Journal of Cleaner Production 87 (2015) 558e566

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Iron oxide red wastewater treatment and recycling of iron-containing

sludge
Zhenguo Chen, Xiaojun Wang*, Qilong Ge, Guanchao Guo
The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, College of Environment and Energy, South China
University of Technology, Guangzhou 51006, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 25 August 2013
Received in revised form
16 October 2014
Accepted 20 October 2014
Available online 28 October 2014

The paper presents a wastewater treatment process and recycling of iron sludge from wastewater
treatment for iron oxide red production. Results show that: (1) Sludge from wastewater treatment
process under the operating parameters: 1.84 g/L of NaOH dosage, 10 mins of aeration with ow rate of
1 L/min and 150 mins of sediment time is potential for seed crystal preparation and excellent iron oxide
red product can be obtained in the secondary oxidation under condition of 85
C, 68 h of reaction time
and 150 mL/min of airow rate, (2) In practical engineering, the average removal rate of Fe2 and SS and
chroma of efuent is 99.75%, 86.7% and less than 40 times, respectively, and all items of product satisfy
demands of industrial standards, (3) Compared with the original wastewater treatment, the new process
can save the cost of wastewater treatment and earn extra 20.0 dollars for a ton of iron oxide red product
and then both economic benet and environmental protection can be realized by this process. It is
proved that the novel method is reliable, economical and promising in iron oxide red industry and
cleaner production of iron oxide red is feasible.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Iron oxide red
Wastewater treatment
Iron sludge recycling

1. Introduction
1.1. Iron oxide red wastewater
Iron oxide red wastewater is a kind of typical acid wastewater.
About 15 tons of wastewater with high concentration of Fe2 and
suspended solids (SS), high chroma and low pH is discharged per
ton of iron oxide red production. This wastewater can seriously
decrease pH of receiving waterbody leading to the damage of
acidebase equilibrium that is important for growth of aquatic organism (Akcil and Koldas, 2006; Peppas et al., 2000). In addition,
excess Fe2 will change the appearance of water. It can reduce the
intensity of light and then hinder the photosynthesis of aquatic
plant (Zhou et al., 2008). So it is necessary to manage this wastewater appropriately to avoid harm to receiving environment.
The common way to treat this wastewater is alkaline neutralization. By means of adding alkali liquor and aerating, Fe2 can
convert to Fe3 by oxidation and pH will increase. With the increase
of pH, a great quantity of brownish black sediment will generate,

* Corresponding author. Room301, College of Environment and Energy, South

China University of Technology, Guangzhou Higher Education Mega Center, 510006,
China. Tel.: 86 20 13802767806; fax: 86 20 85640936.
E-mail address: cexjwang@scut.edu.cn (X. Wang).
http://dx.doi.org/10.1016/j.jclepro.2014.10.057
0959-6526/ 2014 Elsevier Ltd. All rights reserved.

mainly composed of Fe(OH)2 and Fe(OH)3. After sedimentation, the

supernatant can be discharged meanwhile iron-containing sludge
is obtained.

1.2. Iron-containing sludge

About 1.2 m3 of sludge generates from every 10 m3 of wastewater whose iron mass fraction is more than 2%. This sludge is
composed of iron hydroxide and also a kind of iron-containing
resource. Few people have focused on nding a good way to
dispose this sludge. Generally the sludge is disposed as solid waste,
which means cost of sludge disposal, loss of iron resource and risk
of secondary pollution.
The common disposal method for iron-containing resource is
recycling and relevant studies are carried out in different elds. A
novel technology for producing iron oxide red from byproduct
ferrophosphorus is proposed and feasible under desired conditions
(Ji et al., 2011). Moreover, oily mill sludge is mentioned as raw
material for manufacture of iron oxide red (Akizuki and Oshima,
2012). Furthermore, Cyanided tailings are used to prepare nanoiron oxide red pigment powders under the optimum parameters,
obtaining bright, regular seed crystal and laying a good foundation
for preparing excellent nano-iron oxide red pigments (Li et al.,
2008). It is reported that nano-sized iron oxide particles can be

Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

efciently obtained from Acid Mine Drainage using fuel cell technology (Cheng et al., 2011). Comparable quality of iron oxide catalysts/adsorbents can be obtained using Acid Mine Drainage as a
source material (Rubia et al., 2012). Also, iron-containing sludge
producing in wastewater treatment process is feasible for recycling.
Iron-containing sludge generating in Fenton process can be reused
for the process and better wastewater treatment can be achieved
(Naoyuki et al., 2013; Li et al., 2007). The settled oc produced by
ferric chloride occulation was recycled by an economical and ecofriendly occulation process and hematite can be produced as
byproduct by incineration of wastewater sludge (Shon et al., 2009).
All studies aforementioned suggest that recycling is feasible for
disposal of iron-containing resource. Similarly, in order to dispose
the iron-containing sludge from iron oxide red wastewater treatment, recycling should be taken into consideration. Moreover, as
many studies of iron-containing resource just stay at the lab scale,
this recycling should be carried out in large scale to show whether
it is practicable.
1.3. Recycling of iron-containing sludge
There are mainly two kinds of methods to produce iron oxide
red, namely dry method and wet method (including vitriolic
method, nitric acid method and mix-acid method). Nowadays, the
wet method, specially vitriolic method, is mainly employed for iron
oxide red pigment manufacture because of high quality of product
and low energy consumption (Wang et al., 2008). As a tranditional
method, vitriolic method can be divided into two steps, preparation
of seed crystal and secondary oxidation. In order to obtain a-Fe2O3
in liquid phase, crystallization centre should be prepared rstly,
where creating a-Fe2O3 adheres to form larger crystals. In preparation of seed crystal, solution of FeSO4 is mixed with alkali liquor,
acquiring green jelly Fe(OH)2. With the inlet of air, Fe(OH)2 can be
oxidized and seed crystal as a-FeOOH or g-FeOOH appears. The
process can be showed as equations followed. In this process, large
amount of FeSO4 and sodium hydroxide (NaOH) are used.
FeSO42NaOH/Fe(OH)2YNa2SO4

(1)

Fe(OH)2 O2/a-FeOOH/g-FeOOH (seed crystal)H2O

Temp.<30
C, pH > 8.5

(2)

In secondary oxidation, sheet iron and moderate solution of

FeSO4 are added into the mixture of seed crystal obtained in the
rst step. With temperature of 80
Ce90
C and pH of 4.0e5.0, air
is injected into the mixture and iron oxide red product will be
gained after the reaction. The process can be showed as equations
followed. With preparation of inoculating crystal, as the core,
where a-Fe2O3 clads to promote crystallization in secondary
oxidation, the seed grows and iron oxide red is gained with
characters of pigment.
Fe H2SO4/FeSO4H2[

(3)

2FeSO42H2O1/2O2/a-Fe2O3Y2H2SO4

(4)

559

According to the rst step of vitriolic method, the sludge

generating in wastewater treatment may be possible for preparation of seed crystal. Then raw material for preparation of seed
crystal can be saved and the cost of iron oxide red manufacture
will reduce. With efcient wastewater treatment and recycling
of iron-containing sludge, both economic benet and environmental protection can be achieved. And then cleaner production
of iron oxide red pigment will be realized, which is meaningful
for iron oxide red industry. However, few studies of its
cleaner production are reported, which implies that it is very
important to do research for iron oxide red wastewater treatment and recycling of the sludge generating in the treatment
process.
1.4. Contents of the study
This paper presents a treatment process for iron oxide red
wastewater and an approach of iron oxide red manufacture by
using iron sludge. In the study, lab tests are carried out rstly.
The specic objectives of lab test are (1) to determine the effects
on pH, SS, chroma and concentration of Fe2 of efuent with
different dosage of NaOH and aeration time, (2) to determine the
effects on iron oxide red product obtained by the new method
(factors as temperature, reaction time and aeration) and acquire
the optimal process parameters and (3) to explore whether
properties of the iron oxide red product by the new method meet
requirements of relevant industrial standards. Based on the results of lab tests, the process is attempting and operating in
practical production. The optimal parameters of wastewater
treatment and iron oxide red producing with iron sludge recycling from wastewater treatment are investigated and the feasibility of the new process in practical engineering is manifested.
The paper intends to ll the gap of cleaner production of iron
oxide red pigment industry.
2. Materials and methods
2.1. Raw wastewater
Raw wastewater was collected for experiments from a wastewater collecting tank in an iron oxide red plant in Guangdong
province of P.R. China. Its characteristics and discharge standard
relevant in Integrated Wastewater Discharge Standard of China (GB
8978e1996) have been presented in Table 1.
2.2. Reagents
Analytical reagents, sodium hydroxide and FeSO4$7H2O, were
supplied from Guangzhou Chemical Reagent Plant (Guangzhou,
China). 98% H2SO4 was obtained from Tianjin Damao Chemical
Reagent Plant (Tianjin, China).
2.3. Experiment methods

Iron oxide red is formed from a-Fe2O3 and widely used in

different industries, such as pigment, electronic and telecommunication, architecture industry, etc. (Wang et al., 2008). The desired
quantity of iron oxide red in China was more than 520,000 tons in
2013 and the gross export value of China was also higher than 360
million dollars. As the world demand of iron oxide red is rising,
pollution of wastewater should be prevented so that production of
iron oxide red will not be limited and adequate product can be
supplied.

2.3.1. Wastewater treatment jar test

Iron oxide red wastewater was taken in a beaker jar, with sodium hydroxide solution addition. Then wastewater was stirred
and oxidized with aeration by an air pump. Afterwards, The
wastewater was settled statically and the supernatant was investigated for pH, SS, concentration of Fe2, and chroma to evaluate
the effects of aeration time and dosage of sodium hydroxide solution on pH, concentration of Fe2 in efuent, sludge yields. Simultaneously, the relationship between sludge thickening times and on
the change of sludge volume was studied.

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Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

Table 1
Characteristics of raw wastewater and discharge standard relevant.
Major characteristics

Units

Wastewater quality index

Discharge standard

pH
Chroma
SS
Concentration of Fe2

e
times
mg/L
mg/L

3.0e4.0
700
250e400
500e700

6.0e9.0
<50
<70
e

Raw wastewater was determined for its characteristics in lab and taken for latter
experiments.

2.3.2. Experiment of iron oxide red preparation

Wastewater was mixed with sodium hydroxide solution to
adjust pH to 9.0. The mixture was aerated completely and then
settled statically. After that, sludge was collected as iron oxide red
seed crystal for secondary oxidation. Adequate sheet iron was
added and reaction temperature rose. 98% H2SO4 was fed to adjust
pH to 4.0, and solution of FeSO4$7H2O was added until concentration of FeSO4 reached 9.0e12.0 g/L. Concentration of FeSO4 was
determined alternately, which ensured the concentration to
maintain the requirements of the range. The whole reaction was
under aeration of compressed air. Color change of the suspension
was observed during the reaction, which stopped when standard
color appeared. In this experiment, the effects of reaction time,
temperature and aeration on iron oxide red product were studied.
Remainder were obtained from the reaction above, collected,
washed, ltered, dried in an oven and crushed. Then iron oxide red
pigment product was gained and its property examinations were
carried out simultaneously compared with standard sample produced by the process of the plant.
2.3.3. Engineering project
An engineering project was carried out for demonstrating the
feasibility and reliability of the results from the jar test. The engineering process was shown as Fig. 1. Wastewater was treated by a
new process transformed from original wastewater treatment
process in a plant, that consists of a neutralization aeration tank, a
vertical-ow sedimentation tank, a sludge thickener and a seed
crystal preparation tank, meanwhile sludge from sedimentation
was used as iron oxide red seed crystal. The engineering project
stated the practical applicability of this process, as to promote this
process in iron oxide red industry and provide reliable experience
in engineering for application of this process.
In the novel process, iron oxide red wastewater was pumped
into the neutralization aeration tank, reacted with 30 wt.% industrial caustic soda added through a pipeline mixer. pH was
adjusted in the tank and most of Fe2 changed to Fe(OH)2 and
Fe(OH)3, then change to a-FeOOH or g-FeOOH by abundant

Fig. 2. pH of efuent with different dosage of NaOH and aeration time. Average pH of
efuent was determined with different dosage of NaOH and aeration time.

aeration, which also played a role of stirring in the reaction.

Furthermore, wastewater from neutralization aeration tank
stayed in vertical-ow sedimentation tank with an optimal hydraulic retention time. Then supernatant discharged and sedimentary sludge was concentrated in the sludge thickener for
further dehydrating. Concentrated sludge was delivered into seed
crystal preparation tank by a sludge pump, where seed crystal
preparation happened. Finally, iron oxide red product was obtained by secondary oxidation of seed crystal.
The process commissioning was carried out and when inlet ow
was 10 m3/h, 15 m3/h, 20 m3/h, and 25 m3/h, alkali liquor addition
was controlled for 28 L/h, 42 L/h, 56 L/h, and 70 L/h, respectively.
30 wt.% industrial caustic soda was added at the ratio of 2.8 L per
ton of wastewater. The average daily efuent volume of the plant
was around 600 m3, and the ow of alkali liquor metering pump
was set as 70 h/L. Sludge pump started with liquid level more than
4 m and stopped with liquid level lower than 3.5 m in sludge
thickener automatically, for realizing continuous operation of the
system. The system was under continuous operation for a month.
2.4. Analytical methods
Wastewater samples were analyzed for pH, chroma, SS, concentration of Fe2, which were measured by relevant standard

Fig. 1. The process of engineering practice. 1. Collecting tank; 2. Neutralization aeration tank; 3. Verticle-ow sedimentation tank; 4. Sludge thickener; 5. Seed crystal preparation
tank; 6. Alkali liquor tank; 7. Aeration blower.

Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

Fig. 3. The sludge volume with different dosage of NaOH Average volume of ironcontaining sludge with different dosage of NaOH was determined after sludge settled.

561

Fig. 5. Sludge volume varied with sedimentation time. As time changed, sludge volume was determined in a 1 L cylinder and average value was picked to draw the
picture.

3. Results and discussion

methods (APHA, 2005). Iron oxide red pigment product samples
were analyzed for content of Fe2O3, volatile matter under 105
C,
screenings, pH of suspension liquid, color light, water-soluble salt,
etc. All items were measured by standard methods, referring to
Chinese National Standard of Iron Oxide Red Pigments (GB/T
1863e2008). X-ray diffraction (XRD) was used to study the physical
phase of iron oxide red pigments obtained in the test. Particle size
analysis was carried out by laser particle size analyzer. Crystal
structure analysis was performed by scanning electron microscopy
(SEM).
A pH meter (PHS-3E, Shanghai, China) was used for pH measurement of wastewater. Scanning electron microscopy (LS-15,
ZEISS, Germany), X-ray diffraction (XRD-6000, SHIMADZU, Japan)
and laser particle size analyzer (BT-9300S, Dandong Bettersize Instruments Ltd., China) were also used for the study of iron oxide red
product.

3.1.1. Effects on efuent pH with different dosage sodium hydroxide

solution and aeration time
As shown in Fig. 2, with the increase of NaOH dosage, large
amount of OH was added into the wastewater, leading rising of
primary pH of wastewater and efuent pH gradually increased after
reaction of neutralization aeration, consuming certain amount of
OH. The efuent pH value stabilized at 7.46 with the dosage of
1.2 g/L and abundant aeration. It reached to 8.77 when dosage
increased to 1.84 g/L. Thus, dosage of NaOH can be kept in the range
of 1.2 g/L to 1.84 g/L to meet the discharge standard, namely pH
ranging from 6.0 to 9.0. In terms of economic benets, the optimal
dosage of NaOH is 1.2 g/L for neutralization, which is 1.43 times the
dosage of theoretical calculation result, 0.84 g/L. In addition, with

Fig. 4. Concentration of Fe2 in efuent with different dosage of NaOH. Concentration

of Fe2 was measured by potassium dichromate titration method and average value
was picked to draw the picture.

Fig. 6. Volume ratio of sludge varied with thickening times. Sludge was mixed and
settled after last settlement and average value of sludge volume was picked to draw
the picture.

3.1. Results of wastewater treatment

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Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

Table 2
Water quality index of supernatant after neutralization aeration.
Items

Units

Mean value

Discharge standard

pH
SS
Fe2
Chroma

e
mg/L
mg/L
times

7.46
51
<5
40

6.0e9.0
<70
e
<50

The water quality of efuent was measured under the optimal operation parameters
of wastewater treatment.

extension of aeration time, it was found that efuent pH value

showed a trend of decline with different dosage of NaOH. The results may be attributed to the generation of H in the oxidation of
Fe(OH)2, which consumes OH leading to decrease of pH. The
efuent pH value stabilized after 10 mins of aeration. So the aeration time for neutralization aeration should be 10 mins.
3.1.2. Effects on volume of sludge with different dosage sodium
hydroxide solution
It can be found that the volume of sludge increased gradually in
the treatment with increase dosage of NaOH, as shown in Fig. 3.
Sludge yields grew rapidly rstly, then slowed down due to lower
concentration of Fe2. Production of sludge increased inconspicuously when dosage of NaOH was 1.2 g/L, of which the volume was
125 mL. This means that 125 mL of sludge containing iron can be
obtained from 1 L of iron oxide red wastewater, with a volume ratio
of 12.5%. About 1.25 m3 of sludge will generate from 10 m3 of
wastewater treatment.

Fig. 8. Particle size of a-Fe2O3 varied with different aeration. Average particle size was
analyzed with different aeration ow at 85
C for 68 h.





v ac Fe2 PO2 pH < 5:5

(5)

 
 


v bc Fe2 c OH PO2 pH  5:5

(6)

3.1.3. Effects on concentration of Fe2 in efuent with different

dosage sodium hydroxide solution
Experiments were planned to study effects on concentration of
Fe2 in efuent with different dosage of NaOH. The experimental
results (Fig. 4) indicated that pH value of efuent increased while
concentration of Fe2 decreased gradually, with increasing dosage
of NaOH. The concentration of Fe2 decreased from 246.4 mg/L to
7.8 mg/L, with a fast removal rate, when dosage of NaOH ranged
from 0.72 g/L to 1.20 g/L. Moreover, the concentration was lower
than 5.0 mg/L with dosage larger than 1.20 g/L.
The Ksp of Fe(OH)2 and Fe(OH)3 is 8  1016 and 4  1038,
respectively, and Fe(OH)3 precipitates more easily in contrast. The
oxidation rate of Fe2 can be demonstrated as followed (Wang and
Zhu, 2010).

Fig. 7. Particle size of a-Fe2O3 varied with reaction temperature. Samples were taken
for particle size measurement with increase of reaction time at different temperature.

Fig. 9. Color comparison of products. Color in appearance and color light of samples
prepared by the new method were compared with original product of the plant and
standard product, respectively. (For interpretation of the references to color in this
gure legend, the reader is referred to the web version of this article.)

Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

563

and Fe2 almost changed to iron sludge, remaining little Fe2 in

wastewater.

Table 3
Performance detection between two iron oxide red samples.
Test items

Product from
experiments

Primary product
in the plant

Standard of
101 red pigment

Content of Fe2O3 (%)

Volatile matter (%)
Screenings
pH value of supernatant
Colored light
Water-soluble salt (%)

95.8
0.5
0.10
4.0
Approximation
0.20

95.6
0.5
0.3
3.9
Approximation
0.20

95.0
1.0
0.2
/
Approximation
0.30

Sample of iron oxide red product prepared by the new method in lab was picked for
performance detection and compared with primary product and industrial
standard.

3.1.4. Sludge volume varied with sedimentation time

Fig. 5 illustrates effects on sludge yields with different sedimentation time. It can be found that sludge volume decreased with
the increase of sedimentation time. Flocs generating in wastewater
coagulated and occulated each other, precipitated incompletely
during 30 minse150 mins of sedimentation time. Precipitation
process nished with invariance of sludge volume after 150 mins.
Consequently, the optimal precipitation time is 150 mins and hydraulic retention time of sedimentation tank should be more than
150 mins.
3.1.5. Experiment of sludge thickening
In order to reduce volume and increase iron content of sludge,
experiments were carried out to study changes of sludge volume
with thickening times. As shown in Fig. 6, percentage of sludge
reduced gradually with increase of sludge thickening times, and the
percentage changed from 12.5% to 9.8% after 4 times of thickening.
The results suggest that, with concentrate of mixed sludge, percentage of volume of sludge reduce and iron content promotes,
enriching iron element for meeting requirements of seed crystal
producing.
3.1.6. Conditions of neutralization aeration
As results above, the optimal parameters of wastewater treatment were 1.20 g/L of NaOH, 10 mins of aeration time and 150 mins
for precipitation. Supernatant was analyzed for several water
quality indexes and results were listed in Table 2. Apparently, all
items of efuent listed above met the discharge standard after
treatment of neutralization aeration and iron oxide red wastewater
can be treated by a process shown as Fig. 1.

Fig. 10. XRD pattern of iron oxide red sample. Iron oxide red sample prepared by the
new method in lab was analyzed by XRD.

Constant
a
is
1
 1030
Pa1
min1,
b
is
8  108 L2$Pa1$min1$mol2, c(Fe2) is concentration of Fe2,
c(OH) is concentration of OH, and PO2 is partial pressure of oxygen. Compared with constant a and b, oxidation rate of Fe2 is less
with pH value lower than 5.5 while accelerates with pH value over
5.5.
As dosage of NaOH was 0.72 g/L, pH value of wastewater reached
about 5.5, then oxidation rate of Fe2 accelerated with increase
dosage of NaOH, generating sediment as Fe(OH)3. Therefore, the
removal rate of Fe2 was higher with dosage of NaOH over 0.72 g/L

3.2. Iron oxide red preparation

3.2.1. Particle size of a-Fe2O3 with reaction time and different
temperatures
Fig. 7 indicates that particle size of a-Fe2O3 grows gradually in
the reaction. During precious 45 h of reaction, sheet iron was dissolved in solution of H2SO4, Fe2 generated and further hydrolysis
occurred to form ferric hydroxide, while growth rate of particles
was slower. However, large amount of ferric hydroxide started to
dehydrate and changed to a-Fe2O3, which covered surface of seed
crystal, and growth rate accelerated in the following 13 h. At the
time of 68 h, the color of mixture turned to mauve completely and
the reaction ended. Therefore, the optimal reaction time is 68 h.

Fig. 11. Particle size analytical result of iron oxide red sample. Particle size of iron oxide red sample prepared by the new method in lab was analyzed by laser particle size analyzer.
(For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

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Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

It also suggests that high reaction temperature was conducive to

iron oxide red production. Ferric hydroxide was hard to dehydrate
and iron oxide red particles grew slowly at low temperature. On the
contrary, when temperature is high, growth rate of a-Fe2O3
increased, and more and more a-Fe2O3 covered the surface of seed
crystal, which resulted in acceleration of particle accretion. At the
time of 70th hour, color of products at different reaction temperature was observed. It was found that color of iron oxide red was
yellow at temperature lower than 80
C, where ferric hydroxide
changed to a-FeOOH, rather than a-Fe2O3. Thus, the reaction period
could be shortened at temperature higher than 80
C in secondary
oxidation. However, high temperature meant increase of energy
consumption, faster oxidation rate, speeding up the solution
evaporation and inuence of product characteristics. So the optimal
reaction temperature was 85
C.

3.3. Results of engineering project

3.3.1. Wastewater treatment
Iron oxide red wastewater treatment process was carried out for
one month under the optimal parameters obtained from test results. In this project, equipments run well and wastewater treatment was stable. The efuent was analyzed for pH, SS,
concentration of Fe2 and chroma every three days during

3.2.2. Particle size of a-Fe2O3 with aeration

According to results above, experiments of different aeration
were carried out under the optimal reaction time (68 h) and temperature (85
C). As shown in Fig. 8, with increase of aeration,
particle of iron oxide red grew quickly, as the rates of Fe2 oxidized
to ferric hydroxide and ferric hydroxide hydrolyzing improved.
Otherwise, increment of aeration promoted the reaction due to
fully mixing contact of gas-liquid-solid three-phase in the system.
Consequently the optimal aeration is 150 mL/min.
3.2.3. Performance testing
The iron oxide red pigment slurry was ltered, washed 5
times, ltered again and dried in an oven at 101
C, then crushed.
The iron oxide red product was tested for its performance,
compared with primary products of the plant and standard of
iron oxide red pigments, and the results were shown as below.
Fig. 9 showed that two products were similar in both color in
appearance and colored light by color-scrapping with linseed oil.
Table 3 demonstrated that properties of iron oxide red produced
using sludge from the wastewater treatment accords with Chinese National Standard of Iron Oxide Red Pigments (GB/T
1863e2008).
3.2.4. X-ray diffraction
Phase analysis of iron oxide red produced from sludge in the
wastewater treatment was study by X-ray diffraction (XRD).
Referring to standard picture of a-Fe2O3, Fig. 10 showed all characteristics peaks of a-Fe2O3. This result indicated that the main
composition of sample was a-Fe2O3.
3.2.5. Grain size detection
Median diameter, as percentage of size distribution of sample
reached 50%, was picked as average diameter of iron oxide red
particles, and specic surface area of sample were detected by laser
particle analyzer (BT-9300S). The analysis result was shown as
Fig. 11. It was found that median diameter of nished product
prepared from sludge in the wastewater treatment was 2.137 mm
and the specic surface area was 1.901 m2/g.
3.2.6. Scanning electron microscopy (SEM)
Scanning electron microscopy analysis was done to study the
structure of samples from sludge in the wastewater treatment and
primary product of the plant. The structure of a-Fe2O3 is red ball
or spindle (Celen and Trker, 2001). Comparing picture (a) and (b)
in Fig. 12, the structure of two samples was uniform, as ball
structure. Particle size was measured and presented as picture (c).
The smallest particle size was 268.1 nm and regular size was
373.4 nm.

Fig. 12. Scanning electron microscope of two iron oxide red samples. Iron oxide red
sample prepared by the new method and primary product of the plant were analyzed
by SEM for comparison of structure and particle size.

Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

565

Fig. 13. Monitoring data of efuent during engineering operation: (a) pH, (b) SS, (c) Fe2, (d) Chroma. Wastewater treatment was operated under the inlet ow of 10 m3/h, 15 m3/h,
20 m3/h, 25 m3/h, respectively.

operation of the new process. Results were listed in Fig. 13 .

Excellent results of the wastewater treatment system were obtained, with values of pH, SS, average removal rate of Fe2 and
chroma stabilizing at 8.95, 49 mg/L, 99.75% and 35 times,
respectively.

3.3.2. Resource utilization of sludge

Sludge from wastewater treatment was used, as seed crystal, to
manufacture iron oxide red three times in engineering operation.
Properties of products (mean values) obtained from the new process, were listed in Table 4. Physical phase of nal product was
scanned by X-ray diffraction (XRD) and the main composition of
product was a-Fe2O3 (Fig.14) compared with standard XRD pattern
and Fig.10. Results suggested that properties were stable and all
indexes met the demands of standard of iron oxide red pigments.
Concentration of seed crystal was improved by increasing sludge
concentration time, and then yields of iron oxide red products

Table 4
The iron oxide red quality.

Fig. 14. XRD pattern of iron oxide red using iron-containing sludge in engineering
project. Product of iron oxide red produced by the new method in engineering operation was analyzed by XRD to determine whether the main composition is a-Fe2O3.

Items

Mean value

Primary
process

Standard of
pigment red 101

Sludge quantity (m3)

Concentrated time (h)
Solid content of
seed crystal (g/L)
Production time (h)
Content of Fe2O3 (%)
Volatile matter (%)
Screenings (%)
pH of supernatant
Colored light
Water-soluble salt (%)
Output (tons)

60
2.67
7.13

50e60
/
15.87

/
/
/

85.3
95.5
0.5
0.14
3.9
Approximation
0.21
7.72

72.0
95.6
<1.0
<0.30
3.9
Approximation
<0.20
8e10

/
95.0
1.0
0.20
/
Approximation
0.30
/

Three Samples of iron oxide red product prepared by the new method in engineering operation were picked for quality analysis and compared with primary
process and industrial standard.

566

Z. Chen et al. / Journal of Cleaner Production 87 (2015) 558e566

Table 5
Chemical agent cost of seed crystal preparation by vitriolic method.
Chemical agents

Quantity (tons)

Price (dollars/ton)

Sub-total (dollars)

FeSO4
30% industrial NaOH
Total (dollars)

2.0
2.2
/

65.16
179.2
/

130.3
394.2
524.5

The main cost of this step in vitriolic method is consumption of 30% industrial NaOH,
while it can be saved by the new method.

Table 6
Daily operation cost of the new process.
Items

Cost (dollars)

Power consumption
30% industrial NaOH
Total (Yuan)

22.4
322.5
344.9

Power consumption included energy demand of lift pump of

neutralization aeration tank, metering pump of alkali tank, sludge
lift pump and aeration system.

is feasible and practicable in engineering operation. This process

was widely applied in China now. As the world demand of iron
oxide red is rising rapidly, the new process is promising and
competitive in iron oxide red industry.
4. Conclusion
This paper presents a wastewater treatment process for iron
oxide red wastewater and recycling of iron-containing sludge from
the process for iron oxide red manufacture. The optimal parameters
of wastewater treatment and iron oxide red manufacture were
studied and then applied to practical engineering. Results showed
that not only wastewater was treated efciently but also sludge
generating from the process was reused as the seed crystal to
obtain excellent iron oxide red product. The process can avoid
environmental pollution and save the cost of iron oxide red production. It is proved that the process is feasible, economical and
promising and cleaner production of iron oxide red can be realized.
Acknowledgements

increased. Volume of production was highest with sludge concentrated for 150 mins. Moreover, this iron oxide red product has a
market and is sold out at the price close to primary product of the
plant.
3.3.3. Economic benet analysis
For every seed crystal preparation, 2 tons of FeSO4 and 2.2 tons
of industrial sodium hydroxide solution are required for 9 tons of
iron oxide red products by the primary process in the plant. The
cost is 524.5 dollars for every seed crystal preparation by original
method, as listed in Table 5.
The power consumption of the new method, including wastewater treatment and iron resource utilization, is listed in Table 6.
The daily power consumption is 201Kw$h, which costs 22.4 dollars.
In addition, 60 m3 of sludge is needed for 9 tons of iron oxide red
product, with 500 m3~600 m3 of wastewater treated per day and
1.8 tons 30% wt.% industrial NaOH is required, which costs 322.5
dollars. Therefore, the daily cost of new process is 344.9 dollars.
Therefore, the new process can save 179.6 dollars for the plant
with 9 tons of iron oxide red product and extra 20.0 dollars can be
obtained because of a ton of iron oxide red manufacture with
efcient wastewater treatment whose cost is also saved everyday.
3.4. Signicance of the process
The new process, wastewater treated by neutralization aeration
and iron oxide red produced from sludge as seed crystal, could
ensure an efcient wastewater treatment and save cost of production of iron oxide red. The efuent from the process could meet
local discharge standard by the wastewater treatment. Then
pollution of wastewater can be alleviated and it will not be the
limitation for large-scale production of iron oxide red pigment.
Also, the problem of sludge is solved to avoid cost of disposal and
loss of iron resource. The iron-containing sludge could be recycled
appropriately for iron oxide red production. Besides, iron oxide red
produced from the recycling has a market and economic benet can
be obtained. With this benet, cost of wastewater treatment can be
saved and extra income can be obtained. Thus, both environmental
protection and economic benet can be realized by this new process, which demonstrates that cleaner production of iron oxide red

Authors are thankful to the Science and Technology Planning

Project Foundation of Guangzhou City (2009Z1-E751) and Guangdong Province Department of Social Development Research Project
in Guangdong Province (2013B021000007) for supporting this
work. Authors are also like to appreciate kind cooperation of an iron
oxide red plant in Guangdong Province, China for necessary help.
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