Académique Documents
Professionnel Documents
Culture Documents
Available at www.sciencedirect.com
Article history: A fractional factorial design was carried out to investigate the effects of temperature, initial
Received 6 October 2008 pH and glucose concentration on fermentative hydrogen production by mixed cultures in
Received in revised form batch tests and then the experimental data of substrate degradation efficiency, hydrogen
20 November 2008 yield and average hydrogen production rate were described by a neural network, based on
Accepted 20 November 2008 which the simultaneous optimization of the three responses was performed by the method
Available online 23 December 2008 of desirability function. The analysis showed that the neural network could successfully
describe the effects of temperature, initial pH and glucose concentration on the substrate
Keywords: degradation efficiency, hydrogen yield and average hydrogen production rate of this study.
Neural network The maximum substrate degradation efficiency of 95.3%, hydrogen yield of 305.3 mL/g
Genetic algorithm glucose and average hydrogen production rate of 23.9 mL/h were all obtained at the
Method of desirability function optimal temperature of 39.0 C, initial pH of 7.0 and glucose concentration of 24.6 g/L
Biohydrogen production identified by the method of desirability function based on a neural network. In sum, the
Modified logistic model method of desirability function based on a neural network was a useful tool to optimize
several responses for fermentative hydrogen production processes simultaneously.
2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.
1. Introduction hydrogen all day long without light using various kinds of
substrates such as organic wastes [3,4]. Thus fermentative
Environmental pollution due to the use of fossil fuels as well hydrogen production is more feasible and widely used. In
as their shortfall makes it necessary to find alternative energy addition, it is of great significance to produce hydrogen from
sources that are environmentally friendly and renewable. organic wastes by fermentative hydrogen production, because
Hydrogen satisfies the above requirements because it it plays the dual role of waste reduction and energy produc-
produces only water, when it is combusted as a fuel or con- tion. Therefore fermentative hydrogen production has been
verted to electricity [1,2]. Among various hydrogen production receiving increasing attention in recent years [5].
processes, the biological method is known to be less energy Many factors such as temperature, initial pH and substrate
intensive, for it can be carried out at ambient temperature and concentration can influence the fermentative hydrogen
pressure. The biological method mainly includes photosyn- production, because they can affect the activity of hydrogen-
thetic hydrogen production and fermentative hydrogen producing bacteria by influencing the activity of some essen-
production. The efficiency of photosynthetic hydrogen tial enzymes such as hydrogenases for fermentative hydrogen
production is low and it cannot be operated in the absence of production [1]. It has been demonstrated that in an appro-
light, while fermentative hydrogen production can produce priate range, increasing temperature, initial pH and substrate
concentration could increase the ability of hydrogen- was used as the seed sludge. Heat-shock was used in this
producing bacteria to produce hydrogen during fermentative study to enrich hydrogen-producing bacteria by heating the
hydrogen production, but temperature, initial pH and seed sludge at 100 C for 15 min [1,2].
substrate concentration at much higher levels could decrease
it with increasing levels [510]. Thus, appropriate levels of the 2.2. Experimental design and procedures
above three factors can be chosen to optimize the fermenta-
tive hydrogen production process to increase the ability of In this study, a three-factor fractional factorial design was
hydrogen-producing bacteria to produce hydrogen. used to design the experiment for constructing the neural
There have been a great number of studies reporting the network. Temperature, initial pH and glucose concentration
optimization of fermentative hydrogen production process were chosen as the factors, while substrate degradation effi-
with one-factor-at-a-time experimental design, but such ciency, hydrogen yield and average hydrogen production rate
design does not depict the interactive effects among different were chosen as the responses. The experimental design is
factors. On the contrary, response surface methodology based shown in Table 1.
on a factorial design can depict the interactive effects among According to the experimental design in Table 1, batch
different factors and allows the effects of many factors with tests were conducted in 150 mL glass bottles. One liter of the
two or more levels on a response to be studied in a relatively nutrient solution contained NaHCO3, 40,000 mg; NH4Cl,
small number of runs [1114]. In recent years, a neural 5000 mg; NaH2PO4 $ 2H2O, 5000 mg; K2HPO4 $ 3H2O, 5000 mg;
network which is able to depict the interactive effects among FeSO4 $ 7H2O, 15,000 mg; MgCl2 $ 6H2O, 85 mg; NiCl2 $ 6H2O,
different factors in a complicated bioprocess has been applied 4 mg. Fifteen milliliters of the pretreated seed sludge, 10 mL of
successfully in multivariate non-linear bioprocesses as nutrient solution and certain amount of glucose were added to
a useful tool to construct models. It has been shown that each glass bottle. Then the total working volume of the bottles
a neural network is a superior and a more accurate modeling was filled to 100 mL by de-ionized water. The initial pH of the
technique compared with the response surface methodology, mixed solution in each bottle was adjusted by 1 mol/L HCl or
as it represents the non-linearities in a much better way 1 mol/L NaOH. Each bottle was flushed with argon for 3 min to
[1517]. A neural network can be considered as the objective provide anaerobic condition, capped with a rubber stopper,
function for optimization by genetic algorithm, which has and placed in a reciprocal shaker (reciprocation: 150 strokes/
established itself as a powerful search and optimization min) at different temperature. Each batch test was done three-
technique to solve problems with objective functions that are fold.
not continuous or differentiable. It has been reported that the
genetic algorithm based on a neural network had a higher 2.3. Analytical methods
optimizing ability than response surface methodology [1517].
Moreover, the method of desirability function can be used to The water displacement method was used to collect and
optimize several responses simultaneously when there are measure the biogas produced. The fraction of hydrogen in the
many responses to be optimized for a bioprocess. Otherwise, biogas was determined by a gas chromatograph (Model 122,
without multiple-response optimization, several responses Shanghai, China) equipped with a thermal conductivity
would have to be optimized separately [1820]. Simultaneous detector (TCD) and a 2 m column packed with 5 A molecular
optimization of multiple responses by the method of desir- sieves. Helium was used as the carrying gas at the flow rate of
ability function involves first building an appropriate model 12 mL/min. The operating temperature of the column,
for each response and then trying to find a set of operating detector and injector were 40 C, 80 C and 50 C, respectively.
conditions that in some sense optimizes all responses or at All gas production data reported were standardized to the
least keeps them within desired ranges. standard temperature (0 C) and pressure (760 mmHg). The pH
To the best of our knowledge, however, there is little in the solution was measured by a pH meter (Model 526,
literature reporting the optimization of fermentative Germany). The concentration of glucose after reaction was
hydrogen production processes by the method of desirability determined by the DNS colorimetric method [21]. The volatile
function based on a neural network using a genetic algorithm. suspended solid (VSS) of the seed sludge was determined
Thus, in this study the effects of temperature, initial pH and according to the standard methods [22].
glucose concentration on fermentative hydrogen production In this study, using non-linear regression with the software
by mixed cultures were investigated in batch tests and Origin 7.5, the modified Logistic model (Eq. (1)) was used to fit
described by a neural network, and then the process was the cumulative hydrogen production data obtained from each
optimized by the method of desirability function based on the batch test to obtain H, Rm and l [5,23].
neural network, with the purpose of obtaining the optimal
P
conditions for the fermentative hydrogen production process. H (1)
1 exp4Rm ,l t=P 2
The hydrogen yield was calculated by dividing the hydrogen where X is the variable in a group to be scaled, Xmin is the
production potential by the amount of glucose consumed in minimum variable in a group to be scaled, Xmax is the maximum
each batch test. The substrate degradation efficiency was variable in a group to be scaled, and X* is the scaled variable.
estimated by dividing the amount of glucose consumed by the The first step in training the neural network is to design the
amount of initial glucose. topology of the neural network. The number of neurons in
the input layer is fixed by the number of inputs, whereas the
2.4. Neural network number of neurons in the output layer equals the number of
outputs. The critical aspect is the choice of the number of
In general, a feed-forward neural network with one hidden neurons in the hidden layers [24]. To obtain the optimal
layer containing certain hidden neurons has been shown to be number of neurons in the hidden layer of the neural network,
capable of providing accurate approximations to many non- the number of neurons in the hidden layer was investigated. In
linear functions [17]. Thus, a feed-forward neural network the training process, the mean square error between the
with back propagation algorithm was used in this study. The experimental data and the corresponding predicted data is
inputs chosen in this study were temperature, initial pH and calculated and propagated backward through the network.
glucose concentration, respectively, while the outputs were The back propagation algorithm adjusts the weights in each
substrate degradation efficiency, hydrogen yield and average successive layer to reduce the error. This procedure is repeated
hydrogen production rate, respectively. In this study, the until the error between the experimental data and the corre-
transfer function in the hidden layer and the output layer sponding predicted data satisfies certain error criteria.
were logistic function and linear function, respectively. All the Eq. (5) was used to calculate the coefficient of determina-
inputs and outputs were normalized within a uniform range tion (R2) of the neural network.
of (0.1, 0.9) to ensure that they received equal attention during Pk 0 2
2 i1 yi y
the training process [16,24]. The new scaled variables were R Pk 2 (5)
i1 yi y
calculated by Eq. (3). These values were rescaled by Eq. (4).
where yi is the experimental data, y0i is the corresponding
X Xmin predicted data by the neural network, and y is the mean of all
X 0:8 0:1 (3)
Xmax Xmin the experimental data.
1256 international journal of hydrogen energy 34 (2009) 12531259
where yi is the response to be optimized, L is the minimum The genetic algorithm is based on the principles of evolution
acceptable value of yi, U is the maximum value beyond which through natural selection, that is, the survival of the fittest
improvements would serve no further benefit, and w is strategy. It explores all regions of the solution space using
a weight factor. a population of individuals. Each individual represents a set of
Then the optimal conditions for several responses were factors. The individual chosen in this study was a set of
obtained by maximizing the overall desirability D, which is the temperature, initial pH and glucose concentration. Initially,
geometric mean of all the individual desirability functions a population of individuals is formed randomly. The fitness of
(Eq. (7)). each individual is evaluated using a fitness function. Upon
9
Mean square error for average hydrogen
40
Mean square error for substrate degradation
30 6
production rate
efficiency
20
10
0
0 1 2 3 4 5 6 7 8 9 10
1 2 3 4 5 6 7 8 9 10 Number of neurons in the hidden layer of neural
Number of neurons in the hidden layer of neural network network
Fig. 1 Effects of number of neurons in the hidden layer of Fig. 3 Effects of number of neurons in the hidden layer of
the neural network for substrate degradation efficiency on the neural network for average hydrogen production rate
the mean square error. on the mean square error.
international journal of hydrogen energy 34 (2009) 12531259 1257
80
15
70
10
60
5
50
50 60 70 80 90 100 0
Experimental substrate degradation efficiency ( ) 0 5 10 15 20 25
Experimental average hydrogen production rate (mL/h)
Fig. 4 Experimental and predicted data of substrate
degradation efficiency. Fig. 6 Experimental and predicted data of average
hydrogen production rate.
Line of perfect prediction neuron number from 5 to 10. This indicated that when
300 Data points the number of neurons in the hidden layer was from 5 to 10, the
neural network was better able to model the experimental data
250
of substrate degradation efficiency and hydrogen yield data. In
addition, when the number of the neurons in the hidden layer
200
of the neural network is larger, the neural network is very
150 complex and will take a longer time to train the neural
100
Table 3 Experimental design for validating the optimal conditions identified by the method of desirability function based
on neural network.
Response Temperature ( C) Initial pH Glucose concentration (g/L) Identified Experimental
network. Thus, 5 neurons were chosen in the hidden layer of reported by Lin et al. [6], Yokoyama et al. [27] and Valdez-
the neural network for substrate degradation efficiency and Vazquez et al. [28]. The optimal initial pH for fermentative
hydrogen yield, respectively. The neural network architecture hydrogen production obtained in this study was close to that
for substrate degradation efficiency in this study consisted of 3 (6.5) reported by Lin et al. [29], but was much lower than that
neurons (temperature, initial pH and glucose concentration) in (9.0) reported by Lee et al. [7], and much higher than that (4.5)
the input layer, 5 neurons in the hidden layer, and 1 neuron reported by Khanal et al. [8]. The optimal glucose concentra-
(substrate degradation efficiency and hydrogen yield, respec- tion for fermentative hydrogen production obtained in this
tively) in the output layer (topology 3-5-1). In a similar way, 6 study was close to that (23.8 g/L) reported by Pan et al. [13], but
neurons were chosen in the hidden layer of the neural network was much higher than that (1 g/L) reported by Zheng et al. [30].
for average hydrogen production rate. Training a neural Several other experiments (Table 3) were carried out to
network is accomplished by adjusting the weight coefficients validate the optimal conditions identified by the method of
in each successive layer to minimize the mean square error desirability function based on the neural network. As shown
between experimental data and the corresponding predicted in Table 3, under the optimal conditions identified the
data of substrate degradation efficiency, hydrogen yield and experimental data were very close to those identified by the
average hydrogen production rate, respectively. method of desirability function based on the neural network,
Coefficients of determination of the neural network for indicating that the method of desirability function based on
substrate degradation efficiency, hydrogen yield and average the neural network was a useful tool to optimize the
hydrogen production rate were calculated as 0.984, 0.994 and fermentative hydrogen production process.
0.984, respectively. In addition, as shown in Figs. 46, the
experimental and predicted data points of them were very
close to the line of perfect prediction. All of this indicated that 4. Conclusions
the neural network for substrate degradation efficiency,
hydrogen yield and average hydrogen production rate could A fractional factorial design was carried out to investigate the
successfully describe the effects of temperature, initial pH and effects of temperature, initial pH and glucose concentration
glucose concentration on them in this study. on fermentative hydrogen production by mixed cultures in
batch tests and then the experimental data of substrate
3.2. Optimization by the method of desirability function degradation efficiency, hydrogen yield and average hydrogen
production rate were described by a neural network, based on
The method of desirability function was used to obtain the which the simultaneous optimization of the three responses
maximum substrate degradation efficiency, hydrogen yield was performed by the method of desirability function. The
and average hydrogen production rate simultaneously. The following conclusions could be drawn.
parameters for optimization by method of desirability func- The neural network was able to successfully describe the
tion are shown in Table 2. effects of temperature, initial pH and glucose concentration
When yi is between L and U, the overall desirability can be on the substrate degradation efficiency, hydrogen yield and
expressed by Eq. (8). average hydrogen production rate of this study. The
maximum substrate degradation efficiency of 95.3%,
1
y1 90 y2 230 y3 20 3 hydrogen yield of 305.3 mL/g glucose and average hydrogen
D , , (8)
96 90 310 230 25 20 production rate of 23.9 mL/h were all obtained at the optimal
temperature of 39.0 C, initial pH of 7.0 and glucose concen-
Subsequently, the overall desirability was optimized by
tration of 24.6 g/L identified by the method of desirability
genetic algorithm and the maximum overall desirability of
function based on the neural network. In sum, the method of
0.819 was estimated at the temperature of 39.0 C, the initial
desirability function based on a neural network was a useful
pH of 7.0 and the glucose concentration of 24.6 g/L. Accord-
tool to optimize several responses for fermentative hydrogen
ingly, the maximum substrate degradation efficiency of 94.5%,
production processes simultaneously.
hydrogen yield of 307.0 mL/g glucose and average hydrogen
production rate of 23.8 mL/h were predicted at the tempera-
ture of 39.0 C, the initial pH of 7.0 and the glucose concen-
tration of 24.6 g/L. Acknowledgement
The optimal temperature for fermentative hydrogen
production obtained in this study was close to those (3540 C) The authors would also like to thank the National Natural
reported by Wang and Wan [5], Lin et al. [25] and Zhang and Science Foundation of China for financially supporting this
Shen [26]. However, it was much lower than those (5060 C) research under Contract No. 50325824.
international journal of hydrogen energy 34 (2009) 12531259 1259