This study introduces a distributed electrified heating approach that is able to innovate chemical engineering involving endothermic reactions. It enables rapid and uniform heating of gaseous reactants, facilitating efficient conversion and high product selectivity at specific equilibrium. Demonstrated in catalyst-free CH4 pyrolysis, this approach achieves stable production of H2 (530 g h−1 L reactor−1) and carbon nanotube/fibers through 100% conversion of high-throughput CH4 at 1150 °C, surpassing the results obtained from many complex metal catalysts and high-temperature technologies. Additionally, in catalytic CH4 dry reforming, the distributed electrified heating using metallic monolith with unmodified Ni/MgO catalyst washcoat showcased excellent CH4 and CO2 conversion rates, and syngas production capacity. This innovative heating approach eliminates the need for elongated reactor tubes and external furnaces, promising an energy-concentrated and ultra-compact reactor design significantly smaller than traditional industrial systems, marking a significant advance towards more sustainable and efficient chemical engineering society.

Liquefaction of lignocellulosic biomass through fast pyrolysis, to yield fast pyrolysis bio-oil (FPBO), is a technique that has been extensively researched in the quest for finding alternatives to fossil feedstocks to produce fuels, chemicals, etc. Properties such as high oxygen content, acidity, and poor storage stability greatly limit the direct use of this bio-oil. Furthermore, high coking tendencies make upgrading of the FPBO by hydrodeoxygenation in fixed-bed bed hydrotreaters challenging due to plugging and catalyst deactivation. This study investigates a novel two-step hydroprocessing concept; a continuous slurry-based process using a dispersed NiMo-catalyst, followed by a fixed bed process using a supported NiMo-catalyst. The oil product from the slurry-process, having a reduced oxygen content (15 wt%) compared to the FPBO and a comparatively low coking tendency (TGA residue of 1.4 wt%), was successfully processed in the downstream fixed bed process for 58 h without any noticeable decrease in catalyst activity, or increase in pressure drop. The overall process resulted in a 29 wt% yield of deoxygenated oil product (0.5 wt% oxygen) from FPBO with an overall carbon recovery of 68%.

Reducing the use of fossil fuels is an ongoing and important effort considering the environmental impact and depletion of fossil-based resources. The combination of ablative fast pyrolysis and hydroprocessing is explored as a pathway allowing bio-based intermediates (BioMates) integration in underlying petroleum refineries. The proposed technology is validated in industrially relevant scale, identifying pros and cons towards its commercialization. Straw from wheat, rye and barley was fed to ablative fast pyrolysis rendering Fast Pyrolysis Bio-Oil (FPBO) as the main product. The FPBO was stabilized via slurry hydroprocessing, rendering a stabilized FPBO (sFPBO) with 49 % reduced oxygen content, 71 % reduced carbonyl content and 49 % reduced Conradson carbon residue. Fixed bed catalytic hydroprocessing of sFPBO resulted in the production of BioMates, a high bio-content product to be co-fed in established refinery units. Compared to the starting biomass, BioMates has 83.6 wt% C content increase, 92.5 wt% O content decrease, 93.0 wt% water content decrease, while the overall technology has 20 wt% conversion yield (32 wt% carbon yield) from biomass to BioMates. © 2022 The Author(s)

The global Sustainable Development Goals highlight the necessity for affordable and clean energy, designated as SDG7. A sustainable and feasible biorefinery concept is proposed for the carbon-negative utilization of biomass waste for affordable H2 and battery anode material production. Specifically, an innovative tandem biocarbon + NiAlO + biocarbon catalyst strategy is constructed to realize a complete reforming of biomass pyro-vapors into H2+CO (as a mixture). The solid residues from pyrolysis are upgraded into high-quality hard carbon (HCs), demonstrating potential as sodium ion battery (SIBs) anodes. The product, HC-1600-6h, exhibited great electrochemical performance when employed as (SIBs) anodes (full cell: 263 Wh/kg with ICE of 89%). Ultimately, a comprehensive process is designed, simulated, and evaluated. The process yields 75 kg H2, 169 kg HCs, and 891 kg captured CO2 per ton of biomass achieving approx. 100% carbon and hydrogen utilization efficiencies. A life cycle assessment estimates a biomass valorization process with negative-emissions (−0.81 kg CO2/kg-biomass, reliant on Sweden wind electricity). A techno-economic assessment forecasts a notably profitable process capable of co-producing affordable H2 and hard carbon battery anodes. The payback period of the process is projected to fall within two years, assuming reference prices of 13.7 €/kg for HCs and 5 €/kg for H2. The process contributes to a novel business paradigm for sustainable and commercially viable biorefinery process, achieving carbon-negative valorization of biomass waste into affordable energy and materials.

Lignocellulosic biomass from energy crops, i.e., short rotation coppice willows such as Salix spp., can be used as feedstock for production of transportation biofuels. Biomass conversion via fast pyrolysis followed by co-refining with fossil oil in existing refinery infrastructure could enable a fast introduction of large-scale production of biofuels. In this study, Salix was first liquefied using ablative fast pyrolysis in a pilot scale unit. The resulting pyrolysis oil, rich in oxygenates, was thereafter co-refined in 20 wt% ratio with fossil feedstock using two separate technologies, a fluidized catalytic cracking (FCC) laboratory unit and a continuous slurry hydroprocessing pilot plant. In the FCC route, the pyrolysis oil was cracked at 798 K using a commercial FCC catalyst at atmospheric pressure, while in the hydroprocessing route, the oil was processed at 693 K and a hydrogen pressure of 15 MPa in the presence of an unsupported molybdenum sulfide catalyst. Both routes resulted in significant deoxygenation (97 wt% versus 93 wt%). It is feasible to co-refine pyrolysis oil using both methods, the main difference being that the hydroprocessing results in a significantly higher biogenic carbon yield from the pyrolysis oil to liquid and gaseous hydrocarbon products (92 wt%) but would in turn require input of H2. In the cracking route, besides the liquid product, a significant part of the biogenic carbon ends up as gas and as coke on the catalyst. The choice of route depends, among other factors, on the available amount of bio-oil and refining infrastructures. © 2023 The Authors

Biochar, originating from biomass pyrolysis, has been proven a promising catalyst for tar cracking/reforming with great coke resistance. This work aims to evaluate various engineered biochar-based catalysts on syngas production in a biomass pyrolysis and catalytic reforming process without feeding extra steam. The tested engineered biochar catalysts include physical- and chemical-activated, nitrogen-doped, and nickel-doped biochars. The results illustrated that the syngas yields were comparable when using biochar and activated biochar as catalysts. A relatively high specific surface area (SSA) and a hierarchical porous structure are beneficial for syngas and hydrogen production. A 2 h physical-activated biochar catalyst induced the syngas with the highest H2/CO ratio (1.5). The use of N-doped biochar decreased the syngas yield sharply due to the collapse of the pore structure but obtained syngas with the highest LHVgas (18.5MJ/Nm3). The use of Ni-doped biochar facilitated high syngas and hydrogen yields (78.2 wt % and 26 mmol H2/g-biomass) and improved gas energy conversion efficiency (73%). Its stability and durability test showed a slight decrease in performance after a three-time repetitive use. A future experiment with a longer time is suggested to determine when the catalyst will finally deactivate and how to reduce the catalyst deterioration. © 2023 The Authors. 

In order to successfully integrate biomass pyrolysis oils as starting materials for conventional oil refineries, upgrading of the pyrolysis oils is needed to achieve desired properties, something which can be performed either as part of the pyrolysis process and/or by separate catalytic treatment of the pyrolysis intermediate oil products. In this study, the quality of stem wood-derived pyrolysis oil was improved via ex situ catalytic hydropyrolysis in a bench-scale pyrolyzer (stage 1), followed by catalytic hydro-coprocessing with fossil co-feed in a laboratory-scale high pressure autoclave (stage 2). The effect of pyrolysis upgrading conditions was investigated based on the quality of intermediate products and their suitability for hydro-coprocessing. HZSM-5 and Pt/TiO2 catalysts (400 °C, atmospheric pressure) were employed for ex situ pyrolysis, and the NiMoS/Al2O3 catalyst (330 °C, 100 bar H2 initial pressure) was used for hydro-coprocessing of the pyrolysis oil. The application of HZSM-5 in the pyrolysis of stem wood under a N2 atmosphere decreased the formation of acids, ketones, aldehydes, and furans and increased the production of aromatic hydrocarbons and phenolics (guaiacols and phenols). Replacing HZSM-5 with Pt/TiO2 and N2 with H2 resulted in complete conversion of guaiacols and significant production of phenols, with further indications of increased stability and reduced coking tendencies.

A novel pyrolysis followed by in-line cascaded catalytic reforming process without additional steam was developed to produce high-purity syngas from woody biomass. The key to the proposed process is the construction of a cascaded biochar + NiAl2O4 catalytic reforming process in which biochar acts as a pre-reforming catalyst, and NiAl2O4 acts as a primary reforming catalyst. The large oxygenates in the pyro-vapors are deeply cracked in the biochar layer due to the increased residence time in the hot-biochar bed. The remaining small molecules are then reformed with the autogenerated steam from pyrolysis catalyzed by the reduced Ni0 species in the NiAl2O4 catalyst (NiAlO). The results showed that the yield of syngas for the optimized process was 71.28 wt% (including 44.44 mg-H2/g-biomass and 536.48 mg-CO/g-biomass), and the CO2 yield of the process was only 3 kg-CO2/kg-hydrogen. High-purity syngas with 89.47 vol% of (H2 + CO) was obtained, and the gas energy conversion efficiency (GECE) of the process reached 75.65%. The study shows that in the cascaded catalytic reforming process, cracking of the large oxygenates and reforming of the small molecules are promoted sequentially in separated biochar + NiAlO catalyst layers, which maximizes the syngas production and improves the activity and stability of the Ni-based catalyst. © 2022 The Author(s)

In this study, a sustainable in situ catalytic fast pyrolysis (CFP) of lignin was developed by using biochar and activated carbon (AC) as catalysts, which is derived from the same CFP of lignin process. The results showed that using biochar as the catalyst mainly promoted the production of non-condensable gas, water, and guaiacol-rich oil regardless of the biochar-to-lignin ratio. The catalytic effect of the biochar was mainly attributed to the surface sodium and alkali metals. Using AC44.7% and AC48.6% as the catalyst resulted in a high yield of guaiacol-rich oil, whereas using AC64.3% induced a great decrease of the tarry oil yield and a significant increase of the phenol concentration in bio-oil. The diffusion efficiency of the reactive intermediates inside the catalysts determined by the pore size was believed to be the greatest determinant of the catalytic performance of the ACs. The mesopores were large enough to allow most of the reactive intermediates to diffuse quickly and react. Moreover, by using the same catalyst, char agglomeration was almost completely suppressed after in situ CFP. Two major problems, tar production and char agglomeration, which limit the large-scale application of fast lignin pyrolysis are believed to be solved. © 2021 The Authors

Five aluminosilicate catalysts with different textural and acidic properties are used to study the influence of their acidic and porous properties on the coke formation during the fast catalytic pyrolysis of lignin. The competition between coke formation and target product (hydrocarbons) formation in regard to different pore sizes and Si/Al ratios is classified via performing X-Ray Diffraction (XRD), nitrogen adsorption-desorption, pyrolysis–gas chromatography–mass spectrometry (Py-GCMS), kinetic calculations, and thermogravimetric (TG)/temperature programmed oxidation (TPO) measurements. The results indicated that a pore size consistent with the critical diameters of the pyrolysis products of lignin is a prerequisite for a catalyst to reach a high selectivity for the desired products with less coke formation. A relatively large pore size can cause severe coke formation; however, large pores are favorable for increasing the reaction rate by increasing the diffusion efficiency. A catalyst with sufficient acidity is also essential for high selectivity towards target products. © 2022 The Authors