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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7
C.X. Cáceres a,*, R.E. Cáceres a, D. Hein b,**, M.G. Molina c, J.M. Pia a
a
Department of Chemical Engineering, Faculty of Engineering, Universidad Nacional de San Juan, Av. Libertador San Martı́n Oeste, 1109,
J5400ARL San Juan, Argentina
b
Department of Energy and Environmental Process Engineering, Department of Mechanical Engineering, Universität Siegen, Siegen, Germany
c
Instituto de Energı́a Eléctrica, Universidad Nacional de San Juan, Av. Libertador San Martı́n Oeste, 1109, J5400ARL San Juan, Argentina
Article history: In year 2010, the Province of San Juan e Argentina (South America) produced around 81 947
Received 8 September 2011 tons of grape pomace, which is a winery waste by-product. Wineries demand a great
Received in revised form quantity of power during the three months that winemaking time lasts, which involve
16 December 2011 a high installed electric power. This power is used mainly for refrigerating the must during
Accepted 31 January 2012 the fermentation. The control of temperature is crucial in winemaking as the low
Available online 3 March 2012 temperature preserves subtle fruit characters. An alternative for reducing the requirement
of power from the utility electric grid is producing it locally, using the residuals generated
Keywords: by the own wineries. The technology for bioenergy conversion proposed to be imple-
Alternative energy mented in this research for electricity generation is the anaerobic digestion of grape
Biogas production pomace. The aim of this research is to develop the thermodynamic equilibrium analysis of
Grape pomace grape pomace anaerobic digestion based on the equilibrium constants for predicting the
Thermodynamic model potential production of biogas and its composition. In addition, a dynamic model of
Power generation a biogas-fuelled microturbine system for distributed generation applications is derived.
Biogas-fuelled microturbine Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
5
This work was supported in part by the National University of San Juan (UNSJ) under Grant PICUNSJ 2011, No. 1016.
* Corresponding author. Tel.: þ54 264 4211700; fax: þ54 264 4200289.
** Corresponding author.
E-mail addresses: xcaceres@unsj.edu.ar, cxcaceres@gmail.com (C.X. Cáceres).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2012.01.178
Author's personal copy
10112 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7
fermentation) is carried out in only 5% of the wineries of San composition of the produced biogas. With these results,
Juan. a dynamic model of a biogas-fuelled microturbine system for
It is estimated that in 2010, San Juan produced about 81 947 distributed generation applications is derived. In this way, the
tons of grape pomace [1], considering that grape pomace global system enables to generate power from the solid waste
represents 12%e14% of fresh grape weight [2] and the grape of the own wineries (grape pomace); thus reducing the power
production for making wines and musts rises to 11 472 tons. requirements of a winery, especially during its larger demand
Wineries demand a great quantity of energy during the periods.
three months that winemaking time lasts, which involves
a high installed power capacity. This energy is used mainly for
refrigerating the must in fermentation, which reaches
2. Thermodynamic model of the biogas
approximately to 35.39 kcal per litre of must, since grapes in
production process
San Juan arrive wineries with an average of 26 Brix. This
represent a high amount of energy, considering that the
For the development of the model it was considered that the
volume of fermentation tanks is usually of 30 000 L and must
anaerobic digestion process could be divided into three pha-
temperature should not exceed 15 C in white wines and 26 C
ses, i.e. hydrolysis, acid formation and methane formation.
in red ones. The control of temperature is crucial in wine-
making provided that the cooling temperature preserves
subtle fruit characters. 2.1. Phase of hydrolysis
In Argentina, the cost of the electric power is compound of
both a fixed component and a variable one. The fixed In this first phase, the complex structure of organic matter is
component is a function of the installed power. The variable broken down into its fundamental parts during the hydrolysis
component is proportional to the amount of energy consumed process: the proteins are converted into amino acids, complex
in the billing period. carbohydrates such as cellulose, lignin, starch and fibres are
Due to the high installed power capacity, during the nine transformed into simple sugars, like glucose [7]. This phase is
months that wineries are not active the energy costs stay high. not considered for the development of this model.
A form of diminishing the requirement of energy from the
electric system is by producing it locally, using the residuals 2.2. Phase of acids formation
generated by the own wineries. This generation type is
denominated in situ or distributed generation (DG), and This phase includes acidogenesis and acetogenesis, and can
constitutes a radical change of the paradigm of the conven- be expressed by the following general reaction:
tional electric power generation.
In the last years, the use of various kinds of biomass for C6 H12 O6 ðaÞ þ nH2 O H2 OðaÞ ¼ nH2 ðgÞ H2 ðgÞ
producing heat and electricity has been increased [3]. The þ nCH3 CH2 OHðaÞ CH3 CH2 OHðaÞ
main advantage for that are the reduction of greenhouse gas þ nH2 ðaÞ H2 ðaÞ
(GHG) and other pollutant emissions [2].
þ nCH3 CH2 OHðgÞ CH3 CH2 OHðgÞ
The technology for bioenergy conversion proposed to be
þ nCO2ðgÞ CO2 ðgÞ þ nCO2ðaÞ CO2 ðaÞ
implemented in this research for electricity production is the
anaerobic digestion of grape pomace. The selection of this þ n12 Hþ ðaÞ þ nacetato CH3 COO ðaÞ
technology has been carried out keeping in mind the following þ nac:acetðaÞ: CH3 COOHðaÞ
considerations: þ nac:acet:ðgÞ CH3 COOHðgÞ þ nOH OH ðaÞ
þ nac:prop:ðgÞ CH3 CH2 COOHðgÞ
Characteristic of the waste use: grape pomace is a high
þ nac:prop:ðaÞ CH3 CH2 COOHðaÞ
strength organic waste with low levels of nitrogen and
phosphorous with sufficient trace elements for bacterial þ nHCO3 HCO
3 ðaÞ
growth [4]. In addition, the humidity of the grape pomace, þ npropionato: CH3 CH2 COO ðaÞ
which varies between 25% and 65% [5] is not a problem for (1)
anaerobic digestion, however, restrict the implementation
being ni the number of moles of species i; which are unknown.
of others technologies for conversion of biomass.
In order to determine the ni values, a system of equations is
Characteristics of the processes for biogas production: from
proposed, which include the mass balance equations and the
anaerobic digestion, biogas is obtained at atmospheric
equilibrium constants equations of reactions occurring in this
pressure and lower temperatures than the gases obtained
stage. In this way, the mass balance equation for carbon is
with other technologies for conversion of biomass, so that
defined by Eq. (2). Analogously, the mass balance equations
plants are comparatively easier to operate and costs of
for oxygen and hydrogen are determined.
initial investment are lower [6] than that for other
technologies. 2nCH3 CH2 OHðaÞ þ 2nCH3 CH2 OHðgÞ þ nCO2ðgÞ þ nCO2ðaÞ þ 2nacetatoðaÞ
þ 2nac:acet:ðaÞ þ 2nac:acet:ðgÞ þ 3nac:prop:ðaÞ þ 3nac:prop:ðgÞ
The aim of this work is to develop the thermodynamic
þ nHCO3 þ 3npropionatoðaÞ 6 ¼ 0 ð2Þ
equilibrium model of grape pomace anaerobic digestion based
on equilibrium constant in order to determine the optimum The redox equilibrium, electrochemical equilibrium and
operating conditions and subsequently predicting the phase equilibrium reactions in the phase of acid formation are
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7 10113
shown in Table 1 [7]. These equations are used as a basis in reactants. The activity can be written as a function of the
order to get the equilibrium constants equations of this stage. activity coefficient (gi) and molar fraction in liquid (xi):
ai ¼ gi xi (6)
2.3. Phase of methane formation By replacing Eq. (6) in Eq. (5) and considering that solutions
are ideal (gi ¼ 1) for the developed model, then the constant K
The phase of methane formation can be described by Eq. (3). In is:
order to determine the ni values, a system of equations is
Y
proposed, which include the mass balance equations and the K¼ ðxi Þni (7)
equilibrium constants equations of reactions occurring in this i
stage. In this way, the mass balance equation for carbon is In the case of gases, the equilibrium constants can be
defined by Eq. (4). In the same way, the mass balance equa- expressed as a function of fugacity ( fi), as follows:
tions for oxygen and hydrogen are derived. Y n
K¼ fi i (8)
nH2 ðgÞ H2 ðgÞ þ nCH3 CH2 OHðaÞ CH3 CH2 OHðaÞ þ nH2 ðaÞ H2 ðaÞ i
þ nCH3 CH2 OHðgÞ CH3 CH2 OHðgÞ þ nCO2ðgÞ CO2 ðgÞ þ nCO2ðaÞ CO2 ðaÞ The fugacity is stated as a function of the fugacity coeffi-
þ n12 Hþ ðaÞ þ nacetate CH3 COO ðaÞ þ nacet:ac:ðaÞ: CH3 COOHðaÞ cient (f), the molar fraction in the gas ( yi) and the total pres-
þ nacet:ac:ðgÞ CH3 COOHðgÞ þ nOH OH ðaÞ sure (P), in the following way:
¼ nCH4ðgÞ CH4ðgÞ þ nCH4ðaÞ CH4ðaÞ þH2 final þCO2 final (3) By replacing Eq. (9) in Eq. (8) and considering that P¼1 and
the gases of the system are ideal (f ¼ 1) for the proposed
2nCH3 CH2 OHðaÞ þ 2nCH3 CH2 OHðgÞ þ nCO2ðgÞ þ nCO2ðaÞ þ 2nacetateðaÞ model, then K can be expressed as:
þ 2nacet:ac:ðaÞ þ 2nacet:ac:ðgÞ þ 3nprop:ac:ðaÞ þ 3nprop:ac:ðgÞ Y n
þ nHCO3 nCH4ðaÞ nCH4ðgÞ nCO2 final ¼ 0 ð4Þ K¼ yi i (10)
i
Table 1 e Stoichiometric equations evolved in the acids formation phase during the anaerobic digestion.
Redox equilibrium Electrochemical equilibrium Phase equilibrium
þ
C6 H12 O6 ðaÞþ2H2 O ¼ 2CH3 COOHðaÞ CH3 CH2 COO ðaÞþ3H2 OðaÞ ¼ H ðaÞþCH3 COO ðaÞ CH3 CH2 COOHðaÞ¼ CH3 CH2 COOHðgÞ
þ2CO2 ðaÞþ4H2 ðaÞ þHCO3 ðaÞþ3H2 ðaÞ
C6 H12 O6 ðaÞþ2H2 ðgÞ¼ 2H2 OðaÞ CH3 CH2 COHðgÞþ3H2 OðaÞ¼ CH3 COO ðaÞþ2H2 ðaÞ þ Hþ ðaÞ CH3 COOHðaÞ¼ CH3 COOHðgÞ
þ2CH3 CH2 COOHðaÞ
10114 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7
Table 2 e Stoichiometric equations evolved in metanogenesis phase during the anaerobic digestion.
Redox equilibrium Electrochemical equilibrium Phase equilibrium
þ
2CH3 CH2 OHðgÞþCO2 ðaÞ¼ 2CH3 COOHðaÞþCH4 ðaÞ CH3 COOHðaÞ¼ CH3 COO ðaÞ þ H ðaÞ CH4 ðaÞ¼ CH4 ðgÞ
CH3 COOHðaÞ¼ CH4 ðaÞþCO2 ðaÞ CO2 ðaÞþH2 OðaÞ¼ HCO þ
3 ðaÞ þ H ðaÞ CH3 COOHðaÞ¼ CH3 COOHðgÞ
þ
CH3 CH2 OHðgÞþ2H2 ðaÞ¼ 2CH4 ðaÞþH2 OðaÞ H2 OðaÞ ¼ H ðaÞ þ OH ðaÞ CH3 CH2 OHðaÞ¼ CH3 CH2 OHðgÞ
CO2 ðaÞþ4H2 ðaÞ¼ CH4 ðaÞþ2H2 OðaÞ H2 ðaÞ¼ H2 ðgÞ
CO2 ðaÞ¼ CO2 ðgÞ
the equilibrium constants are extracted from literature [8e10]. distribution grid is made through a step-up transformer and
The NewtoneRaphson method is applied in order to solve the a low pass filter.
system of equations used to describe the acid formation phase The model of the microturbine system presented in this
and the methane formation phase and to determine thus the work is based on the following assumptions:
values of ni. The convergence criteria for solution of all
equations were set at 1.0 1014. The microturbine engine is similar to a conventional gas
combustion turbine, but smaller in size and spinning at
higher speeds.
The microturbine system shares a single rotating shaft
3. Dynamic model of the microturbine including the MT engine and the generator.
system A permanent magnet synchronous generator is used to
generate the three-phase AC power.
3.1. Overview of the biogas-fuelled microturbine system The power conditioning system employed, which is
described in-depth in [11], uses a rectifier and an inverter for
Microturbines (MTs) demonstrate some unique attributes for connecting the microturbine to the distribution grid.
running on biogas that enable them to compete against
reciprocating engines, particularly at smaller sites. In fact,
biogas applications are among the most promising recent
3.2. Model of the microturbine engine
applications for microturbines. Biogas is available from many
sources of organic waste, such as landfill sites, wastewater
Analogous to a typical combustion gas turbine, the biogas
treatment plants, agricultural and livestock operations, food
microturbine engine mainly involves an air compression
processing plants, gasified woody biomass, among others. In
section, a burner or combustion chamber for ignition of input
the proposed application, biogas is produced through the
renewable fuel, a pre-treatment system to achieve the desired
anaerobic decomposition of organic materials from grape
biogas quality, a recuperator of thermal energy from exhaust
pomace, a waste of wineries.
gases for improving overall electrical efficiency, and a power
Nowadays, MT manufacturers have modified their systems
microturbine driving the generator, as depicted in Fig. 2.
to better handle the unique qualities of this waste biogas and
Based on the above considerations, the microturbine
the impurities it contains, yielding the so-called renewable
engine dynamics can by modelled as a conventional small gas
microturbines. The combustible portion of this gas is methane
turbine. The dynamic model of a combustion gas turbine is
(CH4), while most of the rest is CO2, with small amounts of
widely discussed in [12,13]. In this research, a simplified single
nitrogen, oxygen, hydrogen, water (the biggest source of
shaft gas microturbine and all its control systems have been
problems in biogas applications), hydrogen sulphide and trace
implemented to represent its dynamics. The control system
elements. So the best environmental solution is to use these
consists mainly of a speed governor, an exhaust gases
waste gases to generate renewable power, and microturbines
temperature control and a fuel (biogas) injection control (also
can do it efficiently, reliably, cleanly and economically.
known as acceleration control). These three controls are
Microturbines are small, compact, lightweight, and simple-
implemented in MATLAB/Simulink, as shown in Fig. 3.
cycle gas turbines used for stationary energy generation
The speed controller is a proportional-integral (PI) block,
applications with outputs ranging from around 25e300 kW.
which includes a droop feedback in order to allow either droop
They are a part of a general evolution in gas turbine tech-
nology. These systems are high speed turbines (50 000 to
120 000 rpm) with air foil bearings. Its thermal efficiency is
more than 30%. A microturbine system, as shown in Fig. 1, is
made up of a gas combustion microturbine engine directly
coupled (gearless) to a multi-pole permanent magnet
synchronous generator (PMSG) that produces electrical power
operating at high speeds. The high-frequency electrical power
(up to 1600 Hz) is converted to DC voltage and then inverted
back to low frequency (50 or 60 Hz) AC voltage through an
electronic power conditioning system (PCS). The PCS is basi-
cally composed of a three-phase rectifier bridge and a DC/AC
voltage source inverter. The connection to the electric Fig. 1 e Schematic diagram of the microturbine system.
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7 10115
10116 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7
5. Conclusion
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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 0 1 1 1 e1 0 1 1 7 10117
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