COMPARISON AND PREDESIGN COST

ESTIMATION OF ADVANCED
OXIDATION PROCESSES FOR OLIVE
MILL WASTEWATER TREATMENT

E. CHATZISYMEON*, E. DIAMADOPOULOS*, D. MANTZAVINOS*, a

*
Department of Environmental Engineering, Technical University of Crete,
Polytechneioupolis, Chania, GR-73100, Greece.

SUMMARY: The comparison of advanced oxidation processes (AOPs) in terms of their total
cost, energy consumption and degradation efficiency was investigated. For this reason, a
predesign cost estimation was brought up for three AOPs namely UV photocatalysis (UV), wet
air oxidation (WAO) and electrochemical oxidation (EO) over boron doped diamond anode.
Experimental data were obtained from laboratory scale trials. It was observed that EO process
was proved to be the most energy effective compared to the other techniques, when applied at
optimal operating conditions. Furthermore, total cost estimation for a prospective AOPs
industrial treatment plant showed that EO achieves the lower expenses than either UV or WAO
treatment. Specifically, EO demands low operating cost, thus yielding the lower total cost (49
/m3) if compared to the other AOPs. Yet, this expense is prohibitively high for an oil mill with
an average annual wastewater production of 3000 m3/y.

1. INTRODUCTION

The foodstuff processing industry based on olive oil extraction is an economically important
activity for many regions of the Mediterranean Sea area. This process results in large quantities
of bio-recalcitrant wastewaters. These wastewaters together with the industry wash-waters, make
up the so-called olive mill wastewaters (OMW). The phytotoxicity and strong antibacterial
action of OMW has been attributed mainly to its phenolic content (Niaounakis M., Halvadakis
C.P., 2006). The presence of these recalcitrant organic compounds constitutes one of the major
obstacles in the detoxification of OMW. Therefore, increasing concern has been expressed about
their effective treatment and safe disposal in the environment. Advanced oxidation processes
(AOPs) have been extensively studied regarding their efficiency to treat OMW (Mantzavinos D.,
Kalogerakis N., 2005). AOPs constitute a suitable treatment for industrial effluents relying upon
the intermediacy of chemical initiators (i.e. free radicals) and energy (i.e. heat) to destroy the
target pollutants. These processes include ozonation, UV or solar irradiation, photocatalysis, the

1
Fentons treatment, electrochemical treatment, wet air oxidation as well as various combinations
of the above. Among them electrochemical oxidation over boron doped diamond anode is an
emerging technology for wastewater treatment (Comninellis C., Kapalka A., & al., 2008).
Generally, research efforts have been mainly directed towards the investigation of the
operating conditions of AOPs that affect OMW mineralization and/or detoxification. However,
the applicability of a process is highly dependent on its total (i.e. capital and operational) cost.
This, together with AOPs degradation efficiency, should be also taken into consideration when
scaling-up the process at pilot or industrial scale. Therefore, comparison of the total costs
associated with different technologies is a subject of major importance. In many publications
various aspects of treatment cost are discussed (Rivas F.J., Beltran F.J. & al., 2001; Sarika R.,
Kalogerakis N. & al., 2005; El-Dein A.M., Libra J., & al., 2006) but very few papers focus
specifically on this topic (Canizares P., Paz & al. 2009; Munoz I., Malato S. & al. 2008). Even in
these cases, it is very difficult to compare technologies studied by different authors, as the cost
analysis is often based on different assumptions or can be implemented at several levels of detail
due to the lack of information on accurate cost estimation. Consequently, the comparison and the
choice of the best process to treat OMW become more difficult.
Thus, the aim of this work is the comparison of three advanced oxidation processes, for
OMW treatment, namely photocatalysis (UV), wet air oxidation (WAO) and electrochemical
oxidation (EO) over boron-doped diamond electrodes, in terms of their total cost (i.e. operational
and fixed), required energy and degradation efficiency. For this reason, a predesign cost
estimation for each of these AOPs took place. All the experimental data that were used are based
on laboratory scale trials.

2. EXPERIMENTAL

First of all, it should be mentioned that the experimental set-ups, procedures and analytical
techniques for each process are described in detail at previous publications of our group where
the treatability of OMW was mainly investigated (Chatzisymeon & al., 2009a; 2009b; 2009c).
Furthermore, the OMW was provided by a three-phase olive oil mill company, located in
Chania, Western Crete, Greece. The effluent was subjected to filtration to remove most of its
total solids. The effluent has a strong olive oil smell and a dark black-brown color. Its main
properties prior to and after filtration are given in detail elsewhere (Chatzisymeon E.,
Diamadopoulos E. & al, 2009a).

3. RESULTS AND DISCUSSION

3.1 Degradation efficiency

Degradation efficiency was investigated by means of COD, TPh and color removal. Moreover, a
full factorial design methodology was applied for each of the AOPs in order to obtain the most
statistical significant effects on treatment efficiency. At this point it should be mentioned that all
the experimental data used in this work were obtained from our previous studies. Thus, it was
observed that during UV and EO, treatment efficiency was significantly positively affected by
treatment time and OMW initial COD. This means that an increase in their level brings about an
increase in degradation efficiency. Thus, process efficiency is favored at high influent COD
values indicating that the application of the AOPs at pilot or industrial scale, where OMW initial
COD is high, can be feasible. On the other hand, WAO was significantly positively affected by

2
treatment time and influent COD until a value above which degradation efficiency remained
constant. These values represent the optimal operating conditions of the process. Specifically, the
comparison of the three AOPs regarding degradation efficiency, energy consumption and total
cost refers to the optimal treatment conditions, which were estimated by the full factorial design
methodology, for each process. These operating parameters are presented at Table 1.

Table 1. Optimal operating parameters for OMW treatment with various AOPs.
Other operating parameters
COD0 Treatment Lamp Reactor Charge
AOP pH [TiO2] PO2
(mg/L) time (h) power temperature passed Anode
(g/L) (MPa)
(W) (oC) (mA/cm2)
UV 5100 4 4.5 2 400 - - - -
WAO 8100 1 4.5 - - 2.5 180 - -
EO 10000 7 4.5 - - - - 286 BDD

Table 2. Removal of COD, TPh and color at optimal conditions of various AOPs for OMW
treatment.
AOPs COD removal, mg/L TPh removal, mg/L Decolorization, %
UV 970 322 66
WAO 2740 776 74
EO 3400 343 33

Table 2 shows AOPs efficiency in terms of COD, TPh and color removal, at optimal treatment
conditions. It is observed that EO treatment achieves higher COD removal than UV or WAO
process. On the other hand, WAO treatment reaches its optimum efficiency more rapid (i.e.
optimal treatment time is 1 h) than all the other processes. Besides, WAO treatment yields the
highest efficiency than all the other processes in terms of TPh removal. In general, it can be said
that both EO and WAO can be competitive processes in terms of their degradation efficiency.
However, it should be mentioned that AOPs will be applied in combination with a suitable
process (i.e. physical, biological, etc.) for an integrated OMW treatment. Thus, high degradation
efficiency of a single process is not of primary importance when integrating a sequence of
techniques. Other economic and energy aspects should be, as well, taken into consideration in
order to proceed and decide on the most suitable oxidation process for OMW treatment.

3.2 Energy Consumption

Advanced oxidation processes are undoubtedly energy-intense processes and their efficiency is
usually assessed in terms of specific energy consumption (SEC) (Bolton J.R., Bircher K.G. & al.,
2001; Chatzisymeon E., Xekoukoulotakis N.P. & al., 2006). This is defined as the amount of
energy consumed per unit mass of organic load (e.g. COD or TPh) removed. Table 3 shows the
SEC for every studied process and, remarkably, EO treatment appears to be more energy
effective than all the other processes.
Regarding WAO treatment electrical energy is consumed during air compression, effluent
mechanical stirring and heating of the reactor. In the present study it was assumed that energy is
mainly consumed for reactor heating and therefore any other electrical power requirements were
considered as negligible. However, at industrial scale this is not common since electrical power
is consumed mainly for air/oxygen compression and delivery. Besides, under most operating
conditions wastewaters generate enough heat to sustain autothermal operation, in particular,
when the effluent COD exceeds 12 15 g/L (Bhargava S., Tardio J. & al., 2006). However, it

3
will be shown further down in the text that electrical power requirements of WAO are not so
high so as to significantly contribute to the total cost.

Table 3. Specific energy consumption (SEC) of various AOPs for OMW treatment.
AOPs SEC, kWh/g COD removed SEC, kWh/g TPh removed
UV 5 14.2
WAO 0.8 2.9
EO 0.15 1.2

3.3 Total cost estimation

In the present work the capital cost was calculated according to a study estimate (factored
estimate) based on knowledge of major items of equipment with a probable accuracy of estimate
up to 30% (Peters M.S. & Timmerhaus K.D., 1991). The capital needed to supply the
necessary manufacturing and plant facilities is called the fixed-capital investment (IF), while that
necessary for the operation of the plant is termed the working capital (IW). The sum of the fixed-
capital investment and the working capital is known as the total capital investment (I). Another
equally important part is the estimation of costs for operating the plant. And this cost is known as
operating cost.
Regarding the IF estimation the logarithmic relationship known as the six-tenths factor rule
was used. According to this rule, if the cost of a given unit at one capacity is known, the cost of a
similar unit with X times the capacity of the first is approximately (X)0.6 times the cost of the
initial unit, according to equation (1).
Q Marshall & Swift( future )
0.6

I F = I FB (1)
Marshall & Swift
B
Q ( past )

IFB and QB are the known fixed-capital investment and capacity of a given unit, respectively. The
Marshall and Swift all industry equipment cost indices were applied so as to update equipment
cost data at a future time (Anonymous, 2008). Moreover, the following assumptions took place
in order to estimate the predesign cost of various AOP at a potential industrial OMW treatment
plant:
An olive oil mill typically operates 100 days per year (about November February).
According to statistical data, the average capacity of OMW for an olive oil mill located at the
prefecture of Chania comes up to 3000 m3/yr (Tzagaroulakis I., Maria E. & al., 2005).
The year 2011 was defined as the opening year of the wastewater AOPs treatment plant. Thus,
all prices were updated to the year 2011.
The useful life of the wastewater AOPs treatment plant is defined at 15 yr (Munoz I., Malato S.
& al., 2008), except for the case that EO treatment is used. At that case the service life of the
equipment is set at 10 yr, since it concerns a brand new technology for wastewater treatment
where the electrochemical stability of the boron-doped diamond electrode has not been tested,
at industrial scale, yet.
The inflation rate and the rate of interest at Greece are assumed to be kept constant at 3% and
6%, respectively.
Process equipment is assumed to have no resale or salvage value at the end of its useful life.
OMW capacity refers to the diluted effluent. For example optimal parameters for UV treatment
demand an OMW with initial COD=5100mg/L (i.e. about eight-fold dilution of the initial
OMW). Therefore, an oil mill with an average OMW production of 3000 m3/yr finally results
at 24000 m3/yr OMW flowrate to be treated.

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 In determining costs for labor, account must be taken of the type of worker required, the
geographical location of the plant, the prevailing wage rates, and worker productivity. In this
study, operating labor estimation is based on the following equation:

0.24
man hr Q
= (2)
days steps days

where coefficient depends on the process and is assumed to be equal to 11 (Peters M.S. &
Timmerhaus K.D., 1991). Furthermore, the process plant is considered to require one process
step and the wage of a man-hour in Greece at 2008 was 10 . Therefore, the required operating
labor can be easily calculated. Nevertheless, because of new technological developments
including computerized controls and long-distance control arrangements, the above equation
can give inaccurate results unless very recent data are used. Therefore, taking into
consideration the fact that during the operation of a Greek olive oil mill the average amount
spent for labor and maintenance is about 30000 /yr (Tzagaroulakis I., Maria E. & al., 2005), it
is assumed that the amount for operating labor is a 20% of the estimated cost, with the above
methodology.
The unitary electricity cost for industrial use in Greece for 2007 is around 0.05 .
Finally, the total cost that consists of the total capital investment and the operating cost, is
calculated according to equation (3) (Peters M.S. & Timmerhaus K.D., 1991; Munoz I.,
Domenech X. & al., 2006):
I Capital Re cov ery Factor
Total Cost = + Operating Cost (3)
Q
where the capital recovery factor is given by equation (4):
r (1 + r )
N
Capital Re cov ery Factor = (4)
(1 + r )N 1
where r: rate of interest, %
: useful life, yr

Table 4 shows all the estimating expenses of the total capital investment, operating and total cost
for various AOPs. Obviously, EO treatment is the most cost effective process in terms of its total
cost. Although the expenses for the total capital investment are higher at EO than UV treatment,
the operating cost for EO is significantly lower than the respective cost for UV process. These
results are consistent with those obtained from energy consumption analysis, where EO
treatment requires the lowest amount of electrical power to operate.
Moreover, UV treatment yields a high operating cost, when compared to the other processes,
and this is mainly attributed to its increased energy requirements. At this case, UV radiation
could be replaced by solar radiation in order to reduce photocatalysis operating along with total
cost. Munoz & al. (2008) calculated the total cost of a hypothetical industrial solar photo-Fenton
treatment plant at 14.1 /m3, indicating that solar radiation does not result in such high operating
costs.
Furthermore, it is observed that the fixed capital cost for WAO is outstandingly high. Yet,
this is a common issue and a major obstacle for the large scale adoption of WAO technology
since the severe conditions of the process demand more resistant materials that can dramatically
increase the capital cost (Bhargava S., Tardio J. & al., 2006).

5
Table 4. Estimation of total capital investment, operating and total cost during OMW treatment
with various AOPs.
UV WAO
Expense Expense estimation EO expenses
expenses expenses
FIXED CAPITAL
* 683 600 16 103 700 908 300
INVESTMENT ( IF),
WORKING CAPITAL (IW), 15% F 102 500 2 415 600 136 200
TOTAL CAPITAL
F + IW 786 100 18 519 300 1 044 500
INVESTMENT (I),

. MANUFACTURING COSTS
. Direct production costs
1. Raw materials, /yr * 84 000 1 000 10 800
2. Operating labor, /yr * 46 900 41 900 25 900
3. Operating supervision, /yr 15% 2 7 000 6 300 3 900
4. Power and utilities, /yr * 6 144 000 1 872 000 282 200
5. Maintenance and repairs,
5% F 34 200 805 200 45 400
/yr
6. Operating supplies, /yr 15% A5 5 100 120 800 6 800
7. Laboratory charges, /yr 15% A2 7 000 6 300 3 900
. Fixed charges
1. Taxes, /yr 1% IF 6 800 161 000 9 100
2. Insurance, /yr 1% IF 6 800 161 000 9 100
C. Plant overhead costs, /yr 50% (A2 + A3 + A5) 44 100 426 700 37 600

. GENERAL EXPENSES
Administrative expenses, /yr 25% A2 11 700 10 500 6 500

. TOTAL PRODUCT COST,

I + II 6 398 000 3 612 700 441 200
/yr

Contingencies, /yr 1% III 64 000 36 100 4 400

OPERATING COST, /yr III + (contingencies) 6 462 000 3 648 800 445 600

TOTAL COST, /m3 * 273 370 49

* Cost estimation is analytically described in the text.

Besides, Figure 1 shows that EO is the most cost effective process under every OMW capacity
studied. Not only this but even when OMW is non-diluted (i.e. OMW capacity Q=3000 m3/yr),
EO is still the most cost effective process to apply among all the others.
Moreover, the total cost of UV and EO technologies is slightly reduced for OMW production
12000 m3/yr, while above this value it practically remains constant. On the other hand, WAOs
total cost is significantly related to OMW production since the reduction slope for the total cost
OMW capacity curve is much higher than this of the other processes.
Although EO treatment was proved to be the most cost effective process for OMW treatment,
yet its total cost of 49 /m3 continues to remain strictly high for its industrial application at an oil
mill with an average effluent capacity of 3000 m3/yr. At this case the potential of transferring,
collecting and treating the OMW from various oil mills of a greater region should be seriously
considered. In this way the treatment cost will be reduced since (a) it will be shared
proportionally by all the olive oil mills, and (b) the OMW capacity for treatment will be
increased. However, oil mill industries will be burdened by the extra cost of transferring the
effluent (Tzagaroulakis I., Maria E. & al., 2005). Moreover, in recent years research interest
turns to OMW treatment together with the recovery of biophenols from these wastewaters.
Because of their beneficial effects on human health olive biophenols are now recognized as

6
potential targets for the food and pharmaceutical industries (Obied H.K., Allen M.S. & al.,
2005). Therefore, the total cost of the treatment would be probably reduced by selling these
biophenolic extracts. On the other hand, the development of a suitable recovery technique of
biophenols from OMW that will not significantly increase the cost of the whole plant is
inevitable.

600 UV
500 WAO
3
Total cost, /m

EO
400
300
200

100
0
0 5000 10000 15000 20000 25000 30000
3
OMW capacity, m /yr

Figure 1. Total cost of the potential industrial OMW treatment plant as a function of OMW
capacity for various oxidation processes.

4. CONCLUSIONS

Three advanced oxidation processes, namely photocatalysis (UV), wet air oxidation (WAO) and
electrochemical oxidation (EO) over boron-doped diamond electrodes, were compared in terms
of their degradation efficiency, required energy and total cost (i.e. operational and fixed). These
processes were applied in a prospective industrial treatment plant for OMW treatment. The main
conclusions are the followings:
(1) EO yields the higher degradation efficiency in terms of COD removal, while WAO is more
efficient regarding TPh removal, at optimal operating conditions. However, when comparing
AOPs for industrial scale application, energy and economic aspects have also to be taken
into consideration for the choice of the best technology.
(2) EO was proved to be the most energy effective treatment when comparing to the others.
(3) WAO technique requires a significantly high total capital investment that comes from the
severe operating conditions of the process that demand highly resistant materials.
(4) On the other hand, EO yielded the lowest operating cost and thus becoming the more cost
effective AOPs than either UV or WAO, achieving a total cost of 49 /m3. Yet, this expense
is prohibitively high for an oil mill with an average annual OMW production of 3000 m3/y.
(5) The proposed predesigning AOPs cost methodology, can be a useful tool for researchers to
get an indicative view of treatment expenses when scaling up the process. However, the
direct scaling-up from laboratory to industrial scale bears serious calculating inaccuracies.
For this reason, performance of the method at pilot scale should take place before any further
larger scale application.

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