Watermatex 2019

Precipitated ferric chloride to improve the activated sludge

hindered settling velocity: Impact and Modelling.

E. Asensi*, E. Alemany **, D. Zambrano***, P. Duque-Sarango****, D. Aguado*

*CALAGUA – Unidad Mixta UV-UPV, Institut Universitari d'Investigació d’Enginyeria de l’Aigua i Medi
Ambient – IIAMA, Universitat Politècnica de València, Camí de Vera s/n, 46022 Valencia, Spain.
**Departamento de Matemática Aplicada. Universitat Politècnica de València. Camino de Vera s/n, 46022.
Valencia. Spain.
***Department of Chemical Engineering and Environmental Technologies - Catalysis, Molecular Separations and
Reactor Engineering Group (CREG-I3A) - Universidad Zaragoza, Mariano Esquillor s/n, 50018 Zaragoza, Spain.
**** Environmental Biotechnology Research Group (INBIAM), Salesian Polytechnic University, Campus el
Vecino, Calle Vieja 12-30 y Elia Liut, Cuenca, Ecuador.

Abstract: This research thoroughly analyses the impact of the precipitated ferric chloride addition on
the activated sludge morphology and settling characteristics. For this purpose, 125 hindered settling
tests were performed with activated sludge samples from an urban wastewater treatment plant at
different precipitated ferric chloride doses. The results have shown that the precipitate addition favours
flocs’ formation, with a linear increase in flocs size and density and also in settling velocity (up to 8x),
and removes phosphorus (soluble and particulate). Standard settling models were fitted and their
usefulness expanded relating their parameters with the reagent concentration through empirical
equations.

Keywords: Activated sludge; Ferric chloride; Floc morphology; Settling velocity; Settling models

Introduction
To avoid the eutrophication risk and meet the increasing effluent wastewater
treatment plant (WWTP) requirements, many WWTPs choose to improve the
suspended solids removal from the final effluent. The more suspended solids are
removed from the WWTP effluent, the lower the particulate phosphorus concentration
is in the effluent. Therefore, he secondary settler in WWTPs plays an important role
in the activated sludge process, removing the sludge flocs. The efficiency of this
solid-liquid separation process clearly impacts in the WWTP effluent quality
(Koivuranta et al., 2015)
Although long-lasting structural options are available for the removal of suspended
solids from the effluent, such as sand filters or membrane processes, they are
expensive and cannot be started-up immediately. An alternative practical approach for
short periods (e.g., disturbances or emergencies) would be to improve the activated
sludge settling characteristics. The addition of inert compounds (e.g., micro-sand,
kaolin,…) has been investigated for almost two decades, showing great potential to
improve the activated sludge settling properties (Wells et al., 2015).
Secondary settling tank widely used mathematical models, like the Vesilind’s
exponential model or the Richardson and Zaki model, are based on the knowledge of
how the activated sludge settling velocity varies with the suspended solids
concentration. Usually, for this purpose, empirical equations are employed in
available commercial tools. However, these empirical equations do not take into
account the effect of chemical precipitation on the settling properties of the activated
sludge. Considering that plant-wide modelling, in which all the involved processes
(physical, chemical and biological) interact, is becoming the standard practice for
WWTP design and optimization, the effect of chemical precipitation on the settling
properties should not be neglected.
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In this work, precipitated ferric chloride was used to improve the
activated sludge settling characteristics and to remove phosphorus via absorption. A
precipitated reagent neutralized at pH 7 was selected to avoid affecting the pH of the
biological process when implementing the process in the WWTP. Ferric chloride was
selected since it is widely used for different purposes in WWTPs (De Gregorio et al.,
2010). Different researches (Wilén et al., 2008; Koivuranta et al., 2014) have shown
that the morphological properties of the activated sludge flocs influence the settling
properties. For this reason, a Matlab program for recognizing the flocs and performing
their morphological characterization based on digital image analysis and statistical
processing was developed. Later, multivariate projection methods were used to
simultaneously study the relationships of all the measured variables (size, fractal
dimensions, morphological parameters…) with the hindered settling velocity.

Material and Methods

To study the influence of the addition of precipitated ferric chloride on the activated
sludge morphology and settling characteristics, different doses of precipitated ferric
chloride were added to activated sludge samples taken from Carraixet full-scale
WWTP (Valencia, Spain).

The tests were performed on a program-controlled jar-test apparatus with 1L of

sludge. The desired dosage of precipitated ferric chloride solution was added at the
beginning of the mixing. In the jar-test apparatus, the following phases were applied:
rapid stirring at 120 rpm for 10 minutes followed by slow stirring at 25 rpm for 20
minutes. After finishing the slow stirring, the sludge was used for optical microscopy
characterization of the flocs, for density and suspended solid determination, and in
settling tests that were conducted to determine the hindered settling velocity. The
duration of the rapid mixing was chosen to eliminate the possible memory effect of
the sludge in the sedimentation process (Asensi et al., 2019).

Hindered settling tests and analytical parameters were performed as described in

APHA (2012) using one-liter glass graduated cylinder. The dilution of the sludge was
performed using supernatant from the secondary settler. The interface height in the
settling test was calculated as a time dependent function. No stirring of the sludge was
performed during the test so as not to interfere with possible floc aggregation (Chen et
al., 1996).

Image analysis techniques were used to determine the distribution of the activated
sludge floc size, fractal dimensions and morphological parameters, calculated as
defined in Costa et al. (2013). The pycnometer method was used to determine the
density of the dry sludge (ρs) while the floc density (ρf) was determined with a
method based on centrifugation in homogenous density solutions.

MATLAB (MathWorks®) was used to develop the image processing program

which included numerical calculus and statistical analysis. Most of the graphics in the
manuscript were elaborated and laid out in Excel. SIMCA-P 10.0 software (Umetrics,
Umea, Sweden) was used for the multivariate analysis.
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Results and Discussion

Hindered settling tests were performed to characterize the activated sludge settling
properties of Carraixet WWTP as well as the influence of the addition of ferric
chloride on the settling velocity and phosphate removal.
Figure 1a shows the variation of the hindered settling velocity (Vs) with the iron
concentration (Fe). As it is shown, the hindered settling velocity clearly improved
with the iron concentration but excessive addition resulted adverse due to the lower
settling velocity increment and the higher reagent expense. The use of previously
neutralized and precipitated ferric chloride exhibited two clear advantages over direct
FeCl3 addition: higher increment in settling velocity (up to 8 times the velocity
without reagent addition) and prevents the risk of affecting negatively the pH of the
biological process. The latter is especially important in wastewater with low alkalinity
to buffer the acid formation during ferric chloride hydrolysis when it is directly dosed,
which could even inhibit the biological process. Figure 1b, demonstrates that soluble
phosphorus was also removed with the precipitated ferric chloride addition.
Moreover, the phosphorus removal experimental data from the different activated
sludge samples were well fitted with the equation included in the figure.
9.0 100.0
Open symbols: 
8.0
Direct FeCl3 dosing 80.0
7.0
P‐PO4‐3 removal (%)

Closed symbols: 
6.0
previously  60.0
Vs / Vso

5.0 neutralized and 
4.0 prepitated FeCl3 40.0
3.0 dosing Premoval=a*Fe/(b+Fe)     
2.0 20.0 a=126.8081 ;  b=212.3783
1.0 R2=0.9757
0.0
0.0 0 100 200 300 400 500
0 500 1000 1500 2000 2500 3000 Fe (mg Fe l‐1)
Fe (mg Fe l‐1)
(a) (b)
Figure 1. Effect of ferric chloride addition on: (a) the hindered settling velocity (being Vso the settling
velocity when no ferric chloride was added) (b) the phosphorus removal (the fitting to the experimental
data is also included, dashed line). Each activated sludge sample is represented with a different symbol.

To gain deeper insight within the ‘practical use’ of the precipitate concentration
range, new settling tests were performed in a limited range (0 – 500 mg Fe l-1). The
non-Volatile Suspended Solids (nVSS) linearly increased with the iron concentration
as expected since the precipitate is formed by iron hydroxides. Thus, the increment of
nVSS reflects the addition of the precipitated.
Figure 2 shows the effect of the precipitated ferric chloride addition on the density
of both, flocs and dry sludge, and on the floc size. As shown in this figure, the floc
size and both densities varied linearly with the added precipitate. In this figure it can
also be observed that the size of the flocs follows a lognormal distribution (Figure
2d), and the same distribution was observed irrespective of the precipitate reagent
dosed.
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1.050 1.800
1.048
1.750
1.046
1.044 1.700
f [g ml‐1] 

s [g ml‐1] 
1.042 1.650
1.040 1.600
1.038
1.550
1.036 y = 0.01897x + 1.03488 y = 0.44976x + 1.52398
R² = 0.9638 1.500 R² = 0.9727
1.034
1.032 1.450
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
_nVSS [g l‐1] _nVSS [g l‐1]
(a) (b)
75
70
65
Deq [µm] 

60
55
50
45 y = 30.529x + 46.705
40 R² = 0.7293
35
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
 nVSS [g l‐1] Deq (m)
(c) (d)
Figure 2. Effect of neutralized and precipitated ferric chloride on: (a) the flocs density (a) the dry
sludge density and (c) the average floc equivalent diameter. The added precipitate is expressed as the
increment of non-Volatile Suspended Solids. A different symbol is used for each activated sludge
sample. (d) Floc size distribution together with the log-normal distribution fitted (red line) in a test
without precipitate addition.

Figure 3a shows that the activated sludge hindered settling velocity increases
linearly with the precipitated ferric chloride addition, but the increment is different
depending of the initial suspended solids concentration (SSo) of the sample. Figure 3b
evidences that the improvement in the settling velocity (slope of the linear fit)
decreased with the SSo sample (as the amount of iron available per unit of suspended
solid decreased). The fitted equation allows determining the hindered settling velocity
for different doses of precipitated ferric chloride added as Vs=Vs(SSo)+0.0721exp(-
1.15 SSo)ꞏFe. Note that the precipitate concentration in a steady-state activated sludge
process, can be calculated as Fe = Fe dose ꞏ SRT / HRT, where SRT is the solids
retention time and HRT the hydraulic retention time. The fitted equation can be
directly used in state point analysis to evaluate and estimate the secondary clarifier
performance when precipitated ferric chloride is added.

To evaluate and optimize the operation of a secondary settler using a simulation

model, the hindered settling velocity was fitted with the Vesilind’s exponential and
Richardson and Zaki models, and in turn, their parameters were related to the
precipitated ferric chloride concentration via empirical equations. The extended
models and their fitting at three different precipitated ferric chloride concentrations
are shown in Figure 4. Richardson and Zaki model allows to explain the improvement
in the settling velocity as a result of the density increment due to the incorporation of
the precipitate into the activated sludge flocs structure.
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5.0 0.012
SSo (g l‐1)

Vs(Fe) slope (cm l mg Fe‐1 min‐1)
S16; 4.888 Vs(Fe) slope = 0.0721e‐1.15 SSo
4.0 0.01 R² = 0.952
S17; 2.660
Vs ‐ Vso (cm min‐1) 

S18; 3.256 0.008
3.0 S19; 5.180
S20; 3.840 0.006
2.0 S21; 2.284
S22; 1.772 0.004
1.0
0.002

0.0 0
0 100 200 300 400 500 1.0 2.0 3.0 4.0 5.0 6.
Fe (mg Fe l‐1) SSo (g l‐1)
(a) (b)
Figure 3. (a) Effect of precipitated ferric chloride addition on the activated sludge hindered settling
velocity (b) Relationship between suspended solid concentration and the slope of each linear fit.

These results evidence that the addition of neutralized and precipitated FeCl3 is a
feasible and interesting option to improve the performance and removal of suspended
solids from the secondary settler thanks to the improvement in the hindered settling
velocity. This low-cost option for short periods (like disturbances or emergency
situations) can help the WWTP to meet the effluent discharge legal requirements. Not
only phosphorus contained in the suspended solids would be removed but also part of
the soluble phosphorus through absorption (as it has been shown in Figure 1b).

Richardson & Zaki

Vesilind’s model

Vs = 98.11525 e ‐1.6508 SSo Vs = 76.56574 e ‐1.34981 SSo Vs = 71.48406 e ‐1.24946 SSo

Vs (cm min‐1)

Vs (cm min‐1)

Vs = 34.2217 (1 ─ Vs = 38.9910 (1 ─ Vs = 41.37565 (1 ─

Vs (cm min‐1)

0.19038898 SSo) 4.65 0.17410597 SSo) 4.65 0.1659644 SSo) 4.65

SSo (g l‐1) SSo (g l‐1) SSo (g l‐1)

(a) (b) (c)
Figure 4. Experimental hindered settling velocity from settling tests carried out at three different
precipitated ferric chloride concentrations (a: 185, b: 370 and c: 462.5 mg Fe l-1) and the
corresponding predictions using the extended Vesilind’s exponential and Richardson and Zaki models.
To deepen into the study of the relationship between settling velocity and other
activated sludge flocs properties that can vary with the addition of the reagent, new
experiments were performed. In these new experiments, size, fractal dimensions and
morphological parameters were determined via digital image analysis and their
correlations were studied via multivariate projection methods.
Partial Least Squares (PLS) regression was used to develop a model to estimate the
hindered settling velocity (y-variable) from the rest of the parameters measured on the
flocs (x-variables): aspect ratio, radius of gyration, perimeter, length, equivalent
diameter, dose of ferric chloride precipitate, volumetric fraction of the sludge, fractal
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dimension that relates area – perimeter, fractal dimension that relates area –
length, roundness, total suspended solids, non-volatile suspended solids, sludge
density, flocs density, and increment of non-Volatile Suspended Solids
The PLS model was developed with all the data from the 19 tests, resulting in two
statistically significant components according to cross-validation. The model showed
a good balance between fit and prediction performance, with an explained variation of
the matrix of measured variables (X-matrix) of 67.9% (R2x), an explained variation of
the predicted variable (settling velocity) of 85.1% (R2y) and a goodness of prediction
performance according to cross-validation of 77.1% (Q2).
Figure 5 shows the loading plot and the coefficient plot from the fitted PLS model.
In this figure, the relationship between the hindered settling velocity (Vs) and the size,
fractal dimensions and morphological parameters of the activated sludge flocs, can be
seen. In the loading plot (Figure 5a), highly correlated variables have similar weights
and are projected close together in the same quadrant when they are positively
correlated while they are projected in diagonally opposed quadrants when they are
negatively correlated. The further away from the plot origin the stronger the
correlation. Similarly, in the PLS regression coefficient plot (Figure 5b), the higher
the absolute value of the coefficient reflects the strength of the correlation of the
variable with the response variable, while the sign of the coefficient shows if the
correlation is positive or inverse. As can be seen in Figure 5 the volumetric fraction of
the sludge, the suspended solids concentration and the fractal dimension that relates
area–perimeter were the variables most correlated with the settling velocity. All three
variables exhibit inverse correlation with the hindered settling velocity. On the
positively correlated side, the variables density, dose and increment of nVSS, appear
but with weaker correlation than the previous three variables.

0.6
0.2
0.4 nVSS s Vs
f d 0.1
0.2 DfA‐L 0
R
w[2] (38,4%)

0 FF rG ‐0.1

nVSS LP
Coeffs

‐0.2 AR Deq ‐0.2

‐0.4 ‐0.3
DfP‐A
‐0.6 SS ‐0.4
Fv ‐0.5
‐0.8
nVSS 

Deq
P

rrG
Fv
SS

FF
DnVSS

R
AR
L

rs
rf

Df_A‐L
d
Df_P‐A

nVSS
s

‐0.8 ‐0.6 ‐0.4 ‐0.2 0 0.2 0.4 0.6

w[1] (46,7%)

(a) (b)
Figure 5. (a) PLS loading plot (b) PLS regression coefficients plot. Variables: aspect ratio (AR), radius
of gyration (rG), hindered settling velocity (Vs), perimeter (P), Length (L), equivalent diameter (Deq),
dose of ferric chloride precipitate (d), volumetric fraction of the sludge (Fv), fractal dimension that
relates area – perimeter (DfP-A), fractal dimension that relates area – length (DfA-L), roundness (R), total
suspended solids (TSS), non-volatile suspended solids (nVSS), sludge density (s), flocs density (f),
increment of non-Volatile Suspended Solids (_nVSS) with respect to the concentration of nVSS in
the test with no added precipitate (i.e., _nVSS =[nVSS – nVSSi]).

Conclusions
The main conclusions that can be drawn from this study are:
 The addition of neutralized and precipitated ferric chloride on the activated
sludge:
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o produces a linear increase in the flocs diameter, in the flocs
density, in the dry sludge density as well as in the hindered settling
velocity of the activated sludge.
o contributes to phosphorus removal in both forms, soluble and
particulate, and it does not impact the pH of the biological process.
 The empirical equations proposed and fitted to the experimental data allows
relating the parameters of the standard WWTP settling models to the
concentration of the added precipitated reagent. Thus, the capability of these
standard models, like the Vesilind’s exponential model and Richardson and
Zaki model, was expanded to reproduce with reliability the zonal
sedimentation behaviour of the activated sludge when precipitated ferric
chloride is dosed in WWTPs.
 Partial least squares regression efficiently related the hindered settling velocity
with the size, fractal dimensions and morphological parameters. The
volumetric fraction of the sludge, the suspended solid concentration and the
fractal dimension that relates area – perimeter were evidenced as the most
related variables.
Acknowledgements
Financial support from the Spanish State Research Agency (project CTM2017-86751-
C2-2-R-AR) is gratefully acknowledged.

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