Journal of Analytical and Applied Pyrolysis 114 (2015) 110

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Journal of Analytical and Applied Pyrolysis

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

Hydrous pyrolysis of heavy oil using solid acid minerals for

viscosity reduction
Oki Muraza a,b,
a
b

Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
Chemical Engineering Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 5 November 2014
Received in revised form 1 April 2015
Accepted 9 April 2015
Available online 11 May 2015
Keywords:
Hydrous pyrolysis
Minerals
Viscosity reduction
Heavy oil
Solid acids

a b s t r a c t
Hydrous pyrolysis, also known as aquathermolysis, has been explored intensively as one of the technologies to reduce the viscosity of heavy oil. The hydrous pyrolysis was also proposed as one of the processes
in the formation of crude oil from kerogen through catagenesis. There is a connection between hydrous
pyrolysis in crude oil formation with hydrous pyrolysis in heavy oil processing. In both reactions, minerals and sub- and supercritical waters were important parts. Strong-acid minerals, especially induce the
breakage of the C C, C O and C S bonds in heavy oil. There are several classes of materials for hydrous
pyrolysis of heavy oil, namely (i) metal-based nanoparticles such as Ni+ , Cu+ , etc. (ii) solid acid minerals
and oxides and (iii) microporous zeolites. The challenges are mostly with the stability of the materials.
Stable oxides such as zirconia, iron oxide, and hydrophobic zeolites are targeted for hydrous pyrolysis in
the presence of hot water and steam. The paper emphasizes the importance of the chemical composition
of heavy oil and how heavy oil is altered by natural minerals, including microporous zeolites. Transferable
knowledge on the formation of petroleum was used to screen minerals for hydrous pyrolysis of heavy oil
to light oil.
2015 Elsevier B.V. All rights reserved.

Contents
1.
2.
3.
4.
5.
6.
7.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Origin of heavy oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Viscosity reduction of heavy oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Hydrous pyrolysis of heavy oil by minerals in the presence of sub- and supercritical water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Stability of clay minerals and zeolites in hot aqueous medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
The role of hydrogen addition in viscosity reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1. Introduction
In the energy hunger world today, where the conventional
resources are depleted, the unconventional energy resources have
a crucial role. There is a clear demand to explore unconventional
resources such as heavy oil and bitumen. Approximately, 25% of

Correspondence address: Center of Research Excellence in Nanotechnology and

Chemical Engineering Department, King Fahd University of Petroleum & Minerals,
Dhahran 31261, Saudi Arabia.
E-mail address: omuraza@kfupm.edu.sa
http://dx.doi.org/10.1016/j.jaap.2015.04.005
0165-2370/ 2015 Elsevier B.V. All rights reserved.

hydrocarbon resources are present as unconventional hydrocarbon; namely heavy oil, extra heavy oil and bitumen [1,2].
With the current technology, the recoverable reserves are
around 500 billion barrels for heavy oil [4,5] (Fig. 1). In addition
to large reserves in Canada and Venezuela, heavy oil is potentially produced from Russia, Saudi ArabiaKuwait partition zone,
Oman, Mexico, USA, Indonesia, China and a few countries in Europe.
Heavy oil contains heavy hydrocarbon compounds, which are commonly called resins and asphaltenes, with long carbon chains more
than sixty carbon atoms. High content of heavier fraction corresponds with high molecular weight, viscosity, and boiling point
[6,7] (Table 1).

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

Fig. 1. Total original oil in place (TOOIP) of heavy oil and bitumen resources [4,5].

Table 1
A typical classication of heavy oil and bitumen.
Properties

API ( )
Viscosity (cp)

Light oil

Heavy oil

Extra-heavy oil

Bitumen

2245
Less than 100

1022
>100

<10
<10,000

79
>10,000

(Adapted from www.centreforenergy.com)

Chemical and physical properties of heavy oil are different from

one eld to another. Heavy oils typically have a low hydrogen
to carbon (H/C < 1.5) ratio, a high content of asphaltene and high
content of carbon residue. Table 2 presents typical chemical and
physical properties of heavy oils from the Middle East and North
America [810]. High concentrations of sulfur and asphaltene create additional difculty in heavy oil processing. Asphaltene is a
high molecular weight component in heavy oil, which consists of
polycyclic aromatics. The values of asphaltene molar mass are in
the range of 500755 g mol1 [11,12]. The number of structural
units of asphaltene is different from one source to another. The
molecular diameters of asphaltene are in the range of 1.42.1 nm
[11,13], while the aggregates are larger, in the range of 2.530 nm
[14]. Abdallah and Yang reported the average size of asphaltene
molecules from 1.52 to 1.88 nm based on Raman measurement,
which consisted of about 78 aromatic rings [15]. A typical asphaltene structure is shown in Fig. 2 [13].
The molecular size of reactant is important to design the most
effective catalysts in valorization of heavy oil. The pores of microporous zeolites, for instance, are too small for asphaltene molecules.

Fig. 2. A typical asphaltene structure.

(Adapted from [13]).

As the asphaltene cannot enter most of micropores in microporous

zeolites, the possible reactivities are only available over the external surface of catalysts.
Viscosity of heavy oil is a function of asphaltene content; the
higher the volume percent of asphaltene in heavy oil, the higher
the viscosity [16].
Heavy oil also contains heavy metals such as vanadium and
nickel. Sometimes, heavy metal such as mercury is also present
in heavy oil. As heavy oil contains large molecules and low H/C

Table 2
Chemical composition and physical properties of heavy oil (after [1214]).
Composition

Khafji VR

Safaniya, Arabian

Bitumen, Athabasca

Heavy oil, Mexico

Heavy oil, Venezuela

Carbon (wt.%)
Hydrogen (wt.%)
Sulfur (wt.%)
Nitrogen (wt.%)
Vanadium (ppm)
Nickel (ppm)
Gravity ( API)
Viscosity (cP)
Asphaltenesb (wt.%)
Carbon residuec (wt.%)

84.0
10.3
4.9
0.33
128
43
6.5
1550a
11.1
20.1

n.r
n.r.
4.3
n.r.
V + Ni = 125
V + Ni = 125
13.0
n.r
n.r
12.8

83.3
10.4
4.6
0.44
190
78
9.6
125
7.7
13.6

18.1
n.r.
0.05
1.2
444
85
12.1
322
19
18.1

n.r.
n.r.
3.0
n.r.
V + Ni = 509
V + Ni = 509
9.4
n.r
n.r
14.1

n.r = not reported.

a
Viscosity at 100 C.
b
Insoluble in n-heptane.
c
Conradson carbon residue.

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

Fig. 3. (a) Lesson learned from natural hydrous pyrolysis and transferable knowledge for heavy oil upgrading.
(Adapted from [27]).

ratio, we would see that the technologies to convert heavy oil to

transportation fuel are classied into major techniques; cracking
(carbon rejection) and hydrogen addition.
2. Origin of heavy oil
Heavy oil formed, theoretically, through catagenesis of kerogen with esters and ethers as cross-links (Fig. 3). These oils are
hypothetically derived from kerogen (trapped organic matters) of
different sources, (a) source rock, as immature oil [3], (b) source
rock followed by oxidation and decomposition, and (c) biodegradation and biodecomposition.
From their solubility in organic solvent, kerogen is dened as
the fraction of organic matters which are not soluble in organic
solvent [17]. The soluble fraction is known as bitumen (Fig. 4). Even
though, heavy oils are also soluble to some extend. The conversion,
which happened slowly with over a million years, progressed in the
presence of water at various pressures depending on the depth. The
types of kerogen was classied according to the atomic composition
of hydrogen, oxygen and carbon (H/C ratio and O/C ratio) using the
van Krevelen diagram [18]. While type I is originated from algae
deposit, type II is transformated from higher plants and is related
with planktonic deposit [17].
It was proposed that the formation of petroleum was catalyzed
by clay minerals in specic geological layers [19]. The typical minerals (for instance bentonites) consist of montmorillonite, which
contains macropores and spacious interlayer porosities. Montmorillonite was reported as active catalysts in the conversion of

Fig. 4. (a) Proposed oil formation from kerogen, (b) hydrous pyrolysis of heavy oil.
(Adapted from [27]).

immature kerogen to light hydrocarbon [20]. The formation of

heavy oil from kerogen was inuenced by acidic materials and
salts [2123]. Seewald proposed that the minerals on sedimentary
component contribute to the transformation from trapped organic
matters to liquid petroleum [24].
Further researches also reported that kerogen reactivity was
also increased at higher temperatures in the presence of sub- and
supercritical water [21,23,2527]. Siskin and Katrizky reviewed
reactions at high temperature in aqueous medium, especially when
water is not as normal present, but in the form of supercritical
water.
In addition, Schimmelmann and co-workers reported experimental works on hydrous pyrolysis to simulate the maturation
of source rock at elevated temperature in a pressurized reactor
[2830]. The hydrous pyrolysis depends on temperature, time and
mineral/water ratio. Vandenbroucke and Largeau reviewed the origin and the evolution of kerogen [17], basically, the types kerogen
were classied according to the interconnection between acids and
oxygen-containing functional groups (esters, carboxylic acids, etc.)
in hydrolysis of kerogen. Strong bonding between oxygen containing functional grups with silicoaluminates and carbonates were
reported by Razvigorova et al. when they studied the interaction
between acids, organics and minerals in hydrolysis of kerogen from
shale oil [31].
In addition to experimental works in hydrous pyrolysis, the
presence of diamondoids was used as biomarkers to evaluate
whether the status of petroleum is low maturity (no cracking) or intensely cracked [32,33]. Diamondoids are isolated from
petroleum, for instance, adamantanes, diamantanes, tri- and tetramantanes. Wei and co-workers used diamondoid hydrocarbon as
a geochemist model for hydrous pyrolysis in oil formation [34,35].
It was proposed that diamondoids (cyclohexane rings) in oil were
the product of catalytic isomerization via carbonium ion chemistry
over acidic clay minerals [32,36]. The role of clay minerals in catalyzing oil formation was summarized in an interesting review by
Wu et al. [37].
Natural minerals such as cretaceous Mowry shale, a whole
core, were also proposed to be involved in production of biogenic
methane in ocean shale oil [38]. Mowry shales are clay minerals composed of bentonites (83%) [39]. Bentonites itself consist
of 2098% montmorillonite, a layered silica with the hypothetical
composition of M0.66 (OH)4 Si8 (Al3.34 Mg0.66 )O20 , where M is a metal
ion.
The maturity of crude oil is linear with the breakdown and
degradation of kerogen at high temperature under elevated pressure. Stankiewicz proposed that the molecular ratios of the
hydrogen to carbon (H/C), oxygen to carbon (O/C) and sulfur to
carbon (S/C), decreased with the higher maturity [40,41]. Correspondingly, the gravity (API) increased and asphaltene content
decreased. Heavy oil consists of saturates (S), aromatic (A), resins
(R) and asphaltenes (A), each of which has different polarity, with
the latter has the highest polarity.
The contribution of sulfur chemistry in heavy oil is also crucial
and an ongoing research topic in exploration and production of
heavy oil [42]. Sulfur compounds in heavy oil originate from the
diagenesis period [43,44]. Sulfur species in saturates and aromatics were characterized by gas chromatograph (GC) and advanced
gas chromatograph coupled with mass spectroscopy (GCMS),
while less volatile (but polar) compounds in resins and asphaltenes
were studied by Fourier transform ion-cyclotron-resonance mass
spectrometry (FT-ICR MS) combined with electrospray ionization (ESI). There are different types of sulfur species in
heavy oil including thiols (R(alkyl) S H), thiophenes (C4 H3 S ),
thiolanes/tetrahydrothiophene (CH2 )4 S, sulde (R S R ), disuldes (R S S R ), Benzothiophene (C8 H6 S), dibenzothiophenes
(C12 H8 S), and many others. S1 is dened as heteroatom compounds

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

which contain one sulfur, correspondingly, S2 and S3 contain two

and three sulfur atoms, respectively.
The presence of sulfur species and supercritical water at 407 C
in nature were reported elsewhere [45,46]. The supercritical water
was released in the sea oor containing sulphide ( SH or anion
S2 ), metals, metal oxides and organics as the binder [47]. Some
metal compounds were reported, including Fe, Cu, Cr, Mn and Zn,
which might be originated from leached rocks. The binders or ligands consist of carboxylic acids, thiols, and amines. Future works
in geochemical characterization of these natural hydrothermal uids may help scientists to further understand the interconnection
between organic matters (the origin of heavy oil), minerals and
sub-/supercritical water where the hydrogen bonds are broken and
water are reactive with heavy oil [48].
3. Viscosity reduction of heavy oil
Hyne dened two regimes in thermoconversion of heavy oil to
light oil in the presence of water (steam), namely aquathermolysis (hydrous pyrolysis at temperature from 200 to 300 C) and
thermolysis (300550 C) [49]. Hydrous pyrolysis and anhydrous
pyrolysis have been used to obtain geochemical ngerprints of oils
and to develop suitable conversion methods in viscosity reduction of heavy oil [50]. It was also reported that the C S containing
species initiate the hydrous pyrolysis reaction networks. Reaction
networks in hydrous pyrolysis of asphaltene were proposed by Belgrave et al. [5153].
asphaltene a heavy oil + b light oil + c coke + d H2 + e CH4
+ f CO + g CO2 + h C2 H6 + i C3+ + j H2 S

(1)

heavy oil k light oil + l coke + m CH4 + n C2 H6 + o C3+

(2)

light oil p coke + r CH4 + s C2 H6 + t C3+

(3)

Kapadia et al. proposed seven reactions in hydrous pyrolysis of

Athabasca heavy oil in the presence of steam, including watergas
shift reaction [54].

Dilution is the most conventional technique to reduce viscosity of heavy oil. Condensates from natural gas production facilities
were utilized for dilution of heavy oil.
There are different solvents used in the classical viscosity reduction of heavy oil using dilution pathway. For some heavy oil and gas
elds near where condensates are available, diluents were reported
using condensates. However, the application of condensates has
different challenges such as (1) natural gas and condensates are
not always available near heavy oil production facilities, (2) low
solvability of asphaltenes, and (3) scales from precipitation an occulation [60,61]. Distillates such as naphtha (C6 C8 ), diesel oil and
kerosene were also used in dilution of heavy oil. This dilution
typically requires approximately 2030% of solvent. Asphaltene
precipitation and a tendency to produce scale and fouling are also
the disadvantages of this approach [62]. Applicability of a diluent
is narrow and limited to specic crude oil properties. Furthermore, most of the time, additional corrosion inhibitors and scale
inhibitors are still required.
Thermal-based processes are also often used in a viscosity
reduction, including steam-assisted process, steam injection, subcritical and supercritical water. Apart from its high cost to generate
steam, the option suffers from uncontrolled free radicals which
could initiate undesired polymerization [63,64]. Catalytic processes
was initiated using different transition metal ions as previously
reported by Clark et al. [65], Chao et al. [66], Strausz et al. [67],
Clark and Kirk [68]. However, metal ions such as Cu2+ , Fe3+ , Mo6+
and others are instable in water with tendency to form complexes
in aqueous medium [69,70]. The composites of zirconia such as
WO3 /ZrO2 and SO4 2 /ZrO2 by Wang and co-workers [71,72] were
reported as excellent catalysts for viscosity reduction of heavy oil.
This manuscript will focus on reviewing the current interest in
a viscosity reduction of heavy oil using oxide nanoparticles, especially solid acid catalysts. The applied materials such as natural
zeolites and synthesized zeolites were compared from different
open literatures. The reaction of heavy oil with the solid catalysts in
the presence of hot water (or steam) is known as aquathermolysis.
This reaction requires catalysts and elevated temperatures to break
the the C C, C O and C S bonds in heavy oil [65] and reduce the
content of resins and asphaltenes [73].

CO + H2 O  CO2 + H2
In addition, production of carbon dioxide (CO2 ) was attributed
to mineral carbonates and carboxylic acids in minerals as only a
small quantity of water/steam was consumed in hydrous pyrolysis.
The potential role of minerals as a catalyst was also reported by
Hyne. In addition to their roles in hydrous pyrolysis, minerals were
reported to induce higher reaction rate on thermolysis [55]. Interestingly, Kapadia et al. also reported that the material of the testing
reactor contributed to the reaction rate. The Hastelloy autoclave
has higher gas production rates than the obtained rates in quartz
reactor [54]. This means that hastelloy, to some extend, has a catalytic role in hydrous pyrolysis. So the catalysts were not only clay
minerals, but also metals such as hastelloys. The metal components
of hastelloy reactor operation in sub- and supercritical water were
reported by different research groups [5659], with results explaining heavy oil conversion might be catalyzed by metal ions or metal
oxides from corrosion of hastelloy reactor.
Viscosity reduction is a crucial step in heavy oil processing.
Different strategies have been studied and applied for viscosity
reduction of heavy oil and bitumen. Conventional techniques in a
viscosity reduction are (1) dilution, (2) delayed coking, (3) catalytic
cracking, (4) visbreaking. These techniques, mostly involve carbon
rejection strategy using the addition of heat. In addition to that,
hydrogen addition is another common strategy. These techniques
require (1) high price of catalysts, (2) hydrogen, and (3) substantial
energy and coke management.

4. Hydrous pyrolysis of heavy oil by minerals in the

presence of sub- and supercritical water
Numerous minerals and solid acid materials have been explored
as heterogeneous catalysts for viscosity reduction of heavy oil via
hydrous pyrolysis reaction (Fig. 5). The activities of the catalysts
are dependent on some material properties such as acidity, particle size, pore size, topology, and stability, which are related to
fabrication techniques [7478].
Historically, transition metals were applied as the catalysts
[68,79,80]. Then, different type of acids were utilized for degradation of heavy oil at 190 C and pressure of 500 psi for 1 h through
hydrogenation and thermolysis [67]. Through these processes, reasonable conversions up to 56% were obtained.
Yi et al. reported the application of iron and nickel compounds
soluble in oil for hydrous pyrolysis of asphaltene [81]. Iron napthenate was found to be the most active catalyst for heavy oil conversion
using cyclohexane as hydrogen donor.
On the other hand, works on theoretical modeling suggested
that iron-based catalysts catalyzed the reactivity of heteroatoms (S
and N) in heavy oil to metalasphaltene complexes in the presence
of water [82]. The C S bonds, with the weakest energy bond, were
activated strongly through charge transfer of electron from metal
to asphaltene. Two important metals for this purpose are nickel and
iron [83,84]. The metals are potential to be reacted with the aro-

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

Fig. 5. Different catalysts applied in viscosity reduction and hydrous pyrolysis of heavy oil.

matic rings in asphaltene structures. Hydrodesulphurization and

hydrodenitrogenation are potentially achieved by manipulating
iron- or nickel based catalysts in the presence of hot water/steam
and acidic mineral to strengthen scission of C C bonds (cracking).
The breakage of C S bond is proposed as the initiator of hydrous
pyrolysis [49]. Even though, there are other ndings that supported the breakage of oxygen containing compounds (C O bonds)
involved in hydrous pyrolysis [85].
Chen et al. reported that the H/C molar ratio increased and the
O/C decreased [85,86] after the hydrous pyrolysis over aromaticsulfonic-H3 PMo12 O40 at 280 C and 30 bar for 24 h. These ndings
supported the hydrogen addition concept and the breakage of
oxygen-containing molecules. Furthermore, the catalyst induced
detachment of resins from asphaltenic clusters and catalyzed the
scission of C C bonds in different cyclic/aromatic compounds in
heavy oil to produce linear parafn. Heavy oil contains fatty acids
from heavy hydrocarbons (C11 C20 ). The content of fatty acid
was changed after the hydrous pyrolysis due to decarboxylation.
The breaking of C C bonds in cyclic compounds (cycloalkane) to
parafn and hydrogenation was also reported in the presence of
carbonaceous catalysts [87].
The adsorption of ironsulfur complexes was experimentally
conrmed by analyzing spent catalyst of mesoporous silica (SBA15) supported iron catalyst in hydrogenation and cracking of
asphaltene [88].
Kida et al. proposed that the supercritical water involved both
as a reactant and a catalyst in the breakage of C S bonds (desulfurization process) [89,90] according to free-radical mechanism [91].
The bridge aromatics in heavy oil are relatively easy to be broken,
while the aromatics are stable in supercritical water [85].
Stoyanov reported the effect of surface acidity of treated natural chabazite zeolites using density functional theory and quantum
mechanics [92]. As the heavy oil compounds are too large to enter
the microporous zeolite pores, the compounds only adsorb on the
external surface of zeolite catalysts. Here, the nanosized particles
showed better catalytic activities with higher acidity as a function

of crystal size. Stable acid sites near the open cages are the key for
aquathermolysis.
The applied materials such as natural zeolites and synthesized
zeolites were compared from different open literatures. Nanometer range size contributed to the larger external surface area of
materials. The framework and topology are less signicant as heavy
oil molecules are too large to diffuse to micropores. The acidity of
zeolites is the key success in viscosity reduction, which related to
surface treatment. The addition of promoter such as iron and nickel
oxide is also crucial to improve catalytic performance.
Natural zeolites are potential for aquathermolysis of heavy oil
due to their solid-acidic properties and low cost (Table 3). Merissa
et al. [93] reported the application of natural zeolites, heulandite
and clinoptilolite from Indonesia. Typically, the natural materials
were treated in a ball milling process and heated at an elevated temperature (above 300 C). Small amount of catalysts (0.5 wt.%) was
enough to obtain 65% viscosity reduction at 200 C for 6 h. Previously, Junaid et al. [94,95] successfully applied natural Ca-chabazite
and clinoptilolite as catalyst in aquathermolysis of bitumen with
81% conversion and 96% of products was lighter oil. It was proposed that the hydrolysis did occur in hydrous pyrolysis of heavy
oil using natural zeolites.
Hydrolysis provided protons to Ca-chabazite to make these
minerals become acidic. FTIR and NMR spectra showed the contribution of acidic hydroxyl(OH) group on natural chabazite (CHA)
and natural clinoptilolite (HEU) [96]. The cracking of heavy oil
proceeded through carbocation chemistry where the proton was
added to heavy oil resulting higher H/C products. Both carbon rejection/rearrangement (beta scission cracking, dehydrogenation, and
aromatization) and hydrogen addition (at beta and gamma position) were accomplished over natural zeolites.
The impurities such as sulfur and nitrogen were decreased substantially, yielding less viscous and lower boiling point liquid.
Kuznicki reported that modied chabazite originated from
cheap natural minerals showed better catalytic performance than
the commercial and expensive zeolite Y [78].

Table 3
Activities of selected natural zeolites, metal oxides and metals in viscosity reduction of heavy oil.
Reactant (s)

Si/Al

Reaction conditions

Impact of the catalyst on

viscosity reduction

Treatment

Ref.

Natural clinoptilolite,
heundalite,
(Ca(Al2 Si7 )O18 6H2 O)

Heavy oil

Si/Al of 2

The viscosity was reduced

up to 69%

Oilsands and
hexadecane

Si/Al ratio varied between

2 and 3

Natural clinoptilolite rock

fragments were crushed
and sieved. Ball milling was
applied at 200 rpm for 8 h
Natural chabazite was
treated in alkaline silicate
solution at 80 C for
2472 h. Ion exchanged
was done to prepare
CaH-chabazite and
H-chabazite

[88]

Ca-H-Chabazite
(chabazite-Ca
|(Ca0.5 ,K,Na)n (H2 O)12 | [Aln
Si12n O24 ]), where n is
between 2.4 and 5.0

HY, H-clinoptilolite,
H-chabazite. Chabazite: (Ca
|(Ca0.5 ,K,Na)n (H2 O)12 | [Aln
Si12n O24 ], where n is in
the range of 2.45.0

Bitumen

Si/Al of HY is 2.4. Si/Al of

clinoptilolite is 5.1

0.3 g of zeolite (0.5 wt.%) in

autoclave at 200 C for 6 h.
The ratio between heavy
oil and water was 3:1 (v/v)
The treated zeolites were
tested in a customized
batch microreactor. 10 wt.%
of catalyst was used for
15 g of raw oilsands at
400 C for a period of 1 h.
Zeolites (10 wt.%) were also
examined in catalytic
cracking of hexadecane at
430 C and 15 atm for
25 min
Reaction at 385 C for 1 h
without agitation. Zeolite
particles were covered
with carbonaceous matter
(coke)

[4,89,91,92]

H-Clinoptilolite,
H-chabazite, Ca-chabazite.
Chabazite: (Ca
|(Ca0.5 ,K,Na)n (H2 O)12 | [Aln
Si12n O24 ], where n is in
the range of 2.45.0

Bitumen, hexadecane
and cumene

Water must be added. A

3 wt.% based of heavy oil
reactant was added.
Reaction at 300 C for 1 h.
Hexadecane cracking at
400 C for 1 h. Cumene
cracking at 350 C for 4 h
Testing was carried out in
500 ml autoclave

Viscosity was reduced to

less than 10,000 cp

Zeolites were grounded to

less than 75 and
dealuminated for 68 h.
Cracking of asphaltene was
carried out with
heavy/cat = 10/1 (w/w)
Water was added to
convert Lewis sites to
Brnsted acid sites

Catalyst was selected to

represent the materials of
reservoir

[2]

Nano range 1222 nm.

Nanosized NiO showed the
best catalytic activities
Copper NPs were the most
effective one for viscosity
reduction

[93]

Montromorillonite
Heavy oil
(M0.66 (OH)4 Si8 (Al3.34 Mg0.66 )O20 ),
where M is a metal ion and
kaolinite
Asphaltene as a model
NiO, Fe3 O4 , Co3 O4
compound for heavy oil
Fex Oy , NiO, Ni, CuO, Cu,
both micron- and
nano-sized particles

Heavy oil

Steam was added in excess.

The temperature was
heated from 180 to 800 C
Heating at 240 C for 6 days
in the presence of steam

The viscosity reduced by a

factor of 4 from 16,000 cp
to approx. 4400 cp

With untreated
clinoptilolite, 64% viscosity
reduction was achieved
from 144,900 cp to
51,600 cp

Viscosity reduced by 26% at

240 C for 36 h. Without
water, there was no lysis
observed
Asphaltene was adsorbed
on nanosized oxides
Viscosity was reduced in
the range of 2533%

[90]

[3,92]

[94]

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

Catalyst

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

Table 4
Characteristics of chemical bonds [95] commonly found during hydrous pyrolysis of heavy oil [81,95].
Energy (kJ/mol)

Mechanism

Electronegativity
difference

Polarity

Products

Remarks

C S: 272

C S bond breakage
products

2.52.5 = 0

Non-polar,
covalent

C
C
C
C
C
C

C O bond breakage
products

3.52.5 = 1

Polar, covalent

H2 S, saturates,
metalasphaltene
complexes
Alcohols, aromatics,
carboxylic acids

Sub- or supercritical water

is involved in the reaction
[85,86]
Decarboxylation,
hydrogenation [80]

C C bond breakage

2.52.5 = 0
3.02.5 = 0.5

Esters, Aromatics,
saturates
Amino acids

Cracking, ring opening [80]

C N bond breakage

Non-polar,
covalent
Non-polar,
covalent

O: 358
O: 799
O: 1072
C: 348
C: 614
N: 293

The sodium and calcium chabazite from Arizona were converted

to the H-form through an ion exchange step and applied to viscosity reduction of bitumen at 400 C. The natural zeolites surprisingly
show extraordinary adsorption capacity for metal removal, desulfurization and denitrogenation. A signicant quantity of sulfur was
removed (up to 30%). Similarly, the catalysts were effective for
nitrogen removal (60%). Kuznicki and co-workers also reported that
the modied natural chabazite zeolites were more superior than
the commercial Y (FAU) zeolites due to several reasons such as (1)
stronger acid strength (2) contain high amount of cations, which
interact with contaminants in the heavy oil, and (3) these natural
zeolites are abundantly available in different continents with very
cheap price. The role of acidity was claried using hexadecane as a
model compound for heavy oil [94,96,97].
Table 4 shows some characteristics of chemical bonds [98] found
during hydrous pyrolysis of heavy oil. Even though, further research
is still required to understand the mechanism of pyrolysis, At least,
some hydrocarbon conversion reactions such as cracking, decarboxylation, ring opening and hydrogenation were observed during
hydrous pyrolysis [85,86].

5. Stability of clay minerals and zeolites in hot aqueous

medium
For treatment of heavy oil, residue, bitumen, natural zeolites, the
cheapest and the greenest technologies are required. Natural zeolites are seen as the ideal catalyst that fullls those requirements.
The price of natural minerals is inexpensive, not to mention environmentally friendly process with ease separation is possible with
current technology. After the reaction in the aqueous medium, oil
and water can be separated using commercial ceramic lters and
membranes. However, there are still challenges remaining with
the deactivation of zeolites in typical hydrocarbon conversions
and possible degradation in aquathermolysis condition. Ideally,
the catalysts should be stable for long periods without structural
degradation and with resistance to poisoning. Sintering at high
temperature is also another potential deactivation mechanism in
aqueous medium reaction. However, the toughest challenge is
with the stability of zeolites in the presence of hot water. It is
well documented that hot water or water vapor is the source of
zeolite instability. The stability of zeolites is a crucial topic in processing heavy oil and also in valorization of biomass in aqueous
phase [99,100]. In the later application with biomass, hydrophobic zeolites were applied in typical acid-catalyzed reactions such
as alkylation and isomerization [100102].
Classically, the hydrophobicity are tunable by reducing Al content in zeolites [74,103105] corresponding to the increase of Si/Al
ratio. The hydrothermal stability of zeolite has been improved by
post-treatment to reduce hydrophilicity of zeolite or by development of hydrophobic zeolites using uoride routes [106,107]. To
handle this problem, catalyst preparation via the uoride routes or

Hydrogenation [80]

modication with organic silane compounds would be very benecial [75]. The application of HF is still challenging for scale-up
and commercialization. Instead of HF, NH4 F and NaF are greener
options for uoride router [108]. In addition, hydrophilic properties
of zeolites can also be modied by surface treatment using silane
precursors [75,100].
6. The role of hydrogen addition in viscosity reduction
Despite of debatable mechanism, many researchers reported
water presence was benecial in aquathermolysis of heavy oil [96].
In addition to the importance of water, some solvents were considered as hydrogen donor. Some chemicals such as tetralin and formic
acids have been applied as source of hydrogen for aquathermolysis [109,110]. Tetralin was used for viscosity reduction of heavy oil
in Venezuela [111]. By addition of a hydrogen donor to heavy oil,
naphthalene was observed in the products when the mixture was
heated at 315 C for 24 h. To further intensify the process, viscosity reduction was applied combining steam injection with tetralin
(as a hydrogen donor) and dilution with methane (the main component of natural gas) at 315 C for a longer period 32 h [111,112]. The
API gravity was decreased from 9.1 to 14.6 API. Correspondingly,
the asphaltene content was reduced from 23.5 to 19%. The composition of the mixture was also crucial. Optimum ratio of solvent to
hydrogen donor was important to obtain greener process [113]. The
acid such as formic acid was also reported as a potential hydrogen
donor [114]. Other solvents such as methyl formate and dihydroanthracene were also explored as hydrogen donor as reported by Zhao
et al. [115] for the Liahoe heavy oil. Syngas (CO + H2 ), a derivative
gaseous mixture from natural gas, was also potential to be applied
as hydrogen donor [116].
Synergy between catalysts and hydrogen donor solvent was
emphasized by different references [117121]. The product of the
heavy oil in an aquathermolysis using cobalt-based catalysts and
formamide as the hydrogen donor resulted in higher hydrogen-tocarbon ratio [121]. In addition, the sulfur content was considerably
reduced. Further fundamental studies on the breakage of C S, C C,
C O bonds are still to be pursued in order to design an intensied
process for viscosity reduction of heavy oil (Table 4). Among those
hydrogen donors, the cheapest hydrogen donor will be applied in
commercial scale together with a form of energy (hot water or
steam) and nanocomposite cracking catalysts. The stabile catalysts
acidic catalysts, metal nanoparticles in cost-effective hydrogen
donor solvents offers a better catalytic system to upgrade heavy
oils.
7. Conclusions
Hydrous pyrolysis was extensively studied not only to understand the formation of oil from kerogen, but also in conversion
of heavy oil to light oil. As natural minerals including montmo-

O. Muraza / Journal of Analytical and Applied Pyrolysis 114 (2015) 110

rillonites and zeolites were active to convert kerogen to petroleum

through hydrous and anhydrous pyrolysis, the knowledge of intrinsic properties of these minerals is also transferable in designing
active catalysts to treat heavy oil and bitumen. Among all options
such as thermal, dilution and many other attempts, hydrous pyrolysis of heavy oil is a remarkable effort to reduce viscosity by
combining catalysis and hydrothermal nature in the reservoir. Natural zeolites have been explored for viscosity reduction aiming to
utilize cheap minerals and to develop a reasonable process based
on solid acid catalysts. The effect of particle size, acidity, and the
composite oxides are discussed in order to design better catalysts for hydrous pyrolysis. The challenge with material design is
the stability of zeolitic materials under hydrothermal condition.
Hydrophobic zeolites can be the solution for the stability issue.
Together with a source of heat (steam or sub-critical water), a cheap
and available diluent and optimized catalytic nanoparticles, viscosity reduction of heavy oil is promising approach to deliver energy
for the world. An integrated process for viscosity reduction must
be considered, including the separation system for the produced
water, where suspended solids from zeolites and slurry catalysts
can be resolved using lters, be it ceramic membranes or decanters.
Acknowledgement
The author would like to acknowledge the support provided by
Saudi Aramco through project CENT2202.
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