Beruflich Dokumente
Kultur Dokumente
Joseph V. Thanikal
CONTENTS
13.1 Introduction................................................................................................. 335
13.1.1 Industrial Wastewater Treatment................................................. 337
13.1.1.1 Inhibition or Toxicity and Persistence........................... 338
13.1.1.2 Eutrophication.................................................................. 338
13.1.1.3 Pathogenic Effects............................................................ 339
13.2 Reactors Used for the Treatment of Wastewater....................................340
13.3 Anaerobic Digestion...................................................................................340
13.3.1 Development of Anaerobic Treatment Systems......................... 341
13.3.2 Anaerobic Reactors for Wastewater Treatment..........................342
13.3.2.1 Fixed Film Reactor...........................................................342
13.3.2.2 Effect of Surface Area of Inert Material........................343
13.3.2.3 Start-Up of Anaerobic Fixed Bed Reactors...................345
13.4 Experimental Case Study..........................................................................346
References..............................................................................................................354
13.1 Introduction
In many parts of the world, economic, social, and political problems have
arisen following rapid industrial development and urbanization, resulting in
adverse effects on the quality of life. Urbanization, in general, initially places
pressure on and overstrains public amenities. However, long-term and wider
issues would eventually be encountered as industrialization and urbanization
exert pressure on the larger resource base that supports the community. This
larger resource base includes forestry, freshwater, and marine resources, as
well as space suitable for further development. The difficulties associated
with environmental degradation often originate from industrial develop-
ment. They are amplified by rapid urbanization, which is responsible for the
growth of many major cities. In Asia, urbanization is exacerbated by large
rural–urban migrations. These migrations emerge in response to perceived
335
336 Wastewater Treatment: Advanced Processes and Technologies
have been underway in many countries have already achieved some suc-
cess. Nevertheless, the problems that are confronted grow in complexity and
intensity. The pollution of freshwater bodies with the consequent deteriora-
tion in the water quality can only worsen the situation. Such pollution has
been brought about by the discharge of inadequately treated sewage and
industrial wastewaters. This chapter has attempted to highlight the impor-
tance of treating industrial wastewater and the treatment methods. The
chapter concludes with an experimental study carried out to treat industrial
wastewater with a high pollution load.
Industrial wastewaters (including agro-industrial wastewaters) are
effluents that result from human activities associated with raw material
processing and manufacturing. These wastewater streams arise from
washing/cleaning, cooling, heating, extraction, reaction by-products,
separation, and quality control resulting in product rejection. Water
pollution occurs when potential pollutants in these streams mix with a
receiving water source. In addition to the industrial wastewaters from
such processing or manufacturing sites, wastewaters from some domestic
sources may also be present; however, they may not constitute a major
component. Domestic sewage may be present because of the washrooms
and hostels provided for workers at the processing or manufacturing
facility. Examples of industrial wastewaters include those arising from
chemical, pharmaceutical, electrochemical, electronics, petrochemical,
and food processing industries. Examples of agro-industrial wastewaters
include those arising from industrial-scale animal husbandry, slaughter-
houses, fisheries, fruits and vegetable processing, and oil seed processing.
Pollutant concentrations are not usually high in agro-industrial wastewaters,
except in the animal processing units.
The impact of the industrial wastewater discharges on the environment
and on the human population can be tragic at times. One of the most classic
examples is Minamata disease, which spread, some 50 years ago, among the
residents in the Yatsushiro Sea and the Agano River basin areas in Japan,
because of methyl mercury in the industrial wastewater. However, trag-
edies as dramatic as the Minamata episode have not occurred frequently.
Nevertheless, instances of pollution with potentially adverse effects in
the longer term have continued to occur. Examples of these, their recogni-
tion, and the efforts made to remedy the situations in the 1980s include the
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 337
in Vietnam and Korea. Toward the end of 2004, the Huai River in China
was reported to have been so seriously polluted by paper-making, tanning,
and chemical fertilizer factories that the farmers in Shenqiu County had
fallen very ill after using the river water. However, there has been progress,
and an example of this is the successful 10-year river pollution cleanup
program in Singapore.
Agro-industrial wastewaters, as a subclass of industrial wastewaters,
can have a considerable impact on the environment in view of their pollut-
ant concentration and the release of large volumes of such wastes. Citing
some examples from ASEAN countries in Asia, in 1981, the Malaysian palm
oil and rubber industries contributed 63% (1460 t/day) and 7% (208 t/day),
respectively, of the biochemical oxygen demand (BOD) load generated per
day, compared with 715 t/day of the BOD from domestic sewage. In the
Philippines, pulp and paper mills generated 90 t/day of the BOD load.
and 50 mg/L.
13.1.1.2 Eutrophication
The discharge of nitrogenous and phosphorous compounds into the receiv-
ing water bodies may alter their fertility. Enhanced fertility can lead to
excessive plant growth. The latter may include algal growth. The subsequent
impact of such growth on a water body can include increased turbidity, oxy-
gen depletion, and toxicity issues. Algal growth in unpolluted water bod-
ies is usually limited because the water is nutrient-limiting. While nutrients
would include macronutrients such as nitrogen, phosphorous, and carbon
and micronutrients such as cobalt, manganese, calcium, potassium, magne-
sium, copper, and iron, which are required only in very small quantities,
the focus over eutrophication would be on phosphorous and nitrogen. The
quantities of the other nutrients in the natural environment are often inher-
ently adequate. In freshwaters, the limiting nutrient is usually phosphorous,
while in estuarine and marine waters, it would be nitrogen. The treatment
of industrial wastewater (or domestic sewage for that matter) can then target
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 339
wastewaters. The anaerobic process has several advantages over the other
available methods of waste treatment. Most significantly, it is able to accom-
modate relatively high rates of organic loading. With the increasing use of
anaerobic technology for treating various process streams, it is expected that
industries would become more economically competitive because of their
more judicious use of natural resources. Therefore, anaerobic digestion tech-
nology is almost certainly assured of increased use of natural resources in
the future.
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tors, a large amount of biomass remains in the filter to secure solid reten-
tion despite a short hydraulic retention time (HRT). These reactors have
several advantages over the aerobic and anaerobic reactors, such as higher
organic loadings, lower HRTs, and smaller reactor volumes. Lower sludge
and SS quantities can also be achieved in these reactors. In addition, these
reactors can tolerate sudden organic shock loads at constant hydraulic load-
ing and recover normal performance within a few days if the alkalinity is
high enough to maintain the pH. The reactors can process different waste
streams with little compromise in capacity and can adapt readily to changes
in temperature. Two kinds of support can be used in this type of reactor:
well-ordered and loose supports. Many different materials have been tested
for biomass retention in the anaerobic systems, and the performance of these
materials appears to be directly related to the ease with which bacteria can
become entrapped in or attached to the supports.
Gas
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Feed Feed
FIGURE 13.1
A schematic diagram of a stationary fixed film bed reactor.
loading and recover normal performance within a few days if the alkalin-
ity is high enough to maintain the pH above 6.2. The reactors can process
different waste streams with little compromise in capacity and can readily
adapt to changes in temperature. This is important for installations where
the wastewater characteristics change rapidly. The reactor start-up can be
very quick after a period of starvation (1 or 2 days to reach maximum capac-
ity after 3 weeks of starvation).
The main limitation of this design is that the reactor volume is relatively
high compared with other high-rate processes due to the volume of the
media. Another common problem associated with stationary fixed film reac-
tors is clogging due to the nonuniform growth of the biofilm thickness and/
or a high SSs concentration in the wastewater. The nonuniform growth and
the consequent clogging occur especially at the influent entry. Some mea-
sures to combat this problem include the recirculation of the effluent and gas
to develop a relatively thin film and sloughing of the biomass; the provision
for a relatively thin layer of media near the load-entering area to accumulate
the excess biofilm; and an improvement in the flow distribution system to
avoid very low liquid velocity. The various types of film support that have
been tried are activated carbon, polyvinyl chloride (PVC) supports, hard
rock particles, and ceramic rings.
Biofilm Biofilm
FIGURE 13.3
Biofilm development.
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 345
The time taken for the colonization to occur is shorter than the total time
necessary for biofilm formation. The growth phase is the sum of the cellular
reproduction and the extracellular polymer production. During this phase,
a quick biofilm development occurs due to the growth of microcolonies and
the adherence of new bacteria, so that at the end of this phase, the surface
is totally covered by the biofilm, with a complex structure of microbial cell
clusters. This growth phase can be divided into two steps, the first step is
a logarithmic biofilm growth and the second step is a constant accumula-
tion rate, which continues until its partial detachment and the steady-state
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1. The inoculation period during which the carrier is put in close con-
tact with an inoculating sludge to initiate biofilm attachment.
2. The progressive increase of the OLR to stimulate the microbial
growth of the biofilm.
13.3.2.3.1 Inoculation
In most cases, anaerobic reactors are inoculated as a batch. During inocula-
tion, the carrier material and the active inoculation sludge are brought into
contact inside the reactor. The length of the contact time is chosen empiri-
cally and can vary from a few days up to more than 1 month. It is gener-
ally believed that a long contact time between a concentrated inoculum and
the carrier is necessary and will favor biofilm growth in batch conditions.
The initial adhesion of bacteria is found from an anaerobic sludge on the
mineral particles in an inverse turbulent bed reactor. It requires a minimum
of 12 h of contact time for the microorganism to attach to the carrier mate-
rial, and usually the biofilm will be close to the inoculum. Compared with
the traditional inoculation protocol, only a very short period is necessary to
obtain adhesion of the microorganisms on the support media and to initiate
biofilm formation. Consequently, it is possible to considerably shorten the
duration of the inoculation period. The physicochemical properties of the
346 Wastewater Treatment: Advanced Processes and Technologies
carrier have a significant influence on the early adhesion of the bacteria and
Archaea, both quantitatively and qualitatively. The Archaea/bacteria ratio of
the adhered microbial communities, as determined by qPCR, was strongly
dependent on the nature of the support material.
Biogas
pH and temperature
probes
Effluent
Low-density
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polyethylene media
UAF
Recycle
(10 L/h)
Influent
FIGURE 13.4
Experimental setup.
a conical bottom. The system was equipped with a water jacket to keep the
temperature of the reactor at 35°C. The reactor was equipped with a sub-
strate feed inlet at the bottom of the reactor and an overflow arrangement
was provided such that the effective height of the liquid inside the reactor
was maintained at 810 mm. A sampling port was fixed at the bottom of the
reactor. A submerged pump (flow rate 480 L/h) was fixed inside the reactor,
at the bottom, to facilitate fluidization of the supports.
The reactor was filled with a polyethylene support (Bioflow 30, manu-
factured by Rauschert) for 60% of the volume of the reactor. This trapezoi-
dal support was 29 mm in height and measured 35 mm at the bottom and
30 mm at the top. It had a density of 930 kg/m3 and a specific surface area of
320 m2/m3. The reactor was fed with a distillery vinasse (wine residue after
distillation) in which the total COD varied between 10 and 24 g/L and the
soluble COD varied between 10 and 19 g/L. The pH of the feed, which was
at 4–5.5, was adjusted to 7–7.5. The reactor was inoculated with anaerobic
sludge collected from an anaerobic reactor treating the distillery vinasse and
was concentrated to 45 g/L by settling. The volume of the sludge was 10% of
the volume of the reactor. The substrate was fed into the reactor through the
348 Wastewater Treatment: Advanced Processes and Technologies
inlet at the bottom of the reactor, using a peristaltic pump. The inlet substrate
was fed at equal intervals of time, sequentially, as per the designed daily vol-
ume. The operation of the pump for fluidization was programmed at every
15 min over 3 h. The soluble COD, the VFAs, and the SSs were determined
daily through off-line analysis. The COD was measured by a colorimetric
method (Jirka and Carter 1975). The VFAs were measured using a gas chro-
matograph with a flame ionization detector (GC 8000, Fisons Instruments)
and an automatic sampler (AS 800, Fisons Instruments). The total and vola-
tile solids inside the reactor and at the outlet of the reactor were measured
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1. During the first stage, the first 81 days, the increase in the OLR was
slow, the HRT was always more than 3.6 days, and the OLR was
always less than 5.6 g/L day.
2. During the second stage, day 82–101, the HRT had to be maintained
constant at a high value (7.7 days) due to a temporary insufficient
availability of vinasse. The OLR was low, that is, between 1.6 and
2.6 g/L day.
40 22
20
35 HRT OLR
Organic loading rate (g COD/L.d)
18
Hydraulic retention time (day)
30 16
25 14
First stage Second stage Third stage
12
20
10
15 8
10 6
4
5
2
0 0
0
10
20
30
40
50
60
70
80
90
0
0
0
0
0
0
0
0
0
0
0
10
11
12
13
14
15
16
17
18
19
20
Time (day)
FIGURE 13.5
The evolution of the hydraulic retention time and of the organic loading rate with time.
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 349
3. During the third stage, days 102–180, the HRT was rapidly decreased
from 7.7 days to a minimum of 0.7 day and the OLR increased from
a value of 1.6 up to 36 g/L day. During the first 81 days, when the
reactor was fed with a low and slowly increasing OLR, the soluble
COD of the treated effluent remained low with values of less than
3.1 g/L (Figure 13.6). The VFA concentration always represented less
than 1.6 g COD/L. The slight increase in the soluble COD at the end
of period 1 (days 60–81) was linked to the use of a new vinasse in
which the nonbiodegradable fraction (1.5 g/L) was higher than that
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of the previous one (0.55 g/L). During this period, the COD removal
efficiency was always more than 85%. During the second stage, the
OLR remained low, and at the end of this period, the soluble COD
was very low with 0.85 g/L and the VFA concentration was nil.
At the third stage, during the rapid increase of the OLR from 1.3
to 36 g COD/L day in 78 days, the global COD removal efficiency
was always good with an average value of 85% and the soluble COD
at the outlet was always less than 5.5 g/L. Up to an OLR of 12.5 g
COD/L day (days 102–153), the average values were 1.4 g/L for the
soluble COD and 0.3 g/L for the VFA concentration. The purification
efficiency was very good with 89% COD removal on average. For a
higher OLR and up to 31 g COD/L day, the purification efficiency
decreased slightly but was still more than 80% with an average value
of 83%. The soluble COD was always less than 3.5 g/L and the VFA
concentration was 1.15 g COD/L on average.
10 OLR
40
Soluble COD at outlet
9
35
Organic loading rate (g of COD/L.d)
8
Soluble COD at outlet (g/L)
30
7
First stage Second Third stage 25
6
stage
5 20
4
15
3
10
2
5
1
0 0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Time (day)
FIGURE 13.6
The evolution of the soluble COD at the outlet and of the organic loading rate with time.
350 Wastewater Treatment: Advanced Processes and Technologies
100
90
80
20
10
0
0 5 10 15 20 25 30 35 40
OLR (g of COD/L.d)
FIGURE 13.7
Purification efficiency as a function of OLR.
The most important data obtained during this experiment are summa-
rized in Figures 13.5 and 13.6, which represent the evolution of the purifi-
cation efficiency with the OLR (Figure 13.7) or with the HRT (Figure 13.8).
These figures clearly show that, when treating a concentrated effluent such
as a distillery vinasse, an anaerobic fixed bed with Bioflow 30 can be oper-
ated at high OLRs of more than 30 g COD/L day and at a low HRT of less
than 1 day with a purification efficiency of more than 80%. It is important
to emphasize that the maximum loading rate obtained in this study (>30 g
COD/L day) is quite high for a fixed bed reactor treating distillery vinasse,
100
90
80
Purification efficiency (%)
70
60
50
40
30
20
10
0
0 2 4 6 8 10 12 14 16 18 20
HRT (day)
FIGURE 13.8
Purification efficiency as a function of HRT.
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 351
6 40
15
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2
10
1
5
0 0
0 20 40 60 80 100 120 140 160 180 200
Time (day)
FIGURE 13.9
The evolution of the suspended solids concentration at the outlet of the reactor and of the
organic loading rate with time.
which showed that Bioflow 30 was an excellent support that could be used
in anaerobic digestion. Indeed, an anaerobic fixed bed containing cloiso-
nyle, which is a well-ordered medium made up of PVC tubes of 102.5 mm
in diameter divided into 14 canals with a specific area of 180 m2/m3, and
treating a distillery vinasse could only reach an OLR of around 14 g COD/L
day (Ouichanpagdee et al. 2004). Furthermore, Malina and Pohland (1992)
reported that full-scale fixed bed processes have been generally designed for
OLRs of up to 16 g COD/L day.
The SS concentration in the reactor was regularly measured to follow the
evolution of the biomass in suspension in the reactor (Figure 13.9). During the
first stage of the experiment (the first 81 days), the SS concentration remained
high with values between 3.5 and 5 g/L. The SSs started to decrease toward
the end of the first stage, indicating the washout of the free biomass. During
the third part of the experiment, the SS concentration stabilized at low con-
centrations with values between 0.4 and 1.5 g/L.
After 2 months of operation, the floating supports were taken from the
top of the reactor to the first 10 cm below the liquid surface. The first sam-
pling of the support on day 66 showed that the quantity of solids on the
supports was around 2.5 g of solids/support. Between day 66 and day
156, the fixed biomass increased by 30% with 3.2 g of solids/support on
day 156. However, it was clear that the quantity of floating supports was
decreasing with time and that the supports were sinking to the bottom of
the reactor. On day 156, the samples were taken close to the surface and
as deep as possible inside the reactor, which was of the order of 60–70 cm
from the surface.
352 Wastewater Treatment: Advanced Processes and Technologies
2
Sampling number
4
5
6
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0 1 2 3 4 5 6
Attached solids per support (g/support)
FIGURE 13.10
The evolution of the attached solids per support according to the height of the reactor.
The quantity of solids was 3.2 g on the floating supports and 4.1 g on the
supports from deep inside the reactor, which represented a difference close to
30%. The distribution of the supports in the reactor did not seem to be homo-
geneous, and the quantity of the attached biomass was not constant from one
support to another. Thus, it was not possible to make an accurate estimation of
the quantity of fixed biomass just by weighing a few supports. However, the
quantity of solids on the floating supports after 66 days of operation was quite
high, suggesting a good aptitude of the biomass to attach onto the support.
At the end of the experiment, after 180 days of operation, the total quantity
of fixed biomass was quantified by weighing all the supports. The supports
were taken out of the reactor from top to bottom, in batches of 40 supports
for the first 5 samplings and of 50 and 67 supports, respectively, for the last 2
samplings (Figure 13.10). The average biomass attached to the supports was
not constant and varied between 3.2 and 5 g of solids/support. For the deeper
supports in the reactor, the attached biomass was the lowest. The decrease in
the attached biomass on the supports close to the bottom of the reactor could
be attributed to the detachment of the biofilm because of the high liquid veloc-
ity generated near the vicinity of the pump. The total quantity of attached
biomass in the reactor was 1300 g. The concentration of attached biomass was
then 57 g/L, and the biomass in the suspension concentration was only 1 g/L.
When emptying the reactor, it was clear that the supports at the bottom of the
reactor were adhered together and that it could no longer be fluidized because
of the small diameter of the reactor and the low flow rate of the mixing pump.
In these conditions, the bottom of the reactor behaved like an anaerobic filter
with a stationary support. A visual observation of the media showed a biofilm
formation on the surface of the support, but the biomass was also entrapped
inside the support, filling most of the voids (Figure 13.11). Similar results were
reported by Young and Dahab (1983) for an anaerobic fixed bed filled with
Anaerobic Fixed Bed Reactor for Treatment of Industrial Wastewater 353
cylindrical Pall rings that are 90 mm long with 90 mm diameter, but with
much lower loading rates.
From the OLR applied at the end of the experiment and the measurement
of the total quantity of the biomass attached to the supports, it was possible
to estimate the specific activity of the fixed biomass. This activity was 0.54 g
COD/g of dried solids. This value is similar to the specific activity measured
by Ruiz (2002) for the biomass in suspension treating sugarcane vinasses
(0.52 g COD/g of dried solids) or molasses vinasses (0.48 g COD/g of dried
solids/day). With cloisonyle, Ouichanpagdee et al. (2004) found a much lower
activity (0.18 g COD/g of dried solids/day) due to the accumulation of min-
eral solids in the biofilm attached to the surface of the PVC support. Lastly,
the specific activity measured in this work is significantly higher than the
specific activity reported by Switzenbaum (1983) for an anaerobic fixed bed
(0.4 g COD/g day), but lower than the specific activity of an expanded bed
(0.8 g COD/g day) and in the lower range of the specific activity of gran-
ular sludge (Henze and Harremoes 1983). The results obtained show that
the activity of the biomass attached on the support remains good and has
a value quite close to that of a suspended biomass. This suggests that the
entrapped biomass may play an important role in the global behavior of the
reactor and that the support serves not only to create a biofilm on its surface,
but also to entrap the biomass in its void space, thereby preventing it from
being washed out of the reactor.
The operation of a fixed bed reactor containing Bioflow 30, a polyethyl-
ene support with a density lower than 1000 kg/m3 and a specific area of 320
m2/m3, demonstrated that Bioflow 30 is a promising support for application
in anaerobic digestion. Indeed, after 6 months of operation, a loading rate
of more than 30 g COD/L day could be applied, while maintaining a COD
removal efficiency of more than 80%.
The study of the attached biomass showed that it was possible to fix a high
quantity of solids on the support. Indeed, the quantity of the biomass in the
reactor was increased around five to six times compared with a reactor with
a suspended biomass. The activity of the fixed solids on the supports was
good with a value close to that of the SSs. It was then possible to operate the
reactor with a very high loading rate (more than 30 g COD/L day) as a result
354 Wastewater Treatment: Advanced Processes and Technologies
of the increase in the quantity of the solids in the reactor with high specific
activity. The visual observation of the supports and the specific activity of
the attached solids suggested that due to their configuration, the supports
entrapped a lot of solids, which played an important role in the overall per-
formance of the reactor. This experimental work illustrated and opened
vistas for different inert materials that could hold more biomass for treating
high organic loading. It also showed the efficiency of a fixed bed reactor in
the treatment of concentrated industrial effluents.
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