A review on reactivity and stability of heterogeneous metal catalysts for deoxygenation of bio-oil model compounds

Andrew Ng Kay Lup,Faisal Abnisa,Wan Mohd Ashri Wan Daud,Mohamed Kheireddine Aroua 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.56 No.-

Catalytic deoxygenation is a fundamental process for bio-oil upgrading due to its high oxygen contentwhich will result in lower heating value, corrosion and instability issues. The discovery of an excellentheterogeneous deoxygenation metal catalyst with high deoxygenation activity is a necessarybreakthrough for an optimized bio-oil catalytic deoxygenation. For an effective deoxygenation supportedmetal catalyst, properties such as high H2 sticking coefficient, optimal metal-oxygen bond strength andsuitable acid strength from support are needed to ensure facile scission of C O bonds and activation ofH2 and O-containing compounds. Metals such as Fe, Ru, Sn, W, Zr and supports such as C, TiO2, ZrO2 whichare oxophilic were also observed to enhance direct removal of oxygen from O-containing compounds dueto their high C O and C¼O bond affinities. The choice of support is important to ensure it has optimalphysicochemical properties for facile deoxygenation and the optimal acid strength to enhance C Ohydrogenolysis activity while minimizing coke formation. The choice of metal is dependent on the type ofmodel compound since different metals catalyze different reaction pathways of the deoxygenation ofmodel compounds. This review presents on the use of heterogeneous metal catalysts in thedeoxygenation of bio-oil model compounds through several perspectives which are catalytic properties,reaction conditions, deactivation and regeneration of metal catalysts. In addition, several outlooks on thefeasible range of reaction condition for catalytic deoxygenation and criteria of excellent deoxygenationsupported metal catalysts were also expressed in this article based on the studies on the literatures.

Catalytic pyrolysis of corn straw for deoxygenation of bio-oil with different types of catalysts

Wenkai Zhang,Ze Wang,Tengze Ge,Cuiguang Yang,Wenli Song,Songgeng Li,Rui Ma 한국화학공학회 2022 Korean Journal of Chemical Engineering Vol.39 No.5

Corn straw can be converted to bio-oil through pyrolysis. However, the application of bio-oil is severelyrestricted due to the high content of oxygen. Catalytic pyrolysis is an available way for deoxygenation of bio-oil, and thedeoxygenation reactions are strongly dependent on the type of catalyst. Whereas, the correlation between the deoxygenatedproducts and the catalyst types is still far from clear. In this work, the migration of O in the pyrolysis processwas investigated, and eight catalysts were screened for deoxygenation of bio-oil, with a lab-scale fixed-bed reactor. Theresults showed that with the increase of pyrolysis temperature, the content of O in bio-oil decreased below 400 oC andthen became stable and finally increased rapidly after 550 oC, indicating that the range of 400-550 oC was the propertemperature for deoxygenation. Eight catalysts (ZSM-5, SAPO-34, ZnO, MgO, -Al2O3, -Al2O3, acidified--Al2O3 andacidified--Al2O3) were tested, and it was found that a higher alkalinity of catalyst was favorable for decarboxylation ofbio-oil with more produced CO2, while a higher acidity was promoted the decrease of alcohols and carbonyls withmore generation of H2O and/or CO. MgO was judged as the optimal catalyst for deoxygenation of bio-oil. The qualityof bio-oil under the catalysis of MgO was best, with higher H/C and lower O/C.

Optimization of Ce(1-x)Zr(x)O2 Catalysts for Bio-diesel Production from Oleic acid using Catalytic Deoxygenation

Yeol-Lim Lee,Dae-Woon Jeong,Hyun-Seog Roh,Jeong-Geol Na,Sang Sub Han,Chang Hyun Ko 한국폐기물자원순환학회 2013 한국폐기물자원순환학회 학술대회 Vol.2013 No.2

Ce(1-x)Zr(x)O2 catalysts were investigated for bio-diesel production from oleic acid using catalytic deoxygenation. In this study, deoxygenation reaction has been carried out at 300 oC under 1 bar of 20% H2/N2 pressure in batch mode. Ce(1-x)Zr(x)O2 catalysts were prepared by co-precipitation method. Ce0.6Zr0.4O2 catalyst showed the highest oleic acid conversion and C9~C17 selectivity. It has been found that the deoxygenation reaction depends strongly on the reduction property and depends partly on the crystallite size of Ce(1-x)Zr(x)O2. Thus, Ce0.6Zr0.4O2 can be selected as the most promising catalyst for deoxygenation reaction.

IS-04 : Optimization of Ce(1-x)Zr(x)O2 Catalysts for Bio-diesel Production from Oleic acid using Catalytic Deoxygenation

( Yeol Lim Lee ),( Dae Woon Jeong ),( Hyun Seog Roh ),( Jeong Geol Na ),( Sang Sub Han ),( Chang Hyun Ko ) 한국폐기물자원순환학회(구 한국폐기물학회) 2013 한국폐기물자원순환학회 추계학술발표논문집 Vol.2013 No.-

Ce(1-x)Zr(x)O2 catalysts were investigated for bio-diesel production from oleic acid using catalytic deoxygenation. In this study, deoxygenation reaction has been carried out at 300 oC under 1 bar of 20% H2/N2 pressure in batch mode. Ce(1-x)Zr(x)O2 catalysts were prepared by co-precipitation method. Ce0.6Zr0.4O2 catalyst showed the highest oleic acid conversion and C9~C17 selectivity. It has been found that the deoxygenation reaction depends strongly on the reduction property and depends partly on the crystallite size of Ce(1-x)Zr(x)O2. Thus, Ce0.6Zr0.4O2 can be selected as the most promising catalyst for deoxygenation reaction.

Production of bio-jet fuel range alkanes from catalytic deoxygenation of Jatropha fatty acids on a WOx/Pt/TiO₂ catalyst

Choi, Il-Ho,Lee, Jin-Suk,Kim, Chul-Ung,Kim, Tae-Wan,Lee, Kwan-Young,Hwang, Kyung-Ran Elsevier 2018 Fuel Vol.215 No.-

<P><B>Abstract</B></P> <P>Bio-jet fuel range alkanes were prepared by catalytic deoxygenation reaction of non-edible acid oils with no added hydrogen. A WOx[6]/Pt[1.6]/TiO<SUB>2</SUB> was used for the deoxygenation of stearic acid and Jatropha fatty acid derived from Jatropha oil by hydrolysis. Tungsten addition to the Pt/TiO<SUB>2</SUB> showed remarkably enhanced performance, a degree of deoxygenation of 86%, which is more than two times higher than that of the Pt/TiO<SUB>2</SUB>, even though the WOx/TiO<SUB>2</SUB> had almost no activity for deoxygenation reaction. The enhanced Pt-related hydrogen uptake, measured by H<SUB>2</SUB>-TPR, and XPS analysis showed the intimate contact of tungsten with Pt nanoparticles supported on TiO<SUB>2</SUB>. This tight contact allows for easier CC cleavage over Pt nanoparticles and this is assisted by the strong bonding between tungsten and oxygen in the reactant, resulting in more C<SUB>17</SUB> hydrocarbon production on the WOx/Pt/TiO<SUB>2</SUB>.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A highly active and selective WOx/Pt/TiO<SUB>2</SUB> catalyst for catalytic deoxygenation with no added hydrogen. </LI> <LI> W addition to Pt/TiO<SUB>2</SUB> catalyst remarkably enhanced the degree of deoxygenation of free fatty acids. </LI> <LI> Intimate contact of W with Pt nanoparticles supported by TiO<SUB>2</SUB> permits easier decarboxylation reaction. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Hydrothermal Deoxygenation of Triglycerides over Carbon-Supported PtRe Catalysts without Hydrogen Source

진민규,최민기 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.0

Hydrothermal deoxygenation in subcritical water is a promising route for producing n-paraffins from triglycerides without an external H₂ source. In this study, bimetallic PtRe catalysts supported on various carbon supports were investigated for the hydrothermal deoxygenation of triglycerides. Bimetallic PtRe catalysts led to a markedly enhanced rate of both glycerol reforming for in situ H₂ production and deoxygenation of fatty acids compared to monometallic Pt catalysts. Investigations with various carbon supports proved that a carbon support with low oxygen content (e.g., CNT) is desirable for supporting highly dispersed and well alloyed PtRe particles. Oxygen-rich carbon surfaces (e.g., activated carbons) caused the segregation of Re species into bulk particles with higher oxidation states. The PtRe/CNT catalyst showed the best performance, yielding 72 wt% n-paraffin for the hydrothermal deoxygenation of palm oil at 558 K without use of an external H₂ source.

미활용 농업부산물로부터 바이오오일 생산을 위한 급속 열분해 시스템 최적화 및 탈산소 반응에 관한 연구

이용희 ( Yong-hee Lee ),정창훈 ( Chang-hoon Jeong ),진홍덕 ( Hong-deok Jin ),구윤정 ( Yun-jeong Gu ),변희주 ( Hui-ju Byeon ),김학민 ( Hak-min Kim ),정대운 ( Dae-woon Jeong ) 한국폐기물자원순환학회 2020 한국폐기물자원순환학회지 Vol.37 No.8

In this study, a fast pyrolysis system is optimized to produce bio-oil with high yield and high heating value (HHV) from agricultural by-products. The agricultural by-products is screened by elemental analysis and HHV analysis. Among the various agricultural by-products, the fruit tree waste is selected as a feedstock to generate bio-oil because it shows the highest HHV. The pyrolysis reaction system is to produce bio-oil optimized by controlling gas velocity and reaction temperature. Consequently, the highest bio-oil yield is obtained when the gas velocity is 3.0 and the reaction temperature is 500℃. This is because the heat transfer rate increases as the gas velocity increases, and the pyrolysis of organic matter accelerates as the temperature increases. In addition, deoxygenation reaction is performed to increase the HHV of the produced bio-oil. The CoMo catalyst have been used for the deoxygenation reaction. The HHV of the bio-oil increases to 7,400 kcal/kg by deoxygenation reaction. This result is due to that the oxygen content is decreased by deoxygenation reaction.

Deoxygenation of vegetable oils and fatty acids: How can we steer the reaction selectivity towards diesel range hydrocarbons?

Sara Alkhoori,Maryam Khaleel,Lourdes F. Vega,Kyriaki Polychronopoulou 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.127 No.-

Fast pyrolysis is a prominent and versatile process that involves thermal decomposition of biomass feedstocksto produce high volumes of liquid bio-oil, which may eventually be upgraded via deoxygenationpathways (hydrodeoxygenation, decarboxylation, or decarbonylation) into high energy content greenfuels like gasoline, diesel and jet fuel. The quality of the bio-oil, its thermal stability, heating value,and the efficiency of the total conversion process can be improved by deoxygenation over properlydesigned catalysts. Despite the success of the available catalysts to significantly improve bio-oil qualityby producing useful aromatic hydrocarbons, phenolics, or alkanes, there are still opportunities for furtherimprovements of the catalytic performance with regards to their activity, product selectivity and resistivityagainst deactivation. The present work provides a comprehensive analysis of the recent developmentsof sulfur-free monometallic and bimetallic transition metal and noble metal supported catalysts forselective deoxygenation of vegetable oils and fatty acids model compounds for biofuel production. Theattention focuses on the design of active sites on these catalysts as well as the acidic nature of the integratedsupports for selectively manipulating mechanistic pathways. Moreover, this review emphasizes onthe role of doping in stabilizing metal oxides to tune metal-support interaction (MSI) and electron donationproperties, all strategies combined for the enhancement of biofuel production. The novelty of thisreview lies on bridging theoretical and experimental investigations aiming at describing and interpretingdeoxygenation pathways of vegetable oils and related model compounds. Current challenges and perspectiveare also provided.

Catalytic deoxygenation of oleic acid over a Ni-CeZrO₂ catalyst

Jeon, Kyung-Won,Na, Hyun-Suk,Lee, Yeol-Lim,Ahn, Seon-Yong,Kim, Kyoung-Jin,Shim, Jae-Oh,Jang, Won-Jun,Jeong, Dae-Woon,Nah, In Wook,Roh, Hyun-Seog Elsevier Ltd 2019 Fuel Vol.258 No.-

<P><B>Abstract</B></P> <P>Ni-loaded Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2</SUB> catalysts were prepared by a co-precipitation method and subsequently employed in the deoxygenation of oleic acid under solvent-free conditions. Among the prepared catalysts, the 20 wt% Ni-Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2</SUB> catalyst exhibited the highest catalytic activity, i.e., 98.3% oleic acid conversion, with 33.9% C<SUB>9</SUB>-C<SUB>17</SUB> selectivity, and a 95.7% oxygen removal rate. The basic fuel properties of the obtained products were then examined to determine their potential for use in a diesel engine. The product produced using the 20 wt% Ni-Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2</SUB> catalyst exhibited a particularly high calorific value (i.e., 10213 cal/g, similar to that of commercial diesel, i.e., 10220 cal/g), the lowest viscosity (25.2cP), and the lowest solidification temperature (−15 °C).</P> <P><B>Highlights</B></P> <P> <UL> <LI> Biofuel was produced by deoxygenation of oleic acid over Ni-Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2.</SUB> </LI> <LI> The Ni-loaded Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2</SUB> catalyst containing 20 wt% Ni loading was optimal. </LI> <LI> 20 wt% Ni-Ce<SUB>0.6</SUB>Zr<SUB>0.4</SUB>O<SUB>2</SUB> exhibited 98.3% conversion and 33.9% selectivity. </LI> <LI> Furthermore, this catalyst showed a superior oxygen removal rate (95.7%). </LI> <LI> The biofuel produced via this catalyst showed a high calorific value (10213 cal/g). </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Site-Selective Deoxygenation of Cellulose-Derived Carbohydrates

서영란,유동원,( Michel R. Gagne ) 한국공업화학회 2023 한국공업화학회 연구논문 초록집 Vol.2023 No.0