-2 by catalytic hydrogenation and with sodium-amalgam was carried out in alcohol solution of pH $3{\sim}4$. The former reduction product was axial-alcohol, and the latter equatorial-alcohol. On reduction of penta-O-acetyl-DL-epi-inosose-2 with sodium borohydride and sodium-amalgam in the previous condition, ax.-alcohol and eq.-alcrhol have been obtained. The synthesis of various inositol-p-hydroxybezoate are described. The esters have been characterized by paper chromatography and saponification, and their antimicrobial activities on some microbes were tested for the application of food industry. As the result, it was found that the antimicrobiol activity of epi-inositol ester was superior to its analogues.

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Desmutagenic Effects of Maillard Reaction Products against Mutagenic Heterocyclic Amines (변이원성 Heterocyclic Amine에 대한 Maillard 반응생성물의 변이원성 억제효과)

  • KIM Seon-Bong;PARK Yeung-Ho;HAYASE Fumitaka;KATO Hiromichi
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.19 no.2
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    • pp.127-135
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    • 1986
  • Each molecular weight (Mw) fraction of melanoidins prepared from a D-glucose and glycine system, i. e., Mw below 1,000, Mw between 1,000 to 5,000 and Mw above 5,000 and nondialyzable and ozone-treated melanoidins were reacted with heat-induced mutagens such as Trp-P-1, Trp-P-2, Glu-P-1, Glu-P-2 and IQ at $37^{\circ}C$ for 30 min. The inhibitory effects of the melanoidins on the mutagens increased with increasing molecular weight. The reducing ability ana antioxidative activity of melanoidins also increased in proportion to the increase in molecular weight, whereas the mutagenic inhibitory effect decreased on reduction of the melanoidins with sodium borohydride. It was also observed that a part of Trp-P-1 was adsorbed to melanoidin molecules. On modification of amino groups of these mutagens with carbonyl compounds derived through the Maillard reaction such as diacetyl and glyceraldehyde, their mutagenic activities were remarkably suppressed. Accordingly, it is speculated that the mutagenic inhibitory action of melanoidins is due to their reducing ability and antioxidative activity, and electrostatic binding and carbonyl groups of the melanoidin molecules.

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Nitrate Reduction without Ammonium Release using Fe-loaded Zeolite

  • Lee Seunghak;Lee Kwanghun;Lee Sungsu;Park Junboum
    • Journal of Soil and Groundwater Environment
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    • v.10 no.1
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    • pp.1-5
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    • 2005
  • Nitrate reduction with zero valent iron $(Fe^0)$ has been extensively studied, but the proper treatment for ammonium byproduct has not been reported yet. In groundwater, however, ammonium is regarded as contaminant species, and particularly, its acceptable level is regulated to 0.5 mg-N/L. for drinking water. This study is focused on developing new material to reduce nitrate and properly remove ammonium by-products. A new material, Fe-loaded zeolite, is derived from zeolite modified by Fe(II) chloride followed by reduction with sodium borohydride. Batch experiments were performed without buffer at two different pH to evaluate the removal efficiency of Fe-loaded zeolite. After 80 hr reaction time, Fe loaded zeolite showed about $60\%$ nitrate removal at initial pH of 3.3 and $40\%$ at pH of 6 with no ammonium release. Although iron filing showed higher removal efficiency than Fe-loaded zeolite at each pH, it released a considerable amount of ammonium stoichiometrically equivalent to that of reduced nitrate. In terms of nitrogen species including $NO_3-N$ and $NH_4^+-N$, Fe-loaded zeolite removed about $60\%\;and\;40\%$ of nitrogen in residual solution at initial pH of 3.3 and 6, respectively, while the removal efficiency of iron filing was negligible.

Hydrolysis Reaction of NaBH4 using Unsupported Co-B, Co-P-B Catalyst (비담지 Co-B, Co-P-B 촉매를 이용한 NaBH4 가수분해 반응)

  • Oh, Sung-June;Jung, Hyeon-Seong;Jeong, Jae-Jin;Na, Il-Chai;Ahn, Ho-Geun;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.53 no.1
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    • pp.11-15
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    • 2015
  • Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells(PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-B, Co-P-B catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of unsupported Co-B catalyst was $75.7m^2/g$ and this value was 18 times higher than that of FeCrAlloy supported Co-B catalyst. The hydrogen yield of $NaBH_4$ hydrolysis reaction by unsupported catalysts using 20~25 wt% $NaBH_4$ solution was 97.6~98.5% in batch reactor. The hydrogen yield decrease to 95.3~97.0% as the concentration of $NaBH_4$ solution increase to 30 wt%. The loss of unsupported catalyst was less than that of FeCrAlloy supported catalyst during $NaBH_4$ hydrolysis reaction and the loss increased with increasing of $NaBH_4$ concentration. In continuous reactor, hydrogen yield of $NaBH_4$ hydrolysis was 90% using 1.2 g of unsupported Co-P-B catalyst with $3{\ell}/min$ hydrogen generation rate.

Characteristics of Byproduct After NaBH4 Hydrolysis Reaction Using Unsupported Catalyst (비담지 촉매를 이용한 NaBH4 가수분해반응에서 부산물의 특성)

  • Lee, Hye-Ri;Park, Dae-Han;Ju, Won;Na, Il-Chai;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.55 no.1
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    • pp.13-18
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    • 2017
  • Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for UAV PEMFC (Unmaned Aerial Vehicle Proton Exchange Membrane Fuel Cells). In order to use for UAV, the weight and volume of byproduct should be small after $NaBH_4$ hydrolysis reaction. Therefore, the weight and volume of byproduct were studied after $NaBH_4$ hydrolysis reaction using unsupported catalyst. The effect of catalyst type, concentration of $NaBH_4$, concentration of NaOH and thickness of catalyst pack on the weight and volume of byproduct were studied. Most of byproduct was $NaB(OH)_4$ and superficial volume of byproduct increased due to foam evolved from byproduct. The weight and volume of byproduct were not affected by concentration of NaOH used stabilizer. The weight of byproduct decreased as concentration of $NaBH_4$ solution increased, but maximum volume of byproduct obtained at 23 wt% of $NaBH_4$. Suitable defoaming agent reduced the volume of byproduct.

Hydrolysis Reaction of NaBH4 Using Activated Cabon Supported Co-B/C, Co-P-B/C Catalyst (활성탄 담지 Co-B/C, Co-P-B/C 촉매를 이용한 NaBH4 가수분해 반응)

  • Oh, Sohyeong;Kim, Youkyum;Bae, Hyojune;Kim, Dongho;Byun, Younghwan;Ahn, Ho-Geun;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.56 no.5
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    • pp.641-646
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    • 2018
  • Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C, Co-P-B/C catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of carbon supported catalyst was over $500m^2/g$ and this value was 2~3 times higher than that of unsupported catalyst. Hydrogen generation of activated carbon supported catalyst was more stable than that of unsupported catalyst. The activation energy of Co-P-B/C catalyst was 59.4 kJ/mol in 20 wt% $NaBH_4$ and 14% lower than that of Co-P-B/FeCrAlloy catalyst. Catalyst loss on activated carbon supported catalyst was reduced to about 1/3~1/2 compared with unsupported catalyst, therefore durability was improved by supporting catalyst on activated carbon.

Generation of Hydrogen from Hydrolysis Reaction of NaBH4 Using Sea Water (바닷물을 이용한 NaBH4 가수분해에 의한 수소발생)

  • Lee, Daewoong;Oh, Sohyeong;Kim, Junseong;Kim, Dongho;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.57 no.6
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    • pp.758-762
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    • 2019
  • Sodium borohydride,$NaBH_4$, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used for marine use, $NaBH_4$ hydrolysis using seawater is economical. Therefore, in this study, hydrogen was generated by using seawater instead of distilled water in the process of hydrolysis of $NaBH_4$. Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C catalyst were studied. The yield of hydrogen decreased as $NaBH_4$ concentration and NaOH concentration were increased during $NaBH_4$ hydrolysis using sea water. At higher concentrations of $NaBH_4$ and NaOH, byproducts adhered to the surface of the catalyst after hydrolysis reaction using sea water, reduced hydrogen yield compared to distilled water. The activation energy of $NaBH_4$ hydrolysis is 59.3, 74.4 kJ/mol for distilled water and sea water, respectively. In order to increase the hydrogen generation rate in seawater as high as distilled water, the reaction temperature has to be increased by $80^{\circ}C$ or more.

Generation of Hydrogen from Hydrolysis Reaction of NaBH4 Using Fresh Water (담수 사용 NaBH4 가수 분해반응에 의한 수소발생)

  • Oh, Sohyeong;Yoo, Donggeun;Kim, Taeho;Kim, Ikgyun;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.59 no.4
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    • pp.503-507
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    • 2021
  • Sodium borohydride, NaBH4, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used outdoors as a transport type, it is economical to hydrolyze NaBH4 using fresh water instead of distilled water. Therefore, in this study, hydrogen was generated using fresh water instead of distilled water during the NaBH4 hydrolysis process. The properties of NaBH4 hydrolysis were studied using an activated carbon-supported Co-P-B/C catalyst. Fresh water did not generate tetrahydrate during the NaBH4 hydrolysis process, and distilled water produced tetrahydrate by-products, which consumed a lot of water during the hydrolysis process, indicating that at the end of the reaction at a high concentration of 25% or more of NaBH4, dry by-products and unreacted NaBH4 remained. As a result, when fresh water was used, the hydrogen yield and hydrogen generation rate were higher than that of distilled water at a high concentration of 25% or more of NaBH4, indicating that it is suitable for use in transport-type fuel cells such as unmanned aerial vehicles.