Application de prétraitements pour augmenter la production de biohydrogène et/ou méthane à partir de résidus lignocellulosiques : lien entre performances et paramètres structuraux et compositionnels

Dans le futur, différentes sources d'énergies renouvelables comme les énergies de seconde génération produites à partir de déchets lignocellulosiques seront nécessaires pour palier à l'épuisement des énergies fossiles. Parmi ces énergies de seconde génération, le biohydrogène, le méthane et l'hythane produits à partir de procédés fermentaires anaérobies représentent des alternatives prometteuses. Cependant la production de biohydrogène et de méthane à partir de résidus lignocellulosiques est limitée par leurs structures récalcitrantes et une étape de prétraitement en amont des procédés fermentaires est souvent nécessaire. Ce travail a pour but d'étudier l'impact des facteurs biochimiques et structurels des résidus lignocellulosiques sur les performances de production d'hydrogène et de méthane, pour pouvoir par la suite développer des stratégies de prétaitements adaptées. Tout d'abord, sur un panel de vingt substrats lignocellulosiques, les potentiels hydrogène et méthane ont été corrélés aux paramètres biochimiques et structurels. Les résultats ont mis en évidence que le potentiel hydrogène est uniquement corrélé positivement à la teneur en sucres solubles. La production de méthane quant à elle est négativement corrélée à la teneur en lignine et, à un moindre degré, à la cristallinité de la cellulose, mais positivement à la teneur en sucres solubles, holocelluloses amorphes et protéines. Par la suite, des stratégies de prétraitements ont été établies pour améliorer la production d'hydrogène et de méthane. Le couplage prétaitements alcalins/enzymatique ainsi que les prétraitements à l'acide dilué, efficaces pour solubiliser les holocelluloses en sucres solubles ont été appliqués en amont de la production d'hydrogène. En combinant le pretraitement alcalin avec une hydrolyse enzymatique, le potentiel hydrogène des tiges de tournesol fut multiplié par quinze. En revanche, suite aux prétraitements acides, la production d'hydrogène fut inhibée à cause de la libération de sous-produits (furfural, 5-HMF et composés phénoliques) engendrant un changement d'espèces bactériennes vers des espèces non productrices d'hydrogène. Pour la production de méthane, cinq prétraitements thermo-chimiques (NaOH, H2O2, Ca(OH)2, HCl and FeCl3) efficaces pour délignifier ou solubiliser les holocelluloses ont été étudiés. Parmi ces prétraitements, la meilleure condition fut 55°C à une concentration de 4% NaOH pendant 24 h, résulant en une augmentation du potentiel méthane variant de 29 à 44 % en fonction des tiges de tournesol. Cette condition fut par la suite validée en réacteurs anaérobies continusavec une augmentation de 26.5% de la production de méthane. Un procédé à deux étages couplant la production d'hydrogène en batch suivi de la production de méthane en continu fut aussi étudié. Néanmoins, aucune différence significative en termes d'énergie produite ne fut observée entre les procédés à deux étages (H2/CH4) et à un étage (CH4).In the future, various forms of renewable energy, such as second generation biofuels from lignocellulosic residues, will be required to replace fossil fuels. Among these, biohydrogen and methane produced through fermentative processes appear as interesting candidates. However, biohydrogen and/or methane production of lignocellulosic residues is often limited by the recalcitrant structure and a pretreatment step prior to fermentative processes is often required. Up to date, informations on lignocellulosic characteristics limiting both hydrogen and methane production are limited.Therefore, this work aims to investigate the effect of compositional and structural features of lignocellulosic residues on biohydrogen and methane performances for further developping appropriate pretreatments strategies. Firstly, a panel of twenty lignocellulosic residues was used to correlate both hydrogen and methane potentials with the compositional and structural characteristics. The results showed that hydrogen potential positively correlated with soluble carbohydrates only. Secondly, methane potential correlated negatively with lignin content and, in a lesser extent, with crystalline cellulose, but positively with the soluble carbohydrates, amorphous holocelluloses and protein contents. Pretreatments strategies were further developed to enhance both hydrogen and methane production of sunflower stalks. Dilute-acid and combined alkaline-enzymatic pretreatments, which were found efficient in solubilizing holocelluloses into soluble carbohydrates, were applied prior to biohydrogen potential tests. By combined alkaline-enzymatic pretreatment, hydrogen potential was fifteen times more than that of untreated samples. On the contrary, hydrogen production was inhibited after dilute-acid pretreatments due to the release of byproducts (furfural, 5-HMF and phenolic compounds) that led to microbial communities shift toward no hydrogen producing bacteria. Similarly, methane production, five thermo-chemical pretreatments (NaOH, H2O2, Ca(OH)2, HCl and FeCl3) found efficient in delignification or solubilization of holocelluloses, were considered. Among these pretreatments, the best conditions were 55°C with 4% NaOH for 24 h and led to an increase of 29-44 % in methane potential of sunflower stalks. This pretreatment condition was validated in one stage anaerobic mesophilic continuous digester for methane production and was found efficient to enhance from 26.5% the total energy produced compared to one stage-CH4 alone. Two-stage H2 (batch) / CH4 (continuous) process was also investigated. Nevertheless, in term of energy produced, no significant differences were observed between one-stage CH4 and two-stage H2 /CH4

Application de prétraitements pour améliorer la production d’hydrogène et/ou méthane à partir de résidus lignocellulosiques : lien entre performances et paramètres structuraux et compositionnels

In the future, various forms of renewable energy, such as second generation biofuels from lignocellulosic residues, will be required to replace fossil fuels. Among these, biohydrogen and methane produced through fermentative processes appear as interesting candidates. However, biohydrogen and/or methane production of lignocellulosic residues is often limited by the recalcitrant structure and a pretreatment step prior to fermentative processes is often required. Up to date, informations on lignocellulosic characteristics limiting both hydrogen and methane production are limited. Therefore, this work aims to investigate the effect of compositional and structural features of lignocellulosic residues on biohydrogen and methane performances for further developping appropriate pretreatments strategies. Firstly, a panel of twenty lignocellulosic residues was used to correlate both hydrogen and methane potentials with the compositional and structural characteristics. The results showed that hydrogen potential positively correlated with soluble carbohydrates only. Secondly, methane potential correlated negatively with lignin content and, in a lesser extent, with crystalline cellulose, but positively with the soluble carbohydrates, amorphous holocelluloses and protein contents. Pretreatments strategies were further developed to enhance both hydrogen and methane production of sunflower stalks. Dilute-acid and combined alkalineenzymatic pretreatments, which were found efficient in solubilizing holocelluloses into soluble carbohydrates, were applied prior to biohydrogen potential tests. By combined alkaline-enzymatic pretreatment, hydrogen potential was fifteen times more than that of untreated samples. On the contrary, hydrogen production was inhibited after dilute-acid pretreatments due to the release of byproducts (furfural, 5-HMF and phenolic compounds) that led to microbial communities shift toward no hydrogen producing bacteria. Similarly, methane production, five thermo-chemical pretreatments (NaOH, H2O2, Ca(OH)2, HCl and FeCl3) found efficient in delignification or solubilization of holocelluloses, were considered. Among these pretreatments, the best conditions were 55°C with 4% NaOH for 24 h and led to an increase of 29-44 % in methane potential of sunflower stalks. This pretreatment condition was validated in one stage anaerobic mesophilic continuous digester for methane production and was found efficient to enhance from 26.5% the total energy produced compared to one stage-CH4 alone. Two-stage H2 (batch) / CH4 (continuous) process was also investigated. Nevertheless, in term of energy produced, no significant differences were observed between one-stage CH4 and two-stage H2 /CH4.Dans le futur, différentes sources d'énergies renouvelables comme les energies de seconde génération produites à partir de déchets lignocellulosiques seront nécessaires pour palier à l'épuisement des énergies fossiles. Parmi ces énergies de seconde génération, le biohydrogène, le méthane et l'hythane produits à partir de procédés fermentaires anaérobies représentent des alternatives prometteuses. Cependant la production de biohydrogène et de méthane à partir de résidus lignocellulosiques est limitée par leurs structures récalcitrantes et une étape de prétraitement en amont des procédés fermentaires est souvent nécessaire. A ce jour, peu d'informations sur les paramètres limitant la conversion des matrices lignocellulosiques en hydrogène ou méthane sont disponibles. Ce travail a pour but d'étudier l'impact des facteurs biochimiques et structurels des résidus lignocellulosiques sur les performances de production d'hydrogène et de méthane, pour pouvoir par la suite développer des stratégies de prétaitements adaptées. Tout d'abord, sur un panel de vingt substrats lignocellulosiques, les potentiels hydrogène et méthane ont été corrélés aux paramètres biochimiques et structurels. Les résultats ont mis en évidence que le potentiel hydrogène est uniquement corrélé positivement à la teneur en sucres solubles. La production de méthane quant à elle est négativement corrélée à la teneur en lignine et, à un moindre degré, à la cristallinité de la cellulose, mais positivement à la teneur en sucres solubles, holocelluloses amorphes et protéines. Par la suite, des stratégies de prétraitements ont été établies pour améliorer la production d'hydrogène et de méthane. Le couplage prétaitements alcalins/enzymatique ainsi que les prétraitements à l'acide dilué, efficaces pour solubiliser les holocelluloses en sucres solubles ont été appliqués en amont de la production d'hydrogène. En combinant le pretraitement alcalin avec une hydrolyse enzymatique, le potentiel hydrogène des tiges de tournesol fut multiplié par quinze. En revanche, suite aux prétraitements acides, la production d'hydrogène fut inhibée à cause de la libération de sous-produits (furfural, 5-HMF et composés phénoliques) engendrant un changement d'espèces bactériennes vers des espèces non productrices d'hydrogène. Pour la production de méthane, cinq prétraitements thermochimiques (NaOH, H2O2, Ca(OH)2, HCl and FeCl3) efficaces pour délignifier ou solubiliser les holocelluloses ont été étudiés. Parmi ces prétraitements, la meilleure condition fut 55°C à une concentration de 4% NaOH pendant 24 h, résulant en une augmentation du potentiel méthane variant de 29 à 44 % en fonction des tiges de tournesol. Cette condition fut par la suite validée en réacteurs anaérobies continus avec une augmentation de 26.5% de la production de méthane. Un procédé à deux étages couplant la production d'hydrogène en batch suivi de la production de méthane en continu fut aussi étudié. Néanmoins, aucune différence significative en termes d'énergie produite ne fut observée entre les procédés à deux étages (H2/CH4) et à un étage (CH4)

Dry chemo-mechanical pretreatments of lignocellulosic biomass: impact on energy consumption, enzymatic hydrolysis and bioethanol yields

The high crude oil prices, the decline of fossil fuel reserves and the increase of greenhousegas emissions are motivating the development of biorefineries that produce energy fromrenewable resources (i.e. lignocellulosic biomass). However, the key driver for the successfulconversion of biomasses into biofuels is the selection of efficient pretreatments that permit tomaximize the sugars recovery and to minimize the consumption of water, chemicals andenergy. This study proposes the application of “dry” chemo-mechanical pretreatments thatpermit to enhance enzymatic hydrolysis and thereafter bioethanol production fromlignocellulosic biomasses.In a first experiment, wheat straw was pretreated with NH3, NaOH, NaOH-H2O2 and NH3-H2O2 at both high (5 kg L-1) and at low (0.2 kg L-1) biomass concentrations, named “dry” and“diluted” pretreatments. Then, untreated and pretreated samples were subjected to centrifugaland ball milling, followed by enzymatic hydrolysis. Compared to diluted mechano -NaOHpretreatments, dry mechano -NaOH and -NaOH-H2O2 were found to be more effective indecreasing the particle size (up to 55%), increasing the surface area (up to 88%) anddecreasing the total energy requirement (up to 50%). Enzymatic hydrolysis was enhanced bypretreatments, as suggested by higher glucose yields (332, 320, 140, 322, 141 g glucose kg-1biomass for diluted –NaOH, dry – NaOH, dry -NH3, dry -NaOH-H2O2 and dry -NH3-H2O2,respectively), compared to that of untreated wheat straw (118 g glucose kg-1). However, lowerenergy efficiency was obtained for dilute mechano -NaOH treatment, compared to drymechano -NaOH treatments.In a second experiment, sugarcane bagasse was pretreated with NaOH and H3PO4 at highbiomass concentration (5 kg L-1) and then milled by using different methods, such asvibratory milling (VBM), ball milling (BM) and centrifugal milling (CM). Results indicatethat NaOH-BM and NaOH-VBM was preferred to enhance glucose yields and bioethanolproduction (up to 76%), while CM consumed 75% and 58% lesser energy than BM and VBM,respectively. The highest energy efficiency was obtained with NaOH-CM. Therefore, thecombination of dry NaOH and CM appears the most suitable and interesting pretreatment forthe production of bioethanol from SB

Bioethanol fermentation as alternative valorization route of agricultural digestate according to a biorefinery approach

This study investigates the feasibility of producing bioethanol from solid digestate after a mechanical fractionation (i.e. centrifugal milling), in order to improve the energy recovery from agricultural wastes and the sustainability of anaerobic digestion plants. A bioethanol yield of 37 g kg−1 TS was evaluated for the solid digestate fraction. Mass and energetic balances were performed and compared between two scenarios: (A) one-stage bioethanol fermentation and (B) two-stage anaerobic digestion–bioethanol fermentation, in order to evaluate the feasibility and the advantages of the two-stage process. Results revealed that, compared to the one-stage process, the dual anaerobic digestion–bioethanol process permitted: (i) to diversify biofuels production; (ii) to provide the thermal energy sufficient for drying digestate (13,351 kWhth day−1), for the subsequent milling step; (iii) to reduce the electric energy requirement for the milling step (from 23,880 to 3580 kWhel day−1); (iv) to produce extra electrical energy of 8483 kWhel day−1; (v) to improve the reduction of waste streams generated (from 13% to 54% of organic matter removal)

Comparison of Dry Versus Wet Milling to Improve Bioethanol or Methane Recovery from Solid Anaerobic Digestate

Biogas plants for waste treatment valorization are presently experiencing rapid development, especially in the agricultural sector, where large amounts of digestate are being generated. In this study, we investigated the effect of vibro-ball milling (VBM) for 5 and 30 min at a frequency of 20 s−1 on the physicochemical composition and enzymatic hydrolysis (30 U g−1 total solids (TS) of cellulase and endo-1,4-xylanase from Trichoderma longibrachiatum) of dry and wet solid separated digestates from an agricultural biogas plant. We found that VBM of dry solid digestate improved the physical parameters as both the particle size and the crystallinity index (from 27% to 75%) were reduced. By contrast, VBM of wet solid digestate had a minimal effect on the physicochemical parameters. The best results in terms of cellulose and hemicelluloses hydrolysis were noted for 30 min of VBM of dry solid digestate, with hydrolysis yields of 64% and 85% for hemicelluloses and cellulose, respectively. At the condition of 30 min of VBM, bioethanol and methane production on the dry solid separated digestate was investigated. Bioethanol fermentation by simultaneous saccharification and fermentation resulted in an ethanol yield of 98 geth kg−1 TS (corresponding to 90% of the theoretical value) versus 19 geth kg−1 TS for raw solid digestate. Finally, in terms of methane potential, VBM for 30 min lead to an increase of the methane potential of 31% compared to untreated solid digestate

Mechanical dissociation and fragmentation of lignocellulosic biomass: Effect of initial moisture, biochemical and structural proprieties on energy requirement

International audienceMechanical size reduction is considered as a primordial step of current and future lignocellulosic biorefinery. In this sense, it is of high interest to understand who are the biochemical and structural features of the lignocellulosic biomass, which affect the Specific Energy Requirement (SER), and in consequence the cost of mechanical size reduction processes. First, it was shown that the initial moisture content of the lignocellulosic biomass affect the SER and the final particle size distribution. The highest the moisture content gives raise the highest SER. Then, at fixed initial moisture content (≈7% DW), structural and biochemical features of lignocellulosic biomass that can affect the SER were determined. It was noticed that both arabinose/xylose ratio and accessible surface area lead to increasing the SER. On the contrary, the content of cellulose, lignin, crystallinity and p-coumaric acids links were found to have a positive effect on the reduction of the SER

A new concept for enhancing energy recovery from agricultural residues by coupling anaerobic digestion and pyrolysis process

In a full-scale anaerobic digestion plant, agricultural residues are generally converted into biogas and digestate, the latter usually produced in large amount. Generally, biogas is converted into heat, often lost, and electricity, which is completely valorized or it is sold to the public grid. In this context, the aim of this study was to investigate the feasibility to combine anaerobic digestion and pyrolysis processes in order to increase the energy recovery from agricultural residues and the sustainability of the anaerobic digestion plant. Results revealed that heat excess produced during anaerobic digestion could cover the drying needs for the solid digestate, while pyrolysis of digestate at 500 °C resulted in 8.8 wt.%, 58.4 wt.% and 32.8 wt.% of syngas, oil and char, respectively. The LHV of syngas was 15.7 MJ N m−3, whereas pyrolysis oil exhibited a HHV of 23.5 MJ kg−1 after water extraction. The hybrid system operating in symbiosis could increase the production of electricity from 9896 kWhel day−1 to 14,066 kWhel day−1 corresponding to an increase of 42% compared to AD stand-alone plant

Twin-Screw Extrusion Mechanical Pretreatment for Enhancing Biomethane Production from Agro-Industrial, Agricultural and Catch Crop Biomasses

This study aimed to evaluate the effects of mechanical treatment through twin-screw extrusion for the enhancement of biomethane production. Four lignocellulosic biomasses (i.e., sweetcorn by-products, whole triticale, corn stover and wheat straw) were evaluated, and two different shear stress screw profiles were tested. Chemical composition, particle size reduction, tapped density and cellulose crystallinity were assessed to show the effect of extrusion pretreatment on substrate physico-chemical properties and their biochemical methane production (BMP) capacities. Both mechanical pretreatments allowed an increase in the proportion of particles with a diameter size less than 1 mm (from 3.7% to 72.7%). The most restrictive profile also allowed a significant solubilization of water soluble coumpounds, from 5.5% to 13%. This high-shear extrusion also revealed a reduction in cellulose crystallinity for corn stover (i.e., 8.6% reduction). Sweetcorn by-products revealed the highest BMP values (338–345 NmL/gVS), followed by corn stover (264–286 NmL/gVS), wheat straw (247–270 NmL/gVS) and whole triticale (233–247 NmL/gVS). However, no statistical improvement in maximal BMP production was provided by twin-screw extrusion. Nevertheless, BMP kinetic analysis proved that both extrusion pretreatments were able to increase the specific rate constant (from 13% to 56% for soft extrusion and from 66% to 107% for the high-shear one)

Comparison of various milling modes combined to the enzymatic hydrolysis of lignocellulosic biomass for bioenergy production: Glucose yield and energy efficiency

Bagasse is an abundant by-product from sugarcane production that can be used for conversion into biofuels. Nonetheless, the recalcitrant structures of lignocellulosic fibers required a pretreatment prior conversion into biofuels. In this study, four mechanical deconstruction methods were compared in terms of energy demand and energy efficiency at lab scale: BM (ball mill), VBM (vibratory ball mill), CM (centrifugal mill) and JM (jet mill). Results indicate that VBM was more effective compared to BM, JM and CM in enzymatic accessibility and sugars solubilization: VBM-3h > BM-72 h > JM-5000 rpm > CM-0.12 mm. However, preliminary energetic assessment showed that at lab scale, the CM (centrifugal mill) as mechanical fractionation process appears to be the most efficient in terms of energy-efficiency (kg glucose/kWh) compared to BM, VBM and JM. A comparison with literature pretreatments data highlighted that fine and/or ultrafine milling process (BM, VBM, CM) are simpler saccharification technologies, which not required any chemical or water inputs, thus minimizing waste generation and treatment

Anaerobic Digestion of Wastewater Sludge and Alkaline-Pretreated Wheat Straw at Semi-Continuous Pilot Scale: Performances and Energy Assessment

International audienceDuring the last decade, the application of pretreatment has been investigated to enhance methane production from lignocellulosic biomass such as wheat straw (WS). Nonetheless, most of these studies were conducted in laboratory batch tests, potentially hiding instability problems or inhibition, which may fail in truly predicting full-scale reactor performance. For this purpose, the effect of an alkaline pretreatment on process performance and methane yields from WS (0.10 g NaOH g−1 WS at 90 °C for 1 h) co-digested with fresh wastewater sludge was evaluated in a pilot-scale reactor (20 L). Results showed that alkaline pretreatment resulted in better delignification (44%) and hemicellulose solubilization (62%) compared to untreated WS. Pilot-scale study showed that the alkaline pretreatment improved the methane production (261 ± 3 Nm3 CH4 t−1 VS) compared to untreated WS (201 ± 6 Nm3 CH4 t−1 VS). Stable process without any inhibition was observed and a high alkalinity was maintained in the reactor due to the NaOH used for pretreatment. The study thus confirms that alkaline pretreatment is a promising technology for full-scale application and could improve the overall economic benefits for biogas plant at 24 EUR t−1 VS treated, improve the energy recovery per unit organic matter, reduce the digestate volume and its disposal cost