Preparation of carbon-supported metal nanoparticle catalysts with high metal loading using ion-exchange resins and their application for selective hydrogen production and hydrodeoxygenation reactions

( Hiroyasu Fujitsuka ),( Teruoki Tago ) 한국공업화학회 2020 한국공업화학회 연구논문 초록집 Vol.2020 No.-

Hydrogen is one of the important materials not only as energy resources for fuel cells but as a chemical feedstock for biomass conversion into valuable chemicals via hydrodeoxygenation. Noble metal catalysts, such as Pt, Ni, and Pd, are reported to exhibit high activity for hydrogen production. Carbon is one of promising catalyst support because they have no acid/base sites, which causes undesired reactions such as cracking and isomerization. On the other hand, the metal fine particles on carbon support are easily aggregated during the catalyst preparation and the reaction, leading to the deactivation of the catalyst. To maintain the metal particle size small, we developed a novel preparation method for carbon-supported Pt and Ni fine particles by using a cation-exchange resin and corresponding metal ammine complexes as initial materials of carbon support and metals, respectively. This preparation method consists of ion exchange at room temperature and carbonization of the metal-loaded resin at 500°C to convert the resin into carbon support. We succeeded in the preparation of Pt-Ni bimetal catalysts with the predetermined metal composition by using this method. The metal loading of the prepared catalysts was 25-49 wt% and the metal particle size was 2-4 nm. We applied the prepared catalysts to hydrogen production from formic acid. The obtained catalysts showed higher hydrogen production rates based on the reactor volume (44,100-2,020 Nm3-H₂/(m3-reactor·h)) than the industrially required level (1,000 Nm3-H2/(m3-reactor·h)) due to the high metal loading and small metal particle size of the active metal. The bimetal catalyst exhibited higher turnover frequency than the single metal catalyst, suggesting that alloy formation enhanced the catalytic activity. Besides, metal catalysts, such as Cu and Ru, are considered to show high activity for hydrodeoxygenation of polyols derived from biomass to valuable diols. To inhibit side reactions such as C-C cleavage and dimerization of polyols over acid sites on catalyst support at temperatures above 200°C, the carbon-supported metal catalyst prepared from the ion-exchange resin was believed to be useful. We prepared a carbon-supported Cu catalyst in the same manner as the Pt and Ni loaded carbon catalyst. The prepared carbon-supported Cu catalyst possessed 67 wt% of metal loading and 15 nm of Cu metal particle size. This catalyst showed high selectivity of the conversion of erythritol (C4H₆(OH)₄) into butanediols. It was worthwhile to point out that the vicinal diols, that is 1,2-butanediol and 2,3-butanediol, were mainly obtained. This result implies that the vicinal OH groups are adsorbed on Cu particle in the prepared catalyst and the OH groups which were not involved in the adsorption was reacted with hydrogen. In conclusion, carbon-supported metal nanoparticle catalysts were successfully prepared by using ion-exchange resin. The prepared catalyst showed high activity for hydrogen production and selective hydrodeoxygenation of polyols because of high metal loading and small metal particle size.

Investigation of chemical modifications of micro- and macromolecules in bio-oil during hydrodeoxygenation with Pd/C catalyst in supercritical ethanol

Oh, Shinyoung,Hwang, Hyewon,Choi, Hang Seok,Choi, Joon Weon Elsevier 2014 CHEMOSPHERE - Vol.117 No.-

<P><B>Abstract</B></P> <P>Miscanthus bio-oil was subjected to hydrodeoxygenation (HDO) with Pd/C at different temperatures (250, 300 and 350°C) and times (30, 45 and 60min) to investigate the chemical modification of micro- and macromolecules in bio-oil. Four main products – char, gas and two immiscible oils (light and heavy oil) – were obtained from the HDO reaction. Yields of heavy oil as a targeting product of HDO varied from 60% to 13%, whereas those of gas and char were ranged from 7% to 36% and 6% to 17%, respectively. Water content was estimated to<1% and heating value was 26–31MJkg<SUP>−1</SUP>.</P> <P>Reduction of unstable oxygen-containing compounds such as acids (2-hydroxy-butanoic acid), aldehydes (furfural), alcohols (butanedial) and sugars (levoglucosan) were characteristic in heavey oil. Apart from hydrogenation and deoxygenation, micromolecules in bio-oil were plausibly modified to stable ketones, esters and saturated components via demethoxylation, dealkylation, decarbonylation, dehydroxylation and ring opening.</P> <P>Macromolecular lignin fragments (referred to as pyrolytic lignins in bio-oil and phenol polymers in heavy oil) were extracted and subjected to several analyses. Approximately 60% of the pyrolytic lignins were decomposed into low molecular weight compounds during HDO reaction. Moreover, essential functional groups, OCH<SUB>3</SUB> and phen-OH groups attached to pyrolytic lignin, were severely modified during HDO reaction.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Miscanthus bio-oil was subjected to hydrodeoxygenation in the presence of Pd/C. </LI> <LI> Structural modification of chemical components in bio-oil was investigated. </LI> <LI> Reduction of unstable oxygen-containing components were characteristic. </LI> <LI> Micromolecules were modified to stable ketones, esters and saturated components. </LI> <LI> Depolymerization of macromolecular lignins were verified during hydrodeoxygenation. </LI> </UL> </P>

Preparation of mesoporous transition metal oxides and their application to hydrodeoxygenation: role of support

고창현,( Phan Tuan Ngoc ) 한국공업화학회 2016 한국공업화학회 연구논문 초록집 Vol.2016 No.0

The hydrogenation of model lignin compound (anisole) was performed over Ru catalysts using a batch reactor at 10 bar H2 pressure and 200 °C. Various mesoporous transition metal oxides including TiO2, Fe3O4, and Co3O4 were prepared by hydrothermal synthesis methods and then used as the support of Ru catalysts. The textural properties of the catalysts were characterized by X-ray diffraction, N2 adsorption-desorption, and CO chemisorption. Ru particle sizes, conversion of anisole, and yield of benzene changed drastically depending on the kind of support indicating the significant influence of the active metallic species-mesoporous support interaction. Among three catalysts, the Ru/meso-TiO2 catalyst showed strongest interation between Ru particle and support resulted in highest anisole conversion and largest amount of benzene produced. Results demonstrate that mesoporous TiO2 support enhanced catalytic activity and directed the reaction pathway toward direct deoxygenation.

Production of deoxygenated high carbon number hydrocarbons from furan condensates: Hydrodeoxygenation of biomass-based oxygenates

Seo, Jangwoo,Kwon, Ji Sun,Choo, Hyunah,Choi, Jae-Wook,Jae, Jungho,Suh, Dong Jin,Kim, Shin,Ha, Jeong-Myeong Elsevier 2019 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.377 No.-

<P><B>Abstract</B></P> <P>Two-step hydrodeoxygenation of furan trimers using supported Ni catalysts was successfully performed by substituting expensive noble metal catalysts for hydrodeoxygenation, which can contribute to the development of feasible hydrodeoxygenation processes with which to prepare high-carbon-number hydrocarbon fuels. Although more cracking of hydrocarbon products was observed for the Ni catalysts, the substitution of noble metal catalysts with Ni catalysts was successful, leading to good HDO activity. The combination of the first step of Ni/CeO<SUB>2</SUB> (hydrogenation) and the second step of Ni/tungstated zirconia (hydrodeoxygenation) led to complete deoxygenation, achieving 87.8% of the theoretical maximum yield of the oil phase product, which is slightly lower than the value of 91.1% for the combination of the first step of Pd/C (hydrogenation) and Ru/tungstated zirconia (hydrodeoxygenation). The roles of first-step hydrogenation were revealed as the hydrogenation of unsaturated furan rings and the hydrolysis of saturated furan rings.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Two-step hydrodeoxygenation of biomass-derivatives using Ni catalysts produces diesel-like fuels. </LI> <LI> Ni catalysts exhibit a good deoxygenation activity comparable to that of noble metals. </LI> <LI> Saturation and hydrolysis of furan rings occur during the first step hydrogenation. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Hydrodeoxygenation of furfural on supported Pt, Ru monometallic catalyists in a fixed-bed reactor

심재욱,리황부,김승수 한국공업화학회 2016 한국공업화학회 연구논문 초록집 Vol.2016 No.1

Hydrodeoxygenation (HDO) is considered as one of the promising methods for upgrading bio-oil from pyrolysis by removal of the oxygencontaining groups. The bio-oil product from pyrolysis of lignocellulosic biomass is a complex mixture of aromatic compounds such as furfural, furanone, phenol and their derivatives. Among these components, furfural is one of the major compositions. In this study, the model compound of furfural underwent HDO in fixed-bed reactor over monometallic catalysts Pt, Ru prepared by incipient-wetness impregnation method. The catalysts were supported on γ-Al₂O₃. The effect of catalyst activity and stability on FMK at different reaction temperatures and metal loading were investigated. The 1 wt% Pt/γ-Al₂O₃ catalyst (calcinated at 500 °C) showed the high activity with 87.04% in furfural conversion at 350 °C. The produced gas and liquid was analyzed by gas chromatography (GC) with TCD/FID detector and GC-MS, respectively, to determine the product compositions.

Recent Progress on the Hydrodeoxygenation of Lignin-Derived Pyrolysis Oil Using Ru-Based Catalysts

김형주,박재현,하정명,김도희 한국화학공학회 2024 Korean Journal of Chemical Engineering Vol.41 No.4

Hydrodeoxygenation (HDO) of lignin-derived pyrolysis oil has received significant attention as a potential technology for replacing conventional petroleum-based fuels and chemicals. Ru-based HDO catalysts are in the limelight as HDO catalysts since they exhibit excellent catalytic activity while being cost-effective compared to other noble metal-based catalysts. Various studies have reported Ru-based catalysts used in the HDO of lignin-derived pyrolysis oil and its model compounds, and a variety of strategies have been utilized to tune the catalytic properties to enhance the performance and advance the understanding of the HDO reaction. This review discusses the recent publications on Ru-based catalysts used in the HDO of lignin-derived pyrolysis oil and its model compounds. Additionally, an overview of HDO reactions and the characteristics of HDO catalysts were summarized, and the general advantages of Ru catalysts, which are extensively used as attractive catalysts in the various reactions, are introduced. Various factors, including reaction conditions, support materials, and promoters, that can affect the performance of Ru-based HDO catalysts are organized, and the strategies utilized to modify the properties of the catalysts are categorized. Finally, the areas that require further development such that Ru-based HDO catalysts can overcome the remaining challenges are outlined. Hydrodeoxygenation (HDO) of lignin-derived pyrolysis oil has received signifi cant attention as a potential technology for replacing conventional petroleum-based fuels and chemicals. Ru-based HDO catalysts are in the limelight as HDO catalysts since they exhibit excellent catalytic activity while being cost-eff ective compared to other noble metal-based catalysts. Various studies have reported Ru-based catalysts used in the HDO of lignin-derived pyrolysis oil and its model compounds, and a variety of strategies have been utilized to tune the catalytic properties to enhance the performance and advance the understanding of the HDO reaction. This review discusses the recent publications on Ru-based catalysts used in the HDO of lignin-derived pyrolysis oil and its model compounds. Additionally, an overview of HDO reactions and the characteristics of HDO catalysts were summarized, and the general advantages of Ru catalysts, which are extensively used as attractive catalysts in the various reactions, are introduced. Various factors, including reaction conditions, support materials, and promoters, that can aff ect the performance of Ru-based HDO catalysts are organized, and the strategies utilized to modify the properties of the catalysts are categorized. Finally, the areas that require further development such that Ru-based HDO catalysts can overcome the remaining challenges are outlined.

Hydrodeoxygenation of 2-furyl methyl ketone as a model compound of algal <i>Saccharina Japonica</i> bio-oil using iron phosphide catalyst

Ly, Hoang Vu,Galiwango, Emmanuel,Kim, Seung-Soo,Kim, Jinsoo,Choi, Jae Hyung,Woo, Hee Chul,Othman, Mohd Roslee Elsevier 2017 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.317 No.-

<P><B>Abstract</B></P> <P>We report the hydrodeoxygenation of 2-furyl methyl ketone over iron phosphide catalyst to reform the C<SUB>6</SUB> structure into C<SUB>7</SUB> compounds with higher octane ratings. High conversion and yield were achievable from the reaction at 400°C when 5wt% Fe<SUB>2</SUB>P/γ-Al<SUB>2</SUB>O<SUB>3</SUB> catalyst calcined at 600°C was used. High calcination temperature and reaction temperature are the favorable conditions to achieve high conversion in the reaction. The highest conversion of 92.60% was achieved with 2-allyl furan yield of 79.34% and methyl cylcohexane yield of 13.26% in the liquid phase and 100% carbon dioxide in the gas phase.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Fe<SUB>2</SUB>P/γ-Al<SUB>2</SUB>O<SUB>3</SUB> and Ni<SUB>2</SUB>P/γ-Al<SUB>2</SUB>O<SUB>3</SUB> catalyzed the hydrodeoxygenation of 2-furyl methyl ketone (FMK). </LI> <LI> Effects of reaction temperature, phosphorous, and metal loading were investigated. </LI> <LI> Phosphide catalyst with iron content produced the predominant selectivity of 2-allyl furan and the least methyl cyclohexane. </LI> <LI> 5wt% Fe<SUB>2</SUB>P/γ-Al<SUB>2</SUB>O<SUB>3</SUB> calcined at 600°C had the highest FMK conversion and yield to 2-allyl furan. </LI> </UL> </P>

Aqueous phase hydrodeoxygenation of polyols using Pt (and/or Ru)-supported catalysts; effects of metal-support interaction to catalytic activity

전성호,배종욱 한국공업화학회 2018 한국공업화학회 연구논문 초록집 Vol.2018 No.0

Aqueous phase hydrodeoxygenation (APH) of biomass-derived polyols such as ethylene glycol (EG) and glycerol (GL) was investigated using as platinum and/or ruthenium supported on various metal oxides in a fixed-bed tubular reactor. Conversion of biomass-derived polyols to value-added chemicals is an important route to produce useful petrochemicals. APH reaction of EG and GL can selectively produce gas-phase products such as hydrogen, carbon monoxide, hydrocarbons as well as oxygen-removed useful liquid products. The novel metals impregnated by incipient wetness impregnation method on various metal oxide supports were synthesized by Sol-Gel method, and their roles to catalytic activity and product distribution were studied in terms of a different metal-support interaction through the surface characterizations such as TPR, CO-chemisorption, XRD and XPS and XAFS analysis.

Aqueous-phase hydrodeoxygenation of sorbitol over bifunctional catalysts

김용태,( James A. Dumesic ),( George W. Huber ) 한국공업화학회 2014 한국공업화학회 연구논문 초록집 Vol.2014 No.1

Hydrodeoxygenation (HDO) is a platform technology for conversion of biomass feedstocks into a range of fuels and chemicals including C1-C6 alkanes, C1-C6 mono-alcohols, C2-C6 polyols, and larger intermediate. The combination of metal and acid sites on the bifunctional catalytic system is important to tune the ratio of C-O bond to C-C bond cleavage during HDO reactions. The challenge with HDO is to selectively produce targeted products that can be used as fuel blendstocks and chemicals tuned by chemistry and reaction engineering. Understanding the reaction networks in HDO has aided in the design of efficient bifunctional catalysts. In this presentation we will discuss the differences between two fundamentally different classes of bifunctional metal-acid catalysts and show how we can modify HDO reaction.

Catalytic hydrodeoxygenation of guaiacol in a fixed-bed reactor

원춘화,박성준,이인구 한국공업화학회 2014 한국공업화학회 연구논문 초록집 Vol.2014 No.1

Fast pyrolysis of lignocellulosic biomass forms bio-oil as a major product. Although bio-oil is a liquid-phase material with much higher energy density than lignocellulosic biomass, it is not widely used as a fuel in industry because of its drawbacks such as chemical instability, high viscosity, and high acidity. Those problems are resulted from high oxygen content in bio-oil. In this study, hydrodeoxygenation (HDO) of guaiacol as a model compound for bio-oil was examined as a method to eliminate oxygen present in bio-oil. Effect of promoters (Ru, Co, W, and Pt) impregnated in Ni/Activated Charcoal catalyst was investigated on the guaiacol conversion and product distribution. The reactions were carried out in a continuous flow fixed-bed reactor at 50 bar and temperatures of 350 and 400°C. The results showed that the Ni-promoters/AC catalysts promoted HDO of guaiacol, resulting in high guaiacol conversion up to100% and deoxygenation degree between 90 and 100. Influence of the promoters on product selectivity and yield was discussed.