e Pergamon War. Sci Tech. Vol 36. No. I. pp. 93-100.1997.

C 1997 IA wQ. Published by ElsevIer SCIence Lid

Pnnled in Grear Britalll.
0273-1223197 $17'00 + 0'00
PH: 50273-1223(97)00341-7

FLUID BED BIOLOGICAL

NITRIFICATION AND DENITRIFICATION
IN HIGH SALINITY WASTEWATER

Leo H. J. Vredenbregt*, Karsten Nielsen**,

Andrea A. Potma*, Gert Holm Kristensen**,
Christina Sund***
KEMA Nederland B. V. Utrechtseweg 310.6812 AR Arnhem. The Netherlands
VKI. Agern Alii II. DK-2970 H;mholm. Denmark
Kruger AlS. Gladsaxevej 363. DK-2860 Sborg. Denmark

ABSTRACf

Wastewater from wet lime(stone)-gypsum flue gas desulphurisation (FGD) processes in coal-fired power
plants contains mlrate. Where case selective catalytic reduction (SCR) of NO x is applied the wastewater can
also contain ammonia. For the removal of both nitrate and ammoma. biological processes are an allracllve
option. A bOllle-neck for applicatIOn of biological processes might be the hIgh chloride concentration and
relatively high temperature of the wastewater. Therefore research work was performed in fluid-bed reactors
at pilol-plant scale for both biological nitrification and denitrification. BiologIcal nitnlicalion was studied up
to 34 gCl-1I and nimte was the main product formed Biological denitrification was effective up 10 allcast 45
gCI-II. Both nitrate and nitrite were removed effectively. ~ 1997 IAWQ. PubliMled by Elsevier SCience Ltd.

KEYWORDS

Carrier; chloride; denitrification; flue gas desulphurisation; fluid bed; nitrification; nitrite; saline; scaling;
wastewater.

INTRODUCTION

Wastewater from coal-fired power plants equipped with a wet Iime(stone)-gypsum flue gas desulphurisation
(FGD) process is characterised by a high chloride concentration. Depending on the location of the power
plant and the process conditions, the chloride concentration varies normally between 5 and 40 gIl (kg/m 3).
Although only a small part of the NO x in the flue gas dissolves in the scrubber liquor during the
desulphurisation process, nitrate accumulates in this water to concentrations varying from 50 up to SOO
mgNOf-NIl. For selective catalytic reduction (SCR) of NO x ammonia is used as a reducing agent. As
ammonia is adsorbed effectively, accumulation can occur up to 100 mgNHTNIl. Furthermore the FGD
wastewater contains traces of heavy metals and is saturated with gypsum. The temperature is relatively high.
typically 35-50C.

The traditional treatment of FGD wastewater today, consists of heavy metals removal by hydroxide
precipitation, often combined with sulphide precipitation. In this process heavy metals and suspended solids
can be removed effectively (Vredenbregt. 1995). However nitrate and ammonia are not removed and due to
93
94 L. H. J. VREDENBREGT ~I al.

the severe eutrophication observed widespread in receiving water bodies, a growing number of branches of
industry are enforced to reduce the discharge of nutrients like nitrogen components.

An attractive process for the removal of nitrogen components is biological treatment. However the
application of these biological processes under extreme conditions like high chloride concentration and
temperature is limited. Therefore a research project called SALWAS was started. In laboratory-scale
activated sludge reactors it was demonstrated that nitrate could be removed effectively from FGD
wastewater with chloride concentrations up to 30 gil and at temperatures up to 45C (Holm Kristensen.
1991). In cooperation with Danish and Dutch power plants the SALWAS research was enlarged and several
reactor systems were tested both at laboratory and pilot scale. This paper describes the results of
experimental work in pilot-scale fluid-bed (FB) systems for biological nitrification and denitrification.

METHODS

The FB reactors were operated with FGD wastewater collected at power plants after the traditional chemical
treatment for the removal of heavy metals and suspended solids. Wastewater from two different powet
plants was used. The wastewater from the Avedf/lre power plant in Denmark contained about 8 gil chloride
and hardly any sodium and magnesium because sweet water was used. The wastewater from the Borssele
power plant in The Netherlands was characterised by a high chloride concentration and contained relatively
large amounts of sodium and magnesium because sea water was used as process water in the
desulphurisation plant. The wastewater of both plants was almost saturated with gypsum. The nitrification
plants were operated in a laboratory and wastewater was collected in large batches. The FB fOI
denitrification was installed at the Borssele power plant and received water directly from the wastewatel
treatment plant. Because the FGD wastewater did not contain phosphor and organic substrates these had te
be added.

Reactor
FGD wastewater

m:J
e~e

nUU1enta

Figure I. Scheme of the fluid bed reaclor SCi-Up for biological nitrificalion.

Nitrification experimenls

The nitrification process was studied in two FB reactors (Fig. I). One reactor was operated with Lytag a:
carrier which consisled of granulated and sintered fly ashes from coal-fired power plants. To obtain the righ
particle size the Lytag was ground and fractionated with sieves to a particle size of 0.7 to 1.0 mm. The Lyta!
was chosen because of its availability, rough surface and a certain amount of porosity (15%) to improvl
adhesion of the slowly growing nitrifying bacteria. The FB using Lytag (FB Lyl ) was operated with FGr
wastewater from the Borssele power plant and diluted with tap water to obtain the desired chlorid.
concentration. The other FB was operated with an internally formed carrier. Owing to the characteristics 0
the wastewater, precipitation of the inorganic materials took place during normal process operation. formin!
a natural heavy and dense "floc". The FB using an internally formed carrier (FB inl) was operated with FOr
wastewater from the Avedf/lre power plant and extra sodium-chloride was used to increase the chlorido
concentration. The dimensions of both FB planls are summarized in Table I.
 Fluid bed biological nllnlicat,on and denitrification 9S

The FB Lyt was started up with 6.7 litres of Lytag and inoculated with biomass from a sequencing batch
reactor in which the biomass was already adapted to a chloride concentration of 13 gil. The FB was started
up batch-wise for two months before the operation was changed over to continuous operation. During the
experimental period the amount of Lytag was increased to 9 litres.

Table I. Characteristic dimensions of the FB reactors for nitrification and denitrification

FBLyO nitrification FB... nitrification FB denitrification

waste water from Borssele Aved"re Borssele
total volume (I) 42 50 276
bed volume (expanded) (I) 8 11 10 11 4055
reactor diameter (m) 0.10 0.10 0.15
bed height (expanded) (m) 1.0 1.4 1.3 1.4 2.43.0
waste water flow (J/h) 1.2 1.0 15 130
superficial upflow velocity (mIh) 3540 1520 25

The FB int differed slightly from the reactor using Lytag. The plant had no separate aerator but instead pure
oxygen was diffused near the outlet of the recycle buffer tank. The temperature was controlled by two
thermostatic heaters placed in the settler. The FB was started up with 10 litres of activated sludge which had
been slowly acclimatized to relatively high saline conditions (10 gCI-1I) in an activated sludge plant at pilot
scale for nitrification and denitrification at the Avedl!lre power plant. During one month the FB inl was
operated in alternating periods of nitrification and denitrification and dense flocs were obtained. However,
during alternating operation nitrification was not stable owing to overgrowth of nitrifiers by heterotrophs
and process operations were changed to continuous nitrification.

Both fluid-bed reactors were maintained at a constant temperature of 30 4C and during the experiments
the pH value ranged between 7 and 8. The average concentrations of nutrients in the influent are
summarized in Table 2. The inlet ammonium concentration in the FB int was adjusted to 30-40 mgNH 3-NII
so that the nitrite concentration would not increase above approximately 40 mgNOf-NII. In a part project of
the SALWAS research (not published yet) it was shown that this nitrite concentration would not affect the
nitrification process significantly. The specific nitrification activity in the FB int was measured after periods
of about 10 days. Therefore the reactor was operated batch-wise and during one day the decrease in
ammonium concentration was monitored. In the FB Lyt the ammonium concentration was kept at a relatively
high concentration to simulate a high load. A small amount of acetic acid was dosed in a ratio of 1-2
gCOD/gNHrN to stimulate biological activity and ensure the maintenance of a biofilm.

Table 2. Average concentration of nutrients in the influent of the FB reactors for nitrification

carrier used influent concentrations (mg/l) Oxygen In top of

1----......- - - - -......-.:....;::..:.----1 reactor (mgn)
NH.-N PO."-P Acetate
Lytag 100 - 310 0.55 200540 16
Intemally formed 30 40 0.4 40 8 10

Denitrification experiments

The FB for denitrification was installed at the Borssele power plant. Some dimensions and other
characteristics are presented in Table 1. The flow scheme of this pilot plant resembles the scheme of the
nitrification reactors shown in Figure 1. However this reactor had no aerator and the temperature was
maintained by a heater in the recycle stream. The water level in the feed tank was maintained automatically
96 L. H. J. VREDENBREGT ~tal.

by adding FOD wastewater from the wastewater treatment plant (called FOD wastewater). The water was
recirculated with a flow rate of approximately 450 1Ih in order to fluidize the 35 litres of sand (grain size 0.3
0.4mm).

The pilot plant was operated by automatic control and was normally visited only two days a week. With a
data acquisition system a number of process parameters were registered such as temperature, pH. Or
concentration. flow of nutrients. influent flow, recycle flow and conductivity. Every week influent and
effluent samples were taken and analyzed for NOf-N. NOf-N. NHrN. P0 4 3-_P and CI-.

On basis of laboratory research acetic acid was chosen as a carbon source and dosed in an excess of about
50-60% with regard to the stoichiometric ratio for denitrification. Further phosphate was dosed and also a
small amount of nitrate to simulate a continuous relative high nitrate load. The nutrients were dosed in a
concentrated solution. and the average final concentrations of these components were: 130 mgNOf-N/l. 5
mgP0 43--P/I and 550 mg(HAc)/1. Apart from the beginning of the experiment the pH was controlled
automatically by dosing hydrochloric acid. The installation was started up with diluted FOD wastewater
having a concentration of 13 gCI-Ii. The reactor was inoculated with biomass (300 ml) from a FB reactor at
laboratory scale which had been inoculated with sludge from a municipal wastewater plant.

Analyses

The concentrations and several parameters in the influent and effluent of the reactors were measured with
analytical methods in accordance with national standards. The chloride concentration was determined
titrimetrically (NEN 6470) and a good direct indication was obtained by measuring the conductivity. The
determination of (volatile) suspended solids (VSS. SS) was carried out in accordance with NEN 6621 or
DS207. Nutrients like ammonia. nitrite. nitrate and phosphate were measured daily (nitrification) or weekly
(denitrification) with a segmented flow analyzer from Skalar or with a Dr Lange spectrophotometer. The
total Kjeldahl Nitrogen (TKN) was measured using Danish standard DS242.

RESULTS AND DISCUSSION

Nitrification

During the continuous operation of the FB reactors the chloride concentration was increased gradually. In
Figure 2 the specific maximum nitrification rate and the variation in the chloride concentration during the
experimental period with the FBint are shown. In Figure 3 the performance of the FB Lyt is presented together
with the variation in the chloride concentration. The maximum nitrification rate was not measured. However
a good impression of the nitrification activity is obtained from the ammonia removal efficiency and the
ammonia load.

10....-------------------, 4
~
en
3 >
z'"
2 z
x'.
~'"
1 !a:
~
~ ..
01
:I
O~--=IS~--StO:----;7*:S--il0::0--l~I;-;S-....+-;:
Day Numb.r
Figure 2. Chloride concentration and maximum nitrification rate during the experimentat period in the reactor with
internally fonned catTier
 Fluid bed bIOlogical nitrification and denitrification 97

a- 80
';;'1
.2~
eo

oD'd(
:-
'lI
- .;,..... :. 100

eo
~
~
1a~40 a c
~g eo ~
fl ... 30
::.,
c ..
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c'3 .9 20
..,z
40 iii
>
0

e
E
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0:C 10 20
:;:z 0 :cOO
l!'
()
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100 200 300 400 508

Day Number

Figure 3. ChlOride concentration and ammonia removal efficiency during Ihe experimental period in the FB using
Lytag.

In both FB reactors no effect due to the chloride elevation up to 20 gil was found. The maximum
nitrification rate observed in the FB int was 3.5 mgNH 3N/gYSS/h. In the FB Lyt the ammonia was removed
almost completely at a rate of 2.35 mgNH 3-N/gYSS/h (60 mgNH3-NlIbe~)' However, at higher chloride
concentrations in the FB Lyl it was found that after each increase the efficiency temporarily dropped about
10-15%. However after two or three days of stable process operation the previous removal efficiency could
be recovered again.

During the elevation from 20 to 25 gCI-1I in the FB int a sudden loss of activity was seen around day 87. The
maximum nitrifying capacity drastically decreased down to some 1-1.5 mgNH 3-N/gYSS/h. From day 100
the activity decreased slowly and was lost completely after day 145. These changes in activity could not be
explained by some toxic compounds being introduced to the reactor system or a phosphorus depletion.

After the chloride concentration was increased further to 23 gil in the FB Lyt' the ammonia removal
efficiency dropped to about 35%. The removal efficiency could not be recovered completely but fluctuated
between 60 and 80%. No analysis results were available between day 140 and 180 but process operation was
continued to keep the biomass active. When the measurements were resumed it was established that the
ammonia removal efficiency ranged between 10 and 40% and the chloride concentration had increased from
23 to 26 gil. It was expected that the chloride concentration was the main reason for the low efficiency and
after a period of 4 weeks (day 215) the concentration was reduced to 22 gCI-II. However, this reduction did
not influence the removal efficiency positively. The relatively high ammonia concentration might have had
some toxic effect, but from the experience gained later in the experiment it was more likely that phosphor
depletion caused the low nitrification activity.

After day 245 it was decided to start batch-wise operation to regain a good actIVIty. The ammonium
concentration was reduced and kept between 100 and 150 mgNHrN/J. The phosphate concentration was
increased to about 3 mgP043-P/I. It proved difficult to keep the phosphate concentration at this level
because of the limited solubility. To avoid precipitation during batch-wise dosing, the phosphate was added
continuously again. However, a frequent plugging of the phosphate feed was still observed. Eventually a
good activity was obtained and after 4 weeks (day 275) continuous operation was resumed at a low ammonia
load. During a period of 6 weeks at a concentration of about 29 gCl-/I, an ammonia removal efficiency of
about 70% was achieved. Again after a period without analysis the load was gradually increased (day 355)
first to values up to 23 and later between 14 and 18 mgNH 3-NlI bcd"h. The chloride concentration was
gradually increased up to 34 gIl and during this period the removal efficiency remained almost 90%. The
removal efficiency is stable at these high chloride concentrations and the activity (product from the ammonia
efficiency and load) can be maintained at 15 mgNHrNlIbe~' Compared with the activity at 20 gCI"1I the
activity is reduced by 75%. Although there is a clear influence of the chloride concentration, it was
concluded that the loss of activity during some periods was caused mainly by insufficient phosphate dosing.
98 L. H. J. VREDENBREGT el 01.

The dosing of phosphate is handicapped by its low solubility in FGD wastewater which is less than 10 mgPI
at pH 7.5.

The dependency of the maximum nitrification rate on the dissolved oxygen (DO) present in the FB int wa:
studied in batch-wise experiments by a series of tests at three different oxygen levels (5. 10 and 16 mg0tl)
Any influence of the variations of the chloride concentration and temperature was investigated in tb4
experiment and the nitrite concentration varied in the range of 40-50 mgNOf-NIl. In general. the three test
demonstrated oxygen diffusion limitations at DO inlet concentrations below 16 mgOtl as the maximum rall
increased with increasing DO concentrations and since no maximum of nitrifying yielding capacity wa
achieved in any of the three tests. The diffusion limitations occurred because pans of the FB solid~
especially in the top of the reactor. were not fully penetrated by oxygen as the bulk liqUid DO concentratiol
decreased up through the FB.

As expected the main product from the nitrification process was nitrite. The amount of nitrate in the influetl
of both reactors varied around 50 mgN0 3--NIl. In Figure 4a it can be seen that almost no nitrate wa
produced during the daily operations in the FB int. However. in the FB Lyt (Figure 4b) the nitrate productio
increased during the period that the chloride concentration was increased up to 23 gil. Finally more tha
50% of the ammonia was converted to nitrate. However after day 130. when the chloride concentration wa
increased further. nitrate formation ceased and nitrite was the only product formed. This is consistent wit
other work in connection with the SALWAS project and with the work of Hill (1977). The ammoni
oxidiZing bacteria group Nitrosomonas seemed to be the most resistant to elevated chloride concentratiOtl
compared with Nilmbaclu.

=80 02
. ....
300
Za
E-
Z
a
.g. 250 I
to

.'.. ' .

.,.1
a
. oHH,N
+NO,H
c
.2
0;
eo
c
.2 200
0;
. Da
-NO N

E 40

U
C
0
~

U
C
o 100
150 cP

0
a""
a

a
. ..
0
~ 20
c
:>
C
:> (a) (b)
::w 0
::
W
0 150 500

Figure 4. NH)"N. NO] 'oN and NOf -N concentration in the effluent during the experimental period in the reactor
usinS internal fonned canier (a) and Lytag (b).

The chloride inhibition of the nitrite oxidizing bacteria group Nitrobacter. resulted in accumulation of nitri
in the reactors. But taking into account the results of the experiments with the FB Lyt it is not likely that tl
nitrite concentrations in the FB int inhibited the oxidation of ammonia. The total loss of activity in the FB,
may be eltplained by a decreasing adhesion capability of the nitrifying bacteria at high chloril
concentrations. The relatively low growth rate of the nitrifying bacteria resulted in a stabilization of tl
biomass concentration at 20 gel-Il. In both reactors it was shown that the net growth of nitrifiers equalled tl
loss of biomass with the effluent. However. during the increase to 25 gCI-/I. the loss of biomass in the FB
increased and is likely to correspond to the loss of nitrifying activity. The carrier Lytag might ha'
prevented the loss of biomass sufficiently at a chloride concentration of 34 gil. On the other hand the high
CODINHrN ratio in the FB LY1 could have contributed to a more stable biofilm on the carrier.

Denitrjfication

After the nitrate removal efficiency was almost complete at an nitrogen load which amounted to 65 mgNO
-N/lbeJh. the chloride concentration was gradually increased (Fig. 5. period b). Within two weeks tl
 Fluid bed biological nilrificalion and denilrificalion 99

transition to FGD wastewater with 33 gCI"1I had been completed. No influence on the N-removal rate could
be observed during that period.

Several restarts were made after maintenance periods. During a maintenance period of one week (Fig. 5.
period d) the sand with biomass was removed and stored at a temperature just above OC. The reactor was
restarted at a flow of 70 Uh and a nitrogen load of 180 mgNOf-NllbeJh. Almost immediately the activity
was restored and within two days the wastewater was denitrified by over 95% (Fig. 5. period e). However a
restart with biomass which had been frozen during the maintenance period was troublesome under the same
start-up conditions (Fig. 5. period g). Only after improving the anoxic conditions by closing the open head
space of the reactor could a good stable denitrification be obtained.

(a) (b) (e) (d) (e) (I) (g)

--.e
=-
:lOO 100

:;; ~-
Jt::. l;c:
c: 0
Z 200 eo:
DO 1l
S i: ::
e c:
'"e0 -~ gB
-1100 eo
~ ! e
o
z .
z~
0
0
-
~

zZ:
0
00 40 eo eo 100
Day Number

Fi,lure 5. The deniuification efficiency. nitrale load and chloride concenlralion during a pan of !he experimenlal
period. The leiters refer 10 evenls which are explained in lhe lext.

During a shon period no phosphate was dosed. which resulted in an almost complete loss of activity within
one week (Fig. 5. period a). The nitrogen load at that time was 65 mgNOf-Nllbed"h with a hydraulic load of
25 Uh. After the phosphate dosing to an effluent concentration of about S mgPII was resumed. the removal
efficiency increased again to more than 95% within a few days.

The nitrogen load was increased from 65 to 180 mgN0 3'-Nll beJh by increasing the influent flow from 2S to
70 Uh (Fig. S. period c). After one week of operating at a pH value of apprOXimately 7.3. s<:aling due to
calcium carbonate formation occurred in the reactor and the rest of the system. and the reactor had to be shut
down. This s<:aling problem was solved by installing a pH control system with hydrochloric acid dosing.
After recovery of stable denitrification. the pH was gradUally lowered over a period of 4 weeks. The removal
efficiency was not affected but even increased slightly from 95% to 98% (Fig. 5, period e). No s<:aling was
observed and it was therefore decided to keep the pH at slightly acid conditions during normal process
operation. Compared with activated sludge systems. reactors with biofilms will be more sensitive to s<:aling
owing to the local higher pH and CO 2 concentration in the biofilm (Arvin, 1982).

The amount of nitrogen which can be removed per volume of reactor has been studied by increasing the
nitrogen load up to 500-600 mgN0 3"-N/l belh. Therefore the nitrate concentration was increased up to 330
mgN03 ' -Nil and the hydraulic load varied between 70 and 90 I/h. Further. a stable removal rate of 90-95%
could be maintained during a period of 3 weeks at pH 6.5. 30C and 32-38 gCI"II. However. after that.
massive scaling on the sand and in the rest of the system occured and il was necessary to take the reactor out
of operation for cleaning.

The fluid-bed reactor has been in operation up to a chloride concentration of 45 gil. No clear correlation
between denitrification efficiency and chloride concentration was found. Even a change in concentration for
example from 35 to 17 grams per litre during 23 hours did not affect the denitrification efficiency. Other
process parameters like oxygen and phosphate concentration seem to inl1uence the denitrification activity
100 L. H. J. VREDENBREGT et al.

more strongly. If the activity is reduced by some event, the efficiency normally can be regained within a few
days of stable process operation. During the experimental period hardly any nitrite was formed and both
nitrate and nitrite were removed effectively.

Several times samples of sand were taken over the entire fluid bed to determine the SS and VSS
concentrations. The SS concentration is constant throughout the bed (average 1.79 kg per litre of
unexpanded bed). As expected the concentration of VSS gradually increases from the bottom to the top of
the bed, however it decreases again in the upper part of the bed probably because biomass is lost due to
carbonate formation on the sand particles. After several weeks of stable denitrification at 180 mgN0 3-
Nflbedlh, the maximum VSS concentration (45 gVSSfl) was found in the middle of the bed.

CONCLUSION

Nitrogen components like ammonium, nitrate and nitrite can be removed from high saline FGD wastewater
from coal-fired power plants with biological processes. Up to 20 gCI-II stable nitrification is possible
without using carrier material because good fluidizable particles are formed during process operation. At
stable process conditions nitrification proved to be possible up to at least 34 gCI-fl in a fluid-bed reactor with
porous sintered fly ash (Lytag) as carrier. Nitrite was the only product formed at chloride concentrations
above 20 gn. Therefore the bacteria group Nitrosomonas seems to be more resistant to elevated chloride
concentrations than Nitrobacter.

Biological denitrification has proved to be stable up to chloride concentrations of 45 gfl in a fluid-bed pilot
plant receiving wastewater directly from a power plant. Owing to the high calcium concentration in FGD
wastewater, carbonates (scaling) are formed easily during denitrification. The risk of scaling is more
pronounced when applying high nitrate loads. If the pH is controlled and maintained at slightly acid
conditions, stable process operation is possible up to a specific activity of at least 200 mgNOf-Nflbed"h.
Both nitrate and nitrite can be removed effectively.

The phosphate concentration has been a limiting factor on several occasions both with nitrification and
denitrification. Owing to the high calcium concentration and the limited solubility of calcium phosphate an
accurate control of phosphate dosing is therefore necessary.

ACKNOWLEDGEMENT

The research presented was part of the SALWAS Project, Biological Nitrification and Denitrification of
High Salinity Wastewater. The SALWAS Project consisted of several part projects which were performed
by VKI and Kri.iger AlS in Denmark and KEMA Nederland B.V. in The Netherlands. This study was
undertaken by order of the Dutch and Danish Electricity Production Companies and Was subsidised by the
Eureka Program.

REFERENCES

Arvim, E. and Holm Kristensen. G. (1982). Effect of denitrification on the pH in biofilms. Wat. Sci. Tech . 14(8), 833-848.
Hill, D. O. and Gelman, S. R. (1977). Effects of nitrification rates in activated sludge systems. I/ldustrial Waste Conference,
Purdue, 32.
Holm Kr,stensen, G. and Jepsen S. E. (1991). Biological denitrification of wastewater from wet lime-gypsum flue gas
desulphunzation plants. War. Sci. Tech., 23, 691-700.
Vredenbregt, L. H. J., Brugghen, F. W. van der and Enoch, G. D. (1995). Treatment of wastewater from flue gas desu1phurization
plants in the Netherlands. In: EPR1-EPA-DOE 1995 502 Control Symposium, Book 4, EPRl, Miami, Florida.