Bio-Based Compounds from Grape Seeds: A Biorefinery Approach.

Food and agricultural waste represents a growing problem with negative effects on the economy, environment, and human health. Winemaking produces byproducts with high added value, which can be used for new productions in several application fields. From the perspective of biorefinery and circular economy, grape seeds could be exploited by extracting bioactive compounds with high added value before using biomass for energy purposes. The markets concerned are, in addition to the food, cosmetics, and pharmaceuticals sectors, which use bioactive compounds, the sector of biopolymeric materials and of energy for the production of biohydrogen and biomethane. Generally, bioactive components should be investigated through an integrated and multidisciplinary study approach based on emerging analytical techniques; in this context, attention is addressed towards green and sustainable procedures; an update of extraction techniques, innovative technologies, and chemometrics are described. Nowadays, processes so far tested on a pilot scale for grape waste are developed to enhance the extraction yields. Here, a picture of the Italian experience applied to the byproducts of the wine industry is given.

Biorefinery of cellulosic primary sludge towards targeted Short Chain Fatty Acids, phosphorus and methane recovery.

Cellulose from used toilet paper is a major untapped resource embedded in municipal wastewater which recovery and valorization to valuable products can be optimized. Cellulosic primary sludge (CPS) can be separated by upstream dynamic sieving and anaerobically digested to recover methane as much as 4.02 m3/capita·year. On the other hand, optimal acidogenic fermenting conditions of CPS allows the production of targeted short-chain fatty acids (SCFAs) as much as 2.92 kg COD/capita·year. Here propionate content can be more than 30% and can optimize the enhanced biological phosphorus removal (EBPR) processes or the higher valuable co-polymer of polyhydroxyalkanoates (PHAs). In this work, first a full set of batch assays were used at three different temperatures (37, 55 and 70 °C) and three different initial pH (8, 9 and 10) to identify the best conditions for optimizing both the total SCFAs and propionate content from CPS fermentation. Then, the optimal conditions were applied in long term to a Sequencing Batch Fermentation Reactor where the highest propionate production (100-120 mg COD/g TVSfed·d) was obtained at 37 °C and adjusting the feeding pH at 8. This was attributed to the higher hydrolysis efficiency of the cellulosic materials (up to 44%), which increased the selective growth of Propionibacterium acidopropionici in the fermentation broth up to 34%. At the same time, around 88% of the phosphorus released during the acidogenic fermentation was recovered as much as 0.15 kg of struvite per capita·year. Finally, the potential market value was preliminary estimated for the recovered materials that can triple over the conventional scenario of biogas recovery in existing municipal wastewater treatment plants.

Effect of enzymatic pretreatment of various lignocellulosic substrates on production of phenolic compounds and biomethane potential.

Pretreatment of lignocellulosic biomass is necessary to enhance the hydrolysis, which is the rate-limiting step in biogas production. Laccase and versatile peroxidase are enzymes known to degrade lignin. Therefore, the impact of enzymatic pretreatment was studied on a variety of biomass. A significant higher release in total phenolic compounds (TPC) was observed, never reaching the inhibiting values for anaerobic digestion. The initial concentration of TPC was higher in the substrates containing more lignin, miscanthus and willow. The anaerobic digestion of these two substrates resulted in a significant lower biomethane production (68.8-141.7 Nl/kg VS). Other substrates, corn stover, flax, wheat straw and hemp reached higher biomethane potential values (BMP), between 241 and 288 Nl/kg VS. Ensilaged maize reached 449 Nl/kg VS, due to the ensilation process, which can be seen as a biological and acid pretreatment. A significant relation (R(2) = 0.89) was found between lignin content and BMP.

Biogas production within the bioethanol production chain: Use of co-substrates for anaerobic digestion of sugar beet vinasse.

Bioethanol production generates large amounts of vinasse, which is suitable for biogas production. In this study, the anaerobic digestion of sugar beet vinasse was optimised using continuous stirred-tank reactors (CSTR) supplemented either with lime fertiliser or with 3% cow manure. In both reactors, the C/N ratio was adjusted by adding straw. The biochemical methane potential (BMP) of vinasse was 267.4±4.5LCH4kgVS(-1). Due to the low content of macro- and micronutrients and low C/N ratio of vinasse, biogas production failed when vinasse alone was fed to the reactor. When co-substrate was added, biogas production achieved very close to the BMP of vinasse, being 235.7±32.2LCH4kgVS(-1) from the fertiliser supplied reactor and 265.2±26.8LCH4kgVS(-1) in manure supplied reactor at steady state. Anaerobic digestion was the most stable when cow manure was supplied to digestion of vinasse.

Thermal pretreatment of olive mill wastewater for efficient methane production: control of aromatic substances degradation by monitoring cyclohexane carboxylic acid.

Anaerobic digestion is investigated as a sustainable depurative strategy of olive oil mill wastewater (OOMW). The effect of thermal pretreatment on the anaerobic biodegradation of aromatic compounds present in (OMWW) was investigated. The anaerobic degradation of phenolic compounds, well known to be the main concern related to this kind of effluents, was monitored in batch anaerobic tests at a laboratory scale on samples pretreated at mild (80±1 °C), intermediate (90±1 °C) and high temperature (120±1 °C). The obtained results showed an increase of 34% in specific methane production (SMP) for OMWW treated at the lowest temperature and a decrease of 18% for treatment at the highest temperature. These results were related to the different decomposition pathways of the lignocellulosic compounds obtained in the tested conditions. The decomposition pathway was determined by measuring the concentrations of volatile organic acids, phenols, and chemical oxygen demand (COD) versus time. Cyclohexane carboxylic acid (CHCA) production was identified in all the tests with a maximum concentration of around 200 µmol L(-1) in accordance with the phenols degradation, suggesting that anaerobic digestion of aromatic compounds follows the benzoyl-CoA pathway. Accurate monitoring of this compound was proposed as the key element to control the process evolution. The total phenols (TP) and total COD removals were, with SMP, the highest (TP 62.7%-COD 63.2%) at 80 °C and lowest (TP 44.9%-COD 32.2%) at 120 °C. In all cases, thermal pretreatment was able to enhance the TP removal ability (up to 42% increase).

A comparative synthesis and physicochemical characterizations of Ni/Al2O3-MgO nanocatalyst via sequential impregnation and sol-gel methods used for CO2 reforming of methane.

Carbon dioxide reforming of methane is an interesting route for synthesis gas production especially over nano-sized catalysts. The present research deals with catalyst development for dry reforming of methane with the aim of reaching the most stable catalyst. Effect of preparation method, one of the most significant variables, on the properties of the catalysts was taken in to account. The Ni/Al2O3-MgO catalysts were prepared via sol-gel and sequential impregnation methods and characterized with XRD, FESEM, EDAX, BET and FTIR techniques. The reforming reactions were carried out using different feed ratios, gas hourly space velocities (GHSV) and reaction temperatures to identify the influence of operational variables. FESEM images indicate uniform particle size distribution for the sample synthesized with sol-gel method. It has been found that the sol-gel method has the potential to improve catalyst desired properties especially metal surface enrichment resulting in catalytic performance enhancement. The highest yield of products was obtained at 850 degrees C for both of the catalysts. During the 10 h stability test, CH4 and CO2 conversions gained higher values in the case of sol-gel made catalyst compared to impregnated one.

Comparison of non-agitated and agitated batch, thermophilic anaerobic digestion of sugarbeet tailings.

Sugar beet tailings were anaerobically digested at non-agitated and agitated conditions in identical thermophilic batch reactors. The average methane yield in the agitated digester was only 74% of that in the non-agitated digester. Ninety percent of the ultimate methane yield was produced in approximately 5 days in the non-agitated digester whereas it took 12 days in agitated digester. Even upon using an active inoculum from non-agitated digester the methane rate and yield was low in the agitated digester. On the other hand when the poorly performing inoculum from the agitated digester was transferred to the non-agitated digester, its activity was immediately enhanced. The non-agitated digester harbored a diverse microbial community with phylotypes Methanoculleus and Methanosarcina being dominant methanogens. Methanosaeta was the only methanogen detected in the agitated digester. It also contained a hydrogen-producing bacterial phylotype Petrotoga in high proportion which was not detected in the other digester.

Biogas production from wheat straw in batch and UASB reactors: the roles of pretreatment and seaweed hydrolysate as a co-substrate.

This research evaluated biogas production in batch and UASB reactors from pilot-scale acid catalysed steam pretreated and enzymatic hydrolysed wheat straw. The results showed that the pretreatment was efficient and, a sugar yield of 95% was obtained. The pretreatment improved the methane yield (0.28 m(3)/kg VS(added)) by 57% compared to untreated straw. Treatment of the straw hydrolysate with nutrient supplementation in a UASB reactor resulted in a high methane production rate, 2.70 m(3)/m(3).d at a sustainable OLR of 10.4 kg COD/m(3).d and with a COD reduction of 94%. Alternatively, co-digestion of the straw and seaweed hydrolysates in a UASB reactor also maintained a stable anaerobic process and can thus reduce the cost of nutrients addition. We have shown that biogas production from wheat straw can be competitive by pretreatment, high methane production rate in UASB reactors and also by co-digestion with seaweed hydrolysate.

[Methanotrophs and their applications in environment treatment: a review].

Methanotrophs can oxidize methane, playing an important role in regulating methane emission, and gaining increasing attention by the researchers around the world. Two biological pathways are involved in methane oxidation, i.e., anaerobic oxidation and aerobic oxidation, which are governed by anaerobic and aerobic methanotrophs, respectively. In this paper, the research advances about methanotrophs were summarized, with the focus on the phylogeny and taxonomy of methanotrophs, the key enzymes responsible for the aerobic oxidation of methane, the microorganisms involved in the anaerobic oxidation of methane, and the mechanisms of microbial methane consumption. The application prospects of the two methane oxidizers in greenhouse gases removal, pollutants degradation, biological denitrification, and recovery of metals and sulfur compounds were also analyzed.

Start-up, steady state performance and kinetic evaluation of a thermophilic integrated anaerobic-aerobic bioreactor (IAAB).

Thermophilic treatment of palm oil mill effluent (POME) was studied in a novel integrated anaerobic-aerobic bioreactor (IAAB). The IAAB was subjected to a program of steady-state operation over a range of organic loading rate (OLR)s, up to 30 g COD/L day in order to evaluate its treatment capacity. The thermophilic IAAB achieved high chemical oxygen demand (COD), biochemical oxygen demand (BOD) and total suspended solids (TSS) removal efficiencies of more than 99% for OLR up to 18.5 g COD/L day. High methane yield of 0.32 LCH(4) (STP)/g COD(removed) with compliance of the final treated effluent to the discharge limit were achieved. This is higher than that of the mesophilic system due to the higher maximum specific growth rate (µ(max)) of the thermophilic microorganisms. Besides, coupling the model of Grau second order model (anaerobic system) with the model of Monod (aerobic system) will completely define the IAAB system.

The effect of particle size and thermal pre-treatment on the methane yield of four agricultural by-products.

One way to optimize methane production in anaerobic digestion plants is to substitute ligno-cellulosic by-products for crops traditionally used as energy sources. However, using these by-products requires introduction of a pre-treatment system to minimize energy input and maximize energy output for an improved net energy equation. In this study, four agricultural byproducts (wheat, barley, rice straw and maize stalks) underwent various mechanical and thermal treatments prior to anaerobic digestion including particle size reduction to 5.0, 2.0, 0.5, and 0.2 cm and heat application to 90 °C and 120 °C. Mechanical pre-treatment increased byproduct methane yields more than 80%; thermal pre-treatment improved yields more than 60% for wheat and barley straw. Pre-treating wheat straw improved methane yields most, regardless of whether the method was thermal or mechanical. An electric net energy balance was also completed to analyze the feasibility of the pre-treatments according to input and output of energy.

Recovery of methane-rich gas from solid-feed anaerobic digestion of ipomoea (Ipomoea carnea).

Studies are presented on new types of anaerobic digesters in which chopped or dry crushed Ipomoea carnea was fed without any other pretreatment, in an attempt to develop commercially viable means of utilizing the otherwise very harmful plant. Two types of solid-feed anaerobic digesters (SFADs) were studied. The first type had a single vessel in which the bottom 35% portion was separated from the top portion by a perforated PVC disk. The weed was charged from the top and inoculated with anaerobically digested cowdung-water slurry. The fermentation of the weed in the reactor led to the formation of volatile fatty acids (VFAs) plus some biogas. The leachate, rich in the VFAs, was passed through the perforated PVC sheet and collected in the lower portion of the vessel. The other type of reactors had two vessels, the first one was fully charged with the weed and the second received the VFA leachate. With both types were attached upflow anaerobic filters (UAFs) which converted the leachate into combustible biogas consisting of approximately 70% methane. All SFADs developed very consistent performance in terms of biogas yield within 17 weeks of start. The two-compartment reactors yielded significantly more biogas than the single-compartment reactors of corresponding total volume, and the reactors with which anaerobic filters (AF) were attached yielded more biogas than the ones without AF. The best performing units generated 2.41m(3) of biogas per m(3) of digester volume, as compared to 0.1-0.2m(3) of biogas, m(-3)d(-1), obtainable with conventional digesters. This indicates the viability of this technology. The spent weed can be vermicomposted directly to obtain good soil-conditioner cum fertilizer; earthworm Eudrilus eugeniae produced 540mg vermicast per animal every day, achieving near total conversion of feed to vermicast in 20 days. The proposed systems, thus, makes it possible to accomplish total utilization of ipomoea.

Noble metal catalysts for methane removal.

Using a bench-scale rig, the activities of Pt, Pd and Pt+Pd catalysts supported on gamma-Al(2)O(3) and on TiO(2) (anatase) for the complete oxidation of methane (300 ppmv) in air have been measured as a function of temperature; values of T(10), T(50) and T(90) together with the Arrhenius parameters (activation energy and pre-exponential factor) are reported. Pt is less active than Pd when deposited on the surface of the TiO(2), but more active when deposited on gamma-Al(2)O(3), however when combined, the Pt+Pd mixture is more active than either metal individually. The T(10) for Pt+Pd/gamma-Al(2)O(3) was being as low as 228 degrees C. The significance of the Arrhenius parameters, for metal containing catalysts is that they exhibit compensation with increasing activation energy, while securing a more rapid increase in conversion from 0% to 100% when the temperature is increased.

A new gypsum-based technique to reduce methane and phophorus release from sediments of eutrophied lakes: (gypsum treatment to reduce internal loading).

The release of nutrients from the sediment into the water column, i.e. internal nutrient loading, is an important problem in the restoration of eutrophied lakes. The ebullition of gases, mainly methane, has been identified as the key process in nutrient transportation in the internal loading. We studied whether methane production in lake sediment and the release of nutrients into the water column could be prevented by the addition of gypsum (CaSO4 x 2H2O). Three different gypsum products were examined in a controlled laboratory microcosm with a continuous water flow. The addition of gypsum (especially Fe-gypsum) into the sediment increased the redox potentials and reduced methane production and release of phosphorus from the sediments during an incubation period of 3 months. Gypsum evidently acted as a slow-releasing source of sulphate in sediment, which likely enhanced the activity of sulphate-reducing bacteria and improved the overall mineralisation rate of organic matter. The liberation of H2S and phosphate, which might be an undesired consequence of increased sulphate reduction rates was prevented by the application of Fe-containing gypsum likely as a result of the formation of pyrite and apatite minerals.