Fuel 332 (2023) 126240

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Full Length Article

Melting solidification of oily sludge with coal fly ash: Fusion characteristics,
phases transformation and metals leaching behavior
Xinyue Zhang a, 1, Jiao Ma a, 1, Lina Liu b, Boxiong Shen c, Zhichuan Li a, Zhikun Zhang a, *
a
Tianjin Key Laboratory of Clean Energy and Pollution Control, School of Energy & Environmental Engineering, Hebei University of Technology, Tianjin 300401, PR
China
b
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Nankai University, Tianjin
300350, PR China
c
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300401, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Melting solidification is a promising method to achieve the harmless treatment of oily sludge (OS). In this study,
Oily sludge the coal fly ash (CFA) was used as an additive to co-treat with OS. The effects of CFA addition on the fusion
Melting solidification characteristics and phases transformation of OS were studied, and the leaching behavior of heavy metals after
Coal fly ash
melting solidification was also evaluated. The results indicated that the addition of CFA had a synergistic effect
Fusion characteristics
Phases transformation
on the thermal characteristics of OS. SiO2 and Al2O3 in CFA reacted with CaO in OS to form gehlenite
Metal leaching behavior (Ca2Al2SiO7), which reduced the ash fusion temperatures (AFTs) of OS. But the AFTs of mixed samples increased
with the addition of CFA from 10 wt% to 50 wt%, and this might be due to more anorthite (CaAl2Si2O8) for­
mation based on the gehlenite. As the increase of CFA into OS, the microstructures of co-treated mixtures were
gradually loose. In addition, the leaching concentrations of heavy metals in the co-melting samples were reduced
by 13.22–76.70 mg/L, which were lower than the standard limit, and the products presented low ecological risk
indices. The obtained results indicated that the CFA effectively regulated the melting behaviors of OS and
promoted the solidification of heavy metals, which provided a safe and stable disposal approach for OS
treatment.

1. Introduction vitrification) have gained extensive application due to their advantages

With the development of economics and industrialization, the con­
sumption of oil in China has been increasing significantly. Concomi­
tantly, amounts of oily sludge (OS) was generated, which reached
approximately 3 million tons every year [1]. The generated oily sludge is
considered to be the major polluted waste in the petroleum industry [2],
and it has been classified as a hazardous waste due to its richness in
heavy oil, toxic and harmful substances [3]. OS could be a serious threat
to the surrounding environment and human health if improperly treated
[4]. It is urgent and meaningful to find a suitable and eco-friendly
approach for the disposal of this hazardous waste.
Nowadays, many technologies for the treatment of OS have been
reported, such as supercritical water treatment [5], biodegradation [6],
thermal treatment [7], and solvent extraction [8], etc. Among, the
thermal treatments (e.g., incineration, pyrolysis, and melting/
of energy recovery and efficient processing capacity [9]. Incineration
and pyrolysis treat wastes at lower temperatures than melting, but their
generated residues need further disposal [10,11]. Specifically, melting
solidification could achieve the safe disposal of hazardous waste, since
the heavy metals could be stabilized in the formed dense lattice structure
and glass matrix [12]. However, the application of this technology is
restricted by the high energy demand resulting from the high melting
temperature. Normally, the melting temperatures are determined by the
chemical compositions and crystal species of raw materials to be treated
[13]. Therefore, studying the fusion characteristics and phases trans­
formation is important for OS treatment, which could provide valuable
information for the reduction of energy consumption during the high-
temperature melting process.
Previous studies reported that the melting behavior was essentially
affected by the chemical compositions and the interaction between

* Corresponding author.
E-mail address: zhangzk@hebut.edu.cn (Z. Zhang).
1
Co-first author: These two authors contributed equally to this work.

https://doi.org/10.1016/j.fuel.2022.126240
Received 2 June 2022; Received in revised form 12 September 2022; Accepted 5 October 2022
Available online 11 October 2022
0016-2361/© 2022 Elsevier Ltd. All rights reserved.
X. Zhang et al.
various compounds [14]. For example, Li et al. [15] studied the ash
fusion behavior of corn stalk by adding sludge ash that contained high
contents of SiO2, Al2O3, Fe2O3, and CaO. The addition of sludge ash led
to the decrease of amorphous phases and the increase of mineral phases,
which changed the ash fusion temperatures of corn stalk. Lin et al. [13]
proposed the thermally co-treatment of municipal solid waste inciner­
ation fly ash and sewage sludge. The rich SiO2 and Al2O3 in sludge were
prone to react with the compounds in fly ash to form low-melting-
temperature eutectics and greatly reduce the ash fusion temperatures.
Folgueras et al. [16] studied the mixed combustion of bituminous coal
and sludge with high SiO2, Al2O3 and Fe2O3, and found that the formed
eutectics in blend ashes were located in the low temperature region.
SiO2 reacted with oxides of coal to form silicates and aluminosilicates,
and this can provide eutectic blends with lower AFTs. According to the
studies mentioned above, the main chemical compositions (SiO2, CaO
and Al2O3, etc.) could affect the melting behaviors of various raw ma­
terials by forming new eutectics. Based on the chemical compositions of
CaO-rich OS, therefore, it is necessary to add the Si- and Al-containing
additives to co-treat with OS, in order to analyze the phases trans­
formation and find ways to reduce energy consumption.
Coal fly ash (CFA) is an industrial by-product and its generation is
about 580 million tons each year in China, which urgently needs recy­
cling and disposal [17]. The main components in CFA are the acidic
constituents, e.g., SiO2 (28 %–80 %) and Al2O3 (8 %–48 %) [18]. Both of
them presented the potential of decreasing ash fusion temperatures of
OS to reduce the energy cost [19]. Specially, the pyrolysis is currently
the main method for treating OS, and it has been proved that CFA
addition could enhance the yields of oil and gas during the pyrolysis of
OS [11]. However, the obtained pyrolysis residues still need secondary
treatments. The melting solidification heated at a higher temperature
than pyrolysis provides a one-step method for the treatment of OS and
CFA.
In this study, the melting solidification was proposed to achieve the
stabilization of OS and CFA, and the involved variation of fusion char­
acteristics and mineral phases during the treatment were investigated
comprehensively. Furthermore, an ecological risk assessment was also
conducted for the molten products. The main contents of this study
included: (I) researching the fusion characteristics and phases trans­
formation of OS during the thermal treatment; (II) investigating the
effect of CFA addition on the ash melting points, crystal phases,
microstructure and functional groups of different molten products; (III)
evaluating the leaching behavior of heavy metals (Pb, Cr, Cu, Ni, Cd, and
As) in the samples before and after melting solidification. This study
could provide further insights into the fusion characteristics and phase
transformation during the melting solidification of OS with CFA, which
is valuable and practical for OS management.
2. Materials and methods
2.1. Material preparation
OS used for this study was collected from Tianjin, China. Before the
melting experiments, it was dried in an oven at 105 ◦ C for 48 h, and the
dried samples were stored in sealed containers. CFA was obtained from
Tangshan, China. The two materials were finely sieved to the particle
size<75 µm (＜200 mesh).
2.2. Experimental design and process operation
To investigate the fusion characteristics of OS, a muffle furnace was
used for the thermal treatment. About 10 g of OS sample were put into
each corundum crucible, sent into the muffle furnace sequentially, and
heated from room temperature to each specified temperature at heating
rate of 50 ◦ C/min. The heating temperatures for OS were selected as
800 ◦ C, 900 ◦ C, 1000 ◦ C, 1100 ◦ C, 1200 ◦ C and 1300 ◦ C. After holding
for 120 min, the corundum crucibles were cooled down spontaneously
2
Fuel 332 (2023) 126240
and taken out from the muffle furnace.
The OS and CFA were mixed and treated at the designated temper­
atures to investigate the effect of CFA addition. First, the CFA samples,
with weight percentages of 10 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt
%, were mixed thoroughly with OS by a ball crusher, and named as OS1,
OS2, OS3, OS4 and OS5, respectively. These samples were put in a
muffle furnace and heated at the designated temperatures for 120 min,
then cooled down as the experiments mentioned above. The mixed
samples after thermal treatment were collected in sealed containers and
used as experimental samples for further characterization.
2.3. Sample characterization
Compared to OS and CFA, a TG analyzer (SDT Q600, TA, USA) was
used to investigate the effect of mixing CFA on the thermal behavior of
OS. Approximately 10 mg of sample was measured at a flow rate of 100
ml/min, and the temperature was controlled from 10 ◦ C to 1200 ◦ C at a
heating rate of 20 ◦ C/min. The chemical compositions of OS and CFA
were analyzed using an X-ray fluorescence spectrometer (XRF-3600 W,
PANalytical Axios). The ash melting point test of the mixed samples was
conducted by a microcomputer intelligent ash melting point tester
(TJHR-6000, Hebei, China) with a heating rate of 5 ℃/ min.
X-ray diffractometer detection (XRD; Rigaku SmartLab, Japan) was
used to study the crystal phases transformation of OS and the mixed
samples after thermal treatment (Cu Kα, scanning speed: 6◦ min− 1,
scanning range: 10–90◦ ), and MDI Jade 6.0 was used to identify and
quantify the mineral species. Micromorphology was observed by a
scanning electron microscope (SEM, JSM-7610F, Japan). The functional
groups were determined by Fourier transform infrared spectroscopy
(FTIR, VERTEX80V, BRUKER, Germany) in the range of 400–4000
cm− 1, and the samples were mingled with KBr on a dry basis, then
prepared using the pressed-flaking methods and evaluated the change of
functional groups. Besides, a method revised from US EPA SW-846
1311-TCLP was selected to investigate the leaching behavior of heavy
metals, and the concentrations of heavy metals were quantified by
inductively coupled plasma optical emission spectrometry (ICP) (iCAP
7000, Thermo Fisher, USA).
3. Results and discussion
3.1. Raw material characteristics
3.1.1. Compositions and crystal phases
The chemical compositions of OS and CFA are presented in Table 1.
The results showed that the main compositions of OS were CaO (35.50
wt%) and SiO2 (21.53 wt%). Compared to CFA, the OS contained higher
levels of alkali and alkaline earth metals (K2O + Na2O + CaO + MgO),
which accounted for more than 46 wt%. The significant compositions of
CFA were SiO2 (51.50 wt%) and Al2O3 (37.30 wt%), which were about
88 wt% of the total mass.
The microscopic morphologies of OS and CFA are shown in the
Fig. S1. The microstructure of the raw materials showed that the particle
size was approximately 10–70 μm, and the two materials presented high
uniformity. It was observed that the OS particles presented dense
microstructure with each other, and exhibited a large degree of
agglomeration properties. Compared to the connected floccule of OS,
most of CFA particles were more regular spheroids. In addition, there
were some irregularly shaped fragments in the particles, and the irreg­
ular fragments were mainly due to the unburned carbon, anhydrous
material, and calcite [1]. The CFA had larger voids between particles
and smoother surfaces without any obvious sintering compared to OS,
which may be related to the difference in the fusion characteristics and
the crystal phases composition of the two materials. The morphological
variation of OS during thermal treatment at 800–1300 ◦ C is shown in
Fig. S2. It can be observed that OS at 800 ◦ C to 1100 ◦ C was still in
powder form, while OS formed a solid state when the heating
X. Zhang et al.
Table 1
The chemical compositions of OS and CFA.
Sample Compositions (wt.%)
SiO2 Al2O3 CaO Fe2O3
Oily sludge 21.53 7.85 35.50 8.43
Coal fly ash 51.50 37.30 2.25 3.73
temperature was 1200 ◦ C. The state of the OS changed significantly
between 1100 ◦ C and 1200 ◦ C. The results suggested that the melting
solidification of OS appeared in this temperature stages.
In addition, the XRD patterns of OS during thermal treatment were
analyzed and shown in Fig. 1. It can be found that the crystal phases at
800 ◦ C and 900 ◦ C were gehlenite (Ca2Al2SiO7, PDF#73–2041), barite
(BaSO4, PDF#72–1378), quartz low (SiO2, PDF#85–0335) and potas­
sium iron oxide (K3FeO2, PDF#48–0957). The diffraction peaks of SiO2
and K3FeO2 disappeared, but more Ca2Al2SiO7 was generated at
1000 ◦ C. However, the main crystal phase of the OS treated at 1100 ◦ C
changed to quartz (SiO2, PDF#85–0798). It can be assumed that the
transformation of Ca2Al2SiO7 to SiO2 and Al2SiO5 occurred at 1100 ◦ C.
But when the temperature was 1200 ◦ C, a new akermanite-gehlenite,
syn. [Ca2(Mg0.5Al0.5)(Si1.5Al0.5O7), PDF#79–2423] was generated.
This synthetic phase presented higher diffraction peak at 1300 ◦ C. The
results indicated that the main crystal phase changes at 1100 ◦ C and
1200 ◦ C, which was from Gehlenite to Quartz and Akermanite-gehlenite,
syn, respectively.
3.1.2. Thermal characterization analysis
The TG and DTG curves of OS, CFA and OS5 during the process were
examined and the results are presented in Fig. 2(a). Compared to OS, the
TG and DTG curves of CFA exhibited unsignificant changes, which
indicated that CFA was an inert material during the temperature range.
The mass losses of OS and OS5 were below 3 wt% in the temperature
range of 10 ◦ C to 180 ◦ C, and this could be attributed to the removal of
residual water. The thermal treatment process of OS could be divided
into three separate stages: the first stage extended from 180 ◦ C to 556 ◦ C
with a mass loss of 27.75 wt%; the second stage extended from 556 ◦ C to
811 ◦ C with a mass loss of 10.3 wt%; and the third stage extended from
811 ◦ C to 1139 ◦ C with a mass loss of 4.58 wt%. Corresponding with OS,
the TG/DTG curves of OS5 could also be divided into three individual
Fig. 1. The XRD analysis of OS after thermal treatment at different tempera­
tures. [1 Gehlenite-Ca2Al2SiO7; 2 Barite-BaSO4; 3 Quartz low-SiO2; 4 Quartz
-SiO2 5 Akermanite-gehlenite, syn.-Ca2(Mg0.5Al0.5)(Si1.5Al0.5O7); 6 Potassium
iron oxide-K3FeO2; 7 Kyanite-Al2SiO5].
3
Fuel 332 (2023) 126240
TiO2 SO3 Na2O MgO K2 O other
0.69 5.20 5.05 2.68 3.46 3.49
1.52 0.66 0.16 0.16 1.29 0.40
stages: 180–556 ◦ C, 556–804 ◦ C and 804–1084 ◦ C. The mass losses of
OS5 in the three stages were 17.81 wt%, 5.56 wt% and 1.72 wt%,
respectively.
According to the reported literatures, the weight loss in the first stage
was due to the decomposition of organic matter and the devolatilization
of some volatile fractions; the weight loss in the second stage was
resulted from the devolatilization of the remaining volatile fractions and
the secondary cracking of the residual products; the weight loss in the
last stage was mainly attributed to the decomposition of inorganic
minerals [20]. The results suggested that the addition of CFA changed
the thermal characteristics of OS. Compared with the residue mass of
OS, the residue mass of OS5 decreased to 71.79 wt%, which was 18.07
wt% higher than that of OS.
To further clarify the interaction between the mixed sample, theo­
retical TG curve was assumed according to the TG curves of OS and CFA,
and the difference between the experimental and theoretical TG was
defined as ΔW and calculated according to Eq. (1). The evolution of ΔW
is shown in Fig. 2(b). When ΔW < 0, the experimental value was less
than the calculated value, indicating that there was a synergistic effect
between OS and CFA.
ΔW = TGOS5 − (0.5 × TGOS + 0.5 × TGCFA ) (1)
At temperature range of 20 C to 1200 C, negative ΔW values of
◦ ◦
0.01–4.71 % were obtained, which indicated that the CFA addition had a
certain synergistic effect on the decomposition of organic components
and the devolatilization of volatile matters in OS. ΔW was less than − 1%
before 310 ◦ C, because at this temperature there was no interaction
obviously between OS and CFA, and the difference might be due to the
different initial weight of sample and thermal conductive conditions
[21]. For OS5, ΔW was below − 2.0 % at the temperatures higher than
400 ◦ C, which indicated that the synergistic effect during thermal
treatment occurred mainly in the high temperature region. This could be
due to the higher proportions of SiO2 and Al2O3 in CFA, which were
often used as catalyst skeletons [22]. The above analysis revealed that
co-treatment of OS and CFA was not a simple superposition, but the
interaction of OS and CFA promoted the reaction during thermal
treatment.
3.2. Co-treatment characterization of OS and CFA
3.2.1. Ash fusion temperatures (AFTs)
The AFTs tests were conducted for the mixed samples of OS and CFA
by an ash melting point testing apparatus, according to GB/T 219–2008.
Four characteristic temperatures were recorded as initial deformation
temperature (DT), softening temperature (ST), hemispherical tempera­
ture (HT) and flow temperature (FT), depending on the specific shape of
the ash cone [23]. These four temperatures characterized the melting
behavior of the prepared sample. All test experiments were in triplicate
to ensure reproducibility. The effects of CFA addition on the charac­
teristic temperatures of samples are shown in Fig. 3.
The four characteristic temperatures DT, ST, HT and FT of OS were
1140 ◦ C, 1250 ◦ C, 1260 ◦ C and 1280 ◦ C, respectively, and for CFA, the
four temperatures were 1290 ◦ C, 1340 ◦ C, 1380 ◦ C, and 1430 ◦ C,
respectively. The AFTs of CFA were significantly higher than those of
OS. For CFA, larger temperature intervals from 1290 to 1430 ◦ C were
identified between DT and FT. This indicated that CFA was rich in high
fusion temperature substances, which could not be melt until a certain
X. Zhang et al.
Fig. 2. (a) TG and DTG curves during thermal treatment of OS, CFA and OS5; (b) theoretical difference ΔW curves of OS5.
Fig. 3. Effects of CFA addition on the characteristic temperatures of samples.
high temperature and support the skeleton of cubic ash sample in the
AFTs test. The ash fusion temperature ranges for OS were extended as
the CFA percentage increased and then reduced. The results indicated
that OS had the higher melting and slagging propensity than CFA ac­
cording to the AFTs tests. The dotted lines in Fig. 3 represented the
theoretical melting point lines for each of the four characteristic tem­
peratures. Based on the mixing ratios of OS1, OS2, OS3, OS4 and OS5,
the theoretical lines were calculated according to the corresponding
characteristic temperatures of OS and CFA. The experimental ST, HT, FT
of the mixed samples were lower than the theoretical melting point, the
experimental DT was lower than the theoretical value when the CFA
addition was <40 wt%. The mixtures exhibited lower AFTs observably.
This might be due to the rich SiO2 and Al2O3 in CFA, which were prone
to react with compounds (e.g., CaO, Na2O, and MgO) in OS to form low-
melting-temperature eutectics and greatly reduce the ash fusion tem­
peratures [13]. The results suggested that thermal co-treatment of OS
with CFA required lower temperature for melting, which was beneficial
for energy reduction. As the addition of CFA into OS increased from 10
to 50 wt%, the DT, ST, HT and FT of the mixed samples gradually
increased. However, the DT and FT of OS4 were slightly higher than
those of OS, and the AFTs of OS5 were higher than that of OS, which
might be ascribed to the formation of several refractory aluminosilicate.
In addition, the chemical compositions of mixed samples after
thermal treatment were analyzed by XRF, and the results are shown in
Table S1 and Table S2. It was noticed that the chemical compositions
4
Fuel 332 (2023) 126240
both contained the acidic oxides (SiO2 and Al2O3) and alkaline oxides
(CaO and Fe2O3). As the adding percentage of CFA in OS increased from
10 to 50 wt%, the SiO2 or Al2O3 content in the mixed samples increased
linearly, and the CaO content gradually decreased. The acidic oxides
could upgrade the ash fusion temperature of materials, but the alkaline
oxides could reduce this temperatures [24]. This also explained the
gradual higher AFTs of mixed samples with the increase of CFA addition.
3.2.2. Influences of CFA addition on mineral phases
According to the AFT variation trend and XRD analysis, 1100 ◦ C and
1200 ◦ C were selected as the two special temperatures for the subse­
quent thermal treatment. In order to investigate the mineral phases
transformation of OS after co-treatment with CFA, the OS1, OS2, OS3,
OS4 and OS5 after heating at 1100 ◦ C and melting at 1200 ◦ C were
characterized by XRD. The analytical results are shown in Fig. 4. It can
be seen that the crystal phases at two temperatures changed gradually as
the addition of CFA increased. Compared to OS, crystals interactions
during this process changed the type and content of crystal phases. Be­
sides, the proportions of different minerals were calculated by the RIR
method based on the XRD results, as shown in Fig. 5. The mixed samples
after heating at 1100 ◦ C were named as OS1-1100, OS2-1100, OS3-
1100, OS4-1100 and OS5-1100, and the mixed samples after melting
at 1200 ◦ C were named OS1-1200, OS2-1200, OS3-1200, OS4-1200 and
OS5-1200.
The crystal minerals in samples after co-treatment were composed of
gehlenite (Ca2Al2SiO7), PDF#99-0054), quartz (SiO2, PDF#99-0088),
orthoclase (KAlSi3O8, PDF#99-0085), anorthite (CaAl2Si2O8, PDF#99-
0012), and diopside (CaMgSi2O6, PDF#99-0045). It was noticed that
the main crystal phase was gehlenite, but more anorthite appeared
based on the gehlenite at OS4 and OS5. Furthermore, Fig. 5 showed that
the proportion of amorphous matter significantly decreased and the
mineral contents increased as the CFA added. The ash fusion tempera­
ture generally increased with increasing mineral content and decreasing
amorphous matter content [15]. This might also explain why the char­
acteristic temperatures of the mixtures increased with CFA addition in
the AFTs test.
As shown in Fig. 4 (a), the CFA addition enhanced the diffraction
peak of Ca2Al2SiO7, which achieved the highest proportion (95.4 wt%)
at OS2. Some SiO2 was contained in OS1 and OS2, then transformed to
KAlSi3O8 until it disappeared in OS4. The new diffraction peaks of
CaAl2Si2O8 and CaMgSi2O6 were generated when CFA reached 30 wt%.
However, the CaAl2Si2O8 gradually reached the highest content (69.7 wt
%) when CFA reached 50 wt% and became the main crystal phase. With
regards to Fig. 4 (b), as the CFA mass ratio increased, the diffraction
peak of Ca2Al2SiO7 was exactly opposite to 1100 ◦ C, which was weak­
ened first and then enhanced (97.8 wt% in OS1 and 18.6 wt% in OS4).
Besides, the crystal phase of SiO2 was not detected because it
X. Zhang et al.
Fig. 4. XRD analysis of the mixed samples after thermal treatment at (a)
1100 ◦ C and (b) 1200 ◦ C. [1 Gehlenite-Ca2Al2SiO7; 2 Quartz-SiO2; 3 Orthoclase-
KAlSi3O8; 4 Anorthite-CaAl2Si2O8; 5 Diopside-CaMgSi2O6].
transformed into Ca2Al2SiO7 at 1200 ◦ C. When the CFA addition was 40
wt%, the peaks of CaMgSi2O6 appeared. And when CFA was added from
30 wt% to 50 wt%, the high CaAl2Si2O8 contents gradually formed
(62.7 wt% in OS5). The reaction equations of this process were pre­
sented in Eq. (2)-Eq. (7) [25,26].
Al2O3(s) + 2CaO(s) + SiO2(s)→Ca2Al2SiO7(s)
KCl(g) + SiO2(s) + Al2O3(s) + H2O(g)→KAlSiO4(s) + HCl(g)
KAlSiO4(s) + SiO2(s)→KAlSi2O6(s)
KAlSi2O6(s) + SiO2(s)→KAlSi3O8(s)
2SiO2(s) + Al2O3(s) + CaO(s)→CaAl2Si2O8(s)
CaO(s) + MgO(s) + 2SiO2(s)→CaMgSi2O6(s)
When the CFA was added during OS melting, the Al and Si contents
in the mixed samples considerably increased, which resulted in more
silica-aluminate crystal phases generated. Compared to the main crystal
phase in OS alone thermal treatment (the melting point of quartz is
Fuel 332 (2023) 126240
Fig. 5. Mineralogical proportion of mixed samples after thermal treatment.
(Amorphous matter: Includes all amorphous substances except the crys­
tal phases).
1750 ◦ C), the main crystal phase of cotreated mixtures has a relatively
low melting point (the melting point of gehlenite is1450 ◦ C). Further­
more, KAlSi3O8 formed during the process was alkaline metal com­
pound, and this improved K-fixation in samples [27]. Mahadevan et al.
also found that such alkaline earth metals helped to promote the
decomposition of the polymer structure, influenced the slagging tem­
perature, and changed the agglomeration of the particles [28]. The
weakened Ca2Al2SiO7 indicated the decomposition reaction occurred
during the process. When the CFA addition was 40 wt% and 50 wt%, the
Ca2Al2SiO7 transformed into more CaAl2Si2O8 (melting point: 1550 ◦ C),
and the increases in Si and Al resulted in the appearances of high-
melting-point minerals, which led to the relatively high AFTs of OS4
and OS5.
3.2.3. Effects of CFA addition on microscopic morphology of OS melting
In order to observe the changes of microstructures, the SEM analysis
of the mixed samples after thermal treatment were carried out, and the
images are shown in Fig. 6. It was observed that the CFA addition had
significant effects on the microcosmic structures. The OS after thermal
treatment showed the properties of relatively compact microstructure
and a great degree of agglomerate, which might be caused by the min­
eral matters produced by alkali metals [29]. In contrast to the samples
melted at 1200 ◦ C, the microstructure of mixtures was looser and less
sintered than that formed at 1100 ◦ C. This might be due to the adequate
(2) formation of melting solidification at 1200 ◦ C, and some molten mate­
rial had not yet reacted at 1100 ◦ C. As shown in Fig. 6, with the increase
(3) of CFA addition in the mixed samples, the relevant gaps between the
structure gradually enlarged, and the compact structures were also
(4) gradually loose. The variation became apparent when the CFA reached
40 wt% at 1200 ◦ C. It was noted that the addition of CFA had distinctly
(5) positive impacts on reducing the slagging tendency of OS, which might
be attributed to the production of CaAl2Si2O8 and CaMgSi2O6 with high
(6)
melting points.
(7)
3.2.4. FTIR analysis
The FTIR spectra of OS and mixed samples after thermal treatment
are shown in Fig. 7. The functional group distribution of OS had changed
after co-treatment with CFA. These differences were not only related to
the variations of peaks, but also reflected in the weakening and
5
X. Zhang et al. Fuel 332 (2023) 126240

Fig. 6. Microscopic morphology of OS and mixtures after thermal treatment at (a) 1100 ◦ C and (b) 1200 ◦ C.

(a) 732 1460 (b) 1460

OS5 OS5
1031 937 1031
536 536

OS4 OS4
Absorbance

OS3
Absorbance

OS3

OS2 OS2

OS1 OS1
2852 3695 2852 2923 3695
2923 3643
3643 OS
OS

500 1000 1500 2000 2500 3000 3500 4000 500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1) Wavenumbers (cm-1)

Fig. 7. FTIR spectra of OS and mixed samples after thermal treatment at (a) 1100 ◦ C and (b) 1200 ◦ C.

enhancement of absorption intensity. The FTIR spectra were analyzed (2800–3000 cm− 1) [31], C–– C in the aromatic ring (1460–1600 cm− 1)
referring to the relevant literature, and the relationship between the [32], -C–O–R (1030–1160 cm− 1) [33] and aromatic C–H (700–900
spectral band of FTIR and characteristic groups were as follows: –OH cm− 1) [34].
and -N–H (3200–3600 cm− 1) [30], –CHn in the aliphatic group It can be seen from the vibration trends of OS in Fig. 7, due to the

6
X. Zhang et al. Fuel 332 (2023) 126240

presence of absorbed water in minerals, the latter vibratory band of OS solidification of OS with CFA. The reason for the low leachability might
was accompanied by two weaker bands at around 3643 cm− 1 and 3695 be that a great quantity of volatile heavy metals were emitted at high
cm− 1 [35]. These two peaks were corresponding to stretching vibration melting temperatures, or the heavy metal ions were replaced with other
of –OH or -N–H in the amine and amide groups, which indicated the ions, such as Si2+ and Al3+ ions, and strongly bonded in the coexisting
presence of phenols, alcohols, water and carboxylic in the OS [30]. structure of crystal phases and dense matrix [41]. With the increase of
Peaks at 2923 cm− 1 and 2852 cm− 1 were caused by aliphatic groups CFA addition, leaching concentrations of heavy metals gradually
such as –CH2, –CH3, together with C–H deformations, indicating the decreased. The study suggested that the large amount of aluminate and
presence of alkanes and alkenes in the OS [36]. The absorption peak silicate in the samples could improve the solidification rate of heavy
centered at 1460 cm− 1 corresponds to the stable C– – C function group. metals [42], and the high contents of Si/Al-compounds in CFA could
The peak at 1031 cm− 1 was the -C–O–R stretching vibration, which promote the stabilization of heavy metals through the formation of
might be attributed to the existence of silicate and minerals in the OS aluminosilicates during the thermal treatment [43], such as Ca2Al2SiO7
[37,38]. Some of the peaks under 1000 cm− 1 were related to the rocking and CaAl2Si2O8. Moreover, the high strength structure formed by Ca-
vibration of aromatic C–H. bearing minerals or aluminosilicates could stabilize the heavy metals
In comparison with OS, the spectra peaks of 2852, 2923, 3643 and by means of ion exchange, migration, and filling [44]. For the melted
3695 cm− 1 in the mixed samples disappeared completely. It might be products, the leaching concentrations of all six heavy metals were lower
attributed to the decomposition of organic compounds and inorganic than the corresponding standard limits. It revealed that the CFA effec­
compounds during the thermal co-treatment, which also indicated the tively helped to immobilize the heavy metals of OS during melting.
reduction of hydroxyl groups of alcohols, phenols, and organic acids Therefore, melting solidification of OS with CFA could be confirmed as a
after melting of OS with CFA [39]. Furthermore, the peaks at 1460 cm− 1 safe way to the environment.
decreased significantly with the CFA addition from 0 wt% to 50 wt% at In addition, according to the potential ecological risk index (RI)
two heating temperatures, which was attributed to the decrease of C– –C introduced by Hakanson, the RI of individual heavy metal (Er) were
− 1
of the aromatic ring [32]. On the contrary, the peaks of 732 cm at introduced to assess the ecological risk of heavy metal contamination in
1100 ◦ C and the peaks of 937 cm− 1 at 1200 ◦ C increased due to the C–H the samples. The indexes of RI and Er were evaluated by Eq. (8).
bonds in aromatics. The absorption of C– – C and –C–O–R gradually
∑ ∑ Ci
decreased with the increase of CFA, while the C–H bond in the aromatic RI = Er = Tr (8)
Cn
ring plane increased. It indicated that the aromatization reaction might
occurred in the co-melted samples at high temperature. These results where, Ci is the concentration of heavy metals in samples; Cn is the
showed that the CFA addition changed the functional group composi­ reference value for metals; and Tr is the toxic factor of individual heavy
tions of OS and the interaction between functional groups occurred metal, which gives values of Pb and Cu (5), Cr (2), Ni (6), Cd (30), and As
during the thermal co-treatment. (10) [45].
The calculated values of Er and RI, together with their indices and
grades, are shown in Fig. 8. The results indicated that the OS exhibited
3.3. TCLP and ecological risk assessment the highest level of heavy metal contamination. All trace heavy metals
posed a low potential ecological risk (Er < 40) except for the OS.
Metals were enriched during the thermal treatment of oily sludge However, the value of Er for Cd in OS was higher than 320, presenting a
and the toxicity of heavy metals was a critical issue. So, the leaching high metal contamination of Cd. And the comprehensive potential
behaviors of heavy metals (Pb, Cr, Cu, Ni, Cd, and As) in the OS, CFA and ecological index of OS was 778.27, other samples were in the range of
mixed samples melting at 1200 ◦ C was discussed. The toxicity was 0.512–35.596 (RI <150). The results indicated that melting solidifica­
examined by comparing the leaching contents of heavy metals in the tion of OS with CFA was efficient in terms of the low grades of ecological
samples, and the ecological risk assessment was conducted. risk from heavy metals.
The results of the leaching concentrations in samples are listed in
Table 2 and compared with the standard limits in GB 5085.3-2007 4. Conclusions
“Identification standards for hazardous wastes-Identification for
extraction toxicity” [40]. It could be found that the leaching concen­ The components of CFA and OS were complementary, and the
trations of the heavy metals in the OS could be ranked in the order Cu > negative ΔW indicated a synergistic impact of CFA on the thermal
Pb > As > Ni > Cd > Cr. And comparing the detected leaching con­ characteristics of OS. Mixtures of OS and CFA presented lower AFTs, and
centration, the heavy metals in the CFA were lower. However, compared the reason might be that the SiO2 and Al2O3 in CFA reacted with CaO in
to OS, the leaching concentrations of heavy metals were significantly OS to form low-melting-temperature eutectics — Ca2Al2SiO7. But the
reduced after the melting treatment of OS with CFA, and the decreased AFTs of mixed samples increased with the addition of CFA from 10 wt%
values ranged from 13.22 to 76.70 mg/L, which indicated the modifi­ to 50 wt%, and this was related with these acidic oxides, e.g., SiO2 and
cation on leaching behaviors of heavy metals due to the melting Al2O3, which could upgrade the ash fusion temperatures. With more
CaAl2Si2O8 formed, the OS4 and OS5 samples presented higher AFTs. As
Table 2 the increase of CFA, the main crystal phase of co-treated samples
Leaching concentrations of heavy metals from OS, CFA and the mixed samples changed from gehlenite to anorthite, and the proportion of amorphous
(mg/L). matter decreased. The microstructure in the co-treated mixtures became
Sample Temp. Pb Cr Cu Ni Cd As loose by the generation of high-melting-point minerals. In addition, as
(◦ C) heavy metals were stabilized in a dense substrate, compared to OS and
OS 25 53.09 14.75 77.66 22.30 20.39 40.38 CFA, the leaching concentrations (Pb, Cr, Cu, Ni, Cd, and As) of the
CFA 25 4.40 1.23 4.61 ND 0.51 7.73 samples after melting were much lower than the standards for hazardous
OS1-1200 1200 3.67 8.70 7.09 ND 0.81 0.33 wastes in China. And the leaching concentrations of heavy metals were
OS2-1200 1200 3.07 7.28 5.38 ND 0.72 0.32
proportionally decreased with CFA addition due to the formation of
OS3-1200 1200 ND 3.38 5.06 ND 0.61 ND
OS4-1200 1200 ND 1.95 5.04 ND ND ND
silica-aluminates. The melting solidification of OS with CFA could pro­
OS5-1200 1200 ND 1.53 0.91 ND ND ND mote stabilization of heavy metals with low ecological risk.
GB 5085.3- <5 <15 <100 <5 <1 <5
2007

ND: Not detected.

7
X. Zhang et al.
Fig. 8. The calculated values of Er and RI of OS, CFA and their co-
melting products.
CRediT authorship contribution statement
Xinyue Zhang: Formal analysis, Investigation, Writing – original
draft. Jiao Ma: Conceptualization, Formal analysis, Writing – original
draft. Lina Liu: Writing – review & editing, Supervision. Boxiong Shen:
Funding acquisition, Supervision. Zhichuan Li: Formal analysis,
Investigation. Zhikun Zhang: Conceptualization, Formal analysis,
Funding acquisition, Investigation, Supervision, Writing – review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
We gratefully acknowledge the funding for this research provided by
National Natural Science Foundation of China (No. 22176048), Natural
Science Foundation of Hebei Province of China (No. E2021202030),
Funding Projects for the Introduction of Overseas Scholars in Hebei
Province (No. C20210332), the Science and Technology Project of
8
Fuel 332 (2023) 126240
Tianjin, China (No. 21YDTPJC00820), and Innovative Group Projects in
Hebei Province (No. E2021202006).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2022.126240.
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