Syngas biomethanation: In a transfer limited process, is CO inhibition an issue?

Syngas biomethanation is a promising technology in the process chain converting wastes to methane. However, gas-liquid mass transfer is a limiting factor of the biomethanation process. To reach high methane productivity, increasing the pressure is an interesting strategy to improve mass transfer. However, the CO content in the syngas raises concerns about a potential inhibition of the microorganisms. Therefore, the aim of the research was to assess the ability to work at high CO partial pressures. In this regard, a pressurized continuous stirred column with a working volume of 10L was implemented and a consortium adapted for syngas-biomethanation for 22 months was submitted to 100% CO and increasing pressure. No inhibition phenomenon was observed for logarithmic PCO as high as 1.8 bar (inlet pressure 5.0 bar), which was the first time that such a high CO partial pressure was tested in continuous mode. Mass transfer limitations allowed for the carboxydotrophic microorganisms to consume CO faster than it was transferred, allowing for the dissolved CO concentration to remain under inhibitory concentrations. These results question the habitual consensus that CO inhibition is a limiting factor of syngas biomethanation.

Syngas biomethanation: Study of process performances at high syngas flow rate in pressurized stirred column.

Syngas biomethanation is a promising technology for waste to energy conversion. However, it had not yet been tested at high syngas flow rates. The aim of this study was to assess the possibility for syngas biomethanation to reach high methane productivity at higher syngas inflow rate. A pressurized stirred column was implemented. The syngas inflow rate was gradually increased, and two different increase strategies were compared. The highest methane productivity achieved yet with syngas-biomethanation was obtained, with 23.2 LCH4/L/d, with high conversion efficiencies of 89% for H2 and 82% for CO. The mass transfer performances of the process were investigated, and the existence of a biological enhancement factor was observed. Considering an enhancement factor in bioprocesses is a pioneering concept that could change the way we design bioreactor to improve mass transfer. The high methane productivity obtained in this study paves the way for the process industrialization.

Sulfur transformations during two-stage anaerobic digestion and intermediate thermal hydrolysis.

The formation of hydrogen sulfide (H2S) during anaerobic digestion (AD) imposes constraints on the valorisation of biogas. So far, inorganic sulfur compounds -mainly sulfate - have been considered as the main contributors to H2S formation, while the contribution of organic sulfur compounds is mostly neglected. This study investigates the fate of organic and inorganic sulfur compounds during two-stage anaerobic digestion with intermediate thermal hydrolysis for treatment of primary and secondary sludge in a WWTP treating domestic wastewater. The results of a seven-week monitoring campaign showed an overall decrease of organic sulfur compounds in both stages of anaerobic digestion. Further fractionation of organic sulfur revealed a high conversion of the particulate organic fraction during the first digestion stage and of the soluble organic fraction during the second digestion stage. The decrease of soluble organic sulfur during the second digestion stage was attributed to the solubilisation and hydrolysis of sulfur-containing organic compounds during thermal hydrolysis. In both digestion stages, more organic sulfur was taken up than particulate inorganic sulfur (metal sulfide) was produced, indicating the formation of other reduced sulfur forms (e.g. H2S). Further batch experiments confirmed the role of organic sulfur uptake in the formation of H2S during anaerobic digestion as sulfate reduction only partly explained the total sulfide formed (H2S in biogas and precipitated FeS). Overall, the conversion of organic sulfur was demonstrated to play a major role in H2S formation (and thus the biogas quality), especially in case of thermal hydrolysis pretreatment.

Plant-wide investigation of sulfur flows in a water resource recovery facility (WRRF).

Even though sulfur compounds and their transformations may strongly affect wastewater treatment processes, their importance in water resource recovery facilities (WRRF) operation remains quite unexplored, notably when it comes to full-scale and plant-wide characterization. This contribution presents a first-of-a-kind, plant-wide quantification of total sulfur mass flows for all water and sludge streams in a full-scale WRRF. Because of its important impact on (post-treatment) process operation, the gaseous emission of sulfur as hydrogen sulfide (H2S) was also included, thus enabling a comprehensive evaluation of sulfur flows. Data availability and quality were optimized by experimental design and data reconciliation, which were applied for the first time to total sulfur flows. Total sulfur flows were successfully balanced over individual process treatment units as well as the plant-wide system with only minor variation to their original values, confirming that total sulfur is a conservative quantity. The two-stage anaerobic digestion with intermediate thermal hydrolysis led to a decreased sulfur content of dewatered sludge (by 36%). Higher (gaseous) H2S emissions were observed in the second-stage digester (42% of total emission) than in the first one, suggesting an impact of thermal treatment on the production of H2S. While the majority of sulfur mass flow from the influent left the plant through the treated effluent (> 95%), the sulfur discharge through dewatered sludge and gaseous emissions are critical. The latter are indeed responsible for odour nuisance, lower biogas quality, SO2 emissions upon sludge combustion and corrosion effects.

"Biomethanation of syngas by enriched mixed anaerobic consortium in pressurized agitated column".

In a circular economy approach, heterogeneous wastes can be upgraded to energy in the form of syngas via pyrogasification, and then to methane via biomethanation. Working at high pressure is a promising approach to intensify the process and to reduce gas-liquid transfer limitations. However, raising the pressure could lead to reaching the CO inhibition threshold of the microorganisms involved in syngas-biomethanation. To investigate the impact on pressure on the process, a 10L continuous stirred tank reactor working at 4 bars and 55 °C was implemented. Syngas (40% CO, 40% H2, 20% CO2) biomethanation was performed successfully and methane productivity as high as 6.8 mmolCH4/Lreactor/h with almost full conversion of CO (97%) and H2 (98%) was achieved. CO inhibition was investigated and carboxydotrophs appeared less resistant to high CO exposition than methanogens.

Characterization of municipal biowaste categories for their capacity to be converted into a feedstock aqueous slurry to produce methane by anaerobic digestion.

Biowaste material is a good candidate for the production of energy in urban territories. The presence of undesirable or constituents mixed with the biowaste collected by municipalities makes it difficult to recycle organic matter of sufficient quality for agricultural uses. Methane production is particularly attractive for energy recovery notably because this energy vector can be distributed using the grid already in place for natural gas in many cities. Depending on the origin and biochemical composition of biowaste, methane can be produced using thermochemical (gasification then syngas methanation) or biological processes (anaerobic digestion). The objective of this work was to characterize the ability of biowaste to be used as a feedstock for anaerobic digestion. Based on considerations such as the quantities produced and the availability, four categories of biowaste produced in the city of Lyon were identified as potential key resources: Garden biowaste (GBW), restauration biowaste (RBW), household biowaste (HBW) and supermarkets biowaste (SMBW). Representative samples were taken from the sites of production and analyzed for parameters including biomethane potential (BMP). Each sample was then fractioned by leaching and the distribution of the BMP between the particulate fraction and the readily soluble fraction was assessed. GBW organic matter exhibited high hemicellulose content (over 81% of VS) and a low BMP which was very poorly distributed into its soluble fraction (2 NL·kgTS-1). RBW, HBW and SMBW showed a much higher BMP with a strong distribution in the soluble fraction (100 NL·kgTS-1). Plastic materials were found to account for up to 40% of the mass of SMBW sample. Altogether, GBW was identified as non-favorable for anaerobic digestion and recommended rather for thermochemical conversion. HBW, RBW and SMBW revealed adapted to anaerobic. Pulping was shown to be applicable in order to convert the 3 biowaste materials into a pumpable slurry with high biomethane potential.

The hydrolytic stage in high solids temperature phased anaerobic digestion improves the downstream methane production rate.

The role of the hydrolytic stage in high solids temperature phased anaerobic digestion was investigated with a mixture of cattle slurry and maize silage with variable ratios (100, 70 and 30% volatile solids coming from cattle slurry). It was incubated for 48 h at 37, 55, 65 and 72 °C. Soluble chemical oxygen demand and biochemical methane potential were measured at 0, 24 and 48 h. Higher temperatures improved the amount of solubilized COD, which confirmed previously reported results. Nevertheless, solubilization mostly took place during the first 24 h. The rate of methane production in post-hydrolysis BMPs increased after 48 h hydrolysis time, but not after 24 h. The first order kinetic constant rose by 40% on average. No correlation was observed between soluble COD and downstream methane production rate, indicating a possible modification of the physical structure of the particulate solids during the hydrolytic stage.

Hydrodynamics of high solids anaerobic reactor: Characterization of solid segregation and liquid mixing pattern in a pilot plant VALORGA facility under different reactor geometry.

One of the main problems of dry anaerobic digestion plants treating urban solid waste is the loss of useful volume by the sedimentation of solids (inerts) into the bottom of the digester, or by accumulation of floating materials in its upper part. This entails a periodic cost of emptying and cleaning the digesters, a decrease in biogas production and complications in maintenance. Usually the sedimentation is a consequence of the heterogeneity of waste that, in addition to organic matter, drags particles of high density that end up obstructing the digesters. To reduce this bottleneck, URBASER has designed a new configuration of VALORGA reactor. That is, the VALORGA central wall has been removed and an inclined bottom has been added. To test the sedimentability and the overall performance of both configurations (current and new design), hydrodynamic tests have been carried out in a pilot digester (digester of 95 m3 capacity). To simulate the liquid phase and the solid phase of the reactor, lithium tracers and tags of different densities with RFID (radio frequency identification reader) have been used respectively. The results of the study showed an improvement in the performance of the new reactor design at pilot level.

Characterization of selected municipal solid waste components to estimate their biodegradability.

Biological treatments of Residual Municipal Solid Waste (RMSW) allow to divert biodegradable materials from landfilling and recover valuable alternative resources. The biodegradability of the waste components needs however to be assessed in order to design the bioprocesses properly. The present study investigated complementary approaches to aerobic and anaerobic biotests for a more rapid evaluation. A representative sample of residual MSW was collected from a Mechanical Biological Treatment (MBT) plant and sorted out into 13 fractions according to the French standard procedure MODECOM™. The different fractions were analyzed for organic matter content, leaching behavior, contents in biochemical constituents (determined by Van Soest's acid detergent fiber method), Biochemical Oxygen Demand (BOD) and Bio-Methane Potential (BMP). Experimental data were statistically treated by Principal Components Analysis (PCA). Cumulative oxygen consumption from BOD tests and cumulative methane production from BMP tests were found to be positively correlated in all waste fractions. No correlation was observed between the results from BOD or BMP bioassays and the contents in cellulose-like, hemicelluloses-like or labile organic compounds. No correlation was observed either with the results from leaching tests (Soluble COD). The contents in lignin-like compounds, evaluated as the non-extracted RES fraction in Van Soest's method, was found however to impact negatively the biodegradability assessed by BOD or BMP tests. Since cellulose, hemicelluloses and lignin are the polymers responsible for the structuration of lignocellulosic complexes, it was concluded that the structural organization of the organic matter in the different waste fractions was more determinant on biodegradability than the respective contents in individual biopolymers.

Understanding the contribution of biofilm in an integrated fixed-film-activated sludge system (IFAS) designed for nitrogen removal.

The objective of this study is to improve knowledge on the integrated fixed-film-activated sludge (IFAS) system designed for nitrogen removal. Biofilm growth and its contribution to nitrification were monitored under various operating conditions in a semi-industrial pilot-scale plant. Nitrification rates were observed in biofilms developed on free-floating media and in activated sludge operated under a low sludge retention time (4 days) and at an ammonia loading rate of 45-70 gNH4-N/kgMLVSS/d. Operational conditions, i.e. oxygen concentration, redox potential, suspended solids concentration, ammonium and nitrates, were monitored continuously in the reactors. High removal efficiencies were observed for carbon and ammonium at high-loading rate. The contribution of biofilm to nitrification was determined as 40-70% of total NOx-N production under the operating conditions tested. Optimal conditions to optimize process compacity were determined. The tested configuration responds especially well to winter and summer nitrification conditions. These results help provide a deeper understanding of how autotrophic biomass evolves through environmental and operational conditions in IFAS systems.

Rapid measurement of the yield stress of anaerobically-digested solid waste using slump tests.

The anaerobic digestion of solid waste is usually performed using dry or semi-dry technology. Incoming waste and fermenting digestate are pasty media and thus, at the industrial scale, their suitability for pumping and mixing is a prerequisite at the industrial scale. However, their rheology has been poorly characterised in the literature because there is no suitable experimental system for analysing heterogeneous media composed of coarse particles. We have developed a practical rheometrical test, a "slump test", for the analysis of actual digested solid waste. It makes it possible to estimate yield stress from the final slump height. From the slump behavior, we conclude that digestates behave as visco-elastic materials. The yield stress of different digested waste was measured between 200 and 800Pa. We show that the media containing smaller particles or with higher moisture content are characterised by smaller yield stresses. This study thus demonstrates the impact of the origin of the digestate on the yield stress.

Dry anaerobic digestion in batch mode: design and operation of a laboratory-scale, completely mixed reactor.

A laboratory-scale (40 l) reactor was designed to investigate dry anaerobic digestion. The reactor is equipped with an intermittent paddle mixer, enabling complete mixing in the reactor. Three consecutive batch dry digestion tests of municipal solid waste were performed under mesophilic conditions and compared to operation results obtained on a pilot-scale (21 m(3)) with the same feedstock. Biogas and methane production at the end of the tests were similar (around 200 m(3) CH(4)STP/tVS), and the dynamics of methane production and VFA accumulation concurred. However, the maximal levels of VFA transitory accumulation varied between reactors and between runs in a same reactor. Ammonia levels were similar in both reactors. These results show that the new reactor accurately imitates the conditions found in larger ones. Adaptation of micro-organisms to the waste and operating conditions was also pointed out along the consecutive batches.

A procedure to estimate proximate analysis of mixed organic wastes.

In waste materials, proximate analysis measuring the total concentration of carbohydrate, protein, and lipid contents from solid wastes is challenging, as a result of the heterogeneous and solid nature of wastes. This paper presents a new procedure that was developed to estimate such complex chemical composition of the waste using conventional practical measurements, such as chemical oxygen demand (COD) and total organic carbon. The procedure is based on mass balance of macronutrient elements (carbon, hydrogen, nitrogen, oxygen, and phosphorus [CHNOP]) (i.e., elemental continuity), in addition to the balance of COD and charge intensity that are applied in mathematical modeling of biological processes. Knowing the composition of such a complex substrate is crucial to study solid waste anaerobic degradation. The procedure was formulated to generate the detailed input required for the International Water Association (London, United Kingdom) Anaerobic Digestion Model number 1 (IWA-ADM1). The complex particulate composition estimated by the procedure was validated with several types of food wastes and animal manures. To make proximate analysis feasible for validation, the wastes were classified into 19 types to allow accurate extraction and proximate analysis. The estimated carbohydrates, proteins, lipids, and inerts concentrations were highly correlated to the proximate analysis; correlation coefficients were 0.94, 0.88, 0.99, and 0.96, respectively. For most of the wastes, carbohydrate was the highest fraction and was estimated accurately by the procedure over an extended range with high linearity. For wastes that are rich in protein and fiber, the procedure was even more consistent compared with the proximate analysis. The new procedure can be used for waste characterization in solid waste treatment design and optimization.

High-solids anaerobic digestion: comparison of three pilot scales.

Two experiments were undertaken in three different experimental set-ups in order to compare them: an industrial 21-m3 pilot reactor, a new 40-l laboratory pilot reactor and bmp type plasma bottles. Three consecutive batch dry digestion tests of municipal solid waste were performed under mesophilic conditions with the same feedstock in all vessels. Biogas and methane production at the end of the tests were similar (around 200 m3 CH4STP/tVS) for both pilot reactors and were different from the bottle tests. The dynamics of methane production and VFA accumulation concurred. However, the maximal levels of VFA transitory accumulation varied between reactors and between runs in a same reactor. Ammonia levels were similar in both reactors. These results show that the new reactor accurately imitates the conditions found in the larger one. Adaptation of microorganisms to the waste and operating conditions was also pointed out along the consecutive batches. Thermophilic semi-continuous tests were performed in both reactors with similar conditions. The methane production efficiencies were similar.

Towards new indicators for the prediction of solid waste anaerobic digestion properties.

The biochemical composition can be seen as a good indicator of both the biodegradability and the methane potential of a given waste. The work presented here is an attempt to elaborate a typology of wastes and to compare it to the anaerobic degradation characteristics. The first data indicate that there is a link between the ligno-cellulosic content of the waste and the biodegradability. When dealing with application to anaerobic digestion processes, having a tool to predict the ability of the waste to be degraded could be of the greatest interest for preventing failures, estimating biogas production, methane content, or for the management of co-digestion processes.

Anaerobic digestion of dairy wastewater by inverse fluidization: the inverse fluidized bed and the inverse turbulent bed reactors.

This paper describes the application of the inverse fluidization technology to the anaerobic digestion of dairy wastewater. Two reactors were investigated: the inverse fluidized bed reactor and the inverse turbulent reactor. In these reactors, a granular floating solid is expanded by a down-flow current of effluent or an up-flow current of gas, respectively. The carrier particles (Extendospheres) were chosen for their large specific surface area (20,000 m2m(-3)) and their low energy requirements for fluidization (gas velocity of 1.5 mm s(-1), 5.4 m h(-1)). Organic load was increased stepwise by reducing hydraulic retention time from more than 60 days to 3 days, while maintaining constant the feed COD concentration. Both reactors achieved more than 90% of COD removal, at an organic loading rate of 10-12 kgCOD m(-3) d(-1), respectively. The performances observed were similar or even higher than that of other previously tested fluidized bed technologies treating the same wastewater. It was found that the main advantages of this system are: low energy requirement, because of the low fluidization velocities required; there is no need of a settling device, because solids accumulate at the bottom of the reactor, so they can be easily drawn out and particles with high-biomass content can be easily recovered. Lipid phosphate concentration has been revealed as a good method for biomass estimation in biofilms since it only includes living biomass.

Model based prediction of the clogging of an anaerobic fixed bed reactor.

This paper presents the use of nonlinear constrained optimization techniques in order to detect and evaluate the degree of clogging in an anaerobic fixed bed reactor. First, experimental results show that the validity of a mass balance model can degrade over the time. Using the available model of the process and nonlinear constrained optimization tools, it is established that these changes can be due to the decrease of the liquid volume into the reactor while the mean values of biomass concentrations increase, leading to the clogging of the reactor. These theoretical results are confirmed experimentally in evaluating the hydraulic retention time of the reactor using a tracer.

Influence of biomass accumulation on bed expansion characteristics of a down-flow anaerobic fluidized-bed reactor.

This article describes the bed expansion characteristics of a down-flow anaerobic fluidized bed reactor treating a synthetic wastewater. Experiments were carried out in a 0.08 m diameter and 1 m length PVC column. The carrier used was ground perlite (an expanded volcanic rock). Particles characteristics were 0.968 mm in diameter, specific density of 213 kg x m-3 and Umf (minimal fluidization velocity): 2.3 m x h-1. Experimental data of terminal velocities and bed expansion parameters at several biofilm thicknesses were compared to different models predicting the bed expansion of up-flow and down-flow fluidized beds. Measured bed porosities at different liquid superficial velocities for the different biofilm thicknesses were in agreement with the Richardson-Zaki model, when Ut (particle terminal velocity) and n (expansion coefficient) were calculated by linear regression of the experimental data. Terminal velocities of particles at different biofilm thicknesses calculated from experimental bed expansion data, were found to be much smaller than those obtained when Cd (drag coefficient) is determined from the standard drag curve (Lapple and Sheperd, 1940) or with others' correlations (Karamanev and Nikolov, 1992a,b). This difference could be explained by the fact that free-rising particles do not obey Newton's law for free-settling, as proposed by Karamanev and Nikolov (1992a,b) and Karamanev et al. (1996). In the present study, the same free-rising behavior was observed for all particles (densities between 213 and 490 kg x m-3).

Mixing and phase hold-ups variations due to gas production in anaerobic fluidized-bed digesters: influence on reactor performance

The influence of mixing and phase hold-ups on gas-producing fluidized-bed reactors was investigated and compared with an ideal flow reactor performance (CSTR). The liquid flow in the anaerobic fluidized bed reactor could be described by the classical axially dispersed plug flow model according to measurements of residence time distribution. Gas effervescence in the fluidized bed was responsible for bed contraction and for important gas hold-up, which reduced the contact time between the liquid and the bioparticles. These results were used to support the modeling of large-scale fluidized-bed reactors. The biological kinetics were determined on a 180-L reactor treating wine distillery wastewater where the overall total organic carbon uptake velocity could be described by a Monod model. The outlet concentration and the concentration profile in the reactor appeared to be greatly influenced by hydrodynamic limitations. The biogas effervescence modifies the mixing characteristics and the phase hold-ups. Bed contraction and gas hold-up data are reported and correlated with liquid and gas velocities. It is shown that the reactor performance can be affected by 10% to 15%, depending on the mode of operation and recycle ratio used. At high organic loading rates, reactor performance is particularly sensitive to gas effervescence effects. Copyright 1998 John Wiley & Sons, Inc.

Comprehensive modeling of methanogenic biofilms in fluidized bed systems: Mass transfer limitations and multisubstrate aspects.

A cognitive model for anaerobic digestion in fluidized bed reactors is developed. The general pathway of the process is divided into five main reactions performed by different bacterial groups. Molecular diffusion of each substrate involved in the reaction scheme is described. Effectiveness factor calculations are performed in steady state for each bacterial group taken into account in the process. The case of a single substrate removal is discussed, and optimal biofilm sizes are found. Sequential substrate removal is investigated, and different kinetic regimes are characterized. The influence of biofilm size and primary substrate removal is discussed in the case of standard concentrations in the liquid phase. This study shows that, according to the theoretical model the limiting step of the process may be different and depends in a large way on mass transfer effects. Finally, importance of biofilm size is compared for acidogenic and methano-genic steps: each reaction is found to be optimized for different biofilm thicknesses. This result may be of interest for design purposes and further dynamic modeling. Concluding remarks concerning the validation of the model are made, and a comparison to experimental data from the literature is presented. (c) 1995 John Wiley & Sons, Inc.