• Clean Technology
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• v.22 no.4
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• pp.250-257
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• 2016

As an attempt to replacing petroleum-based chemicals with bio-based ones, synthesis of furfural from biomass-derived xylose attracts much attention in recent days. Conventionally, furfural from xylose has been produced via the utilization of highly corrosive, toxic, and environmentally unfriendly mineral acids such as sulfuric acid or hydrochloric acid. In this study, microwave-assisted biphasic reaction process in the presence of novel bio-based heterogeneous acid catalysts was developed for the eco-benign and effective synthesis of furfural from xylose. The microwave was irradiated for reaction acceleration and a biphasic system consisting of $H_2O$ : MIBK (1 : 2) was designed for continuous extraction of furfural into the organic phase in order to reduce the undesired side products formed by decomposition/condensation/oligomerization in the acidic aqueous phase. Moreover, sulfonated amorphous carbonaceous materials were prepared from wood powder, the most abundant lignocellulosic biomass. The prepared catalysts were characterized by FT-IR, XPS, BET, elemental analysis and they were used as bio-based heterogeneous acid catalysts for the dehydration of xylose into furfural more effectively. For further optimization, the effect of temperature, reaction time, water/organic solvent ratio, and substrate/catalyst ratio on the xylose conversion and furfural yield were investigated and 100% conversion of xylose and 74% yield of furfural was achieved within 5 h at $180^{\circ}C$. The bio-based heterogeneous acid catalysts could be used three times without any significant loss of activity. This greener protocol provides highly selective conversion of xylose to furfural as well as facile isolation of product and bio-based heterogeneous acid catalysts can alternate the environmentally-burdened mineral acids.

• Applied Chemistry for Engineering
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• v.24 no.3
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• pp.291-298
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• 2013

Conjugated linoleic acid methylester was synthesized through isomerization of linoleic acid methylester by using heterogeneous catalysts. As for heterogeneous catalysts, Ni supported zeolite type catalysts were used. H zoelite Y (HY) were ion exchanged with KCl aqueous solution to synthesize K zeolite Y (KY), and with impregnation method, Ni supported zeolite catalysts were synthesized. Catalysts were used after pre-treatment by using hydrogen. HY catalysts showed a high conversion at low temperatures; but a low selectivity for conjugation reaction. KY catalysts showed a low conversion at low temperatures; but a similar conversion with HY catalysts at high temperatures while a high selectivity at low temperatures. As a result, 4 wt% Ni/KY720 recorded the high conjugation yield of 63.4% at 220.

• Journal of Microbiology and Biotechnology
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• v.28 no.5
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• pp.732-738
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• 2018

Novel carbon-based solid acid catalysts were synthesized through a sustainable route from lipid-extracted microalgal residue of Dunaliella tertiolecta, for biodiesel production. Two carbon-based solid acid catalysts were prepared by surface modification of bio-char with sulfuric acid ($H_2SO_4$) and sulfuryl chloride ($SO_2Cl_2$), respectively. The treated catalysts were characterized and their catalytic activities were evaluated by esterification of oleic acid. The esterification catalytic activity of the $SO_2Cl_2$-treated bio-char was higher ($11.5mmol\;Prod.{\cdot}h^{-1}{\cdot}gCat.\;^{-1}$) than that of commercial catalyst silica-supported Nafion SAC-13 ($2.3mmol\;Prod.{\cdot}h^{-1}{\cdot}gCat.^{-1}$) and $H_2SO_4$-treated bio-char ($5.7mmol\;Prod.{\cdot}h^{-1}{\cdot}gCat.^{-1}$). Reusability of the catalysts was examined. The catalytic activity of the $SO_2Cl_2$-modified catalyst was sustained from the second run after the initial activity dropped after the first run and kept the same activity until the fifth run. It was higher than that of first-used Nafion. These experimental results demonstrate that catalysts from lipid-extracted algae have great potential for the economic and environment-friendly production of biodiesel.

• Clean Technology
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• v.29 no.3
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• pp.163-171
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• 2023

Hydrogen has been gaining a lot of attention as a possible clean energy source that can aid in reaching carbon neutrality. Currently, hydrogen production has relied on the steam reforming of fossil fuels. However, due to the carbon dioxide emissions caused by this process, hydrogen production based on the steam reforming of bio-oil derived from biomass has been proposed as an alternative approach. In order to use this alternative approach efficiently, one of the key issues that must be overcome is that the complexity of bio-oil, which has a large molecular weight and diverse functional groups of hydrocarbons, promotes the catalytic deactivation of nickel-based catalysts. In this review, research efforts to improve nickel-based catalysts for the steam reforming of bio-oil have been discussed in terms of the active phase, support, and promoters. The active phases are involved in activating C-C and C-H bonds of high-molecular-weight hydrocarbons, and noble and transition metals can be utilized. In terms of the support and promoters, the catalytic deactivation of Ni-based catalysts can be inhibited by utilizing reactive lattice oxygen for support or by suppressing the acidity. The development of active and stable Ni-based reforming catalysts plays a critical role in clean hydrogen production based on bio-oils.

• Korean Chemical Engineering Research
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• v.57 no.3
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• pp.387-391
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• 2019

A highly porous Ni@MIL-101catalyst for urea oxidation was synthesized by anchoring Ni into a Cr-based metal-organic framework, MIL-101, particles. The morphology, structure, and composition of as synthesized Ni@MIL-101 catalysts were characterized by X-Ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. The electro-catalytic activity of the Ni@MIL-101catalysts towards urea oxidation was investigated using cyclic voltammetry. It was found that the structure of Ni@MIL-101 retained that of the parent MIL-101, featuring a high BET surface area of $916m^2g^{-1}$, and thus excellent electro-catalytic activity for urea oxidation. A $urea/H_2O_2$ fuel cell with Ni@MIL-101 as anode material exhibited an excellent performance with maximum power density of $8.7mWcm^{-2}$ with an open circuit voltage of 0.7 V. Thus, this work shows that the highly porous three-dimensional Ni@MIL-101 catalysts can be used for urea oxidation and as an efficient anode material for urea fuel cells.

• 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.

• 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.

• Journal of Hydrogen and New Energy
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• v.21 no.6
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• pp.493-499
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• 2010

Steam reforming (SR) of glycerol, a main by-product of manufacturing process of bio-diesel, for the production of hydrogen was investigated over the Ni-based catalysts. The Ni-based catalysts were prepared by an impregnation method, and characterized by $N_2$ physisorption, CO chemisorption, XRD and TEM techniques. It was found that the Ni/${\gamma}-Al_2O_3$ catalyst showed higher conversion and catalytic stability for the carbon formation than the other catalysts in the steam reforming of glycerol under the tested conditions. The results suggest that the steam reforming of glycerol over modified Ni/${\gamma}-Al_2O_3$ catalyst minimized carbon formation can be applied in hydrogen station for fuel-cell powered vehicles and fuel processor for stationary and portable fuel cells.

• 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%.

• 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.