Carte Cioabla Et Al

Adrian Eugen CIOABL, Gabriela-Alina
DUMITREL, Dorin LELEA, Francisc

POPESCU
Biogas in theoretical and

experimental applications
EDITURA MIRTON
Timioara
2017
Acknowledgements
This work was partially supported by a grant of the

Romanian National Authority for Scientific Research and
Innovation, CNCS-UEFISCDI, project number PN-II-
RU-TE-2014-4-1043.
Authors:
Adrian Eugen CIOABL (chapters II, III and VI)
Gabriela-Alina DUMITREL (chapters IV, V and VI)
Dorin LELEA (chapter V)
Francisc POPESCU (chapter I)
Preface
Nowadays, the need for renewable sources of energy becomes

more and more important, meaning that the necessity for research
and viable solutions in this open field is of vital importance.
Romania, as a UE member, must embrace the current policies
relative to finding different solutions tailored to its potential and
needs in order to obtain at least a certain degree of energetic
independence from a renewable energy point of view.
In this context, biogas, as a renewable energy carrier, can be
one of the many possible solutions that have to be taken into
account when it comes to finding a way to capitalize degradable
materials which do not have many other applications.
The present work focuses mainly on the most relevant results
obtained during the period of October 2015 September 2017
inside of the project PN-II-RU-TE-2014-4-1043. The overall
results (theoretical and experimental) indicate that for different
recipes of materials, the produced biogas in terms of quantity and
quality is relevant to be taken into account for further possible
applications in terms of using it inside larger scale experiments and
even industrial applications.
Special acknowledgments are addressed to all of the
collaborators which provided support during this period: BEA
Institut fr Bioenergie, Viena - Austria, University of Belgrade,
Mechanical Engineering Faculty - Serbia and Szeged University,
Department of Biotechnology, Szeged - Hungary.
Contents
I. Renewable biofuels - a sustainable overview . 5
II. Anaerobic digestion systems.. 18
II.1. Bench scale systems 18
II.2. Pilot plant anaerobic digestion system . 27
III. Analytical methods ... 32
III.1. Determination of moisture content. 33
III.2. Ash content determination .. 34
III.3. Calorific value determination .. 36
III.4. Ion chromatography 38
III.5. Carbon, hydrogen and nitrogen
determinations . 40
III.6. Determination of the volatile matter content . 41
IV. Legislation affecting biogas sector . 43
IV.1. Legal framework for the promotion of energy
production from renewable energy sources . 44
IV.2. Romanian mechanism for promoting the
production of electricity from renewable
energy sources 49
V. Mathematical modeling . 56
V.1. The numerical simulations of the thermal
phenomena inside the batch type bioreactor 56
V.2. The microchannel bioreactors .. 61
V.2.1. Introduction ...... 61
V.2.2. The heat transfer and fluid flow of a partially 62
heated microchannels .
V.2.3. The viscous heating issue in micro-channels . 71
V.2.4. Effects of temperature dependent thermal
conductivity on Nu number behavior in
micro-tubes . 79
V.3. Mathematical models for evaluation of
anaerobic digestion performances 85
VI. Case studies ....... 92
VI.1. Characterization of biomass tested .. 92
VI.2. Results of biomass anaerobic digestion .. 95
VI.2.1. Results of the determinations at small scale 95
VI.2.2. Results of pilot installation determinations . 114
VI.3. Characterization of digestate ... 139
VI.4. Results of mathematical modeling .. 146
VI.4.1. Anaerobic digestion modelling of
substrates prepared with wastewater from
treatment plant ............... 148
VI.4.2. Anaerobic digestion modelling of
substrates prepared with wastewater from
beer factory ... 155
VI.5. Catalysts testing in biogas configuration
inside pilot installation .. 163
I. Renewable biofuels - a sustainable
overview
The automotive industry used biofuels since the first days of

motorized vehicles. In 1820s, the American inventor Samuel
Morey used ethanol and turpentine in its first internal combustion
engine. Later, Otto used also ethanol on its spark-ignition engine
and Diesel used peanut oil in its compression ignition engine. As
automobile become popular at the beginning of 1900s, Henry
Ford used for its T model an ethanol-gasoline blend. However, in
the 1900s the cheap petroleum fuels became widely available and
all automotive industry developed engines based almost entirely on
gasoline and diesel fuels [1].
The 1970s oil crises forced automotive industries to seek again
alternatives to fossil fuels based on imported oils. Brazil was the
first champion in automotive biofuels conversion, with is
Proalcool programme, managing to focus on ethanol production,
mainly based on sugar cane and developing new ethanol distilleries
and more important, ethanol-only cars. By the end of the 1980s in
Brazil ethanol replaced almost 60 % of country gasoline needs.
Also in the 1970s USA launched its own ethanol strategies based
on corn. Today, Brazil and USA produce vast majority of world
ethanol, close to 90% of world production [1].
European governments were much slower in promoting and
supporting renewable fuels, starting only in the 1990s. However, as
the ethanol world market was already dominated by the USA and
Brazil, European Union focused on biodiesel. New markets for
farmers were developed, tax reduction policies for biodiesel
production implemented and later on a focus on biodiesel and
5
biogas from various types of organic wastes were introduced, with
Germany leading in biodiesel production.
In the later years China also became a significant player on
biofuel markets, with a rapid growth and expected future
overcome of its competitors. Table I.1 and figure I.1 shows the
evolution of ethanol production capacities and volumes by
countries and region.
Table I.1. World fuel ethanol production, in billion gallons [2]

Country 2010 2011 2012 2013 2014 2015
USA 13.298 13.948 13.300 13.300 14.300 14.806
Brazil 6.922 5.573 5.577 6.267 6.190 7.093
Europe 1.209 1.168 1.179 1.371 1.445 1.387
China 542 555 555 696 635 813
Canada 357 462 449 523 510 436
Rest of World 985 698 752 1.272 1.490 1.147
WORLD 23.311 22.404 21.812 23.429 24.570 25.682
6
Figure I.1. World bio-ethanol production, in billion gallons
The USA and Brazil dominate the world ethanol production

(see table I.1 and figure I.1), with almost half of world ethanol
production being processed in USA, almost all of it distilled from
corn crops. About 25 to 30% of world ethanol came from Brazil,
but unlike USA corn policy the Brazil is focused almost entirely on
sugar cane crops for bio-ethanol production. The remainder on
bio-ethanol production comes from EU, with the leadership of
Sweden, Spain, France and Germany. Chinas bio-ethanol
production raw materials are more diversified, based on wheat,
corn and sugar cane as feedstock.
Biodiesel has seen similar growth but almost entirely in
Europe. About 75% of Europe liquid biofuel production
represents biodiesel, mainly from rapeseed and sunflower seeds as
feedstock. However, biodiesel also has an extremely rapid growth
in USA also, starting from about 1.9 million liters in 1995, reaching
284 million liters in 2005 and 854 million liters in 2006 and
7
reaching 5500 million liters in 2016, USA becoming the major
biodiesel producer worldwide [1, 3].
The United States and Brazil were among the largest biodiesel
producers in the world, totaling 5.5 and 3.8 billion liters,
respectively, in 2016. The United States is projected to reach
production levels of over 1 billion gallons of biodiesel by 2025.
After the implementation of the Energy Policy Act of 2005 which
provided tax incentives for certain types of energy, biodiesel
production in the U.S. began to increase. The Volumetric Ethanol
Excise Tax Credit is currently one of the main sources of financial
support for biofuels in the United States. In 2010, the U.S.
exported about 85 million gallons of their biodiesel products.
Comparatively, Argentina accounted for over half of the worlds
total exports. The United States has one of the highest bioenergy
capacities in the world, totaling 13,764 megawatts in 2015 [3].
Figure I.2 shows an overview of the biodiesel production
capacities in 2016.
Biogas production through anaerobic digestion is an
environmental friendly process utilizing the increasing amounts of
organic waste produced worldwide. A wide range of waste streams,
including industrial and municipal waste waters, agricultural,
municipal, and food industrial wastes, as well as plant residues, can
be treated with this technology. It offers significant advantages
over many other waste treatment processes. The main product of
this treatment, the biogas, is a renewable energy resource, while the
byproduct, the digested residue, can be utilized as fertilizer because
of its high nutrient content available to plants. The performance of
the anaerobic digestion process is highly dependent on the
characteristics of feedstock as well as on the activity of the
microorganisms involved in different degradation steps [4].
8
Figure I.2. World biodiesel production by country, in billion litres
[3]
In Europe, biogas is mainly used for generating heat and

electricity. Some of the produced heat is utilized within the biogas
plant as process heating and the remaining heat is distributed
through districts heating systems to consumers. The produced
power is sold to the grid. In some countries, like Sweden, the
produced biogas is upgraded to bio-methane which is utilized as
vehicle fuel.
9
In 2013, the total number of biogas plants in Europe was
14,572. Germany is from far the country where the biogas industry
is the most developed with 9,035 plants in operation that is to say
62% of the total number of plants, followed by Italy (1,391 plants),
Switzerland (620 plants) and France (610 plants), Fig. 2 (EBA
2014).The increase in the number of plants in 2013 compared to
2012 was rather low with 760 new plants which represent an
increase of only 5.5%, which is much lower than the 12% increase
of the previous year. This is mainly linked to significant changes
which occurred in different parts of Europe, mainly changes in
support schemes [5].
Figure I.3 presents the different types of biogas plants in
Europe per country. The biogas plants are classified into: landfill;
plants treating sewage; agriculture based biogas plants that run on
energy crops, agricultural residues and manure and industrial food
and beverage and bio-waste. Among the 7 countries having the
highest number of biogas plants (Germany, Italy, Switzerland,
France, Czech Republic, Austria and UK), the situation is very
different from one country to another. Germany, Italy, Czech
Republic and Austria are predominantly producers from
agricultural sources and have 87%, 80%, 69% and 46% of their
biogas plants operated with agricultural feedstock, respectively.
Other countries have a rather mixed share of landfill, sewage
sludge and agriculture based plants. France produces biogas mainly
from organic waste and on landfills and Switzerland and the
United Kingdom extracts biogas mainly from sewage sludge [5].
10
Figure I.3. Biogas plants in Europe in 2015 [6]
11
Agriculture based biogas plants that run on energy crops;
agricultural residues and manure have the biggest share (72%) in
the total number of biogas plants. The big share of agricultural
biogas plants in Europe can be explained by the corresponding
shares of such plants in the breakdown of leading biogas
producing countries (Germany, Italy and the Czech Republic)
which make up for almost 75% of total biogas plants and are
predominantly producers from agricultural sources [5].
Most of the biogas is used for electricity production (62%)
followed by heat (27%). Biomethane, for direct use in the
transport sector or injected into the grid to be used in the built
environment or in transport, contributes to about 11% of
generated energy from biogas. However, upgrading of biogas to
biomethane has a substantial percentage of the use of biogas in
Sweden, the Netherlands and Germany only. Energy crops (mainly
maize) provide about half of the biogas production, followed by
landfill, organic waste (including municipal waste), sewage sludge
and manure [7].
Figure I.4 shows the share of the different feedstocks among
European Union member states. Energy crops (mainly maize)
provide about half of the biogas production (318 PJ, 7.6 Mtoe),
followed by landfill (114 PJ, 2.7 Mtoe), organic waste (including
municipal waste) (86 PJ, 2,0 Mtoe), sewage sludge (57 PJ, 1.3
Mtoe) and manure (46 PJ, 1,1 Mtoe). However, in terms of
feedstock input on a mass base, manure contributes about 43%.
This discrepancy is due to the relatively low biogas yield from
manure [7].
12
Figure I.4. Share of feedstock use for biogas (on energy basis),
[7]
Romanias biogas sector is one of the most underdeveloped
ones in Europe. While the environment for renewable energy
sources is quite well established in Romania, with the target of
24% in gross final renewable energy consumption by 2020 having
been already achieved, the biogas sector is almost inexistent. While
at the end of 2015, the total installed capacity for electricity from
RES was approx. 4662 MWel, the share of biogas was only 12
MWel. Further 5 MWel represented the amount of further sludge
gases and 89 MWel of installed capacity for (solid) biomass. Most
of the biogas plants function with a mix of feedstock: 5 employ
among others also energy crops, while the majority use animal
manure and slurry; one plant is based on municipal waste. While
some of the energy is being produced in high efficiency CHP
plants, the heat is being used only for self-consumption [7].
However, in the world, biogas production capacities are
increasing on the yearly basis, with a large increase in China and a
significant stagnation in Germany, due to regulations changes
13
occurred in 2015. Figure I.5 shows an overview of leading biogas
producers in the global market.
Figure I.5. Biogas production by country
Biomass in many forms as solids, liquids or gases can be

burned directly to produce heat for cooking and heating in the
residential sector by means of the traditional use of biomass or in
modern appliances. It also can be used at a larger scale to heat
larger institutional and commercial buildings, or in industry to
produce high-temperature process heat and/or lower-grade heat
for heating or drying. The heat can be produced directly or co-
produced with electricity via combined heat and power (CHP)
systems and distributed from larger production facilities by district
heating systems to provide heating to residential, commercial and
industrial sectors [9].
14
Modern bioenergy applications provided some 14.4 EJ of heat
in 2015, of which an estimated 8.4 EJ was for industrial uses and
6.3 EJ was consumed in the residential and commercial sectors.
Modern biomass heat capacity in 2015 increased by an estimated
10 GWth, reaching approximately 315 GWth.
Figure I.6. Shares of Biomass Sources in Global Heat and

Electricity Generation, 2015 [9]
Figure I.6 shows the share of biomass sources and figure 7
biofuels global production by type and region.
Figure I.7. Biofuels Global Production, Shares by Type and by

Country/Region, 2015 [9]
A long-term solution in terms of climate policy, supply security
and equitable access to energy can be achieved only on a global
15
scale. Today we are far from such solution, with the proportion of
renewable energies in the world primary energy consumption
being at about 15%, with a very small increase from 1970s. This is
due to increased consumption by the world population, since the
overall capacity from renewable energy carriers has doubled in the
same time period.
A serious issue is the traditional burning of biomass. It makes
the statistical contribution of renewable sources to the primary
energy supply appear high but is not really sustainable since the
forests are often completely destroyed in the process. It is
important for developing nations to use state of the art technology
for biomass to biofuels conversion technologies (biogas, biodiesel,
bioethanol) in order to achieve a sustainable use of renewable
energy sources.
16
References
[1] WorldWatch Institute, Biofuels for transport. Global potential
and implications for sustainable energy and agriculture, Earrhscan,
London, ISBN 978-1-84407-422-8, 2007.
[2] ***, Renewable Fuels Association,
http://www.ethanolrfa.org/resources/industry/statistics/
#1454098996479-8715d404-e546, 2016,
[3] ***, https://www.statista.com/statistics/271472/biodiesel-
production-in-selected-countries/, 2016.
[4] I. S. Horvath, M. Tabatabaei, K. Karimi, R. Kumar, Recent
updates on biogas production - a review, Biofuel Research
Journal, 10, 2016, 394-402.
[5] M. Torijjos, State of Development of Biogas Production in
Europe, Procedia Environmental Sciences, 35, 2016, 881 889.
[6] ***, EBA European Biogas Association, 6th edition of the
Statistical Report of the European Biogas Association,
http://european-biogas.eu, 2016.
[7] ***, EU Commission, Optimal use of biogas from waste streams.
An assessment of the potential of biogas from digestion in the EU
beyond 2020, 2016.
[8] ***, https://www.statista.com/statistics/481840/biogas-
production-worldwide-by-key-country/, 2016.
[9] ***, REN21, Renewables 2016 Global Status Report, Paris,
France, ISBN 978-3-9818107-0-7, 2016.
17
II. Anaerobic digestion systems
The experimental systems used to test the anaerobic digestion

performances for different biomasses are presented in this chapter.
Both the bench scale and the pilot installation anaerobic digestion
systems are found in the Multifunctional Laboratory of Mechanical
Engineering Faculty, Politehnica University Timisoara.
II.1. Bench scale systems

The bench scale system was used to test at scales of 1 2 liters
total volumes the chosen materials in order to determine their
potential in terms of producing biogas with good characteristics in
terms of biogas quality and quantity. For this purpose, the first test
rig was composed mainly of a thermostatic bath in which there
were inserted PET reactors with the test batches.
The general overview of the montage is presented in figure
II.1.
The components found in the figure II.1. are [1]:
1 thermostatic bath with 6-8 places for heating up the used
materials for the anaerobic fermentation process (the
temperature is controlled with the help of a thermostat and
can be checked with the help of a thermometer inserted into
the bath);
2 plastic bottles with a total volume of 1 (or 2) L, depending on
the testing setup, filled up to about 0.8 (or 1.5) L with the
materials used for determinations;
3 the corks of the plastic bottles were modified in order to allow
18
both sampling for pH checking, homogenization by means of
plastic syringes, and gas transfer from the bottles into the gas
bags. Also, because of the light sensibility of the anaerobic
bacteria, the bottles were covered with aluminum foil;
4 hose orifice for syringe insertion, used for sampling and
homogenization;
5 connection (small diameter hose) between the plastic bottle
and the gas bag for biogas storage;
6 gas bag for biogas storage.
Figure II.1. Overall view of the thermostatic bath system
19
The first step in preparing the small scale installation consisted
in preliminary measurements and adjustments consistent with
modifying the initial schematics of the existing setup.
In regards with the realized measurements there was made a
processes and instrumentation diagram.
The processes and instrumentation diagram of the small scale
installation design for biogas production is presented in figure II.2
[2].
The scheme was developed taking into consideration the
following technological requirements of the fermentation process:
- to set and control the fluid temperature inside the vessel;
- to measure and to correct the pH value of the suspension;
- to store locally the biogas production for 2-3 days;
- to measure the biogas production of the installation.
The diagram was developed with typically element of circuits
in order to have a robust installation that can be used also for
magnetic and manual stirring / agitation.
20
Figure II.2. Process and Instrumentation diagram of the small scale
installation
The components of the small scale installation are:

1 Thermal glass vessels with a total volume of 6L used for dark
fermentation;
2 Electrical device used for supply the heating required for
fermentation process;
3 pH sensors inside the glass vessels in order to determine in real
time the pH value of the suspension;
4 Thermocouple used for temperature control inside the
fermentation vessels;
5 Temperature controller connected with the thermocouple
21
inside the glass vessel for temperature control to a determined
range;
6 pH controllers connected to pH sensors inside the glass vessels
in order to determine in real time the pH value of the suspension;
7 Gas bags with a total volume of 2L dedicated for sampling the
obtained biogas from the fermentation process;
8 Syringe system for sampling and pH correction of the
suspensions inside the vessels;
9 Tube to extract the biogas production from the glass vessels;
10 Syringe used for flow measurement and sampling of the
biogas production of the system.
After finalizing the initial scheme, there was also made a 3D
representation of the small scale installation.
The graphical representation is presented in figure II.3 [2].
Figure II.3. Schematics of the small scale installation
22
The components of the small scale installation are identical
with the ones described above.
1 thermal glass vessels with a total volume of 6L used for dark
fermentation;
2 magnets positioned at the bottom of the glass vessels used for
magnetic stirring of the used material suspensions; this system
allows also the manual stirring / agitation;
3 device used for heating the suspension inside the glass vessels;
4 thermocouple used for temperature control inside the
fermentation vessels;
5 system for sampling and pH correction of the suspensions
inside the vessels;
6 syringe used for sampling and pH correction system
7 pH controllers connected to pH sensors inside the glass vessels
in order to determine in real time the pH value of the suspension;
8 temperature controller connected with the thermocouple inside
the glass vessel for temperature control to a determined range;
9 gas bags with a total volume of 2L dedicated for sampling the
obtained biogas from the fermentation process.
In order to prepare the small scale installation, several steps
were made.
First, fitting metallic lids to the glass vessels in order to insert
all the systems and assuring good sealing during the process (figure
II.4).
23
Figure II.4. Metallic lid for the anaerobe fermenters (glass vessels)
The component part from figure II.4. are [1]:

1 valve connected with the gas bags for biogas sampling;
2 pH sensor;
3 metallic lid;
4 pipe for liquid samples and pH corrections;
5 thermocouple.
In order to obtain a good fermentation process the glass
vessels used for anaerobe fermentation were covered with a layer
of black paint.
24
Also the gas route was made in order to make it possible to
sample gas both from the gas bag and from the glass vessel, if
necessary. All the connections were sealed and fixed in order to
minimize the potential gas loses from the process.
The final montage allows the usage of two materials or one
combined material (recipe) and the main substrate used for
fermentation in order to compare the characteristics of the process
parameters (pH, produced biogas quantity) during the process
(figure II.5) [1].
Figure II.5. Small scale installation general overview
After the small scale installation preparative operations were

finished, there were made tests in order to verify the good
25
functioning of all the components (figure II.6.) [1].
First, the pH controllers and pH sensors were tested to
observe the good functionality, using buffer solutions to test the
calibration of the devices.
Also, the temperature control system was tested to observe if
the connections are in order.
The electrical part of the small scale installation was remade
and tested for process control.
Figure II.6. Details temperature and pH tests
The preliminary tests were followed by a sealing test in order

to determine if all the connections were in good condition (figure
II.7.) [1].
26
Figure II.7. Overview of the small scale installation operation
under process conditions
After double checking all the components, the installation was

ready to be used further in dark fermentation processes for biogas
production.
II.2. Pilot plant anaerobic digestion system
The final step relative to the experimental determinations for

the tested recipes was the usage of a pilot installation previously
constructed and continuously developed in order to optimize the
process conditions for optimum biogas production both in terms
27
of quality high methane content, over 80% - and quantity (m3 of
biogas / batch / each reactor of the installation).
The pilot installation used for obtaining biogas from biomass
through anaerobic fermentation is presented in figures II.8 and
II.9 [2].
The general working principle for the installation:
The used material is passed through a mill, and then its sent to the
tank where the preparation of the suspension of biomass is made
(1). The biomass suspension is transported with the help of the
pump (2) and introduced into the fermentation reactors (3). The
correction agent tank for the pH assures, through the control
system, the conditions for the process of anaerobic fermentation.
The resulted biogas is passed through a filter for retaining the H2S
(5) and after that, through a system used for retaining CO2 (6),
after which takes place the CO2 desorption and the compression
of the CO2 in the adjacent system (7) and the purified biogas is
sent for being used (8). The used material is discharged through
the means of a gravimetric system (9), and the solid material is
retained for being dried using the natural drying, and after that is
sent to a compost deposit for being used as a soil fertilizer. A part
of the resulting liquid is neutralized when the case, in the system
(10) and sent to the sewerage network, or is transported by the
recirculation pump (2) from the suspension preparation tank (1).
The fermentation reactors are thermostat heated with the system
(11). For the homogenization of the suspension is used a bubbling
system (12) made by polypropylene pipes to avoid the possible
corrosion. Also, for depositing small quantities of biogas of the
purpose of analyzing, the installation is equipped with a small tank
(13) positioned at the top of the reservoirs.
28
Figure II.8. Principle scheme for the pilot installation used for obtaining biogas from biomass [2,3]
29
Figure II.9. Front view of the pilot installation [2,3]
The general conditions of anaerobic fermentation for all the

batches were considered at about 32 36 C, which enters in the
mesophilic temperature regime, pH of 6.5 7.5, characteristic
mostly to the neutral pH domain and residence time on average
between 35 45 days. pH correction was made with the help of
caustic soda for increasing the values, and, when necessary, in
order to decrease high pH values there was used glacial acetic acid
99% concentrated.
All the materials tested in the pilot installation presented good
potential in terms of obtaining high biogas quality, of course the
values differed from one batch to another, but the general point
was to determine if the tested recipes can produce biogas with high
methane content and in high quantities, and for most part of the
tested batches the results were positive from this point of view.
30
References
[1] I. Ionel, Cross-border joint RDI in the field of biogas production, a
suitable renewable energy carrier for Hungary and Romania,
acronym RESGAS 2011, Code HURO/1001/193/2.2.2,
2012-2013.
[2] A.E. Cioabl, Theoretical and Experimental Contributions
Concerning Biogas Production from Biomass Residues, PhD
Thesis, Politehnica Publishing House, ISBN 978-973-625-
968-5, 2009.
[3] A. Savu, I. Ionel, C. Golesteanu, F. Popescu, B. Savu, M.
Savu, UPT-SAVPROD: Procedeu i instalaie pentru obinerea
biogazului din biomasa, Brevet nr. 122047/28.11.2008.
31
III. Analytical methods
After material documentation, the samples were prepared in

order to proceed with laboratory determinations. For this purpose,
the samples undertook a predrying process and size reduction until
a value of 1 mm using a cross hammer mill (figure III.1.).
Figure III.1. Mill for material size reduction (Fritsch P16)

Also, before making the laboratory determinations the
biofuels standards were consulted and also the user manual for the
used equipments for laboratory analysis.
The used standards for laboratory determinations were:
32
- EN ISO 18134 Solid biofuels Determination of
moisture content Oven dry method (3);
- EN ISO 18122- Solid biofuels Determination of ash
content;
- EN 14918 - Solid biofuels Determination of calorific
value;
- EN ISO 16948 Solid biofuels Determination of total
content of carbon, hydrogen and nitrogen
- EN ISO 16994 - Solid biofuels Determination of total
content of sulfur and chlorine
- EN ISO 18123 Solid biofuels Determination of the
content of volatile matter.
III.1. Determination of moisture content

The operations were made according to standard EN ISO
18134 Part 3 [1].
- inside each vessel it was weighed approximately 1 g of
material (balance precision 0.0001);
- there were made 3 time determinations for each sample;
- the samples were introduced inside the furnace at 105 C
for a period until constant mass (figure III.2.);
- after the drying period, the samples were weighed again
and the data were introduced in the specified protocol;
- for precision determinations, for samples with a high
moisture content the determinations were repeated once
more.
33
Figure III.2. Heating furnace (Binder FD 115)
III.2. Ash content determination

The operations were made according to standard EN ISO
18122 [2].
- before introducing the samples inside the furnace (figure
III.3.), the crucibles are let inside for about 2 hours at 550
C and after this operation they are let to cool down for 10
15 minutes;
- after the crucibles are cooled, weighed and inside each of
them it will be weighed minimum 1 g of material (balance
precision 0.0001);
- the furnace is switched off after this step in order to cool
down until a temperature lower than 100 C;
34
- the process of ash content determination is made as
follows: the crucibles with the weighed sample are
introduced inside the furnace, then the program starts, the
furnace is heated up to 250C, during a period of 45
minutes (7-8 C per minute), then the furnace is heated up
to 550 C during a period of about 45 minutes and it stays
there for around 3 hours. After this step, the crucibles are
put out of the furnace, let to cool down for 15 20
minutes, weighted and the obtained value is put inside the
corresponding protocol (figure III.4.).
Figure III.3. Ashing furnace (Nabetherm LE14/11/P300)

- for precision determinations, for samples with a high ash
content the determinations were repeated once more;
35
Figure III.4. Samples after ashing process
- because of the high temperatures it is difficult to number
the crucibles, hence the numbered position inside the
protocols;
- the ash content was corrected to dry basis by using the
moisture content.
III.3. Calorific value determination

The operations were made according to standard EN 14918
[3].
- before calorific value determination, the samples are
prepared for the analysis inside the calorimetric bomb
(figure III.5.);
36
Figure III.5. Calorimetric bomb (IKA C 6000)
- the preparation part is related to using a hydraulic press in
order to make a small pill like pellet of 0.3 0.5 g which is
going to be inserted into the bomb, which in its turn will
be introduced inside a calorimeter (Model IKA C 6000),
because the expected heating value is in the calibrated
range;
- after the material data is introduced in the bomb protocol
(weighed quantity, identification number for the sample
and the user) the determination starts;
- for each material there were made at least 2
determinations, in order to verify if the difference in
calorific value between both determinations is lower than
120 J/g;
- as an observation, during the process there was used only
37
one calorimetric bomb for all determinations. The
determinations were made at least two times for each
sample, and if the value between 2 consecutive
determinations is higher than 120 J/g, there was made a
third determination;
- after the bomb finishes the digestion process, its interior is
washed with ultra-pure water and the washing liquid was
filled into a 100 ml flask until mark with ultra-pure water
for each sample with the corresponding identification
number on it;
- the obtained values are then introduced inside the
corresponding protocol for obtaining the calorific value;
- the calorific value was corrected to dry basis by using the
moisture content, hydrogen content, chloride, sulphate and
nitrate values, that were obtained with the help of the IC
equipment, and so the net calorific value is determined.
III.4. Ion chromatography

This type of chromatography is used in general for liquid
analysis. The apparatus used is a Metrohm 930 model equipped
with calibration for fluoride, chloride, nitrites, nitrates, bromides,
sulfates and phosphates (figure III.6.) [4].
38
Figure III.6. IC equipment (Metrohm 930 + Metrohm 863
Compact Autosampler)
- the obtained values are presented in form of peaks on a
chromatogram from which are selected the retention times
according to the used standard (reference standard
solutions inside the carousel), measured and compared
with the existing etalon (for the used samples there were
determined just the nitrates and sulphates for correcting
the obtained calorific value);
- the carousel has 36 positions, the first position is the
blank sample, positions 2-3 are check standard solutions;
- between positions 4 and 36 are introduced samples (vessels
with a volume of approximately 10 ml) and after this step
there are made system check-ups for all the components.
39
III.5. Carbon, Hydrogen and Nitrogen determinations
The used standard for those determinations is EN ISO 16948
[5].
- before the analysis, a general system check takes place
using blank tests and reference materials for equipment
calibration (figure III.7.);
Figure III.7. CHN analyzer (ELEMENTAR Vario MACRO Cube)

- those results are used also for recalculating the results
using the new calculated value which is made after
obtaining constant values for the three presented elements;
- the calibration is made using a chemical solution composed
of D-Phenylalanine 99%;
- the sample is weighed (at the maximum possible amount
of material for a domain between 0.1 and 0.3 g / sample,
because of the volume of the material) and is introduced
40
inside a Zinc foil and into the carousel of the equipment in
parallel with introducing the sample data inside the
protocol;
- for analysis is used Oxygen of high purity, for a complete
combustion of the resulting combustion gas and Helium
for Nitrogen content determination;
- between samples at regular basis are inserted reference
materials composed by a mixture of wood and bark for
check system precision.
III.6. Determination of the volatile matter content

For volatile matter content, the determinations were made
according to the Standard EN ISO 18123 [6].
- the empty crucibles are introduced inside the furnace at
900 C 10 C for about 60 minutes and after this period
are put out and let to cool down for 20 minutes;
- after the crucibles are cooled down it is weighed a quantity
of minimum 1g 0.1 g of material;
- the crucibles are then inserted into the furnace for exactly
7 minutes and after this time period are let out to cool to
room temperature;
- after the crucibles are cooled down, are weighed again and
the results are inserted into the corresponding protocol;
- through mass difference the volatile matter content is
determined for the considered samples (at least two times
determination);
- the volatile matter was corrected to dry basis by using the
moisture content.
41
References
[1] European Standard ISO 18134-3: 2015 Solid biofuels
Determination of moisture content Oven dry method
Part 3: Moisture in general analysis sample.
[2] European Standard ISO 18122: 2015 Solid biofuels
Determination of ash content.
Determination of calorific value.
[4] European Standard ISO 16994:2015 - Solid biofuels
Determination of total content of sulfur and chlorine.
Determination of total content of carbon, hydrogen and
nitrogen.
[6] European Standard ISO 18123:2 015 Solid biofuels
Determination of the content of volatile matter.
42
IV. Legislation affecting biogas sector
According to National Institute of Statistics, the total area of

the Romania is 238391 km2 (23.8 million ha). Agricultural lands
cover 61.3% of the Romanian territory (arable 64%, orchards
and vineyards 3%, pasture and meadows 33%). Forests cover
28.3% and wetlands about 3.5%. Human settlements (built-up,
roads, railways) cover approx. 4.8%. A small share of 2.1% is
covered by other areas (eg. sand dunes) [1].
In terms of production, compared to other states of the
European Union, Romania ranks first in sunflower production,
2nd in corn production, 4th in volume of wheat exported, 4th in
total number of sheep, 6 to potato production, 4th in total number
of goats and 10 to the total number of cattle and milk production.
Due to these activities, agricultural biomass (animal and
vegetable wastes) is found in a significant amount. According to
the Romanian Association of Biomass and Biogas (ARBIO),
Romania produces 200 million tons of wastes per year. However,
biomass and biogas have a share of only 0.62% of the total energy
produced in our country [2].
In the past few years, Romania has been supported by the
European Union to build wastewater treatment plants. From this
process results sludge, waste which is a valuable raw material for
anaerobic digestion. In Romania, only 2% of sludge from
wastewater treatment plants (estimated at a total of approximately
171 086 t) is used in agriculture and the rest is disposed to landfills
or stored inside the plants [3]. These options are not sustainable to
long periods of time. Anaerobic digestion of sludge can contribute
efficiently to the decrease of organic waste deposits and to the
43
production of biogas [4-7].
IV.1. Legal framework for the promotion of energy

production from renewable energy sources
The legislation that provides the legal framework for the

promotion of energy production from renewable energy sources is:
- Government Decision (GD) no. 443/2003 regarding the
Promotion of Electricity Production from Renewable
Energy Sources (10 April 2003) - repealed by Government
Emergency Ordinance 88/2011;
- GD no. 1535/2003 regarding the approval of the Strategy
for the Capitalization of Renewable Energy Sources (18
December 2003);
- GD no. 1892/2004 establishing the system for promoting
the production of electricity from renewable energy
sources (4 November 2004) - repealed by GD no.
1479/2009;
- GD no. 1429/2004 - Decision for the application of the
Regulation certifying the origin of electricity generated
from renewable sources (2 September 2004) - repealed by
GD 1232/2011;
- GD no. 958/2005 amending GD no. 443 / 2003 on the
promotion of electricity production from renewable energy
sources and amending and supplementing the GD no.
1892/2004 on the establishment of a system to promote
the production of electricity from renewable energy
sources ( 18 August 2005) - repealed by GD 1479/2009;
- Government Ordinance no. 22/2008 on Energy Efficiency
44
and Promotion of the Use of Renewable Energy Sources
by Final Users (August 20, 2008) - repealed by the Law
no.121 / 2014;
- GD no. 750/2008 on the Regional State Aid Scheme for
the Use of Renewable Energy Resources;
- GD no. 1661/2008 approving the National Program for
Increasing Energy Efficiency and the Use of Renewable
Energy in the Public Sector for 2009-2010;
- Law no. 220/2008 establishing the system for promoting
the production of energy from renewable energy sources;
- GD no. 1479/2009 establishing the system for the
promotion of electricity generation from renewable energy
sources (25 November 2009) - repealed by Government
Emergency Ordinance 88/2011;
- GD no. 835/2010 on the modification of the National
Program for Increasing Energy Efficiency and the Use of
Renewable Energy Sources in the Public Sector for the
years 2009-2010, approved by the GD no 1661/2008.
(August 11, 2010);
- Government Ordinance no. 29/2010 on amending and
completing the Law no.220 / 2008 for establishing the
system of promoting the production of energy from
renewable energy sources (August 30, 2010);
- Law no. 139/2010 amending and completing the Law
no.220 / 2008 for establishing the system for promotion of
the production of energy from renewable energy sources;
- Government Emergency Ordinance no. 88/2011
amending and completing the Law no.220 / 2008 for
establishing the system for promotion of the production of
45
energy from renewable energy sources. (October 12, 2011);
- Law no. 134/2012 for the approval of GEO no. 88/2011
on amending and completing the Law no. 220/2008
establishing the system for promoting the production of
energy from renewable energy sources;
- Government Emergency Ordinance no. 57/2013 regarding
the amendment and completion of the Law no. 220/2008
energy from renewable energy sources;
- Government Emergency Ordinance no. 79/2013 regarding
the modification and completion of the Land
Improvement Law no. 138/2004, for the completion of
GEO no. 82/2011 on certain measures for the
organization of the land improvement activity, as well as
for the amendment of letter (e), paragraph 6 of article 3 of
the Law no. 220/2008 establishing the system for
promoting the production of energy from renewable
energy sources;
- GD no. 994/2013 regarding the approval of measures for
reduction of the number of green certificates in the
situations provided by article 6, paragraph 2, letters a), c)
and f) of the Law no. 220/2008 establishing the system for
the promotion of the production of energy from renewable
energy sources;
- Law no. 23/2014 for the approval of Government
Emergency Ordinance no. 57/2013 regarding the
amendment and completion of the Law no. 220/2008
establishing the system for the promotion of the
production of energy from renewable energy sources;
46
- GD no. 224/2014 for the approval of the mandatory
annual quota of electricity produced from renewable
energy sources benefiting from the green certificate
promotion system for 2014;
- GD no. 495/2014 for the establishment of a state aid
scheme for the exemption of certain categories of final
consumers from the application of Law no. 220/2008
energy from renewable energy sources - was amended and
supplemented with the provisions of: GD no. 620/2014,
GD no. 823/2014, GD no. 1104/2014, GD no. 113/2016;
- HG. no. 1110/2014 for the approval of the mandatory
energy sources benefiting from the Green Certificates
Promotion System for 2015;
- Law no. 122/2015 approving measures in the field of
promoting the production of electricity from renewable
energy sources and amending and completing some
normative acts;
- HG. no. 1015/2015 for the approval of the mandatory
energy sources benefiting from the green certificate
promotion system for 2016.
The implementation of energy policy in Romania is controlled
and applied by:
- Ministry of Energy - has the role of continuously
developing Romania's energy strategy
(http://energie.gov.ro/)[8];
- Ministry of Economy - applies the strategy and
government program in the fields of economy, industrial
47
policies, competitiveness, non-energy mineral resources
and sustainable development, consumer protection,
electricity and natural gas transport, quality infrastructure
and market surveillance, in accordance with market
economy requirements and stimulation of economic
operators' initiative (http://www.economie.gov.ro/) [9];
- Ministry of Environment - draws up the National Climate
Change Strategy that illustrate how to prevent and combat
the effects of climate changes (actions to reduce
greenhouse gas emissions) (http://www.mmediu.gov.ro/)
[10];
- National Energy Regulatory Authority ANRE - the
regulatory authority in the energy field: elaborate, approve
and monitor the application of mandatory national
regulations necessary for the good functioning of the
electricity, heating and natural gas markets and sectors in
terms of efficiency, competition, transparency and
consumer protection. (http://www.anre.ro/ro/)[11];
- Romanian Electricity Transmission and System Operator
(Transelectrica SA) the tasks are: electricity transmission,
system operation and market, the safety of the National
Power System
(http://www.transelectrica.ro/web/tel/home)[12];
- Market Operator of Electricity and Gas (OPCOM) the
electricity market operator: aims to manage the electricity
market by ensuring the continuous, orderly, efficient, fair
and transparent progress of transactions and commercial
contracts under regulatory conditions
(http://www.opcom.ro/pp/home.php) [13];
- Competition Council an autonomous body, manages and
implements the Competition Law (No 21/1996), which
48
aims to protect, maintain and stimulate competition and a
normal competitive environment in order to promote the
interests of consumers [14].
(http://www.consiliulconcurentei.ro/en/about-us.html)
IV.2. Romanian mechanism for promoting the

production of electricity from renewable energy sources
The Romanian mechanism for promoting the production of

electricity from renewable energy sources consist of green
certificates (GC) and quota obligation system [15-23].
The number of certificates awarded according to the
technology used by each producer and the year of accreditation is
presented in table IV.1.
The minimum price of GC is 27 and the maximum is 55 .
The maximum price in the year 2016 was 29.40 or 132.41 RON.
GC have a validity period of 12 months after which they are
canceled.
The energy suppliers are obliged to buy each year a number of
green certificates that is calculated by multiplying the mandatory
acquisition quota set by ANRE with the volume of power (in
MWh) delivered to final consumers. For 2017, the mandatory
quota was fixed at 8.3% of gross national electricity consumption.
49
Table IV.1. Number of certificates awarded for 1 MWh
produced, according to the technology used and the year of
accreditation [8]
Technology \ Year of
2011 2012 2013 2014 2015 2016
accreditation
Wind energy 2 2 2 1.5 1.5 1.5
Hydro<10 MW new 3 3 3 2.3 2.3 2.3
Hydro<10 MW
2 2 2 2.3 2.3 2.3
upgraded
Biomass 2 2 2 2 2 2
Solar 6 6 6 3 3 3
The evolution of production capacities from renewable

energies between 2011 and 2015 varied according to the legislative
framework, as presented in table IV.2.
At the end of 2015, ANRE has accredited 25 companies that
produce electricity from biomass and biogas, with a total installed
capacity of 106.5 MW. At that time, the total installed power of
plants producing energy from renewable sources was 4662 MW.
The steps required for starting up a plant for energy
production from renewable energy sources (RES), trading the RES
and benefiting from the RES promotion system are:
- Building up the generation capacity;
- Obtaining the generation license;
- Obtaining the qualification certificate for the electricity
priority production;
- Registration at the Electricity Market Operator (SC
50
OPCOM SA);
- Selling the energy from RES on the DAM (Day Ahead
Market);
- Registration at Romanian Electricity Transmission and
System Operator (CN TRANSELECTRICA SA) for
obtaining the GCs;
- Registration at the Green Certificates Market Operator (SC
OPCOM SA) for registration in the GC Register and for
participating on the GC market.
Table IV.2. Production capacities (MW) for each technology

used and each year [8]
Technology \ Year of
2011 2012 2013 2014 2015
accreditation (MW)
Wind energy new plants 810 1785 2581 2797 2924
Wind energy reused plants 12 12 12 12 12
Micro-Hydro new plants 50 99 213 208 242
Micro-Hydro refurbished
17 47 51 80 84
plants
Micro-Hydro old plants 311 281 267 23 0.16
Biomass 25 29 66 100 106
Solar 1 46 1159 1230 1267
The flow of green certificates in 2016 was as presented in table

IV.3 [23].
51
Table IV.3. Green certificates flow in 2016
Wind Solar Biomass Hydro
GCs awarded 11 357 783 10 061 337 2 128 281 2 254 691
GCs deferred 8 821 560
GCs redeemed 12 566 051
GCs expired (2017) 4 414 480
However, the renewable energy producers are facing a number

of legal problems starting from the development stage to the grid
connection. Another serious problem is related to the mandatory
quota of 8.3% that will determine the sale of less than 40% of
green certificates under the market in 2017. This impossibility to
capitalize green certificates will pose serious financial problems to
renewable energy producers.
Solving these problems, by changing legislation and upgrading
the grid, the biomass potential can be used to boost renewable
energy production and especially, to create a great opportunity for
economic and social development.
52
References
[1] E. Blan, Regional Agriculture in Romania: A Quantitative
Assessment, Global Economic Observer, 3, no.1, 2015, p. 118-
126.
[2] FRD Center (Factor Regional Development), Biofuels
(Biogas, Biomass, Biodiesel) Sector In Romania, 2015.
[3] Ministry of Regional Development and Public
Administration, Regional Operational Programme, 2013.
[4] A. Nielfa, R. Cano, M. Fdz-Polanco, Theoretical methane
production generated by the co-digestion of organic
fraction municipal solid waste and biological sludge,
Biotechnol. Reports, 5, 2015, 14-21.
[5] I. Neamt, I. Ionel, Efficiency Assessment of the Anaerobic
Digestion of Sewage Sludge from Timisoara Municipal
Water Treatment Plant, Rev. Chim. (Bucharest), 65, 9, 2014,
1117-1121.
[6] I. Neamt, I. Ionel, C. Florescu, Sewage Sludge to Energy
Possible strategies for Timisoara water treatment plant, Rev.
Chim. (Bucharest), 63, 7, 2012, 739-742.
[7] Z. Markov, D. Dimitrovski, I. Jovanovski, A. Nenchev,
Production and Utilising of Biogas and Other Measures for
Increasing Energy Efficiency in the Municipal Wastewater
Treatment Plant, J. Environ. Prot. Ecol., 14, 3, 2013, 1014-
1022.
[8] Ministry of Energy, http://energie.gov.ro/ , (accessed in 15
June 2017).
[9] Ministry of Economy, http://www.economie.gov.ro/,
(accessed in 15 June 2017).
[10] Ministry of Environment, http://www.mmediu.gov.ro/,
53
[11] National Energy Regulatory Authority ANRE,
http://www.anre.ro/ro/, (accessed in 15 June 2017).
[12] Romanian Electricity Transmission and System Operator
(Transelectrica SA),
http://www.transelectrica.ro/web/tel/home), (accessed in
15 June 2017).
[13] Market Operator of Electricity and Gas (OPCOM),
http://www.opcom.ro/pp/home.php), (accessed in 15
June 2017).
[14] Competition Council,
http://www.consiliulconcurentei.ro/en/about-us.html,
[15] L. Pvloaia, I. Georgescu, The System of Green
Certificates - Promoter of Energy from Renewable
Resources, Annales Universitatis Apulensis Series Oeconomica,
16(1), 2014, 178-187.
[16] P. Atanasoae, R. Pentiuc, Considerations on the Green
Certificate Support System for Electricity Production from
Renewable Energy Sources, Procedia Engineering, 181, 2017,
796-803.
[17] Flanders Investment & Trade Market Survey, Renewable
Energy in Romania, 2015, 71 p.
[18] C. Vac, S. Sn, F. Arion, Renewable Energy Market in
Romania, Bulletin UASVM Horticulture, 68(2)/2011, 237
240.
[19] KPMG, Taxes and Incentives for Renewable Energy
2015,
https://home.kpmg.com/xx/en/home/insights/2015/09
/taxes-and-incentives-for-renewable-energy-2015.html.
54
[20] L. Bondoc, C. Gavrila, Global Renewable Energy Guide 2014.
[21] NNDKP, Romania Chapter SEE Energy Handbook 2015,
SEE Legals Southeast Europe Energy Handbook 2015,
nndkp.ro/articles/see-legal-energy-2015/.
[22] D. Poputoaia, M. Fripp, European Experience with Tradable
Green Certificates and Feed--in Tariffs for Renewable Electricity
Support, FPL Energy, Juno Beach, Florida December 20,
2008, 28 p.
[23] Economic Consulting Association (ECA), Sustainable
Resource Initiative Policy Dialogue Framework Energy &
Resources Window, Potential Changes to the Romanian RES
Legislation, 2016.
55
V. Mathematical modeling
V.1. The numerical simulations of the thermal

phenomena inside the batch type bioreactor
The mathematical model proposed for conventional column
fixed bioreactor (figure V.1.) considers the following hypotheses:
- axisymmetric 2D domain;
- unsteady regime;
- laminar and incompressible flow;
- neglected viscous dissipation;
- constant physical properties (, , Cp, k);
- internal heat generation.
The energy equation is given by:
T T T . T
Q cp (V.1)
x x y y z z t
The thermal conductivity of the fermentation media might be
obtained from the empirical relation that considers fluid density
and humidity. For the numerical modelling presented in the
present report the following values are used:
- Heat transfer coefficient to ambient: = 30 W/m2 K; The
room temperature: te = 27 oC;
- The heat flux generated inside the heating system: Q =
4800 W.
- The reactor diameter B = 1.5 m;
56
- Width of the heating system: b = 0.8 m;
- The reactor height H = 4 m;
- Height of the heating system: h = 0.6 m.
Figure V.1. The schematic presentation of the bioreactor with the

heating system
57
Numerical details are as follows:
- The upwind scheme is used for discretization of the PDE;
- Thermal conductivity of the fermentation media = 25
W/m K;
- The free convection is considered on the room air
reactor wall contact;
- Time step = 40 s.
The conduction heat transfer is the only phenomena that
occurs in this bioreactor type. In figures V.2 V.5 results of the
transient temperature field inside the bioreactor is presented. The
chemical reactions might be considered for the future analysis.
Figure V.2. The temperature field inside the bioreactor after =

1.2e+4 s
58
Figure V.3. The temperature field inside the bioreactor after
= 3.6e+4 s

= 1.2e+5 s
59
= 1.8e+5 s
Based on numerical results, the following conclusions are

outlined:
- The temperature field is stratified with the layer near
the top of the reactor with the initial temperature;
- The steady state is obtained after = 50 h;
- The maximum temperature is tmax= 49 oC while the
minimum temperature is tmin = 28 oC.
60
V.2. The microchannel bioreactors
V.2.1. Introduction
Microchannel process technology is a developing field of
chemical processing that enables rapid reaction rates by
minimizing heat and mass transport limitations, particularly in
highly exothermic or endothermic reactions [1]. This is achieved
by reducing the dimensions of the reactor systems. In
microchannel reactors, the key process steps are carried out in
parallel arrays of microchannels, each with typical dimensions in
the range 0.1 5 mm. This modular structure enables reduction in
the size and cost of the chemical processing hardware.
Conventional reactors are up to 60m tall. In contrast,
microchannel reactor assemblies are roughly 1.5 m in diameter,
have a low profile and sit horizontally.
Microchannel reactor design is also flexible. For example,
where increasing the size of conventional reactors normally
requires plant designers to increase the size of each reactor unit,
which alters flow and reaction dynamics in the reactor, the
modular structure of microchannel reactors means that increasing
plant size to build demonstration or even commercialized plants
can be done by simply adding more reactors with the same
dimensions. Modular construction also makes the plants more
durable and easier to service because maintenance and catalyst
replacement can be carried out by replacing individual modules,
rather than requiring a prolonged shutdown of the entire system.
The performance of microchannel reactors is related to their
small diameters, which results in enhanced heat and mass transfer
capabilities. Conventional reactor systems rely on the use of bulky
hardware to manage the heat in reactions, and they have relatively
small heat transfer areas per volume of catalyst. On the other
61
hand, in microchannel reactors, each reactor block has thousands
of fine process channels filled with catalyst, which are interleaved
with water-filled coolant channels.
The microchannel process technology is a good candidate not
only for small-scale reactors, but also for a large number of
chemical and process systems that involve thermal processing.
They include, for example, ethane cracking, hydrocracking, SMR,
ethylene oxidation, separations, mixing and emulsification, catalytic
processes, gas processing for operations such as hydrogen
production, and integrated and multiphase systems.
Another advantage of microchannel reactors is their capability
to handle large volumes of feedstock and their ability to produce
quality fuels from a variety of resources, including waste wood and
municipal solid waste.
The following chapters considered some of the fundamental
issues that have to be considered for design process of these
systems: the influence of thermal properties, viscous dissipation or
partial heating.
V.2.2. The heat transfer and fluid flow of a partially

heated microchannels [2]
In most of the studies, the heating length was the same as the
total length of the heat sink [2]. In the electronics cooling
applications, the heating length is not always equal to the total
length of the channel and consequently, the thermal and
hydrodynamic phenomena depend on the heating position. The
scope of this paper is to analyze the influence of the heating
position on hydrodynamic and thermal parameters of the micro-
heat sink.
62
The one-layer microchannel heat sink is presented in the
figure V.6. Due to the symmetry plane, the half cross-section of
one channel is considered in computations. The conventional set
of the Navier-Stokes equations has been used for the conjugate
laminar steady state heat transfer and fluid flow, as follows:
The continuity equation:
u v w
0 (V.2)
x y z
The momentum equation:
u u u dp u u
u v w (V.3)
x y z dz x x y y
v v v p v v
u v w (V.4)
x y z dx x x y y
w w w p w w
u v w (V.5)
x y z dy x x y y
The energy equation (for both fluid and solid):

T T T 2T 2T 2T
c p u v w k 2 2 2 (V.6)
x y z x y z
The fluid properties are constant except for fluid viscosity that
is evaluated with following equation:
t

t 2.6412018 10 4
0.0014009 e 31.0578605 (V.7)
63
Table V.1. The geometric data and working parameters of the
microchannel heat sink
wf wc Hc Ht Lh Lt wt q u Re
2
m m m m cm cm cm W/cm m/s
36 64 280 489 1 2 1.5 34.6 0.275-7 34-743
The rest of the fluid properties are evaluated as follows: =

998.2 kg/m3, cp = 4182 J/kg K, ks = 148 W/m K, kf = 0.6 W/ m
K. The following boundary conditions are prescribed for the
system of the partial differential equations:
Wf / 2 Wc / 2
adiabatic wall
y
z
x symmetry
boundary
symmetry Hc Ht
boundary
fluid
fluid flow
microchannels
silicon
characteristic
Q = const.
cross-section
central heating
Lh
Fluid flow
Ht
upstream downstream
heating heating
Lh Lh
Q Lt
W
t
Figure V.6. The microchannel heat sink, calculation domain and

heating positions. (Reprinted from Int. Comm. Heat Mass Transfer, 36, Lelea,
D., The heat transfer and fluid flow of a partially heated microchannel heat sink,
794-798, Copyright 2009, with permission from Elsevier.)
64
The conjugate heat transfer procedure, implies the continuity
of the temperature and heat flux at the solid liquid interface
defined as,
x = Wf /2: Ts |x+ = Tf |x- (V.8)
T T f
k s s k f

(V.9)
x x x x
y = Ht Hc : Ts |y+ = Tf |y- (V.10)
T T f
k s s k f (V.11)
y
y y y
Also at the inlet cross-section, uniform velocity and

temperature field are considered:
z=0
u = uin and T = Tin (V.12)
The upper boundary is isolated defined as:
T
k 0 (V.13)
y
At the outlet of the microchannel the following boundary
conditions are prescribed:
z Lt (V.14)
T
0 (V.15)
z
At the symmetry boundary:
x = wf/2 + wc/2 (V.16)
65
w u T
v 0; 0; 0; 0 (V.17)
z z z
The working parameters and geometrical data are presented in
the table V.1.
The solution procedure is based on the method used in [3], [4]
and [5] for microtubes and on the Finite Volume Method
described in [6]. First, the parabolic flow field condition is
considered and the velocity field is solved. The temperature field,
as a conjugate heat transfer problem, was then solved as the elliptic
problem using the obtained velocity field. Also k acts as ks for
silicon wall and kf in the case of the water. At the fluid solid
interface k is calculated as the harmonic mean value. The velocity-
pressure coupling is solved using a SIMPLER method. A staggered
grid is used for cross-stream velocities with power-law discretization
scheme.
The results and conclusions
In the figure V.7 the influence of Po variation versus Re is
presented for different heating positions, defined as:
2 p Dh2
Po f Re (V.18)
Ltot uin
It is observed that for low Re and upstream heating, the Po
is decreasing as the Re is decreasing. This is the plausible
observation considering that an average temperature of the water
is increasing and the viscosity decreases. In the case of the
downstream heating the Po is increasing while for the central
heating the Po has almost the constant value as the Re decreases.
66
Figure V.7. Poiseuille number versus Re for different heating
positions. (Reprinted from Int. Comm. Heat Mass Transfer, 36, Lelea, D., The
heat transfer and fluid flow of a partially heated microchannel heat sink, 794-
798, Copyright 2009, with permission from Elsevier.)
In the figure V.8 pumping power ratio (between the no-

heating and heating case) versus mass flow rate is presented. The
pumping power for no-heating case is higher compared to heating
cases regardless the heating position. On the other hand as the
mass flow rate is increasing, the heating cases are approaching the
no-heating condition as the temperature decreases. The pumping
power is lower for almost 30 % compared with no-heating flow,
for the case of the upstream heating and low Re = 34. For the case
of central and downstream heating the benefit is 20 % and
respectively 10 %. So the Po is not a suitable parameter for the
hydrodynamic losses evaluation for the case of the heating flows.
67
Figure V.8. The pumping power ratio for no-heating and heating
case for various heating positions. (Reprinted from Int. Comm. Heat Mass
Transfer, 36, Lelea, D., The heat transfer and fluid flow of a partially heated
microchannel heat sink, 794-798, Copyright 2009, with permission from
Elsevier.)
The pumping power is defined with the following equation:

p
M (V.19)

The total length of the tube was Ltot = 2 cm and the heating
length Lh = 1 cm. For all the cases, it is observed that temperature
at the centerline of the bottom wall of the heat sink is increasing
with axial distance. Also the peak value is obtained approximately
at 0.85z (Figure V.9), except for downstream heating. In the case
of the lower Re = 34, the difference between the temperature of
the upstream and downstream heating is almost 20 %. As the fluid
68
velocity is increasing, the outlet temperature is decreasing and the
fluid viscosity has a less influence on fluid flow conditions.
Figure V.9. The temperature variation at the centerline of the

bottom wall versus axial distance for Re = 34. (Reprinted from Int.
Comm. Heat Mass Transfer, 36, Lelea, D., The heat transfer and fluid flow of a
partially heated microchannel heat sink, 794-798, Copyright 2009, with
permission from Elsevier.)
In figure V.10 the thermal resistance versus Re is presented

for three different heating positions defined as:
T Tin
R max (V.20)
q
It might be outlined that thermal resistance is decreasing as
the Re is increasing. On the other hand the lowest thermal
resistance is observed in the case of upstream heating followed by
central and downstream heating. Difference between them is
69
approximately 20 % as Re is lower than 200 and about 10 % for
Re greater than 200. The reason for lower thermal resistance in the
case of the upstream heating is the axial conduction phenomena
downstream the end of the heating length. This results in a lower
maximum temperature while the heat is spreading through the sink
wall.
Figure V.10. The thermal resistance versus Re for various heating

positions. (Reprinted from Int. Comm. Heat Mass Transfer, 36, Lelea, D., The
heat transfer and fluid flow of a partially heated microchannel heat sink, 794-
798, Copyright 2009, with permission from Elsevier.)
It is concluded that fluid viscosity has a strong impact on

thermal and hydrodynamic behavior of a micro-heat sink.
Moreover the heating position influences both the hydrodynamic
and thermal characteristics of a micro-heat sink. In the case of
hydrodynamic behavior it is observed that pumping power is
70
suitable parameter for estimating the hydrodynamic losses instead
of Po number. Considering the thermal performances, the
upstream heating has a lower thermal resistance compared with
central or downstream heating.
V.2.3. The viscous heating issue in micro-channels [7]

The latest research reports revealed the fact that, below the
certain tube diameter viscous dissipation cannot be neglected at
the microscale [7]. At some circumstances the effect of viscous
heating could affect the classic behaviors of the convective
parameters like Nu or Po numbers. In the present research report
the numerical modeling of the simultaneously developing heat
flow in the microtubes was reported, considering the variable fluid
properties and viscous dissipation term in the energy equation.
Three different fluids have been considered water, HFE-7600 and
FC-70 during cooling and heating to emphasize the behavior of
the local Nu and Po numbers in the presence of viscous heating.
To analyze the temperature dependent thermal conductivity
influence on Nu number behavior, the conjugate heat transfer and
fluid flow phenomena were numerically solved.
The computational domain is presented in figure V.11, as
follows:
- The fluid flow domain defined at r = 0, Ri and z = 0,
L;
- The temperature field domain defined at r = 0, Ro and
z = 0, L.
The following set of partial differential equations is used to
describe the phenomena, considering the variable thermophysical
properties of the fluids and viscous dissipation:
71
Continuity equation:
( (T ) u ) 1 (r (T ) v)
0 (V.21)
z r r
Momentum equation:
( (T )vu) ( (T )uu) dp 1 u
(T )r (V.22)
r z dz r r r
Energy equation:
( (T )c p (T )vT ) ( (T ) c p (T )uT ) 1
k (T ) r
T
k (T )
T
Sv
(V.23)
r z r r r z z
where the viscous dissipation term is defined as:

v 2 v 2 u 2 v u 2
S v 2 (V.24)
r r z z r
Figure V.11. The calculation domain. (Reprinted from Int. Comm.

Heat Mass Transfer, 37, Lelea, D. and Ciobl, AE., The viscous dissipation
effect on heat transfer and fluid flow in micro-tubes, 1208-1214, Copyright
2010, with permission from Elsevier.)
At the inlet of the tube, the uniform velocity and temperature
field is considered, while at the exit the temperature and velocity
gradients are equal to zero.
72
The boundary conditions are:
z = 0 , 0 < r < R o: u = u0 , T = Tw = T0
u T
0 < z < Ltot : r=0, 0, 0,v 0 (V.25)
r r
r = Ri , u = v = 0
The Joule heating of the tube wall can be expressed either by
the uniform heat generation through the tube wall or by the
uniform heat flux imposed on the outer surface of the wall. For
the latter case, the boundary condition is defined as:
T
r = Ro : qo k s (V.26)
r
where qo is the heat flux based on the outer heat transfer area of
the tube wall.
T
z = Ltot , 0 < r < Ro: 0 (V.27)
z
The conjugate heat transfer procedure, implies the continuity
of the temperature and heat flux at the solid liquid interface
defined as,
r = Ri : Ts |Ri+ = Tf |Ri-
T T f
k s s k f (V.28)
r Ri r Ri
The partial differential equations V.21 V.23 together with
boundary conditions are solved using the finite volume method
described in [6].
The following non-dimensional parameters are obtained in the
numerical computations, for water (Re=258-1684, Pr=6.4-6.9),
73
HFE-7600 (Re=186-1130, Pr=29.3-32.2) and FC-70 (Re=7.2-43.2,
Pr=189.8-317.4). The heat transfer rate imposed on the outer wall
of the tube was Q=0.5 W.
Darcy friction factor is defined by the following equation:
dp / dz Di
f (V.29)
um2 / 2
and a Re is defined as:
um Di
Re (V.30)

So, from V.29 and V.30 the local Po can be obtained in the
following form:
2 dp / dz Di2
Po f Re (V.31)
um
While the local Nu number is defined with the following
equation:
h Di
Nu (V.32)
k (Tm )
The Brinkman number for constant wall heat flux is defined
as:
um2
Br (V.33)
q Di
Results and conclusions
Numerical computations were made for three different Br =
0.01, 0.1 and 0.5 and two heat flux directions: heating and cooling.
In the figures V.12 and V13, the relation of Po versus non-
74
dimensional axial distance is presented for water. It might be
observed that Po decreases asymptotically to the fully developed
value for circular channels. On the other hand as the Br increases
and viscous dissipation influences the fluid flow, the thermal
entrance length is longer. On the other hand difference between
the cooling and heating case, for specific Br number is observed
for Br = 0.5.
Figure V.12. The local fRe versus non-dimensional axial distance

for water and Br = 0.01. (Reprinted from Int. Comm. Heat Mass Transfer, 37,
Lelea, D. and Ciobl, AE., The viscous dissipation effect on heat transfer and
fluid flow in micro-tubes, 1208-1214, Copyright 2010, with permission from
Elsevier.)
In the case of HFE-7600 for the heating case the local
distribution of the Po has a conventional behavior with the fully
developed value slightly lower than a usual value for a pipe flow
(Po=64). As the tube wall is cooled, after initial decreasing, the
local Po is increasing and asymptotically is approaching the fully
developed value. The opposite behavior of these two cases is
explained through the temperature dependent viscosity. As the
fluid is heating the viscosity is decreasing and the pressure gradient
is decreasing along the axial distance. On the other hand while the
75
fluid is cooling the viscosity is increasing and the pressure gradient
is increasing. Similar to the water flow, the viscous heating is
observed for the Br = 0.1 and 0.5. For the later, difference
between the cases with and without viscous dissipation is 5 %. It is
observed that for cooling with Br = 0.5, the Po has the non-
heating behavior with fully developed value close to Po = 64. The
plausible explanation is that viscous heating has the same order of
magnitude as the external heating source.
Figure V.13. The local fRe versus non-dimensional axial distance

Elsevier.)
The similar behavior is observed for the FC-70 with longer
hydrodynamic entrance length due to a very high fluid viscosity.
For Br = 0.5 a deviation from the case where the viscosity heating
is neglected is almost 10 %. Once again for the latter case and
cooling of the fluid, the Po exhibits the non-heating behavior with
fully developed Po = 64.
In figures V.14 and V.15 the Nu variation versus non-
dimensional axial distance is presented for water. For Br = 0 the
76
Nu number behavior is in accordance with the conclusions
regarding the effect of the fluid thermal conductivity. If the Br =
0.01 a deviation from the case that includes the viscosity
dissipation is very small. As the Br is increasing a difference is
larger and for Br = 0.5 the Nu number is almost three times larger
for cooling case. Moreover deviation is much larger for cooling
case than for heating because of the smaller temperature difference
between the tube wall and fluid, in the case of cooling. Also as the
Re number increases the Nu number relation for cooling and
heating overlaps if the viscous dissipation is excluded.
Figure V.14. The local Nu versus non-dimensional axial distance

Elsevier.)
77
Figure V.15. The local Nu versus non-dimensional axial distance
Elsevier.)
The similar conclusions are outlined for dielectric fluids HFE-
7600 and FC-70. Moreover for Br = 0.5 the ratio between the
cases with and without viscous dissipation is preserved for all
fluids.
The effect of viscous dissipation on micro-tube fluid flow and
heat transfer was investigated for three different fluids and two
different flux directions, heating and cooling. The following
conclusions might be outlined from the presented results:
o The friction factor and Po are affected at Br=0.5 for water and
starting with Br=0.1 for highly viscous fluids HFE-7600 and FC-
70. The same conclusion is valid for Nu number relation.
o The Nu number is higher for cooling than for a heating case
due to a lower temperature difference as the fluid is cooling. For
78
Br=0.5 the Nu number for a cooling case is about three times
higher compared with a heating case, regardless the fluid type.
For Br=0.5, cooling case and for all fluid types considered, the Po
number approaches conventional fully developed value for pipe
flow, Po=64. The plausible explanation is that the external cooling
and viscous heating are of the same order of magnitude.
V.2.4. Effects of temperature dependent thermal

conductivity on Nu number behavior in micro-tubes [8]
Therefore, the micro-tube heat transfer and fluid flow was
investigated considering the variable fluid properties [8]. The
special attention in this case is paid to a temperature dependent
thermal conductivity and its influence on a local Nu number. At
the same time, two different heat flux directions were considered,
heating and cooling with three fluid types: water and two dielectric
fluids HFE 7600 and FC-70.
The microtube conjugate heat transfer analysis was made for
Di / Do = 0.1/0.3 mm and stainless steel as a tube material with k
= 15.9 W/m K. To investigate the influence of the temperature
dependent thermal conductivity on Nu number behavior, the low
Re range was considered Re < 400. The input heat transfer rate
was constant for all the runs Q0 = 0.5 W considering two heat flux
directions: cooling and heating. For the heating case the inlet
temperature was tin = 20 oC, while for the cooling case tin was equal
to the outlet temperature of the heating case.
The local Nu number is defined with the following equation:
h Di
Nu (V.34)
k (Tave )
where h is defined as:
79
q
h (V.35)
Tw Tb
and the local heat flux is defined as:
T
q k f T (V.36)
r
In the figure V.16, the Nu number relation versus axial
distance is presented for lower Re=69.5 and three different cases.
It is observed for cooling case that, after the initial decreasing, the
Nu number is increasing in the region where the constant behavior
is expecting. In the case of the heating, the Nu number exhibits
the opposite relation to cooling case, it is increasing. If the thermal
conductivity is constant the Nu number approaches the constant
value Nu = 4.36 for the constant heat flux case. It has to be
emphasized that for the water Pr = 4.8-6.6.
Figure V.16. The local Nu versus axial distance for water and Re =
69.5 (Reprinted from Int. Comm. Heat Mass Transfer, 37, Lelea, D., Effects of
temperature dependent thermal conductivity on Nu number behavior in micro-
tubes, 245-249, Copyright 2009, with permission from Elsevier.)
80
If the Re is increasing to Re = 416.9 the Nu number exhibits
the conventional relation (figure V.17). After the initial decreasing
it approaches the constant value very close to the conventional one
Nu = 4.36.
Figure V.17. The local Nu versus axial distance for water and Re =
416.9. (Reprinted from Int. Comm. Heat Mass Transfer, 37, Lelea, D., Effects of
For a dielectric fluid HFE-7600 and lower Re=70.6 (Figure
V.18), the local Nu number relation is different compared with the
water case. In this case, the Nu number decreases for heating and
increases for cooling, the opposite to previous example with a
water as the working fluid. The explanation might be found from
the thermal conductivity variation. For water, the thermal
conductivity increases as the temperature increases while in the
case of a dielectric fluid HFE-7600 the thermal conductivity
decreases as the temperature increases.
81
Figure V.18. The local Nu versus axial distance for HFE-7600 and
Re = 70.6. (Reprinted from Int. Comm. Heat Mass Transfer, 37, Lelea, D.,
Effects of temperature dependent thermal conductivity on Nu number behavior
in micro-tubes, 245-249, Copyright 2009, with permission from Elsevier.)
If the Reynolds number increases to Re=284.1 the Nu

number evolution for heating and cooling cases are the same
(figure V.19). Compared to the constant thermal conductivity
relation it is observed the longer thermal entrance length as the
thermal conductivity is temperature dependent. In this case the
Prandtl number is Pr = 23.6 30.5.
82
Figure V.19. The local Nu versus axial distance for HFE-7600 and
Re = 284.1. (Reprinted from Int. Comm. Heat Mass Transfer, 37, Lelea, D.,
Effects of temperature dependent thermal conductivity on Nu number behavior
in micro-tubes, 245-249, Copyright 2009, with permission from Elsevier.)
For dielectric fluids with higher Pr numbers such as FC-70

(figure V.20), where Re = 14.5 and Pr= 200.2 the Nu number
decreases for both cases. Also, the constant thermal conductivity
variation of the Nu number is close to the heating and cooling
cases. It is observed that the local Nu numbers for cooling are
lower than the Nu numbers for heating case. This is explained
through the velocity profiles near the wall. In the case of the
heated flows, the velocities are higher near the wall, because of the
lower viscosity, that implies the higher heat transfer coefficients.
Contrary, for the cooled flows the velocities are lower near the wall
due to the higher fluid viscosity, and consequently the heat transfer
coefficients are lower.
83
Figure V.20. The local Nu versus axial distance for FC-70 and Re
= 14.7. (Reprinted from Int. Comm. Heat Mass Transfer, 37, Lelea, D., Effects of
The Nu number behavior on micro-tube heat transfer was

investigated for three different fluids: water and two dielectric
fluids HFE-7600 and FC-70. At the same time, two heat flux
directions are considered, heating and cooling compared with
k=const. It is observed that thermal conductivity has the strong
influence on local Nu number behavior, as long as the Re is low.
For water the Nu number increases as the fluid is heating and
decreases as it is cooling. As the Re is increasing the thermal
entrance length is longer so the thermal conductivity has a less
influence on local Nu number.
For a dielectric fluid HFE-7600, the local Nu number has the
opposite behavior compared to the water case. It is increasing
while the fluid is cooling and decreases as it is heating. It is
explained by the thermal conductivity temperature variation. For
84
dielectric fluids such as FC-70 with very large Pr numbers, the
thermal entrance length is very long so the local Nu number has
similar variation for both heating and cooling case. In this case the
heated flow implies higher Nu numbers compared with the cooled
ones.
V.3. Mathematical models for evaluation of anaerobic

digestion performances
The process of obtaining biogas by anaerobic digestion of
biodegradable organic waste is a convenient solution for solving
the world's energy deficit. But bio-chemical reactions to achieving
maximum amount of biogas require in-depth knowledge of the
occurring phenomena. To this end, they developed various
mathematical models.
In 2002, the International Water Association (IWA) has
developed Anaerobic Digestion Model no.1 (ADM1) [9,10]. It
describes the physical and chemical phenomena that occur during
fermentation; it takes into consideration the four stages of
digestion (hydrolysis acidogenesis, acetogenesis methanogenesis)
and how these stages appear to digestion of carbohydrates,
proteins and lipids. The main advantage of ADM1 is its high
precision. The disadvantage is the complexity of the model that
leads to the necessity of knowing many input parameters. This can
be time consuming and costly in terms of experimental approach.
For this reason, it often is preferred to use simplified models to
assess the kinetics of the biogas process in different types of
biomass [10-17].
85
1. Mathematical model Type Monod:
- Mathematical relation for biogas production estimation
(V.37)
- Kinetic equation
(V.38)
2. Mathematical model Type Moser:
(V.39)
- Kinetic equation
(V.40)
3. Mathematical model Type Hill:
(V.41)
- Kinetic equation
86
(V.42)
4. Mathematical model Type Haldane (Andrews):
(V.43)
- Kinetic equation
(V.44)
5. Mathematical model Type uncompetitive (Haldane):
(V.45)
- Kinetic equation
(V.46)
where: R = Specific biogas production (mL/g VS/day); Rmax =
maximum specific biogas production (mL/g VS/day); So = the
initial concentration of volatile solids (g/l); Af = coefficient of
speed limitation stage for the rapid deployment of the substrate; As
= coefficient for limiting step used for very fast or very slow speed
87
of the substrate; Af (s) = coefficient of speed limitation stage or very
slow or rapid use of the substrate; b = percent of initial volatile
solids remaining in the effluent; ks = saturation Monod constant
for half-acid substrates (g/l); Ks = half Monod saturation constant
for volatile solid equivalent (g/l); kn = half saturation constant Hill
for acid substrates (g/l); Kn = saturation constant Hill on half for
volatile solid equivalent (g/l); ki = inhibition constant of the
substrate for the acid substrates (g/l); m = adaptation coefficient
of acidogenic / methanogenic bacteria; n = coefficient of
adaptation for acidogenic bacteria to complex substrate
degradation; Rf = recalcitrant fractions; Sh = acid substrate
generated concentration (g / l); = growth rate of the bacteria (/
day); max = maximum speed of bacteria growth (/day); VS =
volatile solids.
Similar to bacterial growth phase, the biogas production rate
increases at the beginning of anaerobic digestion process beginning
and then decreases. This development was described by means of
statistical mathematical models of linear, exponential or Gaussian
type.
1. Linear mathematical model
(V.47)
where: y = biogas production speed (L/kg/day) in time t (days); t
= time (days); a = line origin or free term (L/kg/day); b = gradient
of regression line ((L/kg/day2).
2. Exponential mathematical model
(V.48)
= time (days); a, b = constants (L/kg/day); c = constant ((1/day).
3. Gaussian mathematical model
88
(V.49)
= time (days); a = constant (L/kg/day); b = constant (days); t0 =
time at which maximum speed of biogas production appears
(days).
Also, time evolution for the total amount of produced biogas
can be described with the help of mathematical models of logistic
growth, exponential growth through maximum or modified
Gompertz models.
1. Logistical growth model
where: y = cumulated biogas production (L/kg) at time t (days); k

= kinetic constant for reaction speed (1/days); t = time (days); a,
b = constants.
2. Exponential growth through maximum model
where: y = cumulated biogas production (L/kg) at time t (days); A

= biogas potential production (L/kg); k = first order kinetic
constant (1/days).
3. Modified Gompertz model
where: y = cumulated biogas production (L/kg) at time t (days); A

= biogas potential production (L/kg); = maximum speed for
biogas production (L/kg/day); = delay period (days).
89
References
[1] D. Atkinson, J. Mcdaniel, Microchannel reactors in fuel
production, PTQ Q2, 95-98, 2010.
[2] D. Lelea, The heat transfer and fluid flow of a partially
heated microchannel heat sink, Int. Comm. Heat Mass
Transfer, 36, 2009, 794-798.
[3] D. Lelea, S. Nishio, K. Takano, The experimental research
on microtube heat transfer and fluid flow of distilled
water, Int. J. Heat Mass Transfer 47, 2004, 28172830.
[4] D. Lelea, Some considerations on frictional losses
evaluation of a water flow in microtubes, Int. Commun.
Heat Mass Transf. 32 (7), 2005, 964973.
[5] D. Lelea, The conjugate heat transfer of the partially
heated microchannels, Heat Mass Transf. 44, 2007, 3341.
[6] S.V. Patankar, Numerical Heat Transfer and Fluid Flow,
McGraw-Hill, New York, 1980.
[7] D. Lelea, AE Ciobl, The viscous dissipation effect on heat
transfer and fluid flow in micro-tubes, Int. Comm. Heat
Mass Transfer, 37, 2010, 1208-1214.
[8] D. Lelea, Effects of temperature dependent thermal
conductivity on Nu number behavior in micro-tubes, Int.
Comm. Heat Mass Transfer, 36, 2009, 245-249.
[9] D.J. Batstone, J. Keller, I. Angelidaki, S.V. Kalyuzhnyi,
S.G. Pavlostathis, et al., The IWA Anaerobic Digestion
Model No 1 (ADM1), Water Sci. Technol., 45, 2002, 65-73.
[10] L. Yu, P.C. Wensel, J. Ma, S. Chen, Mathematical
Modeling in Anaerobic Digestion (AD). J Bioremed Biodeg.
2013, S4: 003. doi:10.4172/2155-6199.S4-003.
[11] I. Colussi, A. Cortesi, V. Gallo, A.S. Rubesa Fernandez,
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R. Vitanza, Modelling of an anaerobic process producing
biogas fro, winerz wastes, Chem. Eng. Trans., 27, 2012, 301
306.
[12] A. Donoso-Bravo, S.I. Prez-Elvira, F. Fdz-Polanco,
Application of simplified models for anaerobic
biodegradability tests. Evaluation of pre-treatment
processes, Chem. Eng. J., 160, 2010, 607-614.
[13] H.M. Lo, T.A. Kurniawan, M.E.T. Sillanp, T.Y. Pai,
C.F. Chiang, K.P.; Chao, M.H. Liu, S.H. Chuang, C.J.
Banks, S.C. Wang, K.C. Lin, C.Y. Lin, W.F. Liu, P.H.
Cheng, C.K. Chen, H.Y. Chiu, H.Y. Wu, Modeling biogas
production from organic fraction of MSW co-digested
with MSWI ashes in anaerobic bioreactors, Bioresource
Technol., 101, 2010, 6329-6335.
[14] Li, C., P. Champagne and B. C. Anderson. Evaluating and
modeling biogas production from municipal fat, oil, and
grease and synthetic kitchen waste in anaerobic co-
digestions, Bioresource Technol. 2011, 102: 9471-9480.
[15] X. Wu, J. Zhu, C. Miller, Kinetics study of fermentative
hydrogen production from liquid swine manure
supplemented with glucose under controlled pH, J.
Environ. Sci. Heal. B. 48, 6, 2013, 477-485.
[16] G.K. Kafle, S. H. Kim, Anaerobic treatment of apple
waste with swine manure for biogas production: Batch
and continuous operation, Appl Energ, 103, 2013, 61-72.
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Saber, N. Tirichine, Modeling of the anaerobic digestion
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91
VI. Case studies
VI.1. Characterization of biomass tested
Table VI.1 presents the materials which were used for the
tests.
Table VI.1. Materials used for determinations (chosen

materials)
No. Material Source of origin and details
Adiacent area from Timioara only
1. Degraded corn
grains
2. Degraded wheat
grains
3. Degraded barley
grains
4. Degraded rye
grains
The liquid material used for determinations was waste water

from Timisoara treatment plant and waste water from a beer
factory located in Timisoara.
In tables VI.2 VI.4 there are presented the general
characteristics of the used materials.
92
Table VI.2. General characteristics for the used materials part 1
No. Moisture Ash Gross Net
content content calorific calorific
MATERIAL (db), [%] (db), value value
(db), (db),
[%]
[J/g] [J/g]
1. Degraded corn 10 1.55 18400 16800
2. Degraded wheat 9.65 5.55 19000 17500
3. Degraded barley 10.5 2.5 18600 17300
4. Degraded rye 10.2 1.65 18600 17300
5. Waste water 5.8 36 15000 14100
treatment plant
6. Waste water beer 5 26.5 17200 16000
factory
db dry basis
Table VI.3.General characteristics for the used materials part 2

Volatile
Carbon Hydrogen Nitrogen matter
No. MATERIAL content content content content
(db)
[%] [%] [%]
[%]
1. Degraded 6.6 1.3 85.7
corn 40.3
2. Degraded 6.1 2.1 78.5
wheat 41.1
93
3. Degraded 6.1 1.45 82.7
barley 40.4
4. Degraded rye 40.5 6.4 1.5 84.5
5. Waste water
treatment 32.1 5.1 5.1 37.7
plant
6. Waste water
36.5 5.5 7.1 42.5
beer factory
db dry basis
Table VI.4. General characteristics for the used materials part 3

No. Sulphur Chlorine
Content Content
MATERIAL
(db) (db)
[%] [%]
1. Degraded corn 0.103 0.034
2. Degraded wheat 0.149 0.042
3. Degraded barley 0.114 0.104
4. Degraded rye 0.111 0.075
5. Waste water treatment plant 0.51 0.11
6. Waste water beer factory 0.44 0.27
db dry basis
The substrates investigates were:

- degraded corn mixed with wastewater from treatment plant
94
(CWTP),
- degraded wheat mixed with wastewater from treatment plant
(WWTP),
- degraded rye mixed with wastewater from treatment plant
(RWTP),
- degraded barley mixed with wastewater from treatment plant
(BWTP),
- degraded corn mixed with wastewater from beer factory
(CWBF),
- degraded wheat mixed with wastewater from beer factory
(WWBF),
- degraded rye mixed with wastewater from beer factory
(RWBF),
- degraded barley mixed with wastewater from beer factory
(BWBF).
VI.2. Results of biomass anaerobic digestion
VI.2.1. Results of the determinations at small scale

Relative to the used materials, at small scale there were tested
recipes containing degraded corn, wheat, rye and barley and waste
waters from treatment plant and beer factory.
1-2L scale determinations

For the 1L scale determinations, the graphical representation
for all the measurements is presented in figures VI.1 VI.3.
95
Figure VI.1. pH time variation for the tested materials
From the figure VI.1, one can observe that the initial pH
had values in the range 4-5 which means acid initial environment.
pH corrections were necessary until reaching higher values, close
to 6-7. Those values were reached after about 12 days and stayed
in this range until the end of the process.
The pH correction was made with the help of solutions
based on NH3, 20% concentration, or lime based solutions when
the pH difference from the desired one was small. In order to
decrease the pH, if necessary, it was used acetic acid, with 99%
concentration.
96
The next step involved studying the methane
concentration obtained during the anaerobic fermentation process,
as it can be seen from the figure below.
Figure VI.2. Methane concentration for the tested materials
The produced methane had a maximum concentration of

about 50% for rye base material, while for barley had a value of
about 30% which represents the minimum concentration for the
obtained biogas relative to the tested materials. In this regard,
further testing was necessary at higher volume 2L batch.
97
The next graphical representation shows the CO2 time
variation, according to the overall gas mixture present in the
produced biogas.
Figure VI.3. CO2 concentration
All the materials produced CO2 in high concentrations during

the process, which is not uncommon dude to the fact that it was
used cereal material. After an initial peak of 80-85% at the end, the
CO2 concentration was in the range of 40-60%.
The production of biogas for the tested materials is presented
in table VI.5.
98
Table VI.5. Biogas production
Substrate Corn + Wheat + Rye + Barley +
wastewater wastewater wastewater wastewater
from from from from
treatment treatment treatment treatment
plant plant plant plant
Biogas, (l) 2.8 3.6 5.2 3.3
From table VI.5 it can be determined that the produced quantities

were low, but in accordance with the test volumes. The higher
value was obtained for the batch containing rye and wastewater
from treatment plant, which implied further testing at larger scale.
The next tests were performed using the same cereal materials but
in combination with wastewater from beer factory.
Figure VI.4. pH variation
99
In figure VI.4 it can be observed the pH time variation for the
same base materials but using wastewater from beer factory. For
this scenario the pH becomes stabile in the region 6-7 after about
20 days. By comparison with the wastewater from treatment plant
this batch takes more time to adjust the pH. This fact can be
related with the low buffer capacity of the wastewater and to the
fact that the bacteria are different than in case of treatment plant
and it can take a longer period of time to adjust to the base
material.
Figure VI.5. CH4 variation
From the figure above it can be observed that the methane

concentration is much lower than from using wastewater from
treatment plant. Still, it is necessary to determine if this type of
wastewater can be used at larger scales.
100
Figure VI.6. CO2 variation
From figure VI.6 one can observe that the CO2 concentration
decreases directly proportional with methane increasing
concentration, having a minimum of about 20%.
The production of biogas is presented in table VI.6.

Substrate Wheat + Barley + Rye +
wastewater wastewater wastewater
from beer from beer from beer
factory factory factory
Biogas, (L) 2 2 2
101
From table VI.6 it can be determined that also the obtained
biogas quantities are low, making this wastewater less productive
than the first solution.
For the 2L batch the results showed a similar behavior of the

materials in terms of pH.
Figure VI.7. pH time variation
It can be observed that the initial pH values are in the range

of 4-5 and after 10-13 days with corresponding pH corrections
they got up to 6-7.
The methane concentration data is presented in figure VI.8.
102
Figure VI.8. Methane concentration values
From the figure VI.8 it can be observed that rye has again
the highest values with a methane concentration of about 55%,
while barley base material presented a methane concentration of
just 35-40%.
103
Figure VI.9. CO2 concentration values
From figure VI.9, one can deduce that the CO2 has a behavior
like the initial 1L batch, with values of over 90% at the beginning
of the process and about 40-45 % at the end.
The biogas quantities are presented in table VI.7.
Table VI.7. Biogas obtained quantities
from from from from
Biogas, (L) 7.3 9.2 14.5 9
104
From table VI.7 it can be observed that the batch containing
rye and wastewater from treatment plant had the highest biogas
quantity produced, while the minimum quantity of biogas was
produced by the batch containing corn as base material.
The same thing applies to using wastewater from beer factory

as it can be observed from figure VI.10. The pH values have a
close evolution as per 1 L batch and adjust to the domain 6-7 after
about 20 days of process. For all the tested materials, this aspect
shows that in the beginning, due to the cereal used in the process,
the buffer of the obtained suspension cannot assure a stable pH
over long periods of time, corrections being needed in order to
stabilize it for attaining the desired value inside the neutral regime.
105
From figure VI.11 it can be deduced that the methane

concentration is slightly high, with values over 20-25%, but still
low by comparison with the first type of wastewater.
106
Like in the first case, the CO2 decreases, the minimum values
in this case being higher about 32-35%. Those values present still
high levels which are not suitable for firing processes.

Biogas, (L) 5 5 5
From table VI.8 it can be observed that the obtained

quantities are higher than for 1L batch. This scenario was also take
into consideration at a higher volume to observe if there are any
modifications in terms of process and parameters.
The next logical step was to test those materials at higher
volumes 5L.
107
5L scale determinations [1-3]
Figure VI.13 underlines the fact that the initial values for pH
were higher that at smaller scale which were advantageous because
implied lower pH correction agent quantities and after about 10-12
days all the materials reached the correct domain for anaerobic
fermentation.
It also can be determined that the mixture between barley and
wastewater from treatment plant was the most constant one from
the pH point of view, while the mixture between corn and
wastewater from treatment plant had a slightly alkaline tendency at
the beginning. The rest of the tested materials presented a normal
108
behavior, having in mind the characteristic steps for anaerobic
fermentation.
From figure VI.14 it can be observed that the methane

concentration values are slightly higher with a maximum value for
rye about 60%.
109
Figure VI.15. CO2 concentration values
According to figure VI.15, the CO2 values indicate a similar

behavior for the used materials inside the range of 90% - 35
40%. The highest value for CO2 was obtained from the batch
containing degraded corn (about 55% by volume), while the batch
containing degraded rye, as cereal base material had a minimum of
less than 40%. Of course, the presence of high values of CO2 can
be used, with proper technology in agriculture with accent on
greenhouses.
The obtained biogas quantities are presented in table VI.9.
110
Table VI.9. Biogas quantities
from from from from
Biogas, (L) 13.8 17.6 27.5 17.1
From table VI.9 the produced quantities indicate a relatively

high potential for biogas production, which is needed to be tested
at larger scale.
The same process was applied, again, also for the batch
containing wastewater from beer factory. In this case it can be
observed that the period of time necessary to enter in the domain
111
6-7 is lower about 15 days, which represents an improvement
from the small scale determinations.
Still, the methane concentration remains in the range 20-25%

which is relatively low by comparison with the initial batch.
This aspect shows that, at least for lower scale testing, a part
of the materials do not achieve a level of biogas with more than
20% methane in concentration.
A solution to help the base materials in order to produce
faster the type of bacteria suitable for biogas with high methane
content could be the insertion of inoculum, but the purpose of the
study was to determine the potential of different mixtures without
this type of intervention.
112
The CO2 concentration presents a minimum of 33-35% which

is still high relative to using this obtained biogas in firing processes.
This aspect is needed to be taken into consideration for further
determinations at higher scale.

Biogas, (L) 6 8 5
113
From table VI.10 it can be observed that the obtained biogas
quantities are not very high by comparison with the 2L batch, but
still present potential for the used recipe to be tested at higher
volumes.
During the process, all the used materials produced biogas in
certain quantities and with different methane concentrations, so
after those steps, it started the pilot installation determinations.
VI.2.2. Results of pilot installation determinations

After testing at small scale, there were made laboratory
determinations using the pilot installation in regard to determining
the best material from the chosen ones in terms of quality and
quantity for the produced biogas [4-6].
VI.2.2.1. Case of substrates prepared with wastewater
from a treatment plant
114
The determinations were made in parallel, having as base
material corn and wheat in mixture with waste water from
treatment plant this was the first batch of material.
From the figure VI.19, it can be observed that the initial
values were about 5 5.2 and after initial pH corrections, between
days 5-8 the pH was risen to values in the range 6.5 7.5. Until the
end of the process the pH remains in this domain.
The temperature of the process was established between 34
o
36 C.
Figure VI.20. Methane concentration
From figure VI.20 it can be observed that from the first 5

days the base materials produced methane in low concentrations,
115
reaching a maximum value of 74-75% after about 20 days and
staying high until the end of the determination. This shows great
potential for both recipes.
The CO2 decreased according to the methane increase in

percentage, showing a minimum value of about 20 25 % at the
end of the determination (figure VI.21).
The second batch of materials was composed by degraded rye
and degraded barley and wastewater from treatment plant.
116
The pH for the two batches (figure VI.22) started atypically,

with values over 7 from the first day, because of initial pH
correction, but decreased to proper values by day 4-5, remaining in
the correct domain until the end of the process. The initial pH
correction had the role to give a buffer value in order for the
material to decrease the initial pH with acid fermentation / CO2
production which is suitable for cereal materials, in order to
shorten the time to reaching correct pH values and decrease the
initial period in order to maximize the biogas production time.
117
From figure VI.23 it can be observed that the methane

production started from the first days of process, reaching a
maximum of 78-81% for barley and 74 76% for rye. The used
materials in this case showed even bigger potential than the first
batch.
118
Figure VI.24. CO2 concentrations
CO2 values (figure VI.24) decreased accordingly, showing

minimum values of under 20% - this aspect is relevant in order to
further try to reduce the concentration of CO2 with other means
and to improve the methane concentration inside the obtained
biogas composition.
The obtained quantities of biogas are presented in table VI.11.
119
from from from from
Biogas, (m3) 14.160 18.449 29.058 18.097
From the table VI.11, one can observe that the mixture
composed by degraded rye and wastewater from treatment plant
had the highest quantity, while the batch composed of degraded
corn and wastewater from treatment plant had the lowest
produced quantity.
The cumulative biogas production during anaerobic digestion
of four co-substrates investigated is presented in figure VI.25.
For all investigated substrates, the biogas production started
very quickly. In the cases of degraded rye mixed with wastewater
from treatment plant (RWTP) and degraded barley mixed with
wastewater from treatment plant (BWTP), the biogas production
started after 3 days of digestion, while, for degraded corn mixed
with wastewater from treatment plant (CWTP) and degraded
wheat mixed with wastewater from treatment plant (WWTP), the
gas production began in the second day of digester operation.
The degraded corn mixed with wastewater from treatment plant
(CWTP) and degraded wheat mixed with wastewater from
treatment plant (WWTP) had a low biogas production until day 9
when both digestion reactors reached a cumulative biogas
production of 2 m3. The other two substrates had a better
behavior: after 4 days of fermentation the degraded barley mixed
with wastewater from treatment plant (BWTP) generated 3.66 m3
120
of biogas and the degraded rye mixed with wastewater from
treatment plant (RWTP) an amount of 4.66 m3 of biogas.
Figure VI.25. Cumulative biogas production during anaerobic

digestion of investigated co-substrates
After day 9, the biogas production from CWTP and WWTP

digesters increased slowly and reached on day 45: 14.5 m3 of
biogas for CWTP and 18.5 m3 of biogas for WWTP. Even if
BWTP and RWTP behaved similarly at the beginning of the
experiment, after 4 days of digestion they showed different biogas
production patterns. The speed of biogas production for BWTP
decreased significantly compared with RWTP. At the end of
121
digestion period, the amount of biogas generated by anaerobic
digestion was 18.1 m3. As concerns the RWTP digester, the
cumulative biogas production has been by far the highest
throughout the entire process of anaerobic digestion, reaching an
amount of 29 m3 of biogas.
The order of investigated substrates, in terms of total amount
of biogas generated after 45 days of anaerobic digestion process
was: degraded rye with wastewater from treatment plant (RWTP)
> degraded wheat with wastewater from treatment plant (WWTP)
> degraded barley with wastewater from treatment plant (BWTP)
> degraded corn with wastewater from treatment plant (CWTP).
The methane content of biogas produced during anaerobic
digestion of investigated substrates is presented in figure VI.26.
Figure VI.26. Methane content of biogas produced during

anaerobic digestion of investigated co-substrates
122
The methane content of biogas formed during anaerobic
digestion process had the same evolution for RWTP and BWTP
substrates. The values of methane concentration increased rapidly
until day 16, reaching a value of 79% for RWTP and 81 % for
BWTP.
As concern the other two substrates (CWTP and WWTP), the
methane content in the biogas had a slowly evolution. The lowest
concentration of methane was found in biogas produced from
anaerobic digestion of RWTP. The methane concentration in the
biogas produced from anaerobic digestion of WWTP was a little
bit higher that in the biogas from RWTP digestion. After 22 days
of digestion both samples reached the same concentration of
methane in the biogas, namely 79%. The highest concentration of
methane was obtained in the biogas produced by anaerobic
digestion of barley.
The experimental data about the biogas yield and its
methane content were used to calculate the cumulative equivalent
methane for each of the four substrates subjected to anaerobic
digestion (figure VI.27).
123
Figure VI.27. Cumulative equivalent methane of the four
substrates subjected to anaerobic digestion
VI.2.2.2. Case of substrates prepared with wastewater

from a beer factory
In the next subchapter there will be presented the

experimental approach for the batches tested inside the pilot
installation using as base material the wastewater from a beer
factory.
124
As it can be observed from figure VI.28, the pH was

monitored during a period of about 45 days, during which it
could be observed the fact that after 2 days of process, the
values decreased for both batches to values between 6.5 and 7.5,
which correspond to the desired domain of pH inside the
reactors.
In the next figure is presented the methane content for
batched containing corn and barley, mixed with wastewater
from a beer factory.
125
It can be observed from the figure below that methane
content reached valued of about 75% by volume for both batches
of material. From this point of view it is considered that the
obtained biogas is suitable for further firing processes.
126
The time variation of carbon dioxide is directly
proportional with the increase in methane for the produced biogas.
In this regard, the lowest value for both batches of materials is
around 25%, a suitable value to be used for further testing as
biofuel.
The next batch of materials were consistent with wheat and
rye, mixed with wastewater from beer factory.
From the figure above it can be determined that the pH

was stable during the process, no important fluctuations appeared,
meaning that the initial correction made with a caustic soda based
suspension was enough to create a sustainable buffer for the entire
testing period for both tested materials.
127
As determined for the first batch, the methane

concentration in this scenario showed lower values for the tested
mixtures, about 70 72% of methane inside the produced biogas.
Even if the resulted biogas has a lower methane percentage, it is
still suitable for firing processes.
128
The CO2 concentration is, like in the first case, directly

proportional with the methane concentration inside the obtained
biogas. The minimum levels are at the same value for both batches
of material around 27 30%. From this point of view it is clear
that the biogas in this scenario will be inferior from a firing point
of view.
The next table synthetizes the cumulative biogas quantities
obtained for all the tested materials.
129
Substrate Corn + Barley + Wheat + Rye +
from beer from beer from beer from beer
factory factory factory factory
Biogas, (m3) 20.461 15.132 15.720 20.745
It can be determined that the batches containing corn and

rye produced higher biogas quantities implying that from a
quantitative point of view they are superior.
Figure VI.34. Cumulative biogas production during anaerobic

digestion of investigated co-substrates
130
From figure VI.34 it can be observed the time distribution
for the produced biogas. It is observed that the last 5 -7 days of
process present maintenance of the same value for the produced
biogas. This implies the fact that the batch is at its limit and new
batch should be prepared for further testing.
Figure VI.35. Methane content of biogas produced during

anaerobic digestion of investigated co-substrates
The figure above states the stability of methane percentage

inside the produced biogas. It can be determined that after a swift
increased in the first 10 days of process, the methane content
becomes stable until the end of the process.
131
Figure VI.36. Cumulative equivalent methane of the four
substrates subjected to anaerobic digestion
From the graphical representation above, it can be determined

that from the equivalent methane quantity produced during the
anaerobic fermentation process, the bath containing barley and
wastewater from beer factory had the highest yield of equivalent
methane, thus making it the most suitable batch from this point of
view. Of course, further testing can be required in order to
establish without any doubt this aspect.
132
VI.2.2.3. Comparison between anaerobic digestion
results of substrates prepared with wastewater from
treatment plant and from beer factory
In the next subchapter there will be presented the main

comparative arguments for using the wastewaters from beer
factory and treatment plant in terms of biogas production.
Figure VI.37. Cumulative biogas production for anaerobic

digestion of corn mixed with wastewater from beer factory and
wastewater from a treatment plant
From a cumulative biogas production stand, in case of using

degraded corn material, the best solution, after testing both types
of wastewaters, is to use beer factory in the mix. It seems that
because of the different bacteria developed inside the process of
133
obtaining beer, there seems to be a good connection with cereal
material, thus making it suitable for obtaining higher methane
yields.
Figure VI.38. Cumulative equivalent methane yield for

anaerobic digestion of corn mixed with wastewater from beer
factory and wastewater from a treatment plant
From the methane yield using the same degraded material, it

seems that at the end of the process the production is about the
same, the speed of the process being the only distinctive factor.
This aspect could be explained in the same manner, being
connected with the bacterial structure present inside the two types
of wastewater. From mesophilic processes, the speed of the
process overall is not that relevant or important, for batch types of
reactors, at least.
134
digestion of wheat mixed with wastewater from beer factory and
For wheat, it seems that the combination with wastewater

from treatment plant is more suitable, but the overall difference is
not very high. This could be explained from the way in which the
process started and counting on the fact that there were no
inhibiting factors.
135
anaerobic digestion of wheat mixed with wastewater from beer
From a cumulative methane yield point of view, the difference
is clear in favor of using wastewater from treatment plant.
Having in mind figure VI.39, it becomes obvious that
wastewater is the logical choice for this material.

digestion of rye mixed with wastewater from beer factory and
136
In case of using degraded rye for anaerobic fermentation,
again, it becomes clear that wastewater from treatment plant is the
better solution, with an overall cumulative production of around
30 m3 of produced biogas.

anaerobic digestion of rye mixed with wastewater from beer
The suitability of using wastewater from treatment plant can

be also observed from the figure above. By comparison with
wastewater from beer factory, which produced about 11 m3 of
equivalent methane, the wastewater batch from treatment plant
produced over 16 m3 of methane.
137
digestion of barley mixed with wastewater from beer factory and
Also, for degraded barley, it seems that the treatment plant
wastewater is the most suitable from a biogas production point of
view. Even if the difference is not very high, it still shows the
compatibility of this material with treatment plant waters.

anaerobic digestion of rye mixed with wastewater from beer
138
Also the equivalent methane yield is higher for the batch with
wastewater from treatment plant, as it can be seen from the figure
above.
As an overall conclusion it can be stated that from the tested
degraded materials, with the exception of corn, all the others
presented a better behavior during anaerobic fermentation with
wastewater from treatment plant. This makes this type of water
more suitable, at least at this level, for further testing, even if
research still has to be continued in order to determine the best
combinations between wastewater from beer factory and other
degraded materials.
VI.3. Characterization of digestate

For the tested materials after the process of anaerobic
fermentation, there were made laboratory analysis in order to
determine the general properties of the used materials.
Table VI.13. The used samples for determinations
No. Origin source
Material Observations
and details
1. Waste water from Predried material Degraded
Timisoara wheat - only
treatment plant and grains -
degraded wheat Timioara
Timisoara barley - only
treatment plant and grains -
degraded barley Timioara
3. Waste water from Predried material Degraded rye -
Timisoara only grains -
139
treatment plant and Timioara
degraded rye
Timisoara beer wheat - only
factory and grains -
degraded wheat Timisoara
Timisoara beer barley - only
factory and grains -
degraded barley Timisoara
6 Waste water from Predried material
Degraded rye -
Timisoara beer
only grains -
factory and
Timisoara
degraded rye
The materials were subjected to a process of 30 35 days

anaerobe fermentation.
After material documentation, the samples were prepared in
order to proceed with laboratory determinations. For this purpose,
the samples undertook a predrying process and size reduction until
a value of 1 mm using a cross hammer mill.
Also, before making the laboratory determinations the biofuels
standards were consulted and also the user manual for the used
equipments for laboratory analysis. The used standards for
laboratory determinations were:
- EN ISO 18134 Solid biofuels Determination of
moisture content Oven dry method (3);
- EN ISO 18122- Solid biofuels - Determination of ash
content;
140
- EN 14918 - Solid biofuels Determination of calorific
value;
- EN ISO 16948 Solid biofuels Determination of total
content of carbon, hydrogen and nitrogen
- EN ISO 16994 - Solid biofuels Determination of total
content of sulfur and chlorine
- EN ISO 18123 Solid biofuels Determination of the
content of volatile matter.
Next tables will underline the obtained results for the
laboratory determinations
Table VI.14. Experimental results (part 1)
No. Material Moisture Ash Gross Net
content content calorific calorific
value value
[%] (db)
(db) (db)
[%]
[J/g] [J/g]
1. Waste water from 2.52 7.03 18626 17187
Timisoara treatment
plant and degraded
wheat
2. Waste water from 3.66 14.2 17566 16199
Timisoara treatment
plant and degraded
barley
3. Waste water from 1.87 10.8 17939 16541
Timisoara treatment
plant and degraded
rye
141
4. Waste water from 1.63 4.41 19525 18022
Timisoara beer
factory and degraded
wheat
5. Waste water from 1.96 3.44 19728 18040
Timisoara beer
barley
6. Waste water from 1.53 3.97 19001 17487
Timisoara beer
rye
* - 35-40 days anaerobe fermentation
As it can be seen from the table VI.14, the water content for
the samples was taken from predried materials. The ash content is
the highest for recipes no. 2 and 3, making them not very suitable
for consequent firing processes in regard to the obtained waste
material after process. The gross and net calorific values show high
energetic potential for all materials, with further possibilities to be
capitalized.
142
No. Carbon Hydrogen Nitrogen Volatile
content content content matter
MATERIAL content
(db) (db) (db)
(db)
[%] [%] [%]
[%]
1. Waste water from
Timisoara treatment
46.5 6.60 1.24 73.8
plant and degraded
wheat
2. Waste water from
Timisoara treatment
43.8 6.27 1.95 70.4
plant and degraded
barley
3. Waste water from
Timisoara treatment
44.5 6.41 1.55 72.4
plant and degraded
rye
4. Waste water from
Timisoara beer factory 47.6 6.89 1.00 76.9
and degraded wheat
5. Waste water from
and degraded barley
6 Waste water from
and degraded rye
db dry basis
143
From the table VI.15 it can be observed that the general
values are relatively normal for this type of materials (agricultural
biomass as base material).
No. Sulphur content Chlorine
content (db)
MATERIAL (db)
[%]
[%]
1. Waste water from
Timisoara treatment 0.135 0.414
plant and wheat
2. Waste water from
plant and barley
3. Waste water from
plant and rye
4. Waste water from
Timisoara beer factory 0.083 0.294
and wheat
5. Waste water from
and barley
6 Waste water from
and rye
db dry basis
144
The sulphur and chlorine concentrations are relatively high,
especially for chlorine content, which could prove to be
problematic if further used in firing processes alone, in terms of
affecting the firing chamber of the equipment.
The obtained data, can be further used, in combination with
literature and further information which is still to be obtained by
laboratory means in order to increase the level of data for the used
materials. This could be an interesting step in terms of material
characterization and possibly creation of predictive models to
better understand the process behavior and possible results in
terms of biogas production.
145
VI.4. Results of mathematical modeling
Experimental models for material / biogas production and thermal
phenomena inside the process.
Previous studies reported the existence of three characteristic
zones during cumulative methane production process
corresponding to different stages of anaerobic digestion, according
to figure VI.45 [7,8]:
18
16
Cumulative equivalent methane yield (m3)
14
12
10
8
1 2 3
6
0
0 5 10 15 20 25 30 35 40 45
Time, (days)
Figure VI.45. Main zones in the process of methane accumulation

- the lag zone (1) - can be noticed at the beginning of the
digestion process and correspond to the period before
the beginning of gas generation.
- the exponential zone (2) - a rapid methane production
phase.
- the steady state zone (3) appear in the end of the
146
process and is characterized by a drastically reduction
of the methane production.
These zones are well highlighted in our study.
According to previous report, in order to calculate and
compare the methane production during anaerobic digestion of
different substrates, three mathematical models were used [9-13]:
a) Logistical growth model
(VI.1)
where: M is the cumulative equivalent methane yield at time t, (m3),
MP is the methane production potential, (m3), b is a constant, k is
kinetic hydrolysis reaction rate constant, (1/days), t is the time
(days), and exp is the exp(1)=2.7183.
b) Exponential growth model
(VI.2)
MP is the methane production potential, (m3), k is kinetic
hydrolysis reaction rate constant, (1/days), is the period of lag
phase (days), t is the time (days) and exp is the exp(1)=2.7183.
c) The modified Gompertz model:
(VI.3)
MP is the methane production potential, (m3), Rm is the maximum
147
methane production rate (m3/days), is the period of lag phase
(days), t is the time (days) and e is the exp(1)=2.7183.
The parameters of the model were calculated by non-linear
unconstrained optimization method, using the Nelder-Mead
algorithm which minimizes a scalar-valued nonlinear function of n
real variables using only function values [14].
The software used to determine those parameters was Matlab
R2008b (version 7.7.0.741). The goodness of model was first
evaluated graphically and then the Pearson correlation coefficient
(r) and the root mean square deviation (RMSD) were calculated.
VI.4.1. Anaerobic digestion modelling of substrates
prepared with wastewater from treatment plant
The results of logistical growth models together with the
experimental results are presented in figure VI.46. The model
parameters and the values of model performances are presented in
table VI.17.
148
18
16
14
12
10
0
0 5 10 15 20 25 30 35 40 45
Time, (days)
Logistical growth model CWTP
Experimental CWTP
Logistical growth model WWTP
Experimental WWTP
Logistical growth model RWTP
Experimental RWTP
Logistical growth model BWTP
Experimental BWTP
Figure VI.46. Experimental data (markers) and logistical growth

models (solid lines) for methane production during anaerobic
digestion of investigated substrates
From figure VI.47 and table VI.17 it can be noticed that
logistical growth model describe very well the methane production
during anaerobic digestion of WWTP and BWTP. The methane
production potential for these two co-substrates is closed to the
experimental quantity of methane produced. The kinetic hydrolysis
reaction rate constant is higher for WWTP than for BWTP. As
149
concern the other two co-substrates (CWTP and RWTP), the
experimental data showed inferior agreements with the model
results.
Table VI.17. Parameters of logistical growth mathematical model
and the values of model performances
Model parameters
Substrate
MP b k ra RMSDb
used
(m3) (1/days)
Corn + 7.7000 3184.3000 0.5000 0.9898 0.2874
wastewater
from
treatment
plant
Wheat + 11.8170 506.0154 0.3031 0.9993 0.0342
wastewater
from
treatment
plant
Rye + 15.7029 189.7370 0.3477 0.9961 0.3386
wastewater
from
treatment
plant
Barley + 11.3132 91.9310 0.1990 0.9994 0.0209
wastewater
from
treatment
plant
a
Pearson correlation coefficient; b the root mean square deviation
150
The results of exponential growth models together with the
table VI.18.
Table VI.18. Parameters of exponential growth mathematical
model and the values of model performances
Model parameters
Substrate used MP k ra RMSDb
(m3) (1/days) (days)
Corn + 8.2658 0.1430 12.3023 0.9838 0.1713
wastewater
from treatment
plant
Wheat + 14.8622 0.0632 11.3407 0.9796 0.6947
wastewater
from treatment
plant
Rye + wastewater 18.9213 0.0734 6.8881 0.9764 1.5078
from treatment
plant
Barley + 33.3129 0.0129 7.8710 0.9650 0.5708
wastewater
from treatment
plant
a
151
20
18
16
14
12
10
0
0 5 10 15 20 25 30 35 40 45
Time, (days)
Exponential growth model CWTP
Experimental CWTP
Exponential growth model WWTP
Experimental WWTP
Exponential growth model RWTP
Experimental RWTP
Exponential growth model BWTP
Experimental BWTP
Figure VI.47. Experimental data (markers) and exponential growth

exponential growth model showed worse agreement with the
experimental data. This model will not be considered in the further
studies.
The results of modified Gompertz models together with the
152
table VI.19.
18
16
14
12
10
0
0 5 10 15 20 25 30 35 40 45
Time, (days)
Modified Gompertz model CWTP
Experimental CWTP
Modified Gompertz model WWTP
Experimental WWTP
Modified Gompertz model RWTP
Experimental RWTP
Modified Gompertz model BWTP
Experimental BWTP
Figure VI.48. Experimental data (markers) and modified

Gompertz models (solid lines) for methane production during
anaerobic digestion of investigated substrates
153
Table VI.19. Parameters of modified Gompertz mathematical
Model parameters
Substrate
MP Rm ra RMSDb
used
(m3) (m3/days) (days)
Corn + 7.8577 0.8405 12.6843 0.9967 0.0765
wastewater
from
treatment
plant
Wheat + 12.1759 0.8683 13.3293 0.9983 0.0858
wastewater
from
treatment
plant
Rye + 16.0930 1.3436 8.9718 0.9980 0.1639
wastewater
from
treatment
plant
Barley + 12.2795 0.5176 11.3802 0.9979 0.0713
wastewater
from
treatment
plant
a
From figure VI.48 and table VI.19 it is clear that the highest
methane production potential is exhibited by degraded rye mixed
with wastewater from treatment plant (RWTP), followed by
degraded barley mixed with wastewater from treatment plant
154
(BWTP), degraded wheat mixed with wastewater from treatment
plant (WWTP) and degraded corn mixed with wastewater from
treatment plant (CWTP). The maximum methane rate (Rm) is
shown in the case of anaerobic digestion of degraded rye mixed
with wastewater from treatment plant (RWTP), while the
minimum was observed for degraded barley mixed with
wastewater from treatment plant (BWTP). The largest lag phase ()
was observed for degraded wheat mixed with wastewater from
treatment plant (WWTP), which suggests that the initial
microbiological composition of this sample is not adequate for
anaerobic digestion. The shorter lag phase was exhibited by
degraded rye mixed with wastewater from treatment plant
(RWTP).
The good values of the Pearson correlation coefficient and of
root mean square deviation indicate that the modified Gompertz
kinetic model describes very well the phenomena that took place
during anaerobic digestion of the investigated substrates. The
results of the mathematical modeling indicates that among the
studied substrates, degraded rye mixed with wastewater from
treatment plant (RWTP) is the most appropriate for anaerobic
digestion, followed by degraded barley mixed with wastewater
from treatment plant (BWTP), degraded wheat mixed with
wastewater from treatment plant (WWTP) and degraded corn
mixed with wastewater from treatment plant (CWTP).
VI.4.2. Anaerobic digestion modelling of substrates
prepared with wastewater from beer factory
The results of logistical growth models together with the
table VI.20.
155
Figure VI.49. Experimental data (markers) and logistical growth
logistical growth model describe well the methane production
during anaerobic digestion of RWBF and BWBF. The methane
production potential for these two co-substrates is closed to the
experimental quantity of methane produced. The kinetic hydrolysis
reaction rate constant is higher for RWBF than for BWBF. As
concern the other two co-substrates (CWBF and WWBF), the
experimental data showed inferior agreements with the model
results.
156
Table VI.20. Parameters of logistical growth mathematical model
and the values of model performances
Model parameters
Substrate used MP b k ra RMSDb
(m3) (1/days)
Corn + 7.6015 10.9957 0.2647 0.9757 0.3352
wastewater from
beer factory
Wheat + 6.0050 47.5239 0.4463 0.9876 0.1171
wastewater from
beer factory
Rye + wastewater 12.9616 109.4627 0.1825 0.9971 0.1313
from beer factory
Barley + 10.7222 25.9255 0.1455 0.9973 0.0804
wastewater from
beer factory
a
Pearson correlation coefficient; bthe root mean square deviation
The results of exponential growth models together with the

table VI.21.
157
Figure VI.50. Experimental data (markers) and exponential growth

exponential growth model showed a relatively good agreement
with the experimental data for substrates WWBF and CWBF. As
concern the other two substrates (RWBF and BWBF), the model
was prove to be inadequate to characterize the anaerobic digestion
process. This model will not be considered in the further studies.
158
Table VI.21. Parameters of exponential growth mathematical
Model parameters
Substrate used MP k ra RMSDb
(m3) (1/days) (days)
Corn + 8.0467 0.1047 2.2370 0.9837 0.2725
wastewater from
treatment plant
Wheat + 6.3748 0.1236 2.8961 0.9703 0.3922
wastewater from
treatment plant
Rye + wastewater Not appropriate
from treatment
plant
Barley + Not appropriate
wastewater from
treatment plant
a
The results of modified Gompertz models together with the

table VI.22.
159
Figure VI.51. Experimental data (markers) and modified
Gompertz models (solid lines) for methane production during
anaerobic digestion of investigated substrates
160
Table VI.22. Parameters of modified Gompertz mathematical
Model parameters
Substrate
MP Rm (days) ra RMSDb
used
(m3) (m3/days)
Corn + 7.7240 0.5199 1.4448 0.9842 0.2117
wastewater
from
treatment
plant
Wheat + 6.0822 0.6430 3.8288 0.9915 0.0776
wastewater
from
treatment
plant
Rye + 14.7895 0.5226 12.9149 0.9940 0.2847
wastewater
from
treatment
plant
Barley + 12.1168 0.3582 6.9504 0.9983 0.0480
wastewater
from
treatment
plant
a
161
From figure VI.51 and table VI.22 it is clear that the highest
methane production potential is exhibited by degraded rye mixed
with wastewater from beer factory (RWBF), followed by degraded
barley mixed with wastewater from beer factory (BWBF), degraded
corn mixed with wastewater from beer factory (CWBF) and
degraded wheat mixed with wastewater from beer factory
(WWBF). The maximum methane rate (Rm) is shown in the case of
anaerobic digestion of degraded wheat mixed with wastewater
from beer factory (WWBF), while the minimum was observed for
degraded barley mixed with wastewater from beer factory (BWBF).
The largest lag phase () was observed for degraded rye mixed with
wastewater from beer factory (RWBF), which suggests that the
initial microbiological composition of this sample is not adequate
for anaerobic digestion. The shorter lag phase was exhibited by
degraded corn mixed with wastewater from beer factory (CWBF).
The good values of the Pearson correlation coefficient and of
root mean square deviation indicate that the modified Gompertz
kinetic model describes very well the phenomena that took place
during anaerobic digestion of the investigated substrates. The
results of the mathematical modeling indicates that among the
studied substrates, degraded rye mixed with wastewater from beer
factory (RWBF) is the most appropriate for anaerobic digestion,
followed by degraded barley mixed with wastewater from beer
factory (BWBF), degraded corn mixed with wastewater from beer
factory (CWBF) and degraded wheat mixed with wastewater from
beer factory (WWBF).
162
VI.5. Catalysts testing in biogas configuration inside pilot
installation
The experimental approach regarding catalytic firing of biogas

using different catalytic materials inside a pilot installation built at
the University of Belgrade, Mechanical Engineering Faculty, Serbia
is presented below.
The test rig used in the studies is presented in figure VI.52
[15].
Figure VI.52. Overall presentation of the test rig [15]

The schematic presentation of the test rig is presented in
figure VI.53.
163
Sdg
PG
T10
T9 FDG
T8
ps T7 AQ-ADG
Tatm pMB T6
patm
T5
T4
T3
NI-AQ-Tc T2 HDG ADG
T1
MG
R1 R2 R3 R4 MK
R5
TV
MB
Vs v
RV 3
RV 1 RV 2 RV 4 LEGEND:
RV Regulating valve FR
R Rotameter (gas flow measurement)
MG Inlet gas mixing chamber
Tv Air temperature
Tatm Atmospheric temperature
pat m Atmospheric pressure
CNG N2 MB Orifice (air flow measurement)
ps Static pressure of the fluid
pMB Differential pressure at orifice
T Temperature within porous media - thermocouple type R (PtRh-Pt)
MK Mixing chamber of a burner
Vsv Air fan
FR Regulating unit for air fan
PG Porous burner
Sdg Flue gas probe
HDG Flue gas cooler
FDG Flue gas filter
ADG Flue gas analyzer
NI-AQ-Tc Acquisition system (temperature measurement)
AQ-ADG Acquisition system (flue gas analysis)
Figure VI.53. Schematics of the test rig [15]
164
As it can be observed from figure VI.52 and VI.53, the overall
circuit is made from the following steps: the gas from the bottles
passes through a flow meter in order to regulate the correct flow
for different regimes, after that it enters inside a premixing
chamber and inside the burner. Inside the burner, on different
levels, are placed temperature sensors (thermocouples type K and
R) in order to better observe and control the temperatures during
the experiments. The data from the sensors is sent to an
acquisition system (HIOKI LR 8401-20). The exhaust gas readings
are made with an HORIBA PG-250 model and correlated with the
pressure differences inside the system, the obtained temperatures
obtained inside the burner and the used type of gas.
The main interest of the presented study was to determine the
optimal temperature burning profile and to locate the position of
the flame in order to determine the optimum characteristics for a
stabile burning regime (figure VI.54).
Figure VI.54. Front view of the burner
165
In the figures VI.55, there can be observed the preliminary
data of the initial testing of the equipment before the experimental
part.
Figure VI.55. Initial measuring of the temperatures inside the

burner
In order to have a stable firing regime, it is important to
attain a thin graphical domain in terms of the temperatures
obtained from all the levels located inside the burner.
The main values that should modify are related with CO2,
CO and O2. In the tested composition there should not be relevant
quantities of NO or SO2 (figure VI.56).
166
Figure VI.56. Preliminary readings flue gas
Figure VI.57. Schematic representation of heat transfer inside the

burner [15]
167
From figure VI.57 there can be observed the main zones of
the burner and the heat transfer relative to the flue gas and the
flame during the firing process.
Figure VI.58a. View of the pebbles inside the burner, cold state[15]
Figure VI.58b. View of the pebbles inside the burner bed is fully
heated (full operation regime) [15]
168
After the initial testing of all the components of the test rig,
the initial tests started, using three sorts of catalysts produced
inside Politehnica University Timisoara and destined to be used for
this type of determinations, using as base fuel a gas mixture
composed of 80% methane and 20% CO2, which represents the
most representative value for the produced biogas during the
experimental testing inside the Multifunctional Laboratory located
at the Mechanical Engineering Faculty, Politehnica University
Timisoara.
The initial step for determinations was to first try a gas made
from the gas mixture without any catalyst in order to observe the
temperature profile during firing (figure VI.59).
Figure VI.59. Test without catalyst excess air 1.6

During the initial test, it was determined the position of the
flame inside the burner, relative to the value t1 measured with the
help of the positioned thermocouple on the burner and the data
acquisitioning system.
169
The initial values of the test are presented in table VI.23.
Table VI.23. Initial data for the first test without any catalysts
MEASUREMENTS: 1 without catalyst
DATE 16.06.2017
START: 12:25
END: 13:20
EXCESS AIR: 1.6
POWER RATIO 1.5 KW
FUEL: CH4:CO2 80.4:19.6
LOWER HEATING [kJ/m3] 28847.52
VALUE:
FUEL [m3/h] 0.1872
CONSUMPTION:
AIR CONSUMPTION: [kg/h] 2.9633
CHARASTERISTICS OF THE BURNER PEBBLE BED:
CERAMIC PEBBLE [mm] 13
DIAMETER:
HEIGHT OF THE [mm] 253
BED:
POROSITY: - 44.94
FLAME ARRESTOR
DIAMETER:
HEIGHT OF FLAME [mm] 107.5
ARRESTOR:
170
Inside table VI.20 there are presented the initial data of the
experimental setup.
Table VI.24. Flue gas analysis air excess = 1.6
Flue gas analysis at the exit of the burner
O2 CO2 NOx CO
[%] [%] [ppm] [ppm]
8.78 8.12 4 442
ppm parts per million
From table VI.24 one can observe the general characteristics
of the flue gas measured in real time inside the burner; the overall
data is in the range of excess air 1.6.
For safety reasons and also in order to determine if the overall
process is suitable for further determinations, there was made
another test with excess air = 2.
In the figure VI.60 is presented the overall graphic for
temperature variation during the firing process.
171
Figure VI.60. Test without catalyst excess air 2.0
From figure VI.60 it can be observed that the flame got a

lower position inside the burner which was directly influenced by
the increased air excess characteristic for this type of process.
Table VI.25. Test without any catalysts involved air excess = 2.0
MEASUREMENTS: 3 Without Catalyst
DATE 16.06.2017
START: 14:11
END: 14:48
EXCESS AIR: 2.0
POWER RATIO 1.5 KW
172
FUEL: CH4:CO2 80.4:19.6
LOWER [kJ/m3] 28847.52
HEATING
VALUE:
FUEL [m3/h] 0.1872
CONSUMPTION:
AIR [kg/h] 3.7041
CONSUMPTION:
CHARASTERISTICS OF THE BURNER PEBBLE BED:
DIAMETER:
HEIGHT OF THE [mm] 253
BED:
POROSITY: - 44.94
FLAME ARRESTOR
DIAMETER:
HEIGHT OF [mm] 107.5
FLAME
ARRESTOR:
From table VI.25 it can be observed the overall parameters

used for this test.
173
Table VI.26. Flue gas analysis air excess = 2.0
Flue gas analysis at the exit of the burner
O2 CO2 NOx CO
[%] [%] [ppm] [ppm]
11.10 6.63 1 28
Making a comparison between tables VI.24 and VI.26 one can

observe easily that the increased air excess affects the overall
composition for the obtained flue gas, by increasing the obtained
composition both in terms of O2 and CO2.
Because the flame attained a lower position, the gas had the
possibility to be better burnt, thus the lower concentration of CO
which represents in fact a good aspect for this measurement.
After determining the initial temperature profile for the gas
mixture, the burner was prepared in order to test the catalysts
inside of it.
There were tested three different types of catalysts inside
the burner, as it can be seen from the figure VI.61 VI.63.
174
Figure VI.61. ZnAl2O4 catalyst, before process
Figure VI.62. ZnCr2O4 catalyst before process
175
Figure VI.63. CoAl2O4 catalyst before the process
First, it was necessary to make some constructive adjustments
inside the burner this meant to open the lower part and insert a
metal pocket which will contain the catalyst (figure VI.64 and
VI.65).
Figure VI.64. The opened lower part of the burner
176
Figure VI.65. Inserting the metal pocket with the catalyst inside
the burner
Figure VI.66 a. Weighing the metal pocket
177
Figure VI.66 b. Weighing the catalyst for the test
After making the initial tests in order to fit the metal pocket
inside the burner and weighing both the metal pocket and the
catalyst (the plastic support was also weighed in order to determine
the mass of the catalyst) (figure VI.66), the firing tests were
performed.
After the tests were made, the materials were weighted again
to observe the mass loss during the firing process this aspect had
just an informal role.
The synthesized data obtained after the tests with catalysts are
presented in figures VI.67 VI.73.
Depending on conditions of combustion (mainly of gaseous
fuel composition, fuel-air ratio and power rate of the burner) it can
be observed different types of temperature profiles in axial
direction of the ceramic burner. If the flame is located in lowest
part of the burner (=0), at the surface of separation the two
zones of different porosities between flame arrestor and main
part of packed bed of pebbles/spheres, it is possible to conclude
178
that the combustion is stable. Marginal position of the flame that
indices stable operating regime of porous burner is zm<55.7 mm
(axial coordinate of packed bed of spheres), measured from the
upper surface of flame arrestor. If the flame passes zm, it can be
underlined the fact that the flame will be eventually pushed out the
porous packed bed and the flame will be extinguished.
Figure VI.67. Temperature distribution in axial direction for

different air-fuel ratio (1.6 to 2.0)
The highest temperatures show where the flame is

stabilized inside the porous bed. For =1.6 flame is located at
relative position =0. Increasing the to 1.8 and 2.0, flame moves
toward exit. For =2.0 flame is located at =0.22 ((=L/z relative
coordinate in axial direction, where L is total height of porous bed
of the burner).
179
Figure VI.68. Comparison of temperature distribution in axial
direction of ceramic burner for =1.6

180
At Figures VI.68 to VI.69 it can be observed that highest
temperatures within packed bed of tabular alumina spheres are
obtained with ZnCr2O4 catalyst. For =1.6, comparing
combustion with and without catalyst the temperature differences
for catalyst ZnCr2O4, depending on the relative position in axial
direction are in the range 3.8 and 60.1 oC. Also, flame is positioned
at relative coordinate =0.22 for combustion without catalyst and
at =0 using ZnCr2O4. This indicates that using catalyst it is
possible to obtain more stable combustion conditions. For higher
air-fuel ratios =1.6 and 2.0, since we used small quantities of
catalyst could not observer distinctive difference between position
of the flame (0.22<<0.33).
181
Figure VI.71. Comparison of temperature in solid phase
distribution in axial direction of ceramic burner for =1.6

182
Figures VI.71 to VI.73 show temperature distribution at the

surface of the spheres at specified position in axial direction. It can
be observed similar conditions with previously explained. Highest
temperatures are measured for combustion conditions =1.6 with
ZnCr2O4 catalyst, and more or less very similar conditions of
combustion for higher air-fuel ratios.
183
Conclusions
Three type of catalyst were investigated:
ZnAl2O4 4.28 gr of catalyst
CoAl2O4 3.975 gr of catalyst
ZnCr2O4 2.27 gr of catalyst
According to presented data of experimental research of
influence different catalyst on stabilization of combustion it is
possible to conclude the following:
- There is slight difference in temperature profiles for
combustion of gaseous fuel (CH4 = 80.6% vol, CO2 =
19.4% vol) within porous inert media without catalyst and
using different type of catalyst.
- For three different regimes (fuel-air ratio in range 1.6 to
2.0) we obtained different temperature profiles in axial
direction of the porous inert media of ceramic burner.
- Possible influence on stabilization of the flame using
catalyst is observed by the position of the flame.
- Lower the flame within porous inert media, more stable
combustion is
- For =1.6 combustion with ZnCr2O4 shows the lowest
position of the flame (highest temperature at relative
position at =0); for =2.0 combustion with ZnAl2O4
shows the lowest position of the flame (highest
temperature at relative position at =0.22).
The experimental research can be expanded, if necessary, in
order to:
- Simulate more different regimes, as well as to investigate
184
influence of catalyst at higher working temperatures.
- Simulate influence of quantity of catalyst on combustion
stabilization.
- Produce different shapes and porosity of catalyst and
investigate the influence of specific area of contact
between reactants.
- Investigate influence and efficiency of commercial catalyst
on combustion stability within porous inert media.
185
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188

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Adrian Eugen CIOABL, Gabriela-Alina

DUMITREL, Dorin LELEA, Francisc

Biogas in theoretical and

This work was partially supported by a grant of the

Nowadays, the need for renewable sources of energy becomes

The automotive industry used biofuels since the first days of

Table I.1. World fuel ethanol production, in billion gallons [2]

The USA and Brazil dominate the world ethanol production

In Europe, biogas is mainly used for generating heat and

Figure I.5. Biogas production by country

Biomass in many forms as solids, liquids or gases can be

Figure I.6. Shares of Biomass Sources in Global Heat and

Figure I.7. Biofuels Global Production, Shares by Type and by

The experimental systems used to test the anaerobic digestion

II.1. Bench scale systems

Figure II.1. Overall view of the thermostatic bath system

The components of the small scale installation are:

Figure II.3. Schematics of the small scale installation

The component part from figure II.4. are [1]:

Figure II.5. Small scale installation general overview

After the small scale installation preparative operations were

Figure II.6. Details temperature and pH tests

The preliminary tests were followed by a sealing test in order

After double checking all the components, the installation was

II.2. Pilot plant anaerobic digestion system

The final step relative to the experimental determinations for

The general conditions of anaerobic fermentation for all the

After material documentation, the samples were prepared in

Figure III.1. Mill for material size reduction (Fritsch P16)

III.1. Determination of moisture content

III.2. Ash content determination

Figure III.3. Ashing furnace (Nabetherm LE14/11/P300)

III.3. Calorific value determination

III.4. Ion chromatography

Figure III.7. CHN analyzer (ELEMENTAR Vario MACRO Cube)

III.6. Determination of the volatile matter content

According to National Institute of Statistics, the total area of

IV.1. Legal framework for the promotion of energy

The legislation that provides the legal framework for the

IV.2. Romanian mechanism for promoting the

The Romanian mechanism for promoting the production of

The evolution of production capacities from renewable

Table IV.2. Production capacities (MW) for each technology

The flow of green certificates in 2016 was as presented in table

However, the renewable energy producers are facing a number

V.1. The numerical simulations of the thermal

Figure V.1. The schematic presentation of the bioreactor with the

Figure V.2. The temperature field inside the bioreactor after =

Figure V.4. The temperature field inside the bioreactor after

Based on numerical results, the following conclusions are

V.2.2. The heat transfer and fluid flow of a partially

The energy equation (for both fluid and solid):

The rest of the fluid properties are evaluated as follows: =

Figure V.6. The microchannel heat sink, calculation domain and

Also at the inlet cross-section, uniform velocity and

In the figure V.8 pumping power ratio (between the no-

The pumping power is defined with the following equation:

Figure V.9. The temperature variation at the centerline of the

In figure V.10 the thermal resistance versus Re is presented

Figure V.10. The thermal resistance versus Re for various heating

It is concluded that fluid viscosity has a strong impact on

V.2.3. The viscous heating issue in micro-channels [7]

where the viscous dissipation term is defined as: