Brajendra K. Sharma

• University of Illinois Urbana-Champaign

Researchers around the world are focusing on the development of biobased lubricating oils due to the depletion of mineral oil and environmental pollution. Soybean, which is one of the most produced crops globally, has been identified as a potential source for such oil. However, soybean oil has poor thermal and oxidative stability, which needs to be...

Hydrothermal processes, as well as hydrothermal carbonization (HTC), have emerged as a promising technology for the conversion of high-moisture feedstocks. A total of six hydrochars were generated from dairy manure via H3PO4-catalyzed HTC at varying reaction temperatures and residence times. The heating value of hydrochars produced using HTC (25.64...

This study aims to develop biobased composite films using hemicellulose (HB), methylcellulose (MC), and carboxymethyl cellulose (CMC) combined with natural additives, including high methoxy pectin (HMP), selected proteins (whey, casein, soy, and pea), and glycerol. Results showed that integrating these components significantly improved the physical...

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soy...

Large quantities of brewer’s spent grains are not fully utilized even as cattle feed. These feedstocks can be used to produce highly functional biomaterials, carbonaceous materials, and additives. In this investigation, four major fractions were isolated and characterized: Hemicellulose A, Hemicellulose B, cellulosic-rich fraction (CRF), and oligos...

Land application of dairy manure is the most common practice for disposal of this waste. Agricultural fields surrounding concentrated animal feeding operations (CAFOs) often have high levels of N and P because of manure over-application. However, its low bulk density limits the amount of manure that can be profitably transported for use as fuel or...

As the demand for biobased lubricating oils continues to rise, there is a growing focus on exploring diverse oil types. Particularly noteworthy is the surge in demand for high oleic oils, which offer enhanced stability, and a richer oleic acid content compared to their regular oil counterparts. However, the performance of high oleic soybean oil (HO...

Greigite (Fe3S4) and millerite (NiS) are important transition metal sulfides that exhibit light‐driven Fenton catalytic activity. In absence of light, they show limited activity. To utilize these properties without relying on light, we synergized these sulfides to prepare a composite Fe3S4–NiS (FSNS). Under fixed reaction conditions, the composite...

CO 2 intensive carbon black (CB) as filler material in natural Hevea rubber-based composites needs to be partially replaced by suitable fillers. In this study, a novel surface modified filler (SuMo FA) was made by encapsulating fly ash (FA) with a polysulphide coating. This SuMo FA was hydrophobic, minimized leaching, and was morphologically ideal...

Low-density polyethylene (LDPE) and polystyrene (PS) were evaluated for incorporation as binder additives to enhance the potential performance of asphalt concrete (AC) mixtures, as well as addressing global rising concerns over nonrecyclable plastics accumulation. Incorporation of LDPE and PS in asphalt binder resulted in an increase in its complex...

Plastic and mixed plastic waste (PW) has received increased worldwide attention owing to its huge rate of production, high persistency in the environment, and unsustainable waste management practices. Therefore, sustainable PW management and upcycling approaches are imperative to achieve the objectives of the United Nations Sustainable Development...

There is an increasing awareness that materials and chemicals produced from fossil fuels are not sustainable, both in terms of the pollution caused by the extraction and production processes, and the fact that there is only a finite supply of these fossil fuels. Therefore, there is a strong incentive to find sources for chemicals and materials from...

Food waste-induced environmental damage has been a primary concern for environmentalists for decades. Several studies have proven that greenhouse gases emitted by food waste worldwide are causing more damage than coal power plants in some cases. Over the years, many solutions have been proposed, but the problem is yet to be resolved. This mini-revi...

It is discovered that noncharged surfactants lead to electric effects that interact with biomimetic membranes made of nitrocellulose filters, which are impregnated with fatty acid esters. At a surfactant concentration as low as 64 microM in one of the solutions, they lead to the transient formation of transmembrane electric potential. Maximum chang...

Fast pyrolysis of five post-consumer plastic waste materials was studied using pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) technique. Prescription medicine bottles, landfill liners, and one type of industrial plastic waste represented polyolefin-based polymers, whereas packaging material represented polystyrene, and other...

Raw lignocellulosic biocrude produced by hydrothermal liquefaction and its supercritical carbon dioxide extract (SE) were hydrotreated at 350–405 °C and for 2–6 h utilizing commercial CoMo and NiMo catalysts. The hydrotreatment reduced the oxygen content of the SE down to 1.6 wt %, while the minimum oxygen content of the hydrotreated biocrude (HBC)...

Fatty epoxides are produced from the corresponding alkenes by oxidation in the presence of peracids or other oxidants. The classic method is the Prilezhaev epoxidation in which peracids are generated by in situ oxidation of formic or acetic acids with hydrogen peroxide. Epoxidized vegetable oils and esters are used directly as biobased plasticizers...

This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed....

Hydrothermal liquefaction (HTL) is promising for the conversion of biowaste into biofuels, but the energy recovery from the HTL aqueous phase (HTL-AP) by anaerobic digestion is limited due to its degradability resistance. Adding biochar was reported to facilitate digestion, but its role has not been explicitly determined. Direct interspecies electr...

The study focusses on using virgin grades of low and linear low density polyethylene for pyrolysis route of fuel production, in order to mimic the most common municipal plastic waste components as a desirable feedstock with the future aim of integration plans to petroleum refining and petrochemical industries. The oil produced was assessed for basi...

Plastic production and use are currently widespread. However, plastic wastes are non-biodegradable and leave a high carbon footprint, posing challenges to ecosystems and the environment. Therefore, innovative recycling technologies should be geared towards waste-to-energy conversion solutions. Chemical recycling technologies that convert plastic wa...

The use of plastic materials is increasing worldwide because of their durability, cost-effectiveness, and light weight. This uncontrolled usage of plastic materials is creating severe disposal and environmental problems. This chapter includes recent and conventional practices for the recovery and recycling of plastic wastes. Brief classifications o...

When impregnated with esters of fatty acids, nitrocellulose filters can be used as a biomimetic membrane. They are easy to make, cheap, and may be used not only as an imitation of biological membranes but also as a sensor to characterize surfactant interactions with dirty fabric. These impregnated filters when fixed in a thermostatically controlled...

Plastic is referred to as a “material of every application”. From the packaging and automotive industries to the medical apparatus and computer electronics sectors, plastic materials are fulfilling demands efficiently. These plastics usually end up in landfills and incinerators, creating plastic waste pollution. According to the Environmental Prote...

With increasing environmental concerns and the depletion of petroleum resources, the development of lubricant additives from bioresources has attracted much attention recently. In this review, we reported a few polymers and polymer composites that are synthesized from vegetable oils (soybean oil, sunflower oil, rice bran oil, and castor oil) and us...

The overwhelming utilization of petroleum-based products and the scarcity of the raw materials in the coming future, along with their negative impacts on the environment, has compelled us to use materials from natural resources. The utilization of vegetable oils (VOs) or plant biomass as potential feedstock for numerous functional materials and the...

A significant fraction of the embedded energy, carbon, and nutrients in biomass is lost to the aqueous phase during the hydrothermal liquefaction of biomass to bio-oil. The feasibility of concentrating the aqueous phase to recover and recycle the organics back to the hydrothermal liquefaction reactor using nanofiltration was investigated. The disso...

The hydrothermal decomposition of cobalt hydroxide is of importance in understanding corrosion in nuclear reactors, in the industrial production of cobaltous oxide and potentially for thermal energy storage. The kinetics of decomposition in the presence of water vapor is poorly understood but nevertheless important in the above situations. The deco...

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The objective of the current study was to investigate environmentally sustainable and energy efficient processes to recover value added material and energy from e-waste as a means to divert these non-degradable materials from landfills. We studied two different types of plastics (1) simple mixtures like polyamide/polycarbonate (PA/PC)) found in cel...

A process of much future-potential for upgrading of biofuels derived from hydrothermal liquefaction (HTL) is catalytic hydrotreatment. HTL bio-oil, manufactured from Chlorella microalgae in a reactor operating in continuous flow mode was processed via hydrotreatment using a bio-Pd/C catalyst. This catalyst comprises a bacterial biomass support deco...

The properties of alternative fuels must be evaluated to determine their suitability for use in existing engines, either as blends with conventional petroleum products or as stand-alone substitutes (drop-in replacements). Alternative fuels made from waste feedstocks are especially attractive since they serve the dual purposes of fuel production and...

Emissions and efficiency of three commercially available furnace types, a horizontal feed, underfeed, and dropdown feed, were characterized using switchgrass pellets and the results compared to wood pellets. The efficiency of the furnaces was determined using a mass balance method. The gaseous emissions including (CO, NOx, and SO2) measurements wer...

We demonstrate hydrothermal (300ºC, 10 MPa) catalytic conversion of real waste lipids (e.g., waste vegetable oil, sewer trap grease) to liquid hydrocarbon fuels without net need for external chemical inputs (e.g., H2 gas, methanol). A supported bimetallic catalyst (Pt-Re/C; 5 wt% of each metal) previously shown to catalyze both aqueous phase reform...

Two phosphate fertilizers, triple superphosphate (TSP) and bone meal (BM), were premixed with sawdust and switchgrass biomass for pyrolytic biochar formation. Carbon retention, P release kinetics, and capacity of biochar for stabilizing heavy metals in soil were evaluated. Results show that TSP and BM pretreatment increased carbon retention from 53...

The thermal and catalytic processes of converting waste plactics into fuels are promising techniques to eliminate the refuse which otherwise is harmful to the enivironment, and decrease the dependence on fossil fuels. Thermal degradation decomposes plastic into three fractions: gas, crude oil, and solid residue. Crude oil from non-catalytic pyrolys...

Birch wood was pyrolyzed to produce bio-oil and biochar. Pyrolysis conditions including reaction temperature, residence time and particle size of the feed were optimized to maximize bio-oil yield. Particle size had insignificant effect whereas yields of up to 56% were achieved using an optimized reaction temperature of 450oC and a residence time of...

Rubber modification of asphalt is one of the most common asphalt modifications used to improve asphalt rheological properties; in such applications, rubber is mainly introduced to the asphalt matrix as a solid particulate matter and referred to as crumb rubber (CR) via wet or dry processing. While the introduction of CR has been shown to improve as...

Thermogravimetric analysis (TGA) was used to investigate thermal and catalytic pyrolysis of waste plastics such as prescription bottles (polypropylene/PP), high density polyethylene, landfill liners (polyethylene/PE), packing materials (polystyrene/PS), and foams (polyurethane/PU) into crude plastic oils. In the first phase of this investigation, a...

This paper investigates physicochemical properties of four different types of bio-oil produced through hydrothermal liquefaction (HTL) and vacuum pyrolysis including wood pallet, corn stover, miscanthus and swine manure. It should be noted that the term bio-oil in this paper is used to refer to synthesized oil from post processing of biomass. Accor...

Hydrothermal liquefaction (HTL) has developed as one of the most promising technologies for biofuel production from wet biomass feedstocks in recent years. In the current study, a microalgae slurry was processed in a continuous flow hydrothermal processing unit capable of 2.5 l/h flow rates, temperatures of 350 °C and pressure of up to 206 bar. 40...

Electronic Supplementary Information for Prediction of Microalgae Hydrothermal Liquefaction Products (DOI: 10.1039/C5GC00574D)

Hydrothermal liquefaction (HTL) uses water under elevated temperatures and pressures (200-350°C, 5-20 MPa) to convert biomass into liquid “biocrude” oil. Despite extensive reports on factors influencing microalgae cell composition during cultivation and separate reports on HTL products linked to cell composition, the field still lacks a quantitativ...

Birchwood feedstock was used to make slow pyrolysis biochar that contained 89% carbon and <2% ash. This biochar was blended with carbon black (CB) as filler for styrene-butadiene rubber (SBR). Composites made from blended fillers of 25/75 biochar/CB were equivalent to or superior to their 100% CB analogs in terms of tensile strength and toughness a...

Finding alternatives to fossil feedstocks is increasing in importance with the challenges of global warming, increasing oil prices and depleting fossil fuel reserves that we currently face. Today, plant oils are important renewable raw materials for the chemical industry and are heavily used for surfactants, cosmetic products and lubricants. This b...

Heat-bodied oils were prepared by thermal treatment of soybean oil under inert atmosphere. Different viscosity grades of heat-bodied oils synthesized by varying the reaction time were investigated for various properties including viscosity, viscosity index, elastohydrodynamic film thickness, and pressureviscosity coefficient. Heat-bodied oils displ...

The current study investigated the effects of hydrothermal liquefaction (HTL) operated under a range of operating conditions on the fate of bioactive contaminants (BACs) often present in wastewater sources. HPLC analysis of BACs before and after HTL treatment showed essentially complete removal of BACs in presence of biomass feedstocks when HTL was...

Chemically-modified fatty acids are prepared by reacting epoxidized fatty acids, their esters or triglyceride oils with amines of cyclic or aromatic hydrocarbons. The fatty acid derivatives produced are of the formula: wherein R is an H, branched or straight chain alkyl or alkenyl group, aromatic-containing group, glycerol, or glyceride, R″ is a C...

Chemically-modified triglycerides are prepared by reacting epoxidized triglyceride oils with phosphorus-based acid hydroxide or esters. The phosphorus-containing triglyceride derivatives are of the formula: wherein R1″, R2″ and R3″ are independently selected from C3 to C29 aliphatic fatty acid residues, at least one of which comprising one or both...

Pyrolysis of HDPE waste grocery bags followed by distillation resulted in a liquid hydrocarbon mixture with average structure consisting of saturated aliphatic paraffinic hydrogens (96.8%), aliphatic olefinic hydrogens (2.6%) and aromatic hydrogens (0.6%) that corresponded to the boiling range of conventional petroleum diesel fuel (#1 diesel 190-29...

Lipids are a promising feedstock to produce renewable hydrocarbon fuels and H2via catalytic hydrothermal processing. Upon exposure to hydrothermal media (e.g., 300 °C, 8–11 MPa), lipids rapidly hydrolyze to produce saturated and unsaturated free fatty acids in varying ratios, depending on the feedstock, as well as glycerol. This report demonstrates...

This study investigated the effects of hydrothermal liquefaction (HTL) on the fate of bioactive compounds (BACs) often present with wet biosolids from wastewater, manure, or algae. Tracking radiolabeled (14)C for two BACs showed that 60-79% of the carbon was transferred to the HTL raw oil product, and most of the rest was found in the aqueous produ...

Oxidation of tertiary nitrogen compounds is an important synthetic transformation as the N-oxides find wider application as oxidants (1–7), offer functional group manipulation, structural modification possibilities (8–10), and can activate the nitrogen-containing ring towards both electrophilic and nucleophilic attack (11). A variety of oxidants—m-...

This study presents the complete utilization of spent coffee grounds to produce biodiesel, bio-oil, and biochar. Lipids extracted from spent grounds were converted to biodiesel. The neat biodiesel and blended (B5 and B20) fuel properties were evaluated against ASTM and EN standards. Although neat biodiesel displayed high viscosity, moisture, sulfur...

Turnip oil (TO; Raphanus sativus L.) produces seeds that contain around 26 wt% of inedible base stock that are suitable as a potential feedstock for biodiesel production. A turnip oil methyl ester (TME) was prepared from acid-catalyzed pretreated TO in an effort to evaluate important fuel properties of turnip oil-based biodiesel, such as kinematic...

A new additive was produced from a natural oil and boron. The synthesis involves the use of the epoxidized form of soybean oil which then undergoes a catalytic ring opening to produce the additive material. Due to their remaining triacylglycerol structure, the products are highly compatible with bio-based lubricants and due to their covalent boron...

A bio-based gear oil was developed from soybean oil (SBO). The SBO was first thermally polymerised and then mixed with additives and diluents. The effect of pour point depressants, co-base oils, antioxidants and anti-wear additives is reported. Lubricity, viscosity index and oxidation stability of the final formulation of the bio-based gear oil are...

The synthesis of lubricant additives based on boron and epoxidized soybean oil are presented. These additives are made from a simple patent pending method involving a ring-opening reaction of the epoxidized oil. A couple of these borates were tested in soybean oil, polyalpha olefin basestock, group III basestock, and hexadecane. An aromatic additiv...

Phosphorus-containing moieties can be added to the ninth and/or tenth positions of a fatty chain of a methyl ester utilising an epoxide route. In this route, methyl oleate is epoxidised, and then ring opened using dibutyl phosphate to yield – among others – a dioxaphospholane-containing derivative of methyl octadecanoate. Progress of the reaction w...

A fatty methyl ester product has been made using two routes. Soybean oil was thermally polymerized anaerobically without a catalyst at 330 °C and the material was then transesterified using base catalyst and methanol. Alternatively, a similar product can be obtained by heating methyl linoleate to the same temperature in a pressure reactor. The prod...

Thermochemical conversion is a promising route for recovering energy from algal biomass. Two thermochemical processes, hydrothermal liquefaction (HTL: 300 °C and 10-12 MPa) and slow pyrolysis (heated to 450 °C at a rate of 50 °C/min), were used to produce bio-oils from Scenedesmus (raw and defatted) and Spirulina biomass that were compared against...

Thermally polymerised soybean oil (SBO) is compared with several other vegetable oils, including ordinary SBO and high-oleic SBO (HO SBO). Acid values (AVs) and kinematic viscosities of the oils were measured over 28 days on oils stored at 85°C. As expected, the AVs and viscosities increased with time and the HO SBO demonstrated similar but smaller...

An isothermal thermogravimetric analysis (TGA) method was used to generate a model capable of predicting the results of the Thin Film Micro-Oxidation (TFMO) test in a soybean oil system. Utilizing a series of pseudorate constants and “activation energies”, weight loss data from the TGA method can predict oxidation, polymerization, evaporation, and...

Before the advent of the modern food industry, vegetable oils (triglycerides) from many sources had a long history of use as condiments in cooking, personal care, and other therapeutic applications. Industrial applications of vegetable oils outside of food usage, on the other hand, have been limited on account of the shorter shelf-life durability o...

Oil in water emulsions of several vegetable oils were studied in order to prepare a useful lubrication fluid. Several previously uncharacterized systems were studied in this paper, including those made from epoxidized vegetable oils. A series of different surfactants were studied in order to obtain emulsions suitable for lubrication applications. T...

This paper describes the preparation of a new type of branched vegetable oil and its methyl ester that involves the formation of acetonides. A facile and environmentally friendly synthesis has been found to produce acetonides that entails the use of ferric chloride as a catalyst and is conducted at room temperature. The products have been fully cha...

Four common beans (black, kidney, great northern, and pinto) were extracted with hexane and found to contain about 2% triacylglycerols. The fatty acids in these bean oils were mainly linolenic (41.7–46 wt%), linoleic (24.1–33.4 wt%), palmitic (10.7–12.7 wt%) and oleic (5.2–9.5 wt%). Because of the high levels of polyunsaturated fatty acids, the bea...

Saturated branched-chain fatty acids (sbc-FAs) are found as minor constituents in several natural fats and oils. Sbc-FAs are of interest since they have lower melting points than their linear counterparts and exhibit good oxidative stability; properties that make them ideally suited in a number of applications. We (and others) have previously synth...

Oxidation of tertiary nitrogen compounds is an important synthetic transformation as the N-oxides find wider application as oxidants (1–7), offer functional group manipulation, structural modification possibilities (8–10), and can activate the nitrogen-containing ring towards both electrophilic and nucleophilic attack (11). A variety of oxidants—m-...

Seed oils consist mainly of triglycerides, that is, they comprise a unit of glycerol backbone esterified with three acyl groups (usually but not limited to C16–C18) which may be saturated or unsaturated with one or more olefinic functionalities per acyl group. Very rarely do seed oils contain additional functional groups, such as hydroxyls as in ca...

The jojoba plant (Simmondsia chinensis L.) produces seeds that contain around 50 to 60wt.% of inedible long-chain wax esters that are suitable as a potential feedstock for biodiesel (BD) production. Jojoba oil methyl esters (JME) were prepared from acid-catalyzed pretreated jojoba oil in order to evaluate important fuel properties of jojoba-based B...

The majority of biodiesel fuels are produced from vegetable oils or animal fats by transesterification of oil with alcohol in the presence of a catalyst. In this study, a new class of biofuel is explored by acetylation of fatty alcohols from Jojoba oil. Jojobyl methyl acetate (JMA) was produced using direct acetylation of purified jojobyl alcohol o...

The large-scale production of biodiesel has led to a surplus of glycerol, so the new commercial uses of this co-product are being sought. Twenty-three vegetable oils were screened using glycerol tris(2-ethylhexanoate)+AFs-GTEH+AF0- as a diluent to improve the low temperature properties. Epoxidized soybean oil (ESBO) and palm oil (PO) have shown max...

Diesel-like fuels were synthesized by a pyrolysis method using soybean oil (pyrodiesel, PD) and soybean soapstock (SPD), respectively, as starting material. These pyrodiesel samples were compared with soy biodiesel (BD) samples. All these three biofuels (PD, SPD and BD) and their blends with high sulfur (HSD) and low sulfur (LSD) diesel fuels were...

A facile (and environmentally friendly) reaction between epoxidized methyl oleate and aniline to produce an oleate-aniline adduct, without the formation of fatty amide, was discovered. This reaction was carried out neat, with a catalytic amount of an ionic liquid. No solvent was used, no byproducts were produced, and the ionic liquid could be recov...

A diesel-like fuel, pyrodiesel (PD), was synthesized by a pyrolysis method using soybean oil as starting material. Some physical properties of the material were studied, both neat and in blends with high-sulfur (HSD) and low-sulfur (LSD) diesel fuels, and compared with blends of biodiesel (BD) in fossil fuels. It was observed using different method...

The increasing application of biobased lubricants could significantly reduce environmental pollution and contribute to the replacement of petroleum base oils. Vegetable oils are recognized as rapidly biodegradable and are thus promising candidates for use as base fluids in formulation of environment friendly lubricants. Although many vegetable oils...

In this work, we studied the catalytic activity of commercial alumina, and laboratory-synthesized alumina doped with Lewis acid metals, in the epoxidation of methyl oleate with aqueous hydrogen peroxide. It was observed that the reaction yields increased when the amount of catalyst, the quantity of hydrogen peroxide, the concentration of the hydrog...