• Title/Summary/Keyword: Hydrogenolysis

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Synthesis of Aromatic and Aliphatic Compound from Kraft Oak Lignin and Acetosolve Straw Lignin by Thermochemical Liquefaction (참나무 크라프트 리그닌과 볏짚 아세토솔브 리그닌의 열-화학적 분해에 의한 방향족(Aromatic)과 지방족(Aliphatic)화합물의 합성)

  • Lee, Byung-G.
    • Journal of the Korean Wood Science and Technology
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    • v.25 no.1
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    • pp.1-7
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    • 1997
  • Kraft oak lignin and ricestraw lignin from acetosolve pulping were dissolved in 50/50 mixture of tetralin/m-cresol solvent. The dissolved lignin was reacted in the pressurized autoclave which was operating at $350{\sim}500^{\circ}C$ of reaction temperature and 10~20 atms of reaction pressure respectively_Hydrogen pressure of 60~80kg/$cm^2$ was exercising into the pressurized autoclave reactor to create thermochemical hydrogenolysis reaction. It was identified by GLC, GC-MS and HPLC that the alkyl-aryl-${\beta}$-O-4 ether bond of lignin was cleaved and degraded into various smaller molecules of aromatic compound such as phenols and cresols under the reaction conditions around $300^{\circ}C$ and 10 atms of reaction temoerature and pressure. Hydrogenolysis reaction of lignin compound which was done above $500^{\circ}C$ of reaction temperature and 20 atms of reaction pressure showed that the amount of aromatic compound such as phenols and cresols degraded from reactant lignin was decreasing with newly present and increasing water out of product mixtures. It was supposed that new aliphatic compound of high molecular weight hydrocarbon is composed due to higher reaction temperature and pressure of hydrogenolysis reaction such as $500^{\circ}C$ and 20 atms, even though it was almost impossible, to identify what kind of degraded products it was by HPLC.

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Liquid-Phase Synthesis of Biaryl Compounds by the Hydrogenolysis of Pentaerythritol-Supported Biarylsulfonates

  • Kim, Chul-Bae;Lee, Sung-Kyung;Park, Kwang-Yong
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2459-2466
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    • 2010
  • Unfunctionalized biaryl compounds were parallelly and combinatorially prepared by the traceless hydrogenolysis of biarylsulfonates supported on pentaerythritol. The hydrogenolysis using 2-propylmagnesium chloride in the presence of $dppfNiCl_2$ efficiently generated corresponding biaryl derivatives without any memory of the support. The strategy using pentaerythritol as a small soluble support was disclosed to have a potential to combine the benefits of both SPOS and solution-phase reaction with fast reaction rate, facile isolation of intermediates, easy analysis of intermediates and atom economical manner. The novel tetrapodal support is expected to be an efficient substitute for polymeric supports in many circumstances.

Nickel-Catalyzed Hydrogenolysis of Arenesulfonates Using Secondary Alkyl Grignard Reagents

  • Kim, Chul-Bae;Cho, Chul-Hee;Park, Kwang-Yong
    • Bulletin of the Korean Chemical Society
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    • v.28 no.2
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    • pp.281-284
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    • 2007
  • Neopentyl arenesulfonates react with secondary alkylmagnesium chlorides in the presence of dppfNiCl2 to produce the corresponding arenes via the reductive cleavage of carbon-sulfur bond. Highest yield is obtained by using three equivalents of Grignard reagent to a mixture of arenesulfonate and dppfNiCl2 in Et2O at room temperature. This reaction represents a novel method allowing the efficient hydrogenolysis of sulfur-containing groups in aromatic compounds.

Cleavage of Benzyl and p-Methoxybenzyl Ethers Using Chlorosulfonyl Isocyanate Reaction

  • Kim, Ji-Duck;Jung, Young-Hoon
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.349.2-350
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    • 2002
  • Deprotection of the benzyl group has been widely used in multi-step organic synthesis with a variety of reaction conditions. including catalytic hydrogenolysis. Lewis acids such as FeCl$_3$ or MgBr$_2$ and lithium naphthalenide. However. these procedures sometimes can be problematic with multifunctional substrates. such as unsaturated bonds during hydrogenolysis. an acid-labile moiety in FeCl$_3$ and a easily reducible functional group in lithium naphthalenide. (omitted)

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Catalytic Reactions of 3-Phenyl-2-propen-1-ol with Perchloratocarbonylbis (triphenylphosphine) rhodium (I)$^\dag$

  • Park, Jeong-Han;Chin, Chong-Shik
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.324-328
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    • 1987
  • Reaction of Rh $(ClO_4)(CO)(PPh_3)_2$ (1) with trans-$C_6H_5CH = CHCH_2OH$ (2) produces a new cationic rhodium(Ⅰ) complex, $[Rh(trans-C_6H_5CH = CHCHO)(CO)(PPh_3)_2]ClO_4$ (3) where 2 is coordinated through the oxygen atom but not through the olefinic group. At room temperature under nitrogen, complex 1 catalyzes dehydrogenation, hydrogenolysis, and isomerization of 2 to give $trans-C_6H_5CH$ = CHCHO (4), trans-$C_6H_5CH = CHCH_3$ (5) and $C_6H_5CH_2CH_2CHO$ (6), respectively, and oligomerization of 2 whereas under hydrogen, complex 1 catalyzes hydrogenation of 2 to give $C_6H_5CH_2CH_2CH_2OH$ (7) and hydrogenolysis of 2 to 5 which is further hydrogenated to $C_6H_5CH_2CH_2CH_3$ (8). The dehydrogenation and hydrogenolysis of 2 with 1 suggest an interaction between the rhodium and the oxygen atom of 2, whereas the isomerization and hydrogenation of 2 with 1 indicate an interaction between the rhodium and the olefinic system of 2.

Synthesis of Propylene Glycol via Hydrogenolysis of Glycerol over Mixed Metal Oxide Catalysts (혼합 금속산화물 촉매에서 글리세롤의 수소화 분해반응을 통한 프로필렌 글리콜의 합성)

  • Kim, Dong Won;Moon, Myung Joon;Ryu, Young Bok;Lee, Man Sig;Hong, Seong-Soo
    • Clean Technology
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    • v.20 no.1
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    • pp.7-12
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    • 2014
  • Hydrogenolysis of glycerol to propylene glycol was performed over binary and ternary metal oxide catalysts. The conversion of glycerol and selectivity to propylene glycol were increased on Cu/Zn and Cu/Cr mixed oxides compared to pure CuO and ZnO oxides. The addition of alumina into Cu/Zn mixed oxide very highly increased the conversion of glycerol and selectivity to propylene glycol. The conversion of glycerol was increased with increasing the reaction temperature but the selectivity to propylene glycol was shown to have maximum value at $200^{\circ}C$ and then decreased at $250^{\circ}C$. The conversion of glycerol and selectivity to propylene glycol were decreased with increasing the glycerol concentration.

Advancing Towards a Sustainable Future: Recent Trends in Catalytic Upcycling of Waste Plastics (지속가능한 미래를 위한 폐플라스틱의 촉매 업사이클링 연구 동향)

  • Taeeun Kwon;Insoo Ro
    • Korean Chemical Engineering Research
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    • v.61 no.4
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    • pp.505-516
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    • 2023
  • Plastic's ease of processing drives its growing production, resulting in a surge of plastic waste. Addressing this issue, catalytic upcycling emerges as a promising remedy. Various metals (Ru, Pt, etc.) and supports (TiO2, CeO2, etc.) have been employed for the chemical recycling of polyolefin plastics. Strategies to enhance liquid fuel selectivity and minimize methane include manipulating particle size, introducing heterogeneous metals, and tuning support characteristics. Simultaneously, endeavors to optimize catalysts by reducing precious metal usage were pursued. This study explores enhancing economic viability in hydrogenolysis and hydrocracking reactions, underscoring the potential of catalystdriven upcycling to tackle plastic waste.

Hydrogenolysis of CFC-113a$(CF_3CCl_3)$ Catalyzed by Heterogeneous Catalysts in the Liquid Phase (불균일 촉매를 이용한 CFC-113a$(CF_3CCl_3)$의 액상 가수소 분해 반응)

  • Jo, Uk Jae;Lee, Ik Mo;Kim, Hong Gon;Kim, Hun Sik
    • Journal of the Korean Chemical Society
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    • v.38 no.9
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    • pp.695-700
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    • 1994
  • Hydrogenolysis reactions of CFC-113a catalyzed by various heterogeneous catalysts $(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$ were investigated in the liquid and gas phases. In the liquid phase reaction, different catalysts showed different activities, but all catalysts used gave high selectivities toward HCFC-123 over 95%. It was noticeable that the neutral $Al_2O_3$ showed both a high activity and a selectivity in the liquid phase reaction. In the gas phase reaction, transition metals on carbon(Pd/C, Pt/C) were so active for hydrogenolysis of CFC-113a that they even catalyzed the production reaction of overhydrogenated compounds such as $HCFC-133a(CF_3CH_2Cl)\;and\;HFC-143a(CF_3CH_3)$. $Al_2O_3$, which showed the high activity in the liquid phase reaction, did not show a remarkable activity. When $Al_2O_3$ was used in the liquid phase reaction, the hydrogenolysis of CFC-113a proceeded without any side products in THF. However, the same reaction in MeOH produced side products, such as $CH_3OCH_3\;and\;CH_3CH_2OCH_3$ from solvent. Based on this result, including heterogeneous catalysts, it was concluded that the solvent played an important role in the liquid phase reaction.

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Development of a Liquid-Phase Methanol Synthesis Process for Coal-derived Syngas (석탄가스 전환용 액상 메탄올 합성 공정 개발)

  • Shin, Jang-Sik;Jung, Heon;Lee, Jong-Dae
    • Journal of the Korean Applied Science and Technology
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    • v.19 no.4
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    • pp.251-257
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    • 2002
  • Liquid-phase methanol synthesis via methyl formate using coal-derived syngas was carried out in a bench-scale(diameter 173 mm and dispersion height 1200 mm) slurry bubble column reactor(SBCR) Under the condition of $180^{\circ}$. 61 atm, 30 L/min, $H_{2}$/CO=2 and a slurry mixture of 2 kg of copper chromite and 0.5 kg of $KOCH_{3}$ suspended in 14 L of methanol, the per pass conversions of syngas is 6 %, maximum concentration of methyl formate 3.088 mol% and maximum synthesis, rate of methanol 0.8 gmole/kg ${\cdot}$ hr. It is a significant evidence that copper chromite powder as heterogeneous catalyst didn't active for the hydrogenolysis of methyl formate to methanol, resulting copper chromite powder was not efficiently suspended in a slurry mixture. To enhance the hydrogenolysis of methyl formate in liquid-phase methanol synthesis process, the designed SBCR have need to use the higher specific gravity solvent and/or decrease the catalyst particle size.