Crude Bio-oil Research Articles

Performance of sulfided NiMo catalyst supported on pillared bentonite Al and Ti under hydrodeoxygenation reaction of guaiacol

Bio-crude oil is known to be sustainable, eco-environmentally, and an alternative energy source produced by biomass pyrolysis. However, its quality remains relatively low due to a higher oxygen concentration compared to liquid fuels from fossils. Therefore, an upgrading process is necessary through the catalytic hydrodeoxygenation (HDO) process. This work synthesized pillared bentonite using Al and Ti metals as the pillaring agent to produce Al-PILC and Ti-PILC as catalyst support for sulfided NiMo. Their catalytic activity in HDO reaction using guaiacol as a model compound of bio-crude oil were also evaluated. Characterization of the bentonite-pillared materials, including Al-PILC, Mo/Al-PILC, NiMo/Al-PILC, Ti-PILC, Mo/Ti-PILC, and NiMo/Ti-PILC, was performed using Surface Area Analyzer, X-ray Diffractometer (XRD), Temperature-Programmed Desorption of ammonia (NH3-TPD), X-Ray Fluorescence (XRF), and Scanning Electron Microscope (SEM) techniques. The characterization results confirm the pillarization process of bentonite using Al and Ti metals as the pillaring agent, and the preparation of the NiMo catalyst using the stepwise impregnation method was successfully prepared. The NiMo/Ti-PILC catalyst performs a superior conversion value on the HDO guaiacol reaction than other catalysts. A well dispersion of Mo and Ni metals on the surface support (NiMo/Ti-PILC), thus creating numerous active sites of the catalyst after the sulfidation. Variations in time and temperature during the HDO guaiacol reaction significantly affected the conversion.

An investigation of the longevity wear assessment during the utilisation of biofuel-diesel blends in a diesel engine: a case study of crude palm and crude jatropha oil

A longevity test was conducted to evaluate the impact of biofuels on engine degradation. Two varieties of blended fuel were generated by adding crude palm oil or crude jatropha oil to B5 diesel. The amounts of additional crude oil were 5, 10, and 15%. The testing period lasted 600 h, which is equivalent to 3–5 years of actual service. Before and after the test, the dimensions of engine elements were measured to determine the level of wear. Inspecting engine components revealed that combining crude bio-oils in proportions ranging from 0 to 15% increased engine wear. Components located in the combustion chamber exhibited greater wear when blended fuels were used, whereas fuel pump and injector components, which were not exposed to the heat, exhibited lower levels of wear. Even though engine wear was observed when mixed fuels were used, the vast majority of wear rates were incredibly low, ranging from 0.001 to 0.002 mm per 100 h. The only exception to this rule was the piston attrition rate, which was measured at 0.007 mm per 100 h. It can be concluded that engine wear is negligible when biofuel is blended with diesel in a ratio not exceeding 15% compared to B5 diesel.

Investigating the Impacts of Wastewaters on Lettuce (Lactuca sativa) Seed Germination and Growth

There is an opportunity for agriculture to utilize the many different waste streams in our world and capitalize on what would otherwise be viewed as waste products. Hydrothermal liquefaction (HTL) is an emerging technology for converting wet biomass to bio-crude oil, while aquaponics is a practice tracing back to indigenous communities around the world; both technologies have the potential to sustainably provide the necessary nutrients for crop growth. Food systems worldwide are actively transitioning to address the many challenges of climate change in a sustainable and efficient manner. Urban agriculture (UA) has the potential to generate localized crops in densely populated areas year-round, but has its challenges, involving high capital requirements, especially for vertical farming and controlled-environment agriculture, and being energy intensive due to artificial lighting and fossil fuel-based synthetic fertilizers. This study investigated the potential for aquaponic and HTL effluents to be used in hydroponic systems through a seed germination screening experiment. Buttercrunch lettuce (Lactuca sativa L.) seeds were placed in Ziploc plastic bags on paper towels saturated with the wastewater treatments for 10 days while their total length of growth was routinely measured from the tip of the root to the tip of the cotyledons. The Chicago High School for Agricultural Sciences (CHSAS) aquaponic effluent with a 5.8× times higher nitrate concentration and 4.25× higher ammonia concentration outperformed the Bevier aquaponic effluent and improved any other source water it was combined with. Results also showed that seed germination was not inhibited in the presence of 2–8% solutions of hydrothermal liquefaction aqueous phase (HTL-AP), which performed on par with standard hydroponic fertilizer; solutions of a higher percentage, though, may lead to inhibitory effects in plants, and those of a lower percentage may not provide enough nutrients in the proper forms to sustain plant growth. However, the nutrient analyses revealed that there is still much to investigate regarding the combination of wastewaters to provide a complete, well-rounded, and sustainable source for hydroponic crop production.

Wastewater Nutrient Recovery via Fungal and Nitrifying Bacteria Treatment

In efforts to reduce the consumption of fossil fuels and promote recycling biowaste, there is an interest in the production of post-hydrothermal liquefaction wastewater (HTL-AP) from the hydrothermal liquefaction (HTL) process that converts wet biomass into biocrude oil. This study explores ways of transforming potentially toxic HTL-AP into a fertilizer source for hydroponic cropping systems. This study specifically investigates the integration of the white-rot fungus Trametes versicolor with nitrifying bacteria (Nitrosomonas and Nitrobacter) to convert the organic nitrogen compounds into inorganic nitrogen while also producing the enzyme laccase, which has been shown to remove toxic compounds. This study aims to increase the concentration of nitrate-N to valorize wastewater as a suitable fertilizer by measuring several parameters, including laccase activity, pH, nitrate-N, and ammonia/ammonium-N concentrations, and analyzes interactions to optimize the conversion process. The data support the claim that the simultaneous inoculation of T. versicolor and nitrifying bacteria significantly increases nitrate-N concentrations in HTL-AP, as it increased by 17 times, or an increase of 32.69 mg/L. In addition, HTL-AP treated with T. versicolor and nitrifying bacteria reduced the treatment time by 120 h, highlighting a reduction in personnel time and energy consumption. Therefore, this research accentuates sustainability through fungal and bacterial treatments to develop eco-friendly hydroponic fertilizers. Future research should explore the potential of utilizing the combination of T. versicolor and nitrifying bacteria for the treatment of other industrial wastewaters.

Sulfur-free liquid fuel production via continuous catalytic hydrotreating of crude bio-oils from straws

Sulfur-free liquid fuel production via continuous catalytic hydrotreating of crude bio-oils from straws

Physicochemical characterization, valorization of lignocellulosic waste (Kola nut seed shell) via pyrolysis, and ultrasonication of its crude bio-oil for biofuel production

Kola nut seed shell is a largely generated food waste that can be explored as an alternative energy source to reduce the damaging effects of the combustion of fossil fuels on the environment and reduce its usage since it’s limited in nature. The seed shell’s proximate and ultimate data were obtained using standard procedures; ash deposition indices were obtained using XRF data; crystallinity of its cellulosic component was determined using XRD data; pyrolysis was done using a fixed bed pyrolyzer; and ultrasonication of crude bio-oil and its alcoholic blends was done using an ultrasound bath rated at 55 W. Its shell has moderate Moisture Content (MC) (5.84%), high C (51.92%), low amounts of S (0.020%), N (0.11%), ash content (5.26%), high VM (84.85%), Fixed Carbon (FC) (4.05%), C/N (472), H/C (0.096), and Higher Heating Value (HHV) (17.23 MJ/kg). Its mass ratio combination gave the empirical formula CH0.096O0.82N0.002. It pyrolytically degrades at a thermal temperature range of 400–550 °C. XRF analysis of its ash base on Na2O+K2O/SiO2 was 0.0897, which means no sintering inclination; B/A (0.27, low ash deposition tendency); SiO2/Al2O3 (22.92) and Fe2O3/CaO (0.135) (low and high ash deposition tendencies, respectively); slagging viscosity index (83.48, high slagging tendency); %SiO2 (71.52); babcock (Rs, 5.4×10−5); fouling indices (1.7×10−2, low deposition tendencies); and total alkalis (0.0642, low fouling tendency). GC and FTIR of the upgraded bio-oil showed complex compounds suitable as biofuel. Its co-pyrolysis with other biomass could reduce fouling, sintering, ash, and corrosion issues.

Integrated biorefinery approach for seaweed Sargassum fusiforme: A step towards green circular economy

This study aims to maximize the utilization of Sargassum fusiforme (SF), embedding the concept of a green circular economy. We developed a green extraction process using water and ultrasound assistance to extract high-value SF polysaccharides (SFPS). A 2k factorial design coupled with center points evaluated the curvature effect in the extraction process. Optimal extraction conditions were identified to be a mass-liquid ratio of 1:59 (w/v), an extraction temperature of 70 °C and time of 88 min, yielding 15.30 wt% SFPS, validated through experiments. SFPS demonstrated significant antioxidant capacity, indicated by their ferric ion reduction ability and superoxide anion scavenging ability. Post-extraction, the waste ethanol solution and SF residue were employed as feedstock for hydrothermal liquefaction (HTL), aiming to produce biocrude oil. We explored various parameters affecting the yield and quality of the resultant biocrude. The optimal HTL conditions for SF residue included a temperature of 280 °C and a reaction time of 45 min. The biocrude obtained using the waste solution exhibited higher carbon content (69.83%) and higher heating value (33.42 MJ/kg) compared to freshwater, indicating enhanced energy recovery (87.65% vs. 15.39%). Also, the presence of ethanol in waste solution facilitated a decrease in fatty acid content from 48.50% to 24.50%, while simultaneously increasing ester content from 6.37% to 35.54%, presumably due to the trans-esterification of fatty acids into esters. Utilizing the waste ethanol solution as HTL processing medium also led to a much lower greenhouse gas emissions (1714.0 kg CO2-eq) compared to that of freshwater (7735.4 kg CO2-eq) as evidenced by the life cycle assessment. This study's innovative approach not only valorizes the waste streams from SFPS extraction but also adds value by generating high-quality biocrude oil, offering practical solutions for waste reduction and resource recovery, fostering sustainable development and circular economy initiatives.

Pyrolysis of macroalgae residue from the agar industry for silica‐rich biochar and other sustainable chemicals: Process performances, product applications, and simple business scenario

AbstractThe macroalgae residue from the industrial agar extraction process contains a significant amount of carbon and has potential as a renewable feedstock. Unfortunately, it is often overlooked and is poorly utilized. This study aims to valorize this macroalgae residue through pyrolysis to produce silica‐rich biochar and other value‐added products in the form of biocrude oil (BCO) and biopyrolysis gas. The macroalgae residue was pyrolyzed at 300–700 °C with a heating rate of 20–40 °C/min. Yields of biochar, BCO, and gas of 62%, 25%, and 13% were obtained at a temperature of 700 °C and a heating rate of 20 °C/min. Biochar has a porous structure, a surface area exceeding 15 m2/g, and is dominated by amorphous silica of up to 13%. This silica‐rich biochar also contains Na and K, which hold potential benefits in agriculture, serving as soil ameliorants and playing a crucial role in enhancing soil fertility and promoting plant growth. In the meantime, BCO contains 29.3% carboxylic acid group as the most important chemical component. Other than that, the biopyrolysis gas contains mainly CH4 and H2 (up to 24–32%), which can act as chemical building blocks. Finally, a simple business scenario of silica‐rich biochar production reveals that it has a specific cost of 0.37 US$/kg. It could be economically viable as a soil ameliorant or fertilizer. However, challenges persist in scaling up production to an industrial scale.

Investigation of high water content in bio-crude oil (BCO) produced from empty oil palm fruit bunches pyrolysis

Investigation of high water content in bio-crude oil (BCO) produced from empty oil palm fruit bunches pyrolysis

Waste Sludge: Entirely Waste or a Sustainable Source of Biocrude? A Review.

Biomass-derived biocrude is gaining greater recognition from people in general as an alternative fuel source to traditional fossil fuels. Worldwide, a great deal of research is being done to develop fuels made from sustainable biomass in order to replace the current conventional energy sources. Waste sludge has been thought of as a viable raw biomass source because of its accessibility, affordability, high lignin content, and higher heating value. Additionally, considering sludge contains a high proportion of moisture and water acts as a catalyst during the hydrothermal liquefaction (HTL) process, it is the best choice for thermochemical conversion. From the ultimate component value ranges obtained from elemental analysis, it can be demonstrated that the C, H, and higher heating value (HHV) of petrocrude are approximately 8.78%, 23.5%, and 10.66% higher than those of biofuel. According to the overall analysis, co-liquefaction of waste vegetable oil and swine manure can result in 87.97% bio-oil at 340°C. The temperature, retention period, inclusion of catalysts, and use of solvents, however, can all affect this proportion. To support this illustration, it has been assessed from the study that municipal wet sewage sludge can produce an HHV of 28.52MJ/kg when water is used as the solvent. However, 34.14MJ/kg, or 16.5% more than the previous one, can be produced for the same amount of biomass, when the mixture of water and methanol serves as the solvents. This review article highlights an array of waste sludge categories, their chemical properties, and their conversion through the HTL process. It also features a Van Krevlen diagram with a graphical representation of essential operating parameters. This review research illustrates one of the best strategies for producing biofuel in which waste sludge can be used as raw material through the HTL conversion process, considering the prospective mass commercial production of biocrude oil.

Sustainability assessment of biofuel and value-added product from organic fraction of municipal solid waste

The current study aims to examine the techno-economic and environmental assessment of biorefinery development within a circular bioeconomy context by using an organic fraction of municipal solid waste (OFMSW) by extraction of lipids, carbohydrates, and proteins with 98, 51 and 62 % by mass of conversion efficiency and yield recovery, and value-added fractions production as well. Fatty acid methyl ester (biodiesel) and glycerol (biofuel) were produced by applying transesterification process, and the remaining biomass was converted into biocrude oil by thermal liquefication. The biorefinery using 613 kg of OFMSW produced biodiesel, glycerol, and bioethanol with 126 litter, 14.3 kg, and 172 litter respectively, as well as value-added fractions, such as biocrude oil with 78 kg. The environmental impact was assessed using the life cycle assessment (LCA) framework, ReCiPe2016 Mid-point (H) approach, through 18 different environmental categories. The key findings elucidate that Terrestrial ecotoxicity, Climate change, Fossil depletion and Human toxicity were the main impact categories which are potentially contributed 9.81E+02 kg 1,4-DB eq., 1.43E+03 kg CO2 eq., 2.04E+02 kg oil eq., and 8.08E+01 kg 1,4-DB eq. The normalization (person per equivalent) analysis revealed that only categories of resource reduction (fossil and metal depletion) are the key contributors to environmental degradation. The biorefinery system's total revenue was estimated at USD 6.817,509 million annually. The calculated revenue was USD 0.026 million daily in a shift of 8 h. The Net present worth (NPW) was calculated at USD 499.97 million by assuming a discount factor of 10 % and inflation rate of 5 % for 15 years. The project is considered feasible by demonstrating 7.15 payback year. This research showcased the efficient portrayal of the biorefinery system and succinctly conveyed the significant circular bioeconomy for a greener future. Thus, it could be helpful to the stakeholder's context towards techno-economic and environmental evaluation.

Fe-catalyzed low-temperature hydrothermal liquefaction of coffee shells: Influence of operating parameters on bio-oil yield, distribution of bio-oil products

Coffee shells were hydrothermally liquefied under FeCl3 catalysis to produce crude bio-oils at temperatures ranging from 190 to 300 °C. This study investigated the impact of operational parameters (hydrothermal temperature, residence time, Fe3+ catalyst concentration, extraction solvents) on the bio-oil yield. Optimized hydrothermal conditions resulted in a conversion rate of 68.47 % for coffee shells, leading to an 11.51 % yield of light bio-oil extracted from the aqueous phase and a 35.99 % yield of heavy bio-oil from the solid phase. The chemical composition and distillate distribution of the bio-oil were determined through organic element analysis, GC-MS analysis, and TG/DTG analysis. The light bio-oil primarily consisted of furfural derivatives and phenolic derivatives; however, it only accounted for approximately 14.50 % of the total energy recovered from the feedstock. The components present in heavy bio-oils varied depending on the extraction solvents used but mainly comprised fatty acids and their derivatives. Acetone extraction yielded the highest amount of bio-oil; however, its high O/C ratio reduced its higher heating value (HHV). Ethanol extraction also resulted in higher yields but TG/DTG analysis indicated that these fractions contained more refractory volatiles and solid residues compared to other solvents used for extraction. In comparison, n-hexane extraction had a lower yield than both previous methods but offered a lower O/C ratio and higher HHV instead. Our study demonstrated that Fe-catalyzed hydrothermal liquefaction is an efficient method for obtaining value-added compounds and hydrocarbon fuels from coffee shells.

Catalytic upgrading of palm oil derived bio-crude oil for bio-hydrocarbon enrichment using protonated zeolite-Y as catalyst

<abstract> <p>This research was conducted to study upgrading bio-crude oil (BCO) produced by pyrolysis of palm oil without the use of a catalyst, using protonated zeolite-Y designated as H-Y. Preparation of H-Y was carried out by subjecting zeolite-Y synthesized from rice husk silica (RHS) and food grade aluminium foil (FGAF) to a cation exchange process using ammonium nitrate solution with different concentrations of 2.0, 2.5, 3.0, and 3.5 M to obtain (H-Y) samples with different protonation extents. To confirm the formation of Na-Y, the sample was characterized using XRD and SEM, and to evaluate the protonation, the Na-Y and H-Y samples were analyzed using XRF. Characterization using XRD showed that the Na-Y sample is faujasite, which is the characteristic phase of zeolite-Y, and supported by the existence of particles with octahedral structure as seen by SEM. Successful protonation resulted in a reduction of Na content up to 89.948% from that of the Na-Y, which was demonstrated by the XRF results. Catalytic upgrading experiments demonstrated that H-Y zeolites functioned to increase the bio-hydrocarbon content from 80.23% in the BCO to practically 100% in the upgraded oil. In addition, no acids were identified in the upgraded fuels, implying that H-Y zeolite is a promising catalyst for BCO upgrading for bio-hydrocarbon enrichment of the oil.</p> </abstract>

Hydrothermal coliquefaction of anaerobic digestate with polyphenolic extracts from agricultural byproducts producing nearly nitrogen-free biocrude oil

Hydrothermal coliquefaction of anaerobically digested sewage sludge and polyphenols from agricultural residues yielded nearly nitrogen-free biocrude compatible with upgrading in oil refineries.

Removals of Some High- and Low-Density Polyethylene (HDPE and LDPE), Polypropylene (PP) and Polyvinyl Chloride (PVC) Microplastics Using Some Microalgae Types, Energy Production and Energy Recovery

Waste plastic conversion involves the treatment of plastic waste to transform in different forms of energy (heat, electricity, liquid fuels). Plastic can be converted into different forms of biofuel via thermochemical conversion methods (gasification, pyrolysis and liquefaction). Algal biomass can be converted into different forms of biofuel (crude bio-oil, bioethanol, biogas, biodiesel and bio-hydrogen) well as value added chemicals. Microalgal cells can accumulate more lipids over a shorter life cycle, they are discussed as a promising feedstock for third-generation biodiesel. The utilization of microalgae as biofuel feedstocks offers an economic, ecofriendly alternative to the use of fossil fuels the aim of microplastics (MPs) removals. Interactions between MPs and microalgal cells could enhance several important features for possible microalgal harvest and MPs accumulation. One hypothesis is microalgal biomass hypothesis can accumulate lipids and carbohydrates under microplastic stress, supporting biomass conversion into biodiesel and bioethanol. In such systems, algal cells act as bio-scavengers for MPs, binding the particles to algal surfaces or incorporating them into their cells; they are filtered from the water body and finally destroyed by further downstream processing of the polluted biomass. In this study, in order to determine biofuel (1-butanol) and methane gas [CH4(g)] production; High- and low-density polyethylene (HDPE and LDPE), polypropylene (PP), and polyvinyl chloride (PVC) MPs were removed using biomass composed of microalgae Chlamydomonas reinhardtii and Chlorella vulgaris. The algal inhibition test results proved that small groups of MPs with a size of ≈ 100 nm did not show algal inhibition. According to the algae inhibition test results, the production of 1-butanol from 100 mg/l microalgae biomass under aerobic conditions were determined as 93 ml/g for HDPE, 236 ml/g for LDPE, 387 ml/g for PP and 459 ml/g for PVC. According to the algae inhibition test results, the production of CH4(g) from 400 mg/l microalgae biomass under anaerobic conditions were measured as 452 ml/g for HDPE, 510 ml/g for LDPE, 529 ml/g for PP and 541 ml/g for PVC. 91.26%, 94.52%, 98.34% and 96.17% energy recoveries were measured for HDPE, LDPE, PP and PVC MPs, respectively, after microalgae biomass experiments, at pH=7.0 and at 35oC. Maximum 98.34% energy recovery was obtained for PP MPs after microalgae biomass experiments, at pH=7.0 and at 35oC.

High-temperature high-pressure electrochemical hydrogenation of biocrude oil

Hydrothermal liquefaction (HTL) occurs at high pressures (160–200 bar) and temperatures (300–350 °C), where the conditions in the reactor drive the conversion of wet biomass to biocrude oil (BC). Before drop-in, BC needs further upgrading (hydrogenation) to increase the energy content and decrease the concentration of heteroatoms. Normally this is done in hydrogenation reactors at high pressures and temperatures, which require an external high pressure H2 source. The main HTL by-product is process water (PW), which is either recirculated or cleaned before being disposed. Herein we investigated a membrane-less electrochemical method, which uses PW as hydrogen source and can be seamlessly integrated in HTL plants. We demonstrate a proof-of concept of a membrane-less electrochemical reactor that oxidizes PW at the anode and uses hydrogen in form of protons and electrons to hydrogenate BC at the cathode. We report BC upgrading (atomic H/C ratio increase up to 17 %) at high-pressure (up to 100 bar) and high-temperature (up to 200 °C), which mimic the conditions of an actual HTL plant. The proof-of-concept discussed here is a novel way of increasing the hydrogen content of biocrude oil within HTL reactor by using electricity, with no need of an external high-pressure H2 source.

Electrochemical Oxidation of Hydrothermal Liquefaction-Derived Aqueous Phase for Simultaneous H2 Production

Hydrothermal liquefaction (HTL) is a thermochemical process in which high water containing feedstocks (95%-75%) such as food waste or sewage sludge is converted into fuels. There are four different phases generated during HTL, namely biocrude (oil phase), biochar (solid phase), aqueous phase and gaseous phase. The biocrude phase needs to be processed with hydrogen (H2) via catalytic hydrotreating to produce gasoline, diesel, jet oil. The aqueous phase (AP) contains up to 5 wt% organic compounds mostly in the form of carboxylic acids and amines and inorganics (e.g., Na, K) and cannot be treated with traditional wastewater treatment technologies (e.g., anaerobic digestion). Hence, it is necessary to treat this wastewater so it can be released safely.Electrocatalysis represents a novel approach to treat this AP waste stream while simultaneously generating the H2 needed for hydrotreating. Instead of using traditional water electrolysis (H2O → 2 H+ + 2 e- + ½ O2, E° = − 1.18 V, ∆H° = 275 kJ/mol H2), we explore electrocatalytic oxidation (ECO) of organic molecules (e.g., CH3COOH + 2 H2O → 2 CO2 + 8 e- + 8 H+, E° = − 0.02 V, ∆H° = 53 kJ/mol H2) to simultaneously remove organics from the HTL-derived AP while simultaneously producing H2. The HTL-derived AP can have different concentration and composition of both organics as well as inorganics, which depend on the source feedstock. The ECO of different HTL-derived wastewaters was evaluated in this study. It was studied, how the concentration and source of AP as well as the electrochemical reaction conditions affect the organic removal as well as the H2 production in both batch cell and continuous flow-cell configuration. Our results show that the presence of organics decreases the current density as well as causes anode deactivation after 40 h of operation in the continuous flow cell. However, the cathode performance and stability remained unaffected for more than 1,000 h. Different strategies were evaluated to enhance the life of the electrode and running the system under alkaline conditions improved the anode stability 5 folds References Andrews, E.; Lopez-Ruiz, J. A.; Egbert, J. D.; Koh, K.; Sanyal, U.; Song, M.; Li, D.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Gutiérrez, O. Y.; Holladay, J. D., Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds. ACS Sustainable Chemistry & Engineering 2020, 8 (11), 4407-4418.Lopez-Ruiz, J. A.; Qiu, Y.; Andrews, E.; Gutiérrez, O. Y.; Holladay, J. D., Electrocatalytic valorization into H2 and hydrocarbons of an aqueous stream derived from hydrothermal liquefaction. Journal of Applied Electrochemistry 2021, 51 (1), 107-118.Lopez-Ruiz, J. A.; Andrews, E.; Akhade, S. A.; Lee, M.-S.; Koh, K.; Sanyal, U.; Yuk, S. F.; Karkamkar, A. J.; Derewinski, M. A.; Holladay, J.; Glezakou, V.-A.; Rousseau, R.; Gutiérrez, O. Y.; Holladay, J. D., Understanding the Role of Metal and Molecular Structure on the Electrocatalytic Hydrogenation of Oxygenated Organic Compounds. ACS Catalysis 2019, 9 (11), 9964-9972. Figure 1

Aniline Derivatives from Lignin under Mild Conditions Enabled by Electrochemistry.

The development of environmentally friendly methods for the valorization of important phenolic platform chemicals originating directly from lignin-first depolymerization into value-added N-chemicals, such as aniline derivatives, is of high industrial interest. In this work, we tackle this challenging transformation by the judicious combination of electrochemical conversion and chemical functionalization steps. In the first step, lignin-derived para-substituted guaiacols and syringols undergo an atom-efficient, room-temperature anodic oxidation using methanol both as solvent and reagent towards the formation of the corresponding cyclohexadienone derivatives, which are subsequently converted to synthetically challenging ortho-methoxy substituted anilines by reaction with ethyl glycinate hydrochloride under mild conditions. The developed method was applied to crude lignin depolymerization bio-oils, derived from reductive catalytic fractionation (RCF) mediated either by copper-doped porous metal oxide (Cu20 PMO) or Ru/C, allowing the selective production of 4-propanol-2-methoxyaniline (1Gb) and 4-propyl-2-methoxyaniline (2Gb), respectively, from pine lignocellulose. Finally, the application of 2Gb was further studied in the synthesis of carbazole 2Gc, a lignin-derived analogue of biologically active alkaloid murrayafoline A.

Evaluation of Bio-Oils in Terms of Fuel Properties

In response to the global climate challenge and the increasing demand for energy, exploring renewable energy alternatives has become crucial. Bio-oils derived from biomass pyrolysis are emerging as potential replacements for fossil fuel-based liquid fuels. This paper shares findings from the Institute of Energy and Fuel Processing Technology on the quality of crude biomass pyrolysis bio-oil samples. These findings highlight their potential as motor liquid fuels. The article details the results of tests on the physicochemical properties of four distinct bio-oil samples. Additionally, it presents preliminary test results on the hydrodeoxygenation of bio-oils in a batch reactor. The production of homogeneous, stable mixtures using other fuel additives, such as diesel oil, rapeseed methyl ester (RME), and butanol, is also discussed.

Storage stability of biocrude oil fractional distillates derived from the hydrothermal liquefaction of food waste

Biocrude oil produced via hydrothermal liquefaction (HTL) is a promising precursor for transportation fuels and biochemicals. Present studies have highlighted the inherent instability of the biocrude oil, which poses significant challenges for its subsequent storage, upgrading and transportation. On the other hand, biocrude oil distillates showed the potential to serve as a transportation fuel blendstock. To this end, this study aimed to investigate the influence of the distillation temperature (199–238 °C and 238–274 °C), storage atmosphere (air and nitrogen), temperature (25 °C and 55 °C), and time (0–16 weeks) on the physical, chemical, and boiling point distribution properties of the distillates. Results demonstrated that changes in the stored distillates due to different distillation temperature were drastically higher than that between different storage atmospheres and temperatures. Comparing with the raw distillate, the distribution of compounds with a molecular weight < 300 Da in low-temperature (199–238 °C) distillates (LD) and medium-temperature (238–274 °C) distillates (MD) was improved with the increasing storage time. In addition, storage led to a decrease in O:C ratio (21.6 % and 86.5 %), and an increase in the HHV (3.6 % and 12.3 %) in the LD and MD, respectively. Furthermore, only slight deviations were observed in the density (5.2 % and 7.4 %) and viscosity (5.2 % and 0.8 %) for LD and MD, respectively. In particular, the MD group exhibited comparable characteristics to transportation fuels with decreased acidity (1.8–2.8 mg KOH/g) and increased HHV (46.2–46.8 MJ/kg) after long-term storage. At last, the mechanism of superior distillates stability was discussed. This study indicated that distillation not only presents a potential approach for producing transportation fuel blendstock but also improves the stability of HTL biocrude oil.