What is the best catalyst for biomass pyrolysis?
Introduction
Pyrolysis of biomass has become an increasingly popular technique for creating hydrocarbons that have traditionally been derived from petroleum [1,2]. The increase in its popularity is primarily due to two main issues: worldwide depletion of crude oil and environmental pollution due to indiscriminate dumping of wastes. However, the main disadvantage of thermal pyrolysis of biomass is that the bio-oil contains a complex mixture of oxygen functional groups that are responsible for its highly corrosive nature and low heating value. This is the main reason for restricting the production of biomass bio-oil on an industrial scale. The oxygen functional groups attached to hydrocarbons should be eliminated via deoxygenation processes. The most conventional method in deoxygenating oil is catalytic hydrodeoxygenation (HDO), which is widely applied in the petrochemical industry. However, in the renewable energy sector, it is not recommended to involve multiple processes. A system based on pyrolysis and HDO consumes a lot of energy and hydrogen. Thus, multifunctional hydrogenous catalysts have received increasing attention by preventing the implementation of another process. These kinds of catalysts have dual characteristics that are simultaneously applied for both deoxygenation and cracking during pyrolysis [3,4].
Catalytic pyrolysis is performed in two ways, either by mixing biomass and catalyst (in-situ), where the catalyst plays an important role in carrying the heat, or in a dual-bed reactor, where biomass and catalyst beds are separated (ex-situ). The in-situ method requires a lower capital investment as is only requires a single reactor. However, catalyst deactivation from coke formation occurs more quickly. Moreover, poor contact between the two solid surfaces (biomass and catalyst bed) leads to poor heat transfer. The ex-situ mode is highly selective to desirable aromatics because this configuration allows individual control of both the pyrolizer and the upgrading reactor’s operating conditions. However, this configuration is more complex and leads to a higher capital cost [5].
One of the economically most interesting methods is the use of commercial catalysts such as silicon and zeolite-based catalysts in the pyrolysis of lignocellulosic biomass. These catalysts are commonly used in catalytic processes in the petrochemical and refining industries. Literature on the pyrolysis of biomass in the presence of such catalysts is vast; however, none of the catalysts could generate a compatible bio-oil with conventional liquid transportation fuels because the chemistry in the field of biomass stands in great contrast with the field of petrochemistry, where it deals with petrochemical hydrocarbons [6]. One of the challenges in lignocellulose degradation is the breaking down of natural polymers, which are much bulkier than petrochemical molecules. The narrow pores of commercial catalysts make them unsuitable for larger applications in the field of biomass. As a result, the coupling of a secondary level of porosity with conventional catalysts is recommended because it creates a multidimensional structure (micro, meso, and macro pores in 1, 2, or 3D) and better molecular traffic control [7]. An insightful comparison between commercial catalysts and biocarbon suggested that a catalyst based on hydrochar and zeolite (hydrochar/zeolite composite) can resolve present limitations and challenges for developing and commercializing advanced biofuels such as biodiesel and bio-gasoline. Composite catalysis could play a significant role in facilitating diffusion inside the catalyst and increasing the number of closely accessible active sites [8].
Several review articles have outlined the progress and development of heterogeneous catalysts for upgrading bio-products obtained from catalytic pyrolysis of biomass [5,[9], [10], [11], [12], [13]]. Previous review papers have mainly summarized recent progress on the production of value-added hydrocarbons, phenols, anhydrosugars, and nitrogen-containing compounds from catalytic pyrolysis of biomass over zeolites, metal oxides, aluminosilicate, metal-loaded zeolites, metal-organic frameworks, and modified mesoporous silica [10,11]. A few papers are available on the shape selectivity of acid-catalyzed pyrolysis, reaction chemistry in biomass catalytic fast pyrolysis, process complexity with acid catalysts and, catalyst modification approaches [12]. However, there are not many papers describing the preparation and application of biochar-based nano catalysts to improve desired products in the pyrolysis process [9].
In this contribution, we first highlight the progress made in synthesizing mesoporous silica, zeolites, and biocarbon-based catalysts for pyrolysis of lignocellulose biomass. Finally, we propose future directions for the use of advanced composite in the field of biomass energy.
The overall goal of the study is to present bio/hydrochar based composites as a clean source of carbon and an alternative to commercial heterogeneous catalysts. To reach this point, we have done a comprehensive literature review study around biochar-based functional materials applied in energy storage systems. We believe that this study will open a new field of catalytic opportunities for biochar-based materials.
Section snippets
Methodology
At the initial stages of this study, Google Scholar, Web of Science, PubMed, and Scopus were used as search engines to look for the following keywords: pyrolysis, zeolites, silica, activated carbon, biomass, and catalysis. The search was narrowed down to articles from within the last ten years to keeping information recent and relevant. The articles were screened to specifically target studies that were conducted on catalytic pyrolysis of biomass using either zeolites, silica, carbonaceous
Zeolites
Zeolites, such as aluminosilicate crystalline solids, with complex pore structures, are used widely and efficiently in the catalytic pyrolysis of biomasses. These catalysts can promote cracking, dehydration, deoxygenation reactions into mostly monoaromatic components production. Typical pore size and structure of zeolite catalysts provide them as a sieve for special pore size and shape selectivity toward different components in bio-oil [[14], [15], [16]]. Zeolites are categorized into three
Mesopore silica (MS)
Mesoporous silica (M41S-type) offer distinctive properties, including high surface areas (800−1400 m2/gr), meso-nanoscale pores (2−50 nm), adjustable pore size, and versatile morphology (using tunable synthesis techniques) are of considerable importance with respect to their applications in catalysis, adsorption, and sensing. The characteristic structural features and properties of these porous materials are summarized in Table 3. The relatively large pores in mesoporous silica facilitate mass
Biochar derived carbonaceous catalysts
Carbon has the potential to play the role of catalyst support for chemical and enzymatic reactions due to its high specific surface area, porosity, chemical inertness, and electron conductivity. Furthermore, they can be derived from biomass, thus reducing the carbon footprint of such supports. Carbon has conventionally been considered a sustainable alternative source of fuels, chemicals, and materials via thermochemical conversion processes such as pyrolysis, gasification, and hydrothermal
Abstract
Bio-oil is thought to be an upcoming alternative product in place of petroleum-based fuel. However, pilot plant and industrial scale-production are still limited. Currently, scientists essentially concentrate on bio-oil production at a laboratory scale and have also concentrated mostly on an infeasible mechanism. As one of the possible recent promising options, multi-functional catalytic pyrolysis has made great progress throughout the past years and yielded substantial technological
Author contribution
Omid Norouz, Somayeh Taghavi, Precious Arku, Sajedeh Jafarian, Michela Signoretto, and Animesh Duttaǂ These authors contributed equally.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was funded by the NSERC Discovery Grant. The authors wish to thank supporting organizations, The Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA), Biomass Canada of BioFuelNet Canada Network (Project Number: ASC-16) and the University of Guelph for ongoing HQP training support.
References (163)
- et al.
Catalytic upgrading of bio-products derived from pyrolysis of red macroalgae Gracilaria gracilis with a promising novel micro/mesoporous catalyst
Bioresour. Technol.
(2017) - et al.
Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char
Bioresour. Technol.
(2016) - et al.
Development of biochar-based nanocatalysts for tar cracking/reforming during biomass pyrolysis and gasification
Bioresour. Technol.
(2020) - et al.
A review on catalytic pyrolysis of microalgae to high-quality bio-oil with low oxygeneous and nitrogenous compounds
Renew. Sustain. Energy Rev.
(2019) - et al.
A review on selective production of value-added chemicals via catalytic pyrolysis of lignocellulosic biomass
Sci. Total Environ.
(2020) - et al.
Multi-scale complexities of solid acid catalysts in the catalytic fast pyrolysis of biomass for bio-oil production – a review
Prog. Energy Combust. Sci.
(2020) - et al.
Catalytic fast pyrolysis of biomass over zeolites for high quality bio-oil – a review
Fuel Process. Technol.
(2018) - et al.
Producing petrochemicals from catalytic fast pyrolysis of corn fermentation residual by-products generated from citric acid production
Renew. Energy
(2016) - et al.
Investigation into the shape selectivity of zeolite catalysts for biomass conversion
J. Catal.
(2011) - et al.
First pilot scale study of basic vs acidic catalysts in biomass pyrolysis : deoxygenation mechanisms and catalyst deactivation
Appl. Catal. B Environ.
(2018)
Microwave-assisted catalytic fast pyrolysis of spent edible mushroom substrate for bio-oil production using surface modified zeolite catalyst
J. Anal. Appl. Pyrolysis
Catalytic pyrolysis of larch sawdust for phenol-rich bio-oil using different catalysts
Renew. Energy
Comparison of HZSM-5 catalyzed and non-catalyzed bio-oil produced using fast pyrolysis from pine needles
Biomass Bioenergy
Catalytic pyrolysis of wheat bran for hydrocarbons production in the presence of zeolites and noble-metals by using TGA-FTIR method
Bioresour. Technol.
Photobioreactor cultivation and catalytic pyrolysis of the microalga Desmodesmus communis (Chlorophyceae) for hydrocarbons production by HZSM-5 zeolite cracking
Bioresour. Technol.
Characterization of deactivated and regenerated zeolite ZSM-5-based catalyst extrudates used in catalytic pyrolysis of biomass
J. Catal.
On the effectiveness of tailored mesoporous MFI zeolites for biomass catalytic fast pyrolysis
Appl. Catal. A : Gen.
Production of hydrocarbon-rich bio-oil from soapstock via fast microwave-assisted catalytic pyrolysis
J. Anal. Appl. Pyrolysis
Selective aromatic formation from catalytic fast pyrolysis of Jatropha residues using ZSM-5 prepared by microwave-assisted synthesis
J. Anal. Appl. Pyrolysis
Bio-oil production by lignocellulose fast-pyrolysis: isolating and comparing the effects of indigenous versus external catalysts
Fuel Process. Technol.
Potentiality of combined catalyst for high quality bio-oil production from catalytic pyrolysis of pinewood using an analytical Py-GC / MS and fixed bed reactor
J. Energy Inst.
Design of a ternary 3D composite from hydrochar, zeolite and magnetite powder for direct conversion of biomass to gasoline
Chem. Eng. J.
Lamellar and pillared ZSM-5 zeolites modified with MgO and ZnO for catalytic fast-pyrolysis of eucalyptus woodchips
Catal. Today
Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst
JES
Consequence of replacing nitrogen with carbon dioxide as atmosphere on suppressing the formation of polycyclic aromatic hydrocarbons in catalytic pyrolysis of sawdust
Bioresour. Technol.
Production of renewable aromatics and heterocycles by catalytic pyrolysis of biomass resources using rhenium and tin promoted ZSM-5 zeolite catalysts
Process Saf. Environ. Prot.
Catalytic pyrolysis over transition metal-modified zeolites: a comparative study between catalyst activity and deactivation
J. Anal. Appl. Pyrolysis
Catalytic pyrolysis of sugarcane bagasse using molybdenum The 15th International Symposium on District Heating and Cooling modified HZSM-5 zeolite Assessing the feasibility of a, using temperature function demand
Energy Procedia
Enhancement of bio-oil yield and selectivity and kinetic study of catalytic pyrolysis of rice straw over transition metal modified ZSM-5 catalyst
J. Anal. Appl. Pyrolysis
Enhancement of the production of bio-aromatics from renewable lignin by combined approach of torrefaction deoxygenation pretreatment and shape selective catalytic fast pyrolysis using metal modified zeolites
Bioresour. Technol.
Catalytic pyrolysis of Mediterranean sea plant for bio-oil production
Int. J. Hydrogen Energy
Enhancement of aromatics from catalytic pyrolysis of yellow poplar: role of hydrogen and methane decomposition
Bioresour. Technol.
Modification and regeneration of HZSM-5 catalyst in microwave assisted catalytic fast pyrolysis of mushroom waste
Energy Convers. Manage.
Co-precipitation, impregnation and so-gel preparation of Ni catalysts for pyrolysis-catalytic steam reforming of waste plastics
Appl. Catal. B Environ.
Elucidating the effect of desilication on aluminum-rich ZSM-5 zeolite and its consequences on biomass catalytic fast pyrolysis
Appl. Catal. A, Gen.
Catalytic pyrolysis of lignin over hierarchical HZSM-5 zeolites prepared by post-treatment with alkaline solutions
J. Anal. Appl. Pyrolysis
Effect of alkali-treated HZSM-5 zeolite on the production of aromatic hydrocarbons from microwave assisted catalytic fast pyrolysis (MACFP) of rice husk
Sci. Total Environ.
Enhancement in the aromatic yield from the catalytic fast pyrolysis of rice straw over hexadecyl trimethyl ammonium bromide modified hierarchical
Bioresour. Technol.
Synthesis and physicochemical characterization of hierarchical ZSM-5: effect of organosilanes on the catalyst properties and performance in the catalytic fast pyrolysis of biomass
Microporous Mesoporous Mater.
Enhancement of aromatics production from catalytic pyrolysis of biomass over HZSM-5 modified by chemical liquid deposition
J. Anal. Appl. Pyrolysis
Saw dust pyrolysis: effect of temperature and catalysts
Fuel
Catalytic fast pyrolysis of Millettia (Pongamia) pinnata waste using zeolite Y
J. Anal. Appl. Pyrolysis
Catalytic pyrolysis of straw biomasses (wheat, flax, oat and barley) and the comparison of their product yields
J. Anal. Appl. Pyrolysis
Non-catalytic and catalytic fast pyrolysis of Schizochytrium limacinum microalga
Fuel
Quality of bio-oil from catalytic pyrolysis of microalgae Chlorella vulgaris
Fuel
Catalytic pyrolysis of sweet sorghum bagasse in the presence of two acid catalysts
J. Energy Inst.
Influence of HSAPO-34, HZSM-5, and NaY on pyrolysis of corn straw fermentation residue via Py-GC / MS
J. Anal. Appl. Pyrolysis
Catalytic pyrolysis of soda lignin over zeolites using pyrolysis gas chromatography-mass spectrometry
Bioresour. Technol.
Catalytic pyrolysis of raw and hydrothermally carbonized Chlamydomonas debaryana microalgae for denitrogenation and production of aromatic hydrocarbons
Fuel
Catalytic fast pyrolysis of Arthrospira platensis (spirulina) algae using zeolites
J. Anal. Appl. Pyrolysis
Cited by (41)
Investigation of the effect of metal-impregnated catalyst on the kinetics of lignocellulosic biomass waste pyrolysis
2024, Journal of Environmental Chemical EngineeringA review on the modified red mud for biomass catalytic pyrolysis: Preparation, mechanisms and perspectives
2024, Journal of Analytical and Applied PyrolysisRecent advancement in biochar production and utilization – A combination of traditional and bibliometric review
2024, International Journal of Hydrogen EnergyActivated biochars as sustainable and effective supports for hydrogenations
2023, Carbon TrendsPhosphorus-modified mesoporous niobium pentoxide catalyst for fast pyrolysis of cellulose to selective production of levoglucosenone
2023, Industrial Crops and ProductsAdvances in design of heterogeneous catalysts for pyrolysis of lignocellulosic biomass and bio-oil upgrading
2023, Microporous and Mesoporous Materials