What is the best catalyst for biomass pyrolysis?

https://doi.org/10.1016/j.jaap.2021.105280Get rights and content

Highlights

  • The Role of alkali and alkaline earth metals in product distribution and deactivation of zeolites.

  • Carbon chemisorption or physisorption, metal particle encapsulation, and pore plugging.

  • Hierarchical zeolite/carbon/mesoporous silica synthesis and performance in biomass pyrolysis.

  • Preparation method of 3D biochar architecture and their surface morphology.

  • Development of advanced composites to overcome the major challenges in CP.

Abstract

Biomass pyrolysis has played an important role in environmental management by providing fuel and value-added chemicals from renewable resources. However, the variability in the properties of biomass necessitates the need for tunable catalysts that can favor specific reactions to target desirable compounds. Acid sites on catalysts are required for the cleavage of Csingle bondC and Csingle bondO bonds. While zeolite has been the most historically used catalyst for these processes, other materials such as silica and biomass-derived activated carbon have garnered the interest of researchers. All three types of catalysts have their strengths and weaknesses. In this study, the authors detail the synthesis and application of these catalysts in pyrolysis reactions. Advancements made in recent years were explored in detail, and key factors that influence the activity and stability of each type of catalysts are highlighted. The authors also provide their perspective on all three materials in terms of their potential to provide potential advancements in the field of catalytic pyrolysis. Finally, future research directions are indicated and summarized, based on results published in the literature with a particular focus on the development of composite to overcome the major challenges posed by the conventional catalysts.

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.

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