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Wet oxidation can be an effective process for the pretreatment of complex biomass such as lignocellulose. However, studies on the use of wet oxidation for treating solid waste such as dairy manure are limited. The use of partial wet oxidation to convert dairy manure into low molecular weight carboxylic acids as final products were investigated. This work focuses on the performance of the sub-critical wet oxidation treatment of dairy cattle manure as a conversion/pretreatment process to release matter from the lignocellulosic fraction rather than a destructive process. The operating conditions were controlled at the short residence time and optimal temperature in the presence of oxygen under a pressure of 120 psi. The thermal hydrolysis under wet oxidation significantly affected conversion manure slurry into organic acids. The concentration of acetic acid reached 1778 mg L -1 , achieved at 190°C (60 minutes reaction time) as the reaction temperature increased within the range of 150°C-200°C, total organic carbon was reduced and monomers in the process liquids decreased. On the other hand, soluble COD in process liquids increased with an increment in reaction temperature. The results provide insights into technical options to pretreat dairy manure to improve biochemical conversion yield., Competing Interests: Declaration of conflicting interestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Due to phosphate's necessity in agriculture and its danger to the environment, the development of adsorbents for its removal has been the subject of intensive research activity. Although the introduction of nitrogen functionality to chars and modification of biochar with metals have proven to change the character of the char structure, making it more active toward nutrients, there is no study regarding the doping of biochar with metals and nitrogen simultaneously for the adsorption of phosphates. This paper is the first of two in which we report the production, characterization, and evaluation of N-metal-doped biochars from cellulose for phosphate removal from liquid effluents. In this part, we describe the production and characterization of N-Ca-, N-Fe-, and N-Mg-doped biochars. The elemental composition and surface area of each of the materials produced is reported. Elemental and surface characterization of the chars are reported with the largest N content appearing at a temperature of 800 °C (12.5 wt %) and a maximum surface area for biochar produced at 900 °C (1314 m 2 /g). All of the adsorbents were visualized by scanning electron microscope (SEM), confirming that although there are some crystals on the surface of the biochar produced, most of the N, Mg, and Ca are part of the polyaromatic ring structure. Transmission electron microscope (TEM) images clearly show the formation of nanoclusters with the metals in the case of N-Fe and N-Ca biochars. The N-Mg biochars show a uniform distribution of the Mg through the carbon surface. X-ray photoelectron spectroscopy (XPS) studies of the biochars produced with metals and varying nitrogen levels clearly show Mg and Ca peaks shifting their position in the presence of N, suggesting the formation of stable structures between metals and N in the carbon polyaromatic ring system. To elucidate the nature of these structures, we conducted DFT-based calculations on different configurations of the nitrogenated structures. The calculated binding energy shifts were found to closely match the XPS experimental binding energy, confirming the likelihood of these structures in biochar. Finally, based on our experimental and modeling results, we hypothesize that an important fraction of the Mg and Ca is introduced to these biochars at the edges. Another fraction of Mg and Ca is in the form of phthalocyanine-like internal structures. More experimental studies are needed to confirm the formation of these very interesting structures and their potential use as adsorbents or catalysts., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Lipids are a biorefinery platform to prepare fuel, food and health products. They are traditionally obtained from plants, but those of microbial origin allow for a better use of land and C resources, among other benefits. Several (thermo)chemical and biochemical strategies are used for the conversion of C contained in lignocellulosic biomass into lipids. In particular, pyrolysis can process virtually any biomass and is easy to scale up. Products offer cost-effective, renewable C in the form of readily fermentable molecules and other upgradable intermediates. Although the production of microbial lipids has been studied for 30 years, their incorporation into biorefineries was only described a few years ago. As pyrolysis becomes a profitable technology to depolymerize lignocellulosic biomass into assimilable C, the number of investigations on it raises significantly. This article describes the challenges and opportunities resulting from the combination of lignocellulosic biomass pyrolysis and lipid biosynthesis with oleaginous microorganisms. First, this work presents the basics of the individual processes, and then it shows state-of-the-art processes for the preparation of microbial lipids from biomass pyrolysis products. Advanced knowledge on separation techniques, structure analysis, and fermentability is detailed for each biomass pyrolysis fraction. Finally, the microbial fatty acid platform comprising biofuel, human food and animal feed products, and others, is presented. Literature shows that the microbial lipid production from anhydrosugars, like levoglucosan, and short-chain organic acids, like acetic acid, is straightforward. Indeed, processes achieving nearly theoretical yields form the latter have been described. Some authors have shown that lipid biosynthesis from different lignin sources is biochemically feasible. However, it still imposes major challenges regarding strain performance. No report on the fermentation of pyrolytic lignin is yet available. Research on the microbial uptake of pyrolytic humins remains vacant. Microorganisms that make use of methane show promising results at the proof-of-concept level. Overall, despite some issues need to be tackled, it is now possible to conceive new versatile biorefinery models by combining lignocellulosic biomass pyrolysis products and robust oleaginous microbial cell factories., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Biochar modified with calcium source is acted as an effective adsorbent for phosphorous recovery. In this research, eggshell is used as a low-cost and environmentally friendly calcium source to replace chemical reagents such as CaCO 3 , Ca(OH) 2 and CaCl 2 used in the modified biochar production. Biochar derived from rape straw and modified with eggshell shows prominent phosphorous adsorption performance (e.g., equilibrium adsorption amount, 109.7 mg/g). The kinetic and isotherm analysis demonstrate that chemical adsorption process is performed as the main controlled step for the modified biochar adsorption, and the phosphate adsorption process is composed of both monolayer adsorption and multi-layer adsorption. Moreover, it is found from the physicochemical structures comparison before and after phosphate adsorption that Ca-P precipitation, hydrogen bonding and electrostatic attraction are identified as main adsorption mechanisms. In addition, the adsorbed phosphates are mainly distributed inside the space with pore sizes of 15-50 nm., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Catalytic liquefaction of lignin is an attractive process to produce fuels and chemicals, but it forms a wide range of liquid products from monomers to oligomers. Oligomers represent an important fraction of the products and their analysis is complex. Therefore, rapid characterization methods are needed to screen liquefaction conditions based on the distribution in monomers and oligomers. For this purpose, UV spectroscopy is proposed as a fast and simple method to assess the composition of lignin-derived liquids. UV absorption and fluorescence were studied on various model compounds and liquefaction products. Liquefaction of Soda lignin was conducted in an autoclave, in ethanol and with Pt/C catalyst (H 2 , 250 °C, 110 bar). Liquids were sampled at isothermal conditions every 30 min for 4 h. UV fluorescence spectroscopy is related to GC-MS, gel-permeation chromatography (GPC), MALDI-TOF MS, and NMR characterizations. A depolymerization index is proposed from UV spectroscopy to rapidly assess the relative distribution of monomers and oligomers., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study explores the use of an engineered char produced from the pyrolysis of anaerobically digested fiber (ADF) to adsorb phosphate from aqueous solutions. Two series of engineered chars were produced. The first series was a CO 2 activated (CA) char produced via slow pyrolysis between 350 and 750 °C. The second series was a nitrogen doped (ND) char activated in the presence of ammonia at comparable temperatures. Proximate analysis, elemental composition, gas physisorption, Inductively coupled plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray powder diffraction (XRD) techniques were used to characterize properties of resulting products. The surface area of the carbon product increased after nitrogen doping through ammonization (166.6-463.1 m 2 /g) compared to CO 2 activated chars (156.5-413.1 m 2 /g). Phosphate adsorption isotherms for both CO 2 activated and nitrogen doped chars can be described by the Langmuir- Freundlich and Redlich Peterson adsorption models. Nitrogen doped carbon phosphate sorption capacity in aqueous solutions was twice compared to CO 2 activated carbons. As carbonization/activation temperature increased the sorption capacity increased from 3.4 to 33.3 mg g -1 for CA char and 6.3-63.1 mg g -1 for nitrogen doped char., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The ever-increasing consumption of material goods with economic growth is resulting in an increasing generation of municipal solid waste (MSW) and the rapid filling of landfills. Fractions of municipal solid waste containing wood-based products have the potential to be used for the development of value added products. In this paper we produced and characterized biochar and pyrolysis vapors from municipal solid waste (MSW) woody fractions to demonstrate their suitability towards soil amendments. Carbonization work focused on compost overs, molded wood pallets, treated wood, sawmill cut ends, wood derived fuels, furniture, painted wood, plywood, oriented strand board and particle boards from Washington State recycling facilities. The goal of this research is to use these biochars as soil amendments; however, there are concerns with both the potential presence of condensed organic pollutants and trace metals. The presence of trace metals and polycyclic aromatic hydrocarbons (PAH) in all the biochars produced were examined. GC-MS analyses of liquid extracts did not reveal the presence of soluble PAH compounds. High concentrations of mercury (Hg) and arsenic (As) were found in the biochar made from painted wood and treated wood, respectively. Among the methods tested for the removal of trace metals, acid washing was found to be the most effective. The volatiles released from the analyzed MSW fractions were also analyzed in Py-GC-MS studies. Among these volatile compounds, many contained Cl, N, or S, which could be potential sources of pollution if the pyrolysis vapors are combusted., (Published by Elsevier Ltd.)

The alcohol-to-jet (ATJ) process is a method for the conversion of alcohols to an alternative jet fuel blendstock based on catalytic steps historically utilized by the petroleum refining and petrochemical industry. This pathway provides a means for producing a sustainable alternative jet fuel (SAJF) from a wide variety of resources and offers a near-term opportunity for alcohol producers to enter the SAJF market and for the aviation sector to meet growing SAJF demand. Herein, the technical background is reviewed and selected variations of ATJ processes evaluated. Simulation and modeling were employed to assess some ATJ conversion schemes, with a particular focus on comparisons between the use of an ethanol or isobutanol intermediate. Although the utilization of isobutanol offers a 34 % lower conversion cost for the catalytic upgrading process, the cost of alcohol production is estimated to contribute more than 80 % of the total cost at the refinery. The cost of feedstock and alcohol production has a dominant effect on the overall process economics., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Anaerobically digested fibrous solid (AD fiber) is an abundant material that offers potential to produce value-added products such as biochar. The objective of this paper is to better understand how thermochemical processing conditions affect the capacity of biochars derived from AD fiber to adsorb H 2 S from biogas. AD fiber was pyrolyzed in an electric tube reactor at temperatures up to 600 °C and 60 min. The chars were employed for H 2 S scrubbing tests from a synthetic biogas. Results showed that the chars' capacity for H 2 S removal is comparable to that of activated carbon. An additional step consisting of impregnation of the chars with Na 2 CO 3 resulted in an improved capacity for H 2 S removal. To study the effect of ash, the AD fiber was also subjected to an alternative thermal treatment, hot water extraction (HWE), at 200 °C for 60 min. The resulting HWE material showed no removal of H 2 S from biogas, indicating that the ash and the environment employed for the thermal treatment of AD fiber play an important role in the char's performance for H 2 S removal. Results also suggest that a portion of the S in the charcoal after the H 2 S sorption process exists as free or adsorbed S (i.e., not chemically bonded to the charcoal)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The aim of this work was to improve sugarcane bagasse thermochemical conversion to pyrolytic sugars production, particularly to levoglucosan. The experiments were carried out evaluating the effect of acid washing with HNO 3 (0.1wt.%) followed by H 2 SO 4 addition (0.1, 0.2 and 0.3wt.%) at pyrolysis temperatures of 350, 400, 450, 500, 550 and 600°C was studied by Py-GC/MS. The experimental results showed that HNO 3 washing, followed by H 2 SO 4 concentration of 0.2wt.% at 350°C resulted in an increase in levoglucosan yield between 5 and 7 times the yield obtained when the raw bagasse was processed. Thus, these results are very attractive to improve pyrolytic sugars production in sugarcane bagasse by previously acid treatment to pyrolysis technology., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Oleaginous strains of Rhodococcus including R. jostii RHA1 have attracted considerable attention due to their ability to accumulate triacylglycerols (TAGs), robust growth properties and genetic tractability. In this study, a novel metabolic pathway was introduced into R. jostii by heterogenous expression of the well-characterized gene, lgk encoding levoglucosan kinase from Lipomyces starkeyi YZ-215. This enables the recombinant R. jostii RHA1 to produce TAGs from the anhydrous sugar, levoglucosan, which can be generated efficiently as the major molecule from the pyrolysis of cellulose. The recombinant R. jostii RHA1 could grow on levoglucosan as the sole carbon source, and the consumption rate of levoglucosan was determined. Furthermore, expression of one more copy of lgk increased the enzymatic activity of LGK in the recombinant. However, the growth performance of the recombinant bearing two copies of lgk on levoglucosan was not improved. Although expression of lgk in the recombinants was not repressed by the glucose present in the media, glucose in the sugar mixture still affected consumption of levoglucosan. Under nitrogen limiting conditions, lipid produced from levoglucosan by the recombinant bearing lgk was up to 43.54 % of the cell dry weight, which was comparable to the content of lipid accumulated from glucose. This work demonstrated the technical feasibility of producing lipid from levoglucosan, an anhydrosugar derived from the pyrolysis of lignocellulosic materials, by the genetically modified rhodococci strains.

Wheat straw is a potential feedstock in biorefinery for sugar production. However, the cellulose, which is the major source of sugar, is protected by lignin. Ozonolysis deconstructs the lignin and makes cellulose accessible to enzymatic digestion. In this study, the change in lignin concentration with different ozonolysis times (0, 1, 2, 3, 5, 7, 10, 15, 20, 30, 60min) was fit to two different kinetic models: one using the model developed by Garcia-Cubero et al. (2012) and another including an outer mass transfer barrier or "cuticle" region where ozone mass transport is reduced in proportion to the mass of unreacted insoluble lignin in the cuticle. The kinetic parameters of two mathematical models for predicting the soluble and insoluble lignin at different pretreatment time were determined. The results showed that parameters derived from the cuticle-based model provided a better fit to experimental results compared to a model without a cuticle layer., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Compost is used in bioretention systems to improve soil quality, water infiltration, and retention of contaminants. However, compost contains dissolved organic matter, nitrate, and phosphorus, all of which can leach out and potentially contaminate ground and surface waters. To reduce the leaching of nutrients and dissolved organic matter from compost, biochar may be mixed into the bioretention systems. Our objective was to test whether biochar and co-composted biochar mixed into mature compost can reduce the leaching of organic carbon, nitrogen, and phosphorus. There was no significant difference between the effects of biochar and co-composted biochar amendments on nutrient leaching. Further, biochar amendments did not significantly reduce the leaching of dissolved organic carbon, nitrate, and phosphorus as compared to the compost only treatment. The compost-sand mix was the most effective in reducing nitrate and phosphorus leaching among the media., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Pyrolysis is a thermochemical process to convert ligno-cellulosic materials into bio-char and pyrolysis oil. This oil can be further upgraded or refined for electricity, transportation fuels and chemicals production. At the time of writing, several demonstration factories are considered worldwide aiming at maturing the technology. Research is focusing on understanding the underlying processes at all relevant scales, ranging from the chemistry of cell wall deconstruction to optimization of pyrolysis factories, in order to produce better quality oils for targeted uses. Among the several bio-oil applications that are currently investigated the production and fermentation of pyrolytic sugars explores the promising interface between thermochemistry and biotechnology., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

In this work we report on the preparation, characterization, and properties of a thermally treated lignin-derived, phenolic-rich fraction (PRF) of wood pyrolysis bio-oil obtained by ethyl acetate extraction. The PRF was characterized for viscoelastic and rheological behavior using dynamic mechanical analysis (DMA) and cone and plate rheology. A unique thermoplastic behavior was evidenced. Heat-treated PRFs acquire high modulus but show low temperatures of thermal flow which can be systematically manipulated through the thermal pretreatment. Loss of volatiles, changes in molecular weight, and glass transition temperature (Tg) were investigated using thermogravimetric analysis (TGA), mass spectrometry (MS), and differential scanning calorimetry (DSC), respectively. Underlying mechanisms for the thermal and rheological behavior are discussed with regard to interactions between pyrolytic lignin nanoparticles present in the system and the role of volatile materials on determining the properties of the material resembling in several aspects to colloidal suspension systems. Low thermal flow temperatures and reversible thermal effects can be attributed to association of pyrolytic lignin particles due to intermolecular interactions that are easily ruptured at higher temperatures. The thermoplastic behavior of PRF and its low Tg is of particular interest, as it gives opportunities for application of this fraction in several melt processing and adhesive technologies.

This paper reports the production of lipids from non-hydrolyzed levoglucosan (LG) by oleaginous yeasts Rhodosporidium toruloides and Rhodotorula glutinis. Enzyme activity tests of LG kinases from both yeasts indicated that the phosphorylation pathway of LG to glucose-6-phosphate existed. The highest enzyme activity obtained for R. glutinis was 0.22 U/mg of protein. The highest cell mass and lipid production by R. glutinis were 6.8 and 2.7 g/L, respectively from pure LG, and 3.3 and 0.78 g/L from a pyrolytic LG aqueous phase detoxified by ethyl acetate extraction, rotary evaporation and activated carbon. This corresponded to a lipid yield of 13.5 wt.% for pure LG and only 3.9 wt.% for LG in pyrolysis oil., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The presence of very reactive C1-C4 molecules adversely affects the quality bio-oils produced from the pyrolysis of lignocellulosic materials. In this paper a scheme to produce lipids with Cryptococcus curvatus from the carboxylic acids in the pyrolytic aqueous phase collected in fractional condensers is proposed. The capacities of three oleaginous yeasts C. curvatus, Rhodotorula glutinis, Lipomyces starkeyi to ferment acetate, formate, hydroxylacat-aldehyde, phenol and acetol were investigated. While acetate could be a good carbon source for lipid production, formate provides additional energy and contributes to yeast growth and lipid production as auxiliary energy resource. Acetol could slightly support yeast growth, but it inhibits lipid accumulation. Hydroxyacetaldehyde and phenols showed high yeast growth and lipid accumulation inhibition. A pyrolytic aqueous phase with 20 g/L acetate was fermented with C. curvatus, after neutralization and detoxification to produce 6.9 g/L dry biomass and 2.2 g/L lipid., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

This paper describes a new scheme to convert anhydrosugars found in pyrolysis oils into ethanol and lipids. Pyrolytic sugars were separated from phenols by solvent extraction and were hydrolyzed into glucose using sulfuric acid as a catalyst. Toxicological studies showed that phenols and acids were the main species inhibiting growth of the yeast Saccharomyces cerevisiae. The sulfuric acids, and carboxylic acids from the bio-oils, were neutralized with Ba(OH)(2). The phase rich in sugar was further detoxified with activated carbon. The resulting aqueous phase rich in glucose was fermented with three different yeasts: S. cerevisiae to produce ethanol, and Cryptococcus curvatus and Rhodotorula glutinis to produce lipids. Yields as high as 0.473 g ethanol/g glucose and 0.167 g lipids/g sugar (0.266 g ethanol equivalent/g sugar), were obtained. These results confirm that pyrolytic sugar fermentation to produce ethanol is more efficient than for lipid production., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

This paper describes the use of Differential Scanning Calorimetry (DSC) to evaluate the impact of varying mix ratios of bio-oil (pyrolysis oil) and bio-diesel on the oxidation stability and on some cold flow properties of resulting blends. The bio-oils employed were produced from the semi-continuous Auger pyrolysis of pine pellets and the batch pyrolysis of pine chips. The bio-diesel studied was obtained from poultry fat. The conditions used to prepare the bio-oil/bio-diesel blends as well as some of the fuel properties of these blends are reported. The experimental results suggest that the addition of bio-oil improves the oxidation stability of the resulting blends and modifies the crystallization behavior of unsaturated compounds. Upon the addition of bio-oil an increase in the oxidation onset temperature, as determined by DSC, was observed. The increase in bio-diesel oxidation stability is likely to be due to the presence of hindered phenols abundant in bio-oils. A relatively small reduction in DSC characteristic temperatures which are associated with cold flow properties was also observed but can likely be explained by a dilution effect., ((c) 2010 Elsevier Ltd. All rights reserved.)