Special Issue "Catalytic Fast Pyrolysis"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 31 December 2019.

Special Issue Editors

Guest Editor
Prof. Young-Kwon Park Website E-Mail
School of Environmental Engineering, University of Seoul, Seoul 02504, Korea
Interests: Heterogeneous catalysis for biomass and plastic conversion, Catalysis pyrolysis, Hydrodeoxygenation, Supercritical liquefaction, VOC removal, DeNOx, Removal of particulate matter
Guest Editor
Prof. Jungho Jae Website E-Mail
School of Chemical and Biomolecular Engineering, Pusan National University, Busan 46241, Korea
Interests: Heterogeneous catalysis for biomass conversion, Catalysis pyrolysis, Hydrodeoxygenation, Supercritical liquefaction
Guest Editor
Prof. Young-Min Kim E-Mail
Department of Environmental Sciences and Biotechnology, Hallym University, Chuncheon 24252, Korea
Interests: thermal and catalytic pyrolysis of biomass and waste plastics, analytical pyrolysis of polymeric materials

Special Issue Information

Dear Colleagues,

Owing to the increasing attention paid to organic polymers as a renewable energy source—including biomass, plastic wastes, and other municipal solid wastes (MSW)—research into the pyrolysis of these polymeric materials into liquid fuels or high-value chemicals has been rapidly expanding in the last decade. The primary pyrolysis vapors produced by the thermal decomposition of waste polymers, especially biomass, are the mixture of highly functionalized monomeric and oligomeric compounds such as aldehydes, acids, anhydrosugars, phenols, etc., which are unsuitable for use as fuels or chemicals. To date, a range of different catalytic materials, including zeolites, metal catalysts, and mixed metal oxides, have been applied to the pyrolysis process to shift the product distribution to value-added chemicals, such as aromatic hydrocarbons, olefins, paraffins, naphthenes and ketones. However, many of them suffer from several disadvantages, such as fast deactivation, low selectivity, high process costs, and so on. More research should be added to the catalytic pyrolysis of renewable polymer materials to increase the yield and selectivity to the targeted chemicals and extend the catalyst lifetime. In this regard, this Special Issue is dedicated to topics such as the catalytic pyrolysis of waste organic polymers and the catalytic upgrading of the pyrolysis oils derived from these polymers (e.g., hydrotreating). The study of new catalysts, new upgrading chemistry, co-processing with conventional feedstock, catalyst deactivation/regeneration, and so on, which can be implemented to the pyrolysis process, will be the primary topics for this Special Issue.

It is our pleasure to invite you to submit a manuscript to this Special Issue. Reviews, short communications, full research papers related to the catalytic pyrolysis of biomass or the catalytic upgrading of biomass pyrolysis oils are especially welcome.

Prof. Young-Kwon Park
Prof. Jungho Jae
Prof. Young-Min Kim
Guest Editors

Manuscript Submission Information

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Keywords

  • Catalytic fast pyrolysis
  • Biomass
  • Plastic
  • Upgrading
  • Bio-oil
  • Pyrolysis oil
  • Hydrodeoxygenation

Published Papers (7 papers)

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Research

Open AccessArticle
Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration
Catalysts 2019, 9(9), 700; https://doi.org/10.3390/catal9090700 - 21 Aug 2019
Abstract
In the upgrading of biomass pyrolysis vapors to hydrocarbons, dehydration accomplishes a primary objective of removing oxygen, and acidic zeolites represent promising catalysts for the dehydration reaction. Here, we utilized density functional theory calculations to estimate adsorption energetics and intrinsic kinetics of alcohol [...] Read more.
In the upgrading of biomass pyrolysis vapors to hydrocarbons, dehydration accomplishes a primary objective of removing oxygen, and acidic zeolites represent promising catalysts for the dehydration reaction. Here, we utilized density functional theory calculations to estimate adsorption energetics and intrinsic kinetics of alcohol dehydration over H-ZSM-5, H-BEA, and H-AEL zeolites. The ONIOM (our Own N-layered Integrated molecular Orbital and molecular Mechanics) calculations of adsorption energies were observed to be inconsistent when benchmarked against QM (Quantum Mechanical)/Hartree–Fock and periodic boundary condition calculations. However, reaction coordinate calculations of adsorbed species and transition states were consistent across all levels considered. Comparison of ethanol, isopropanol (IPA), and tert-amyl alcohol (TAA) over these three zeolites allowed for a detailed examination of how confinement impacts on reaction mechanisms and kinetics. The TAA, seen to proceed via a carbocationic mechanism, was found to have the lowest activation barrier, followed by IPA and then ethanol, both of which dehydrate via a concerted mechanism. Barriers in H-BEA were consistently found to be lower than in H-ZSM-5 and H-AEL, attributed to late transition states and either elevated strain or inaccurately estimating long-range electrostatic interactions in H-AEL, respectively. Molecular dynamics simulations revealed that the diffusivity of these three alcohols in H-ZSM-5 were significantly overestimated by Knudsen diffusion, which will complicate experimental efforts to develop a kinetic model for catalytic fast pyrolysis. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessFeature PaperArticle
Hydrotreating of Jatropha-derived Bio-oil over Mesoporous Sulfide Catalysts to Produce Drop-in Transportation Fuels
Catalysts 2019, 9(5), 392; https://doi.org/10.3390/catal9050392 - 26 Apr 2019
Abstract
The bio-oil was largely produced by thermal pyrolysis of Jatropha-derived biomass wastes (denoted as Jatropha bio-oil) using a pilot plant with a capacity of 20 kg h-1 at Thailand Institute of Scientific and Technological Research (TISTR), Thailand. Jatropha bio-oil is an unconventional [...] Read more.
The bio-oil was largely produced by thermal pyrolysis of Jatropha-derived biomass wastes (denoted as Jatropha bio-oil) using a pilot plant with a capacity of 20 kg h-1 at Thailand Institute of Scientific and Technological Research (TISTR), Thailand. Jatropha bio-oil is an unconventional type of bio-oil, which is mostly composed of fatty acids, fatty acid methyl esters, fatty acid amides, and derivatives, and consequently, it contains large amounts of heteroatoms (oxygen ~20 wt.%, nitrogen ~ 5 wt.%, sulfur ~ 1000 ppm.). The heteroatoms, especially nitrogen, are highly poisonous to the metal or sulfide catalysts for upgrading of Jatropha bio-oil. To overcome this technical problem, we reported a stepwise strategy for hydrotreating of 100 wt.% Jatropha bio-oil over mesoporous sulfide catalysts (CoMo/γ-Al2O3 and NiMo/γ-Al2O3) to produce drop-in transport fuels, such as gasoline- and diesel-like fuels. This study is very different from our recent work on co-processing of Jatropha bio-oil (ca. 10 wt.%) with petroleum distillates to produce a hydrotreated oil as a diesel-like fuel. Jatropha bio-oil was pre-treated through a slurry-type high-pressure reactor under severe conditions, resulting in a pre-treated Jatropha bio-oil with relatively low amounts of heteroatoms (oxygen < 20 wt.%, nitrogen < 2 wt.%, sulfur < 500 ppm.). The light and middle distillates of pre-hydrotreated Jatropha bio-oil were then separated by distillation at a temperature below 240 °C, and a temperature of 240–360 °C. Deep hydrotreating of light distillates over sulfide CoMo/γ-Al2O3 catalyst was performed on a batch-type high-pressure reactor at 350 °C and 7 MPa of H2 gas for 5 h. The hydrotreated oil was a gasoline-like fuel, which contained 29.5 vol.% of n-paraffins, 14.4 vol.% of iso-paraffins, 4.5 vol.% of olefins, 21.4 vol.% of naphthene compounds and 29.6 wt.% of aromatic compounds, and little amounts of heteroatoms (nearly no oxygen and sulfur, and less than 50 ppm of nitrogen), corresponding to an octane number of 44, and it would be suitable for blending with petro-gasoline. The hydrotreating of middle distillates over sulfide NiMo/γ-Al2O3 catalyst using the same reaction condition produced a hydrotreating oil with diesel-like composition, low amounts of heteroatoms (no oxygen and less than 50 ppm of sulfur and nitrogen), and a cetane number of 60, which would be suitable for use in drop-in diesel fuel. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessArticle
Catalytic Cleavage of Ether Bond in a Lignin Model Compound over Carbon-Supported Noble Metal Catalysts in Supercritical Ethanol
Catalysts 2019, 9(2), 158; https://doi.org/10.3390/catal9020158 - 06 Feb 2019
Abstract
Decomposition of lignin-related model compound (benzyl phenyl ether, BPE) to phenol and toluene was performed over carbon-supported noble metal (Ru, Pd, and Pt) catalysts in supercritical ethanol without supply of hydrogen. Phenol and toluene as target products were produced by the hydrogenolysis of [...] Read more.
Decomposition of lignin-related model compound (benzyl phenyl ether, BPE) to phenol and toluene was performed over carbon-supported noble metal (Ru, Pd, and Pt) catalysts in supercritical ethanol without supply of hydrogen. Phenol and toluene as target products were produced by the hydrogenolysis of BPE. The conversion of BPE was higher than 95% over all carbon-supported noble metal catalysts at 270 °C for 4 h. The 5 wt% Pd/C demonstrated the highest yield (ca. 59.3%) of the target products and enhanced conversion rates and reactivity more significantly than other catalysts. In the case of Ru/C, BPE was significantly transformed to other unidentified byproducts, more so than other catalysts. The Pt/C catalyst produced the highest number of byproducts such as alkylated phenols and gas-phase products, indicating that the catalyst promotes secondary reactions during the decomposition of BPE. In addition, a model reaction using phenol as a reactant was conducted to check the secondary reactions of phenol such as alkylation or hydrogenation in supercritical ethanol. The product distribution when phenol was used as a reactant was mostly consistent with BPE as a reactant. Based on the results, plausible reaction pathways were proposed. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessArticle
High-Throughput Production of Heterogeneous RuO2/Graphene Catalyst in a Hydrodynamic Reactor for Selective Alcohol Oxidation
Catalysts 2019, 9(1), 25; https://doi.org/10.3390/catal9010025 - 30 Dec 2018
Abstract
We report on the high-throughput production of heterogeneous catalysts of RuO2-deposited graphene using a hydrodynamic process for selective alcohol oxidation. The fluid mechanics of a hydrodynamic process based on a Taylor–Couette flow provide a high shear stress field and fast mixing [...] Read more.
We report on the high-throughput production of heterogeneous catalysts of RuO2-deposited graphene using a hydrodynamic process for selective alcohol oxidation. The fluid mechanics of a hydrodynamic process based on a Taylor–Couette flow provide a high shear stress field and fast mixing process. The unique fluidic behavior efficiently exfoliates graphite into defect-free graphene sheets dispersed in water solution, in which ionic liquid is used as the stabilizing reagent to prevent the restacking of the graphene sheets. The deposition of RuO2 on a graphene surface is performed using a hydrodynamic process, resulting in the uniform coating of RuO2 nanoparticles. The as synthesized RuO2/IL–graphene catalyst has been applied efficiently for the oxidation of a wide variety of alcohol substrates, including biomass-derived 5-hydroxymethylfurfural (HMF) under environmentally benign conditions. The catalyst is mechanically stable and recyclable, confirming its heterogeneous nature. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessArticle
Increased Aromatics Formation by the Use of High-Density Polyethylene on the Catalytic Pyrolysis of Mandarin Peel over HY and HZSM-5
Catalysts 2018, 8(12), 656; https://doi.org/10.3390/catal8120656 - 12 Dec 2018
Abstract
High-density polyethylene (HDPE) was co-fed into the catalytic pyrolysis (CP) of mandarin peel (MP) over different microporous catalysts, HY and HZSM-5, with different pore and acid properties. Although the non-catalytic decomposition temperature of MP was not changed during catalytic thermogravimetric analysis over both [...] Read more.
High-density polyethylene (HDPE) was co-fed into the catalytic pyrolysis (CP) of mandarin peel (MP) over different microporous catalysts, HY and HZSM-5, with different pore and acid properties. Although the non-catalytic decomposition temperature of MP was not changed during catalytic thermogravimetric analysis over both catalysts, that of HDPE was reduced from 465 °C to 379 °C over HY and to 393 °C over HZSM-5 because of their catalytic effects. When HDPE was co-pyrolyzed with MP over the catalysts, the catalytic decomposition temperatures of HDPE were increased to 402 °C over HY and 408 °C over HZSM-5. The pyrolyzer-gas chromatography/mass spectrometry results showed that the main pyrolyzates of MP and HDPE, which comprised a large amount of oxygenates and aliphatic hydrocarbons with a wide carbon range, were converted efficiently to aromatics using HY and HZSM-5. Although HY can provide easier diffusion of the reactants to the catalyst pore and a larger amount of acid sites than HZSM-5, the CP of MP, HDPE, and their mixture over HZSM-5 revealed higher efficiency on aromatics formation than those over HY due to the strong acidity and more appropriate shape selectivity of HZSM-5. The production of aromatics from the catalytic co-pyrolysis of MP and HDPE was larger than the theoretical amounts, suggesting the synergistic effect of HDPE co-feeding for the increased formation of aromatics during the CP of MP. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessFeature PaperArticle
Catalytic Co-Pyrolysis of Kraft Lignin with Refuse-Derived Fuels Using Ni-Loaded ZSM-5 Type Catalysts
Catalysts 2018, 8(11), 506; https://doi.org/10.3390/catal8110506 - 31 Oct 2018
Cited by 1
Abstract
The catalytic co-pyrolysis (CCP) of Kraft lignin (KL) with refuse-derived fuels (RDF) over HZSM-5, Ni/HZSM-5, and NiDHZSM-5 (Ni/desilicated HZSM-5) was carried out using pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) to determine the effects of the nickel loading, desilication of HZSM-5, and co-pyrolysis of KL with [...] Read more.
The catalytic co-pyrolysis (CCP) of Kraft lignin (KL) with refuse-derived fuels (RDF) over HZSM-5, Ni/HZSM-5, and NiDHZSM-5 (Ni/desilicated HZSM-5) was carried out using pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) to determine the effects of the nickel loading, desilication of HZSM-5, and co-pyrolysis of KL with RDF. The catalysts were characterized by Brunauer–Emmett–Teller surface area, X-ray diffraction, and NH3-temperature programed desorption. The nickel-impregnated catalyst improved the catalytic upgrading efficiency and increased the aromatic hydrocarbon production. Compared to KL, the catalytic pyrolysis of RDF produced larger amounts of aromatic hydrocarbons due to the higher H/Ceff ratio. The CCP of KL with RDF enhanced the production of aromatic hydrocarbons by the synergistic effect of hydrogen rich feedstock co-feeding. In particular, Ni/DHZSM-5 showed higher aromatic hydrocarbon formation owing to its higher acidity and mesoporosity. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Open AccessArticle
Catalytic Pyrolysis of Polyethylene and Polypropylene over Desilicated Beta and Al-MSU-F
Catalysts 2018, 8(11), 501; https://doi.org/10.3390/catal8110501 - 26 Oct 2018
Cited by 1
Abstract
The catalytic pyrolysis (CP) of different thermoplastics, polyethylene (PE) and polypropylene (PP), over two types of mesoporous catalysts, desilicated Beta (DeBeta) and Al-MSU-F (AMF), was investigated by thermogravimetric analysis (TGA) and pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS). Catalytic TGA of PE and PP showed lower [...] Read more.
The catalytic pyrolysis (CP) of different thermoplastics, polyethylene (PE) and polypropylene (PP), over two types of mesoporous catalysts, desilicated Beta (DeBeta) and Al-MSU-F (AMF), was investigated by thermogravimetric analysis (TGA) and pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS). Catalytic TGA of PE and PP showed lower decomposition temperatures than non-catalytic TGA over both catalysts. Between the two catalysts, DeBeta decreased the decomposition temperatures of waste plastics further, because of its higher acidity and more appropriate pore size than AMF. The catalytic Py-GC/MS results showed that DeBeta produced a larger amount of aromatic hydrocarbons than AMF. In addition, CP over AMF produced a large amount of branched hydrocarbons. Full article
(This article belongs to the Special Issue Catalytic Fast Pyrolysis)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Hydrotreating of Jatropha-derived Bio-oil over Mesoporous Sulfide Catalysts to Produce Drop-in Transportation Fuels
Authors: Shih-Yuan Chen,a,* Takehisa Mochizuki,a Masayasu Nishi,a Hideyuki Takagi,a Albert Chang,b Chia-Min Yang,b,c Yuji Yoshimura,d Sugimoto Yoshikazu,a Makoto Tobaa
Affiliations: a Research Institute of Energy Frontier (RIEF), Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan.
b Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan
c Frontier Research Center on Fundamental and Applied Sciences of Matters, National Tsing Hua University, Hsinchu 30013, Taiwan.
d Materials for Energy Research Unit, National Metal and Materials Technology Center (MTEC), Pahonyothin Rd. Klong 1, Klong Luang Pathumtani 12120, Thailand.
Abstract: This study reported several strategies for catalytic hydrotreating of 100 wt.% Jatropha-derived bio-oil using mesoporous sulfide catalysts of CoMo/γ-Al2O3 and NiMo/γ-Al2O3 to produce drop-in transportation fuels including gasoline- and diesel-like fuels, which are very different from our recent work on co-processing of 10 wt.% Jatropha bio-oil with petroleum distillates to produce a hydrotreated oil as a diesel-like fuel (Chen et al., Catalysts 2018, 8, 59; http://dx.doi.org/10.3390/catal8020059). The Jatrophaderived bio-oil was largely produced by thermal pyrolysis of Jatropha biomass wastes using a Pilot Plant with a capacity of 20 kg h-1 at TISTR, Thailand, and it was an unconventional type of bio-oil which contained around 20-30 wt.% of phenol and its derivatives (denoted as the light part A) and around 70-80 wt.% of fatty acid amides and their derivatives (denoted as the heavy part B). Because Jatropha-derived bio-oil contained large amounts of heteroatoms (oxygen ~ 20-40 wt.%, nitrogen ~ 4 wt.%, sulfur ~ 1000 ppm.), nitrogen especially, it was pre-treated through a slurry-type high pressure reactor under severe condition, resulting in a pre-treated Jatropha-derived bio-oil with relatively low amounts of heteroatoms (oxygen < 20 wt.%, nitrogen < 2 wt.%, sulfur < 500 ppm.). The light part of pre-hydrotreated Jatropha-derived bio oil (corresponded to light part A) was then extracted through the process of distillation at temperature below 240 oC, followed by hydrotreating again with mesoporous sulfide CoMo/γ-Al2O3 catalysts using a batch-type high pressure reactor under severe conditions (ca. 350 oC and 7 MPa of H2 gas for 5 h). The hydrotreated oil A was a gasoline-like fuel, which contained 29.5 vol.% of n-paraffins, 14.4 vol.% of iso-paraffins, 4.5 vol.% of olefins, 21.4 vol. % of naphthene compounds and 29.6 wt.% of aromatic compounds, and little amounts of heteroatoms (nearly no oxygen and sulfur, and 40 ppm of nitrogen), corresponding to an octane number of 44. Consequently, the hydrotreated oil A would be suitable for blending with petro-gasoline. The heavy part of pre-hydrotreated Jatropha-derived bio oil (corresponded to heavy part B) was the residues of the process of distillation (> 240 oC) as aforementioned. With hydrotreating with mesoporous sulfide NiMo/γ-Al2O3 catalysts using a batch-type high pressure reactor under the same reaction condition, the hydrotreated oil B with a diesel-like composition, low amounts of heteroatoms, and a cetane number of 60 was obtained, which would be suitable for use in drop-in diesel fuel.
Keywords: Hydrotreating, mesoporous silfide materials, Jatropha biomass,
transportation fuels, upgrading technology

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