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Denitrificationkinetics in A Rotating Disk Biofilm Reactor PDF
Denitrificationkinetics in A Rotating Disk Biofilm Reactor PDF
Chemical
Engineering
Journal
Denitrification
of Separation
and Reaction
Engineering,
Faculty
ofEngineering,
University
of Pam,
4099 Port0
Codex. Portugal
Abstract
Denitrification kinetics of a synthetic substrate containing molasses, sodium nitrate, Na2HPOA.12H20,F&PO, andtapwatertreatedwith
Na,SOI wasstudiedin a rotatingdiskbiofilmreactor(RDBR).
Experimentswereperformedat variousconditions:biofilm thicknessin the range100-I 100km andnitrateconcentrationin the feedof
S to 50 mg N 1- . Biofilm density decreases with increasing biofilm thickness.
1. Introduction
The scientific design of biofilm reactors requires information on denitrification kinetics. Several authors [ 8-101
have found that zero-order approximation is appropriate for
the denitrification rate law. In practical applicationsthe nitrate
speciesis the limiting substrateand the zero-order approximation isjustified due to the low saturation constant (KS< 1
mg NO?-N l- ). Denitrification kinetic data can be obtained
in a laboratory biofilm reactor [ II]. A good review of laboratory biofilm reactorscan be found in Ref. [ 121.
The choice of a laboratory biofilm reactor for the study of
denitrification kinetics is guided by three factors: welldefined hydraulic characteristics, biofilm homogeneity and
easyoperation.Jansen[ 131comparedvarious biofilm reactor
types, namely horizontal cylinder, sloping plane, two compartment, submergedrotating drum and rotating disk. The
horizontal cylinder and sloping plane systemshave the
disadvantage of being distributed systems leading to nonhomogeneousconditions for growth with licluid flow in a
laminar regime. The two compartment system developed
by Williamson and McCarty [ 141 is an austiciousone; the
two compartmentshave different substratesseparatedby a
biofilm artificially obtained (by filtration of a culture medium
through a support), This raisesthe questionof whether or not
biofilm propertiesaresimilar to thoseof a naturally developed
biofilm. In the submergedrotating drum, film masstransfer
resistancecan be eliminatedby increasingthe rotating speed;
228
R.A.R. Boaventura,
A. E. Rodrigues
/ Chemical
however, the biofilm does not grow equally in both fixed and
rotating cylinders. Also one needs to empty the reactor for
measurement of biofilm thickness.
The rotating disk biofilm reactor (RDBR) is a fixed cylindrical vessel in which a disk rotates in the culture medium.
By adjusting the disk rotating speed the system behaves as a
perfectly mixed reactor which is convenient for the analysis
of results. It also provides conditions for homogeneous biofilm development [ 15,161. Changes in the disk position can
be made from time to time to obtain similar biofilms both
sides of the disk. Biofilm thickness can be measured just by
removing the disk from the solution. This system was chosen
because it is simple to build and easy to operate.
The design of denitrification processes such as fluidized
beds [ 171 and packed beds [ 181 can be improved by using
reaction rates and diffusivities of substrates measured in simple experiments in RDBR.
The objectives of this work are:
(i) to measure denitrification kinetics in a rotating disk biofilm reactor using molasses as the carbon source for different
biofilm thicknesses and feed nitrate concentrations;
(ii) to analyse the competition between reaction and diffusion in biofilms in order to obtain the zero-order kinetic constant and the effective diffusivity of the substrate inside the
biofilm, accounting for the fact that biofilm density changes
with biofilm thickness;
(iii) to test simple design equations for biofilms operating
under diffusion controlled conditions.
Enginrering
Journal
65 (I 997) 227-235
(3a)
4,
v= d/(b)
(3b)
Eq. (3) shows that in the diffusional regime the apparent reaction order is l/2 as we know from the competition
of an intrinsic zero-order reaction and diffusion [21]. The
apparent kinetic constant of a l/2-order reaction is
(kg biofilm) - s-
(4)
(1)
(5)
R.A.R.
Boavmtura,
A.E. Rodrigues/
Chemical
(6a)
and
E, = Jc
- (Y (diffusion
controlled regime)
(6b)
2. Experimental
The rotating disk biofilm reactor used in this work was
built according to Ref. [ 21. It is a cylindrical reservoir made
of plexiglass. The shaft holds a plexiglass disk which is the
biofilm support. In order to easily measure biofilm thickness
both sides of the disk have slabs which can be taken out.
The synthetic substrate is fed through a tube located at the
disk level; the outlet level is at l/3 of the height. Nitrogen is
dispersed near the reactor bottom in order to keep an anoxic
atmosphere above the liquid phase. The system was covered
with an aluminium sheet to avoid algae development.
The reactor characteristics are summarized in Table 1. In
further analysis it is considered as a CSTR. This is supported
by tracer experiments done using KC1 as tracer. The experimental set-up shown in Fig. 1 includes the RDBR, a thermostated bath, reservoirs and pumps for liquid circulation.
The synthetic substrate is made of molasses, sodium nitrate,
Table 1
Characteristics
of the rotating
disk biofilm
reactor
5954
2000
19
I
153.4
0.8
Engineering
Table 2
Compositions
Journal
65 (1997)
of synthetic
227-235
substrate
Synthetic substrate *
NO3-N (mg I-)
molasses (mg I I )
Na,HPO,
12H,O-P
(mg I-)
KH,PO,-P
( mg I - )
Inoculum (ml I )
Molasses
COD (mg g- of molasses)
TOC (mg g- of molasses)
NH,-N
(mg g of molasses)
soluble P (mg g of molasses)
PH
COD/TOC
dry matter
sucrose
ash
a In tap water previously
dechlorinated
229
and molasses
20
800
100
100
2
790
262.5
6.3
0.12
1.5
3
75%
59% of dry matter
12.54 of dry matter
and deoxygenated
Fig. 1. Experimental
set-up for kinetic studies in a rotating disk biofilm
reactor (RDBR):
R, RDBR; M. stirrer; T. thermostated bath; P. pumps; T.
reservoirs.
230
R.A.R. Boaventura,
Fig. 2. Biofilm
development:
AX
(a) biotilm
Rodri,que.\
/ Chemical
thickness,
200 km,
3. I. Biojilm density
The biofilm thickness was measured at the removable slabs
of the disk using a microscope equipped with a stage micrometer and following the procedure described by Ref. [ 21.
Engineering
(b) biotilm
Journal
thickness,
65 (1997)
227-235
detachment.
R.A.R. Boaventura,
Table 3
Nitrate removal
Run
rates in a rotating
Biotilm
L (km)
A.15
A.12
A.13
A.16
A.17
A.14
B.21
B.19
B.20
B.22
B.18
B.23
c.4 il
C.6
C.5
Cl
c.2
c.3
c.1
D.11
D.8
D.9
D.10
E.24
E.28 *
E.26
E.29
E.25
E.27
disk biofilm
thickness
reactor:
ph
(&mm)
1 IO
100
100
120
120
100
210
200
200
214
191
214
363
415
363
497
497
510
445
799
721
721
754
895
1100
1000
1 loo
929
IO00
A.E. Rodrigurs
experimental
/ Chemiwl
fooumal65
(1997)
227-235
231
data
FlowrateQ
(ml min-)
90.6
91.9
91.9
89.4
89.4
91.9
78.2
79.4
79.4
77.1
80.5
71.1
59. I
52.6
59.1
42.4
42.4
40.8
48.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
26.9
Engineering
47
47
49
48
48
46
41
53
53
46
52
46
41
46
41
4X
48
SO
47
47
41
41
47
48
47
47
46
36
46
Feed nitrate
concentration
(rngl- )
Outlet nitrate
concentration
(mg I-)
5.1
9.3
13.9
29.5
29.x
40. I
9.5
19.2
24.5
48. I
so.4
53.0
14.6
17.6
18.8
22.8
42.0
46.5
47.3
12.6
16.9
19.7
33.5
Il.2
21.3
26.6
36.0
36.8
3X.8
2.3
6.4
11.0
26.0
27.0
37.0
5.2
15.0
20.0
43.5
46.0
48.0
X.7
II.2
12.8
16.5
35.5
31.0
41.0
7.1
10.2
13.3
26.4
6. I
14.3
18.7
26.5
28.5
30.0
N,,
N,?,,
Observed nitrate
removal rate.
r*.d?* x 1on
(kg rn-s-l)
Observed nitrate
removal rate.
r*.&,\ x I Oh
(kg kg-Is)
7.15
7.40
7.12
9.12
7.30
7.34
10.97
12.09
12.95
I 1.49
12.42
12.49
15.06
15.99
15.31
16.42
16.94
14.93
16.33
14.04
17.10
16.31
IX.14
13.29
17.86
20.16
23.73
20.73
2 I .98
7.11
8.06
8.40
8.50
6.81
7.99
6.68
7.6 I
8.15
691
8.137
7.51
7.02
1.32
7.13
7.78
8.03
7.17
1.50
6.53
X.82
8 41
8.94
5.52
6.04
7.49
8.02
8.30
8.17
Temperature
T= 25 C; area of Biotilm (both sides) A = 3.069 X 10 m.
Runs with partially penetrated biofilms (diffusion
controlled regime).
0.12446L(~m)forO<L<622~mand~=26.9kgVSm3
of wet biofilm- for L > 622 Km.
3.2. Stoichiometyy of the denitri$icution reaction
Fig. 4 shows experimental data for the nitrate removal in
the reactor A NO,-N (mg I- ) as a function of the carbon
consumed ATOC (mg I-). A linear fitting leads to ATOC/
AN03-N = 2.52. This result agrees with data obtained in a
batch operation [ 231. In all experiments a TOC/N-NO3 ratio
of 9.3 to 14 in the feed was used to guarantee that nitrate was
the limiting substrate.
The stoichiometry of the denitrification process (neglecting assimilation) has been considered by several authors.
When methanol is the carbon source the denitrification reaction is:
NO, +$H,OH+;Nz+gO,+;H,O
200
Fig. 3. Biotilm
LOO
600
BOO
density ph as a function
1000
of biofilm
1200
lLO0
Lap
thickness L.
232
R.A.R. Boaventura,
A.E. Rodrigues
/ Chemical
10
Fig. 4. Nitrate
removal
ANO?-N
12
as a function
Enginerring
l4
Journal
16
of total organic
65 (I Y97J 227-235
LB
20
carbon consumed
A &,mg?i
ATOC in a RDBR.
lo t(a)
-0
*
4P
LB
2-
n*L,/,,jl
0
20
10
30
40
50
60
N (mg I-)
(b)
fL=1004
Table 4
Measured values of the intrinsic zero-order
under kinetic controlled regime)
pin
. L=749 pm
0 L=441 pm
.
l
10
r \-
20
0 L=lOS pl
30
40
50
60
70
Average biotilm
thickness LX 10
Cm)
Average kinetic
constant k,, X IO
(kg kg-Is-)
A.
B.
c.
D.
E.
108
205
441
749
1004
7.95
7.65
7.49
8.72
8.00
12-14, 16, 17
18-20,22,23
I-3.5-7
8-10
25.27, 29
Temperature
T= 25 C; total biohlm
N (mg I")
Run
A~=205~m
Ah
0
0
Table 5
Comparison
of observed
by Janscn and Kristensen
This work
zero-order
[ 251
(T= 25 C)
kinetic
constants
[ 251
Biofilm thickness
LX IO(m)
&,
(gm-s-l)
Biofilm thickness
LX 10h (m)
L?,,
(g m-s-r)
108
205
441
749
1004
0.72
0.60
0.37
0.23
0.22
60
200
500
1000
0.64
0.35
0.26
0.21
R.A.R.Boawnmra. A. E. Rorfrigues/
Clrm~ical
Engineering
0.7
controlled
Q
0.6
65 (1997)
regime).
0.1
0.2
0.3
0.4
0.5
0.6
Nr
0.1
ot,.
0
0,l
002
003
0.5
0.4
with
Eq. (6);
biofilm
in the diffusion-controlled
that critical
,I::,,
r!;,, &yf$Nk;o;
of a perfectly
Reactor
efficiency
mixed
E,
bioiilm
reactor
Equivalent
thickness
(km)
for partially
penetrated
Number
reaction
of
units
biofilms
(diffusion
Number
diffusion
controlled
of biofilm
units
(exp.)
I-2
IV,
Nhr=Nhr=&AJQLr
A.15
B.21
c.4
D.l 1
0.55
0.44
96
157
206
206
0.61
0.54
0.46
0.53
0.62
0.37
0.29
0.29
E.24
E.28
0.46
0.33
231
284
0.66
0.43
0.25
0.2 I
0.45
0.40
value, experi-
regime.
233
0.7
227-235
Below
y$$-$yyx
0.5
Run
Journal
regime)
a
Thiele
9
modulus
Reactor
efticiency
(model)
0.378
0.200
0.133
0.154
0.165
0.090
1.48
1.62
1.64
I.82
0.57
0.46
0.40
0.42
2.20
I .77
0.43
0.34
15,~
234
R.A.R.
Bonventuru,
A.E. Rodrigues
/ Chemiccrl
Enginwring
ra.oh\
w.oha
vh
x
X*
Journal
65 (I 997)
227-235
4. Conclusions
Subscripts
The rotating disk biofilm reactor (RDBR) is a convenient
tool for understanding biofilm development, to distinguish
different working regimes of biofilms (fully penetrated biofilms and partially penetrated biofilms) and to analyse the
influence of different carbon sources on denitrification processes. Biofilms with different thickness have been grown;
biofilm density decreases as the thickness increases. Denitrification kinetics obtained from RDBR experiments follows a
zero-order law; the intrinsic kinetic constant as well as the
nitrate diffusivity in the biofilm were measured. These data
coupled with batch studies (which provide information on
the effect of pH, nutrients, etc.) have been used to analyse
the operation of a biological fluidized bed reactor for water
denitrification [ 28,291.
in
out
reactor inlet
reactor outlet
Greek symbols
ff
4
Ph
Pmax
77
7
References
5. Notation
A
Dh
E,
f
k I I2
L
L
N
N
N,
Nh
Nhe
Q
r
R.A. R. &mmrrtm,
A.E. Rodr;,qw.s
/ Chemicui
[ 151 W. Characklis.
Fouling biofilm development:
a process analysis,
Biotechnol. Bioeng. 23 (1981) 1923
[ 161 J. Bryers, W. Characklis.
Process governing
biofim
formation.
Biotechnol. Bioeng. 124 ( 1982) 245 I.
[ 171 L. Mulcahy,
W. Shieh, E. La Motta, Simplified mathematical
model
for a fluidized bed biofilm reactor, AlChE 77 (209) ( 198 I ) 273.
[ I8 1 A. Parker, L. Sikora, R. Hughes. Denitrification
kinetics in packed
beds. AIChEJ 22 (5) (1976) 851.
[ I9 ] B. Atkinson, Biochemical
Reactors. Pion Limited, London. 1974.
[ 20) P. HarremGes. Biotilm kinetics, in: R. MilchelI (ed.), Water Pollution
Microbiology.
Wiley, New York. 1978.
j2l ] R. AriS. The Mathematical
Theory of Diffusion
and Reaction in
Permeable Catalysts, Vol. I - The Theory of the Steady State.
Clarendon Press. Oxford,
1975.
1221 A. Rodrigues.
A. Grasmick,
S. Elmaleh.
Modelling
of Biofilm
Reactors. Chem. Eng. J. 27 (2) ( 1983) B39.
[ 231 R. Boaventura.
Biological
Denitrificarion
in Fixed Biotilm Reactors,
Ph.D. Thesis, University
of Porto, 1986.
En,qinerrinsq
Jotrnrcd
65 (1997)
227-235
235