• Journal of Hydrogen and New Energy
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• v.31 no.2
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• pp.223-233
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• 2020

Fast pyrolysis is one of the most promising technologies for converting biomass to liquid fuels. Pyrolysis bio-oil can replace petroleum-based fuels used in various thermal conversion devices. However, pyrolysis bio-oil is completely different from petroleum fuels. Therefore, in order to successfully use pyrolysis bio-oil, it is necessary to understand the fuel characteristics of pyrolysis bio-oil. This paper focuses on fuel characteristics and upgrading methods of pyrolysis bio-oil and discusses how these fuel characteristics can be applied to the use of pyrolysis bio-oils. In addition, the fuel quality standards of fast pyrolysis bio-oil were examined.

• Korean Chemical Engineering Research
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• v.45 no.4
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• pp.340-344
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• 2007

Catalytic upgrading of pyrolytic bio-oil produced from Japanes Larch was carried out over MCM-41 catalyst. Oil with enhanced stability was produced by the MCM-41 catalyst due to transform oxygen known as a main cause for the instability of bio-oil into $H_2O$, CO and $CO_2$. In addition, the MCM-41 catalyst produced the larger amount of phenolic compounds in the pyrolytic bio-oil product compared with that in the bio-oil produced without catalyst. Especially, the catalytic activity of Al-MCM-41 for the bio-oil upgrading was higher than that of Si-MCM-41 because Al-MCM-41 has the larger amount of acid sites. Also, the better reforming result was obtained when pyrolytic bio-oil vapor passed through catalytic layer rather than Japanese Larch was mixed with catalyst directly.

• Applied Chemistry for Engineering
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• v.20 no.1
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• pp.1-8
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• 2009

Bio-oil has attracted considerable interest as one of the promising renewable energy resources because it can be used as a feedstock in conventional petroleum refineries for the production of high value chemicals or next-generation hydrocarbon fuels. Currently, catalytic vapor cracking is considered the most potential upgrading method for stabilization of bio-oil, which is a pre-process required prior to feeding bio-oil into refineries. This review introduces the recent research and development trends on bio-oil upgrading via catalytic vapor cracking, focusing on catalysts and upgrading methods used.

• Clean Technology
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• v.26 no.1
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• pp.79-87
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• 2020

The bio-oil produced from the fast pyrolysis of lignocellulosic biomass contains a high amount of oxygenates, causing variation in the properties of bio-oil, such as instability, high acidity, and low heating value, reducing the quality of the bio-oil. Consequently, an upgrading process should be recommended ensuring that these bio-oils are widely used as fuel sources. Catalytic fast pyrolysis has attracted a great deal of attention as a promising method for producing upgraded bio-oil from biomass feedstock. In this study, the fast pyrolysis of tulip tree was performed in a bubbling fluidized-bed reactor under different reaction temperatures, with and without catalysts, to investigate the effects of pyrolysis temperature and catalysts on product yield and bio-oil quality. The system used silica sand, ferric oxides (Fe₂O₃ and Fe₃O₄), and H-ZSM-5 as the fluidized-bed material and nitrogen as the fluidizing medium. The liquid yield reached the highest value of 49.96 wt% at 450 ℃, using Fe₂O₃ catalyst, compared to 48.45 wt% for H-ZSM-5, 47.57 wt% for Fe₃O₄ and 49.03 wt% with sand. Catalysts rejected oxygen mostly as water and produced a lower amount of CO and CO₂, but a higher amount of H₂ and hydrocarbon gases. The catalytic fast pyrolysis showed a high ratio of H₂/CO than sand as a bed material.

• 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.

• Applied Chemistry for Engineering
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• v.19 no.6
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• pp.592-599
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• 2008

Oil sands had not received enough attention due to high production cost. However, as oil price significantly increases, oil sands are receiving more and more interest as unconventional crude oil. The value and applicability of oil sands can be enhanced by upgrading oil sands bitumen to produce synthetic crude oil (SCO). This study analyzed 213 oil sands upgrading patents applied between 1969 and 2006 in US, Canada, Japan, Europe, and Korea. The upgrading technologies could be classified into 9 detailed technologies; hydrocracking, coking, thermal cracking, deasphalting, supercritical technology, bio-technology, hydrotreating, gasification, and others. The number of patents applied for oil sands upgrading increased after 1970, reached a maximum in the early 1980, and slowly increases again in recent years. Korea has a lack of technologies for oil sands. Therefore, the technologies for oil sands production and application, specially, upgrading technologies based on accumulated oil refinery technologies need to be developed to increase self-development ratio of energy resource.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.1951-1955
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• 2014

Catalytic pyrolysis of Geodae-Uksae 1, a kind of miscanthus found in Korea, was carried out over mesoporous MCM-48 catalysts. For rapid product analysis and catalyst evaluation, pyrolysis-gas chromatography/mass spectrometry was used. X-ray diffraction, nitrogen sorption, pyridine adsorbed Fourier transform infrared, and NH3 temperature programmed desorption were utilized to analyze the properties of the catalysts. Compared to non-catalytic reaction, catalytic upgrading over mesoporous Al-MCM-48 catalysts produced a higher-quality bio-oil with a high stability and low oxygen content. Al-MCM-48 exhibited higher deoxygenation ability than Si-MCM-48 due to its higher acidity.

• Journal of the Korean Applied Science and Technology
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• v.35 no.3
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• pp.731-743
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• 2018

In bio-jet fuel production, selecting operating conditions of hydro-upgrading is of great importance to make iso-Paraffin rich hydrocarbons with carbon distribution including jet fuel range. Herein, iso-Paraffin rich biofuel including jet fuel range hydrocarbons ($C_8-C_{16}$) is produced from simultaneous cracking and isomerization using n-Paraffin rich hydrocarbon derived from hydrotreated vegetable oil over 0.5 wt..% Pt/Zeolite catalyst. We report and analyze the yields and compositions in the produced hydrocarbons affected by various operating conditions, such as reaction temperature, reaction pressure, molar ratio of reactants, and weight hourly space velocity. Aforementioned operating conditions not only can help interpret the reaction dynamics of hydro-upgrading, but also further produce bio jet-fuel after distillation.

• 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.

• Environmental Engineering Research
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• v.22 no.1
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• pp.19-30
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• 2017

Direct catalysis of vapors from vacuum pyrolysis of biomass was performed on MCM-41 to investigate the effects of operating parameters including catalyzing temperature, catalyzing bed height and system pressure on the organic yields. Optimization of organic phase yield was further conducted by employing response surface methodology. The statistical analysis showed that operating parameters have significant effects on the organic phase yield. The organic phase yield first increases and then decreases as catalyzing temperature and catalyzing bed height increase, and decreases as system pressure increases. The optimal conditions for the maximum organic phase yield were obtained at catalyzing temperature of $502.7^{\circ}C$, catalyzing bed height of 2.74 cm and system pressure of 6.83 kPa, the organic phase yield amounts to 15.84% which is quite close to the predicted value 16.19%. The H/C, O/C molar ratios (dry basis), density, pH value, kinematic viscosity and high heat value of the organic phase obtained at optimal conditions were 1.287, 0.174, $0.98g/cm^3$, 5.12, $5.87mm^2/s$ and 33.08 MJ/kg, respectively. Organic product compositions were examined using gas chromatography/mass spectrometry and the analysis showed that the content of oxygenated aromatics in organic phase had decreased and hydrocarbons had increased, and the hydrocarbons in organic phase were mainly aliphatic hydrocarbons. Besides, thermo-gravimetric analysis of the MCM-41 zeolite was conducted within air atmosphere and the results showed that when the catalyst continuously works over 100 min, the index of physicochemical properties of bio-oil decreases gradually from 1.15 to 0.45, suggesting that the refined bio-oil significantly deteriorates. Meanwhile, the coke deposition of catalyst increases from 4.97% to 14.81%, which suggests that the catalytic activity significantly decreases till the catalyst completely looses its activity.