Journal of Environmental Management 154 (2015) 177e182

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Journal of Environmental Management

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

Recovery of energy and iron from oily sludge pyrolysis in a uidized

bed reactor
Linbo Qin a, Jun Han a, *, Xiang He a, Yiqiu Zhan a, Fei Yu b
a
b

College of Resources and Environment Engineering, Wuhan University of Science and Technology, Wuhan, 430081 Hubei, China
Department of Agricultural and Biological Engineering, Mississippi State University, MS 39762, USA

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 21 March 2013
Received in revised form
12 February 2015
Accepted 16 February 2015
Available online 27 February 2015

In the steel industry, about 0.86 ton of oily sludge is produced for every 1000 tons of rolling steel. Due to
the adverse impact on human health and the environment, oily sludge is designated as a hazardous
waste in the Resource Conservation and Recovery Act (RCRT). In this paper, the pyrolysis treatment of oily
sludge is studied in a uidized bed reactor at a temperature range of 400e600
C. During oily sludge
pyrolysis, a maximum oil yield of 59.2% and a minimum energy loss of 19.0% are achieved at 500
C. The
energy consumption of treating 1 kg oily sludge is only 2.4e2.9 MJ. At the same time, the energy of
produced oil, gas and solid residue are 20.8, 6.32, and 0.83 MJ, respectively. In particular, it is found that
the solid residue contains more than 42% iron oxide, which can be used as the raw material for iron
production. Thus, the simultaneous recovery of energy and iron from oil sludge by pyrolysis is feasible.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Oily sludge
Pyrolysis
Fluidized bed
Energy
Iron
Recovery

1. Introduction
Oily sludge, generated from the rolling steel process, is a waste
product comprising dense slurry of iron nes in lubricating oil and
water with other contaminants such as heavy metals (Biswal et al.,
2009). It was estimated that about 0.86 ton of oily sludge was
produced for every 1000 tons of rolling steel in China (Liu, 1997).
Due to the adverse impact on human health and the environment,
oily sludge is designated as a hazardous waste in the Resource
Conservation and Recovery Act (RCRT) (Liu et al., 2011;
Ramaswamy et al., 2007; Zhou et al., 2009). Hence, the disposal
of oily sludge without treatment is strictly prohibited. At present,
the conventional disposal methods include landlling (Bossert
et al., 1984; Hejazi et al., 2003), chemical extraction (Zubaidy and
Abouelnasr, 2010), incineration (Li et al., 1995; Sankaran et al.,
1998), biodegradation (Biswal et al., 2009; Liu et al., 2009) and
pyrolysis (Liu et al., 2008; Schmidt and Kaminsky, 2001). Landlling
is becoming unfeasible because of the rapid depletion of available
sites and the high cost. Chemical extraction is either too costly or
only partially effective (Zubaidy and Abouelnasr, 2010). Incineration has the shortcomings of high energy consumption with

* Corresponding author.
E-mail address: hanjun@wust.edu.cn (J. Han).
http://dx.doi.org/10.1016/j.jenvman.2015.02.030
0301-4797/ 2015 Elsevier Ltd. All rights reserved.

producing secondary pollutants such as SOX, NOX, heavy metals,

and particulate matter, which inhibits the wide application of this
technique (Karamalidis and Voudrias, 2007; Yao and Naruse, 2009).
Compare with combustion or incineration, oily sludge pyrolysis
has received more attentions because of its mild operation conditions, energy recovery (pyrolysis oil and gas), and less pollutants.
Liu et al. (2008) studied the effects of the operating temperature
(350e550
C) on the products during oily sludge pyrolysis in an
externally heated xed bed reactor. The results indicated that the
mass fractions of solid residues, liquids, and gases products were
56.00e67.00%, 25.60e32.35%, and 7.40e11.65%, respectively. The
heating values of solid residues, liquids, and gases products were
13.8e34.4 MJ/kg, 44.41e46.6 MJ/kg, and 23.94e48.23 MJ/Nm3,
respectively. Moreover, the main compositions of the liquid fraction
were alkanes and alkenes (C5eC29), and the gaseous fractions were
predominantly HCs and H2. Schmidt and Kaminsky (2001) claimed
that about 70e84% of the oils could be separated from oily sludge
during pyrolysis in a uidized bed reactor at a temperature range of
460e650
C. They also found that the yield of CxHy was highest at
600e700
C. However, the yield of oil decreased signicantly with
increasing the heating rate, which was also demonstrated by Shie
et al. (2000). Although numerous studies of pyrolyzing the oily
sludge from oil rening or petrochemical industries have been reported (Karayildirim et al., 2006; Liu et al., 2008; Schmidt and

178

L. Qin et al. / Journal of Environmental Management 154 (2015) 177e182

Kaminsky, 2001; Shie et al., 2000), only a few reports focus on the
oily sludge from the steel industry (Houbart, 2012; Liu et al., 2013).
In fact, the components of oily sludge from steel industry are
different with those from the oil rening industry. The iron concentration in the oily sludge from iron and steel industry is relatively high. Hence, the investigation of simultaneous recycling of
energy and iron during oily sludge treatment is very interesting
(Houbart, 2012).
The aim of this study was to investigate the simultaneous recovery of energy and iron resources from oily sludge using pyrolysis
in a uidized bed reactor at a relatively low temperature
(400e600
C). Meanwhile, the effect of temperature on the distribution and composition of the pyrolysis products (non-condensable gases, oil and solid residue) was also studied.
2. Experimental
2.1. Materials
The oily sludge used in this experiment was obtained from the
rolling steel process of an iron and steel company in Wuhan city,
China. The proximate analysis and ultimate analysis were summarized in Table 1.
The oil content of oily sludge is measured by solvent extraction,
also as Table 1. The oil extraction method was described by Zubaidy
and Abouelnasr (2010). 40 g of oily sludge were added to specied
amounts of chloroform. The mass ratio of solvent-to-sludge was
5:1. After mixing oily sludge and solvent, the sample was ltered,
dried to remove solvent, and then weighed. The ltrate was
distilled using a batch simple distillation apparatus. In addition, the
inorganic materials of the solid residues in the oily sludge are
analyzed by X-ray uorescence spectrometry (XRF).
2.2. Experimental apparatus and procedures
The oily sludge pyrolysis was carried out in a uidized bed
reactor with an internal diameter of 0.4 m and a vertical length of
1.2 m. The system consisted of a stainless steel reactor, a cooling
system for separating water and the condensable oil, and a gas
cleaning/drying system followed by gas measurement devices. The
reactor was electrically heated, and the temperature was measured
with thermocouples and controlled. The experimental temperatures were 400, 450, 500, 550, and 600
C. In order to maintain an
inert atmosphere, nitrogen was fed into the reactor at a ow rate of
1.0 L min1 for 30 min. The residence time of the gaseous products
in the reactor was about 13 s.
When the temperature of the reactor reached the pre-determined temperature, the oily sludge was continuously fed by an
injector with a feeding rate of approximately 2.0 g/min, and the
feed time was 50 min in each runs. The gases released from oily

Ultimate analysis (W%)

C

72.72

a,b

5.20

14.96

Proximate analysis (W%)

4.05

2.07

Low heating
value/MJ Kg1
28.28

Components (W%)

Fixed carbona

Asha

Volatilea

Moisturec

Oil contentc

Solid residuec

9.35

16.67

73.98

32.64

48.06

19.30

a
b
c

Dry base.
Calculated by difference.
As received basis.

3. Results and discussions

3.1. Characteristics of oil sludge
The amount of solvent recovered through distillation was
recorded and compared to the amount originally added prior to the
mixing step. The volume of the distillate bottoms, comprising the
recovered oil, was recorded. The results indicate that the original
oily sludge contains more than 48 wt.% of oils. The composition of
the oil from the original oily sludge is shown in Table 2. It is

Table 2
Chemical composition of the oil extracted from the original oily sludge.
Chemical composition of the oil

Table 1
Chemical characteristics of the oily sludge.

sludge passed through two consecutive condensers to collect the

condensed oil and water. After a lter, the pyrolysis gas was
analyzed by a gas analyzer (Gasboard-3100, Cubic optoelectronic
Co., China) to record the caloric value and concentrations of CO,
CO2, H2, CH4, CmHn, and O2. The total volume of the non-condensable gas was also measured by a cumulative ow-meter. After
the pyrolysis process, the solid residue, liquid fraction including oil
and water were collected and weighed. In this experiment, each
run was repeated 3 times and the average data were used.
The water content in the liquid fraction was analyzed according
to Chinese standard: Coking products-Determination of moisture
content (GB/2288-2008). 100 g of pyrolysis oil were added to the
ask contained 50 ml toluene. After mixing pyrolysis oil and solvent in the ask, the ask was heated, and the water in the oily
sludge was evaporated and condensed in the receiving tube. After
all water was condensed in the receiving tube, the volume of water
in the receiving tube was recorded.
Finally, the oil samples were ltered and dried to remove dust
and moisture. And then the sample was characterized using
GCeMS (Agilent 19091S-433, Agilent Corp. USA). The GC was tted
with a 30 m  0.25 mm capillary column coated with a 0.25 mm
thick lm of 5% phenyl methyl silox (HP-5 MS). The carrier gas ow
(He) was 1 ml/min, and the split ratio was 10:1. The initial oven
temperature of 40
C was kept isothermal for 4 min and then
heated to 300
C at a heating rate of 10
C/min, and held at this
temperature for 10 min. The injector was pulsed split at 250
C and
the temperatures of the MS source and MS quad were 230
C and
150
C, respectively. The full-scan mode with mass-to-charge (m/z)
ratios from 30 to 500 was used, and the solvent delay was 2 min.
The chromatographic peaks were identied with the help of the
National Institute of Standards and Technology (NIST) mass spectra
data library.
X-ray uorescence spectrometry (XRF, Rigaku Corp, Japan) and
scanning electron microscopy (SEM, JCM-5000, JEOL Corp, Japan)
were also used to further understand the composition and morphologies of the solid residues.

No.

Compounds

Conc./%

No.

Compounds

Conc./%

1
2
3
4
5
6
7
8
9
10
11
12
13

Undecene
Undecane
Dodecene
Dodecane
Tridecylene
Tridecane
Tetradecene
Pentadecane
Naphthalene
Hexadecene
Hexadecane
Heptadecene
Pentadecanone

2.34
4.16
3.44
2.22
2.22
2.84
6.14
5.16
2.36
5.18
4.82
3.86
3.88

14
15
16
17
18
19
20
21
22
23
24
25
26

Tetradecanoic acid
Heptadecane
Heptadecanone
Dibutyl phthalate
Hexadecanoic acid
Octadecenic acid
Eicosane
Docosane
Myristic acid
Hexacosane
Octacosane
Nonacosane
Others

3.18
2.12
5.46
1.21
7.80
7.10
2.58
1.26
4.08
1.66
4.30
1.32
9.31

L. Qin et al. / Journal of Environmental Management 154 (2015) 177e182

179

indicated that the oils contain about 32.44% alkanes, 23.18% alkenes, 22.16% aliphatic acid, 9.34% ketones, 2.36% aromatic hydrocarbons, and 10.52% substituted aromatics. The X-ray uorescence
spectrometry (XRF) results show that iron oxide in the solid residues of the oily sludge is as high as 42.10% (in Table 3).
3.2. Effect of temperature on the product yields
Fig. 1 shows the distribution of gas, condensed oil, solid residue
and water yields during oily sludge pyrolysis under different reaction temperatures. It can be seen that there is no signicant
variation in the gas yield when the temperature increases from 400
to 500
C. As the temperature is further increased, the gas yield
increases dramatically and reaches its maximum value (57.48 wt.%)
at 600
C. Meanwhile, the water content seems to be independent
of the reaction temperature. As for solid residue, the yield slightly
decreases with increasing the reaction temperature. It is also found
that the oil yield increases from 45.54 to 59.20 wt.% with increasing
temperature from 400 to 500
C, and then signicantly decreases
from 59.20 to 11.21 wt.% as the temperature increases from 500 to
600
C, which is consistent with other studies (Liu et al., 2008). The
vaporization of oil has not been completed when the temperature
is below 500
C. The oil contents in the solid residue pyrolyzed
under 400 and 500
C are 8.15% and 0, respectively. Hence, the
increase of gaseous products at 400e500
C was predominantly
due to the further vaporization of oil, which was proven by the
variation of the solid residue yield and oil content in the solid
residues. While the increase of the gaseous products at 500e600
C
was predominantly due to the secondary cracking or thermal
decomposition of the oils because there was a greater decrease in
oil yield (Permsubscul et al., 2007).

Fig. 1. Products distribution of oily sludge pyrolysis.

Fig. 2. Gases composition at different temperatures.

3.3. Effect of temperature on the gas composition

The effect of temperature on the gas composition is shown in
Fig. 2. The results indicates that H2, CO, CO2, CH4 and some C2 and
C3 hydrocarbons (C2H2, C2H4, C2H6 and C3H8) are the main components (N2 free-vol.%) during oily sludge pyrolysis. The H2 content
increases from 13.28 to 28.29 % as the temperature increased from
400 to 600
C. It is also found that the CO and CH4 contents
decrease, follow by increase when the temperature increase from
400 to 600
C. The percentage of CO and CH4 reached their minimum value (3.98 and 18.85%, respectively) at 500
C. In contrast,
the content of CmHn increased from 28.22 to 32.44% at 400e550
C,
followed by a decrease to 30.9% at 600
C. While the percentage of
CO2 sharply decreased from 34.02 to 10.46% with increasing temperature. The formation of CO and CO2 at low temperatures
(<450
C) was mainly caused by the breaking of carbonyl and
carboxyl functional groups in the oily sludge. Meanwhile, the
presence of steam promoted the steam reforming reaction of the
volatile matter and partial gasication of the solid carbonaceous
material, as shown by Eqs. (1) and (2) (Midilli et al., 2002; Wang
et al., 2007), which cause the increase of CO concentration when

Table 3
Chemical components of the solid residue.
Chemical composition of the solid residue
No.

Compounds

Wt.%

No.

Compounds

Wt.%

No.

Compounds

Wt.%

1
2
3
4
5

Na2O
MgO
Al2O3
SiO2
P2O5

4.57
2.80
1.61
2.93
3.98

6
7
8
9
10

SO3
K2O
CaO
TiO2
MnO

12.02
0.67
27.64
0.21
0.28

11
12
13
14

Fe2O3
Ni2O3
CuO
ZnO

42.10
0.58
0.21
0.40

temperature is above 550
C. Non-condensable products may also

undergo heterogeneous reactions with each other. For example,
CH4 and CO concentration may be affected by methane reforming
and CO shift reactions, as shown in Eqs. (3) and (4) (Leung et al.,
2002).
Steam reforming reaction:

Organicsg H2 Og4CO H2

(1)

Steam gasication reaction:

CS H2 Og4CO H2 ;

DH298K 131 KJmol1

(2)

DH298K 206:1 KJmol1

(3)

CH4 reforming reaction:

CH4 H2 O4CO2 3H2 ;

CO shift reaction:

CO H2 O4CO2 H2 ;

DH298K 41:5 KJmol1

(4)

Meanwhile, high temperatures can promote the cracking reactions of CmHn (C2H4, C2H6 and C3H8). The typical reactions are
(Zhang et al., 2011):

C2 H6 4C2 H4 H2

(5)

C2 H4 4CH4 C

(6)

In addition, it was also found that the pyrolysis gas produced

from treating 100 kg oily sludge under 400, 450, 500, 550 and
600
C were 7.34, 10.89, 11.23, 56.22 and 64.58 m3, respectively. At
the same time, the low heating value of pyrolysis gas (including N2)

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L. Qin et al. / Journal of Environmental Management 154 (2015) 177e182

under 400, 450, 500, 550 and 600
C were 13.47, 14.23, 15.33, 23.14
and 24.90 MJ/Nm3, respectively. Therefore, pyrolysis gas can be
used as a fuel for boiler or furnace, and it also may be reused in the
pyrolysis system as an auxiliary fuel to supply energy.

Table 5
Detail analyses of the oil obtained from the original oily sludge and pyrolysis
process.
No. Compounds

Conc. %
Original 400
C 450
C 500
C 550
C 600
C

3.4. Effect of temperature on the oil composition

The main components of the pyrolysis oil are summarized in
Tables 4 and 5. The total ion count (TIC) of chromatograms for the
oils can be found in the Supplementary material (Figs. 1e5).
Generally, the main components of the oil can be divided into ve
groups: alkane, alkenes, aromatic hydrocarbons, heavy oxygenated
hydrocarbons and substituted aromatics hydrocarbons. The alkanes
include tridecane (Peak 8), cyclopropane (Peak 10), pentadecane
(Peak 11), and heptadecane (Peak 14), while the alkenes contain
dodecene (Peak 4), tridecene (Peak 9), tetradecene (Peak 12), and
hexadecene (Peak 19). Aromatic hydrocarbons include benzene and
their respective alkyl derivatives (Peak 35e38) and the heavy
oxygenated hydrocarbons are carboxylic acids (Peak 23e28) and
ketones (Peak 29e33). The substituted aromatics containing N, S,
Cl, and O, such as quinoline and aromatic hydrocarbons, are also
detected in the oil. From Table 4, it can be seen that the concentrations of alkanes increase from 16.00 to 20.24% with increasing
temperature from 400 to 600
C. Similarly, the amounts of alkenes
also increase from 7.44 to 18.92% with the temperature increase.
While the content of carboxylic acids in the pyrolysis oil rstly
increase and then decrease at 400e600
C, the maximum yield
occurs at about 500
C. In contrast, the amount of ketones in the
pyrolysis oil decrease from 16.55 to 8.18% when the pyrolysis
temperature increase from 400 to 550
C, followed by increase to
16.80% at 600
C. Moreover, aromatic compounds are also detected
in the pyrolysis oil. Compared with the original oil obtained from
the oily sludge, the yields of alkanes and alkenes in the pyrolysis
oils are low, while the fractions of ketones and aromatic compounds are considerably higher than those of the original oil. The
pyrolysis oils are more complex and the main compositions of the
oils are dependent on the reaction temperature. The above phenomena can be explained by the following reasons: the main formation mechanism of the oils includes vaporation, secondary
cracking of oil, and the breaking of peptide bonds in the proteins.
Moreover, the cyclization and amidation also have some contributions to the distribution and component of oil. The DielseAlder
reaction mechanism is considered as the main contributor for the
formation of aromatic compounds (Zhang et al., 2011). Table 6
shows the nal analysis and low heating value of the pyrolysis
oils. The results indicates that the mass fractions of carbon and
hydrogen in pyrolysis oil are 67.47e72.19% and 10.82e14.14%,
respectively, and the low heating value varies from 34.46 to
36.79 MJ/kg. According to Chinese standard Automobile diesel
fuels GB/19147-2009, the recovery oil can be reused as fuel for
boiler or the raw material of producing diesel.
3.5. Effect of temperature on the solid residue composition

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34

Nonane
Cyclopentane
Decane
Dodecene
Undecane
Undecene
Dodecane
Tridecane
Tridecene
Cyclopropane
Pentadecane
Tetradecene
Tridecanoic acid
Heptadecane
Heptacosane
Eicosane
Docosane
Hexacosane
Hexadecene
Octacosane
Nonacosane
Heptadecene
Dodecanoic acid
Tetradecanoic acid
n-Hexadecanoic acid
Octadecanoic acid
Phthalic acid
Myristic acid
Pentadecanone
Hexadecanone
Heptadecanone
Tridecanone
Nonadecanone
3,4-Dihydro-3,3,9trimethyl-1(2H)acridone
35 Benzene
36 Benzenamine
37 Dibutyl phthalate
38 Naphthalene
39 Pyrene
Others (Wt.%<0.3%)

e
e
e
4.16
4.16
2.34
2.22
2.84
2.22
e
5.16
6.16
e
4.82
2.12
2.58
1.26
1.66
5.18
4.30
1.32
3.86
e
3.18
7.80
7.10
1.21
4.08
3.88
e
5.46
e
e
e

0.23
0.51
0.29
2.01
0.84
1.26
0.63
1.58
1.58
3.21
6.29
e
1.13
1.09
1.33
e
e
e
2.59
e
e
e
8.63
3.58
3.73
1.67
0.55
e
3.81
0.34
5.30
1.80
0.93
4.37

0.38
0.54
0.52
2.90
1.49
1.65
0.90
1.82
1.70
3.42
4.93
2.01
0.85
1.17
1.29
e
e
e
2.91
e
e
e
9.00
4.28
6.10
1.16
0.73
e
3.44
0.43
4.80
1.88
0.90
4.08

0.17
1.32
0.61
2.92
1.17
2.37
0.99
1.91
2.51
4.78
4.42
2.99
1.85
2.11
1.14
e
e
e
3.15
e
e
e
6.28
5.25
8.68
0.81
0.82
e
3.04
e
4.15
1.73
1.03
3.88

e
0.85
0.85
5.17
1.27
2.96
0.66
2.55
3.46
5.84
5.48
2.02
1.00
1.24
0.78
e
e
e
3.79
e
e
e
5.96
3.54
3.42
2.01
4.43
e
1.94
e
2.91
0.64
0.92
1.77

0.32
0.15
e
4.99
0.77
2.68
0.65
2.97
3.55
6.11
7.11
2.63
0.34
0.80
1.36
e
e
e
5.07
e
e
e
4.86
2.06
2.11
2.73
6.73
e
3.72
0.28
5.75
1.74
0.82
4.49

e
e
e
2.36
e
9.31

12.44
2.90
3.02
e
e
22.36

7.30
2.14
1.98
e
e
23.3

1.16
1.98
1.41
2.13
e
22.61

11.89
1.43
7.16
3.06
e
11.00

0.85
0.74
9.98
3.36
0.66
9.62

also investigated, as shown in Table 7. The amount of oil in the

residue decreases from 8.15 to 0% with increasing reaction temperature from 400 to 500
C, and there is no oil in the residue as
temperature is above 500
C. Moreover, the elemental composition
in the residues is independent of the reaction temperature when it
is above 450
C. The morphologies of the solid residues are presented in Fig. 3. At 400
C, the surface of the residue is smooth,
which mean that there is some oil in the residue (consistent with
the ultimate analysis). When the reaction temperature increases to
450
C, the solid residue is easily aggregated, and part of the surface
is still smooth. Above 450
C, the residue is loose and porous. These

The elemental composition and oil content in the residues are

Table 4
The oil obtained from the original oily sludge and pyrolysis process.
Compounds

Alkane
Alkenes
Arboxylic acids
Ketones
Aromatic hydrocarbons

Table 6
The elemental analysis and lower heating value of the pyrolysis oil.
Temp/
C

Conc. %

Original

400 C

450 C

500 C

550 C

600 C

32.44
23.18
22.16
9.34
2.36

16.00
7.44
19.29
16.55
18.36

16.46
11.17
22.12
15.53
11.42

18.62
14.57
23.69
13.83
6.68

19.52
17.40
20.36
8.18
23.54

20.24
18.92
18.83
16.80
15.59

400
450
500
550
600

Elemental analysis/%

Low heating value (MJ/Kg)

O(diff.)

68.72
71.44
72.19
70.69
67.47

11.20
10.82
13.69
13.07
14.14

14.46
12.01
11.14
10.64
12.94

4.75
4.65
4.08
4.53
4.43

0.87
1.08
0.90
1.07
1.02

34.46
35.84
36.79
36.40
34.59

L. Qin et al. / Journal of Environmental Management 154 (2015) 177e182

Table 7
Analysis of the residues.
Temp./
C

400
450
500
550
600

Ultimate analysis (Wt.%)

C

O(diff.)

42.72
38.44
31.19
31.69
31.47

4.20
3.82
3.19
3.07
3.14

44.26
47.91
55.64
55.49
55.74

4.75
4.65
4.78
4.58
4.63

4.07
4.18
4.20
4.17
4.02

Low heating
value (MJ/kg)

Oil content/%

13.71
7.69
7.14
7.02
7.11

8.15
0.78
0
0
0

181

calcium oxide in the residues are approximately 42 and 26%,

respectively, which are the dominant compounds in the solid residue. Interestingly, the iron content of iron ore in China is only
30e60%. Hence the content of iron in the residue is satisfactory for
iron-making. Meanwhile, calcium oxide in the residue can be used
as a desulphurization and uxing agent during the iron-making
process. Thus, the reuse of the residues from oil sludge pyrolysis in
the iron industry is feasible.
3.6. Energy balances of the products

phenomena could be explained by the oils in the residue being

completely decomposed. Fig. 4 demonstrates that the inorganic
composition of the pyrolysis residue is independent of the reaction
temperature. Moreover, the mass fractions of iron oxide and

The effect of the pyrolysis temperature on the energy distribution of the products obtained from oily sludge pyrolysis is presented in Table 8. It can be seen that the energy fraction of the
pyrolysis oils increases slightly when the temperature increases

Fig. 3. SEM analyses of the residues at different temperatures.

182

L. Qin et al. / Journal of Environmental Management 154 (2015) 177e182

Acknowledgments
This work was partly supported by National Natural Science
Foundation of China (50806053) and Foundation of State Key
Laboratory of Coal Combustion (FSKLCC1113).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2015.02.030.
References
Fig. 4. XRF analyses of the residues at different temperatures.

Table 8
Mass and energy distribution of the products.
Energy balance

Reaction
400
450
500
550
600
temperature/
C
Energy distribution Energy fraction 41.82 49.27 58.78 27.20 10.02
of the products of oil/%
Energy fraction 14.76 17.11 19.87 42.00 61.64
of gaseous/%
Energy fraction 11.42
3.84
2.34
2.78
2.13
of residue/%
Fraction of
32.01 29.77 19.00 21.02 26.21
energy loss/%

from 400 to 500
C. As the temperature is further increased, the

energy fraction of the oils is increased dramatically and reaches the
maximum value of 61.64% at 600
C. These results are consistent
with the variations in the mass fractions of products for oily sludge
pyrolysis over the temperature range 400e600
C. In contrast, the
energy fraction of the residue slightly decreases with increasing
reaction temperature. It is also found that the fraction of the energy
loss rstly decreases, and then increase when the temperature increases from 400 to 600
C, and the minimum energy loss occurs at
500
C. At 500
C, the energy fractions of the oil, gaseous and solid
residues are 58.78, 19.87 and 2.34%, respectively. The total recovery
of the energy was 81% and energy loss was 19%. The energy consumption of treating 1 kg oily sludge is only 2.4e2.9 MJ. At the same
time, the energy of produced oil, gas and solid residue are 20.8,
6.32, and 0.83 MJ, respectively.
4. Conclusions
The pyrolysis of oily sludge from an iron company was studied in
a uidized bed reactor at a temperature range of 400e600
C. The
energy and iron from the oily sludge were simultaneous recycled
when the hazardous oily sludge was safely disposed by pyrolysis.
The recovery oil (59.20%) was composed of alkane, alkenes, carboxylic acids, ketones and a few types of aromatic hydrocarbons,
which can be used as fuel for boiler or the raw material of producing diesel. In addition, the solid residues after pyrolysis contained more than 42% iron oxide, which could be recycled as a raw
material for iron-making.

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