JOURNALOF FERMENTATION ANDBIOENGINEERING

Vol. 86, No. 4, 421-423. 1998

Improvement of Microalgal NOx Removal in Bubble Column and

Airlift Reactors
HIROYASU NAGASE, KAORU EGUCHI, KEN-ICHI YOSHIHARA, KAZUMASA HIRATA,
AND KAZUHISA MIYAMOTO*
Environmental Bioengineering Laboratory, Graduate School of Pharmaceutical Sciences, Osaka University, l-6
Yamadaoka, Suita, Osaka 565-0871, Japan

Received 4 March 199WAccepted 29 June 1998

Nitric oxide (NO), a major nitrogen oxide component in fossil fuel flue gas, was removed by the green alga
DunalieZla tertiolecta cultivated in bubble column and airlift reactors. As NO removal was enhanced by
increasing the dissolution of NO in water, increasing the gas-liquid contact area and time was deemed as an
effective method for improving NO removal. The highest level of NO removal, %%, was achieved with a
counter-flow type airlift reactor when 100 ppm NO was aerated with smaller bubbles.

[Key words: nitric oxide, algae, Dunaliella tertiolecta, bubble column, airlift reactor]

The emission of nitrogen oxides (NOx) contained in bubble size was changed by using stainless steel tubes of
fossil fuel flue gas is one of the major causes of acid two different gauges (i.d. 0.30mm, o.d. 0.55 mm [24
rain. The removal of nitrogen dioxide using higher gauge]; i.d. 0.13 mm, o.d. 0.31 mm [30 gauge]) or glass-
plants has been studied (1). Nitric oxide (NO), the main ball filters of three different particle sizes (lOO-120pm
NOx component, has low solubility in water, and is [no. 11, 40-50 pm [no. 21, and 20-30pm [no. 31). When
difficult to remove by conventional methods. NO a steady state was reached, which occurred one hour
removal by denitrifying bacteria in soil has also been after the supply of the model flue gas was started, the
reported (2, 3), but their NO removal ability was low. NO concentration in the outlet gas was measured. A
We have previously studied the removal of NO in a non-dispersive, infrared absorption spectrometer (ZRF;
bioreactor system using microalgae by supplying a model Fuji Electric Co. Ltd., Tokyo) was used to measure the
flue gas at the bottom of a bubble column reactor NO concentration in the gas phase. The rate of NO
through a glass-ball filter (4, 5). On the basis of the removal was calculated based on the measured NO con-
results, the process of NO removal in the system is centrations in the inlet and outlet gases (5). The concen-
explained as follows. NO in the gas phase is dissolved tration of oxygen (02) in the gas phase was measured
in the aqueous phase, and is then oxidized by algal cells using a zirconia-type O2 analyzer (ZFK; Fuji Electric,
using O2 supplied by photosynthesis or dissolution from Yokosuka, Kanagawa).
the gas phase. The presence of both algal cells and dis- One simple method of improving NO removal, which
solved 02 is essential for NO removal. Furthermore, in was investigated in the present study, is to reduce the
the previous paper, it was shown that dissolution of NO bubble size in order to increase the gas-liquid contact
in the aqueous phase is the rate-limiting step (5). There- area and thereby ensure a higher NO dissolution rate;
fore, increasing the gas-liquid contact area by using i.e., a higher rate of NO removal can be expected. Table
smaller bubbles was deemed as one method for improv- 1 shows the effect of bubble size on NO removal. The
ing NO removal; increasing the gas-liquid contact time mean bubble diameters were determined from photo-
by decreasing the rising rate of bubbles was another graphs. It is evident from Table 1 that NO removal
method considered. In this study, modification of the increased with decreasing bubble size. If the diffusion of
reactor system for reducing bubble size and decreasing NO into the liquid film of the gas-liquid interface is a
the rising rate of bubbles was investigated to improve rate-limiting step, the relationship between the column
NO removal by increasing the dissolution of NO in the height, h(m), and the ratio of the NO concentrations in
aqueous phase. the inlet and outlet gases, [NO],,,/[NO]h, can be derived
The green alga Dunaliella tertiolecta (ATCC30929) based on Henry’s law and NO mass balance as follows:
was cultivated in a modified f/2 seawater medium in a
long, tubular bioreactor as described previously (5). D. ln [NOlout _ RTha h

[NOli,---’ WJ&O (1)

tertiolecta was precultivated in the reactor at 25°C until
the optical density of the cell culture at 680nm (OD6*,,) where kLa (s-l) is the volumetric mass-transfer coef-
reached 2.5 (about 0.7 g ash free dry weight/r). The reac- ficient in the liquid film, E (-) the gas hold up, ub
tor was illuminated from one side by a bank of white (m/s) the superficial rising rate of bubbles, HNO (Pa.m3/
fluorescent lamps, at a light intensity at the surface of mol) the Henry constant of NO, R (=8.314 J/mol.K)
the reactor of 38 W/m2. For the preculture, 15% CO, in the ideal gas law constant, and T(K) the temperature.
air was supplied at a flow rate of 150ml/min. After the As Fig. 1 shows that there is a good linear relationship
preculture, 15% CO2 in Nz was supplied for 1 h to purge between In ([NO],“,/[NO]i,) and column height (h), Eq. 1
O2 from the medium, and then a model flue gas is thought to be applicable for explaining NO removal in
(100 ppm NO and 15% CO2 in N2) was supplied. The the column reactor. Therefore, the kLa values were calcu-
lated based on the data in Fig. 1 and Eq. 1, as shown in
* Corresponding author. Table 1. Since it was clear that supplying small gas bub-

421
422 NAGASE ET AL. J. FERMENT.BIOENG.,

TABLE 1. Effect of bubble size on removal of nitric oxide (NO) by

D. tertiolecta in light

Mean bubble No removala

Sparger diameter
(mm)
\-~ , (%)

Stainless steel tube 24 gauge 4.5 20 2.7 x lo-)

(i.d. 0.30mm, o.d. 0.55mm)
Stainless steel tube 30 gauge 2.0 26 4.1 x 10-r
(i.d. 0.13 mm, o.d. 0.31 mm)
Glass-ball filter no. 1 1.6 35 5.5 x 10-r
(particle size 100-120 pm)
Glass-ball filter no. 2 0.46 65 1.2 x 10-Z
(particle size 40-50 ,am)
- 1.0
Glass-ball filter no. 3 0.26 n.d.’ n.d.
0 0.5 1.0 1.5 2.0 2.5
(particle size 20-30 pm)
Column height (m)
a The algal culture in the 2-m bubble column was aerated by
100 ppm NO and 15% CO2 in Nz at a flow rate of 150 ml/min in light, FIG. 1. Relationship between column height and In ([NO],,,/
using the indicated spargers. [NOh,,). Symbols: 0, stainless steel tube 24 gauge; q , stainless steel
b Calculated from the data in Fig. 1 and Eq. 1 in the text. tube 30 gauge; A, glass-ball filter no. 1; 0, glass-ball fdter no. 2.
c Removal of NO and k,a could not be determined because of cell
separation by froth floatation.
would result in 88% removal, because the percentage
bles to the column reactor was an effective method of of NO removal in this system is constant irrespective of the
improving NO removal, the highest NO removal rate was NO concentration in the inlet gas. In fact, when such a
expected to be obtained by using a no. 3 glass-ball filter, system was tested, about 90% of the NO was removed
which produced the smallest bubbles among the spargers from the gas exhausted at the outlet of the second
used in this study. When this filter was employed, column. However, such a method would not be so
however, D. tertiolecta cells became concentrated at the efficient for practical use because the amount of NO
top of the reactor as a result of froth floatation and removed per unit volume of the reactor would decrease.
could not be cultivated in the column, and therefore sus- It is possible to change the gas-liquid contact time
tained NO removal could not be achieved. by altering the reactor design. Figures 2A and 2B show
Another method to improve NO removal would be schematic diagrams depicting the newly designed systems
to employ a longer column in order to increase the gas- for algal NO removal using parallel-flow- and counter-
liquid contact time. As we previously found that about flow-type airlift reactors, respectively. A draft tube was
65% of the NO was removed by an algal culture in a 2- fitted in the center of the column. The model flue gas
m bubble column with a no. 2 glass-ball filter (5), it was was supplied outside the draft tube, where oxygen was
calculated that two 2-m columns connected serially actively generated by photosynthesis. The draft tube was

R
Outer tube

T‘ f
Draft tube

1
0 - ring

St3tz;ess steel

(-) Medium flow

$
!.O I (+) Gas flow

---+ Draft tube

30 mm

50 mm

‘Outer gas
(for NO removal)
(A) ,9r;I;lee (6) Counter-
flow-type

FIG. 2. Schematic diagrams of NO removal systems using airlift reactors.

VOL. 86, 1998 NOTES 423

TABLE 2. Removal of nitric oxide (NO) by D. tertiolecta in light the column even when the smallest bubbles were sup-
using parallel-flow- and counter-flow-type airlift reactors plied through the no. 3 glass-ball filter, and growth inhi-
Inner flow NO
bition of algal cells by froth floatation in the column
Reactor type Glass-ball filter Inner gasa rate removalb reactor was prevented. As a result, NO removal dramati-
(ml/min) (%) cally increased from 57% to 82% at 150ml/min, and
Parallel flow No. 2 (40-50 pm) - 0 51 73% to 83% at 350mVmin of inner gas flow rate. These
No. 3 (20-30 pm) - 0 75 improvements in the rate of NO removal were consid-
ered to be due to both increase in gas-liquid contact
Counter-flow No. 2 (40-50 pm) Nz + CO1 150 57
area and gas hold up, namely, increase in k~a value.
NZ+C02 350 73
Another important parameter for NO removal is dis-
No. 3 (20-30 pm) N,+CO, 150 82 solved oxygen concentration. When 85% N2 and 15%
N,+C02 350 83 CO1 was supplied, a part of the dissolved oxygen
Air +CO, 150 91 produced by algal photosynthesis might be purged.
Air+coz 350 96 Therefore, air was used instead of nitrogen to supply
a Carbon dioxide at 15% was supplied to the culture with 85% N2
oxygen to the cell culture. By supplying 85% air and
or 85% air in the absence of NO at the indicated flow rates through 15% COz inside the draft tube at 350ml/min, the rate
the draft tube. of NO removal was increased to 96%. It was clear that
b Nitric oxide at 100 ppm was supplied to the culture with 15% supplying O2 was important for NO removal. It might
CO* and 85% Nz in the light at a flow rate of 150 ml/min outside the be possible to improve NO removal by devising a
draft tube. method to supply 02. The relationship between algal
cells, NO, and O2 will be investigated in further
cut near the top of the reactor and the two parts were research.
connected by a fine-mesh stainless steel netting, as In conclusion, a counter-flow-type airlift reactor has a
enlarged view of which is shown in Fig. 2. In this way, three times higher NO removal ability than a simple bub-
the mixing of bubbles inside and outside the draft tube ble column, implying that the same high rate of NO
was avoided and circulation of the culture medium in removal which can be achieved with a 6-m simple bubble
the reactor column was facilitated. column using a no. 2 glass-ball filter, can be achieved
Table 2 shows the NO removal rates when 100ppm using a no. 3 glass-ball filter in a 2-m counter-flow-type
NO was supplied to the parallel-flow- and counter-flow- airlift reactor.
type airlift reactors. In the parallel-flow reactor, the NO
removal was only 51% with the no. 2 glass-ball filter, This study was supported by a Grant-in-Aid for Scientific
which is lower than that obtained in the bubble column Research (B), No. 09555254, from the Ministry of Education,
reactor, because an upward flow of the culture medium Science, Sports and Culture of Japan. The authors would like to
was caused outside the draft tube, and this increased the thank Mr. Satoshi Nishikata of Fuji Electric Corporate Research
and Development Ltd. for his valuable suggestions on the study.
speed at which the bubbles rose.
The counter-flow-type airlift reactor has almost same
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