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Chen2015 PDF
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,
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)
(2)
(3)
2FeSO42H2O1/2O2/a-Fe2O3Y2H2SO4
(4)
559
560
Table 1
Characteristics of raw wastewater and discharge standard relevant.
Major characteristics
Units
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.
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.
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.
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.
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.
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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.
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)
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.)
563
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
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.
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
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.)
564
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.
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.
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
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.
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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
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