Abstract

Biomass pyrolysis has emerged as a flexible platform for converting low-value residues into higher-value energy carriers (bio-oil, biochar and gas) and carbon-rich materials, with realistic potential for negative emissions when biochar is deployed in long-lived sinks. Over the last decade, three developments have driven the field forward: first, a finer mechanistic understanding of devolatilization and secondary reactions; second, major improvements in analytical techniques for characterising feedstocks and products; and third, more rigorous techno-economic and life-cycle assessments that place pyrolysis in a broader energy-system context. Recent experimental work on forestry and agro-industrial residues has clarified how biomass composition, ash chemistry and operating conditions jointly govern product yields, energy content and stability. Parallel advances in GC×GC–MS, high-resolution mass spectrometry, NMR and thermogravimetric methods have shifted the discussion from bulk “bio-oil” and “char” to families of molecules and well-defined structural domains, which can be deliberately targeted by reactor and catalyst design. Data-driven models, ranging from support vector machines applied to TGA curves to ANFIS and random forests for yield prediction, are now accurate enough to support process screening and multi-objective optimisation. At the system level, commercial fast pyrolysis biorefineries report overall useful energy efficiencies on the order of 80–86%, while slow pyrolysis configurations centred on biochar can be economically viable when carbon storage and co-products are appropriately valued. Thermodynamic analyses confirm that indirect gasification via fast-pyrolysis oil sacrifices some energy and exergy efficiency relative to direct solid-biomass gasification but may offer logistical and integration advantages. This review synthesises recent work on (i) feedstock and process characterisation; (ii) state-of-the-art analytical methods for bio-oil, biochar and gas; (iii) modelling and machine-learning tools; and (iv) energy-system deployment of pyrolysis products. Throughout, the emphasis is on how characterisation and modelling inform concrete design choices and on the trade-offs that arise when pyrolysis is considered as part of a wider decarbonisation portfolio. By integrating laboratory-scale characterisation with system-level modelling, this review aligns biomass pyrolysis with several United Nations Sustainable Development Goals (SDGs). The optimisation of thermochemical conversion pathways for forestry and agro-industrial residues directly supports SDG 7 (Affordable and Clean Energy) by enhancing the efficiency of bio-oil and syngas production. Furthermore, the deployment of biochar as a stable carbon sink for negative emissions and soil amendment addresses SDG 13 (Climate Action) and SDG 15 (Life on Land). By converting low-value waste streams into high-value energy carriers and chemicals within a circular bioeconomy framework, the research further contributes to SDG 12 (Responsible Consumption and Production) and SDG 9 (Industry, Innovation and Infrastructure).