Determination of optimum operating conditions of an acidication

reactor treating a chemical synthesis-based pharmaceutical wastewater

Yalcin Askin Oktem
a
, Orhan Ince
b
, Tom Donnelly
c
, Paul Sallis
c
, Bahar Kasapgil Ince
d,
*
a
Istanbul University, Department of Environmental Engineering, 34320 Avcilar, Istanbul, Turkey
b
Istanbul Technical University, Department of Environmental Engineering, 34469 Maslak, Istanbul, Turkey
c
University of Newcastle Upon Tyne, School of Civil Engineering & Geosciences, NE1 7RU, UK
d
Bogazici University, Institute of Environmental Science, 34342 Bebek, Istanbul, Turkey
Received 29 November 2005; received in revised form 28 April 2006; accepted 10 May 2006
Abstract
In this study, the optimum operating conditions of a lab-scale completely stirred acidogenic reactor treating a chemical synthesis-based
pharmaceutical wastewater were determined. Individual effects of hydraulic retention time (HRT), organic loading rate (OLR) and pH on the
degree of acidication were investigated at a mesophilic temperature (35 1 8C), for HRTin the range 824 h, OLRup to 14 kg COD/m
3
d and pH
in the range of 5.06.3. A maximum acidication level of 44% and COD removal efciency of 13%, were obtained at an OLR of 13 kg COD/m
3
d
at pH of 5.5 0.1 with an HRTof 12 h. Under these conditions, acetic, propionic and n-butyric acids were found to be predominant volatile fatty
acids in the acidogenic reactor.
# 2006 Elsevier Ltd. All rights reserved.
Keywords: Anaerobic digestion; Degree of acidication; Chemical synthesis-based pharmaceutical wastewater; Optimum operating conditions; HRT; OLR
1. Introduction
Anaerobic processes have become a viable option for the
treatment of medium-high strength industrial wastewaters. The
pharmaceutical industry is a major source of industrial waste-
waters andthese comprise substrates whichare difcult totreat in
biological treatment systems. Wastewaters from pharmaceutical
plants are characterized by a high COD and variable concentra-
tions of salts [1,2]. Based on the production processes, the
pharmaceutical industry can be divided into ve categories,
namely fermentation, natural product extraction, chemical
synthesis, formulation and research and development. Among
these processes, the most important one is chemical synthesis, in
which solvent-intensive processes are involved. The processes
generate wastewaters containing a variety of organic and
inorganic constituents including priority pollutants such as
methylene chloride, toluene, isopropyl alcohol, chloroform,
chlorobenzene, chloromethane, cyanide, phenol andbenzene [3].
A substantial part of the COD may be made up of relatively
biodegradable solvents, but may also contain specic com-
pounds that are difcult to biodegrade and/or inhibit biological
treatment systems [4]. Physical and/or chemical processes
without a biological treatment are not generally considered to be
suitable for treating pharmaceutical wastewaters because of their
lowefciency for dissolved CODremoval and high consumption
of chemicals [5]. The high COD content of pharmaceutical
wastewaters makes them particularly amenable to treatment
processes based on anaerobic technology. However, relatively
few studies on the anaerobic treatment of chemical synthesis-
based pharmaceutical efuents have been reported in literature.
Although, the specic operational conditions for acetogenic/
methanogenic phases have been extensively studied, generally
relevant literature on the acidogenic phase is still scarce [6].
The acid-phase digestion products, such as volatile fatty acids
(VFA), CO
2
and H
2
can be greatly inuenced by operational
and design parameters such as hydraulic retention time (HRT),
solid retention time (SRT), environmental factors such as pH,
temperature, oxidationreduction potential (ORP), as well as
reactor conguration, wastewater characteristics and avail-
ability of trace minerals [7]. To increase the efciency of two-
phase digestion it is particularly important to optimize the
conditions within the acid-phase digester since hydrolysis and
liquefaction is often considered to be the rate limiting
fermentation step [8].
www.elsevier.com/locate/procbio
Process Biochemistry 41 (2006) 22582263
* Corresponding author. Tel.: +90 212 359 70 16; fax: +90 212 257 50 33.
E-mail address: bahar.ince@boun.edu.tr (B.K. Ince).
1359-5113/$ see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.procbio.2006.05.016
Studies have been conducted into the effect of temperature
on acidication of a synthetic substrate, mainly glucose, over
the range 2060 8C, with an HRTof 810 h and a pH5.8 [9] and
showed that the optimum temperature for maximum acidica-
tion was at 37 8C for mesophilic and 52 8C for thermophilic
processes. Although a slightly higher degree of acidication
occurred in the thermophilic ranges, it was pointed out that
mesophilic ranges are more robust due to the advantages of
having greater stability. Acetic, propionic and n-butyric acids
were found to be the main VFA. Similar studies investigated the
effects of temperature and pH on the acidication of dairy
wastewater at a constant HRT (12 h) [8]. It was reported that the
optimum operating conditions were found within the tempera-
ture range of 3436 8C and pH in a range of 5.75.8. It was also
stated that acetic acid was the predominant VFA. In a study
investigating effect of HRTon mesophilic acid-phase digestion
of a dairy wastewater [10], it was observed that the degree of
acidication increased from 28 to 54% with increases in HRT
from 4 to 12 h; however, further increases in HRT from 16 to
24 h only increased acidication slightly from 56 to 59%. In
contrast, other studies showed the degree of acidication
increased from 6 to 56% as the HRT was decreased from 24 to
12 h [11]. Effect of pH on acidication of various wastewaters
has been investigated [12,13] and the optimum pH range for
acidication of gelatin-rich wastewater was found to be 72% at
pH 6.5 [14].
However, despite these studies on the acidication of
industrial wastewaters, there is still lack of specic information
on acidication of chemical synthesis-based pharmaceutical
wastewaters. Therefore, the aim of this study was to determine
the optimum design and operating conditions of a laboratory-
scale completely mixed acidogenic reactor treating a chemical
synthesis-based pharmaceutical wastewater.
2. Materials and methods
2.1. Acidogenic reactor
The acidogenic reactor was constructed from acrylic with an active volume
of 5 l (Fig. 1). The reactor included a sampling port, a gas collection unit, an
inuent and efuent line and was operated continuously over a period of
approximately 280 days. Mixing was provided by a magnetic stirrer. The reactor
was placed in a water bath where the temperature was maintained between
35 1 8C using temperature controller. The pH value was controlled by
automatic addition of 1 N NaOH and/or 1 N HCL.
2.2. Wastewater characteristics
The wastewater was taken from a local chemical synthesis-based pharma-
ceutical manufacturing plant. The main production at the site was bacampicil-
Y.A. Oktem et al. / Process Biochemistry 41 (2006) 22582263 2259
Fig. 1. Schematic diagram of the experimental system.
line and sultampicilline toshylate. The major chemical contaminants arising
from production activities were n-butyl acetate, dimethyl formamide, isopropyl
alcohol, ethyl acetate and methylene chloride. Although the site had a solvent
recovery system in place, the nal combined efuent from the manufacturing
process still contained a signicant quantity of solvents due to the malfunction
of the solvent extraction unit. The general characteristics of the wastewater are
given in Table 1.
2.3. Seed sludge
The acidogenic reactor was inoculated with sludge taken from a full-scale
up-ow anaerobic sludge blanket (UASB) reactor treating an alcohol industry
efuent. Due to the granular characteristics of the sludge, ltration could not be
accomplished, therefore, total solids (TS) and total volatile solids (TVS)
parameters were used; TS concentration of the seed sludge was approximately
105 g/l of which 96% of TVS and after inoculation the reactor had a sludge
concentration of 10 g/l TS.
2.4. Analytical methods
During the operation of the acidogenic reactor, routine analyses such as
COD, TS and TVS, pH, total Kjeldahl nitrogen (TKN), ammoniacal nitrogen
(NH
3
-N), orthophosphate phosphorus (PO
4
-P) and alkalinity were carried out in
accordance with standard methods [15]. VFAwere measured using a HP Model
5890 Series II Gas Chromatograph (GC) (HP FFAP Column,
10 m 530 mm 1 mm) with nitrogen as a carrier gas.
2.5. Reactor operation
After inoculation the reactor was ushed with nitrogen gas for a period of
15 min in order to maintain anaerobic conditions inside the acidogenic reactor.
Temperature inside the acidogenic reactor was increased gradually over 24 h
from room temperature to the operational temperature of 35 1 8C which was
maintained throughout the study. The acidogenic reactor was initially fed with
glucose solution of 1000 mg COD/l. During the initial study employing glucose
feeding, a HRT of 24 h was applied and the OLR was gradually increased to
6 kg COD/m
3
d. Then, the glucose containing feed was replaced with increasing
proportion of the pharmaceutical wastewater from 10 (w/v), 30 (w/v), 70 (w/v),
to 100% (w/v) at above conditions. Overall feeding regime is given in Table 2.
This stepped feeding strategy was used in order to allow microorganisms to
acclimatize gradually to the pharmaceutical wastewater from the glucose feed
which was totally biodegradable substrate under anaerobic conditions [16,17].
OLR was then increased to 13 kg COD/m
3
d as 100% pharmaceutical waste-
water to determine performance at high organic loading to the acidogenic
reactor. In addition, the optimum operating conditions for HRT and pH were
also determined in Stage 3 (Table 2).
2.6. Calculation for degree of acidication
As VFA concentration is the most widely used parameter to assess acid-
ication [18], the combined CODequivalent of each individual VFAwas used to
express the total COD of VFA in the efuent (COD of VFA
eff
) and this was
compared to the soluble COD of the inuent (Soluble COD
inf
) and the degree of
acidication calculated by Eq. (1). The COD equivalents and percentage of
organic carbon for individual VFA are given in Table 3.
Degree of acidification%
CODof VFAmg=l
eff
soluble CODmg=l
inf
100 (1)
3. Results and discussion
3.1. Acclimation to pharmaceutical wastewater
During the initial study (Stage 1), the acidogenic reactor was
gradually loaded with increasing levels of glucose in the feed,
OLR of 16 kg COD/m
3
d, at a HRTof 24 h and pH in a range
of 5.5 0.1. The degree of acidication achieved was
approximately 47% at OLR of 6 kg COD/m
3
d (Stage 1). It
has been recommended that pre-acidication should be partial
(2040%) in achieving higher organic loading rates [19].
Similarly, other researchers have stated that degree of
acidication should be in a range of 4050% to maintain
stability of process [20]. Following the initial study (day 41),
the glucose containing feed was replaced with increasing
proportion of the pharmaceutical wastewater, until at the end of
Y.A. Oktem et al. / Process Biochemistry 41 (2006) 22582263 2260
Table 1
Characteristics of the chemical synthesis-based pharmaceutical wastewater
Parameter Concentration (mg/l)
COD 4000060000
TKN 800900
PO
4
-P 36
Volatile suspended solids/suspended solids (VSS/SS) 0.60.7
Alkalinity (as CaCO
3
) 9001000
pH
a
78
a
Unitless.
Table 3
Conversion factors for each VFA
VFA Carbon (%) COD equivalent
Acetic 40.00 1.066
Propionic 48.64 1.512
Butyric 54.53 1.816
Valeric 58.80 2.036
Caproic 62.04 2.204
Table 2
Summary of the operating schedule with feeding strategy applied to the acidogenic reactor
Stage Operation Time (d) Feeding strategy OLR (kg COD/m
3
d) HRT(h) Period
1 Initial studies 141 Glucose 16 2412 Acidication with glucose
2 Steady-state 4153 10% wastewater 6 12 Acclimation to the wastewater
90% glucose
Steady-state 5379 30% wastewater 6 12
70% glucose
Steady-state 7993 100% wastewater 6 12
3 Steady-state 98285 100% wastewater 614 812 Determination of maximum
organic loading and operating conditions
Y.A. Oktem et al. / Process Biochemistry 41 (2006) 22582263 2261
Fig. 2. Effect of organic loading rate (OLR) on the degree of acidication (*) and COD removal efciency (*) during different stages of the investigation.
Fig. 3. Composition and concentration of VFA produced within the acidogenic reactor during initial study with glucose (Stage 1), acclimation to the pharmaceutical
wastewater (Stage 2) and determination of maximum organic loading rate (Stage 3). Total volatile fatty acids ( ), acetate (*), butyrate (^), propionate ().
the acclimation period (day 93) the reactor received 100%
pharmaceutical wastewater and achieved a 37% degree of
acidication in Stage 2 (Fig. 2).
3.2. Determination of maximum organic loading rate and
optimum operating conditions
In order to determine the maximum organic loading
applicable to the acidogenic reactor, OLR was gradually
increased during Stage 3 from 7 to 14 kg COD/m
3
d and a 39%
degree of acidication and a 17%CODremoval efciency were
achieved at an OLR of 7 kg COD/m
3
d. Changes in COD
removal and degree of acidication throughout this part of the
study were observed (Fig. 2). VFA in the acidogenic reactor
mainly comprised acetic (41%), propionic (20%) and n-butyric
(29%) acids. Every step increase in OLR was followed by an
increase in VFA production until OLR of 13 kg COD/m
3
d at
which point 43% acidication degree was obtained and VFA
composition did not change (48%) acetic, (18%) n-butyric and
(13%) propionic. Further increase in OLR to 14 kg COD/m
3
d
(day 136) resulted in a dramatic decrease in the degree of
acidication to 19%. Moreover, total VFA concentration
decreased from 3410 to 1370 mg/l as acetate, which can be
explained by the stress imposed on the acidogenic bacteria.
Therefore, OLR was reduced to 13 kg COD/m
3
d and the
acidogenic reactor recovered within 15 days. Fig. 3 shows the
composition and concentration of VFA produced within the
acidogenic reactor to determine maximum OLR.
After the determination of the most applicable OLR, the
effects of HRT and pH on the acid-phase reactions were
investigated by varying these parameters (Fig. 2). Optimum
HRT was investigated by gradually decreasing from 24 to 18,
12, then 10 and nally 8 h. The degree of acidication was
determined to be approximately 40, 43, 44, 35 and 30% at HRT
of 24, 18, 12, 10 and 8 h, respectively. Therefore, an HRT of
12 h was considered to be optimum for acidication of the
pharmaceutical wastewater under pre-determined conditions of
OLR of 13 kg COD/m
3
d, pH of 5.5 0.1 and temperature of
35 1 8C and acetic, propionic and butyric acids were still the
main VFA products under these conditions. Previously
published studies do not agree on the role of HRT in
determining the degree of acidication, one group concluding
that product distribution (i.e. VFA composition) is not
inuenced to any substantial degree by HRT [21,22], whereas,
the other group maintains that VFAcomposition in acidication
of biological sludge, primary sludge and dairy wastewater was
strongly affected by HRT [7,23,24]. A summary of related
studies is presented in Table 4. Results fromthis study indicated
that the pharmaceutical wastewater was acidied at HRTas low
as 8 h and the VFA composition was not inuenced to any
substantial degree by HRT (Fig. 4).
During the nal part of the Stage 3 investigation, the effect of
pHon the degree of acidication was determined by varying pH
under the above pre-determined conditions (OLR 13 kg COD/
m
3
d and HRT 13 h). The degree of acidication increased from
30% at pH 5.0 to 44% at pH 5.5, but reduced to 35% at pH 6.3,
therefore, a pH of 5.5 0.1 was considered to be optimum for
acidication of the pharmaceutical wastewater. The predomi-
nant VFA products were acetic acid, butyric acids and
propionic acids at pH 5.05.5, whereas acetic and propionic
acids became the main products at pH 6.3. The VFA
distribution was therefore sensitive to pH changes during the
acidication of the pharmaceutical wastewater, a result that
agrees with the results of other researchers who also found that
the VFA composition was dependent on pH [21,25,26].
In another study, carried out to determine the inuence of
dairy wastewater strength (230 g COD/l) on acidication at pH
5.5 and temperature of 37 8C [7], it was reported that the degree
of acidication decreased from 57 to 33% with increases in
wastewater CODfrom2 to 20 g/l andfurther increases in CODto
30 g/l decreased degree of acidication to 29%. Acetic, butyric
and propionic acids were main VFA products. It was also stated
that COD had a considerable effect on the distribution of VFA.
However, some researchers have claimed that acidication
Y.A. Oktem et al. / Process Biochemistry 41 (2006) 22582263 2262
Table 4
Summary of related studies
Wastewater Reactor
type
pH
range
HRT
(h)
Acidication
degree (%)
Loading
(kg COD/m
3
d)
Temperature
(8C)
Reference
Dairy Lab-scale CSTR No control 0.5 56 3.1 35 1 [11]
Dairy Lab-scale UAR 5.5 0.51 5459 4 37 [10]
Gelatinaceous Lab-scale UAR 5.5 0.161 8490 230 37 [30]
Gelatinaceous -rich Lab-scale UAR 47 0.5 3267 4 37 [14]
Synthetic Lab-scale UAR 5.5 5927 424 3755 [31]
This study Lab-scale CSTR 5.5 0.5 44 13 35 1 [32]
UAR: upow anaerobic reactor; CSTR: continuously mixed stirred tank reactor.
Fig. 4. Effect of HRTon the degree of acidication. (OLR of 13 kg COD/m
3
d,
pH of 5.5 0.1 and temperature of 35 1 8C).
products were dependent on pH [26,27] and whereas other
researchers stated have that HRTwas more effective than pH in
determining the acidication products [25,28,29]. However, it is
difcult to make direct comparisons between these different
investigations since they all used different wastewaters, reactor
congurations and operating conditions.
4. Conclusions
Based on above results, an HRTof 12 h, pH of 5.5 0.1 and
OLR of 13 kg COD/m
3
d were found to be the best combination
of conditions, withinthe ranges studied, for efcient acidication
of a chemical synthesis-based pharmaceutical wastewater. Under
these conditions, a maximum acidogenic conversion of 44% of
the inuent soluble COD was achieved. Throughout the
investigation, COD removal was in a range of 1025% and
the main VFAwere found to be acetic, propionic and n-butyric
acids. Acetic acid was produced in higher concentrations than
other VFA in the acidogenic reactor at all HRT and pH ranges
investigated. HRT had only a minor effect on the composition of
VFA produced, however, VFA distribution was found to be
highly sensitive to the operating pH within the reactor.
Acknowledgements
O. Ince would like to acknowledge the project coded 1536 of
the Institute of Science and Technology of Istanbul Technical
University. Author Y. Oktem also acknowledges Institute of
Environmental Sciences, Bogazici University and Engineering
Faculty of Istanbul University.
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