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An Efficient System For Carbonation
An Efficient System For Carbonation
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
a r t i c l e i n f o a b s t r a c t
Article history: High-rate algal ponds have the potential to produce 59 T of dry biomass ha1 year1 based on the specific
Received 16 August 2010 productivity of 20 g m2 day1. Atmospheric air provides only 5% of the CO2 to the pond surface required
Received in revised form 4 November 2010 for photosynthesis. Hence, CO2 is usually provided via bubbling of concentrated CO2-air mixture into the
Accepted 9 November 2010
algae ponds. This process is, however, not significantly effective in terms of mass transfer. Use of bubble
Available online 13 November 2010
column to increase the interfacial area of contact available for gas exchange is proposed as an efficient
alternative. A carbonation column (CC) was modeled and designed to measure CO2 absorptivity in-pond
Keywords:
water at various pH regimes. The CC performed at 83% CO2 transfer efficiency. An air-to-pond mass trans-
Algae
Bubble column
port coefficient of 0.0037 m min1 was derived. The proposed device can be used with any exhaust gas
CO2 stream with higher concentrations of CO2 in conjunction with raceways for optimizing algae production.
High-rate pond Published by Elsevier Ltd.
Mass transfer
system, aimed at increasing interfacial area of gas bubbles and on the acid–base neutralization reaction between carbonic acid
gas–liquid contact time, leads to enhanced CO2 mass-transfer effi- and sodium hydroxide was used to calculate CO2 absorptivity.
ciency of the bubble column (Sanchez et al., 2000). Membrane dif-
fusion systems theoretically seemed better when compared to
bubbling system, viz., no CO2 loss, accurately controlled CO2 trans- 2. Methods
fer rates and better overall efficiencies. However, such a system
can be cost intensive due to requirement of long tubing mem- 2.1. Description of carbonation column and CO2 supplying facility
branes (Carvalho et al., 2006). The gas–liquid interfacial area and
contact time are reported to be the key parameters to improve Two raceway ponds of identical dimensions, each with a surface
the gas–liquid mass transfer (Carvalho et al., 2006). Thus, the major area of 1.1 m2 and 420 L of tap water at 15 cm height (Figs. 1 and
challenge in the microalgae research is to design an efficient and 2), were used in this test. One pond was connected to the CC and
cost effective carbonation system for the existing high-rate ponds the other (control pond) was fitted with a 5 cm long air sparger
to satisfy the high CO2 requirement that will eventually improve at the bottom. The paddle wheel motor in the raceway was oper-
the biomass productivity. ated at 30% capacity giving a surface water velocity of approxi-
In the present study, a carbonation column (CC) was modeled mately 20 cm s1. The CC was made of 3.3 mm thick transparent
and designed for CO2 supplementation with 90% efficiency polyvinylchloride (Schedule 40 PVC) pipe with internal diameter
(Fig. 1). The transfer efficiency and absorptivity of CO2 were stud- of 0.076 m and height of 3.0 m. An air sparger (5 cm) was fitted
ied for the CC and compared with those observed via traditional at 10 cm above the bottom of the column. Water was pumped into
gas sparging directly into pond water. A simple technique based the carbonation column at 7 L min1 from the top to provide coun-
ter-current water flow relative to the gas bubbles. The CC and con-
trol pond were supplied with 5% CO2-air mixture from a certified
5% CO2 -air cylinder at 1.5 L min1.
V qC
MNaOH ¼ ð3Þ
MW
Q sC
MCO2 ¼ ð4Þ
Vm
M NaOH
ECO2 transfer ¼ 100 ð5Þ
2M CO2
Fig. 1. A view of the Carbonation column. (A) gas inlet, (B) Drain, (C) vertical loop
on effluent to maintain proper water height in column (pipe connector to column is
The second and third runs were performed under similar condi-
only for support; it is blanked off to flow), (D) pond water effluent, (E) pond water tions with different initial and final pH values viz. 9.0 to 8.0 and 8.0
influent. to 7.0, respectively.
3242 R. Putt et al. / Bioresource Technology 102 (2011) 3240–3245
8
6
7
1
6 6
5
1 2
Fig. 2. The schematic diagram of experiment facility used for carbonation of pond water. (1) Raceway pond; (2) Gas sparger; (3) Carbonation column; (4) 5% CO2-air pressure
cylinder; (5) Valve; (6) Flowmeter; (7) Pump; (8) Gas exhaust.
2.3.4. CO2 requirement et al., 1998). The other way of measuring CO2 transfer rates would
Assuming average algae biomass productivity at 20 g m2 be to grow algae in the pond and measure dry mass production and
day1, the daily biomass productivity of 1.1 m2 raceway pond with carbon content. However, this would introduce many uncontrolled
1.5 times overdesign consideration would be 32 g algae biomass variables into the measurements, notably those associated with
day1. As the carbon content of algae is 50% of its dry weight photosynthesis (Sobczuk et al., 2000). The observed CO2 mass-
(Grobbelaar, 2004), 1.35 mol CO2 day1 is required to achieve the transfer efficiency of CC was 83% as compared to 37% efficiency ob-
target algal biomass. Recalculating CO2 volumes in terms of served in control pond at alkaline pH range of 10 to 9 (Table 1). The
L min1 resulted in a flow rate of 0.93 L min1 of 5% CO2 air mix- rate of CO2 transfer for CC was 58% higher than control pond as it
ture to the CC. took only 29 min for CC to decrease the pond pH from 10 to 9,
whereas, the identical results could only be achieved in 50 min
2.3.5. Calculation of column diameter via direct sparging of gas into control pond (Table 1). In the second
The area of column cross-section (Ac) was modeled as ten times run for pH regime 9 to 8, again CC performed better than control
of area of gas bubble (Ag = 0.52 cm2), and was calculated as follows: pond with 82% efficiency whereas in control pond only 36% effi-
ciency could be achieved. The CO2 transfer rate was 64% higher
Ac ¼ 10ðAg Þ ¼ 10ðQ=tÞ ¼ 5:2 cm2 ð11Þ for CC against control. Interestingly, the carbonation rate was more
than 3 times faster in case of pH range 9 to 8 than pH range 10 to 9
where Q , gas flow rate (0.93 L min1); t, bubble rise velocity
for both ponds. This indicated that high alkalinity of water could
(30 cm s1).
decrease the CO2 absorptivity. At these two pH ranges the efficien-
Thus the minimum diameter of column should be 2.57 cm.
cies were reproducible for both the column and the control. The
However, a Schedule 40 PVC pipe of 7.6 cm (diameter) was se-
column efficiencies were 7–8% (absolute) below the model predic-
lected taking into consideration, the structural stability of the
tions, which could be attributed to the observed coalescence of
3.1 m high column and also because of its availability off the shelf.
bubbles, thus resulting into decreased specific gas–liquid interfa-
cial area (Carvalho and Malcata, 2001). The control efficiency of
3. Results and discussion 36–37% could be predicted by the CC model. It was observed that
the bubbles rising from the sparger in the bottom of the control
The diameter of the column was sized to ensure that only 10% of pond took about two seconds to reach the surface and break open.
the volume is gas. The gas bubbles, estimated to be 0.003 m in From Eq. (10) in Section 2.3.2., for a time of 2 s the partial pressures
diameter, then rise individually at their terminal velocity of ratio is 0.64, which corresponds to a transfer efficiency of 36%.
0.3 m s1 without coalescence into larger bubbles, which is impor- The third run done below pH 8 was even more instructive. The pH
tant for achieving efficient mass transport (Shah et al., 1982). The never reached 7, but reached steady state values of 7.11 and 7.56 for
mass transport of an individual bubble can be followed as it rises the CC and the control, respectively (data not shown). This illus-
through the water column, to calculate the number of seconds, trated the volatility of dissolved CO2 below pH 8. As shown in
and thus the column height, required for the bubble to lose 90% Fig. 3, the inorganic carbon may exist in several interconvertible
2
of its carbon dioxide. The 90% recovery was selected because the chemical forms, CO2 (aq), H2CO3, HCO 3 and CO3 based on the pH
concentration of CO2 in the bubble will decline exponentially with of aqueous environments (Goldman et al., 1981; Becker, 1994).
time, so that it would take the same additional column height to go Although HCO 3 is easily absorbed by algal cells, CO2 is reported to
from 10% (absolute) CO2 remaining to 1% (absolute) CO2 remaining be the most preferred source of inorganic carbon (Goldman et al.,
as it would for the 100% to 10% reduction, which may not be eco- 1981). However, at the pH > 10.3 the CO23 form dominates and
nomically attractive. The mass transfer of CO2 from gas phase to li- the chemical precipitation of salts is highly likely to occur and hence
quid phase occurs via sequential stages: transport from the bulk of could lead to medium deterioration and algal cell injury. It is thus
the gas bubble to the thin gaseous film at the interface; diffusion proposed that the pH range for such measurements should be in
through this gas film; transport across gas–liquid interface; diffu- the range of 8–10, at least for systems where the water is exposed
sion through the adjacent liquid film and finally transport from to the atmosphere, owing to the loss of CO2 which would otherwise
the thin liquid film to the bulk of the liquid (Carvalho et al., occur when at least some of the dissolved carbon is in a volatile form,
2006). The gas molecules experience resistance at every stage of namely CO2 or carbonic acid. Above pH 8 all the carbon is in the non-
transfer as they occur in series and the overall resistance over volatile form of either bicarbonate or carbonate.
the entire path can be calculated as sum of these resistances at We propose that the steady state pH values are the result of
every stage. It has been reported that most of the resistance oc- pond-to-air transport of carbon dioxide. Below pH 8, a significant
curred during transfer through liquid film, thus confirming that percentage of the CO2 is in a volatile form (i.e. H2CO3 or dissolved
CO2 transport is mainly controlled by resistance offered by the li- CO2) (Fig. 3) and so pond concentrations above that set by the sat-
quid film (Becker and Kyle, 1998). As given in Eq. (6), the rate of uration value for CO2 in air (385 ppm) will result in loss of CO2 by
mass transfer is proportional to concentration difference between the pond water to the atmosphere. The calculated rates of CO2
one actual bulk concentration of one phase and an equivalent bulk injection by the CC and control at 82% and 36% efficiencies were
concentration of the other phase and the area available for transfer calculated as 2.6 103 and 1.1 103 mol min1 respectively
(area of bubble). It is therefore reasonable to denote the overall based on the data from the runs made above pH 8.
mass-transfer coefficient (k), which is the sum of the reciprocals After several calculations, the H2CO3 concentration for the CC
of resistances to transfer, as liquid-phase mass-transfer coefficient and control ponds were calculated as 0.63 and 0.22 mol m3
(kl) because of the dominance of resistance at liquid-phase mass respectively, from the amount of NaOH added to them.
transfer. Talbot et al., 1991, reported that in CO2 transfer, the kLA We propose that the steady state pH values reflect a balance be-
is one of the most important parameters in design, scale-up and tween CO2 supply by the spargers and loss at the surface of the
operation steps for algal mass culture system. ponds. The rate equation (Eq. (6)) can thus be explained as:
The rate of CO2 uptake could be calculated, by raising quantita-
tively the pH of clear, algae-free water with a strong base such as Rloss ¼ kL AðC pond Þ ð12Þ
NaOH, and then by measuring the amount of time required to re-
duce the pH by a given amount, knowing that one mole of CO2 where Rloss is the rate of loss in moles per minute, kl is a rate con-
added to the water would neutralize 2 mol of NaOH (Matsumoto stant, A is the pond surface area in square meters, and Cpond is the
3244 R. Putt et al. / Bioresource Technology 102 (2011) 3240–3245
Table 1
Values of CO2 transfer efficiencies of CC and control pond.
Pond NaOH added (moles) CO2 added (Carbonation time) -moles (min) Carbonation efficiency (%)
pH 9 to 10 pH 8 to 9 pH 10 to 9 pH 9 to 8 pH 10 to 9 pH 9 to 8
CC 0.15 0.046 0.091(29) 0.028 (9) 83 82
Control 0.11 0.04 0.15 (50) 0.056 (14) 37 36
plot of the data is shown in Fig. 4.The rate constant was then calcu-
lated as 0.0037 m min1.
Using this value of rate constant the Eq. (6) was modified as be-
low to calculate the growth rate of algae supported by atmospheric
CO2 transport to the pond surface if that was the only source of car-
bon dioxide:
Rgain ¼ kL AðC s C b Þ
where Rgain is the CO2 uptake by the pond from the atmosphere
(assuming no artificial supply of carbon dioxide to the pond), Cb is
the carbon dioxide concentration in the bulk of the pond, and Cs
is that at the surface. For the maximum rate of transfer we set
Cb = 0.Then,
1
Fig. 3. Distribution coefficients for CO2 in water (Bialkowski, 2004). Rgain ¼ 0:0037 m min ð0:011 mol m3 0Þ
1
¼ 0:000041 mol m2 min :
concentration of volatile CO2 in the pond, in moles per cubic meter. Converting to an algae production rate, assuming CO2 transfer
Therefore to the pond water day and night, the biomass productivity was cal-
culated as1.3 g m2 day1 which is only 6.5% of the average bio-
Rloss
¼ kL A ¼ constant mass productivity of high-rate algae ponds. These CC model
C pond predictions are in accordance with Stepan et al., 2002.
This confirms the previously reported results by Stepan et al.
which was 0.0041 m min1 for CC and 0.0050 m min1 for control (2002), which showed that atmospheric supply of CO2 to the ponds
pond. Around the average of 0.0045 m min1 the spread is 10%. A would only be about 5–7% of that needed to support high-rate algae
growth. Thus the CC technology can satisfy the CO2 demand for
3
high-rate algae ponds and significantly reduce the production cost
of algae biomass by enhancing the biomass productivity per unit
2.5
Rate x 1,000 molmin -1
area. The usual practice, to date, is to submerge the gas sparger into
2 the pond. In some instances a rectangular well, crosswise in the
pond, is provided to increase the contact time for the bubbles before
1.5 they reach the surface. The depth of this well is generally less than
three feet. This would be less expensive to install than a 10 foot
1 deep carbonation pit for the same purpose, although the cost of
the pit would represent less than 1% of the installed cost for the
0.5 farm. The well in the pond, however, would be less efficient in
carbon dioxide transfer, increasing the cost of the carbon dioxide.
0 For example, at US $ 0.11 kg1 of carbon dioxide (the current
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 commercial bulk price), a three foot deep well, at a transfer effi-
-1
Concentration, mol L ciency of 48% (taken from our model) would contribute US $
463 T1 to the cost of the algae. This is nearly double the US $
Fig. 4. CO2 transfer rates at pond surfaces.
242 T1 of algae paid when the carbonation pit is used, at a transfer
Table 2
Comparison chart of methods for gas transfer in photobioreactors (adapted and modified from Carvalho et al., 2006).
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installed cost of the farm, the cost of the carbon dioxide when a car-
265–272.
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bonation well reported in the literature. This CC design is an enclosed systems designs and performances. Biotechnol. Prog. 22, 1490–1506.
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