You are on page 1of 6

Q IWA Publishing 2008 Water Science & TechnologyWST | 58.

4 | 2008

957

Reducing operating costs for struvite formation with a


carbon dioxide stripper
K. P. Fattah, N. Sabrina, D. S. Mavinic and F. A. Koch

ABSTRACT
One of the major operational costs of phosphorus recovery as struvite is the cost of caustic
chemical that is added to maintain a desired level of operative pH. A study was conducted at the
Lulu Island Wastewater Treatment Plant (LIWWTP), Richmond, BC, using a struvite crystallizer and
a cascade stripper designed at the University of British Columbia (UBC). The stripper was tested
under different operating conditions to determine the effectiveness of CO2 stripping in increasing
the pH of the water matrix and thereby reducing caustic chemical use. This reduction is expected
to reduce the operational costs of struvite production. Throughout the project, a high percentage
(90%) of phosphorus removal was achieved under each condition. The cascade stripper was very
effective in saving caustic usage, ranging from 35% to 86%, depending on the operating
conditions. However, the stripper showed relatively poor performance regarding ammonia
stripping.
Key words

K. P. Fattah
D. S. Mavinic
F. A. Koch
Department of Civil Engineering,
University of British Columbia,
2002-6250 Applied Science Lane, Vancouver, BC,
Canada V6T 1Z4
E-mail: parvez@interchange.ubc.ca;
dsm@civil.ubc.ca;
koch@civil.ubc.ca
N. Sabrina
International Federation of Red Cross and Red
Crescent Societies (IFRC),
65-66, Bashu Lodge,
Alekanda, Barisal 8200,
Bangladesh
E-mail: nandinisabrina@yahoo.com

| carbon dioxide stripping, crystallization, nutrient removal, phosphorus recovery,


struvite

INTRODUCTION
The application of phosphorus recovery from municipal

supersaturation ratio (SSR), the primary control variable

wastewater, through struvite precipitation, provides a viable

used by the research team at UBC (Britton et al. 2005).

and sustainable alternative to mined rocks as a source of

The supersaturation ratio is given by:

phosphorus (Berg 1982; Jaffer et al. 2002). Controlled and


intentional struvite precipitation in wastewater treatment

SSR Ps sample=Ps equilibrium

plants, especially those employing biological nutrient

where Ps sample struvite conditional solubility product

removal (BNR) technologies, also provides necessary

32
[Mg2 ]total [NH
4 ]total [PO4 ]total and Ps equilibrium is

phosphorus removal from the system (Adnan 2003). The

the struvite conditional solubility product at equilibrium

reduction of phosphorus can also reduce the probability of

(Britton et al. 2005). The concentrations of the species,

unintentional struvite formation, a costly nuisance common

32
[Mg2 ]total, [NH
4 ]total, [PO4 ]total, as well as Ps equilibrium,

in wastewater treatment plants.

depend on the pH, conductivity and temperature of the

Studies have shown that more than 90% of dissolved

system in which they exist (Adnan et al. 2003).

phosphorus can be removed from anaerobic digester

Areas of high turbulence, such as pipe elbows, mixer

supernatant and centrate in the form of struvite precipi-

blades, valves and pumps are main locations of struvite

tation (Britton et al. 2005; Fattah et al. 2008a). However,

deposits (Neethling & Benisch 2004). In these locations, a

this method is costly, due to the need for large amounts

reduction of partial pressure of CO2 takes place. Hence,

of caustic to keep the pH of the system steady. The pH

Loewenthal et al. (1994) concluded that partial pressure of

is especially important in preserving the set reactor

CO2 is one of the driving forces for struvite precipitation.

doi: 10.2166/wst.2008.722

958

K. P. Fattah et al. | CO2 stripper for reduced costs of phosphorus (struvite) recovery

Water Science & TechnologyWST | 58.4 | 2008

Battistoni et al. (2001) showed that the pH can be controlled

agitation of air-water interface. Theoretically, the greater

by applying air stripping of carbon dioxide only, without the

these values are, the more efficient the stripping will be.

addition of caustic; this can reduce a large fraction of

Usually, as the temperature decreases, the amount of

operating costs. Carbon dioxide stripping in a cascade

air required increases significantly for the same degree of

striper was also shown to increase pH of synthetic feed

removal (Tchobanoglous et al. 2003). Again, care should be

(Fattah et al. 2008b).

taken as too high an air to water flow rate can result in a

Hiroyuki & Toru (2003) used 1 L bench scale reactors to

cooling effect (Liao et al. 1995).

demonstrate the affect of aeration on phosphorus precipitation. Along with aeration, NaOH solution was also fed
continuously to increase the pH. They found that, by
increasing

the

aeration

intensity

from

2.l mg/L

to

METHODS

10.5 mg/L, the rate of phosphorus removal was also

The study was carried out at Metro Vancouvers Lulu Island

increased. The authors concluded that aeration influenced

Wastewater Treatment Plant in Richmond, B.C. Canada,

the quantities of CO2 in solution, which helped in raising

using centrate generated at the plant. Struvite precipitation

pH, and resulted in the increased rate of phosphorus

was carried out in a struvite crystallizer (Figure 1); caustic

removal. A simplified explanation on how CO2 stripping

and magnesium chloride was externally added to the flow

helps raise the pH of a solution is:

to provide suitable conditions for struvite precipitation.

2
HCO2
3 ! CO2 " OH

The stripper was located between the overflow pipe of the


crystallizer and the clarifier. Figure 2 illustrates the basic

Detailed chemistry relating the increase of pH through

design of the cascade stripper. The cascade stripper was

carbon dioxide stripping can be found in Cohen &

made of plexiglass and designed for a maximum hydraulic

Kirchmann (2004).

loading rate of 20 L/min. Each of the baffles had a surface

Air stripping of ammonia from wastewater requires that


the ammonia be present as a gas. Ammonium ions in

area of 225 cm2. Additional description of the stripper can


be found in Fattah et al. (2008b).
The study was carried out in three runs. In the first run

wastewater exist in equilibrium with gaseous ammonia:

(Run1) the struvite crystallizer was operated without the

NH
4 $ NH3 H

As the pH of the wastewater is increased above 7, the


equilibrium is shifted to the right and ammonium ion is
converted to ammonia, which may then be removed by
air/gas stripping. However, Henrys law constant of
ammonia is only 0.75 atm (mol H2O/mol air), which
makes this compound marginally strippable (Tchobanoglous et al. 2003). The result obtained by Musvoto et al.
(2000) was in agreement with this fact. They compared the
stripping rates of ammonia and CO2, and found that the
stripping rate for CO2 was higher by two orders of
magnitude than that for ammonia. This happens since
Henrys law constant for ammonia is much lower than that
for CO2 (the dimensionless Henrys law constant for
ammonia and CO2 are 0.011 and 0.95 respectively).
The rate of ammonia stripping is influenced by
pH, temperature, relative ammonia concentrations, and

Figure 1

Flow diagram of the struvite crystallization process.

959

K. P. Fattah et al. | CO2 stripper for reduced costs of phosphorus (struvite) recovery

Water Science & TechnologyWST | 58.4 | 2008

Table 1

Characteristics of centrate used in the study

PH

Minimum

Temp

Cond

Mg

PO4ZP

NH3ZN

Molar Ratio

(8C)

(mS)

(mg/L)

(mg/L)

(mg/L)

Mg:P

7.2 15.3

Maximum 8.1 34
Average

7.6 25

4.11

N:P

4.1

42.6 500

0.01 18

12.48 17.4

100.0 916

0.39 36

77.7 782

0.17 23

7.01

9.8

Analytical measurements of phosphorus and ammonium


were carried out using colorimetric flow injection analysis
(model LaChat QuikChemw 8,000). Magnesium ion was
analyzed using flame atomic spectrophotometery (model
Varian Inc. SpectrAA220w). Concentration of dissolved
gaseous carbon dioxide in liquid solution was measured
by an Accumet Gas-Sensing Combination ISE. The pH,
temperature and conductivity of the samples were recorded
on-site, using a Horiba D54 portable meter.

Figure 2

Front view of the cascade stripper.

RESULTS AND DISCUSSION


The water matrix used, centrate, had different character-

stripper. In subsequent runs, the stripper was operated with

istics from day to day. A summary of centrate characteristics

air (Run 2) and without air (Run 3), to determine the

during the study period is given in Table 1 and shown

influence of air on CO2 stripping. Air was supplied through

graphically in Figures 3 and 4.

an airflow meter from the top of the stripper. The maximum

As expected, the magnesium concentration in the

airflow rate provided was 107.5 L/min. While running

centrate was the limiting factor for struvite crystallization.

without external air supply, the top surface of the stripper

The molar ratio of Mg:P was always below 1, the lowest

was kept open. With the introduction of the airflow, the top

ratio required for struvite precipitation. Hence, magnesium

surface of the stripper was covered with a plexiglass lid.

feed (in the form of MgCl2) was injected into the reactors,

The total flow through the stripper was 18.24 L/min.

to raise the Mg:P ratio. The average supersaturation ratio


(SSR) of centrate during the study period was 0.96.

Sample analyses
Several parameters were monitored and recorded each day.
These include grab samples of centrate and effluents for
determining Mg2 , NH42 and PO32
concentrations; pH,
4
temperature and conductivity of the centrate and effluents.
Feed and recycle flows were measured daily and adjusted
(if required). Caustic samples were collected and amount
of caustic used by the stripper was recorded daily. CO2
samples were collected from the seed hopper and clarifier
effluent.

Figure 3

Centrate pH variations during study period.

K. P. Fattah et al. | CO2 stripper for reduced costs of phosphorus (struvite) recovery

960

Water Science & TechnologyWST | 58.4 | 2008

Ammonia stripping
During some days, the molar removal of ammonium
exceeded that of magnesium and phosphate. The removal
of this extra amount of ammonia from the system might
be attributed to. Without the stripper, some stripping of
ammonia also occurs in the downpipe leading to the
clarifier.
|

Figure 4

Magnesium, phosphate and ammonium concentration in centrate.

Caustic use

Performance of crystallizer
The operating conditions of the crystallizer is given in
Table 2. The definition of the respective parameters can
be found in Fattah et al. (2008a).

Although the with-stripper and without-stripper does not


show any improvement on the phosphate removal rates, on
an average, the process with the CO2 stripper in use
consumed less caustic (0.84 kg/d and 0.91 kg/d) than the
without-stripper (1.23 kg/d). This results in a 32% and 26%
savings in caustic use, when the stripper is in operation.

Nutrient removal

Cost implication of this reduction is mentioned later.

Without the stripper, the crystallizer was able to efficiently

The overall CO2 removal rate was 20% and 17%, during

remove, on an average, 90% of the incoming phosphate

this period.

load and 66% and 10% of magnesium and ammonium,


respectively. With the incorporation of the stripper in the
process cycle, a comparable amount of phosphate was
removed. As expected, the ammonium removal percentage

POTENTIAL FOR STRIPPER FOULING

also increased, up to 14.5%. However, the magnesium

As previously mentioned, the stripper was made of

removal was reduced to 39%. With external air into the

plexiglass and, therefore, relatively smooth at first. As

stripper, the removal rates achieved for magnesium,

expected, with the stripping of carbon dioxide, some

ammonium and phosphorus were 75%, 5%, and 90%,

struvite and suspended solids build up was visible on the

respectively. Similar results were found in earlier studies

sides, after prolonged use. This phenomenon can be

(Munch & Barr 2001; Ueno & Fujii 2001; Zhang 2006).

explained in terms of the increase in pH of the water

A summary of results are given in Table 3.

matrix. As the pH increases, the SSR of the water matrix

Although the chemistry of struvite formation requires a

increases, and this provides suitable conditions for struvite

Mg:P molar ratio of 1:1, the data presented here shows that

growth. However, since the water matrix passing through

the average removal of magnesium, relative to phosphate,

each baffle is low in magnesium and phosphatemost of it

is less than unity. The higher proportion of phosphate

removed in the crystallizerthere is a lower potential for

removed is probably due to the formation of other

struvite growth. The amount of struvite present did not

phosphate species, such as calcium phosphates and

hamper the operation or clog the stripper. The path of the

orthophosphates.

water flow was always clean, as struvite did not accumulate

Table 2

Summary of operating conditions

Total feed

Centrate flow

Mg feed flow

Recycle flow

Total flow

Upflow velocity

External air flow

Unit

(L/min)

(L/min)

(mL/min)

Recycle ratio

(L/min)

(L/min)

pH

(cm/min)

(L/min)

Value

2.61

2.51

100

15.63

18.24

8.1

400

107.5

K. P. Fattah et al. | CO2 stripper for reduced costs of phosphorus (struvite) recovery

961

Table 3

Summary of study results (average values)

Water Science & TechnologyWST | 58.4 | 2008

Table 4

Cost analysis for caustic usage

Without
Strippers

With Strippers

Run 1

Run 2p

Run 3

Phosphate removal (%)

90

90

90

Ammonium removal (%)

10

14.5

Magnesium removal (%)

66

75

39

Molar phosphate removal

2.44E-03

2.42E-03

1.55E-03

Molar ammonium removal

5.73E-03

2.98E-03

7.66E-03

Molar magnesium removal

2.19E-03

2.28E-03

1.13E-03

Molar ratio (Mg:N:P)

0.9:2.3:1

0.9:1.2:1

0.7:4.9:1

Caustic use (kg/d)

1.23

Without Strippers

With Strippers

Run 1

Run 2p

Run 3

Caustic use (kg/d)

1.23

0.84

0.91

Caustic savings (kg/d)

0.39

0.32

32

26

1.00

0.82

Annual savings at Lulu


Island WWTP (CAD$)

12,200

10,000

Annual savings at Annacis


Island WWTP (CAD$)

54,500

44,500

Caustic savings (%)


Current caustic savings
(CAD$/day)

0.84

0.91

Caustic savings (%)

32

26

CO2 stripping (%)

20

17

Stripper run with external air.


Stripper run without external air.
Caustic cost CAD 2.57/kg.

Stripper run with external air.


Stripper run without external air.

COST STUDY
in place. Moreover, cleanup of the stripper was straightfor-

The construction cost of the stripper was reasonable,

ward as the accumulation was easily removed by hosing it

relative to the cost of the struvite reactor (including

with hot water. Figure 5 shows a cross-section of the

materials and labor). Once installed, there was little, or no

stripper, showing the struvite accumulation.

costs associated with its maintenance. As mentioned


previously, the incorporation of the stripper resulted in
lower caustic use to keep the crystallizer at the desired pH
level. Lower caustic use can be directly correlated to
operational costs. Lulu Island WWTP is a relatively small
secondary treatment plant treating, on average, seventy five
million litres per day (75 MLD). The study was operated
with a centrate flow of only 2.61 L/min, which relates to
approximately 3,800 L/day. This is only 2% of the total
centrate production at the treatment plant. Based on the
current caustic price of CAD$2.57/kg, the potential yearly
plant savings in caustic is CAD 12,200 and CAD 10,000 for
operation conditions Run1 and Run 2, respectively. Based
on this calculation, the potential caustic saving at the larger
(average 469 MLD) treatment plant in Metro Vancouvers
Annacis Island is CAD 54,500 and CAD 44,500. A summary
of the cost study (Sabrina 2007) is given in Table 4.

CONCLUSIONS
Based on the results from the pilot-scale study of phosphorus recovery with carbon dioxide stripping, the followFigure 5

Struvite accumulation in stripper during operation.

ing conclusions can be drawn.

962

K. P. Fattah et al. | CO2 stripper for reduced costs of phosphorus (struvite) recovery

Through the process, over 90% of phosphorus was easily


removed from the centrate at a pH of 8.1, with or
without air stripping.
With air and without air stripping, an average of 32%
and 26% caustic savings was achieved using the stripper,
compared to the no-stripper condition, respectively. It is
expected that, with a lower operating pH (if conditions
satisfy all criteria for struvite formation), the cost of the
stripper could be recovered in less than three years, and
the cost of producing struvite pellets will be significantly
reduced.
Although struvite did accumulate on the sides and baffles
of the stripper, there were no plugging problems related
to the presence of struvite. The accumulation was easily
removable by washing it off with hot water.
The study validates that stripping off carbon dioxide, to
raise pH in the production of struvite is a viable option in
reducing caustic usage, and thereby reducing operating
and production costs.

ACKNOWLEDGEMENTS
The authors would like to thank the Natural Science and
Engineering Research Council of Canada (NSERC), Metro
Vancouver, Ostara Nutrient Recovery Technologies Inc.
and Stantec Consulting Ltd., for their generous funding
towards this study. Also, deeply appreciated is the helping
hand provided by staff at the Lulu Island Wastewater
Treatment Plant.

REFERENCES
Adnan, A., Mavinic, D. S. & Koch, F. A. 2003 Pilot-scale study of
phosphorus recovery through struvite crystallization
examining the process feasibility. J. Environ. Eng. Sci. 2,
315 324.
Battistoni, P., De Angelis, A., Pavan, P., Prisciandaro, M. & Cecchi, F.
2001 Phosphorus removal from a real anaerobic supernatant by
struvite crystallization. Water Res. 35(9), 2167 2178.
Berg, E. 1982 Handbook for Sampling and Sample Preservation for
Water and Wastewater. United States Environmental
Monitoring and Support Laboratory, USEPA, Cincinnati,
Ohio, USA.
Britton, A., Koch, F. A., Mavinic, D. S., Adnan, A., Oldham, W. K.
& Udala, B. 2005 Pilot scale struvite recovery from anaerobic

Water Science & TechnologyWST | 58.4 | 2008

digester supernatant at an enhanced biological phosphorus


removal wastewater treatment plant. J. Environ. Eng. Sci. 4(4),
265 277.
Cohen, Y. & Kirchmann, H. 2004 Increasing the pH of wastewater
to high levels with different gasesCO2 stripping. Water, Air
and Soil Pollut. 159, 265 275.
Fattah, K. P., Mavinic, D. S., Koch, F. A. & Jacob, C. 2008a
Determining the feasibility of phosphorus recovery as struvite
from filter press centrate in a secondary wastewater treatment
plant. J. Environ. Sci. Health Part A. 43(7), 756 764.
Fattah, K. P., Zhang, Y., Mavinic, D. S. & Koch, F. 2008b
Application of carbon dioxide stripping for struvite
crystallizationI: Development of a carbon dioxide stripper
model to predict CO2 removal and pH changes. J. Environ.
Eng. Sci. 7, 345 356.
Hiroyuki, H. & Toru, S. 2003 Nitrogen and phosphorus recovery
from a piggery waste water treatment facility. Proc. 2003 Third
International Symposium on Environmentally Conscious
Design and Inverse Manufacturing, Tokeyo, Japan,
pp. 422 426.
Jaffer, Y., Clark, T. A., Pearce, P. & Parsons, S. A. 2002 Potential
phosphorus recovery by struvite formation. Water Res. 36,
1834 1842.
Liao, P. H., Chen, A. & Lo, K. V. 1995 Removal of nitrogen from
swine manure wastewaters by ammonia stripping. Bioresour.
Technol. 54(1), 17 20.
Loewenthal, R. E., Kornmuller, U. R. C. & van Heerden, E. P. 1994
Modelling struvite precipitation in anaerobic treatment
systems. Water Sci. Technol. 30(12), 107 116.
Munch, E. & Barr, K. 2001 Controlled struvite crystallization for
removing phosphorus from anaerobic digester sidestreams.
Water Res. 35(1), 151 159.
Musvoto, E. V., Ekama, G. A., Wentzel, M. C. & Loewenthal, R. E.
2000 Extension and application of the three-phase weak acid/
base kinetic model to the aeration treatment of anaerobic
digester liquors. Water SA 26(4), 417 438.
Neethling, J. B. & Benisch, M. 2004 Struvite control through
process and facility design as well as operation strategy. Water
Sci. Technol. 49, 191199.
Sabrina, N. 2007 Comparing the effectiveness of CO2 strippers to
reduce operating costs for struvite formation. M.A.Sc. Thesis,
Department of Civil Engineering, The University of British
Columbia Vancouver, B.C., Canada.
Tchobanoglous, G., Burton, F. L. & Stensel, H. D. 2003 Wastewater
Engineering: Treatment and Reuse. McGraw-Hill, New York,
USA.
Ueno, Y. & Fujii, M. 2001 Three years experience of operating and
selling recovered struvite from full-scale plant. Environ.
Technol. 22, 1373 1381.
Zhang, Y. 2006 Struvite Crystallization from Digester Supernatant
Reducing Caustic Chemical Addition by CO2 Stripping.
M.A.Sc. Thesis, Department of Civil Engineering, The
University of British Columbia Vancouver, BC, Canada.

You might also like