Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297

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Journal of Analytical and Applied Pyrolysis

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

Production of oil with potential energetic use by catalytic co-pyrolysis

of oil sludge from offshore petroleum industry
D.C. Silva, A.A. Silva, C.F. Melo, M.R.C. Marques ∗
Chemistry Institute, State University of Rio de Janeiro (UERJ), Rio de Janeiro, RJ, 20550-900, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Oil sludge from offshore petroleum industry in Brazil was pyrolyzed to produce oil with potential ener-
Received 1 September 2016 ®
getic use. It was studied the effect of the temperature and the addition of an acid catalyst (K-10 clay) and
Received in revised form 18 January 2017
polyethylene (PE) wastes on the production of pyrolytic oil. The quality of the pyrolytic oil was evaluated
Accepted 19 January 2017
Available online 22 January 2017
based on the hydrocarbon composition determined by NMR and GC–MS analysis. Increasing the temper-
ature from 450 to 500 ◦ C, the yield of pyrolytic oil and gases was increased by 15% while the residues
decreased by 50%. The production of gas at 450 ◦ C was increased by 50% when K-10 clay (5 or 10% w/w)
Keywords:
Offshore oil sludge waste plastics was added. GC–MS analysis showed that thermal and catalytic pyrolysis is able to convert the oil sludge
Co-pyrolysis into a pyrolytic oil with a light hydrocarbon content higher than 95%. Hydrocarbon-type analysis showed
K-10 Clay that both thermal and catalytic pyrolysis produced pyrolytic oil with high paraffin content (higher than
Chemical characterization 80% v/v) and low aromatics and olefins (lower than 10% of each). The addition of PE wastes to the oil
Diesel fraction sludge decreased the oil production. The pyrolytic oil from the thermal pyrolysis of oil sludge with HDPE
(5% w/w) was mainly composed of light hydrocarbons while that using LDPE was composed of 64% heavy
hydrocarbons. Catalytic pyrolysis produced an oil fraction with (i) a higher content of light hydrocar-
bons than the pyrolytic oil from thermal pyrolysis and (ii) a low content of aromatics and olefins. The
mean calorific value (44.1 MJ/kg) of these pyrolytic oils was similar to the default caloric value for diesel
(43.7 MJ/kg). That result demonstrates that the thermal and catalytic pyrolysis can be potentially used to
convert the mixture PE wastes and oil sludge into a diesel fraction oil.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction Environmental agencies are increasingly concerned about the

potential adverse impacts of wastes from petroleum industry
In recent years, the management of solid wastes from petroleum wastes [4]. However, those wastes are a potential energy source
industry has become an important environmental issue. According due to the high contents of carbon and hydrogen. For this purpose,
to the latest data released by Brazilian National Waste Plan, in 2010, pyrolysis is technology that can be used for the conversion of oil
the sector of exploration and production of oil and gas generated sludge into greener and cost effective fuels [5–8]. Several studies
approximately 51,000 tons per year of hazardous solid waste. Those have proven that pyrolysis is one of the most promising options for
residues can cause serious damages to the environment if they are the treatment of solid wastes. That technology can reduce signifi-
improperly handled, treated, transported or disposed [1]. cantly the volume of waste and can be used for the input production
Oil sludge and plastic waste contaminated with chemicals are to the petrochemical industry [9–16].
the most studied wastes from petroleum industry are they are The pyrolysis treatment converts solid wastes into three main
very they are produced in large quantities [2]. The processes of products (i) the pyrolytic oil (liquid fraction), (ii) char (solid frac-
exploration, refining, transportation, storage and the wastewater tion) and (iii) gas fraction. All those fractions can be reused in
treatment in those refineries generate the oil sludge [3]. Plastic con- the oil industry or used as raw material in the chemical industry
tainers from that industry are also a waste of concern, since they can [6,17–21]. There is plenty of studies dealing with the conversion of
be contaminated by oil, including metals and heavy polycyclic aro- plastic waste into fuels by pyrolysis. Sharma et al. [22] character-
matic hydrocarbons (PAHs), which are known to be carcinogenic. ized the pyrolytic oil produced from the pyrolysis of low and high
density polyethylene (LDPE and HDPE) wastes. It was observed the
presence of light hydrocarbons fraction in the liquid fraction [22].
∗ Corresponding author. Co-pyrolysis of plastic wastes with mineral oil, such as oil shale
E-mail address: [email protected] (M.R.C. Marques). [23], coal [24] and heavy gas oil [25] changes the degradation

http://dx.doi.org/10.1016/j.jaap.2017.01.021
0165-2370/© 2017 Elsevier B.V. All rights reserved.
 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297 291

mechanisms and has influence on the chemical composition of the Table 1

Experimental conditions used in the thermal and catalytic pyrolysis of sludge oil
pyrolytic oil. It has been suggested that the pyrolysis of the mix-
with or without PE wastes a .
ture of plastic wastes and fossil results in an increased production
of pyrolytic oil compared to those obtained from wastes pyrolyzed Run PE type PE content (% w/w) K-10 content (% w/w)
separately. That synergistic effect can be due to the high hydrogen 1 0 0
content of plastic waste, which favors the oil cracking. On the other 2 0 5
hand, the mineral oil can provide good solvency for the straight 3 0 10
4 LDPE 5 0
chain thermoplastics [26]. In a study of our group, the co-pyrolysis
5 LDPE 10 0
of heavy gas oil with HDPE waste was studied. The pyrolytic oil 6 LDPE 30 0
showed a yield of 94%, and distillation characteristics very similar 7 HDPE 5 0
to those of the diesel fuel. Lam et al. [27] studied the co-pyrolysis 8 HDPE 10 0
9 HDPE 30 0
of scrap tires with oil waste [27]. The authors reported that the oil
10 LDPE 5 5
waste did not affect the product distribution from the pyrolysis of 11 LDPE 10 5
tires, but the fuel properties of the pyrolytic oil were improved. 12 LDPE 10 10
Pyrolysis is the thermal cracking of the plastic waste to give 13 LDPE 30 5
low molecular weight compounds. It is attractive but unfortunately 14 LDPE 30 10
15 HDPE 5 5
gives a very broad range of products and requires high temperature.
16 HDPE 5 10
Catalytic pyrolysis has some advantages over the thermal pyroly- 17 HDPE 10 10
sis, since the latter demands higher temperatures and its products 18 HDPE 30 5
require further processing to improve their quality to fuel [28]. 19 HDPE 30 10
Miskolczi and Ates [29] evaluated the use different zeolites a
Each run was carried at 450 and 500 ◦ C.
in the co-pyrolysis of recovered heavy oil and municipal plastic
wastes, which was carried out in stirred batch reactor, at 500 ◦ C
[29]. The addition of catalyst and the reuse of heavy oils increased catalyst can increase the amount of pyrolytic oil, since it has a good
the fractions oil and gas compared with the pyrolysis of only pore-size distribution and many weak acid sites [30]. Before being
®
municipal plastic wastes. Both pyrolysis oil and heavy oil con- used as catalyst, the K-10 clay was activated by heating at 300 ◦ C
tained paraffin, olefins, aromatics and cyclic compounds, while for 2 h.
the heavy oil had predominantly heavy hydrocarbons. Based on
GC–MS analyses, the hydrocarbon composition of the pyrolysis oils
2.2. Experimental apparatus and procedure
was significantly affected by both the waste plastic/heavy oil ratio
and catalyst concentration. Low waste plastic/heavy oil ratio and
The pyrolysis experiments were carried out using the
selected catalyst increased efficiently the light hydrocarbon con-
experimental apparatus described by Joppert et al. [25]. The
tent.
stainless-steel tubular reactor was fitted with a condenser and a
Although the co-pyrolysis of coal or oil shale with waste plastic
glass vase collector. The reactor was heated by an electrical vertical
has been extensively studied, to the best of our knowledge, there is
furnace and operated in a fixed bed mode. During the pyrolysis, the
no study related to pyrolysis of oil sludge from offshore heavy-oil
liquid fuel was collected by the condenser in an ice bath. Thermo-
field in Brazil. About 75% of the oil produced in Brazil comes from
couples were placed at different points (bottom, middle and top)
the Campos Basin, located in the North of the State of Rio de Janeiro.
along the heating block to ensure a homogeneous temperature in
In the process of crude oil extraction, it is generated above 100
the reactor.
ton/month of oil sludge. This waste comes from the separation of
The reactor was initially loaded with oil sludge (2.000 g) with or
raw oil solid and liquid impurities in offshore production platforms. ®
without PE wastes (5 and 10 or 30%) and K-10 catalyst, following
Most of them have been disposed in landfills or stocked in tanks.
the experimental design described in Table 1.
The aim of this study is to convert offshore oil sludge from Brazil-
Initially, the reaction mixture in the reactor was purged with
ian petroleum industry into a product with potential energetic use
nitrogen (30 mL min −1 for 10 min) to avoid unwanted oxidation
by pyrolysis treatment. For this purpose, it was evaluated the effect
of the sample. Then, it was heated for 15 min under nitrogen
of the experimental conditions (temperature and the addition of
flow. After pyrolysis, it was allowed to reach room temperature.
catalyst and PE wastes) to produce a pyrolytic oil with similar
Thereafter, residues and pyrolytic oil fractions were determined by
chemical composition and calorific value of diesel fuel.
weight and the gas fraction was calculated by weight difference.
The residues fraction from thermal and catalytic pyrolysis is
composed of very heavy waxes and coke-coated catalyst, respec-
2. Experimental
tively. However, the study of the solid and gases fractions is beyond
the scope of this work. The reproducibility of the experiments
2.1. Materials
is acceptable, and the experimental data presented in this paper,
corresponding to the different operating conditions, are the mean
The oil sludge used in this study was sampled from the crude oil
values of runs carried out three times. Significance was tested with
storage tanks of an offshore platform located in the Campos Basin
a 95% confidence interval.
(Rio de Janeiro State, Brazil). High-density polyethylene (HDPE) and
low-density polyethylene (LDPE) wastes collected from the same
platform were first cut into small pieces (1–2 mm) and then used 2.3. Characterization
in the co-pyrolysis experiments.
®
Montmorillonite K-10 (Sigma-Aldrich Co.) is a commercial acid The CHNS analyses of oil sludge were performed, in triplicate,
®
activated clay, which has been used as a solid Bronsted acid. K-10 on a CHNS analyzer (Elementar, Vario ELIII). Considering that the
clay contains a high silica/aluminum ratio (Si/Al = 6.0) and a small oxygen content cannot be determined by any suitable method,
concentration (7%) of metal oxides, such as MgO, CaO, K2 O and TiO2 . its estimation was carried out by subtracting the sum of other
That clay is a mesoporous material (pores 55 Å diameter), which constituents from 100.00: %C = 78.16; %H = 11.62; %N = 0.64 and
has high external surface area (254 m2 /g). The use of K-10 clay as %O = 7.71.
292 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297

of 2924–2854 cm−1 and 1462–1373 cm−1 that is representative

of the CH2 and CH3 vibrations. No O H stretching vibration was
observed in the region of 3500–3100 cm−1 , which suggests there
is no carboxylic groups or water in the sample. The low intensity
bands at 1709 (C O stretching of carbonyl) suggests the presence
of very low levels of carbonyl compounds.
Thermogravimetric analyses of the oil sludge and PE wastes
were performed on a Thermogravimetric analyzer (SDT 2960,
Dupont, USA). The mass loss and mass loss rates of the samples were
monitored under a heating rate of 20 C min−1 , from 25 to 600 ◦ C and
nitrogen gas flow of 100 mL/min.
In the TG/DTG curves of the oil sludge (Fig. 2a), no mass loss was
observed in the range of 25–250 ◦ C, demonstrating that there was
no loss of water and light hydrocarbons. The weight loss started
at 250 ◦ C and completed at around 500 ◦ C. Only one peak could be
identified, which can be explained by the decomposition of more
complex organic structures. The maximum thermal degradation
was observed at 422.12 ◦ C and the mass percentage of final residue
was 13.44%.
Fig. 1. FT-IR spectrum of oil sludge sample.
TG curves of the LDPE waste (Fig. 2b) exhibited an apparent sin-
gle decomposition process between 400 and 525 ◦ C, a maximum
degradation rate at 471.34 ◦ C and the final residue (at 600 ◦ C) was
The water content of oil sludge was determined by Karl Fisher 0.688%. On the other hand, decomposition of HDPE waste (Fig. 2c)
titration Metrohm 831–KF Coulometer). This material contains only occurs at a slightly higher temperature. A maximum in the deriva-
0.0463% of water. tive plot (DTG) was observed at 480.16 ◦ C, and the residue at 600 ◦ C
The metal analysis of oil sludge was performed by Inductively was 2.7%.
Coupled Plasma Mass Spectrometry (ICP/MS, Bruker, Aurora M80) Oil sludge and the pyrolytic oil were completely soluble in
after a microwave assisted digestion with 1.0 mL HNO3 (P.A. Sigma) n-hexane (indicating the absence of asphaltene fractions) and
and 1 mL of H2 O2 (30%, Vetec). The elements detected were: V, Cr, analyzed by gas chromatography-mass spectrometry (CG–MS)
Mn, Co, Ni, Cu, As, Ag, Ba, Pb, Mg, Fe and Ca. However, the main using a gas chromatography mass spectrometry Bruker Scion
elements were: Cu (0.02%); Mg (0.18%); Fe (0.27%) and Ca (2.69%). 456 GCAR-TQ. Analyses were performed using column BR–5 ms,
The oil sludge was characterized by FT-IR spectrometer (Num- (30 m × 0.25 mm × 0.1 ␮m) and the following temperature pro-
ber One Perkin Elmer Fourier Transformed) using KBr windows gram: the initial temperature was 80 ◦ C and then increased up
(Fig. 1). FT-IR spectrum shows a broad absorption band in the range

Fig. 2. TG analysis of the samples of (a) oil sludge; (b) LDPE; (c) HDPE.
 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297 293

Table 2
Proton NMR ranges for proton types of the main hydrocarbons found in oil sludge.

Symbol Proton type Chemical shift range (ppm)

A Ring aromatics 6.6–8.0

B Olefin 4.5–6.0
C ␣-methyl 2.0–3.0
D Methine (paraffins) 1.5–2.0
E Methylene (paraffins) 1.0–1.5
F Methyl (paraffins) 0.6–1.0

to 270 ◦ C, at a heating rate of 4 ◦ C min−1 ; increased to 300 ◦ C at

10 ◦ C min−1 and kept at this temperature for 25 min. Helium was
used as a carrier gas. The detector had a mass range from 40 to
400 amu and the identification was done by find the spectrum of the
NIST library which matches with the spectrum of a given chromato-
graphic peak. The diesel fraction of pyrolytic oil was determined by
comparing of the chromatogram of the sample and the standard
C10 -C23 diesel fraction (Petrobras Brazil Corp.). The hydrocarbon
distribution of the pyrolytic oil and oil sludge was determined by
a semi-quantitative method based on the percentage area of two Fig. 3. Effect of the addition of K-10 clay on the pyrolytic conversion of OS into gases,
pyrolytic oil and solid residues. Experiments were carried out at 450 and 500 ◦ C.
groups of chromatographic peaks: (i) the light fraction contain-
ing hydrocarbons from n-C10 to n-C24, showing to the peaks with
retention time in the range of 0–54 min; and (ii) the heavy fraction, Furthermore, the gas fraction from oil sludge pyrolysis at 450 ◦ C
which contains hydrocarbons of more than 24 carbon atoms, corre- was increased by 50% when K-10 clay (5 or 10% w/w) was added.
sponding to the peaks in the range of 54–78 min. The hydrocarbon On the other hand, the addition of catalyst had no effect on the
types in the oil sludge and all pyrolytic oils were determined by residues yield. As an acid catalyst, the K-10 clay favors the cracking
the 1 H NMR spectra (Agilent VNMRS 500, 11, 74 T), using CDCl3 as of the oil sludge into low molecular weight compounds, such as C1
solvent. The acquisition parameters for qualitative spectra were: to C5 hydrocarbons [32].
pulse 30, number of accumulation = 128, interval between pulses Although the crystalline structure of K-10 clay is formed by
equal to 1 s and 25 ◦ C. 1 H NMR spectral regions used in the Myers’s partially destroyed aluminosilicate layers arranged in a triangu-
formula [31] are shown in Table 2. A–F indicate the integrated area lar structure [30], it is quite possible that Brönsted acid sites have
of the spectral regions defined by chemical shifts, in ppm, from acted as catalyst in the conversion of the pyrolytic oil.
tetramethylsilane (TMS). Interestingly, the oil sludge pyrolysis at 500 ◦ C, using a K-10 con-
To determine volume percent’s of the hydrocarbon types includ- tent of 10% (w/w), showed an oil yield of 78% and a very low content
ing aromatics, paraffins and olefins, Myers et al. [31] made of residues (10%). At 500 ◦ C, the K-10 addition did not influence the
corrections for the varying densities of the different hydrocarbon oil production.
types (Eqs. (1)–(3)). GC–MS analyses showed that the composition of oil sludge
 
A + C/3 0.97x102 (Fig. 4a) is more complex than the pyrolytic oils from the thermal
Aromatics, vol.% =   (1) (Fig. 4c) and catalytic pyrolysis (Fig. 4d). The following compounds
(A + C/3)0.97 + D − 2B + E/2 + F/3 1.02 + 3.33B
were detected in the oil sludge: 1-decene, 1-methyl-cyclo-
(D − 2B + E/2 + F/3)1.02x102 undecene, cyclo-dodecane, dodecane, 1-tridecene, 1-tetradecene,
Paraffins, vol.% =   (2)
(A + C/3)0.97 + D − 2B + E/2 + F/3 1.02 + 3.33B tetradecane, 1-heptadecene, heptadecane, 1-nonadecene, nonade-
cane, eicosane, 1-heneicocene, docosane, tricosane, pentacosane
3.33Bx102
Olefins, col.% =   (3) and heptacosane.
(A + C/3)0.97 + D − 2B + E/2 + F/3 1.02 + 3.33B
As pyrolytic oil must contain a significant amount of n-alkanes,
The gross calorific value of pyrolytic oils was determined by alkenes and branched hydrocarbons, its chromatogram was com-
combustion in a pump calorimeter IKA C-200. pared with that of standard diesel (Fig. 4b). The heavy fraction of
the oil sludge determined by GC/MS was 64%. (Fig. 4c, d). It was
3. Results and discussion shown that thermal and catalytic pyrolysis reduce significantly the
heavy fraction of the oil sludge and produce pyrolytic oil with a
3.1. Pyrolysis of the offshore oil sludge light fraction higher than 95%.
The pyrolytic oil from the thermal pyrolysis of oil sludge, at
The effect of temperature and addition of K-10 clay on the yield 450 ◦ C, contained predominantly paraffinic hydrocarbons (90% v/v,
of gas, pyrolytic oil and residues from the oil sludge pyrolysis is determined by NMR) and a low amount of olefins (8% v/v, deter-
presented in Fig. 3. Roughly, increasing the temperature from 450 mined by NMR). On the other hand, the pyrolytic oils from the
to 500 ◦ C, the yield of pyrolytic oil and gases was increased by 15% catalytic pyrolysis (450 or 500 ◦ C) and from the thermal pyrolysis
in thermal pyrolysis while the residues yield decreased by 50% in (500 ◦ C) produced a pyrolytic oil with a high content of paraffinic
all conditions. The residues yield decreases as a consequence of the hydrocarbons (80% v/v) and a low amount of aromatics (10% v/v).
high production of volatile products (pyrolytic oil and gases). The High molecular weight compounds such as waxes and heavy
fraction of solid residues (15%) from the thermal pyrolysis at 500 ◦ C hydrocarbons are generated by oil sludge pyrolysis through the
was similar to that of the final residue from the TG analysis of oil mechanism of random chain scission. While low molecular weight
sludge, indicating that the operating conditions of thermal cracking compounds such as gases and light hydrocarbons are formed by
can lead to the oil sludge degradation. Since the GC/MS profile of chain end scission of pyrolytic oil. These primary cracking prod-
the pyrolytic oil (Fig. 4c) was quite different of the expected profile ucts can be removed from the reaction medium or subjected
(diesel fuel – Fig. 4b), the pyrolysis was carried out in presence of to secondary reactions (such as oligomerization, cyclization and
the catalyst K-10. aromatization) [33].
294 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297

Fig. 4. GC–MS-total ion chromatogram of (a) oil sludge from offshore field, (b) standard diesel, (c) oil from oil sludge pyrolysis (500 ◦ C) and (d) oil catalytic pyrolysis (500 ◦ C,
10% K-10).

Considering that the addition of K-10 did not increased the

diesel fraction in the pyrolytic oil (Fig. 4D), it was added PE wastes
in order to increase the diesel fraction.

3.2. Co-pyrolysis of oil sludge and PE wastes

The effect of the addition of plastic wastes (LDPE and HDPE)

on the yield of the products from the co-pyrolysis of oil sludge is
presented in Fig. 5.
At 450 ◦ C, the pyrolytic oil yield decreased by 25% when the
LDPE content increased from 5 to 30%. Considering that the pyrol-
ysis experiments were carried out at a temperature inferior to
the maximum degradation temperature of LDPE, the production
of pyrolytic oil was reduced by the non-degraded plastic waste and
by the recombination of the radicals in the reaction medium. For
the co-pyrolysis with HDPE, a similar trend was observed as the
pyrolytic oil yield decreased from 66 to 54% when increasing the
HDPE content (5–30%). However, the pyrolytic oil yield from the
co-pyrolysis of HDPE/oil sludge was higher than that of LDPE/oil
sludge pyrolysis. This was a not an expected result from the TG
analysis, since the degradation temperature and the mass of HDPE
residues are higher than those observed for LDPE. At the pyrolysis
temperature, that synergetic effect can be due to the solvency of
oil sludge causes the unpacking of HDPE chains, which favors the
cracking of high molecular weight molecules.
The pyrolysis of oil sludge in presence PE wastes gives a higher
amount of pyrolytic oil than that of only oil sludge. The highest
pyrolytic oil yields were obtained when 30% (w/w) of PE waste was
added into the oil sludge: 92% for LDPE and 81% for HDPE. Besides, Fig. 5. Effect of the addition of (a) LDPE and (b) HDPE on of liquid, residues and gas
the amount of residues from the co-pyrolysis experiments at 500 ◦ C from the co-pyrolysis. Experiments were carried at 450 ◦ C and 500 ◦ C, using 5, 10 or
30% of PE waste.
were much lower than those conducted at 450 ◦ C, showing that
 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297 295

Fig. 6. GC–MS TIC of the oil from the co-pyrolysis of oil sludge and PE waste (30%) at 500 ◦ C: (a) LDPE; (b) HDPE.

Fig. 7. Total ion chromatograms of the oil from the co-pyrolysis of oil sludge and 30% PE waste:(a) LDPE with 5% K-10 at 500 ◦ C; (b) LDPE with 10% K-10 at 500 ◦ C; (c) LDPE
with 10% K-10 at 450 ◦ C; (d) HDPE with 5% K-10 at 500 ◦ C; (e) HDPE with 10% K-10 at 500 ◦ C; (f) HDPE with 10% K-10 at 450 ◦ C;.
296 D.C. Silva et al. / Journal of Analytical and Applied Pyrolysis 124 (2017) 290–297

temperature is a crucial parameter for the degradation of wastes.

A part of the residues from experiments at 450 ◦ C is non-degraded
PE wastes and waxes.
Although the pyrolytic oil yields from pyrolysis, at 500 ◦ C,
were similar for both PE wastes, GC–MS analysis showed that the
pyrolytic oils are chemically different (Fig. 6). The pyrolytic oil
from the co-pyrolysis of oil sludge and 5% LDPE is predominantly
composed of light hydrocarbons. However, when the LDPE content
increases, the heavy fraction also increases due to the accumulation
of high molecular weight hydrocarbons from the co-pyrolysis. On
the other hand, the pyrolytic oil from the co-pyrolysis of HDPE-oil
sludge was predominantly composed of heavy hydrocarbons (64%).
Considering that K-10 clay is a mesoporous material that has
lower acidity than zeolites, this catalyst can lead to high yields
of pyrolytic oil containing predominantly aliphatic hydrocarbons.
That can be explained by the low occurrence of hydrogen- transfer
secondary reactions, since K-10 has lower acidity than zeolites [34].
The influence of the K-10 clay on the diesel fraction in the Fig. 8. Hydrocarbon-type distribution and content of light hydrocarbons of oils from
pyrolytic oil from the PE-oil sludge pyrolysis was evaluated. GC–MS the thermal and catalytic pyrolysis of oil sludge without or with 30% of PE wastes
chromatograms of samples of pyrolytic oil from the catalytic co- (LDPE or HDPE). All experiments were conducted at 500 ◦ C.

pyrolysis, at 500 ◦ C and 5% K-10 clay, showed a profile quite similar

to that of the standard diesel, as shown in Fig. 7. When the amount 4. Conclusions
of catalyst was increased to 10%, the light hydrocarbons content in
the pyrolytic oil increased. On the other hand, the light fraction in This work confirms the potential of pyrolysis technique for the
the pyrolytic oil from the catalytic pyrolysis at 450 ◦ C was higher degradation of oil sludge from the crude oil storage tanks of an
than that fraction in the pyrolytic oil from the thermal pyrolysis at offshore platform to produce oils with low molecular weight hydro-
the same temperature. carbons and high content of paraffinic hydrocarbons. The addition
The content of light hydrocarbons (determined by GC/MS) in the of K-10 clay, at 450 ◦ C, increases de gas production from oil sludge
pyrolytic oil from the PE-oil sludge catalytic pyrolysis was higher pyrolysis. As an acid catalyst, the K-10 clay favors the cracking of
than that from the thermal pyrolysis. The pyrolytic oil has a high the oil sludge into low molecular weight compounds, such as C1 to
content of paraffins and a low content of olefins and aromatics, C5 hydrocarbons.
as determined by NMR (Fig. 8). It is widely accepted that thermal The pyrolytic oil production from the HDPE-oil sludge pyrolysis
degradation of long-chain hydrocarbons, such as oil sludge and PE, was higher than the production from the pyrolysis using LDPE-oil
occurs by free-radical mechanism, where the transfer of hydro- sludge. The solvency of oil sludge causes the unpacking of HDPE
gen atom from a tertiary carbon in the hydrocarbon chain forms chains, which favors the cracking of complex molecules into low
oligomers of different chain lengths. Besides the thermal degrada- molecular weight compounds
tion, in the presence of an acid catalyst, the degradation of heavy The amount of residues from co-pyrolysis were significantly
hydrocarbons can also proceed through a carbenium-ion interme- reduced by increasing the temperature from 450 to 500 ◦ C, demon-
diate mechanism. The initial step is the proton transfer Brönsted strating that temperature is a crucial parameter for the waste
acid sites in the K-10 clay to the C C bonds of the hydrocarbon degradation.
molecule. Thereafter, the cracking of hydrocarbon carbocation pro- The light hydrocarbons content in the pyrolytic oil from the
ceeds systematically into lower molecular weight hydrocarbons. catalytic pyrolysis of PE-oil sludge was higher than that in the
The porous structure of the catalyst restricts the entry of molecules pyrolytic oil from thermal pyrolysis. The pyrolytic oil from catalytic
based on the size; large molecules formed at the external surface co-pyrolysis can be a suitable fuel since it is mainly composed of
cannot enter into the catalyst micropores. Consequently, surface paraffins, with a low content of olefins and aromatics. In addition,
acid sites catalyze the cracking of heavier hydrocarbons. Hydro- the mean calorific value of the pyrolytic oils was similar to that
gen transfer reactions, involving the formation of bulky bimolecular of the default caloric value of diesel, suggesting its potential for
reaction intermediates, are mainly controlled by steric constraints energetic use.
inside the porous. Branched and linear paraffins are examples of
products from bimolecular reactions not limited by steric con- Acknowledgments
straints. In the case of K-10 clay, a mesoporous catalyst, oil sludge
and PE are cracked on the surface acid sites. Some of these products The authors thank the Mineral Technology Center for the anal-
can diffuse into the internal active surface through the pores, where ysis of the catalysts. In the Foundation for Research Support of the
they are over cracked into compounds lighter than the residues State of Rio de Janeiro (FAPERJ) by the D.Sc. scholarship. In addi-
from the external cracking. Due to the dimensions of their porous, tion, we express our thanks to Environmental Alliance for donating
K-10 clay does not inhibit bimolecular reactions, by which paraffins sample of offshore heavy oil sludge. Petrobras, CNPq (INOG) FAPERJ
are formed. The reaction products have very high concentrations of and CAPES for financial support.
C10 -C23 hydrocarbon (light hydrocarbons), which corresponds to
the diesel fraction [35].
References
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