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.

"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.

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.

Experimental and theoretical assessment of the multi-domain flow behaviour in a waste body during leachate infiltration.

The optimisation of landfill operation is a key challenge for the upcoming years. A promising solution to improve municipal solid waste (MSW) management is the bioreactor technology. A meso-scale (around 1m(3)) experimental set-up was performed to study the effect of moisture control in low density conditions with different leachate injection operations and bioreactor monitoring including the use of a neutron probe. The moisture content distribution evolution demonstrates a multi-domain flow behaviour. A classic van Genuchten-Mualem description of the connected porosity proved insufficient to correctly describe the observed phenomena. A bimodal description of the connected porosity is proposed as solution and a connected/non-connected porosities numerical model was applied to the results. The model explains the experimental results reasonably well.

Long-term moisture measurements in large-scale bioreactor cells using TDR and neutron probes.

This paper investigates the measurement of moisture content in municipal solid waste using two different indirect techniques: neutron scattering and time-domain reflectometry (TDR). Therefore, six laboratory-scale landfill bioreactors were instrumented with both neutron and TDR probes; in addition to that a gravimetric moisture balance was established for each cell. Different leachate recirculation modes were applied to perform different wetting conditions. In a first step, both probes were calibrated based on the water balance from three cells presenting homogeneous water distributions and sufficient temporal moisture variations. The calibration functions were then used for temporal and spatial moisture monitoring of all six cells. The results show that both methods are sensitive to moisture variations and provide interesting information on the complexity of vertical flows within the municipal solid waste. Nevertheless, it appears that neutron scattering offers better accuracy at the laboratory scale.

Effect of leachate injection modes on municipal solid waste degradation in anaerobic bioreactor.

Three pilots simulated landfill bioreactors were used to investigate the effect of leachate injection modes on anaerobic digestion and biogas production from municipal solid waste. The technical modes used to increase waste moisture consisted of an initial saturation of the waste by flushing with leachate followed by a quick drainage, or weekly leachate injections with two different rates. The results confirmed that increasing moisture content is a key parameter to boost the biological reactions. Weekly leachate injection with high flow rate led to better results than the initial saturation of the waste in terms of biogas production kinetics. Water percolation was found to be an important factor to accelerate the degradation of solid waste. However, a modelling of the collected data by Gompertz model clearly showed that the intrinsic biogas potential determined on the initial solid waste was not reached with any of the progressive leachate injection modes.

Oxidation pathways for ozonation of azo dyes in a semi-batch reactor: a kinetic parameters approach.

In this study ozone and the H2O2/O3 oxidation system are used to decolorize aqueous solutions of Orange II (Or-II) and Acid Red 27 (AR-27). Investigations are carried out in a semi-batch bubble column reactor. A system of series-parallel reactions is proposed to describe the mechanism of dye oxidation. The stoichiometric ratio for the first reaction is found to be 1 mol dye per mol O3, while the overall ozone demand for both reactions one and two is found to be 5 and 6 moles for Or-II and AR-27 respectively. Molecular and radical kinetics are compared: a radical scavenger, t-butanol, can be added to ensure only the molecular reaction of ozone, or hydrogen peroxide can be supplied through a peristaltic pump, to initiate radical reactivity. Results reveal that colour removal is ensured by direct ozone attack. For both dyes, TOC removal efficiencies of 50 - 60 % are obtained by the action of the hydroxyl free radical. However, this is not improved by addition of H2O2, thus demonstrating that organic species alone ensure HO degrees radical production during ozonation. Both the mass transfer and the ozone reactivity with the dyes are considered to evaluate the kinetic parameters for the molecular pathway.

Taking mass transfer limitation into account during ozonation of pollutants reacting fairly quickly.

Various situations observed when oxidizing organic compounds via ozone in a semi-batch reactor are illustrated. The resistance to the transfer of ozone from gas to liquid is accounted for using the film model. The mass balances are numerically solved simultaneously within the reactor and within the film to produce time dependent profiles of concentrations, Hatta, enhancement and depletion factors. Firstly, theoretical profiles are exemplified for various kinetic regimes from slow to fast; reaction occurs either in the bulk, in the film or in both. This shows the drastic importance of the shapes of the gas concentration profiles both at the exit of the reactor and in the liquid phase - in determining the regime. Then, a typical example dealing with fumaric acid ozonation is shown. Firstly, the acid itself oxidizes rapidly producing an intermediate regime: part of the reaction occurs within the film, part within the bulk and the rate constant can be determined. Then, the by-products oxidize more slowly producing a typical regime: reaction occurs within the bulk, the concentration of dissolved ozone is almost 0 and the mass transfer coefficient can be determined. Finally, when all organics have oxidized, the self-decomposition of ozone governs a slow kinetic regime: the concentration of dissolved ozone is close to equilibrium.