Raport An 3 Te

Synthetic report regarding the period 01.10.2015 30.09.
2017
Project no. 65 / 01.10.2015
(PN-II-RU-TE-2014-4-1043)
During the period 01.10.2015 31.12.2016 the following activities were performed:
Presentation of general models existing in literature
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 requires 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). It describes the physical and chemical phenomena that occur during
fermentation, consider 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.
Table 1.1 simplified mathematical models for estimation of biogas production through
anaerobic digestion and microbial growth respectively.
Mathematical
Mathematical relation for biogas production estimation Kinetic equation
model
Type Monod 0
= =
+
+ 0
( )
Type Moser 0
= =

+ 0 +

( )
Type Hill 0
= =
+
+ 0
( )
Type Haldane 0
= =
(02 )(() ( ) ) 2
(Andrews) 0 + +( ) + +
() ( )
Type
uncompetitive 0 () ( )
= =
(Haldane) 0 () ( )
( + 0 () ( ) ) (1 +

) ( + ) (1 + )

where: 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 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; Rmax =
maximum specific biogas production (mL / g VS / day); R = Specific biogas production (mL / g
VS / day); So = the initial concentration of volatile solids (g / l); 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 increased rate of production for biogas from
anaerobic digestion is at process beginning and then decreases. This development was described
by means of statistical mathematical models of linear, exponential or gausienne. type
Table 1.2. Mathematical models which describe the evolution for speed of biogas
production
Mathematical Model equation
model
Liniar =+
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).
Exponenial = +

(days); a, b = constants (L/kg/day); c = constant ((1/day).
Gaussian 0 2
= 0.5(
)

(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.
Table 1.3. Mathematical models which describe the time evolution of total biogas
production
Mathematical model Model equation
Logistical growth
=
1 +
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.
Exponential growth = (1 )
through maximum
where: y = cumulated biogas production (L/kg) at time t (days); A =
biogas potential production (L/kg); k = first order kinetic constant
(1/days).

Modified Gompertz ()+1

=
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).
Relative to solid state fermentation phenomena in bioreactors, a mathematical model was

proposed for a conventional column fixed bioreactor. The following hypotheses were considered
in the mathematical model [26, 28]:
- axisymmetric domain;
- unsteady regime;
- laminar and incompressible flow;
- neglected viscous dissipation;
- constant physical properties (, , Cp, k);
- internal heat generation.
Considering the above assumptions the mass conservation equation can be written as

+ () =

The momentum equation is given by

() + () = + () +

The energy equation is given by

() + (( + )) = () +

The thermal conductivity of the fermentation medium might be obtained by using some of
the the empirical models, which is a function of the packing density of the bed and moisture.
The system of the partial differential equations is solved with finite volume finite element
code along with the boundary conditions. The velocity-pressure coupling is solved using some of
the SIMPLE-like method. A staggered grid is used with a series of discretization schemes. The
commercial Ansys Fluent solver is used for this purpose.
Ansys Fluent has the modeling capabilities for a wide range of incompressible and
compressible, laminar and turbulent fluid flow problems. Steady-state or transient analyses can be
analyzed. In Ansys Fluent, a broad range of mathematical models for transport phenomena (like
heat transfer and chemical reactions) is combined with the ability to model complex geometries.
Examples of Ansys Fluent applications include laminar non-Newtonian flows in process
equipment; conjugate heat transfer in turbomachinery and automotive engine components;
pulverized coal combustion in utility boilers; external aerodynamics; flow through compressors,
pumps, and fans; and multiphase flows in bubble columns and fluidized beds [27].
The modeling of fluid flow and related transport phenomena in industrial equipment and
processes including porous media, lumped parameter (fan and heat exchanger), periodic of cyclic
flow and heat transfer, swirl, and moving reference frame models. The moving reference frame
family of models includes the ability to model single or multiple reference frames.
A time-accurate sliding mesh method, useful for modeling multiple stages in
turbomachinery applications.
Another very useful group of models is the set of free surface and multiphase flow models.
These can be used for analysis of gas-liquid, gas-solid, liquid-solid, and gas-liquid-solid flows.
For these types of problems, Ansys Fluent provides several multiphase models such as: the
volume-of-fluid (VOF), mixture, and Eulerian models, as well as the discrete phase model (DPM).
The DPM performs Lagrangian trajectory calculations for dispersed phases (particles, droplets, or
bubbles), including coupling with the continuous phase.
Examples of multiphase flows include channel flows, sprays, sedimentation, separation,
and cavitation. The accurate and reliable turbulence models are a vital component of the Ansys
Fluent suite of models. The turbulence models provided have a broad range of applicability, and
they include the effects of other physical phenomena, such as buoyancy and compressibility.
Particular care has been devoted to addressing issues of near-wall accuracy via the use of extended
wall functions and zonal models.
Various modes of heat transfer can be modeled, including natural, forced, and mixed
convection with or without conjugate heat transfer, porous media, etc. The set of radiation models
and related to the modeling participating media and can take into account the complications of
combustion.
A particular strength of a code is its ability to model combustion phenomena using a variety
of models, including eddy dissipation and probability density function models. A host of other
models that are very useful for reacting flow applications are also available, including coal and
droplet combustion, surface reaction, and pollutant formation models.
Using Matlab language and Ansys Fluent, there will be investigated various simplified
mathematical models in order to describe the experimental process of anaerobic digestion and at
the same time, to understand the phenomena that occur in the process and the parameters that
influence the course stages of digestion (biomass type, temperature, pH, etc.).
Identification of materials which are to be further used inside laboratory determinations
Relative to the practical approach (experimental part), the chosen substrates are going to
be mixtures of cereal degraded material (eg. wheat, barley, rye) and waste water from local sources
(eg. beer factory, local treatment plant).
The initial step is to prepare the solid materials in order to be mixed with the waste waters.
In this sense there is performed size reduction to a measure of about 1-2mm. After this step,
preliminary measures are taken in order to determine the general characteristics of the cereal
material and preliminary measurements are made in order to determine the partial characteristics
for the mixture of cereal degraded material and waste waters.
Tables 4 and 5 underline preliminary analysis performed on the liquid mixture between
waste waters and cereal degraded materials.
Table 1.4 General characteristics for material mixtures (part 1)
Sample TS OTS Conductivity Acetic Propionic Butyric Valeric
(g/l) (g/l) (mS/cm) acid acid acid acid
(g/l) (g/l) (g/l) (g/l)
Residual water 57.29 49.48 5.53 2.10714 0.20112 0.0588 0

treatment plant
+ wheat
residual water 32.84 20.04 4.09 0.3054 0.31464 3.90144 0.02046
treatment plant
+ barley
residual water 45.31 38.59 4.22 2.09592 0.1695 0.19716 0

treatment plant
+ rye
residual water 48.24 42.2 4.97 2.0709 2.3202 0.79698 1.0104

beer factory +
wheat
residual water 24.63 21.04 5.00 1.57296 1.79988 0.70728 0.9681

beer factory +
barley
residual water 40.53 36.2 4.93 2.6142 2.17374 0.6231 0.93822

beer factory +
rye
Table 1.5 General characteristics for material mixtures (part 2)

Sample Density pH (- NH4+
(g/cm3) log (mg/l)
cH+)
Residual 1.01 3.97 189

water
treatment
plant + wheat
residual water 0.993 4.55 84

treatment
plant + barley
treatment
plant + rye
residual water 1 3.98 153

beer factory +
wheat

beer factory +
barley

beer factory +
rye
Further analysis are to be made for the solid substrates alone and initial testing at small
scale will be made in order to establish the fermentation potential in terms of biogas production
for the tested material combinations.
Material testing, mathematical modeling and preparation of catalysts in order to be
further tested
After the initial determinations relative to a part of the chosen substrates, the material
analysis continued to be performed in order to establish part of the chemical characteristics.
Table 2.1 presents the materials which will be used in testing at small and pilot scale.
Table 2.1 Materials used for determinations (chosen materials)

No. MATERIAL ORIGIN SOURCE AND DETAILS
1. CORN Adiacent area from Timioara
2. WHEAT Adiacent area from Timioara
3. BARLEY Only grains - Adiacent area from Timioara
4. RYE Only grains - Adiacent area from Timioara
The liquid material used for determinations was waste water from Timisoara treatment
plant and waste water from a beer factory located in Timisoara.
Also there were made some initial testing using beet molasses and cow whey but the results
at small scale were not very high (also the procurement of materials is relatively difficult) and thus,
those materials were used just for testing and will not be further underlined in this report.
In tables 2.2, 2.3 and 2.4 there are presented the general characteristics of the used
materials.
Table 2.2 general characteristics for the used materials part 1

No. Moisture Ash Gross calorific Net calorific
MATERIAL content content value (db), value (db),
(db), [%] [J/g] [J/g]
(db), [%]
1. Corn 10 1.55 18400 16800
2. Wheat 9.65 5.55 19000 17500
3. Barley 10.5 2.5 18600 17300
4. Rye 10.2 1.65 18600 17300
5. Waste water treatment plant 5.8 36 15000 14100
6. Waste water beer factory 5 26.5 17200 16000

No. Carbon Hydrogen Nitrogen Volatile matter
MATERIAL content content content content (db)
[%] [%] [%] [%]
1. Corn 40.3 6.6 1.3 85.7
2. Wheat 41.1 6.1 2.1 78.5
3. Barley 40.4 6.1 1.45 82.7
4. Rye 40.5 6.4 1.5 84.5
5. Waste water treatment plant 32.1 5.1 5.1 37.7
6. Waste water beer factory 36.5 5.5 7.1 42.5
No. Sulphur Chlorine
MATERIAL Content (db) Content (db)
[%] [%]
1. Corn 0,103 0,034
2. Wheat 0,149 0,042
3. Barley 0,114 0,104
4. Rye 0,111 0,075
5. Waste water treatment plant 0,51 0,11
6. Waste water beer factory 0,44 0,27
After the determination of general properties for the used materials, the process of
anaerobic fermentation began for the materials, at small scale, using 1 and 2 liter plastic vessels.
The test rig is presented in figure 2.1. The components are described as follows:
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 the thermocouple and can be
checked with the help of a thermometer inserted into the bath);
2 plastic bottles with a total volume of 1 L / 2 L, filled up to about 0.8 L / 1.5 L with the
materials used for determinations;
3 the corks of the plastic bottles were modified in order to allow 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 aluminium 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 2.1 test rig for material testing at small scale
Also, for the 5 L test rig there was used the stand presented in figure 2.2 and 2.3.
Figure 2.2 test rig for 5 L determinations
The components of the small scale installation are:

1 thermal glass vessels with a total volume of 5 L 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.
Figure 2.3 front image of the test rig for 5 L determinations
After the made determinations, the materials were tested inside the pilot installation which
is presented below in order to determine the potential of producing biogas by using this type of
material mixtures in terms of quality and quantity for the obtained biogas.
The pilot installation was built in this purpose, namely to obtain biogas using different types
of biomass in liquid formulas. The general schematics of the pilot installation are presented in
figure 2.4.
Figure 2.4 Principle scheme for the pilot installation used for obtaining biogas from
biomass
The general working principle for the installation:
From the biomass deposit, 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.
The next section will describe in short the main preparation steps for the test rigs (small scale
and pilot installation)
For the small scale installation thermostatic bath and 1-2L total volume for plastic bottles,
first there were tested the corks and fittings in order to determine potential leaks (liquid and gas),
also there were checked the plastic connectors and gas bags and after this initial step, the laboratory
determinations were started.
For the small scale installation with 5L reactors, the steps were consistent with: changing
the pH electrode, testing the electrical and mechanical components (temperature loop,
thermocouple, temperature controller, pH controller and sensors testing with buffer solution,
metallic plate placed on the reactors).
The details are presented inside figures 2.5 and 2.6.
Figure 2.5 Initial montage and checking of equipment

1 connector for gas transfer, 2 pH sensor, 3 metallic plate, 4 connector for
homogenization and sampling, 5 thermocouple for temperature control
Figure 2.6 pH and temperature controllers (pH on the left and right sign, temperature in
the middle)
After those steps, the laboratory determinations were started.
For the pilot installation, there were made more operations (figure 2.7, 2.8 and 2.9):
- Checking all the electrical connections,
- Replacing the electrovalves which were no longer functioning properly,
Figure 2.7 Changing the electrovalves and gas piping
Figure 2.8 Adding supplementary branches for gas part in order to potentially measure in
parallel
- Modifying the gas and water piping for better control
Figure 2.9 Changing initial piping with copper piping for better heat transfer to the reactors
Sealing checking before starting the laboratory determinations
After the initial steps and double checking all the components of the installation there were
started the laboratory determinations.
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 2.10 2.12.
10
6
pH
0
0 5 10 15 20 25 30 35 40
Time (days)
Corn + wastewater treatment plant

Wheat + wastewater treatment plant
Rye + wastewater treatment plant
Barley + wastewater treatment plant
Figure 2.10 pH time variation for the tested materials
From the figure 10, one can observe that the initial pH had values between 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.
50
Methane content, (%)

40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.11 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.
100
90
80
CO2 content, (%)
70
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.12 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 is presented in table 2.5.
Table 2.5- Biogas production

Substrate Corn + Wheat + Rye + Barley +
wastewater wastewater wastewater wastewater
from treatment from treatment from treatment from treatment
plant plant plant plant
Biogas, (l) 2.8 3.6 5.2 3.3
4
pH
0
0 5 10 15 20 25 30 35 40
Time (days)
Wheat + wastewater beer factory Barley + wastewater beer factory

Rye + wastewater beer factory
Figure 2.13 pH variation
In figure 2.13 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.
20
18
16
Methane content,(%)
14
12
10
8
6
4
2
0
0 5 10 15 20 25 30 35 40
Time (days)

Figure 2.14 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.
35
30
25
CO2 content,(%)
20
15
10
0
0 5 10 15 20 25 30 35 40
Time (days)

Figure 2.15 CO2 variation
From figure 2.15 one can observe that the CO2 concentration decreases directly
proportional with methane increasing concentration, having a minimum of about 20%.

Substrate Wheat + Barley + Rye +
wastewater wastewater wastewater
from beer from beer from beer
factory factory factory
Biogas, (l) 2 2 2
From table 2.6 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.
10
9
8
7
6
pH
5
4
3
2
1
0
0 5 10 15 20 25 30 35 40
Time (days)

Figure 2.16 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 2.17.
60
40
20
0
0 10 20 30 40
Time (days)
Figure 2.17 Methane concentration values

From the figure 2.17 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%.
100
90
80
CO2 content, (%)
70
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40
Time (days)

Figure 2.18 CO2 concentration values
From figure 2.18, 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 2.7.
Table 2.7 Biogas obtained quantities

Biogas, (l) 7.3 9.2 14.5 9
From table above 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.
7
4
pH
0
0 10 20 30 40
Wheat + wastewater beer
factory Time (days)
Barley + wastewater beer
factory
The same thing applies to using wastewater from beer factory as it can be observed from
figure 2.19. 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.
25
Methane content,(%)
20
15
10
0
0 10 20 30 40
Time (days)
Wheat + wastewater beer factory
Barley + wastewater beer factory
From figure 2.20 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.
50
40
CO2 content,(%)
30
20
10
0
0 5 10 15 20 25 30 35 40
Time (days)

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 2.8 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.
5L scale determinations
10
8
pH 6
4
2
0
0 10 20 30 40
Time (days)

Figure 22 pH time variation
Figure 2.22 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.
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.23 Methane concentration values

From figure 2.23 it can be observed that the methane concentration values are slightly
higher with a maximum value for rye about 60%.
100
90
80
CO2 content, (%)
70
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.24 CO2 concentration values
According to figure 2.24, the CO2 values indicate a similar behavior for the used materials
inside the range of 90% - 35 40%.
The obtained biogas quantities are presented in table 2.9.
Table 2.9 Biogas quantities

Biogas, (l) 13.8 17.6 27.5 17.1
From table 2.9 the produced quantities indicate a relatively high potential for biogas
production, which is needed to be tested at larger scale.
7
6
5
pH 4
3
2
1
0
0 10 20 30 40
Wheat + wastewater beer factory
Time (days)
Barley + wastewater beer factory
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 6-
7 is lower about 15 days, which represents an improvement from the small scale determinations.
20
Methane content,(%)
15
10
0
0 5 10 15 20 25 30 35 40
Time (days)


Still, the methane concentration remains in the range 20-25% which is relatively low by
comparison with the initial batch.
90
80
70
CO2 content,(%)
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40
Time (days)

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
From table 2.10 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.
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.
10
9
8
7
6
pH
5
4
3
2
1
0
-5 5 15 25 35 45
Time (days)
Corn + wastewater treatment plant Wheat + wastewater treatment plant
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 2.28, 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 36 deg. C.
90
80
70
Methane content,(%)
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)
Figure 2.29 Methane concentration
From figure 2.29 it can be observed that from the first 5 days the base materials produced
methane in low concentrations, 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.
100
90
80
CO2 content,(%)
70
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)
Figure 2.30 CO2 concentration
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 30).
The second batch of materials was composed by degraded rye and degraded barley and
wastewater from treatment plant.
10
6
pH
0
0 5 10 15 20 25 30 35 40 45
Time (days)
Rye + wastewater treatment plant Barley + wastewater treatment plant
The pH for the two batches (figure 2.31) 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 / CO 2
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.
90
80
Methane content,(%)
70
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.32 methane concentration values
From figure 2.32 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.
100
90
80
70
CO2 content,(%)
60
50
40
30
20
10
0
0 10 20 30 40
Time (days)

Figure 2.33 CO2 concentrations

CO2 values (figure 2.33) 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 11.
Table 2.11 Biogas quantities

Biogas, (m3) 14.160 18.449 29.058 18.097
From the table 2.11, 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.
Laboratory determinations for the obtained materials

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 2.12 The used samples for determinations
No. ORIGIN SOURCE AND

MATERIAL OBSERVATIONS
DETAILS
1. Waste water from PREDRIED
Timisoara treatment MATERIAL Only grains - Timioara
plant and wheat
plant and barley
plant and rye
Timisoara beer MATERIAL Only grains - Timisoara
factory and wheat
Only grains - Timisoara
Timisoara beer MATERIAL
factory and barley
6 Waste water from PREDRIED
Timisoara beer MATERIAL Only grains - Timisoara
factory and 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.
Figure 2.34 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:
- 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.
- Methods
Determination of moisture content.
- The operations were made according to standard EN ISO 18134 Part 3 Solid biofuels
Determination of moisture content Oven dry method;
Figure 2.35 Heating furnace (Binder FD 115)
- 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,
- 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.
Ash content determination.
The operations were made according to standard EN ISO 18122.
- before introducing the samples inside the furnace, 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,
- the process of ash content determination 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 2.36. Ashing furnace (Nabetherm LE14/11/P300)
- for precision determinations, for samples with a high ash content the determinations were
repeated once more,
Figure 2.37 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.
Calorific value determination.
The operations were made according to standard EN 14918.
- before calorific value determination, the samples are prepared for the analysis inside the
calorimetric bomb,
Figure 2.38 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 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.
Ion chromatography
- this type of chromatography is used in general for liquid analysis. the used apparatus is a
Metrohm 930 model equipped with calibration for fluoride, chloride, nitrites, nitrates,
bromides, sulfates and phosphates,
Figure 2.39 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,
Carbon, Hydrogen and Nitrogen determinations
The used standard for those determinations is EN ISO 16948
- before the analysis, a general system check takes place using blank tests and reference
materials for equipment calibration
Figure 2.40 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-Phenylalanina 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 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.
Determination of the volatile matter content
For volatile matter content, the determinations were made according to the Standard EN ISO
18123
- 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.
Results
Next tables will underline the obtained results for the laboratory determinations
Table 2.13 Experimental results (part 1)
No. Moisture Ash content Gross Net

content calorific calorific
MATERIAL (db)
value (db) value (db)
[%]
[%]
[J/g] [J/g]
1. Waste water from 2,52 7,03 18626 17187

Timisoara treatment
plant and wheat
2. Waste water from 3,66 14.2 17566 16199

Timisoara treatment
plant and barley
3. Waste water from 1,87 10,8 17939 16541

Timisoara treatment
plant and rye
4. Waste water from 1,63 4,41 19525 18022

Timisoara beer factory
and wheat
5. Waste water from 1,96 3,44 19728 18040

and barley
6. Waste water from 1,53 3,97 19001 17487

and rye
* - 35-40 days anaerobe fermentation
As it can be seen from the table above, 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.
Table 2.14 - Experimental results (part 2)
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 wheat
2. Waste water from

plant and barley
3. Waste water from

plant and rye
4. Waste water from

Timisoara beer factory 47,6 6,89 1,00 76,9
and wheat
5. Waste water from

and barley
6 Waste water from

and rye

From the table above it can be observed that the general values are relatively normal for this type
of materials (agricultural biomass as base material).
No. Sulphur Chlorine

content content
MATERIAL
(db) (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
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.
Also for the obtained material there were made supplementary analysis in order to better
characterize the materials from a chemical point of view.
Figure 2.41 Supplementary data for analyzed materials
From the figure 2.41 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.
Experimental models for material / biogas production and thermal phenomena inside the
process.
The cumulative biogas production during anaerobic digestion of four co-substrates
investigated is presented in figure 2.42.
30
25
Cumulative biogas production (m3)
20
15
10
0
0 5 10 15 20 25 30 35 40 45
Time (days)
Corn + wastewater treatment plant Wheat + wastewater treatment plant

Rye + wastewater treatment plant Barley + wastewater treatment plant
Figure 2.42. Cumulative biogas production during anaerobic digestion of investigated co-
substrates
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 of biogas and the degraded rye mixed
with wastewater from treatment plant (RWTP) an amount of 4.66 m3 of biogas.
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 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 2.43.
90
80
70
Methane content,(%)
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45
Time (days)
Corn + wastewater Wheat + wastewater

Rye + wastewater Barley + wastewater
Figure 2.43. Methane content of biogas produced during anaerobic digestion of investigated co-
substrates
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 2.44).
18
16.465
16
Cumulative equivalent methane yield (m3)
14
12.045
12 10.973
10
8.282
8
0
Corn + wastewater Wheat + wastewater Rye + wastewater Barley + wastewater
treatment plant treatment plant treatment plant treatment plant
Figure 2.44. Cumulative equivalent methane of the four substrates subjected to anaerobic
digestion
Previous studies reported the existence of three characteristic zones during cumulative
methane production process corresponding to different stages of anaerobic digestion, according to
figure 2.45 [1]:
18
16

14
12
10
8
1 2 3
6
0
0 5 10 15 20 25 30 35 40 45
Time, (days)
Figure 2.45. 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 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 model were used [2-6]:
a) Logistical growth model
= /(1 + exp( ))
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
= (1 exp( ( )))
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:
= exp( ( exp(1)/ ( ) + 1))

potential, (m3), Rm is the maximum 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 [7].
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.
The results of logistical growth models together with the experimental results are presented
in figure 2.46. The model parameters and the values of model performances are presented in table
2.16.
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 2.46. Experimental data (markers) and logistical growth models (solid lines) for methane
production during anaerobic digestion of investigated substrates
Table 2.16. Parameters of logistical growth mathematical model and the values of model
performances
Model parameters
Substrate used MP b k (1/days) ra RMSDb
(m3)
Corn + wastewater from treatment 7.7000 3184.3000 0.5000 0.9898 0.2874

plant
Wheat + wastewater from 11.8170 506.0154 0.3031 0.9993 0.0342
treatment plant
Rye + wastewater from treatment 15.7029 189.7370 0.3477 0.9961 0.3386

plant
Barley + wastewater from 11.3132 91.9310 0.1990 0.9994 0.0209

treatment plant
a
Pearson correlation coefficient; b the root mean square deviation
From figure 2.46 and table 2.16 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
concern the other two co-substrates (CWTP and RWTP), the experimental data showed inferior
agreements with the model results.
The results of exponential growth models together with the experimental results are
presented in figure 2.47. The model parameters and the values of model performances are
presented in table 2.17.
Table 2.17. Parameters of exponential growth mathematical model and the values of model
performances
Model parameters
Substrate used ra RMSDb
MP (m ) k (1/days) (days)
3
Corn + wastewater from treatment plant 8.2658 0.1430 12.3023 0.9838 0.1713
Wheat + wastewater from treatment plant 14.8622 0.0632 11.3407 0.9796 0.6947
Rye + wastewater from treatment plant 18.9213 0.0734 6.8881 0.9764 1.5078
Barley + wastewater from treatment plant 33.3129 0.0129 7.8710 0.9650 0.5708
a
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 2.47. Experimental data (markers) and exponential growth models (solid lines) for
methane production during anaerobic digestion of investigated substrates
From figure 2.47 and table 2.17 it can be noticed that 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 experimental results are
presented in figure 2.48. The model parameters and the values of model performances are
presented in table 2.18.
18
Cumulative equivalent methane yield (m3) 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 2.48. Experimental data (markers) and modified Gompertz models (solid lines) for
Table 2.18. Parameters of modified Gompertz mathematical model and the values of model
performances
Model parameters
Substrate used MP Rm (days) ra RMSDb
(m3) 3
(m /days)
Rye + wastewater from treatment plant 16.0930 1.3436 8.9718 0.9980 0.1639
Barley + wastewater from treatment plant 12.2795 0.5176 11.3802 0.9979 0.0713
a
From figure 2.48 and table 2.18 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 (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).
The numerical simulations of the thermal phenomena inside the batch type bioreactor
The mathematical model proposed for conventional column fixed bioreactor 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
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 modeling 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;
- Width of the heating system: b = 0.8 m;
- The reactor height H = 4 m;
- Height of the heating system: h = 0.6 m.
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 occur in this bioreactor type. In
figures 2.50-2.53 results of the transient temperature field inside the bioreactor is presented. The
chemical reactions might be considered for the future analysis.
Figure 2.49 - The schematic presentation of the bioreactor with the heating system
Figure 2.50 - The temperature field inside the bioreactor after = 1.2e+4 s
Figure 2.52- The temperature field inside the bioreactor after = 1.2e+5 s
From the figures presented below it can be observed that the The temperature field is
stratified with the layer near the top of the reactor and The maximum temperature is t max = 49 oC
while the minimum temperature is tmin = 28 oC.
Initial development of catalysts which are to be further used inside firing processes
The spinel-type oxides, due to their chemical, thermal stability and high mechanical
resistance, represent a new class of materials with a wide range of applications, such as: magnetic
catalysis, devices, ceramics, thin films and adsorbent materials [8-13]. Among this class of
materials, mixed oxides received a lot of attention due to its scientific properties being used as:
electrochemical sensor; ceramic pigment; thin films, catalyst. A lot of researchers focused to find
the best method of the spinel obtaining, which could be processed at lower temperatures and to
control homogeneity, purity, size and shape of the product.
From these reasons we are working on the obtaining of three mixed oxide: CoAl2O4, ZnAl2O4
and ZnCr2O4. The mixed oxides will obtain through the thermal decomposition of oxalates
coordination compounds precursors at different temperatures. The method for the synthesis of the
precursors is based on the redox reaction between 1,2-ethanediol and nitrates ions, in the presence
of nitric acid.
Obtaining and characterization of cobalt aluminate (CoAl2O4)

Figure 2.54 presents IR spectra of the products obtained after independent calcinations for one
hour of the oxalate coordination compound, Al3+-Co2+-C2O42-.
Figure 2.54 - IR vibrational spectra of products obtained after the calcinations of the precursor at
various temperatures (500-1000C)
The calcinations occurred in the temperature range of 500-1000C, with a heating rate of
10 C min-1, in static air atmosphere. From the IR spectra (Fig. 2.54) it is observed that for the
o
samples decomposed at 500 and 600C appeared the specific bands for Co3O4 spinel at 669 cm-1
and 563 cm-1 [14]. Starting with the samples obtained at 700 C are evidenced the bands
characteristic for CoAl2O4 spinel (502 cm-1, 542 cm-1 and 670 cm-1).
The formation of pure CoAl2O4 after the calcination at 700C for one hour of the
coordination compound is also evidenced by XRD patterns presented in figure 55. The diffraction
lines are in accordance with JCPDS 01-082-2249 file. As it can be seen, the cobalt aluminate is
relatively well crystallized. The formed cobalt aluminate (700C) is characterized by a lattice
parameter of 8.109 , close with the one reported by the literature and an average crystallites size
of 16 nm.
Figure 2.55 - XRD patterns of products obtained after the calcinations of the coordination
compound at various temperatures (500-1000C)
TEM image (fig. 2.56a) performed on the CoAl2O4 (700C) indicates the formation of small
particles, almost homogeneous as shape and size, with a pronounced agglomeration tendency.
Figure 2.56 - (a) TEM image, (b) HRTEM image, (c) SAED pattern of the cobalt aluminate
obtained after the calcination at 700C
The values of the particles sizes obtained by TEM image were in good agreement with the
particles size calculated using XRD data, demonstrating the single crystal nature of these particles.
The high crystallinity degree is pointed out by the ordered fringes corresponding to the crystalline
planes of the spinel structure, as resulted from the HRTEM image presented in Fig. 56b. SAED
image revealed the presence of the pure cobalt aluminate and the crystallinity of the particles (Fig.
56c).
Conclusions
During the second year of implementing the project there were analyzed and tested at small
scale and pilot scale different degraded cereal materials in combinations with waste waters from
treatment plant and beer factory.
After initial testing the most suitable material from the point of view of obtaining biogas
of good quality in terms of methane concentration and high gas quantities was considered to be
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. All the materials produced at pilot scale biogas with high methane
percentage over 70%, which shows great potential for each of the used materials to be used as
base material in anaerobic fermentation processes.
Relative to modeling part, the present study was focused on the use of three simple models
in the anaerobic digestion of four co-substrates. Exponential growth model was not appropriate for
characterization of studied materials. Logistical growth model simulated better the methane
accumulation during anaerobic digestion of degraded wheat mixed with wastewater from treatment
plant (WWTP) and degraded barley mixed with wastewater from treatment plant (BWTP), while
modified Gompertz model was applicable for degraded corn mixed with wastewater from
treatment plant (CWTP) and degraded rye mixed with wastewater from treatment plant (RWTP).
The values of parameters generated by the models could provide valuable information for
future experiments under various operating conditions.
In regard, to the thermal phenomenon inside the batch reactors, the main conclusions traced
are:
- 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
o
C.
Also during the second year, it was started the process of obtaining the catalysists which
are to be used in the last year of the project in firing processes and it was presented in short the
means of obtaining the first catalyst.
There are still necessary steps to be made, as planned, in the last year in terms of testing
the same degraded cereal in combination with waste water from beer factory at pilot scale and to
test a recipe of biogas in firing process with the produced catalysts and trace the necessary
conclusions.
Dissemination activities
During the second year, the next articles were developed and disseminated in conferences
proceedings / journals:
1. Comparative Analysis of Agricultural Materials Influenced by Anaerobic Fermentation for

Biogas Production in Terms of Ash Melting Behavior, Adrian Eugen Cioabl, Nicolina
Pop, Gavril Trif-Tordai & Delia-Gabriela Clinoiu, Journal of Thermal Analysis and
Calorimetry, ISSN 1388-6150, DOI 10.1007/s10973-016-5637-x, volume 125, no. 2,
august 2016 - article in press.
2. Comparative Determination of Cofermentation Using Residual Waters for Biogas

Production at Small Scale, Lucia Varga, Adrian Eugen Cioabl, Ioana Ionel, Revista de
Chimie, http://www.revistadechimie.ro, ISSN 0034-7752, Vol 67, no. 1, ianuarie 2016, pp
174 176 published paper.
3. Experimental Approach in Biogas Production from Agricultural Substrates, Adrian Eugen

Cioabl, Gabriela-Alina Dumitrel, Chemical Bulletin of Politehnica University of
Timisoara, Romania, Series of Chemistry and Environmental Engineering, Volume
61(75), 2, 2016 article in press.
4. Environmental Impact Assessment in Transboundary Areas. A Case Study on Advance

Gaussian Air Dispersion Model Used to Evaluate a Closed Mining Dump Cross-Border
Impact, Francisc Popescu, Bogdana Vujic, Adrian Eugen Cioabl, Delia Clinoiu,
Aleksandar Djuric, Gavril Trif Tordai, 11 th International Conference on environmental
legislation, safety engineering and disaster management ELSEDIMA, mai 2016, Cluj,
Romania - paper under review.
5. Emission Dispersion Modelling of a Coal Fired 420 T/H Steam Boiler in a Coal/Biomass
Co-Firing Scenario. Air Quality Assessment, Francisc Popescu, Bogdana Vujic, Milan
Pavlovic, Adrian Eugen Cioabl, Aleksandar Djuric, Adrian enchea, V International
Conference Ecology of Urban Areas 2016, September 2016, Zrenjanin, Serbia, ISBN 978-
86-7672-291-4, pp. 26 29 published paper in conference proceedings.
6. Statistical Analysis for Biogas Production from two Different Batches under the Same
Conditions, Gavril Trif-Tordai, Adrian Eugen Cioabl, Delia-Gabriela Clinoiu, V
International Conference Ecology of Urban Areas 2016, September 2016, Zrenjanin,
Serbia, ISBN 978-86-7672-291-4, pp. 219 224 published paper in conference
proceedings.
7. Comparative Results in Anaerobic Fermentation of Some Agro-Industrial Recipes Inside

a Pilot Installation, Adrian Eugen Cioabl, Dorin Lelea, Francisc Popescu, Gavril Trif-
Tordai, Gabriela-Alina Dumitrel, V International Conference Ecology of Urban Areas
2016, September 2016, Zrenjanin, Serbia, ISBN 978-86-7672-291-4, pp. 240 244
published paper in conference proceedings.
8. Biogas Production from Waste Waters through Anaerobic Co-Fermentation Processes at

Laboratory Scale, Lucia Varga, Adrian Eugen Cioabl, Ioana Ionel, 24th European
Biomass Conference and Exhibition, ISBN 978-88-89407-165, DOI
10.5071/24thEUBCE2016-1BV.4.104,pp.290293,
http://www.etaflorence.it/proceedings/index.asp?detail=13336&mode=topic&categories=
0&items=%2D%2D&searchstring=Cioabl?&limit=2016 published paper in conference
proceedings..
9. Biogas Production Using Residual Waters in Co-fermentation Processes, Adrian Eugen
Cioabl, Gabriela-Alina Dumitrel, Francisc Popescu, Dorin Lelea, Gavril Trif-Tordai,
13th International Conference on Nanosciences & Nanotechnologies & 9th International
Symposium on Flexible Organic Electronics - paper under review.
The main activities performed during the period 01.01.2017 30.09.2017 are
presented inside the next pages
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.
Figure 3.1. pH time variation
As it can be observed from figure 3.1, 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.
Figure 3.2. Methane concentration
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.
Figure 3.3. CO2 concentration

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.
Figure 3.4. pH time variation

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.
Figure 3.5. Methane concentration

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.
Figure 3.6. CO2 concentration
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.
Table 3.1. Biogas quantities

Substrate Corn + Barley + Wheat + Rye + wastewater
wastewater wastewater wastewater from beer
from beer from beer from beer 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 3.7. Cumulative biogas production during anaerobic digestion of investigated co-
substrates
From figure 3.7 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 3.8. 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.
Figure 3.9. 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.
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 3.10. 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 obtaining beer, there seems to be
a good connection with cereal material, thus making it suitable for obtaining higher methane
yields.
Figure 3.11. 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.
Figure 3.12. Cumulative biogas production for anaerobic digestion of wheat mixed with
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.
Figure 3.13. Cumulative equivalent methane yield for anaerobic digestion of wheat mixed
with wastewater from beer factory and wastewater from a treatment plant
From a cumulative methane yield point of view, the difference is clear in favor of using
wastewater from treatment plant.
Having in mind figure 3.11, it becomes obvious that wastewater is the logical choice for this
material.
Figure 3.14. Cumulative biogas production for anaerobic digestion of rye mixed with
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.
Figure 3.15. Cumulative equivalent methane yield for anaerobic digestion of rye mixed with
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.
Figure 3.16. Cumulative biogas production for anaerobic digestion of barley mixed with
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.
Figure 3.17. Cumulative equivalent methane yield for anaerobic digestion of rye mixed with
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.
The obtained residual material after the anaerobic fermentation process was predried and
prepared for further determinations. The analysis were accomplished during a research stage was
made by the researcher inside BEA Institut fr Bioenergie - Austria
The first step was documentation upon a part of the used residual materials after the
fermentation process for a period of 35 days, inside the pilot installation for biogas production.
Table 3.2 The used samples for determinations

No. ORIGIN SOURCE AND
MATERIAL OBSERVATIONS
DETAILS
1. Waste water PREDRIED
from Timisoara beer MATERIAL Only grains - Timioara
factory and wheat
factory and corn
factory and barley
from Timisoara beer MATERIAL Only grains- Timioara
factory and rye
The materials were subjected to a process of about 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 [1-6]:
- 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.
Methods
Determination of moisture content.
- The operations were made according to standard EN ISO 18134 Part 3 Solid biofuels
Determination of moisture content Oven dry method;
- 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,
- 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.
Ash content determination.
The operations were made according to standard EN ISO 18122.

- before introducing the samples inside the furnace, 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,
- the process of ash content determination has 2 steps: first, the crucibles with the weighed
samples are introduced inside the furnace and let at least 1 hour at 250 C to allow volatile
matter elimination before ignition (the temperature is raised up constantly to 250 C over
a period of 30 50 minutes),
- after this initial step, the temperature inside the furnace will be raised to 550 C and thee
samples will reside for a minimum of two hours
- after the determination the samples are put down from the furnace and let to cool for 2 -3
-5 minutes outside, and the cooled samples are then weighed and the results are introduced
inside the corresponding protocol,
- for precision determinations, for samples with a high ash content the determinations were
repeated once more
Fig 3.18 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.
Calorific value determination.

The operations were made according to standard EN 14918.
- before calorific value determination, the samples are prepared for the analysis inside the
calorimetric bomb,
- 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,
- 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,
Ion chromatography
- this type of chromatography is used in general for liquid analysis. the used apparatus is a
Metrohm 930 model equipped with calibration for fluoride, chloride, nitrites, nitrates,
bromides, sulfates and phosphates,
- 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),
- inside the carrousel 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,
Carbon, Hydrogen and Nitrogen determinations
The used standard for those determinations is EN ISO 16948
- before the analysis, a general system check takes place using blank tests and reference
materials for equipment calibration,
- 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,
- between the samples are put standard materials in order to keep the equipment calibrated
and the measurement precise
- 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 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.
Determination of the volatile matter content
For volatile matter content, the determinations were made according to the Standard EN ISO
18123
- 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 (three times determination),
- the volatile matter was corrected to dry basis by using the moisture content.
Results
Next tables will underline the obtained results for the laboratory determinations
Table 3.3 Experimental results (part 1)
No. Moisture Ash content Gross Net calorific
content calorific value (db)
MATERIAL (db)
value (db)
[%] [J/g]
[%]
[J/g]
1. Waste water from
Timisoara beer factory 6,13 6,67 18500 17000
and wheat
2. Waste water from
and corn
3. Waste water from
and barley
4. Waste water from
and rye
* - 35 days anaerobe fermentation
No. Carbon Hydrogen Nitrogen Volatile
content content content matter
MATERIAL content (db)
(db) (db) (db)
[%]
[%] [%] [%]
1. Waste water from
Timisoara beer factory 48,7 6,62 2,17 76
and wheat
2. Waste water from
and corn
3. Waste water from
and barley
4. Waste water from
and rye

No. Sulphur Chlorine Oxygen
content content Content
MATERIAL (db) (db) (db)
[%] [%] [%]
1. Waste water from
Timisoara beer factory 0,213 0,277 35,4
and wheat
2. Waste water from
and corn
3. Waste water from
and barley
4. Waste water from
and rye
From the laboratory determinations it can be deduced that all the materials present potential
in terms of being capitalized inside anaerobic fermentation processes. The sulphur and chlorine
content are not very high, which is a good indicator for the possibility of using those materials in
firing processes, if necessary.
Also, as complementary analysis there were made laboratory determinations in order to

determine the general heavy metal content of the use materials.
UV-VIS Spectrophotometry analysis
Ultraviolet (UV) and visible radiation comprise only a small part of the electromagnetic
spectrum, which includes such other forms of radiation as radio, infrared (IR), cosmic, and X rays
(see Figure 3.19).
Figure 3.19. The electromagnetic spectrum [7]
The energy associated with electromagnetic radiation is defined by the following equation:
=
where E is energy (in joules), h is Plancks constant (6.62 10-34 Js), and is frequency (in
seconds).
Electromagnetic radiation can be considered a combination of alternating electric and
magnetic fields that travel through space with a wave motion. Because radiation acts as a wave, it
can be classified in terms of either wavelength or frequency, which are related by the following
equation [8]:

=

where is frequency (in seconds), c is the speed of light (3 108 ms-1), and is wavelength
(in meters). In UV-visible spectroscopy, wavelength usually is expressed in nanometers (1 nm =
10-9 m) [7]
When light passes through or is reflected from a sample, the amount of light absorbed is the
difference between the incident radiation (Io) and the transmitted radiation (I). The amount of light
absorbed is expressed as either transmittance or absorbance. Transmittance usually is given in
terms of a fraction of 1 or as a percentage and is defined as follows [7]:

= or = ( ) 100 %
0 0
Absorbance is defined as follows:

=
For most applications, absorbance values are used since the relationship between absorbance
and both concentration and path length normally is linear [7]
SPECORD 250 PLUS
The spectrophotometer used in the analyses performed for current project was SPECORD 250
PLUS, the hi-end UV/VIS photometer produced by Analytik Jena.
The double-beam spectrophotometers of the SPECORD PLUS family have been designed for
measuring the transmission, extinction, reflectance and energy of liquid and solid samples. They
have been designed for measurements in the spectral range of 190 to 1100 nm. The devices can
implement different spectral resolutions: SPECORD 250 PLUS 0.5; 1; 2 and 4 nm, with upstream
monochromator. The optical system of the SPECORD PLUS without electromagnetic modulator
guarantees a true real-time operation allowing even for the compensation of changing absorptions
of the reference samples during the measurement. An internal wavelength calibration with
holmium oxide filter ensures a very good wavelength accuracy and reproducibility. The
SPECORD PLUS meets the regulations of DAB (German pharmacopoeia) as well as international
regulations, such as PhEur., BP, USP or JPXIII. Together with the powerful software WinASPECT
PLUS the SPECORD 250 PLUS is especially suited for use in routine labs with high sample
throughput, but with its versatile accessories also provides solutions for special applications [8].
Among the technical caracteristics of the Specord 250 Plus, one may note:
- Optical principle: Double-beam spectrophotometer
- Wavelength range: 190 - 1100nm
- Photometric display range: -8 to 8 A
- Wavelength accuracy of deuterium line at 656.1 nm: 0.1 nm
- Wavelength reproducibility (with holmium oxide filter): 0.02 nm
- Photometric accuracy VIS at 546nm with neutral glass filter Hellma F4: 0.003
- Photometric accuracy UV with potassium chromate according to Ph.Eur.: 0.01
- Long-term stability at 500nm: 0.0005
Figure 3.20. Principle design optical diagram of the SPECORD PLUS [8]
Inside the table below there are presented the obtained results for the tested materials in terms
of heavy metal analysis.
Table 3.6. Heavy metal analysis for the considered materials
No. Lead Chrome Zinc
[mg/l] [mg/l] [mg/l]
MATERIAL (detection (detection (detection
limit (DL) = limit(DL) = limit (DL) =
0.013 mg/l) 0.003 mg/l) 0.014 mg/l)
1. Waste water from
Timisoara beer factory < DL 0.011 0.071
and wheat
2. Waste water from
and corn
3. Waste water from
and barley
4. Waste water from
Timisoara beer factory < DL 0.010 0,070
and rye
5. Waste water from
Timisoara treatment < DL 0.012 0.065
plant and wheat
6. Waste water from
plant and corn
7. Waste water from
plant and barley
8. Waste water from
plant and rye
From Table 3.6. it can be deduced that the Zn content is over the detection limit, the rest of
the tested heavy metals being in the considered range.
The next part involves the mathematical modeling part relative to the obtained results during
the experiments.
Anaerobic digestion modelling of substrates prepared with wastewater from beer
factory
The results of logistical growth models together with the experimental results are presented in
figure 3.21. The model parameters and the values of model performances are presented in table
VI.20.
Figure 3.21.. Experimental data (markers) and logistical growth models (solid lines) for methane
production during anaerobic digestion of investigated substrates
From figure 3.21 and table 3.7. it can be noticed that 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.
Table 3.7. Parameters of logistical growth mathematical model and the values of model
performances
Substrate used Model parameters ra RMSDb
MP (m3) b k (1/days)
Corn + wastewater from 7.6015 10.9957 0.2647 0.9757 0.3352
beer factory
Wheat + wastewater from 6.0050 47.5239 0.4463 0.9876 0.1171
beer factory
Rye + wastewater from 12.9616 109.4627 0.1825 0.9971 0.1313
beer factory
Barley + wastewater from 10.7222 25.9255 0.1455 0.9973 0.0804
beer factory
a
Pearson correlation coefficient; bthe root mean square deviation
The results of exponential growth models together with the experimental results are presented
3.8.
Figure 3.22. Experimental data (markers) and exponential growth models (solid lines) for
From figure 3.22 and table 3.8 it can be noticed that 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.
Table 3.8. Parameters of exponential growth mathematical model and the values of model
performances
Model parameters
MP (m ) k (1/days) (days)
3
Rye + wastewater from treatment plant Not appropriate
Barley + wastewater from treatment plant Not appropriate
a
The results of modified Gompertz models together with the experimental results are presented
3.9.
Figure 3.23. Experimental data (markers) and modified Gompertz models (solid lines) for
Table 3.9. Parameters of modified Gompertz mathematical model and the values of model
performances
Model parameters
MP (m )3 3
Rm (m /days) (days)
Corn + wastewater 7.7240 0.5199 1.4448 0.9842 0.2117

from treatment plant
Wheat + wastewater 6.0822 0.6430 3.8288 0.9915 0.0776

Rye + wastewater 14.7895 0.5226 12.9149 0.9940 0.2847
Barley + wastewater 12.1168 0.3582 6.9504 0.9983 0.0480

a
From figure 3.23 and table 3.9 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).
The numerical modeling of Methane combustion
In order to simulate the methane combustion there was used the Ansys modeling program.
The cylindrical combustor is presented in Fig. 3.24. The flame considered is a turbulent diffusion
flame. A small nozzle in the center of the combustor introduces methane at 80 m/s . Ambient air
enters the combustor coaxially at 0.5 m/s .The overall equivalence ratio is approximately 0.76
(approximately 28 excess air).
Wall: Tw = 300 K
225 mm
Air: 0.5 m/s , Ta = 300 K
CH4: u = 80 m/s , Tg = 300 K

5 mm axis
1.8 m
Figure 3.24. The calculation domain
The high-speed methane jet initially expands with little interference from the outer wall, and
entrains and mixes with the low-speed air.The Reynolds number based on the methane jet diameter
is approximately Re = 5.7x103.
The combustion will be modeled using a global one-step reaction mechanism, assuming complete
conversion of the fuel to CO2 and H2O.The reaction equation is
CH4 + 2O2 + CO2+2H2O
This reaction will be defined in terms of stoechiometric coefficients, formation enthalpies, and
parameters that control the reaction rate. The reaction rate will be determined assuming that
turbulent mixing is the rate-limiting process, with the turbulence-chemistry interaction modeled
using the eddy-dissipation model.
The k-epsilon model is used for turbulent flow.
The eddy-dissipation reaction model ignores chemical kinetics (i.e., the Arrhenius rate) and uses
only the parameters in the Mixing Rate group box in the Reactions dialog box.The Arrhenius Rate
group box will therefore be inactive.The values for Rate Exponent and Arrhenius Rate parameters
are included in the database and are employed when the alternate finite-rate/eddy-dissipation
model is used.
The initial calculation will be performed assuming that all properties except density are
constant.The use of constant transport properties (viscosity, thermal conductivity, and mass
diffusivity coefficients) is acceptable because the flow is fully turbulent.The molecular transport
properties will play a minor role compared to turbulent transport.
The default under-relaxation parameters in ANSYS FLUENT are set to high values. For a
combustion model, it may be necessary to reduce the under-relaxation to stabilize the solution.
Some experimentation is typically necessary to establish the optimal under-relaxation. For this
case, it is sufficient to reduce the species under-relaxation to 0.95 for stability and later increase
them to 1 to speed up the convergence.
In Figures 3.25 3.28 the simulations results are presented.
Figure 3.25. The temperature field
From figure 3.25 there can be determined that the maximum temperature is in the right
quadrant, low part of the cylindrical combustor, with a value of 3.08 e+3.
Figure 3.26. The stream function

From figure 3.26 one can observe a laminar distribution on layers inside the cylinder with
overall values between 7.723 e 4 and 1.55 e -2.
Figure 3.27. The mass fraction of CH4
Relative to the mass fraction of CH4 it can be observed that the overall distribution shows
a maximum inside the area of the flame, the rest of methane being burned and just small quantities
of unburned biogas remaining inside of the cylinder. The maximum value is 1 in the flame area.
Figure 3.28. The Mass fraction of CO2

Inverse proportionally, the CO2 mass fraction is present in large quantities after the flame
area, because, as a known fact, CO2 cannot be burned, in the rest of the cylinder, with a maximum
value of 9.1 e-2.
Finalizing the catalyst preparation.
Obtaining, characterization and testing of the photocatalytic activity of ZnAl2O4 for

degradation of water doxorubicin
The precursor, the coordination compound Al2Zn(C2O4)44H2O, was obtained through the redox
reaction between 1,2-ethanediol and nitrate ion:
3C2H4(OH)2 + 8NO3- + 2H+ 3C2O42- + 8NO + 10H2O
Figure 3.29. is presented IR spectrum of the oxalate coordination compound, Al2Zn(C2O4)44H2O.
Figure 3.29. IR vibrational spectrum of coordination compound, Al2Zn(C2O4)44H2O

Table 3.10 shows the characteristic bands in IR [cm-1] for the coordination compound and the
corresponding assignments.
Table 3.10. Characteristic absorption bands in IR [cm-1] for Al2Zn(C2O4)44H2O and the
corresponding assignments
Al2Zn(C2O4)44H2O
Wavenumber Assignment
[cm-1]
3451 s, b (OH), hydrogen bonds
1695 vs asym (O=C-O)
1649 vs asym (OCO)
1381 m sym (OCO) + (C-C)
1288 m sym (O=C-O)
1091 w (C-O)
913 w asym (OCO)
820 w lattice water
590 w (Al(III)-O); (Zn(II)-O)
492 w
s- strong (v - very); b broad; m medium; w weak.
The thermal analytical TG, DTG and DSC curves obtained for the thermal decomposition of
compound in static air atmosphere is shown in Figure 3.30. The thermal decomposition of
Al2Zn(C2O4)44H2O is carried out in four steps. The first step was attributed of the dehydration
process in the temperature range 25-168C (Tmin DSC = 131.7C) with the loss of four water
molecules (loss of mass exp/calc. (%) = 12.54 / 13.25). The next step occurs in the temperature
range 168-304C and corresponds to the loss of two CO2 molecules, with the formation of a mixture
of carbonates (mass loss exp/calc (%) = 15.53/16.19). The third stage of thermal decomposition
(304-424C) associated with an endothermic effect (Tmin DSC = 381.4C, loss of mass exp/calc
(%) = 33.07/32.39) takes place with the formation of zinc aluminate ZnAl2O4 along with residual
carbon. In the last stage of thermal decomposition (424-800C) associated with an exothermic
effect (Tmax DSC = 758.2C), the residual carbon is transformed into carbon dioxide, with
obtaining the pure zinc aluminate.
Figure 3.30. Thermal analytical curves (TG, DTG and DSC) for the coordination compound
decomposition at the heating rate of 10 C min-1
The X-ray diffraction pattern prove that pure zinc aluminate (JCPDS 04-014-1594) is formed after
the calcination at 800C for one hour of the coordination compound used as precursor (Figure
3.31).
Figure 3.31. XRD pattern of zinc aluminate obtained after the calcination of the coordination
compound at 800C
The IR spectrum (Figure 3.32) of the conversion product obtained at 800C exhibits only the bands
characteristic for zinc aluminate (663 cm-1, 556 cm-1 and 502 cm-1).
Figure 3.32. IR vibrational spectrum of zinc aluminate
The ZnAl2O4 obtained was tested as photocatalyst in the removal of cytostatics (doxorubicin,
DOX) from water. For evaluation of the photocatalytic activity and performance of photocatalysis
of zinc aluminate, samples were taken at a time interval of 30 minutes for a period of 180 minutes
and doxorubicin removal rate was determined.
The UV-VIS spectrum for 2 mg/L doxorubicin (curve i) is shown in Figure 3.33. compared to
its evolution during the photocatalysis process (Figure 3.33.a) and photolysis (Figure 3.33. b).
After the 30-minute adsorption step as a necessary stage in the photocatalytic process, it is noticed
that DOX's UV-VIS spectrum does not change even though peak intensity decreases as expected.
It can be assessed that after the adsorption for 30 minutes, the removal rate of DOX is about 20%.
Once the UV irradiation process is started, a very significant decrease in the absorption maxima
of the DOX spectrum is observed, especially due to the color. The evolution of the degradation
and decolourisation efficiency, evaluated by the peak wavelength of 291 nm (UV range) and 487
nm, respectively (VIS range), is shown in Figure 3.34. It can be seen that both processes using the
ZnAl2O4 photocatalyst resulted in a higher degree of decolourisation than the degradation. The
presence of the photocatalyst improves both processes, a greater contribution to the degradation
process. The degree of mineralization determined after completion of the two processes was
approximately 33% for photocatalysis versus 5% for photolysis.
Figure 3.33. Evolution of UV-VIS spectrum for 2 mg / L doxorubicin during of the processes:
a) photocatalysis and b) photolysis

Figure 3.34. The evolution of the efficiency of the discoloration and degradation process of
2mg / L DOX during of the photolysis and photocatalysis processes using ZnAl2O4 catalyst at pH
= 5.5
The photocatalytic activity of ZnAl2O4 has been tested for the discoloration, degradation and
mineralization of doxorubicin, a cystotoxic pharmaceutical product that is widely used in cancer
therapy and can even be found in drinking water sources.
The photocatalytic process performance was compared with the photolithic process performance
for DOX degradation and it was found that the presence of the photocatalyst improved the degree
of discoloration from 92 to 99%, the degree of degradation from 41 to 79% and the degree of
mineralization from 5 to 33%. These results show that ZnAl2O4 exhibits photocatalytic activity for
mineralization of doxorubicin and is of interest for the development of photocatalytic processes
applicable to the treatment of water containing pharmaceutical products.
Obtaining, characterization and testing of the photocatalytic activity of ZnCr2O4 in the

removal of humic acid from drinking water
The precursor, the coordination compound [Cr2Zn(C2O4)4(OH2)6]4H2O, was obtained through the
redox reaction between 1,2-ethanediol and nitrate ion:
2
3C2H4(OH)2 + 8NO 3 + 2H+
3C2O 4 + 8NO + 10H2O
Figure 3.35 is presented IR spectrum of the oxalate coordination compound,

[Cr2Zn(C2O4)4(OH2)6]4H2O.
Figure 3.35. IR vibrational spectrum of coordination compound, [Cr2Zn(C2O4)4(OH2)6]4H2O
Table 3.11 shows the characteristic bands in IR [cm-1] for the coordination compound and the
corresponding assignments.
Table 3.11. Characteristic absorption bands in IR [cm-1] for [Cr2Zn(C2O4)4(OH2)6]4H2O and the
corresponding assignments
[Cr2Zn(C2O4)4(OH2)6]4H2O
Wavenumber Assignment
[cm-1]
3565 s, b (OH)
1719 vs asym (O=C-O)
1622 vs asym (OCO) + (H2O*)
1391 m sym (OCO) + (C-C)
1268 m sym (O=C-O)
1081 w (C-O)
910 w asym (OCO)
813 w lattice water
556 w (Cr(III)-O); (Zn(II)-O)
489 w
s- strong (v - very); b broad; m medium; w weak; H2O*- coordinated water.
The profile of TG, DTG and DSC curves obtained for the thermal decomposition of compound in
static air atmosphere is shown in Figure 3.36.
The above study suggests the following sequence for thermal decomposition in static air
atmosphere:
[Cr2Zn(C2O4)4(OH2)6]4H2O(s) 4 H2O(g) + [Cr2Zn(C2O4)4(OH2)6](s)

(I )
[Cr2Zn(C2O4)4(OH2)6](s)
6 H2O(g) + Cr2Zn(C2O4)4(s)
(II )
1 / 21 / 8 O ;
Cr2Zn(C2O4)4(s) 4 CO2(g) +4 CO(g) + ZnO(s) + Cr2O3,25(s)
2 ( III )
Cr2O3,25(s) 1/8 O2(g) + Cr2O3(s)

(IV )
ZnO(s) + Cr2O3(s) ZnCr2O4(s)

(IV )
Figure 3.36. Thermal analytical curves (TG, DTG and DSC) for the coordination compound
decomposition at the heating rate of 10 C min-1
The proposed conversiom mechanism is also confirmed by the values presented in table 3.12
Table 3.12. Mass loss exp/calc. (%) for thermal decomposition of coordination compound
Stages I II III IV I-IV
Mass loss exp. (%) 9,80 14,62 40,74 1,23 66,39
Mass loss exp calc. (%) 10,26 15,39 41,06 0,57 67,28
The X-ray diffraction pattern prove that pure zinc chromite (JCPDS 04-012-1026) is formed after
the calcination at 800C for one hour of the coordination compound used as precursor (Figure 3.
37).
Figure 3. 37. XRD pattern of zinc chromite obtained after the calcination of the coordination
compound at 800C
The IR spectrum (Figure 3.38) of the conversion product obtained at 800C exhibits only the bands
characteristic for zinc chromite (626 cm-1 and 512 cm-1).
Figure 3.38. IR vibrational spectrum of zinc chromite
The ZnCr2O4 obtained was tested as photocatalyst in the removal of humic acid from drinking
water. For evaluation of the photocatalytic activity and performance of photocatalysis of zinc
chromite (ZnCr2O4), samples were taken at a time interval of 30 minutes for a period of 180
minutes and humic acid removal rate was determined.
The UV-VIS spectrum for 50 mg/L humic acid is shown in Figure I.5 compared to its evolution
during the photolysis process. It is noted that after 30 minutes, the removal rate of humic acid is
about 30% for both parameters. Once the UV irradiation process is started, a very significant
decrease of the humic acid spectrum maxima is observed.
The evolution of degradation and decolorization efficiency, assessed by reducing the wavelengths
of 254 nm and 365 nm is shown in Figures 3.39 and 3.40. It can be seen that the photocatalyst
process using ZnCr2O4 photocatalyst resulted in a lower decolorization than the degradation,
whereas the photolysis process resulted in a higher degree of decolorization than the degradation.
It should be noted that the efficiency of the photolysis process is very low for decolorization and
degradation. The presence of the photocatalyst improves both processes, with a greater
contribution to the degradation process.
Figure 3.39. The evolution of the UV-VIS spectrum for 50 mg/L humic acid during the
photocatalytic process
Figure 3.40. The evolution of the efficiency of the process of decolorization and degradation of
50 mg / L humic acid by photocatalysis using a ZnCr2O4 catalyst at pH = 5.5
Figure 3.41. The evolution of the efficiency of the process of decolorization and degradation of
50 mg/L humic acid by photolysis at pH = 5.5
The degree of mineralization determined after the completion of the two processes was
approximately 60% for photocatalysis compared to 7% for photolysis.
Testing the catalysts inside firing processes with gas mixture.
The present report presents 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.
The initial steps relative to the experimental part involved documentation over experiments
previously made on the installation and general data of the used test rig.
Figure 3.42 Overall presentation of the test rig [9]
From the figure above one can observe the overall test rig installation. The schematic
presentation of the test rig is presented below. As it can be determined for both pictures the overall
presentation and the schematics of the test rig, 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.
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 3.43 Schematics of the test rig [9]
The main interest of the study is 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 3.44. Front view of the burner
In the figures below, there can be observed preliminary data of the initial testing of the
equipment before the experimental part.
Figure 3.45 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.
Figure 3.46 Preliminary readings flue gas
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 3.47 Schematic representation of heat transfer inside the burner [9]
From figure 3.47 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 3.48 a View of the pebbles inside the burner cold state [9]
Figure 3.48 b View of the pebbles inside the burner bed is fully heated (full operation
regime) [9]
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 Universtiy 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 3.49 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.
The initial values of the test are presented below.
MEASUREMENTS: 1 WITHOUT ANY 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 VALUE: [kJ/m3] 28847.52
FUEL CONSUMPTION: [m3/h] 0.1872
AIR CONSUMPTION: [kg/h] 2.9633
CHARASTERISTICS OF THE BURNER PEBBLE BED:
CERAMIC PEBBLE DIAMETER: [mm] 13
HEIGHT OF THE BED: [mm] 253
POROSITY: - 44.94
FLAME ARRESTOR
HEIGHT OF FLAME ARRESTOR: [mm] 107.5
Table 3.13 test values without catalyst
Inside table 3.13 there are presented the initial data of the experimental setup.
Flue gas analysis at the exit of the burner
O2 CO2 NOx CO
[%] [%] [ppm] [ppm]
8.78 8.12 4 442
Table 3.14 Flue gas analysis air excess = 1.6
From table 3.14 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 below is presented the overall graphic for temperature variation during the firing
process.
Figure 3.50 - Test without catalyst excess air 2.0
From figure 3.50 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.
MEASUREMENTS: 3 WITHOUT ANY CATALYST

DATE 16.06.2017.
START: 14:11
END: 14:48
EXCESS AIR: 2.0
POWER RATIO 1.5 KW
FUEL: CH4:CO2 80.4:19.6
LOWER HEATING VALUE: [kJ/m3] 28847.52
FUEL CONSUMPTION: [m3/h] 0.1872
AIR CONSUMPTION: [kg/h] 3.7041
CHARASTERISTICS OF THE BURNER PEBBLE BED:
HEIGHT OF THE BED: [mm] 253
POROSITY: - 44.94
FLAME ARRESTOR
HEIGHT OF FLAME ARRESTOR: [mm] 107.5
Table 3.15 - Test without any catalysts involved air excess = 2.0
From table 3.15 it can be observed the overall parameters used for this test.
Flue gas analysis at the exit of the burner

O2 CO2 NOx CO
[%] [%] [ppm] [ppm]
11.10 6.63 1 28
Table 3.16 - Flue gas analysis air excess = 2.0
Making a comparison between tables 3.14 and 3.16 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
images below.
Figure 3.51 ZnAl2O4 catalyst, before process
Figure 3.52 ZnCr2O4 catalyst before process
Figure 3.53 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 3.54 The opened lower part of the burner
Figure 3.55 Inserting the metal pocket with the catalyst inside the burner
Figure 3.56 a Weighing the metal pocket

Figure 3.56 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), the firing tests were performed.
After the tests were made, the materials were weighded again to observe the mass loss during
the firing process this aspect had just an informal role.
In the next part there will be presented the synthesized data obtained after the tests using
catalysts.
Depending on conditions of combustion (mainly of gaseous fuel composition, fuel-air ratio and
power rate of the burner) we can observe 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 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, we can conclude that the flame will be eventually pushed out the porous packed bed and the
flame will be extinguished.
1.6 1.8 2.0
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
-0.2 0 0.2 0.4 0.6 0.8 1 1.2
Figure 3.57 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).
Without catalyst ZnAl2O4 CoAl2O4 ZnCr2O4
1400.0
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
Figure 3.58 Comparison of temperature distribution in axial direction of ceramic burner for
=1.6
Without catalyst CoAl2O4 ZnAl2O4
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
=1.8
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
-0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
=2.0
At Figures 3.58 to 3.60 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
indices 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).
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
0 0.2 0.4 0.6 0.8 1
Figure 3.61 Comparison of temperature in solid phase distribution in axial direction of

ceramic burner for =1.6
1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

1200.0
1000.0
800.0
600.0
400.0
200.0
0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Figures 3.61 to 3.63 show temperature distribution at the surface of the spheres at specified
position in axial direction. We can observe 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.
Conclusions
During the last year of the project there were finalized the pilot installation tests using
residual water from beer factory and the chosen degraded cereal materials from previous
experiments. Also it was made a comparison from the point of view of using wastewaters with
different degraded cereal materials, the main conclusion being that from a biogas production point
of view, all of the materials except degraded corn presented higher quantity in combination with
treatment plant wastewater. For corn, the results were better in combination with beer factory
wastewater.
Also, there were finalized the catalysts and also tested in firing processes with gas mixture
similar to biogas.
Three type of catalyst were investigated:
1. ZnAl2O4 4.28 gr of catalyst

2. CoAl2O4 3.975 gr of catalyst
3. 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 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.
Several kinetic models were used to evaluate anaerobic digestion performances of substrates
formed by mixing degraded biomasses with wastewaters from a beer factory or from a treatment
plant. The experimental date were compared with the results obtained from Matlab simulates
processes. The simulations were well comparable with the experimental results.
References
1- EN ISO 18134 Solid biofuels Determination of moisture content Oven dry method
(3);
2- EN ISO 18122- Solid biofuels - Determination of ash content;
3- EN 14918 - Solid biofuels Determination of calorific value;
4- EN ISO 16948 Solid biofuels Determination of total content of carbon, hydrogen
and nitrogen;
5- EN ISO 16994 - Solid biofuels Determination of total content of sulfur and chlorine
6- EN ISO 18123 Solid biofuels Determination of the content of volatile matter;
7- Tony Owen, Agilent Technologies, Fundamentals of UV-visible spectroscopy, 2000
8- ***, Analytik Jena, Specord 250 Plus, UV-VIS Spectrophotometer, Operating
Instructions, 2010
9- Mirjana Stameni, RESEARCH ON WORKING PARAMETERS OF COMBUSTION
THE LOW CALORIFIC GASEOUS FUELS AND WASTE INDUSTRIAL GASES
IN POROUS CERAMIC BURNER, Doctoral Dissertation, University of Belgrade,
Faculty of Mechanical Engineering, 2014
Dissemination activities
1. Anaerobic co-digestion of agricultural biomasses with wastewater: a potential better source

of biogas, Adrian Eugen Cioabla, Gabriela-Alina Dumitrel, International BENA UAB
Conference, Environmental Engineering and Sustainable Development, Alba Iulia,
Romania, 25 27 mai 2017 article under review
2. Thermochemical properties and kinetic study of residual waters used inside anaerobic
fermentation for biogas production, Adrian Eugen Cioabla , G. N. Bandur , Gavrila. Trif-
Tordai, Gerlinde Rusu, Francisc. Popescu , Ion Vetres, International BENA UAB
Conference, Environmental Engineering And Sustainable Development, Alba Iulia,
Romania, 25 27 May 2017 article under review
3. Comparative study concerning anaerobic fermentation of cereal degraded materials,

Adrian Eugen Cioabla, Ioana Ionel, Gabriela-Alina Dumitrel, Mircea Vasilescu, 25th
European Biomass Conference and Exhibition, 12 15 June, 2017, Stockholm Sweden,
Conference Proceedings
4. Biogas production using waste waters influence of process parameters for test rig at
laboratory scale, Adrian Eugen Cioabl, Aleksandar Djuric, Gabriela-Alina Dumitrel,
Daniel Chiril, Vasile Pode, STUDIA UBB CHEMIA, LXII, 1, 2017 pp. 51-60, article in
press ISI paper
5. Experimental and modelling approach of biogas production by anaerobic digestion of

agricultural resources, Gabriela-Alina Dumitrel, Adrian Eugen Cioabla, Ioana Ionel, Lucia
Ana Varga, Revista de Chimie, Nr. 6, 2017, pp 1391- 1395, ISI paper
6. Anaerobic digestion performances of agricultural biomasses mixed with different kinds of

wastewaters, Adrian Eugen Cioabla, Gabriela-Alina Dumitrel, Chemical Bulletin of
Politehnica University of Timisoara, Romania Series of Chemistry and Environmental
Engineering, Vol. 62(76), 1, 2017, article in press, BDI paper

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Synthetic report regarding the period 01.10.2015 30.09.

Presentation of general models existing in literature

The process of obtaining biogas by anaerobic digestion of biodegradable organic waste is

where: y = biogas production speed (L/kg/day) in time t (days); t = time

where: y = biogas production speed (L/kg/day) in time t (days); t = time

where: y = biogas production speed (L/kg/day) in time t (days); t = time

where: y = cumulated biogas production (L/kg) at time t (days); k =

where: y = cumulated biogas production (L/kg) at time t (days); A =

Relative to solid state fermentation phenomena in bioreactors, a mathematical model was

Identification of materials which are to be further used inside laboratory determinations

(g/l) (g/l) (g/l) (g/l)

Residual water 57.29 49.48 5.53 2.10714 0.20112 0.0588 0

residual water 45.31 38.59 4.22 2.09592 0.1695 0.19716 0

residual water 48.24 42.2 4.97 2.0709 2.3202 0.79698 1.0104

residual water 24.63 21.04 5.00 1.57296 1.79988 0.70728 0.9681

residual water 40.53 36.2 4.93 2.6142 2.17374 0.6231 0.93822

Table 1.5 General characteristics for material mixtures (part 2)

Residual 1.01 3.97 189

residual water 0.993 4.55 84

residual water 1 3.98 153

residual water 0.989 4.27 93

residual water 0.996 4.1 120

Table 2.1 Materials used for determinations (chosen materials)

Table 2.2 general characteristics for the used materials part 1

Table 2.3 general characteristics for the used materials part 2

Figure 2.2 test rig for 5 L determinations

The components of the small scale installation are:

Figure 2.3 front image of the test rig for 5 L determinations

The general working principle for the installation:

Figure 2.5 Initial montage and checking of equipment

Figure 2.7 Changing the electrovalves and gas piping

Results of the determinations at small scale

1-2L scale determinations

Corn + wastewater treatment plant

Figure 2.10 pH time variation for the tested materials

Methane content, (%)

Corn + wastewater treatment plant

Figure 2.11 Methane concentration for the tested materials

Corn + wastewater treatment plant

Figure 2.12 CO2 concentration

Table 2.5- Biogas production

Biogas, (l) 2.8 3.6 5.2 3.3

Wheat + wastewater beer factory Barley + wastewater beer factory

Figure 2.13 pH variation

Wheat + wastewater beer factory Barley + wastewater beer factory

Figure 2.14 CH4 variation

Wheat + wastewater beer factory Barley + wastewater beer factory

Figure 2.15 CO2 variation

Table 2.6- Biogas production

Corn + wastewater treatment plant

Figure 2.16 pH time variation

Figure 2.17 Methane concentration values

Corn + wastewater treatment plant

Figure 2.18 CO2 concentration values

Table 2.7 Biogas obtained quantities

Biogas, (l) 7.3 9.2 14.5 9

Figure 2.19 pH variation

Figure 2.20 CH4 variation

Wheat + wastewater beer factory Barley + wastewater beer factory

Figure 2.21 CO2 variation

Table 2.8- Biogas production

Corn + wastewater treatment plant

Figure 22 pH time variation