Alkali, thermal, or thermo-alkali pre-treatment to improve the anaerobic digestion of poly(lactic acid)?

Replacing petroleum-based plastics with biodegradable polymers is a major challenge for modern society especially for food packaging applications. To date, poly(lactic acid) represents 25 % of the total biodegradable plastics and it is estimated that, in the future, it could become the main contributor to the biodegradable plastics industry. Anaerobic digestion is an interesting way for the poly(lactic acid) end of life, even if its biodegradability is limited in mesophilic conditions. The aims of this study were to identify the best pre-treatment for maximizing the methane yield, minimizing the anaerobic digestion duration and limiting residual plastic fragments in the digestate. A systematic comparison was carried out between thermal, chemical, and thermo-chemical pre-treatment. Pre-treatment with 4 M KOH for 48 h at 35°C was effective in improving the mesophilic anaerobic digestion of the poly(lactic acid). Such pre-treatment allows obtaining 90 % of the theoretical methane potential, in 24 - 30 days. Importantly, such pre-treatment completely solubilized the poly(lactic acid), leaving no solid residues in the digestate. In addition, using KOH permits to avoid the sodication of the soil due to the digestate application as fertilizer.

Simulation of biowastes and biodegradable plastics co-digestion in semi-continuous reactors: Performances and agronomic evaluation.

The development of selective biowaste collection in most European countries provides new opportunities for the anaerobic digestion sector. In parallel, extensive development of biodegradable plastics like polylactic-acid (PLA) and polyhydroxybutyrate (PHB), which facilitates the replacement of conventional plastics, has taken place in the past decade. This study investigated anaerobic co-digestion in semi-continuous reactors of biowastes (75 % Volatil Solids) and biodegradable plastics (25 % Volatil Solids, PLA and PHB). PHB was estimated to be fully biodegraded in the reactors. By contrast, PLA accumulated in the reactor, and an average biodegradation of 47.6 ± 17.9 % was estimated during the third hydraulic retention time. Pretreatment of PLA, by thermo-alkaline hydrolysis at 70 °C, with 2.5 w/v of Ca(OH)2 for 48 h, improved the biodegradation yield of PLA to 77.5 ± 9.3 %. Finally, it was highlighted that PLA or PHB addition to the feed did not further affect the agronomic properties of the digestate.

Simultaneous detoxification and bioethanol fermentation of furans-rich synthetic hydrolysate by digestate-based pyrochar.

Pyrolysis is a sustainable pathway to transform renewable biomasses into both biofuels and advanced carbonaceous materials (i.e. pyrochar) which can be used as adsorbent of furan compounds. In particular, the aim of this study was to: i) evaluate the effect of vibro-ball milling on physical characteristics of pyrochar and its consequent performance on solely detoxification of a synthetic medium, containing furans and soluble sugars; ii) study the simultaneous detoxification and bioethanol fermentation, by adding activated pyrochar into fermentation medium. Results demonstrated that, compared to untreated pyrochar, the use of milled pyrochar increased by 52% furfural removal from the synthetic medium. Furfural removal rate was also increased (adsorption kinetic constant increased from 0.015 min-1 up to 0.215 min-1), at a pyrochar loading of 40 g L-1. Although, the simultaneous addition of pyrochar into the fermentation medium did not improve the bioethanol yield of the synthetic medium, it has significantly increased the bioethanol production rate.

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 37gkg(-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 (13,351kWhthday(-1)), for the subsequent milling step; (iii) to reduce the electric energy requirement for the milling step (from 23,880 to 3580kWhelday(-1)); (iv) to produce extra electrical energy of 8483kWhelday(-1); (v) to improve the reduction of waste streams generated (from 13% to 54% of organic matter removal).

Pyrochars from bioenergy residue as novel bio-adsorbents for lignocellulosic hydrolysate detoxification.

The robust supramolecular structure of biomass often requires severe pretreatments conditions to produce soluble sugars. Nonetheless, these processes generate some inhibitory compounds (i.e. furans compounds and aliphatic acids) deriving mainly from sugars degradation. To avoid the inhibition of the biological process and to obtain satisfactory sugars conversion level into biofuels, a detoxification step is required. This study investigates the use of two pyrochars derived from solid anaerobic digestates for the detoxification of lignocellulosic hydrolysates. At a pyrochar concentration of 40gL(-1), more than 94% of 5-HMF and 99% of furfural were removed in the synthetic medium after 24h of contact time, whereas sugars concentration remained unchanged. Furfural was adsorbed faster than 5-HMF by both pyrochars and totally removed after 3h of contact. Finally, the two pyrochars were found efficient in the detoxification of corn stalks and Douglas fir wood chips hydrolysates without affecting the soluble sugars concentrations.

One-Pot dry chemo-mechanical deconstruction for bioethanol production from sugarcane bagasse.

The aim of this study was the application of an innovative dry chemo-mechanical pretreatment using different mechanical stresses to produce bioethanol from sugarcane bagasse (SB). The effect of different milling methods on physicochemical composition, enzymatic hydrolysis, bioethanol production and energy efficiency was also evaluated. SB was pretreated with NaOH and H3PO4 at high materials concentration (5 kg/L). Results indicate that vibratory milling (VBM) was more effective in the reduction of particles size and cellulose crystallinity compared to centrifugal (CM) and ball (BM) milling. NaOH pretreatment coupling to BM and VBM was preferred to enhance glucose yields and bioethanol production, while CM consumed less energy compared to BM and VBM. Moreover, the highest energy efficiency (η=0.116 kg glucose/kWh) was obtained with NaOH-CM. Therefore, the combination of dry NaOH and CM appears the most suitable and interesting pretreatment for the production of bioethanol from SB.

Do furanic and phenolic compounds of lignocellulosic and algae biomass hydrolyzate inhibit anaerobic mixed cultures? A comprehensive review.

Nowadays there is a growing interest on the use of both lignocellulosic and algae biomass to produce biofuels (i.e. biohydrogen, ethanol and methane), as future alternatives to fossil fuels. In this purpose, thermal and thermo-chemical pretreatments have been widely investigated to overcome the natural physico-chemical barriers of such biomass and to enhance biofuel production from lignocellulosic residues and, more recently, marine biomass (i.e. macro and microalgae). However, the pretreatment technologies lead not only to the conversion of carbohydrate polymers (ie cellulose, hemicelluloses, starch, agar) to soluble monomeric sugar (ie glucose, xylose, arabinose, galactose), but also the generation of various by-products (i.e. furfural and 5-HMF). In the case of lignocellulosic residues, part of the lignin can also be degraded in lignin derived by-products, mainly composed of phenolic compounds. Although the negative impact of such by-products on ethanol production has been widely described in literature, studies on their impact on biohydrogen and methane production operated with mixed cultures are still very limited. This review aims to summarise and discuss literature data on the impact of pre-treatment by-products on H2-producing dark fermentation and anaerobic digestion processes when using mixed cultures as inoculum. As a summary, furanic (5-HMF, furfural) and phenolic compounds were found to be stronger inhibitors of the microbial dark fermentation than the full anaerobic digestion process. Such observations can be explained by differences in process parameters: anaerobic digestion is performed with more complex mixed cultures, lower substrate/inoculum and by-products/inoculum ratios and longer batch incubation times than dark fermentation. Finally, it has been reported that, during dark fermentation process, the presence of by-products could lead to a metabolic shift from H2-producing pathways (i.e. acetate and butyrate) to non-H2-producing pathways (i.e. lactate, ethanol and propionate) and whatever the metabolic route, metabolites can be all further converted into methane, but at different rates.

Enzymatic and metabolic activities of four anaerobic sludges and their impact on methane production from ensiled sorghum forage.

Biochemical methane potential (BMP) tests were run on ensiled sorghum forage using four inocula (urban, agricultural, mixture of agricultural and urban, granular) and differences on their metabolic and enzymatic activities were also discussed. Results indicate that no significant differences were observed in terms of BMP values (258±14NmLCH4g(-1)VS) with a slightly higher value when agricultural sludge was used as inoculum. Significant differences can be observed among different inocula, in terms of methane production rate. In particular the fastest biomethanization occurred when using the urban sludge (hydrolytic kinetic constant kh=0.146d(-1)) while the slowest one was obtained from the agricultural sludge (kh=0.049d(-1)). Interestingly, positive correlations between the overall enzymatic activities and methane production rates were observed for all sludges, showing that a high enzymatic activity may favour the hydrolysis of complex substrate and accelerate the methanization process of sorghum.

Benefit of sodium hydroxide pretreatment of ensiled sorghum forage on the anaerobic reactor stability and methane production.

The assessment of the pretreatment effect on the anaerobic digestion process is generally based on the results of batch tests, which may fail in truly predicting full-scale anaerobic reactors performance. Therefore, in this study, the effect of alkaline pretreatment on the anaerobic digestion of ensiled sorghum forage was evaluated by comparing the results of two semi-continuous CSTR (Continuously Stirred Tank Reactor) anaerobic reactors. Results showed that an alkaline pretreatment step, prior to the anaerobic digestion of ensiled sorghum forage, can have a beneficial effect both in enhancing methane production (an increase of 25% on methane production was observed, if compared to that of untreated sorghum) and in giving more stability to the anaerobic digestion process.

Sodium hydroxide pretreatment of ensiled sorghum forage and wheat straw to increase methane production.

The aim of this study was to determine the effect of sodium hydroxide pretreatment on the chemical composition and the methane production of ensiled sorghum forage and wheat straw. NaOH pretreatment was conducted in closed bottles, at 40 °C for 24 h. Samples were soaked in a NaOH solution at different dosages (expressed in terms of total solids (TS) content) of 1 and 10% gNaOH/gTS, with a TS concentration of 160 gTS/L. At the highest NaOH dosage the reduction of cellulose, hemicelluloses and lignin was 31, 66 and 44%, and 13, 45 and 3% for sorghum and wheat straw, respectively. The concentration of soluble chemical oxygen demand (CODs) in the liquid phase after the pretreatment was also improved both for wheat straw and sorghum (up to 24 and 33%, respectively). Total sugars content increased up to five times at 10% gNaOH/gTS with respect to control samples, suggesting that NaOH pretreatment improves the hydrolysis of cellulose and hemicelluloses. The Biochemical Methane Potential (BMP) tests showed that the NaOH pretreatment favoured the anaerobic degradability of both substrates. At 1 and 10% NaOH dosages, the methane production increased from 14 to 31% for ensiled sorghum forage and from 17 to 47% for wheat straw. The first order kinetic constant increased up to 65% for sorghum and up to 163% for wheat straw.