Desalination 185 (2005) 307–316

Hexavalent chromium reduction using a fixed bed of scrap

bearing iron spheres

A.H. El-Shazly*, A.A. Mubarak, A.H. Konsowa

Chemical Engineering Department, Faculty of Engineering, Alexandria University, Alexandria, Egypt
email: Elshazly_a@yahoo.com

Received 20 February 2005; accepted 10 March 2005

Abstract
Kinetics of hexavalent chromium reduction to trivalent chromium in a fixed bed of scrap bearing iron
spheres was investigated under different conditions of initial concentration of a synthetic solution of acidified
potassium dichromate, solution flow rate, bed height, iron spheres diameter, and solution temperature. the
activation energy of the reaction was found to be 4.51 kcal/mol which shows that the reaction is diffusion
controlled. The mass transfer coefficient of the reaction was related to other parameters by simple equations.
Implications of the present results for treatment of industrial wastewater containing Cr such as metal finishing
industry effluents are noted.

Keywords: Hexavalent chromium; Reduction; Fixed bed; Iron spheres

1. Introduction and chromating, pigment industry, corrosion

Hexavalent chromium compounds are
highly toxic by ingestion or inhalation, the
current public health recommends less than
0.05 mg/L of chromium in drinking water [1],
for hexavalent chromium the limit for dis-
charge into sea is 1 ppm, while for trivalent
chromium it is 4 ppm [2]. Cr6þ exists in the
effluents of many industries such as, metal
finishing industries, e.g. chromium plating
*Corresponding author.
inhibition in cooling towers, pickling wastes
and from drug and organic chemicals indus-
tries which use Cr6þ as oxidizing agent.
Removal of Cr6þ from industrial effluents is
not only essential because of its toxicity to
humans but also because it inhibits biodegra-
dation of organic pollutant due to its ability
to kill bacteria. Many techniques have been
considered to reduce the content of chro-
mium ion in waste water streams such as ion
exchange and activated carbon adsorption

0011-9164/05/$– See front matter Ó 2005 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.03.083
308 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316
[3–5], electrochemical techniques [6,7] and
chemical reduction using reducing agents
such as SO2, FeSO4, etc. and precipitation
method [8–10]. Although ion exchange and
activated carbon adsorption have been suc-
cessfully demonstrated on the laboratory
scale, they have not been employed to any
significant degree in full scale operation and
are only suitable for low concentrations of
chromium ion (less than 100 ppm) [3–5]. Elec-
trochemical techniques such as electrodialysis
(E.D) can be used to remove Cr6þ. Unfortu-
nately E.D is expensive because it needs costly
membranes and its power consumption is
high, however there are indications that elec-
trodialysis has a potential application in pro-
cessing of concentrated chromic acid wastes.
Even though the efficiencies of removing
metallic contaminants from strong chromic
acid solutions may not be high, this method
may prove useful in hard chromium plating.
On the other hand reduction of Cr(VI) to
Cr(III) by different reducing agents such as
NaHSO3, FeS, FeSO4, SO2, etc., followed by
chemical precipitation of Cr(III) by lime as
Cr(OH)3 has received a great attention
[8–11], and was found to operate effectively
with higher rate and higher % recovery at
pH values 2–3. These methods are controlled
by the cost of the chemicals used and the
dosage required of each one. Typically it was
found that, the chemical dosage required for
Cr(VI) reduction is twice the stoichiometric
required [11,12].
Zinc dust or Aluminium foil, can be used to
reduce Cr(VI) to Cr(III) in acidic medium at
pH range 2–3, but being relatively expensive
and of course generating an additional toxic
component in the waste, it is less attractive
than other alternatives [13]. With regard to
cost considerations metallic Iron has received
a great attention as a reducing agent for Cr(VI).
The reduction of Cr(VI) to Cr(III) using a rela-
tively pure iron wire was investigated by Gould
[14], who concluded that iron surface is effective
in reducing Cr(VI) to Cr(III) under pH condi-
tions of 2–3. Bowers et al. [15], have examined
the use of scrap iron filings to treat Cr(VI)
containing metal plating wastewaters and
came to the conclusion that using iron filings
to treat Cr(VI) containing solutions have the
advantages that the chemical costs using scrap
iron filings are substantially lower than conven-
tional reducing agents such as SO2, NaHSO3,
FeS, FeSO4, etc. also the dissolved iron provide
a well conditioned sludge product. The indirect
reduction of hexavalent chromium to trivalent
chromium with scrap iron and simultaneous
generation of electrical energy using a divided
parallel plate cell and fixed bed electrodes was
investigated by Abdo et al. [16], who came to
the conclusion that this technique can reduce
Cr(VI) to the permissible limit value effectively
while it neither consumes energy nor expensive
chemicals.
The present work deals with the removal of
Crþ6 from industrial waste solutions using a
fixed bed of scrap bearing iron spheres
through which the chromium bearing solution
passes through the bed in batch re-circulating
mode. The reduction reaction can be repre-
sented by the following simple equation :
Cr6þ þ Fe ¼ Crþ3 þ Fe3þ
Fixed bed reactors have the advantage over
other geometries that it offers the highest
space- time yield owing to its high area per
unit volume and its turbulent promoting
ability.
2. Experimental part
The experimental setup used in the experi-
ments is shown in Fig. 1. It consisted of a
storage tank, control valves, plastic centrifugal
pump, and Plexiglass column, which was
divided into two sections from the bottom,
 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316
3
1. Overflow weir
2. Fixed bed of iron spheres
3. Calming section of glass spheres
4. Storage tank
5. Control valves
6. Centrifugal pump
Fig. 1. Experimental setup.
calming section and the reactor. The calming
section consisted of 40 cm height glass spheres
in the entrance of the column to overcome the
effect of turbulences generated due to entrance
effect, while the reactor consisted of a fixed
bed of scrap bearing iron spheres packed at
random in a perforated cylindrical basket held
on the top of the calming section. The basket
was made of stainless steel wire gauze insu-
lated with epoxy. The spheres were abraded
with suitable abrasive material and were
soaked in 0.1 N HCl for a few minutes to
remove the Ni coated surface layer of the
309
5
bearing. The fixed bed height ranged from
2 to 6 cm while iron spheres of 0.5, 0.8 and
1.0 cm in diameter were used. A plastic
centrifugal pump was used to circulate the
solution through the fixed bed reactor, the
flow rate was regulated by means of a by-
pass provided with plastic needle valve and
measured by a graduated cylinder and a stop-
watch. Before each run, the system was first
cleaned and new iron spheres were used as an
active fixed bed. 15 l of fresh acidified potas-
sium dichromate solution were prepared and
placed in the storage tank, in the mean time
310 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316
solution was subjected to circulation at the
required solution velocity.
To follow the change in dichromate
concentration with time samples of the solu-
tion, 10 ml were withdrawn at regular time
intervals ranged from 1.5 to 3 minutes at high
and low solution flow rates respectively, these
samples were titrated against standard 0.1 N
ferrous ammonium sulphate using diphenyla-
mine barium salt as indicator [17]. Different
initial concentrations of potassium dichromate
solution were used in the present study namely,
0.005, 0.025, 0.05 and 0.1 M, all solutions con-
tained 0.5 M H2SO4, and prepared using A.R.
chemicals and distilled water. Experiments were
carried out at temperatures which ranged from;
25–60 C, while the pH of the solutions was
adjusted at 2.5 in all experiments using a por-
table digital pH meter and 0.1 N NaOH solu-
tion. Physical properties of the solutions such as
viscosity, density were measured using visc-
ometer and density bottle while diffusivity at
different temperatures were calculated using
Stokes-Einstein equation (Dm/T = constant),
and the literature [18,19].
3. Result and discussion
Reduction of acidified chromate by iron is
a heterogeneous reaction which involve the
following steps:
(i) diffusion of the chromate ion from the
solution bulk to the iron surface across a
diffusion layer
(ii) reaction of chromate ion with the iron
surface according to the equation [20,21]
2HCrO4 þ 3Fe þ 14Hþ ! 2Crþþþ
ð1Þ
þ 3Feþþ þ 8H2 O
(iii) diffusion of Feþþ ions along with
þþþ
Cr from the interface to bulk of the solution
where the following reaction takes place [20]
HCrO4  þ 3Feþþþ þ 7Hþ ! 3Feþþþ
ð2Þ
þ Crþþþ þ 4H2 O
To test whether the reaction is diffusion con-
trolled or chemically controlled the effect of
solution velocity and the effect of temperature
on the reaction rate were examined. Assuming a
first order reaction the rate constant K was
determined under different conditions from the
equation [22]
dc
V s ¼ KAC ð3Þ
dt
Which upon integration leads to the equation
that:
 
C0 KAt
ln ¼ ð4Þ
C Vs
Where C0 and C are the initial concentration
and the concentration at any time t of acid-
ified potassium dichromate solution respec-
tively, K is the mass transfer coefficient, A is
the active area of the iron spheres, Vs is the
circulating solution volume. By plotting
Ln(C0/C) Vs time for different operating con-
ditions the mass transfer coefficient can be
calculated from the slope of the resulting
straight line (KA/Vs) as shown in fig. 2.
Figs. 2 and 3 show that the rate constant
increases with increasing solution flow rate
through the bed; The sensitivity of the reac-
tion rate to solution flow suggests that the
reaction is either diffusion controlled or
under mixed control. Fig. 3 shows that the
data fit the equation:
K ¼ a1 V 1:5 ð5Þ
The high log K/log V slope indicate that
the reaction is fully diffusion controlled. To
confirm the diffusion controlled nature of the
 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316 311

Initial K2Cr2O7 Concentration = 0.05 M

Bed Height = 4 cm
1.4 Sphere Diameter = 10 mm
Solution Temperature = 25oC
Solution Velocity, (cm/s)
1.2 6.63
8.32
9.24
1 10.56
12.16

0.8
Ln Co/C

0.6

0.4

0.2

0
0 5 10 15 20 25
Time (min)

Fig. 2. Ln C0/C vs time for different solution velocities.

Bed Height = 4 cm
45 Sphere Diameter = 5 mm
Solution Temperature = 25oC
Initial Concentration of K2Cr2O7, (M)
40
0.005
0.025
35
0.05
0.1
30
K x 103 (cm/s)

25

20

15

10

0
4 6 8 10 12 14 16
Solution Velocity (cm/s)

Fig. 3. Mass transfer coefficient vs solution velocity at different initial K2Cr207 concentration.
312 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316

Initial K2Cr2O7 Concentration = 0.05 M

45 Bed Height = 4 cm
Sphere Diameter = 5 mm
Temperature, (oC)
40 25
35
35
45
60

30
K x 103 (cm/s)

25

20

15

10

0
5 6 7 8 9 10 11 12 13
Solution velocity (cm/s)

Fig. 4. Mass transfer coefficient vs solution velocity at different temperatures.

reaction the activation energy of the reaction
was determined by plotting lnK vs. 1/T, Fig. 4
shows that the data fit arrhenius equation:
K ¼ A0 eðE=RT Þ
With an activation energy of 4.51 kcal/mol.
This low value of activation energy confirms
the diffusion controlled nature of the
reaction.
The high velocity exponent (1.5) in equa-
tion 5 compared to the theoretical value 0.5
[23] may be attributed to the enhancing
effects of H2 evolution which occurs simulta-
neously with chromate reduction at the
spheres surface (observed visually) as a result
of the reaction:
Fe þ 2Hþ ¼ Feþþ þ H2
H2 bubbles enhances the rate of mass transfer
through the following effects
(i) H2 bubbles decrease the available solu-
tion flow area and this leads to increasing the
effective interstitial velocity of the solution
with a consequent increase in the rate of
ð6Þ mass transfer.
(ii) as the solution flow rate increases
more H2 bubbles are detached from the
spheres surface by virtue of shear stress of
the flowing solution. Bubbles detachment
from the sphere surface leaves a void to
which solution rushes to fill, this process is
accompanied with the generation of micro
turbulences which enhance the rate of mass
transfer at the void locations on the sphere
surface [24].
(iii) the rising H2 bubbles collide with the
bed spheres and disturb the diffusion layer with
a consequent increase in K (K = D/).
ð7Þ Fig. 3 shows that the rate constant K
which is the mass transfer coefficient for the
diffusion controlled reactions decreases with
increasing initial chromate concentration, this
 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316 313

may be explained by the decrease in chromate
diffusivity with increasing concentration due
to the increase in solution viscosity and inter-
ionic attraction.
Fig. 6 shows that despite the use of calming
section to eliminate the disturbing effects of
flow entrance to the bed the mass transfer coef-
ficient decreases with increasing active bed
height. The decrease in the mass transfer coeffi-
cient with increasing bed height may be attrib-
uted to the decrease in the effective chromate
concentration as the solution progresses
through the bed. The progressive decrease in
the driving force for diffusion along the bed is
reflected in a decreased value of the mass trans-
fer coefficient. The results show that, the data
fit the equation that
Fig. 7 shows that the mass transfer coeffi-
cient K decreases with increasing bed sphere
diameter owing to the increase in the length
of the hydrodynamic boundary layer and the
consequent increase in the average thickness
of the diffusion layer. The results show that,
the data fit the equation that:
K ¼ a3 d 0:007
In view of the complex mass transfer
mechanism inside the bed as a result of simulta-
neous H2 evolution with direct chromate reduc-
tion on the sphere surface, mass transfer data
correlation by the method of dimension analysis
was not possible. Accordingly the data corre-
lated by the following dimensional equation

K ¼ a2 H0:002 K ¼ aV 1:5 H 0:002 d 0:007 ð8Þ

Initial K2Cr2O7 Concentration = 0.05 M

-2.5
Bed Height = 4 cm
Sphere Diameter = 5 mm
Solution Velovity, (cm/s)
6.63
8.32
-3 9.24
10.56
12.16

-3.5
Ln K

-4

-4.5

-5
2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35 3.4
1/T x 103 (K-1)

Fig. 5. LnK vs 1/T.

314 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316

Initial K2Cr2O7 Concentration = 0.05 M

30 H2SO4 Concentration = 0.5 M
Sphere Diameter = 5 mm
Solution Temperature = 25oC
Bed Height, (cm)
25 2
4
6

20
K x 10 (cm/s)

15
3

10

0
5 6 7 8 9 10 11 12 13 14
Solution Velocity (cm/s)

Fig. 6. Mass transfer coefficient vs solution velocity at different bed height.

Initial K2Cr2O7 Concentration = 0.05 M

H2SO4 Concentration = 0.5 M
20 Bed Height = 4 cm
Solution Temperature = 25oC
18 Sphere diameter, (mm)
5
16
8
10

14

12
K x 103 (cm/s)

10

0
6 7 8 9 10 11 12 13
Solution Velocity (cm/s)

Fig. 7. Mass transfer coefficient vs solution velocity at different spheres diameter.

 A.H. El-Shazly et al. / Desalination 185 (2005) 307–316 315

The equation valid for 792 < Sc < 960, D — Diffusivity of chromate ion
6.63 < V < 12.16 cm/s, 2 < H < 6 cm, 0.5 < E — Activation energy.
d < 1.0 cm. H — Bed height
Equation 8 shows that the effect of both K — Mass transfer coefficient
bed height and spheres diameter may be R — Gas constant
neglected, as the exponents of both of T — Time.
them is very small and may be neglected, T — Absolute temperature
thus the equation may be written in the V — Solution velocity
form that: Vs — Solution volume
 — Solution density
E ¼ a1 V 1:5  — Solution viscosity
 — Diffusion layer thickness

4. Conclusion
The reduction kinetics of hexavalent chro-
mium to trivalent chromium in a fixed bed of
scrap bearing iron spheres was investigated
under different conditions of initial concen-
tration of a synthetic solution of acidified
potassium dichromate, solution flow rate,
bed height, iron spheres diameter, and solu-
tion temperature. It was found that the mass
transfer coefficient and the rate of reduction
reaction increased by increasing solution
velocity and decreasing both bed height,
iron spheres diameter and the initial concen-
tration of the acidified dichromate solution.
The activation energy of the reaction was
calculated to be 4.51 kcal/mol and this result
shows that the reaction is diffusion
controlled.
For the rational design and operation of
fixed beds used in hexavalent chromium
removal from waste solutions the following
mass transfer correlation was obtained K =
a1V1.5.
5. Symbols
A — Active surface area of Iron spheres
A0 — Constant in Arrhenius equation
C0, C — Initial concentration and concentra-
tion at any time of K2Cr2O7
d — sphere diameter
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