Because biomass is a widely available, renewable resource, its utilisation for the production of energy has great potential for reducing CO2 emissions and thereby preventing global warming. In this mini-review the `state of the art' of several fermentation processes is discussed, starting with the most advanced process of ethanol production. This is followed by methane production, an established process for waste water purification which is gaining more attention because of the inherent energy production. Subsequently ABE fermentation is discussed and finally the biological production of hydrogen. The last section proposes a new way to assess and compare the different processes by relating their merit to `work content' values and `lost work' instead of the combustion values of their products. It is argued that, especially when dealing with energy from biomass, the application of this methodology will provide a uniform valuation for different processes and products. The described fermentation processes enable the supply of pure energy carriers, either gaseous or liquid, from biomass, yet the introduction of these processes is hampered by two major problems. The first is related to technological shortcomings in the mobilisation of fermentable components from the biomass. The second, having a much greater impact, is linked with socio-economics: until full externality costs are attributed to fossil fuels, accounting for their role in pollution and global warming, the competitiveness of the processes described here will hardly stand a chance.

Utilisation of biomass for the supply of energy carriers

The biological production of hydrogen from the fermentation of different substrates was examined in batch tests using heat-shocked mixed cultures with two techniques: an intermittent pressure release method (Owen method) and a continuous gas release method using a bubble measurement device (respirometric method). Under otherwise identical conditions, the respirometric method resulted in the production of 43% more hydrogen gas from glucose than the Owen method. The lower conversion of glucose to hydrogen using the Owen protocol may have been produced by repression of hydrogenase activity from high partial pressures in the gastight bottles, but this could not be proven using a thermodynamic/rate inhibition analysis. In the respirometric method, total pressure in the headspace never exceeded ambient pressure, and hydrogen typically composed as much as 62% of the headspace gas. High conversion efficiencies were consistently obtained with heat-shocked soils taken at different times and those stored for up to a month. Hydrogen gas composition was consistently in the range of 60-64% for glucose-grown cultures during logarithmic growth but declined in stationary cultures. Overall, hydrogen conversion efficiencies for glucose cultures were 23% based on the assumption of a maximum of 4 mol of hydrogen/ mol of glucose. Hydrogen conversion efficiencies were similar for sucrose (23%) and somewhat lower for molasses (15%) but were much lower for lactate (0.50%) and cellulose (0.075%).

Biological hydrogen production measured in batch anaerobic respirometers

Perspectives on anaerobic membrane bioreactor treatment of domestic wastewater: a critical review.

A mathematical model is developed to describe the dynamic behavior of mesophilic (35 +/- 5 degrees C) and thermophilic digestion (55 +/- 5 degrees C) Special emphasis is given to acetotrophic methanogenesis and propionate degradation, as the steps that determine the stability of anaerobic digestion, as well as to hydrolysis rate, which determines the degradation efficiency of particulate degradable organic carbon Within the range of 6-20 (mesophilic) and 2-8 d (thermophilic) hydraulic retention time (HRT), the observed maximum growth rates for acetotrophic methanogens are 033 and 13 d(-1), respectively, with a 15% decay rate Temperature and pH dependence as well as ammonia inhibition of acetate and propionate conversion are determined and included in the model, which allows us to simulate the effect of protein- and nitrogen-rich waste addition and the consequences of temporarily increased free ammonia at high pH No inhibition of hydrogen conversion was observed in the same free ammonia range The pH optimum is between 66 and 73 Acetotrophic methanogenesis is strongly inhibited below pH 62, whereas above pH 74 it can be inhibited by free ammonia For digesters fed with ordinary municipal sewage sludge, free ammonia inhibition of acetate conversion leads to an increase in acetate at about 35 and 140 mg of N/L for mesophilic (HRT = 20 d) and thermophilic (HRT = 6 d) conditions, respectively The hydrolysis rate constant is 025 and 04 d(-1) respectively for these two conditions The model is validated with load variation experiments in laboratory and full-scale digesters for step and shock loads

Mathematical model for meso- and thermophilic anaerobic sewage sludge digestion.

Substrate and product inhibition of hydrogen production during sucrose fermentation by the extremely thermophilic bacterium Caldicellulosiruptor saccharolyticus was studied. The inhibition kinetics were analyzed with a noncompetitive, nonlinear inhibition model. Hydrogen was the most severe inhibitor when allowed to accumulate in the culture. Concentrations of 5-10 mM H2 in the gas phase ( partial hydrogen pressure (pH2) of (1-2) · 104 Pa) initiated a metabolic shift to lactate formation. The extent of inhibition by hydrogen was dependent on the density of the culture. The highest tolerance for hydrogen was found at low volumetric hydrogen production rates, as occurred in cultures with low cell densities. Under those conditions the critical hydrogen concentration in the gas phase was 27.7 mM H2 ( pH2 of 5.6 · 104 Pa); above this value hydrogen production ceased completely. With an efficient removal of hydrogen sucrose fermentation was mainly inhibited by sodium acetate. The critical concentrations of sucrose and acetate, at which growth and hydrogen production was completely inhibited (at neutral pH and 70°C), were 292 and 365 mM, respectively. Inorganic salts, such as sodium chloride, mimicked the effect of sodium acetate, implying that ionic strength was responsible for inhibition. Undissociated acetate did not contribute to inhibition of cultures at neutral or slightly acidic pH. Exposure of exponentially growing cultures to concentrations of sodium acetate or sodium chloride higher than ca. 175 mM caused cell lysis, probably due to activation of autolysins. © 2003 Wiley Periodicals, Inc. Biotechnol Bioeng 81: 255-262, 2003. (Less)

/pdf/substrate-and-product-inhibition-of-hydrogen-production-by-z03xmuud8p.pdf

Substrate and product inhibition of hydrogen production by the extreme thermophile caldicellulosiruptor saccharolyticus

The experimental validation of on-line estimation of multiple specific growth rates for the bakers' yeast fed-batch process is presented. Pole placement based parameter estimation combined with an asymptotic biomass observer constitute the basic algorithm. The full process model being ill-conditioned for estimation using the available measured state variables, the use of two partial models related to two different states of the process is suggested. An alternating procedure between two sets of estimation algorithms designed from the partial models is proposed. The performance of the alternating procedure is validated both with simulated and experimental data. The accuracy of the estimates of the three specific growth rates involved in this process is verified according to two criteria based on the respiratory quotient and on the evaluation of the ethanol production/consumption rate.

Estimation of multiple specific growth rates: Experimental validation

Processand Hydrogen in the Biomethanation Processes: Inevitable Transfer Limitations of Liquid-to-Gas Mass Transfer in Anaerobic

Liquid-to-gas mass transfer in anaerobic processes was investigated theoretically and experimentally. By using the classical definition of kLa, the global volumetric mass transfer coefficient, theoretical development of mass balances in such processes demonstrates that the mass transfer of highly soluble gases is not limited in the usual conditions occurring in anaerobic fermentors (low-intensity mixing). Conversely, the limitation is important for poorly soluble gases, such as methane and hydrogen. The latter could be overconcentrated to as much as 80 times the value at thermodynamic equilibrium. Such overconcentrations bring into question the biological interpretations that have been deduced solely from gaseous measurements. Experimental results obtained in three different methanogenic reactors for a wide range of conditions of mixing and gas production confirmed the general existence of low mass transfer coefficients and consequently of large overconcentrations of dissolved methane and hydrogen (up to 12 and 70 times the equilibrium values, respectively). Hydrogen mass transfer coefficients were obtained from the direct measurements of dissolved and gaseous concentrations, while carbon dioxide coefficients were calculated from gas phase composition and calculation of related dissolved concentration. Methane transfer coefficients were based on calculations from the carbon dioxide coefficients. From mass balances performed on a gas bubble during its simulated growth and ascent to the surface of the liquid, the methane and carbon dioxide contents in the gas bubble appeared to be controlled by the bubble growth process, while the bubble ascent was largely responsible for a slight enrichment in hydrogen.

Liquid-to-Gas Mass Transfer in Anaerobic Processes: Inevitable Transfer Limitations of Methane and Hydrogen in the Biomethanation Process

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Estimation of multiple specific growth rates: Experimental validation

Processand Hydrogen in the Biomethanation Processes: Inevitable Transfer Limitations of Liquid-to-Gas Mass Transfer in Anaerobic

Liquid-to-Gas Mass Transfer in Anaerobic Processes: Inevitable Transfer Limitations of Methane and Hydrogen in the Biomethanation Process