The chemistry of chemical recycling of solid plastic waste via pyrolysis and gasification: State-of-the-art, challenges, and future directions

Drop-in biofuels have been defined as functionally equivalent to petroleum-based transportation fuels and are fully compatible with the existing petroleum infrastructure. They will be essential in sectors such as aviation if we are to achieve emission reduction and climate mitigation goals. Currently, ‘conventional’ drop-in biofuels, which are primarily based on upgrading of lipids / oleochemicals, are the only significant source of commercial volumes of drop-in biofuels. However, the necessary increased, future volumes will likely come from ‘advanced’ drop-in biofuels based on biomass feedstocks such as forest and agriculture residues. Biocrudes / bio-oils produced from lignocellulosic feedstocks using thermochemical technologies such as gasification, pyrolysis, and hydrothermal liquefaction need to be further upgraded to drop-in biofuels. However, advanced drop-in biofuels have been slow to reach commercial maturity due to significant technical challenges, high capital costs, and the challenge of generally lower oil prices. It is likely that the co-processing of drop-in biofuels with conventional petroleum refining could considerably reduce capital costs. Initially, co-processing is likely to be established through the upgrading of conventional / oleochemical feedstocks (lipids). Lipids are readily available in large volumes (global production in 2017 was ~185 million metric tonnes) and can be more easily integrated into oil-refinery processes. In contrast, lignocellulose-derived biocrudes / bio-oils are not yet available in significant volumes and are more complex to co-process in a refinery. The likely strategies for co-processing of oleochemicals (lipids) and bio-oil and biocrude feedstocks based on different insertion points within the refinery infrastructure are discussed. © 2019 The Authors. Biofuels, Bioproducts, and Biorefining published by Society of Chemical Industry and John Wiley & Sons, Ltd.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/bbb.1974

Potential synergies of drop‐in biofuel production with further co‐processing at oil refineries

Techno-economic and environmental analysis of bio-oil production from forest residues via non-catalytic and catalytic pyrolysis processes

The delay in the energy transition, focused in the replacement of fossil diesel with biodiesel, is mainly caused by the need of reducing the costs associated to the transesterification reaction of vegetable oils with methanol. This reaction, on an industrial scale, presents several problems associated with the glycerol generated during the process. The costs to eliminate this glycerol have to be added to the implicit cost of using seed oil as raw material. Recently, several alternative methods to convert vegetable oils into high quality diesel fuels, which avoid the glycerol generation, are being under development, such as Gliperol, DMC-Biod, or Ecodiesel. Besides, there are renewable diesel fuels known as “green diesel”, obtained by several catalytic processes (cracking or pyrolysis, hydrodeoxygenation and hydrotreating) of vegetable oils and which exhibit a lot of similarities with fossil fuels. Likewise, it has also been addressed as a novel strategy, the use of straight vegetable oils in blends with various plant-based sources such as alcohols, vegetable oils, and several organic compounds that are renewable and biodegradable. These plant-based sources are capable of achieving the effective reduction of the viscosity of the blends, allowing their use in combustion ignition engines. The aim of this review is to evaluate the real possibilities that conventional biodiesel has in order to success as the main biofuel for the energy transition, as well as the use of alternative biofuels that can take part in the energy transition in a successful way.

Biodiesel at the Crossroads: A Critical Review

Atmospheric hydrodeoxygenation (HDO) of wheat straw fast pyrolysis vapors was studied as a promising route for the production of renewable liquid transportation fuels. The performance of TiO2-supported Pt (0.5 wt%) and MoO3 (10 wt%) catalysts was compared to an industrial Mo-based catalyst using a bench scale reactor operated at atmospheric pressure and up to high biomass-to-catalyst ratios (B:C). Mass and energy balances were complemented by detailed bio-oil characterization including advanced methods such as GC×GC-ToF/MS or -FID and 13C NMR. At 50 vol% H2, all three HDO catalysts effectively reduced the oxygen content of the bio-oils to ∼7–12 wt% (dry basis) compared to a non-catalytic reference (23 wt% O). MoO3/TiO2 was least efficient in conversion of acids (TAN = 28 mg per KOH), while Pt/TiO2 and MoO3/Al2O3 obtained oils with TAN ∼ 13 mg KOH/g (non-catalytic = 66 mg KOH/g). Compared to the TiO2-supported catalysts, the industrial Mo/Al2O3 catalyst produced higher yields of coke at the expense of condensed bio-oil. MoO3/TiO2 performed similar to Pt/TiO2 in terms of deoxygenation and energy recovery of condensed bio-oil, and by increasing the H2 concentration to 90 vol% the energy recovery of bio-oil increased to 39 and 42% at 8 and 10 wt% O (d.b.), respectively. Pt/TiO2 showed the highest selectivity to aliphatics and the lowest coke yields, e.g. the coke yield at B:C ∼ 8 was only 0.6 wt% of fed biomass. This study demonstrates that by using low-pressures of hydrogen and appropriate HDO catalysts, the quality of bio-oil can be improved without severely compromising its quantity (carbon yield) as observed under catalytic fast pyrolysis conditions.

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Athanassios Dimitriadis

Papers

Refinery co-processing of renewable feeds