Use of activated carbons for detoxification of a lignocellulosic hydrolysate: Statistical optimisation.

In order to improve bioethanol production from hydrolysates from olive tree pruning residues the present study assessed a detoxification method using the same waste material. The objective was to develop optimal removal without diminishing fermentable sugars. A statistical optimisation study was performed for the production of activated carbons using the same olive tree pruning residue as raw material. The effect of the impregnation ratio, activation temperature and the time needed for maximum removal of the phenolic compounds was assayed. The conditions for maximum adsorption were as follows: 799.18 °C, IR 4.88 and 101.38 min of activation, removing 55%, 64% and 41% of total phenolic compounds, HMF and furfural, respectively. The activated carbon obtained under optimum conditions (Aop) was submitted to adsorption kinetics and equilibrium assays. Experimental kinetic data were well represented by a pseudo-first order kinetic and intraparticle diffusion model, which helped explain the adsorption mechanism. Experimental isotherms were analysed with Langmuir, Freundlich and Temkin models, and Langmuir best fitted the experimental data. Hydrolysate from olive tree pruning residues, detoxified with the optimum activated carbon, was fermented with a commercial Saccharomyces cerevisiae yeast, obtaining a 100% theoretical maximum ethanol yield and a 56% bioconversion of fermentable sugars.

Chemical, Thermal and Antioxidant Properties of Lignins Solubilized during Soda/AQ Pulping of Orange and Olive Tree Pruning Residues.

Some agroforestry residues such as orange and olive tree pruning have been extensively evaluated for their valorization due to its high carbohydrates content. However, lignin-enriched residues generated during carbohydrates valorization are normally incinerated to produce energy. In order to find alternative high added-value applications for these lignins, a depth characterization of them is required. In this study, lignins isolated from the black liquors produced during soda/anthraquinone (soda/AQ) pulping of orange and olive tree pruning residues were analyzed by analytical standard methods and Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (solid state 13C NMR and 2D NMR) and size exclusion chromatography (SEC). Thermal analysis (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) and antioxidant capacity (Trolox equivalent antioxidant capacity) were also evaluated. Both lignins showed a high OH phenolic content as consequence of a wide breakdown of ß-aryl ether linkages. This extensive degradation yielded lignins with low molecular weights and polydispersity values. Moreover, both lignins exhibited an enrichment of syringyl units together with different native as well as soda/AQ lignin derived units. Based on these chemical properties, orange and olive lignins showed relatively high thermal stability and good antioxidant activities. These results make them potential additives to enhance the thermo-oxidation stability of synthetic polymers.

The use of olive tree pruning waste compost to sequestrate methylene blue dye from aqueous solution.

Considering that quality water supplies are diminishing and climate disorder affects water cycle, wastewaters should be decontaminated for reuse either by the same establishment or in agriculture for the growth of industrial plants. In that context, much research work has been focused on the development of low cost biosorbents. In this study, the effect of composting on the adsorption capacity of olive tree pruning waste (OTPW) biomass for methylene blue (MB) removal from aqueous solutions was examined. Composting procedure may improve the sorption properties of the raw organic materials, is economical and easy to apply. MB adsorption on both OTPW and composted olive tree pruning waste (COTPW) biomasses was found to be fast. The maximum monolayer adsorption capacity obtained from Langmuir isotherm was estimated to be 129.87 and 250.00 mg/g for OTPW and COTPW, respectively, indicating that composting procedure greatly improved the adsorptive properties of OTPW. The raise of temperature from 25°C to 60°C decreased the efficiency of OTPW for MB removal whereas the adsorption capacity of COTPW was not affected at high temperatures. Moreover, COTPW showed constant adsorption over the 2-8 solution pH range.

Obtaining Cellulose Nanocrystals from Olive Tree Pruning Waste and Evaluation of Their Influence as a Reinforcement on Biocomposites.

The objective of this work is to improve the mechanical properties of polylactic acid (PLA) by incorporating cellulose nanocrystals (CNC) previously obtained from a cellulose pulp extracted from olive tree pruning (OTP) waste. Composites were manufactured by melt processing and injection moulding to evaluate the effect of the introduction of CNC with conventional manufacturing methods. This OTP-cellulose pulp was subjected to a further purification process by bleaching, thus bringing the cellulose content up to 86.1%wt. This highly purified cellulose was hydrolysed with sulfuric acid to obtain CNCs with an average length of 267 nm and a degradation temperature of 300 °C. The CNCs obtained were used in different percentages (1, 3, and 5%wt.) as reinforcement in the manufacture of PLA-based composites. The effect of incorporating CNC into PLA matrix on the mechanical, water absorption, thermal, structural, and morphological properties was studied. Maximum tensile stress and Young's modulus improved by 87 and 58%, respectively, by incorporating 3 and 5%wt. CNC. Charpy impact strength increased by 21% with 3%wt. These results were attributed to the good dispersion of CNCs in the matrix, which was corroborated by SEM images. Crystallinity index, glass transition, and melting temperatures were maintained.

Nitrogen availability in biochar-based fertilizers depending on activation treatment and nitrogen source.

Different activation and N-doping treatments were used to produce biochar-based fertilizers (BBFs) with increased N concentration and slow N release. Pristine biochars were produced by pyrolysis of olive tree pruning feedstock at low and high temperatures (400 and 800 °C). These biochars were activated either by ultrasonication, or oxidation with hydrogen peroxide (H2O2) or nitric acid (HNO3) to increase their N retention potential. Subsequently biochars were enriched with N with either urea or ammonium sulfate. The activation of low-temperature biochars with HNO3 was the most effective treatment leading to new surface carboxylic groups that facilitated the later enrichment with N. When treated with urea, BBFs reached 7.0 N%, whereas the H2O2 activation only allowed an increase up to 2.0 N%. The use of urea as the external N source was the most efficient for incorporating N. Urea treated biochars had a water-soluble fraction that represented up to 14.5 % of the total N. The hydrolyzable N fraction, composed by amides and simple N heterocycles originated by the N-doping treatments, and nitro groups generated from HNO3 activation, represented up to 60 % of the total N. This study relates the N chemical forms in the new BBFs to potential N availability in soil. The presence of water-soluble, hydrolyzable and non-hydrolyzable N implied that these BBFs may supply N that would be progressively available for plants, acting as slow-release fertilizers.

Competitive adsorptive removal of promazine and promethazine from wastewater using olive tree pruning biochar: operational parameters, kinetics, and equilibrium investigations.

This research aims to remove two phenothiazines, promazine (PRO) and promethazine (PMT), from their individual and binary mixtures using olive tree pruning biochar (BC-OTPR). The impact of individual and combinatory effects of operational variables was evaluated for the first time using central composite design (CCD). Simultaneous removal of both drugs was maximized utilizing the composite desirability function. At low concentrations, the uptake of PRO and PMT from their individual solutions was achieved with high efficiency of 98.64%, 47.20 mg/g and 95.87%, 38.16 mg/g, respectively. No major differences in the removal capacity were observed for the binary mixtures. Characterization of BC-OTPR confirmed successful adsorption and showed that the OTPR surface was predominantly mesoporous. Equilibrium investigations revealed that the Langmuir isotherm model best describes the sorption of PRO/PMT from their individual solutions with maximum adsorption capacities of 640.7 and 346.95 mg/g, respectively. The sorption of PRO/PMT conforms to the pseudo-second-order kinetic model. Regeneration of the adsorbent surface was successfully done with desorption efficiencies of 94.06% and 98.54% for PRO and PMT, respectively, for six cycles.

Optimizing hydrothermal carbonization of olive tree pruning: A techno-economic analysis based on experimental results.

In this study the optimization of the hydrothermal carbonization process for the conversion of olive tree pruning into biofuel is presented. To this end, a combined experimental-economic assessment is performed. Experimental data obtained at laboratory scale were used to estimate the economic performance of a hypothetical industrial scale plant. To evaluate the viability of the project, three different plant sizes according to their capacity were selected (1250-625-312.5 kg/h). The discounted cash flow method was applied for the profitability analysis. Different scenarios were analyzed considering the reduction of associate costs or the improvement of the revenues compared to the baseline case. Results indicate that with the sizes studied, none of the alternatives are profitable. Despite that, the larger capacity shows the best outcomes. In this case, minimum selling price of 0.39 €/kg for hydrochar is required to reach profitability. Lower plant sizes would require higher selling prices (i.e., 0.46 €/kg for 625 kg/h capacity and 0.59 €/kg for 312.5 kg/h capacity). Similarly, a reduction of 33% in the electrical energy consumption can make the plan be profitable for the larger capacity. Likewise, a reduction until 0.053 €/kWh in the electricity price must be reached for achieving profitability. Thus, importance of government incentives is revealed in this work given that the reduction of costs along with the improvement in the revenues for the selling of the product can make the project economically viable. Other parameters like the number of workers are also interesting to consider as for example the reduction by two units improves the NPV value in almost 600 k€ for all the plant sizes.

Analytical Characterization of Water-Soluble Constituents in Olive-Derived By-Products.

Olive trees constitute one of the largest agroindustries in the Mediterranean area, and their cultivation generates a diverse pool of biomass by-products such as olive tree pruning (OTP), olive leaves (OL), olive stone (OS), and extracted olive pomace (EOP). These lignocellulosic materials have varying compositions and potential utilization strategies within a biorefinery context. The aim of this work was to carry out an integral analysis of the aqueous extractives fraction of these biomasses. Several analytical methods were applied in order to fully characterize this fraction to varying extents: a mass closure of >80% was reached for EOP, >76% for OTP, >65% for OS, and >52% for OL. Among the compounds detected, xylooligosaccharides, mannitol, 3,4-dihydroxyphenylglycol, and hydroxytyrosol were noted as potential enhancers of the valorization of said by-products. The extraction of these compounds is expected to be more favorable for OTP, OL, and EOP, given their high extractives content, and is compatible with other utilization strategies such as the bioconversion of the lignocellulosic fraction into biofuels and bioproducts.

Management of off-specification compost by using co-hydrothermal carbonization with olive tree pruning. Assessing energy potential of hydrochar.

In this work the management of a waste called off-specification compost (OSC) was proposed via hydrothermal carbonization (HTC). The composition of this residue makes it not suitable for agronomic purposes because of the Spanish regulation requirements. Therefore, a way of management and/or valorisation needs to be found. The energy recovery through co-HTC with olive tree pruning (OTP) was evaluated. Blending of OSC with lignocellulosic biomass allows to obtain a coal-like product with physicochemical properties similar to those of a lignite, characterised by its high carbon content. Blends of 25, 50 and 75% of OSC with OTP were analysed. The individual OSC does not present good parameters for being used as solid fuel based on its chemical composition, however, the blend of 75% of biomass with 25% of OSC does. With a higher heating value of 26.19 MJ/kg, this blend shows the best energy yield and energy densification ratio. Thermogravimetric and kinetic analysis reveal that as biomass content in the blend increases, the more the hydrochar behaves as a solid fuel, therefore OSC can be used for energy purposes while its current use of landfill disposal can be reduced.

Optimization of ultrasound-assisted extraction of biomass from olive trees using response surface methodology.

Olive tree pruning biomass (OTP) and olive mill leaves (OML) are the main residual lignocellulosic biomasses that are generated from olive trees. They have been proposed as a source of value-added compounds and biofuels within the biorefinery concept. In this work, the optimization of an ultrasound-assisted extraction (UAE) process was performed to extract antioxidant compounds present in OTP and OML. The effect of the three parameters, ethanol/water ratio (20, 50, 80% of ethanol concentration), amplitude percentage (30, 50, 70%) and ultrasonication time (5, 10, 15 min), on the responses of total phenolic content (TPC), total flavonoid content (TFC) and antioxidant activities (DPPH, ABTS and FRAP) were evaluated following a Box-Behnken experimental design. The optimal conditions obtained from the model, taking into account simultaneously the five responses, were quite similar for OTP and OML, with 70% amplitude and 15 min for both biomasses and a slight difference in the optimum concentration of ethanol. (54.5% versus 51.3% for OTP and OML, respectively). When comparing the antioxidant activities obtained with OTP and OML, higher values were obtained for OML (around 40% more than for OTP). The antioxidant activities reached experimentally under the optimized conditions were 31.6 mg of TE/g of OTP and 42.5 mg of TE/g of OML with the DPPH method, 66.5 mg of TE/g of OTP and 95.9 mg of TE/g of OML with the ABTS method, and 36.4 mg of TE/g of OTP and 49.7 mg of TE/g of OML with the FRAP method. Both OTP and OML could be a potential source of natural antioxidants.

Assessing cellulose nanofiber production from olive tree pruning residue.

Pruning operation in olive trees generates a large amount of biomass that is normally burned causing severe environmental concern. Therefore, the transformation of this agricultural residue into value-added products is imperative but still remains as a technological challenge. In this study, olive tree pruning (OTP) residue is evaluated for the first time to produce cellulose nanofibers (CNF). The OTP bleached pulp was treated by TEMPO-mediated oxidation and subsequent defibrillation in a microfluidizer. The resulting CNF was characterized and compared to CNF obtained from a commercial bleached eucalyptus kraft pulp using the same chemi-mechanical procedure. CNF from OTP showed higher carboxylate content but lower fibrillation yield and optical transmittance as compared to eucalyptus CNF. Finally, the visco-elastic gel obtained from OTP was stronger than that produced from eucalyptus. Therefore, the properties of CNF from OTP made this nanomaterial suitable for several applications. CNF from OTP showed higher carboxylate content as compared to eucalyptus CNF (1038 vs. 778µmol/g) but lower fibrillation yield (48% vs. 96%) and optical transmittance. Finally, the visco-elastic gel obtained from OTP was stronger than that produced from eucalyptus. Therefore, the properties of CNF from OTP made this nanomaterial suitable for several applications.

Kinetic analysis of pyrolysis and combustion of the olive tree pruning by chemical fractionation.

This paper presents a kinetic analysis of thermal decomposition of olive tree pruning from its basic compounds in pyrolysis and combustion reactions. Experiments were performed by TGA under inert and oxidant conditions and results indicated that the decomposition of the olive tree pruning was related to the material composition. Pseudo-mechanistic models were proposed estimating the yield of pyrolysis on its basic compounds (hemicelluloses, cellulose and lignin). Validity and reliability of the proposed kinetic models were verified by the good fitting between the simulated and experimental curves (with values of R2 higher than 0.99 in most cases). Moreover, during the fractionation process, an acid fraction was obtained with great fuel properties, a high calorific value and a low residue after its combustion.

Mobile Elevated Work Platforms versus Ladders in Olive Tree Pruning: Evaluation of Physical Activity and Pruning Performance.

The use of mobile elevated work platforms (MEWPs) versus ladders was studied to evaluate the physical activity (PA) of workers and their performance during olive tree pruning. Accelerometers worn by the workers were used to measure triaxial accelerations, which were converted into PA using Freedson's equation. The mean values of acceleration on the three axes for workers on ladders led to statistically higher results than for workers on MEWPs. The energy expenditure (EE) and metabolic equivalent (MET) values were statistically different (about 1.8 times higher) for the ladder work site than for the MEWP work site. The use of an MEWP leads to more time spent on moderate activity (84.30%) than when using a ladder (71.90%) but no time on vigorous activity compared to a ladder (13.88%). The pruning performance was 3.8 for the MEWP and 1.4 for the ladder, while the labor productivity was 11.4 for the MEWP and 4.2 for the ladder. Thus, it is possible to reduce worker employment and costs by about 2.7 times with MEWPs.

Evaluation of lignins from side-streams generated in an olive tree pruning-based biorefinery: Bioethanol production and alkaline pulping.

In modern lignocellulosic-based biorefineries, carbohydrates can be transformed into biofuels and pulp and paper, whereas lignin is burned to obtain energy. However, a part of lignin could be converted into value-added products including bio-based aromatic chemicals, as well as building blocks for materials. Then, a good knowledge of lignin is necessary to define its valorisation procedure. This study characterized different lignins from side-streams produced from olive tree pruning bioethanol production (lignins collected from steam explosion pretreatment with water or phosphoric acid as catalysts, followed by simultaneous saccharification and fermentation process) and alkaline pulping (lignins recovered from kraft and soda-AQ black liquors). Together with the chemical composition, the structure of lignins was investigated by FTIR, 13C NMR, and 2D NMR. Bioethanol lignins had clearly distinct characteristics compared to pulping lignins; a certain number of side-chain linkages (mostly alkyl-aryl ether and resinol) accompanied with lower phenolic hydroxyls content. Bioethanol lignins also showed a significant amount of carbohydrates, mainly glucose and protein impurities. By contrast, pulping lignins revealed xylose together with a dramatical reduction of side-chains (some resinol linkages survive) and thereby higher phenol content, indicating rather severe lignin degradation during alkaline pulping processes. All lignins showed a predominance of syringyl units.

Combustion of a Pb(II)-loaded olive tree pruning used as biosorbent.

The olive tree pruning is a specific agroindustrial waste that can be successfully used as adsorbent, to remove Pb(II) from contaminated wastewater. Its final incineration has been studied in a thermobalance and in a laboratory flow reactor. The study aims at evaluating the fate of Pb during combustion, at two different scales of investigation. The flow reactor can treat samples approximately 10(2) larger than the conventional TGA. A detailed characterization of the raw and Pb(II)-loaded waste, before and after combustion is presented, including analysis of gas and solids products. The Pb(II)-loaded olive tree pruning has been prepared by a previous biosorption step in a lead solution, reaching a concentration of lead of 2.3 wt%. Several characterizations of the ashes and the mass balances proved that after the combustion, all the lead presents in the waste remained in ashes. Combustion in a flow reactor produced results consistent with those obtained in the thermobalance. It is thus confirmed that the combustion of Pb(II)-loaded olive tree pruning is a viable option to use it after the biosorption process. The Pb contained in the solid remained in the ashes, preventing possible environmental hazards.

Thermal behaviour and kinetic study of the olive oil production chain residues and their mixtures during co-combustion.

The kinetic behaviour of olive tree pruning (PR), two- (2PH) and three-phase (3PH) olive pomace and their blends was investigated under combustion condition using thermogravimetric analysis. PR was blended with 2PH and 3PH at different ratios (25:75, 50:50 and 75:25) and tested in the temperature range from ambient to 1000°C in order to evaluate the co-combustion behaviour. Results showed that the thermal degradation of all samples can be divided into three regions (drying, devolatilisation, char oxidation) with different combustion properties, depending on the percentage of PR. Significant interaction was detected between the fuels, and reactivity of 2PH and 3PH was improved upon blending with PR. The iso-conversional methods, Ozawa-Flynn-Wall and Vyazovkin, were employed for the kinetic analysis of the oxidation process. The results revealed that the activation energy of PR was higher than the one of 2PH and 3PH, and the minimum value was obtained for 25PR752PH sample.

Ethanol production from glucose and xylose obtained from steam exploded water-extracted olive tree pruning using phosphoric acid as catalyst.

In this work, the effect of phosphoric acid (1% w/w) in steam explosion pretreatment of water extracted olive tree pruning at 175°C and 195°C was evaluated. The objective is to produce ethanol from all sugars (mainly glucose and xylose) contained in the pretreated material. The water insoluble fraction obtained after pretreatment was used as substrate in a simultaneous saccharification and fermentation (SSF) process by a commercial strain of Saccharomyces cerevisiae. The liquid fraction, containing mainly xylose, was detoxified by alkali and ion-exchange resin and then fermented by the xylose fermenting yeast Scheffersomyces stipitis. Ethanol yields reached in a SSF process were close to 80% when using 15% (w/w) substrate consistency and about 70% of theoretical when using prehydrolysates detoxified by ion-exchange resins. Considering sugars recovery and ethanol yields about 160g of ethanol from kg of water extracted olive tree pruning could be obtained.