• Clean Technology
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• v.28 no.2
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• pp.174-181
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• 2022

Biomass is a sustainable alternative resource for production of liquid fuels and organic compounds that are currently produced from fossil fuels including petroleum, natural gas, and coal. Because the use of fossil fuels can increase the production of greenhouse gases, the use of carbon-neutral biomass can contribute to the reduction of global warming. Although biological and chemical processes have been proposed to produce petroleum-replacing chemicals and fuels from biomass feedstocks, it is difficult to replace completely fossil fuels because of the high oxygen content of biomass. Production of petroleum-like fuels and chemicals from biomass requires the removal of oxygen atoms or conversion of the oxygen functionalities present in biomass derivatives, which can be achieved by catalytic hydrodeoxygenation. Hydrodeoxygenation has been used to convert raw biomass-derived materials, such as biomass pyrolysis oils and lignocellulose-derived chemicals and lipids, into deoxygenated fuels and chemicals. Multifunctional catalysts composed of noble metals and transition metals supported on high surface area metal oxides and carbons, usually selected as supports of heterogeneous catalysts, have been used as efficient hydrodeoxygenation catalysts. In this review, the catalysts proposed in the literature are surveyed and hydrodeoxygenation reaction systems using these catalysts are discussed. Based on the hydrodeoxygenation methods reported in the literature, an insight for feasible hydrodeoxygenation process development is also presented.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.380-386
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• 2018

A sustainable method was developed for the upgrade of biomass derived vanillin (a typical model compound of lignin) into the potential liquid biofuels over a layered double hydroxide supported Pd catalyst (abbreviated as CoAl-LDH/Pd). The CoAl-LDH/Pd catalyst showed high catalytic activity towards the hydrodeoxygenation of vanillin into 2-methoxy-4-methylphenol (MMP) under mild conditions in aqueous media. High MMP yield up to 86% was produced at $120^{\circ}C$ after 4 h. Kinetic studies revealed that the rate-determining step for the hydrodeoxygenation of vanillin was the hydrogenolysis of vanillyl alcohol. More importantly, the CoAl-LDH/Pd catalyst was highly stable without the loss of activity.

• Clean Technology
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• v.25 no.2
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• pp.168-176
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• 2019

Spent coffee is one of biomass sources to be converted into bio-oil. However, the bio-oil should be further upgraded to achieve a higher quality bio-oil because of its high oxygen content. Deoxygenation under hydrotreating using different catalysts (catalytic hydrodeoxygenation; HDO) is considered as one of the promising methods for upgrading bio-oil from pyrolysis by removal of O-containing groups. In this study, the HDO of spent coffee bio-oil, which was collected from fast pyrolysis of spent coffee ($460^{\circ}C$, $2.0{\times}U_{mf}$), was carried out in an autoclave. The product yields were 72.16 ~ 96.76 wt% of bio-oil, 0 ~ 18.59 wt% of char, and 3.24 ~ 9.25 wt% of gas obtained in 30 min at temperatures between $250^{\circ}C$ and $350^{\circ}C$ and pressure in the range of 3 to 9 bar. The highest yield of bio-oil of 97.13% was achieved at $250^{\circ}C$ and 3 bar, with high selectivity of D-Allose. The carbon number distribution of the bio-oil was analyzed based on the concept of simulated distillation. The $C_{12}{\sim}C_{14}$ fraction increased from 22.98 wt% to 27.30 wt%, whereas the $C_{19}{\sim}C_{26}$ fraction decreased from 24.74 wt% to 17.18 wt% with increasing reaction time. Bio-oil yields were slightly decreased when the HZSM-5 catalyst and dolomite were used. The selectivity of CO was increased at the HZSM-5 catalyst and decreased at the dolomite.

• Journal of the Korean Wood Science and Technology
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• v.47 no.3
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• pp.344-359
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• 2019

Effects of various types of zeolite on the catalytic performance of hydrodeoxygenation (HDO) of bio-oil obtained from waste larch wood pyrolysis were investigated herein. Bifunctional catalysts were prepared via wet impregnation. The catalysts were characterized through XRD, BET, and SEM. Experimental results demonstrated that HDO enhanced the fuel properties of waste wood bio-oil, such as higher heating values (HHV) (20.4-28.3 MJ/kg) than bio-oil (13.7 MJ/kg). Water content (from 19.3 in bio-oil to 3.1-16.6 wt% in heavy oils), the total acid number (from 150 in bio-oil to 28-77 mg KOH/g oil in heavy oils), and viscosity (from 103 in bio-oil to $40-69mm^2/s$ in heavy oils) also improved post HDO. In our experiments, depending on the zeolite support, NiFe/HBeta exhibited a high Si/Al ratio of 38 with a high specific surface area ($545.1m^2/g$), and, based on the yield of heavy oil (18.3-18.9 wt%) and HHV (22.4-25.2 MJ/kg), its performance was not significantly affected by temperature and solvent concentration variations. In contrast, NiFe/zeolite Y, which had a low Si/Al ratio of 5.2, exhibited the highest improved quality for heavy oil at high temperature, with an HHV of 28.3 MJ/kg at $350^{\circ}C$ with 25 wt% of solvent.

• Advances in Energy Research
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• v.8 no.4
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• pp.223-231
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• 2022

An ex-situ gravitational fixed bed pyrolysis reactor was used over Al₂O₃ supported Ni₂P based catalyst with various Ni/P molar ratios (0.5-2.0) and constant nickel loading of 5.37 mmol/g Al₂O₃ to determine the hydrodeoxygenation of rubberwood sawdust (RWS) at atmospheric pressure. The 3D catalysts formed were characterized structurally as well as acidic properties were determined by hydrogen-temperature programmed reduction (TPR). The Ni₂P phase formed completely on Al₂O₃ for 1.5 Ni/P ratio, although lesser crystallite sizes of Ni₂P were seen at Ni/P ratios less than 1.5. Additionally, it was shown that when nickel loading level increased, acidity increased and specific surface area dropped, probably because nickel phosphate is not easily converted to Ni₂P. When Ni/P ratio was 1.5, Ni₂P phase fully formed on Al₂O₃. The catalytic activity was explained in terms of impacts of reaction temperature and Ni/P molar ratio. At relatively high temperature of 450℃, the high-value deoxygenated produce was predominantly composed of n-alkanes. Based on the findings, it was suggested that hydrogenolysis, hydrodeoxygenation, dehydration, decarbonylation, and hydrogenation are all part of mechanism underlying hydrotreatment of RWS. In conclusion, the synthesized Ni₂P/ Al₂O₃ catalyst was capable of deoxygenating RWS with ease at atmospheric pressure, primarily resulting in long chained (C₉-C₂₄) hydrocarbons and acetic acid.

• KEPCO Journal on Electric Power and Energy
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• v.2 no.3
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• pp.447-452
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• 2016

It is imperative to develop an effective pathway to depolymerize lignin into liquid fuel that can be used as a bioheavy oil. Lignin can be converted into liquid products either by a solvent-free thermal cracking in the absence air, or thermo-chemical degradation in the presence of suitable solvents and chemicals. Here we show that the solvent-assisted liquefaction has produced promising results in the presence of metal-based catalysts. The supercritical ethanol is an efficient liquefaction solvent, which not only provides better solubility to lignin, but also scavenges the intermediate species. The concentrated sulfuric acid hydrolysis lignin (CSAHL) was completely liquefied in the presence of solid catalysts (Ni, Pd and Ru) with no char formation. The effective deoxy-liquefaction nature associated with scEtOH with aid hydrodeoxygenation catalysts, resulted in significant reduction in oxygen-to-carbon (O/C) molar ratio up to 61%. The decrease in oxygen content and increase in carbon and hydrogen contents increased the calorific value bio-oil, with higher heating value (HHV) of $34.6MJ{\cdot}Kg^{-1}$. The overall process is energetically efficient with 129.8% energy recovery (ER) and 70.8% energy efficiency (EE). The GC-TOF/MS analysis of bio-oil shows that the bio-oil mainly consists of monomeric species such as phenols, esters, furans, alcohols, and traces of aliphatic hydrocarbons. The bio-oil produced has better flow properties, low molecular weight, and high aromaticity.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.527-527
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• 2009

1세대 바이오디젤인 fatty acid methyl ester(FAME)의 문제점을 극복하기 위하여 많은 연구가 진행 중 이다. 소위 차세대 바이오디젤은 triglyceride의 산소 화합물을 제거하여 정유 공정을 통해 생산된 디젤과 동일한 특성을 지닌 탄화수소로 전환시킨 오일이다. 이를 위하여 수소를 첨가하여 산소를 제거 시키는 Hydrodeoxygenation(HDO) 반응이 필요하다. 고온($300-400^{\circ}C$), 고압(50-100 bar)의 혹독한 조건에서 높은 수율과 안정성을 보이는 촉매 개발이 필요하다. 이를 위하여 반응물중의 산소를 효과적으로 제거하기 위하여 산소 전달능이 뛰어난 $CeO_2$ 담체에 열안정성을 높이는 $ZrO_2$를 조합한 $Ce-ZrO_2$ 담체를 선정하였으며 수소첨가 탈산소 반응에 활성을 나타낼 것으로 예상되는 니켈을 활성성분으로 선정하였다. 본 연구에서는 15%Ni-$Ce_{(1-x)}Zr_{(x)}O_2$ ($0{\leq}x{\leq}1$)촉매를 공침법(co-precipitation)으로 제조하였으며 $500^{\circ}C$에서 소성하였다. 촉매 특성분석은 XRD, BET, H2-TPR을 이용하였다.

• Journal of the Korean Applied Science and Technology
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• v.35 no.3
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• pp.865-875
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• 2018

Selection of optimum reaction conditions during deoxygenation process of palm oil is essential factor to obtain the maximum yield of bio-jet fuel. In this context, the deoxygenation of palm oil was carried out in a fixed bed reactor with an internal diameter of 1 inch loaded with a 1 wt.% $Pt/Al_2O_3$ catalyst. The composition of the organic liquid product(OLP), which can be utilized as a transportation fuel through the upgrading process, was analyzed by a gas chromatography method. The palm oil/hydrogen ratio and hydrogen pressure in the feed affected the decarboxylation(DCB) and hydrodeoxygenation(HDO) reactions, resulting in a change in the composition of the OLP. As the reaction temperature increased, the continuous cracking reaction of the deoxygenation product was promoted and the product composition in the $C_5{\sim}C_{14}$ region was increased. Thus, the results can help to understand the characteristics of deoxidation reaction of palm oil as well as the subsequent process, hydro-upgrading, to obtain the maximum yield of bio-jet fuel.

• Applied Chemistry for Engineering
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• v.2 no.2
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• pp.108-118
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• 1991

Interactions between pyridine hydrodenitrogenation (HDN) and m-cresol hydrodeoxygenation(HDO), and the kinetic analysis were studied over sulfided $CoMo/{\gamma}-Al_2O_3$ catalyst at the range of temperatures between 473 K and 723 K, the total pressures between $10{\times}10^5Pa$ and $50{\times}10^5Pa$, and the contact times between 0.0125 g-cat. hr/ml-feed and 0.03g-cat. hr/ml-feed. HDN of pyridine and HDO of m-cresol were inhibited by each other and the inhibition effect of HDO by pyridine is higher than that of HDN by m-cresol. But reactivity of m-cresol is higher than that of pyridine. The rate equations of pyridine and m-cresol were given to be ${\gamma}_{HDN}=k_{HDN}{\cdot}K_pC_p/(1+K_cC_c+K_pC_p)$ and ${\gamma}_{HDO}=k_{HDO}{\cdot}K_cC_c/(1+K_cC_c+K_pC_p)$ in terms of Langmuir-Hinshellwood-Hougen-Watson model. At each temperature, reaction rate constants and adsorption equilibrium constants were determined and activation energies of pyridine HDN and m-cresol HDO are 13.83kcal/mol, respectively and the heat of adsorption are -6.458 and -5.045kcal/mol, respectively.

• Clean Technology
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• v.27 no.1
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• pp.69-78
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• 2021

Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.