Advanced process integration for supercritical production of biodiesel: Residual waste heat recovery via organic Rankine cycle (ORC).

Biodiesel production using supercritical methanolysis has received immense interest over the last few years. It has the ability to convert high acid value feedstock into biodiesel using a single-pot reaction. However, the energy intensive process is the main disadvantage of supercritical biodiesel process. Herein, a conceptual design for the integration of supercritical biodiesel process with organic Rankine cycle (ORC) is presented to recover residual hot streams and to generate electric power. This article provides energy and techno-economic comparative study for three developed scenarios as follows: original process with no energy integration (Scenario 1), energy integrated process (Scenario 2) and advanced energy integrated process with ORC (Scenario 3). The developed integrated biodiesel process with ORC resulted in electric power generation that has not only satisfied the process electric requirement but also provided excess power of 257 kW for 8,000 tonnes/annum biodiesel plant. The techno-economic comparative analysis resulted in favouring the third scenario with 36% increase in the process profitability than the second scenario. Sensitivity analysis has shown that biodiesel price variation has significant effect on the process profitability. In summary, integrating supercritical biodiesel production process with ORC appears to be a promising approach for enhancing the process techno-economic profitability and viability.

Furan-based acetylating agent for the chemical modification of proteins.

We have synthesized a furan-based acetylating agent, 2,5-bisacetoxymethylfuran (BAMF) from carbohydrate derived 5-hydroxymethylfurfural (HMF) and studied its acetylation activity with amines and cytochrome c. The results show that BAMF can modify proteins in biological conditions without affecting their structure and function. The modification of cytochrome c with BAMF occurred through the reduction of heme center, but there was no change in the coordination property of iron and the tertiary structure of cytochrome c. Further analysis using MALDI-TOF-MS spectrometer suggests that BAMF selectively targeted lysine amino acid of cytochrome c under our experimental conditions. Kinetics study revealed that the modification of cytochrome c with BAMF took place at faster rates than aspirin.

Application of Raman spectroscopy in forensic investigation of questioned documents involving stamp inks.

Stamp pad inks from different manufacturers across India have been analyzed to investigate the feasibility of Raman scattering as a tool for forensic analysis of questioned documents involving stamp inks. Nine different stamping inks were analyzed by both Raman spectroscopic and HPTLC methods. The results demonstrate the effectiveness of these methods in classifying the investigated stamping inks based on their spectral pattern and HPTLC chromatogram. Raman scattering tool was able to determine the sequence of heterogeneous intersection strokes involving a blue stamp pad ink and other writing instruments, such as ballpoint pen ink (red and black), pencil and laser printer toner. However, this method was unable to resolve the exact sequencing for the intersection strokes involving investigated stamp ink and blue ballpoint ink or gel pen ink (all colors).

Chemical Recycling Processes of Waste Polyethylene Terephthalate Using Solid Catalysts.

Polyethylene terephthalate (PET) is a non-degradable single-use plastic and a major component of plastic waste in landfills. Chemical recycling is one of the most widely adopted methods to transform post-consumer PET into PET's building block chemicals. Non-catalytic depolymerization of PET is very slow and requires high temperatures and/or pressures. Recent advancements in the field of material science and catalysis have delivered several innovative strategies to promote PET depolymerization under mild reaction conditions. Particularly, heterogeneous catalysts assisted depolymerization of post-consumer PET to monomers and other value-added chemicals is the most industrially compatible method. This review includes current progresses on the heterogeneously catalyzed chemical recycling of PET. It describes four key pathways for PET depolymerization including, glycolysis, pyrolysis, alcoholysis, and reductive depolymerization. The catalyst function, active sites and structure-activity correlations are briefly outlined in each section. An outlook for future development is also presented.

Branched Bio-Lubricant Base Oil Production through Aldol Condensation.

Currently, lubricant base oils are derived from petroleum, a nonrenewable feedstock that contributes to greenhouse gas emissions. Bioderived, renewable lubricant base oils can mitigate environmental challenges and offer superior cold flow properties by incorporating branches to the base oil's hydrocarbon backbone with an appropriate synthetic strategy. A strategy was developed to synthesize branched alkanes for lubricant base oil in two steps from 12-tricosanone, obtained from bioderived fatty acids, and furfural, obtained from lignocellulosic biomass. The reaction pathway involves carbon-carbon coupling through aldol condensation followed by hydrodeoxygenation (HDO). Various solvents (non-polar, aprotic and polar, protic) and reaction conditions were screened to achieve a maximum yield of 94.3 % of aldol condensation products, containing the majority of a C33 furan (79.5 %) followed by a C28 furan (14.8 %). Subsequent HDO of aldol condensation products over an Ir-ReOx /SiO2 catalyst produced lubricant-ranged branched alkanes (C28 and C33 ) with 61.4 % yield and small fractions (<11 %) of alkanes with carbon numbers between C15 and C10 . The viscous properties of the produced bio-lubricant base oil were comparable to commercial petroleum-derived Group III and Group IV base oils. This approach serves as a potential stepping-stone to replace petroleumderived base oils and, in turn, reduce greenhouse gas emissions associated with current lubricant production.

Branched Bio-Lubricant Base Oil Production through Aldol Condensation.

Invited for this month's cover is the group of Dionisios G. Vlachos at the Catalysis Center for Energy Innovation, University of Delaware. The cover design shows the application of renewable feedstocks to make a lubricant base oil that can be used in a racecar. The Full Paper itself is available at 10.1002/cssc.201901838.

Renewable lubricants with tailored molecular architecture.

We present a strategy to synthesize three types of renewable lubricant base oils with up to 90% yield using 2-alkylfurans, derived from nonfood biomass, and aldehydes, produced from natural oils or biomass through three chemistries: hydroxyalkylation/alkylation (HAA), HAA followed by hydrogenation, and HAA followed by hydrodeoxygenation. These molecules consist of (i) furan rings, (ii) saturated furan rings, and (iii) deoxygenated branched alkanes. The structures of these molecules can be tailored in terms of carbon number, branching length, distance between branches, and functional groups. The site-specific, energy-efficient C-C coupling chemistry in oxygenated biomass compounds, unmatched in current refineries, provides tailored structure and tunable properties. Molecular simulation demonstrates the ability to predict properties in agreement with experiments, proving the potential for molecular design.

Use of Rhizopus oligosporus produced from food processing wastewater as a biosorbent for Cu(II) ions removal from the aqueous solutions.

Dried biomass of Rhizopus oligosporus produced from food processing wastewater was used as an adsorbent for copper ions in water. The adsorption process was carried out in a batch process and the effects of contact time (1-48 h), initial pH (2.0-6.0), initial metal ion concentration (20-100 mg L(-1)) and temperature (20-38 degrees C) on the adsorption were investigated. Experimental results showed that the maximum adsorption capacity was achieved at pH 5.0 and adsorbed Cu(II) ion concentration was increased with increasing initial metal concentration and contact time. The isothermal data could be described well by the Langmuir equations and monolayer capacity had a mean value of 79.37 mg g(-1). A pseudo-second order reaction model provided the best description of the data with a correlation coefficient 0.99 for different initial metal concentrations. Thermodynamic parameters indicated that biosorption of Cu(II) on R. oligosporus dried biomass was exothermic and spontaneous. To observe the copper pellets on the biosorbent surface after biosorption SEM was used and copper was characterized by EDX. The results of FTIR analyses indicated that amide I and hydroxyl groups of adsorbent played important role in binding Cu(II).

Aerobic Oxidation of Xylose to Xylaric Acid in Water over Pt Catalysts.

Energy-efficient catalytic conversion of biomass intermediates to functional chemicals can make bio-products viable. Herein, we report an efficient and low temperature aerobic oxidation of xylose to xylaric acid, a promising bio-based chemical for the production of glutaric acid, over commercial catalysts in water. Among several heterogeneous catalysts investigated, Pt/C exhibits the best activity. Systematic variation of reaction parameters in the pH range of 2.5 to 10 suggests that the reaction is fast at higher temperatures but high C-C scission of intermediate C5 -oxidized products to low carbon carboxylic acids undermines xylaric acid selectivity. The C-C cleavage is also high in basic solution. The oxidation at neutral pH and 60 °C achieves the highest xylaric acid yield (64 %). O2 pressure and Pt amount have significant influence on the reactivity. Decarboxylation of short chain carboxylic acids results in formation of CO2 , causing some carbon loss; however, such decarboxylation is slow in the presence of xylose. The catalyst retained comparable activity, in terms of product selectivity, after five cycles with no sign of Pt leaching.

Catalytic Hydrotreatment of Humins to Bio-Oil in Methanol over Supported Metal Catalysts.

Valorization of humins, the polymeric byproducts formed during the acid-catalyzed production of HMF (5-hydroxymethylfurfural) or furfural, is necessary to improve process economics and make biorefineries viable. We report the one-step catalytic hydrotreatment of humins in methanol to humin oil containing fully or partially deoxygenated compounds. First, we compare four commercial noble-metal catalysts (Ru/C, Rh/C, Pt/C, and Pd/C). Aromatic hydrocarbons, phenols, and esters are the main products detected by GC. Rh/C achieves the best GC-detectable oil yield and 75 % humins conversion in 3 h at 400 °C, 30 bar H2 , and a catalyst-to-humins mass ratio of 1:10. High H2 pressures and intermediate temperatures, reaction times, and catalyst loadings enhance GC-detectable oil yields. In contrast, high temperatures and long reaction times enhance gasification. Aromatics and phenols are found at high temperatures and long reaction times, whereas esters are the major species at short reaction times and high catalyst loading. 13 C-isotopic labeling studies confirm, for the first time, that methanol participates in the alkylation and esterification reactions to form aromatic, phenolic and ester products. The reactivity in isopropanol is also discussed.

Selective Hydrodeoxygenation of Vegetable Oils and Waste Cooking Oils to Green Diesel Using a Silica-Supported Ir-ReOx Bimetallic Catalyst.

High yields of diesel-range alkanes are prepared by hydrodeoxygenation of vegetable oils and waste cooking oils over ReOx -modified Ir/SiO2 catalysts under mild reaction conditions. The catalyst containing a Re/Ir molar ratio of 3 exhibits the best performance, achieving 79-85 wt % yield of diesel-range alkanes at 453 K and 2 MPa H2 . The yield is nearly quantitative for the theoretical possible long-chain alkanes on the basis of weight of the converted oils. The catalyst retains comparable activity upon regeneration through calcination. Control experiments using probe molecules as model substrates suggest that C=C bonds of unsaturated triglycerides and free fatty acids are first hydrogenated to their corresponding saturated intermediates, which are then converted to aldehyde intermediates through hydrogenolysis of acyl C-O bonds and subsequently hydrogenated to fatty alcohols. Finally, long-chain alkanes without any carbon loss are formed by direct hydrogenolysis of the fatty alcohols. Small amounts of alkanes with one carbon fewer are also formed by decarbonylation of the aldehyde intermediates. A synergy between Ir and partially reduced ReOx sites is discussed to elucidate the high activity of Ir-ReOx /SiO2.

From Tree to Tape: Direct Synthesis of Pressure Sensitive Adhesives from Depolymerized Raw Lignocellulosic Biomass.

We report a new and robust strategy toward the development of high-performance pressure sensitive adhesives (PSAs) from chemicals directly obtained from raw biomass deconstruction. A particularly unique and translatable aspect of this work was the use of a monomer obtained from real biomass, as opposed to a model compound or lignin-mimic, to generate well-defined and nanostructure-forming polymers. Herein, poplar wood depolymerization followed by minimal purification steps (filtration and extraction) produced two aromatic compounds, 4-propylsyringol and 4-propylguaiacol, with high purity and yield. Efficient functionalization of those aromatic compounds with either acrylate or methacrylate groups generated monomers that could be easily polymerized by a scalable reversible addition-fragmentation chain-transfer (RAFT) process to yield polymeric materials with high glass transition temperatures and robust thermal stabilities, especially relative to other potentially biobased alternatives. These lignin-derived compounds were used as a major component in low-dispersity triblock polymers composed of 4-propylsyringyl acrylate and n-butyl acrylate (also can be biobased). The resulting PSAs exhibited excellent adhesion to stainless steel without the addition of any tackifier or plasticizer. The 180° peel forces were up to 4 N cm-1, and tack forces were up to 2.5 N cm-1, competitive with commercial Fisherbrand labeling tape and Scotch Magic tape, demonstrating the practical significance of our biomass-derived materials.

Oxidation of As(III) by potassium permanganate.

The oxidation of As(III) with potassium permanganate was studied under conditions including pH, initial As(III) concentration and dosage of Mn(VII). The results have shown that potassium permanganate was an effective agent for oxidation of As(III) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(III) by Mn(VII). Although theoretical redox analyses suggest that Mn(VII) should have better performance in oxidization of As(III) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(III) under basic and acidic conditions were similar, which may be due to the adsorption of As(III) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(III).

Process Intensification for Cellulosic Biorefineries.

Utilization of renewable carbon source, especially non-food biomass is critical to address the climate change and future energy challenge. Current chemical and enzymatic processes for producing cellulosic sugars are multistep, and energy- and water-intensive. Techno-economic analysis (TEA) suggests that upstream lignocellulose processing is a major hurdle to the economic viability of the cellulosic biorefineries. Process intensification, which integrates processes and uses less water and energy, has the potential to overcome the aforementioned challenges. Here, we demonstrate a one-pot depolymerization and saccharification process of woody biomass, energy crops, and agricultural residues to produce soluble sugars with high yields. Lignin is separated as a solid for selective upgrading. Further integration of our upstream process with a reactive extraction step makes energy-efficient separation of sugars in the form of furans. TEA reveals that the process efficiency and integration enable, for the first time, economic production of feed streams that could profoundly improve process economics for downstream cellulosic bioproducts.

Catalytic Hydrodeoxygenation of High Carbon Furylmethanes to Renewable Jet-fuel Ranged Alkanes over a Rhenium-Modified Iridium Catalyst.

Renewable jet-fuel-range alkanes are synthesized by hydrodeoxygenation of lignocellulose-derived high-carbon furylmethanes over ReOx -modified Ir/SiO2 catalysts under mild reaction conditions. Ir-ReOx /SiO2 with a Re/Ir molar ratio of 2:1 exhibits the best performance, achieving a combined alkanes yield of 82-99 % from C12 -C15 furylmethanes. The catalyst can be regenerated in three consecutive cycles with only about 12 % loss in the combined alkanes yield. Mechanistically, the furan moieties of furylmethanes undergo simultaneous ring saturation and ring opening to form a mixture of complex oxygenates consisting of saturated furan rings, mono-keto groups, and mono-hydroxy groups. Then, these oxygenates undergo a cascade of hydrogenolysis reactions to alkanes. The high activity of Ir-ReOx /SiO2 arises from a synergy between Ir and ReOx , whereby the acidic sites of partially reduced ReOx activate the C-O bonds of the saturated furans and alcoholic groups while the Ir sites are responsible for hydrogenation with H2 .

A Review of Biorefinery Separations for Bioproduct Production via Thermocatalytic Processing.

With technological advancement of thermocatalytic processes for valorizing renewable biomass carbon, development of effective separation technologies for selective recovery of bioproducts from complex reaction media and their purification becomes essential. The high thermal sensitivity of biomass intermediates and their low volatility and high reactivity, along with the use of dilute solutions, make the bioproducts separations energy intensive and expensive. Novel separation techniques, including solvent extraction in biphasic systems and reactive adsorption using zeolite and carbon sorbents, membranes, and chromatography, have been developed. In parallel with experimental efforts, multiscale simulations have been reported for predicting solvent selection and adsorption separation. We discuss various separations that are potentially valuable to future biorefineries and the factors controlling separation performance. Particular emphasis is given to current gaps and opportunities for future development.

Current technologies, economics, and perspectives for 2,5-dimethylfuran production from biomass-derived intermediates.

Since the U.S. Department of Energy (DOE) published a perspective article that described the potential of the top ten biomass-derived platform chemicals as petroleum replacements for high-value commodity and specialty chemicals, researchers around the world have been motivated to develop technologies for the conversion of biomass and biomass-derived intermediates into chemicals and fuels. Among several biorefinery processes, the conversion of biomass carbohydrates into 2,5-dimethylfuran (DMF) has received significant attention because of its low oxygen content, high energy content, and high octane value. DMF can further serve as a petroleum-replacement, biorenewable feedstock for the production of p-xylene (pX). In this review, we aim specifically to present a concise and up-to-date analysis of DMF production technologies with a critical discussion on catalytic systems, mechanistic insight, and process economics, which includes sensitivity analysis, so that more effective catalysts can be designed. Special emphasis has been given to bifunctional catalysts that improve DMF yields and selectivity and the synergistic effect of the bifunctional sites. Process economics for the current processes and the scope for further improvement are discussed. It is anticipated that the chemistry detailed in this review will guide researchers to develop more practical catalytic processes to enable the economic production of bio-based DMF. Processes for the upgrade of DMF to pX are also described.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed.

Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92 % C9 -aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-ß catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate.

In situ silver nanoparticles synthesis in agarose film supported on filter paper and its application as highly efficient SERS test stripes.

Highly efficient multifunctional agarose SERS test stripes has been fabricated by a convenient facile approach. SERS stripes were found to be highly sensitive, robust, and capable to alleviate the two major drawbacks of filter paper based SERS substrate i.e. the weak adhesion of plasmonic nanoparticles and the diffusion of analyte into the paper surface. The fabricated stripes have been used successfully for the ultra-trace detection of analytes of forensic interest including a dye, pesticide and explosive.