Sludge production from chemical precipitation

Helena Snurer
Department of Chemical Engineering, Lund Institute of Technology
Abstract
The sludge production when adding coagulants to tap water, tap water containing orthophosphate and
municipal wastewater was studied. The sludge weight was thereafter compared with calculations based on
stoichiometric relationships. A model for estimating the sludge production that a coagulant contributes for a
given coagulant dose and given phosphorus and suspended solids removal was developed. Results showed
that the sludge production from chemical treatment of municipal wastewater was considerably higher than
theoretical calculations. The higher sludge mass mainly depended on the amount of agglomerated colloidal
particles. The study of sludge production when adding aluminium or iron based coagulants to wastewater
resulted in two mathematical models for estimating sludge production. These models gave higher results
compared to the models based on stoichiometric relationships. However, two published models gave
similar results when the molar ration between the amount of metal salt added and total phosphorus
concentration was above 1.5.
Keywords: sludge production, chemical precipitation, wastewater, coagulants, modelling sludge production
Introduction
Chemical treatment by addition of a metal salt,
usually aluminium or iron based, is widely used
in wastewater treatment. These metal salts,
called coagulants, play a vital role in the removal
of phosphorus and particles in polluted water.
The addition of a coagulant for removal of
impurities in wastewater results in a large
amount of sludge. The cost of sludge treatment
and disposal, represent a large amount of the
total operating costs for wastewater treatment
plants. Therefore, estimating the sludge
production for a given coagulant and coagulant
dose is of great interest. This is unfortunately
very complex since the amount of sludge
depends on several factors such as; general
wastewater characteristic as well as type of
chemicals, chemical dosage and the point at
which the chemicals are added in the wastewater
treatment.

Calculating sludge production

The sludge production, expressed in mg dry
sludge/l (mg DS/l), from chemical treatment of
wastewater can be calculated based on a
stoichiometric relationship by assuming that the
addition of a coagulant will result in formation of
metal phosphate, MePO4, and metal hydroxides,
Me(OH)3. The quantity of formed MePO4 is
dependent on the removed portion of phosphate.
The remaining portion of the metal is
precipitated as Me(OH)3 with exception of the
metal that stays in solution. The models are
shown in equation 1 and 2.

3+
3+
S Al = 1.42 (Pin Pout ) + 2.89 Aladded
Aldis
.

3+
3+
S Fe = 1.42 (Pin Pout ) + 1.91 Feadded
Fedis
.

(1)

(2)

Models found in the literature

Models based on experimental data are found in
the literature for predicting the sludge
production; however, the models and the results
reveal variability.

The sludge production when adding coagulants

to tap water, tap water containing orthophosphate
and municipal wastewater was studied. The
sludge weight was thereafter compared with
calculations based on stoichiometric relationships. A model for estimating the sludge
production that a coagulant contributes for a
given coagulant dose and given phosphorus and
suspended solids removal was developed.

Veldkamp [1] developed a model by performing

an analysis of variance on experimental data.
This was done for two coagulants, aluminium
and ferric chloride. All the experiments were
performed with phosphate solution, made by
adding KH4PO4 to tap water. The models are
shown in equation 3 and 4. is the molar ratio
between the amount of metal salt added and total

phosphorus concentration in the wastewater. The

sludge production is expressed in mg DS/l.
S Al = 1.61 + 2.55 (Pin Pout ) + 2.50 Pin
S Fe = 3.50 + 3.37 (Pin Pout ) + 2.79 Pin

S Al = 5.3

(3)

S Fe = 6.8

(4)

Weidi [2] conducted laboratory and full scale

research to estimate the sludge production when
using iron and aluminium based coagulants.
Weidi used original wastewater and measured
the suspended solids before precipitation. After
addition of the coagulant, the suspended solids,
previously calculated, were subtracted from the
sludge production. By doing this, Weidi were
able to compare his results with other models
found in the literature. The formulas are
presented in equation 5-8. Equation 5 and 6 is
valid for pre-precipitation and equation 7 and 8
is valid for simultaneous and post-precipitation.
The sludge production is expressed in
mg DS/mg metal.
(5)

S Fe = 4.14 1.01 ln

(6)

S Al = 4.85 0.35 ln
S Fe = 3.15 0.55 ln

(7)

(Pin Pout )
BOD5

1. 5

1.5

(10)

(11)

The experiments were performed with four

different coagulants, two based on iron and two
based on aluminium. The coagulants selected for
the experiments were: FeCl3, Fe2(SO4)3 and
Al2(SO4)3, products which have been used
traditionally
in
coagulationflocculation
processes applied to wastewaters and a
polyaluminium chloride, PAX-18.

(8)

degaard [3] presented a model for predicting

the sludge production, see equation 9, were Kc is
a coagulant coefficient and depends on which
coagulant is used. The D-term represents the
dosage of the given coagulant expressed in g/m3.

S = (SS in SS out ) + K c D

BOD5

Material and Methods

The experiments were divided in to three major
parts. In the first part, tap water with
approximately the same pH and alkalinity as the
raw sewage was prepared. This was done by
adding sodium hydrogen carbonate. The final pH
as well as the sludge production was measured.
Tap water was used for investigating the
maximum metal hydroxide mass that can be
formed when adding different coagulant doses.
In the second part, tap water containing added
orthophosphate was used. Alkalinity and pH was
also corrected to approximately the same value
as the sewage. The final pH and the residual
orthophosphate concentration were measured as
well as the sludge production, containing
precipitated hydroxide and phosphate. In the last
part of the laboratory experiments sewage was
used, which was collected after the grit chamber
at resundsverket in Helsingborg. The SS, pH,
orthophosphate and the total phosphorus
concentration was studied before and after the
addition of the metal salts. Finally the sludge
production was measured.

Veldkamp showed that the sludge production

calculated from the stoichiometric model was
lower than the experimental results. Veldkamp
meant that a portion of crystalline water is
bounded to the produced flocs, thus leading to
higher sludge production compared to the model
based on stoichiometric relationship.

S Al = 6.21 1.05 ln

(Pin Pout )

The experiments were carried out in 1 litre

beakers with Kemiras Flocculator 90. This
flocculator can handle up to six glass beakers.
Each beaker is equipped with a stirrer with an
individual motor. The rotational speed of the
propeller and the time of the rotation can be
regulated individually for all the beakers.
Following procedure with Kemiras flocculator
was carried out for the samples.

(9)

The coagulant coefficients expressed in

g SS/g metal, were obtained by laboratory
experiments with constructed wastewater.
Other formulas for estimating the sludge
production are presented in equation 10 and 11.
These models are used as a guideline when
designing wastewater plants in Germany [4].

Coagulation: 10 seconds with a speed of 350 rpm

Flocculation: 10 minutes with a speed of 40 rpm
Sedimentation: 10 minutes

experiments both the aluminium based and the

iron based coagulants had higher sludge mass
than the sludge production calculated based on
stoichiometric relationships, see Figure 2a and
2b.
% of theoretical value

Results and discussion

Experiments performed with tap water
The sludge production from chemical
precipitation of tap water can be calculated
theoretically if the assumption is made that all
the metal added to the solution is precipitated as
metal hydroxide. This implies that the measured
sludge production would be 100 in percent of the
calculated value if all the aluminium/iron in the
solution is precipitated as metal hydroxide. It
should however be noted that some of the metal
stays solved in the solution. This has been taken
into account in all experiments when calculating
the sludge weight.

% of theoretical value

Figure 2a The influence of on the weight of solids formed

in percent of theoretical weight when solutions of FeCl3 (blue
colour) and Fe2(SO4)3 (red colour) were added to phosphate
solution containing 5.00 and 7.50 mg P/l, respectively. The
experiment was performed threefold where () represents
series 1, () series 2 and () series 3. (-) represent the
complementary series.

% of theoretical value

160
140
120
100

Al2(SO4)3

80
60

Al(OH)1.2Cl1.8

40
20
0
0

(mole Me/mole P)

Figure 2b The influence of on the weight of solids formed

in percent of theoretical weight when solutions of Al2(SO4)3
(orange colour) and Al(OH)1.2Cl1.8 (green colour) were added
to phosphate solution containing 5.00 and 7.50 mg P/l,
respectively. The experiment was performed threefold where
() represents series 1, () series 2 and () series 3. (-)
represent the complementary series.

100
FeCl3
Fe2(SO4)3
Al2(SO4)3

40

Crystalline water, bounded to the flocs, may

explain why the sludge mass for the experiments
is higher than the theoretical calculations.
Additionally, the presence of calcium in tap
water can give some disturbance as calcium
phosphate
(Ca10(PO4)6(OH)2)
can
be
precipitated. The calcium concentration was
therefore measured in this study. However, the
results showed no precipitation of calcium.

Al(OH)1.2Cl1.8

20
0
300

Fe2(SO4)3

(mole Me/mole P)

120

60

FeCl3

The metal hydroxide mass was lower than the

theoretical calculations when using iron based
coagulants, see Figure 1. This could be explained
by that not all the iron precipitates as Fe(OH)3
but some FeOOH is probably also formed.
However, the hydroxide sludge production for
the aluminium based coagulants was higher than
the theoretical calculations. One theory for the
higher hydroxide production when Al2(SO4)3 is
used as coagulant is that not only Al(OH)3 is
formed but also Al(OH)3-2x(SO4)x, where x is
approximately 0.25. PAX-18 contains some
sulphate, maximum 0.5 percent and the higher
hydroxide production for this coagulant can
partially be explained by that some
Al(OH)3-2x(SO4)x is formed.

80

160
140
120
100
80
60
40
20
0

400

500

600

700

800

coagulant dose (mole Me/l)

Figur 1 The influence of the amount of Me3+ added on the

weight of solids formed in percent of theoretical weight when
solutions of FeCl3 (blue colour), Fe2(SO4)3 (red colour),
Al2(SO4)3 (orange colour) and Al(OH)1.2Cl1.8 (green colour)
were added to tap water. The experiment was performed
threefold where () represents series 1, () series 2 and ()
series 3.

It can be seen in Figure 3 that the sludge

production/mg metal decreases as the coagulant
dose increases. An increase in -value leads to
more formation of metal hydroxides, resulting in
lower sludge mass/mg metal due to metal
hydroxides lower molar weight compared to
metal phosphates.

Experiments performed with phosphate

solution
The sludge production from chemical
precipitation of phosphate solution can be
calculated theoretically if the assumption is made
that precipitated orthophosphates result in
formation of metal phosphate and that the excess
Me3+ is precipitated as metal hydroxides except
for the amount of dissolved Me3+. In these

500
% of theoretical value

sludge production
(mg/mg Me)

6
5
FeCl3

Fe2(SO4)3

Al2(SO4)3

Al(OH)1.2Cl1.8

1
0
0

400
300

Al2(SO4)3

200

Al(OH)1.2Cl1.8

100
0

(mole Me/mole P)

Figure 3 Sludge production versus when solutions of FeCl3

(blue colour), Fe2(SO4)3 (red colour), Al2(SO4)3 (orange
colour) and Al(OH)1.2Cl1.8 (green colour) were added to
phosphate solution containing 5.00 mg P/l and 7.50 mg P/l,
respectively. The experiment was performed threefold where
() represents series 1, () series 2 and () series 3. (-)
represent the complementary series.

% of theoretical value

300

FeCl3

200

Fe2(SO4)3

100
0
3

The sludge production expressed in mg/mg metal

from chemical precipitation of municipal
wastewater is much higher than the experiments
with phosphate solution; compare Figure 5 with
Figure 3. The reason is as previously mentioned
agglomeration of colloidal particles in municipal
wastewater after addition of the metal salt.

400

The higher sludge mass can be explained by an

agglomeration of colloidal particles after
addition of the metal salt. These particles were
not filtered when measuring the SS due to their
small particles size. The filters used in these
experiments had a pore size of 1.2 m, hence
particles with a smaller diameter passed through
the filter. However, these colloidal particles were
agglomerated after addition of coagulants and
could thereby be removed through filtration
leading to higher sludge mass than theoretically
calculated. COD was measured on the filtrate
before and after the addition of the coagulants.
The results showed a decrease in COD with
increasing coagulant dose which indicate that
colloids agglomerate after addition of a metal
salt.

500

Figure 4b The influence of on the weight of solids formed

excluding SSin in percent of theoretical weight when
solutions of Al2(SO4)3 (orange colour) and Al(OH)1.2Cl1.8
(green colour) were added to municipal wastewater. The
experiment was performed threefold where () represents
series 1, () series 2 and () series 3. (-) represent the
complementary series.

Experiments performed with sewage

The sludge production from chemical
precipitation of municipal wastewater can be
calculated theoretically by the same procedure as
when calculating the sludge production for
phosphate solution. The SS in the wastewater
were measured before the precipitation. After the
addition of the coagulant, the SS that were
previously measured were subtracted from the
sludge production. In doing so, the sludge
production from wastewater can be compared
with the sludge mass obtained from the
phosphate solution and the theoretical
calculations. Figure 4a and 4b show that the
sludge production, without the suspended solids
that were measured before the chemical
treatment, is much higher than the theoretical
calculations.

(mole Me/mole P)

sludge production excluding

SS in (mg/ mg Me)

(mole Me/mole P)

Figure 4a The influence of on the weight of solids formed

excluding SSin in percent of theoretical weight when
solutions of FeCl3 (blue colour) and Fe2(SO4)3 (red colour)
were added to municipal wastewater. The experiment was
performed threefold where () represents series 1, () series
2 and () series 3. (-) represent the complementary series.

25
20
FeCl3
15

Fe2(SO4)3

10

Al2(SO4)3
Al(OH)1.2Cl1.8

5
0
0

(mole Me/mole P)

Figure 5 Sludge production excluding SSin versus when

solutions of FeCl3 (blue colour), Fe2(SO4)3 (red colour),
Al2(SO4)3 (orange colour) and Al(OH)1.2Cl1.8 (green colour)
were added to municipal wastewater. The experiment was
performed threefold where () represents series 1, () series
2 and () series 3. (-) represent the complementary series.

Model for calculating sludge production

The multivariate data analysis program,
Modde 7, was used to analyse the results made in
this study. The program connects results by
means of a mathematical model. Following
factors were used: reacted phosphorus (Pin-Pout)
and added metal (Aladded3+ or Feadded3+). The
response was the sludge production. In this study
no interaction was found between the two
variables with a 95 percent confidential interval,
leading to linear models. These are presented in
equation 12 and 13. The sludge production is
expressed in mg DS/l.
3+
S Al = 21.34 + 2.77 (Pin Pout ) + 3.07 Al added

(12)

3+
S Fe = 27.41 + 2.65 (Pin Pout ) + 1.78 Feadded

(13)

sludge production
(mg/mg Me)

10
8
6

=1.5

=1.75

2
0
1

9*

9**

10

12

equation

Figur 6b Calculated sludge production for =1.5 and =1.75

when using aluminium based coagulants (*Kc= 8, **Kc= 9).

Equation 5, 6 and 9 agree the most with the

mathematical models. It should however be
mentioned that the sludge production for
equation 9 vary; depending on which coagulant
coefficient (Kc) is used. Because of this variation
the model is presented twice in the figures, one
for the lower coagulant coefficient and one for
the higher.

were R2 = 0.94 for equation 12

R2 = 0.90 for equation 13

160
sludge production
(mg/l)

Comparison of the models

A comparison was done between the models
based on the results in this study, the models
based on stoichiometric relationship and the
published models. The sludge production for the
different models were calculated by assuming a
phosphorus content of 10 mg/l in influent
wastewater, a phosphorus removal of 100
percent and a -value of 1.5 and 1.75,
respectively. The results are illustrated in
Figure 6a and 6b (aluminium based coagulants)
and in Figure 7a and 7b (iron based coagulants).
The comparison of the models and hence the
results should be interpreted carefully, since the
experiments were not performed under identical
conditions.

120
=1.5

80

=1.75

40
0
2

9*

9**

11

13

equation

Figure 7a Calculated sludge production for =1.5 and

=1.75 when using iron based coagulants (*Kc= 3, **Kc= 5).

sludge production
(mg/mg Me)

10
8
6

=1.5

=1.75

2
0

As expected, the lowest sludge production is

obtained when using the models based on
stoichiometric relationships. This would be due
to
the
theoretical
calculations
being
oversimplified in its setup, since it only accounts
for the formation of MePO4 and Me(OH)3.

sludge production
(mg/l)

=1.75

40
0
5

9*

9**

10

9*

9**

11

13

Conclusions
The study showed that the sludge production
from chemical treatment of municipal
wastewater was considerably higher than
calculations
based
on
stoichiometric
relationships. The higher sludge mass mainly
depended on the amount of agglomerated
colloidal particles. These particles were filtered
when measuring the SS due to their small
particles size. The filters used in this study had a
pore size of 1.2 m, hence particles with a
smaller diameter passed through the filter.
However, these colloidal particles were

=1.5

Figure 7b Calculated sludge production for =1.5 and

=1.75 when using iron based coagulants (*Kc= 3, **Kc= 5).

120

equation

160

80

12

equation

Figur 6a Calculated sludge production for =1.5 and =1.75

when using aluminium based coagulants (*Kc= 8, **Kc= 9).

agglomerated after addition of coagulants

leading to an increased sludge mass.

Kc
SS
SSin
SSout
S
SAl

This study of sludge production when adding

aluminium or iron based coagulants to
wastewater resulted in two mathematical models
for estimating sludge production.

SFe

3+
S Al = 21.34 + 2.77 (Pin Pout ) + 3.07 Al added
+ (SS in SS out )

3+
S Fe = 27.41 + 2.65 (Pin Pout ) + 1.78 Feadded
+ (SS in SS out )

References
[1] Veldkamp R.G., Modelling phosphate sludge
production, Water Science and Technology 17
(2-3): 107-119, 1985

The sludge production is expressed in mg DS/l.

The models give higher results compared to the
models based on stoichiometric relationships.
However, two published models give similar
results for -values above 1.5.

[2] Weidi, D., Einsatz saurer metallhaltiger

Fllungsmittel bei Anlagen mit bio-P,
Verffentlichungen
des
Institutes
fr
Siedlungswasserwirtschaft und Abfallstechnik
der Universitt Hannover, Heft 92, 1995, 17-117-19

Acknowledgement
This article is based on a Master Thesis that has
been carried out at Kemira Kemi AB with Lars
Gillberg as supervisor, who is gratefully
acknowledged along with the examiner, Jes la
Cour Jansen, Water and Environmental
Engineering at the Department of Chemical
Engineering, Lund Institute of Technology.

[3] degaard H., Karlsson I., Chemical

Wastewater TreatmentValue for Money,
Chemical Water and Wastewater Treatment III,
1994

Table of Symbols
P
phosphorus
Pin
phosphorus content in the
influent (mg/l )
Pout
phosphorus content in the
effluent (mg/l)
Al
aluminium
+
amount of aluminium added (mg/l)
Al3added
+
Al3dis.

Fe
+
Fe3added
+
Fe3dis.

Me
+
Me3added

+
Me3dis.

DS
D

suspended solids per gram metal

(g SS/g metal)
suspended solids (mg/l)
suspended solids in the influent (mg/l)
suspended solids in the effluent (mg/l)
sludge production
sludge production when using
aluminum based coagulant
sludge production when using iron
based coagulant

[4] Aqua Designer, Handbuch - Aqua Designer,

http://www.aquaoffice.de/download/Handbuch_
AD60.pdf#search=%22ATVA%20131%20schlammproduktion%22

amount of aluminium that stays in

solution (mg/l)
iron
amount of iron added (mg/l)
amount of iron that stays in solution
(mg/l)
metal (aluminium or iron)
amount of aluminium or iron added
(mg/l)
amount of aluminium or iron that
stays in solution (mg/l)
phosphorus elimination, (Pin Pout )
Pin
molar ratio between the metal added
and phosphorus
dry solids
coagulant dose (mg/l)