Bio-additives for CI engines from one-pot alcoholysis reaction of lignocellulosic biomass: An experimental activity

In the recent years the progressive decrease in fossil petroleum resources and gradual deprivation of the environment have attracted increasing interest towards the use of biomass as renewable carbon source for the production of chemicals and transportation fuels. In particular, lignocellulosic biomass represents an abundant and inexpensive renewable resource with high carbon sequestration ability and non-polluting. In this paper, the valorisation of mixtures made of n-butanol (n-BuOH), butyl levulinate (BL) and dibutyl ether (DBE), in different percentages, as additive fuel for compression ignition (CI) internal combustion engine (ICE) was studied. These mixtures can be directly obtained from the catalytic alcoholysis reaction of the cellulosic fraction of raw and pre-treated lignocellulosic biomasses. Moreover, the possibility to recycle and reutilize the excess alcohol (n-Butanol), during the catalytic alcoholysis reaction, has been considered since it represents an opportunity to reduce the overall costs of the process. Therefore, a blend constituted only by BL and DBE has been also tested. The model mixtures were prepared by using commercial reactants, characterized by compositions analogous to those of the reaction mixtures. These model mixtures were tested as blend with Diesel fuel in a CI-ICE with the measurement of pollutant emission and performance. Results have been compared with those obtained fuelling the engine with a commercial Diesel fuel. As a whole, tests results have evidenced the potentiality of these novel blending mixtures to reduce the emissions of particulate without any significant increase in the other pollutants and negligible changes in engine power and efficiency

Integrated Cascade Process for the Catalytic Conversion of 5-Hydroxymethylfurfural to Furanic and TetrahydrofuranicDiethers as Potential Biofuels

The depletion of fossil resources is driving the research towards alternative renewable ones. Under this perspective, 5-hydroxymethylfurfural (HMF) represents a key molecule deriving from biomass characterized by remarkable potential as platform chemical. In this work, for the first time, the hydrogenation of HMF in ethanol was selectively addressed towards 2,5-bis(hydroxymethyl)furan (BHMF) or 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) by properly tuning the reaction conditions in the presence of the same commercial catalyst (Ru/C), reaching the highest yields of 80 and 93 mol%, respectively. These diols represent not only interesting monomers but strategic precursors for two scarcely investigated ethoxylated biofuels, 2,5-bis(ethoxymethyl)furan (BEMF) and 2,5-bis(ethoxymethyl)tetrahydrofuran (BEMTHF). Therefore, the etherification with ethanol of pure BHMF and BHMTHF and of crude BHMF, as obtained from hydrogenation step, substrates scarcely investigated in the literature, was performed with several commercial heterogeneous acid catalysts. Among them, the zeolite HZSM-5 (Si/Al=25) was the most promising system, achieving the highest BEMF yield of 74 mol%. In particular, for the first time, the synthesis of the fully hydrogenated diether BEMTHF was thoroughly studied, and a novel cascade process for the tailored conversion of HMF to the diethyl ethers BEMF and BEMTHF was proposed

Closing a biorefinery cycle of giant reed through the production of microporous and reusable activated carbon for CO2 adsorption

The complete valorisation of all biomass components represents a crucial strategy for developing new biorefinery schemes. This study completed a cascade biorefinery process for the exploitation of holocellulose and lignin fractions of the non-food biomass giant reed (Arundo donax L.). The residual lignin-rich solid fraction, obtained after the selective conversion of hemicellulose and cellulose fractions to valuable bioproducts, was characterised and activated by KOH treatment into microporous activated carbon (AC), to be proposed for CO2 adsorption. The production of AC was optimised by the Design of Experiments technique. Under the optimised process conditions (630 degrees C, KOH/lignin 3.0 wt/wt, 60 min) the AC yield was 34.4 wt% and the CO2 uptake reached 72.3 mg/g, confirming the promising application of this biomaterial. Moreover, the obtained AC showed similar CO2 uptake values over 10 cycles of adsorption/desorption tests, demonstrating its good recyclability, keeping its pristine CO2 uptake capacity

Integrated cascade biorefinery processes for the production of single cell oil by Lipomyces starkeyi from Arundo donax L. hydrolysates

Giant reed (Arundo donax L.) is a promising source of carbohydrates that can be converted into single cell oil (SCO) by oleaginous yeasts. Microbial conversion of both hemicellulose and cellulose fractions represents the key step for increasing the economic sustainability for SCO production. Lipomyces starkeyi DSM 70,296 was cultivated in two xylose-rich hydrolysates, obtained by the microwave-assisted hydrolysis of hemicellulose catalysed by FeCl3 or Amberlyst-70, and in two glucose-rich hydrolysates obtained by the enzymatic hydrolysis of cellulose. L. starkeyi grew on both undetoxified and partially-detoxified hydrolysates, achieving the lipid content of 30 wt% and yield values in the range 15–24 wt%. For both integrated cascade processes the final production of about 8 g SCO from 100 g biomass was achieved. SCO production through integrated hydrolysis cascade processes represents a promising solution for the effective exploitation of lignocellulosic feedstock from perennial grasses towards new generation biodiesel and other valuable bio-based products

Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

5-hydroxymethylfurfural (HMF), accessible from various feedstocks, represents an important renewable platform-chemical, precursor for valuable biofuels and bio-based chemicals. In this work, the continuous hydrogenation of an aqueous solution of HMF to give strategic monomers, 2,5-bis(hydroxymethyl)furan (BHMF) and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) was investigated in a continuous flow reactor adopting a commercial Ru/C (5 wt%) as catalyst. The influence of the main process variables on products yield and selectivity was studied and optimized. The highest BHMF and BHMTHF yields of 87.9 and 93.7 mol%, respectively, were achieved by tuning the catalyst contact time, keeping all other variables constant (temperature, pressure, hydrogen flow rate, initial HMF concentration). Intraparticle diffusion limitation for hydrogen and HMF was shown to occur at some of the tested conditions by performing the HMF hydrogenation with different catalyst particle sizes, confirmed by calculations. Constant catalyst activity was observed up to 6 h time-on-stream and then gradually reduced. Fresh and spent catalyst characterization showed no significant sintering and negligible leaching of ruthenium during time-on-stream. A decrease of the specific surface area was observed, mainly due to humin deposition which is likely the reason for catalyst deactivation. Catalyst performance could be restored to initial values by a thorough washing of the catalyst

Biomass-derived catalysts: synthesis and characterization of hydrochars and pyrochars

Lignocellulosic biomass is one of the more important renewable sources and it will play a strategic role in many future markets, taking into consideration that a renewable energy share of 32% is binding at the European level by 2030. Deconstruction of lignocellulosic biomass can be carried out via hydrothermal processes and, among them, hydrothermal carbonization (HTC) represents a versatile process, which promotes the progressively deoxygenation of the biomass, under relatively mild reaction conditions. The obtained solid-rich product, called hydrochar, can be used in a wide range of applications, such as adsorption, energy storage, CO2 sequestration, catalysis etc. In this last field, within the project PRIN 2020 LEVANTE “LEvulinic acid Valorization through Advanced Novel Technologies” (2020CZCJN7), different hydrochars have been synthesized starting from cellulose and the effects of the main reaction parameters have been investigated employing statistical modelling. Under the selected set of processing parameters, the yield of hydrochars was in the range 38-48 wt%, with a carbon content of 60-70 wt% and corresponding higher heating values amounting to 17-27 MJ/kg, confirming the successful conversion of cellulose into a carbonaceous material. Finally, on the basis of final applications, also pyrochars have been prepared starting from the optimal hydrochars, in order to increase the aromatization degree and the surface areas. All the synthesized hydrochars and pyrochars will be further functionalized and employed, as acid catalysts, for the valorization of levulinic acid, in particular for its conversion to diphenolic acid, in agreement with the objectives of the project LEVANTE

Valorization of a Levulinic Acid Platform through Electrospinning of Polyhydroxyalkanoate-Based Fibrous Membranes for in Vitro Modeling of Biological Barriers

In vitro models of biological barriers provide a reliable tool for investigating the physiopathological processes involved in the development of numerous diseases. Producing sustainable in vitro models obtained from solvents and biopolymers derived from industrial by-products add an important value to this underestimated source of valuable (bio)materials. This works aims at demonstrating the suitability of processing together solvents derived from levulinic acid (LA) (extracted from biomasses) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) (whose production is facilitated by LA) to produce electrospun membranes as proof-of-concept of a sustainable, engineered biological barrier fully derived from LA as the starting feedstock. The electrospinning process is initially optimized by identifying the most suitable conditions for obtaining self-supporting microporous membranes. In particular, LA-derived solvents (γ-valerolactone, 2-methyltetrahydrofuran, methyl ethyl ketone, and methyl and ethyl levulinate), PHBV concentration, and electrospinning process parameters were investigated. Self-standing and hydrophobic PHBV mats with a micropore size in the range of 1–7 μm and an average elastic modulus of 75 MPa are successfully obtained by using methyl ethyl ketone/formic acid as solvent. Preliminary cell experiments demonstrate that the developed fibrous PHBV mats promote the formation of a confluent monolayer of epithelial cells after 48 h and therefore they can potentially be used to mimic biological epithelial barriers

Conversion of the hydrochar recovered after levulinic acid production into activated carbon adsorbents

Levulinic acid production by acid-catalyzed hydrothermal conversion of (ligno)cellulosic biomass generates significant amounts of carbonaceous hydrochar, which is currently considered a final waste. In this work, the hydrochar recovered after the levulinic acid production, was subjected to cascade pyrolysis and chemical activation treatments (by H3PO4 or KOH), to synthesize activated carbons. The pyrolysis post-treatment was already effective in improving the surface properties of the raw hydrochar (Specific Surface Area: 388 m2/g, VP: 0.22 cm3/g, VMESO: 0.07 cm3/g, VMICRO: 0.14 cm3/g), by removing volatile compounds. KOH activation resulted as the most appropriate for further improving the surface properties of the pyrolyzed hydrochar, showing the best surface properties (Specific Surface Area: 1421 m2/g, VP: 0.63 cm3/g, VMESO: 0.10 cm3/g, VMICRO: 0.52 cm3/g), which synergistically makes it a promising system towards adsorption of CO2 (∼90 mg/g) and methylene blue (∼248 mg/g). In addition, promising surface properties can be achieved after direct chemical activation of the raw hazelnut shells, preferably by H3PO4 (Specific Surface Area: 1918 m2/g, VP: 1.34 cm3/g, VMESO: 0.82 cm3/g, VMICRO: 0.50 cm3/g), but this choice is not the smartest, as it does not allow the valorization of the cellulose fraction to levulinic acid. Our approach paves the way for possible uses of these hydrochars originating from the levulinic acid chain for new environmental applications, thus smartly closing the biorefinery loop of the hazelnut shells

Electro-oxidative depolymerisation of technical lignin in water using platinum, nickel oxide hydroxide and graphite electrodes

In order to improve the lignin exploitation to added-value bioproducts, a mild chemical conversion route based on electrochemistry was investigated. For the first time, soda lignin Protobind™ 1000 (technical lignin from the pulp & paper industry) was studied by cyclic voltammetry to preliminarily investigate the effect of the main reaction parameters, such as the type of electrode material (platinum, nickel oxide hydroxide, graphite), the pH (12, 13, 14), the scan rate (10, 50, 100, 250 mV s-1), the substrate concentration (2, 20 g L-1) and the oxidation/reduction potential (from -0.8 to +0.8 V). Under the optimal reaction conditions among those tested (NiOOH electrode, pH 14, lignin 20 g L-1, 0.4 V), the electro-oxidative depolymerisation of lignin by electrolysis was performed in a divided cell. The reaction products were identified and quantified by ultra-pressure liquid chromatography coupled with mass spectrometry. The main products were sinapic acid, vanillin, vanillic acid, and acetovanillone. The obtained preliminary results demonstrated the potential feasibility of this innovative electrochemical route for lignin valorisation for the production of bio-aromatic chemicals

Sustainable exploitation of paper mill wastes: a resource to re-use in the paper factory

In the papermaking industry, billions of tonnes of paper mill wastes are globally produced as wastes every year. These include cellulosic and inorganic sludges, which are traditionally landfilled, leading to environmental and economic issues. For these reasons, it is urgent to develop new sustainable strategies to exploit these fractions. Up to now, these sludges have been exploited i) for land application (as soil amendment/substrate), ii) for energy recovery and iii) for the production of bio-composites. However, the above possibilities involve the direct use of the bulk wastes, without fractionating/exploiting each feedstock component. In the perspective of the valorisation of the different components, the present investigation has considered different strategies: i) a thermal treatment, ii) an alkaline and iii) a mechanical one, aimed at the fractionation and recovery of the two main components of cellulosic and inorganic sludge, cellulose and calcium carbonate, respectively, that could be advantageously reused within the same papermaking process