• 제목/요약/키워드: Hydrogenolysis

검색결과 29건 처리시간 0.026초

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

  • 이병근
    • Journal of the Korean Wood Science and Technology
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    • 제25권1호
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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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    • 제31권9호
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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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    • 제28권2호
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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
    • 대한약학회:학술대회논문집
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    • 대한약학회 2002년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2
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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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    • 제8권4호
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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.

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

  • 김동원;문명준;류영복;이만식;홍성수
    • 청정기술
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    • 제20권1호
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    • pp.7-12
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    • 2014
  • 이원계 및 삼원계 금속산화물 촉매에서 프로필렌 글리콜의 글리세롤의 전환반응을 행하였다. Cu/Zn 및 Cu/Cr 혼합산화물 촉매에서는 단일 금속 산화물에 비해 글리세롤의 전환율과 프로필렌 글리콜의 선택도가 증가하였다. 또한, Cu/Zn 촉매에 Al이 첨가된 혼합산화물 촉매에서는 글리세롤의 전환율과 프로필렌 글리콜의 선택도가 매우 크게 증가하였다. 반응온도가 증가함에 따라 글리세롤의 전환율은 점차 증가하지만 프로필렌 글리콜의 선택도는 $200^{\circ}C$에서 최대값을 보이다가 $250^{\circ}C$에서는 오히려 감소하였다. 글리세롤의 농도가 커질수록 글리세롤의 전환율과 프로필렌 글리콜의 선택도가 감소하였다.

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

  • 권태은;노인수
    • Korean Chemical Engineering Research
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    • 제61권4호
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    • pp.505-516
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    • 2023
  • 플라스틱은 가공과 처리가 간단하여 매년 생산량이 증가하고 있으며 이에 따라 플라스틱 폐기물의 양 또한 매년 증가하고 있다. 플라스틱 폐기물 문제를 해결하기 위하여 촉매를 활용한 업사이클링 공정은 유망한 해결책으로 제시되고 있다. 다양한 금속(Ru, Pt 등) 및 지지체(TiO2, CeO2 등)가 폴리 올레핀계 플라스틱의 화학적 재활용에 적용되었다. 입자 크기를 조절하고, 지지체의 특성 및 이종 금속을 도입하여 액체 연료의 선택도를 향상시키고 메탄 생성 양을 줄이려는 시도가 있었다. 한편으로는 값비싼 귀금속의 양을 줄임으로써 최적의 촉매를 찾기 위한 연구를 진행하였다. 본 논문에서는 이러한 hydrogenolysis 반응 및 hydrocracking 반응에서 경제성을 높이기 위하여 어떠한 시도들이 있었는지 살펴보고자 한다. 이러한 관점에서 촉매 업사이클링 공정을 통해 플라스틱 폐기물 문제를 해결할 가능성을 제시하고자 한다.

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

  • 조욱재;이익모;김홍곤;김훈식
    • 대한화학회지
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    • 제38권9호
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    • pp.695-700
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    • 1994
  • 여러가지 불균일 촉매$(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$를 이용하여 CFC-113a의 가수소 분해반응을 액상과 기상에서 각각 조사하였다. 액상반응에서는 각 촉매에 따라 반응성은 차이가 났지만, 95% 이상의 높은 선택성으로 $HCFC-123(CF_3CHCl_2)$을 주었다. 특히 $Al_2O-3$가 액상반응에서 상당히 높은 반응성과 선택성을 보인 것은 주목할 만하다. 기상반응의 경우, 전이금속이 포함된 촉매(Pd/C, Pt/C)를 사용하였을 때에는 과수소화물인 $HCFC-133a(CF_3CH_2Cl)$HFC-143a(CF_3CH_3)$가 생성되었다. 한편, 액상반응에서 활성을 보이던 $Al_2O_3$는 기상반응에서는 거의 반응성을 보이지 않았다. $Al_2O_3$의 경우 용매로 THF를 사용하였을 경우에는 비교적 부반응 없이 깨끗하게 반응이 진행되었지만, MeOH를 사용하였을 때는 용매로 부터 $CH_3OCH_3$$CH_3CH_2OCH_3$ 등이 생성되면서 가수소 분해반응이 진행되었다. 따라서 액상반응에서는 용매의 역할이 중요한 것으로 해석하였다.

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

  • 신장식;정헌;이종대
    • 한국응용과학기술학회지
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    • 제19권4호
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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.