Abstract

In-situ catalytic pyrolysis of biomass has been extensively studied in recent years for cost-competitive production of high quality bio-oil. To achieve that, numerous catalysts have been studied to facilitate in-situ upgrading of low-grade condensable vapors (bio-oil) by converting oxygenated compounds and large-molecule species. In this review, these catalysts are categorized in different families and a systematic evaluation of the catalyst effects on pyrolysis products and their characteristics is carried out with respect to the scale of the experimental setup. Among these catalysts, microporous zeolites are considered as most promising in terms of performance and the potential to tailor the desired bio-oil properties. More specifically, the prominent advantages of zeolites include efficient deoxygenation and molecular weight reduction of the resultant bio-oil, while the main drawbacks are decreases in the yield of bio-oil’s organic phase and catalyst deactivation by coke deposition. In addition to the zeolite-based catalysts, other catalysts including mesoporous aluminosilicates, a widely-applied class of catalysts used for deoxygenation of bio-oil as well as alkaline compounds are also reviewed and discussed herein. The research on the latter has not been extensive but the preliminary results have revealed their potential for deoxygenation of bio-oil, production of hydrocarbons, and reduction of undesired compounds. Nevertheless, these catalysts need to be further investigated systematically. Overall, further development of dedicated catalysts for selective deoxygenation and cracking of bio-oil would be essential for scaling up the existing pyrolysis technologies to achieve commercial production of biofuels through pyrolysis.

Highlights

  • Performance of widely used catalysts for online catalytic upgrading of bio-oil is systematically reviewed and compared with respect to the scale of application, i.e., analytical, bench, and pilot scale

  • Similar findings were reported in a series of previous studies in which ZSM-5, Y-type zeolites, and activated alumina were found effective for deoxygenation of biooil during ex-situ upgrading of biomass vapors in packed bed reactors leading to enhanced formation of single ring aromatics and polycyclic aromatic hydrocarbons (PAHs) (Williams and Horne, 1994; Horne and Williams, 1995; Williams and Horne, 1995b; Williams and Nugranad, 2000)

  • It should be noted that the main interest in application of these mineral compounds in biomass catalytic pyrolysis lies in their abundance in nature and being inexpensive, favoring the economic aspects of biofuels production

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Summary

Catalyst selection criteria for catalytic pyrolysis of biomass

A wide range of organic compounds is found in the bio-oil produced via fast pyrolysis of biomass. Hydrocarbons are a desirable fraction for fuel applications while compounds like phenol and its alkylated derivatives have high commercial values especially for resin or adhesive industry, making the process economically attractive. Oxygen could be removed by different reactions, i.e., dehydration, decarbonylation, and decarboxylation leading to the generation of water, CO, and CO2, respectively. Selective removal of oxygen by decarboxylation of carboxylic acids (formic, acetic acids) could decrease the acidity of bio-oil while selective decarbonylation of organic fractions (aldehydes, unsaturated species, etc.) could contribute to improved stabilization of the oil. Since the heavy lignin derivatives contain a high proportion of oxygen, reducing these compounds and simultaneously increasing hydrocarbons yields would decrease the oxygen content of bio-oil and increase its heating value. A catalyst for biomass pyrolysis should be capable of simultaneously catalyzing several reactions including dehydration, decarboxylation, decarbonylation, (de)alkylation, cracking, isomerization, cyclization, oligomerization, and aromatization. The application of zeolite-based catalysts, aluminosilicates, and alkaline compounds for catalytic pyrolysis of biomass are reviewed and discussed

Catalytic pyrolysis of biomass model compound and biomass at analytical scale
Ex-situ catalytic pyrolysis of biomass at bench scale
Mesoporous aluminosilicates for catalytic biomass pyrolysis
Effect of different metal incorporation to mesoporous aluminosilicates
Alkaline compounds for catalytic pyrolysis of biomass
Alkali metal-based catalysts for catalytic pyrolysis of biomass
Alkaline earth metal-based catalysts for catalytic pyrolysis of biomass
Catalytic fast pyrolysis of biomass at pilot and demonstration scale
Findings
Concluding remarks and future prospects
Full Text
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