Ultrasonics - Sonochemistry 42 (2018) 493–507

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Ultrasonics - Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Review

Current knowledge and potential applications of cavitation technologies for T

the petroleum industry
⁎
Balasubrahmanyam Avvaru , Natarajan Venkateswaran, Parasuveera Uppara, Suresh B. Iyengar,
Sanjeev S. Katti
Reliance Research and Development Centre, Reliance Corporate Park, Ghansoli, Navi Mumbai 400701, India

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

Keywords: Technologies based on cavitation, produced by either ultrasound or hydrodynamic means, are part of growing
Cavitation literature for individual refinery unit processes. In this review, we have explained the mechanism through which
Crude oil these cavitation technologies intensify individual unit processes such as enhanced oil recovery, demulsification
Desulphurisation of water in oil emulsions during desalting stage, crude oil viscosity reduction, oxidative desulphurisation/de-
Crude upgrading
metallization, and crude oil upgrading. Apart from these refinery processes, applications of this technology are
Enhanced oil recovery
Oil sand extraction
also mentioned for other potential crude oil sources such as oil shale and oil sand extraction. The relative
Oil shale advantages and current situation of each application/process at commercial scale is explained.
Petroleum industry

1. Introduction cavitation ‘bubbles’ oscillate under the influence of varying pressure,

Crude oil, as a petroleum reserve and a principal feedstock for
transportation and chemical manufacturing is a fast dwindling natural
resource. Conventionally divided into light crude and heavy Crude,
they together will need to address the growing demand for transpor-
tation fuels and chemical manufacturing feed-stocks. The light crude is
easy to process but its availability is on the decline. The heavy crude
however is widely available. Countries such as Canada, United States
and Venezuela have extremely large deposits of ‘oil shale’ and ‘heavy
oil’. It is estimated that there is more heavy oil in Venezuela than there
is petroleum in the Middle East. Canada is currently the world’s leading
producer of heavy oil and it is estimated that the oil sands in Canada is
enough to supply its current demand for well over 200 years [1]. Be-
cause of high reliance on petroleum for transportation and also for
manufacturing speciality chemicals, we have to process heavy, extra
heavy crude oils. The present conventional refining technologies cannot
process these extra heavy oil reserves economically, without polluting
the environment.
In the last few decades, cavitation technology, produced by either
ultrasound or by hydrodynamic means, has attracted the attention of
chemical industry [2,3]. Cavitation is defined as the formation, growth
and subsequent collapse of the bubbles. Acoustic cavitation occurs in
liquids under high intensity sound wave irradiation (in industrial ap-
plications between 20 and 50 kHz [4]). As the sound wave passes, the
eventually growing to an unstable size. Finally, the violent collapse of
the cavitation ‘bubbles’ result in implosions. It is these implosions
which produce the physico-chemical transformations observed in sono-
chemistry. Each of these imploding bubbles can therefore be seen as a
micro-reactor, with temperatures reaching an estimated 5000 °C, and
pressures of several hundred atmospheres [5]. Another energy efficient
way of producing cavitation is through hydrodynamic cavitation [6].
This cavitation is generated by passage of a liquid through a constric-
tion such as throttling valve, orifice plate, venturi etc. A careful design
of the system allows generating cavity collapse conditions similar to
acoustic cavitation of varying intensities but at much lower energy
inputs as compared to sono-chemical reactors. Several designs of hy-
drodynamic cavitation equipment are available commercially, based on
the Bernoulli’s principle [7]. One of the successful applications of the
cavitation technology is for production of biodiesel at industrial scale
[8].
This review takes a comprehensive look at ultrasound based cavi-
tation applications in various processes related to crude oil including
enhanced oil recovery, extraction of oil from unconventional energy
sources such as oil shale and tar-sands, refinery downstream processes
such as demulsification, desulfurization, demetallization, cracking or
upgrading of heavy oil to useful lower boiling point components and
intermediate processes like pipeline transport (asphaltene suspension).
These processes are discussed next in sequence, beginning with

⁎
Corresponding author.
E-mail address: balasubrahmanyam.avvaru@ril.com (B. Avvaru).

https://doi.org/10.1016/j.ultsonch.2017.12.010
Received 6 January 2017; Received in revised form 2 November 2017; Accepted 4 December 2017
Available online 05 December 2017
1350-4177/ © 2017 Elsevier B.V. All rights reserved.
B. Avvaru et al.
enhanced oil recovery, oil extraction from unconventional sources, pi-
peline transport and downstream refinery processes. Finally, industrial
scale cavitation reactors, reactor configurations and their operating
strategy are discussed.
2. Ultrasound enhanced oil recovery
Declining production of oil from the reservoir is of major concern to
the oil companies. The various oil production methods can be classified
as primary, secondary and tertiary. Under primary production, the
natural well pressure in the reservoir generally allows 30 percent re-
covery of the oil present in the formation. The residual oil after primary
production is difficult to produce because of its very low mobility
caused by decreased permeability in the producing wellbore by the
deposition of scales and precipitants, increased viscosity of the oil,
blockage of pores etc. [9,10]. The secondary production methods in-
clude gas and brine reinjection or water flooding. The injected fluid
displaces the produced reservoir fluid directly into the production wells
or maintains the reservoir pressure. A most common method involves
flooding the reservoir with water. The ultimate recovery factor can be
increased to 40–50% using these secondary recovery methods [10–12].
However during such production, the steam or water addition to the
reservoir may cause stable emulsion formation with the polar hydro-
carbon compounds. These production methods are affected by the
disadvantages of stable water-in-oil emulsions on flow owing to higher
friction factor, viscosity and correspondingly larger pressure drop [13].
The tertiary production methods, also known as enhanced oil recovery
(EOR) methods, focus on recovery of the remaining oil in the reservoir
after the primary and secondary methods. They include layer burning,
solvent and acid injection treatment by mechanical scrapers and high
pressure fracturing. These methods may not be suitable for every type
of reservoir either due to uneconomical, technical limitations, or due to
undesirable side effects. They may require shutting in production, or
may create harmful ecological consequences, and may be economically
not feasible.
Before we examine various ultrasound based applications for en-
hanced oil recovery, it is instructive to know the possible reasons for
decrease in production of oil from wells. These can be based on factors
that would affect the permeability of the near-well zone of the reservoir
as stated below [14]:
1. Fluid-fluid incompatibilities, for example, emulsions generated be-
tween invading oil based mud filtrate and formation water.
2. Deposition of organic or inorganic scale precipitation, solid plugging
are the main causes of this problem.
3. Fines migration, for example the internal movement of fine parti-
culates within a rock’s pore structure resulting in the bridging and
plugging of pore throats.
4. Deposition of reaction products as a result of widely used treatments
near-well zone of formation of chemical reagents and paraffin/as-
phaltene deposition.
In addition, the physical and chemical characteristics of the impact
of these factors on the formation are different in nature. Ultrasound
based applications work on improving the well production from the
adverse impact of above mentioned factors as examined further.
The early use of sound to revitalize oil wells involved audible sound
i.e. sonic waves of a much longer wavelength than ultrasound, often
termed seismic waves [15]. The use of elastic wave stimulation has
been suggested as an alternative or complementary tool to conventional
EOR methods. This technique first attracted the attention of researchers
in the US and USSR in the late 1950 s. A good review on elastic wave
stimulation for enhanced oil recovery has been available in the litera-
ture [15]. The penetration of low frequency elastic waves through
porous medium, creates harmonics with higher frequencies [16]. Ni-
kolaevskiy [17] speculates that excitation by elastic waves may
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Ultrasonics - Sonochemistry 42 (2018) 493–507
considerably reduce the influence of capillary forces on oil percolation,
coalescence of oil drops due to the Bjerknes forces, resulting in an in-
creased rate of migration through the porous medium. Mechanical vi-
brations destroy the surface films adsorbed on the pore boundaries,
thereby increasing the effective cross-section of pores and accelerating
the process of the penetration of liquids into capillaries (Sono-capillary
effect) [18]. A complete analysis of oil percolation, capillary interaction
and oil recovery under ultrasonic waves has been well explained with
laboratory experiments. It is reported [19] that ultrasound irradiation
enhances surfactant solubility and capillary imbibition recovery of oil
for various fluid pairs besides reducing surfactant adsorption onto the
rock matrix [20]. Venkitaraman et al. [21] studied the removal of near
well bore damage by ultrasonic radiation. Based on a laboratory study
focussed on removal of mud solids on a plug, they mentioned that
acoustic streaming and cavitation generated from ultrasonic waves can
remove the damages by mud particles and also increase the perme-
ability several times. Substantial amount of work [22–29] has been
carried out using laboratory model systems to find the exact me-
chanism. Hamidi et al. [30] revealed through laboratory experiments,
that oil recovery can be improved considerably by using ultrasound-
assisted CO2 flooding compared to conventional CO2 flooding, and
found that the changes were more pronounced for uncontrolled tem-
perature conditions of ultrasound-assisted CO2 flooding.
The first industrial tests of the ultrasonic method for reservoir sti-
mulation reported the treatment of several productive wells at
Samotlorskoye and Fedorovskoye oil fields in Western Siberia [31,32]
with an overall success rate of about 52 percent. For a successful
treatment, the effect of enhanced production may last for 3–24 months
with a significant increase in production. However, in some other wells
the enhanced oil recovery effect lasted for 1.5 months only before the
production dipped far below the initial level. During 1991 Shaw Re-
source services conducted tests on seventeen wells using their patented
“Sona-Tool” on the wells showing declining oil and water production
rates before the stimulation [33]. They reported a 40–50% success rate
for three minutes of ultrasonic excitation with the duration of the effect
lasting up to one month in most effective cases. Shaw Resource services
[33] have described the criteria for the selection of wells for successful
acoustic treatment. The reservoir should show declining production
attributed to near borehole zone plugged by deposits and should not
exhibit a significant drop of internal pressure. Other reservoir char-
acteristics should include: Porosity of internal well structure should be
5% or above, significant gas content (more than 10 m3 gas/m3 total
fluid) and a maximum oil viscosity of 10−2 Pa s. Abramov et al. [34]
reported that in wells with permeability above 20 mD and porosity
greater than 15%, ultrasonic treatment can increase oil production by
50% or even more in some cases. The effect of ultrasonic treatment lasts
from 3 to 12 months. For wells of lower permeability and porosity,
ultrasonic treatment alone is less successful but high production rates
can be achieved when it is applied in conjunction with chemical re-
agents. In this case, an average productivity increase of nearly threefold
can be achieved by synergistically combining ultrasound with chemical
treatment (Sono-Chemical) methods. The ultrasonic treatment not only
contributes to the cleaning of the perforation zone and increasing the
mobility of oil, but also increases the penetration of the reagent into the
formation and hence accelerates the chemical reaction in the porous
media of formation.
The sono-chemical method of EOR can also be applied to horizontal
wells. Abramov et al. [34] described the theoretical background of
applying sono-chemical technology in horizontal wells including
equipment required. The ultrasound EOR equipment consisted of
downhole equipment including a sonotrode, a system for injection of
chemicals and a probe for acquiring geophysical data (temperature,
pressure and flow). The equipment has a special cable with a hydraulic
channel for injection of technological fluids (surfactant formulations)
and includes electrical cores to power the equipment and the geophy-
sical probe. For other than the injection of reagents directly to the zone
B. Avvaru et al.
Fig. 1. Cross sectional view of the cable used for ultrasonic EOR.
of the acoustical treatment, the cable can be used to wash and clean the
horizontal area of the well with technological fluid (surfactant for-
mulations) prior to and after the treatment. The cross sectional view of
the cable is shown in the Fig. 1. Abramov et al. [35] have treated 3
horizontal wells in sandstone reservoirs in Western Siberia with pro-
mising results showing an increase in average oil production from 23 to
33 tons per day. Abramova et al. [36], have performed more than 100
ultrasonic operations in Western Siberia (WS) and Samara region (SR)
in the period from 2010 to 2013. An average increase in oil production
by 4.4 tons/day for WS and 10.2 tons/day for the SR was achieved.
They have concluded that the method has shown a success rate of 90%
with an increase in oil production from 40 to 100%. The main ad-
vantages of the ultrasonic EOR technology are low energy consumption,
the possibility to treat the reservoir selectively, no harm to the well and
its casing, and the technology is eco-friendly and economically accep-
table.
The ultrasonic equipment developed by Viatech was successfully
tested on the Samotlor oil field by the specialists of CUT-Service Ltd.
[37–39]. The down hole equipment includes a sonotrode PSMS-42
(with the diameter 42 mm) and a geophysical probe for acquiring
geophysical data (temperature, pressure, flow). The ultrasonic tool has
the form of a cylinder shape. It converts longitudinal oscillation into
radial, which affect the wellbore perforation zone. Progress Ultrasonic
group also developed the technology of ultrasonic EOR on the same
principle [40]. They have special type of transducers of power varying
from 1 to 20 kW, working frequencies from 1 to 50 kHz, length of acid
resistance transducers varying from 1.5 to 2.24 m and diameters of 4.4,
7.6 and 10.1 cm, and these transducers can work under temperature
and pressure up to +150 °C, 50 MPa respectively. An average oil pro-
duction increase of 40% has been achieved after the sono-chemical
treatment in horizontal wells [35]. Authors [41–43] published a state-
of-the art ultrasonic technique for EOR, and reviewed the recent de-
velopment of this technology. They proposed that the development of
robust ultrasonic transducer is an important research activity for the
near future. They mentioned although the sono-chemcial treatment for
EOR gives synergistic results, from the reservoir protection and sus-
tainable development of oilfield point of view however the chemical
methods should be replaced by ultrasonic treatment.
3. Extraction of kerogen from oil shale using ultrasound
cavitation
Oil shale is a fine grained sedimentary rock which contains a solid
hydrocarbonaceous material (kerogen) that can be converted to crude
shale oil. The world reserves of oil shale are vast, being many times
more than the proven remaining resources of conventional crude oil
and natural gas combined, as shown in Table 1 [44]. These un-
conventional resources could play an important role in energy supply
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Ultrasonics - Sonochemistry 42 (2018) 493–507
Table 1
World reserves of Oil shale deposits [44].
S. No Country Deposits (in billion barrels)
1. United States 3706
2 China 354
3 Russia 247
4 Brazil 82
5 Morocco 53.3
6 Jordan 34
7 Australia 31.7
8 Estonia 16.3
9 Canada 15.2
for future, and conversion of these solid fuels to chemicals feedstock
and cleaner burning liquid are main challenges.
The organic part of oil shale, kerogen, is a cross-linked macro-
molecular system. The essence of an oil shale liquefaction process is the
structural degradation with or without the addition of hydrogen to a
kerogen material, with hetero-atom removal. The current technology
for the recovery of oil from oil shale is based on pyrolysis (retorting) at
about 500 °C [45]. At this high temperature the rate of kerogen pyr-
olysis is fast and complete decomposition occurs. But along with
cracking reactions, coking also occurs, leading to gas and solid forma-
tion that decreases the oil yield. Retorting has certain limitations such
as high energy requirement, low conversion of the organic matter to
liquid, and the presence of hetero-atoms which causes the formation of
olefins in the product. Hence there is considerable interest in alter-
native methods to convert kerogen into soluble products, preferably
methods that operate at near-ambient temperatures.
Most of the studies reported in the literature are based on extraction
by solvents or supercritical fluids in the temperature range of
300–400 °C under pressure [46]. In solvent extraction process, the oil
shale from the field is generally crushed/powdered to the required size
and contacted with a solvent at high temperature. Comparatively su-
percritical fluid extraction offers better separation of hydrocarbons
from oil shale. However it requires high energy to maintain the super
critical temperature (approx. 400 °C) and pressure conditions to pro-
duce higher conversion rate. It should be noted that at these conditions
significant coking reactions also were reported [47–49]. Thus the above
mentioned disadvantages have let down the commercial implementa-
tion of supercritical fluid extraction for oil shale processes.
Extraction using the ultrasound based cavitation process can en-
hance kerogen recovery. Oil shale is often considered to be made by two
parts: a solvent insoluble fraction consisting of a covalently cross linked
network, and the solvent soluble fraction of low molecular weight
substances trapped in the network. These covalent interactions result
into low extraction rates and recoveries [50,51]. For this type of ex-
traction conditions, the ultrasonic energy through cavitation process
causes intense agitation. The produced micro jets causes the breakdown
of the covalent interactions and intensify the penetration of solvents
into different regions of multi-phase systems. The solvent selection and
ultrasonic parameters plays an important role for better extraction
yields. Haddadin [51] studied the effect of ultrasonic parameters such
as frequency, ultrasonic power and operating parameters such as ex-
traction temperature, time of extraction, and type of solvent. All these
parameters have shown significant effect on oil yield.
Matouq et al. [52] carried ultrasonic extraction of kerogen from
Jordan oil shale using 20 kHz frequency horn type reactor. Among the
studied solvents THF (tetrahydrofuran) is the best solvent for better
extraction yield of 90%. The extraction yield is three times higher than
silent (stirring) conditions and the extraction time was reduced four
times. The rate of extraction was observed to follow two regimes.
During an initial period of 5 min there is not much difference in the
extraction yield compared to silent conditions, and thereafter the ex-
traction rate increased drastically four-fold. It takes some time for
B. Avvaru et al.
Table 2
Total world reserves of original Natural bitumen (Tar-sands) and Extra-Heavy oil [54].
Region Natural bitumen Extra Heavy oil
(Tar-sands) (in BBO)
(in BBO)
Africa 64.34 0.5
North America 2488.63 3.05
South America – 2113.55
Asia 426.77 17.72
Europe 348.86 15.11
Total world 3328.0 2149.88
BBO – Billion Barrels of Oil.
solvent to reach inside the oil shale structure and thereafter the cavi-
tational events causing them to break down the insoluble cross linked
structure of kerogen. Zhao et al. [53] carried out ultrasonic extraction
of kerogen from Huadian oil shale with 60 kHz frequency of ultrasound.
They achieved a maximum extraction of 15.6% using a solvent having
60 wt% CHCl3 and 40 wt% of CS2. The optimised mass ratio of demi-
neralized oil shale to CHCl3-CS2 was found to be 1:20.
As discussed, other than a few laboratory literature available for
extraction of kerogen from oil shale using cavitation, no work has been
reported at pilot scale. May be the high cost associated with the
grinding of whole rock to target size and solvent regeneration in the
process may be hampering the application to the pilot scale level.
Considering the large reserves of world oil shale resources, further
developments are needed to process them by these cavitation methods.
4. Oil sand extraction using ultrasound cavitation
Oil sand is made up of grains of quartz sand, surrounded by a layer
of water and clay, and then covered in a slick of heavy oil called bi-
tumen. Deposits of oil sand and extra heavy oils exist throughout the
world, and as shown in Table 2 [54] most of them were found in Alberta
(Canada) and in Orinoco (Venezuela) respectively [55,56]. In view of
rising oil consumption, the extraction of bitumen/residual oil from oil
bearing sand has become increasingly important. To use bitumen as an
energy source, it must be first extracted from oil sand and then up-
graded to light oils. Wen et al. [57] described bitumen as consisting of
following fractions: gas oil (saturated/aromatic hydrocarbons), resin,
asphaltene, and carbene/carboid (preasphaltenes). Although the bi-
tumen saturation of tar sands may vary from 10 to 18%, the bitumen
content of high grade Athabasca tar sands is relatively constant, at
14.5% by weight. A number of technologies are available for the ex-
traction of oil from tar sands. They all use hydro-mechanical (me-
chanical mixing or hydro transport), thermal (mixing with hot water or
steam), or/and chemical (addition of reagents) procedures. Hot water
processes are currently used by Suncor and Syncrude in Alberta, Ca-
nada, to recover the bitumen [58–61].
Avvaru et al. [62,63] reported ultrasonic cavitation in solid slurries
produces micro jets, which lead to particle breakage. Ultrasound im-
proves the local transport in the pores of the suspended solids at solid-
liquid interfaces. Hence ultrasound cavitation is a promising method for
extraction of heterogeneous mixtures and therefore in combination
with other methods (for e.g. chemical ones) can be an effective alter-
native to conventional process of oil sand extraction. Sadeghi et al. [64]
conducted a series of experiments on a wide variety of fuel sources such
as coal liquids, oil sand, oil shale, asphalt and heavy oils. These ex-
periments indicated that ultrasound cavitation could be a feasible up-
grading technology. In all the above cases, upgrading (conversion) of
asphaltenes to resins were observed, and the rate of conversion in-
creased with externally added surfactants. In presence of ultrasound,
the components of bitumen in alkaline solution (e.g. sodium hydroxide)
and the in situ formed surfactants facilitate the bitumen separation and
upgrading to useful components. The surfactants interact with resin
496
Ultrasonics - Sonochemistry 42 (2018) 493–507
Fig. 2. Sono-chemical recovery of Bitumen from oil-sands Region A: Extraction of oily
fractions of bitumen Region B: Neutralisation of resinous compounds/production of in
situ surfactants Region C: Cracking of asphaltene micelles.
molecules in a membrane-mimetic fashion [65–67]. Sadeghi et al. [68]
carried out kinetic studies on three different oil sand samples, and re-
vealed that formation of these in situ formed surfactants follow an
autocatalytic mechanism. For all the samples, the cumulative recovery
curves for the experiments performed so far resembled the ‘S’ shaped
characteristic rate curve shown in Fig. 2. Extraction of bitumen dy-
namics can be represented by three regions (A, B, and C) as shown in
the Fig. 2. Region ‘A’ is where the oily fraction of bitumen is released. In
region ‘B’, neutralization of resinous compounds occurs and production
of in situ surfactants are initiated. These natural surfactants then dis-
rupt the already exposed asphaltene micelles through the inversion
process to form Hartley micelles. Region ‘C’ illustrates an advantage of
using the power of cavitation. In this region, actual cracking of as-
phaltene micelles occurs. In this way, without exhaustion these sur-
factants can be reused by maintaining the pH of the solution in alkaline
region. The bitumen from Athabasca oil sand has an average API
gravity of 8°. The bitumen recovered by ultrasonic process has an
average API gravity of 15° [68]. With the addition of radical initiators
such as H2O2 to the in situ surfactants, it can further shorten the mi-
cellar inversion time into a matter of minutes to extract the bitumen
from Athabasca oil sands [69].
Abramov et al. [70–72] carried out series of extraction experiments
using ultrasound on Athabasca oil sands using various alkaline reagents
such as sodium silicate, NaOH and Na2CO3. They observed that bi-
tumen extraction decreased with increasing alkaline reagent con-
centration until a certain value beyond which bitumen extraction im-
proved with increase of reagent concentration. At very low reagent
concentration (C < 0.01%), author has observed entrapment of sand
along with bitumen and with increasing reagent concentration bitumen
extraction has decreased. At 1–1.2% reagent concentration the bitumen
extraction was observed to be very low and thereafter it increased to
95% extraction with increase in reagent concentration to 12%. Similar
improvement in the extraction yield were found with Venezuelan heavy
oils as well [73]. Spent alkali solution shows initial extraction rate
much higher than fresh alkali solution, due to readily available sur-
factant micelles for the extraction process. Recycling of spent alkali
allows the ultrasonic oil sand extraction to be an environmentally be-
nign process. Okawa et al. [74], have carried out the effect of fre-
quencies on ultrasonic oil sand extraction at 28 & 200 kHz. The bitumen
B. Avvaru et al.
extraction rate at 200 kHz was slightly higher than compared to 28 kHz
at 75 °C temperature. This could be due to increased cavitational events
at higher ultrasound frequency. In presence of small concentration of
H2O2 recovery rate of bitumen has been observed to be maximum at
28 kHz ultrasound. Similarly, laboratory studies by Zhao et al. [75] on
Mongolian oil sands showed improved oil extraction rate.
The ultrasonic apparatus required for oil sand extraction were de-
signed and installed at the Ultrasonic devices laboratory of Institute of
general and inorganic chemistry, Russian academy of sciences. The
acoustic system was equipped with computer-aided ultrasonic gen-
erators and 1–7 kW magneto-striction transformers for operation at
frequencies of 25–40 kHz. The soil contaminated with a large amount of
fuel oil was purified at the pilot scale. The pilot trial results confirmed
the results obtained at the laboratory studies [70]. Petrosonic heavy oil
processes [76] have shown the conversion of heavy sour oil (HSO) and
bitumen (heavy oil and oil sands fields of Athabascan) having an API
gravity of 8–14° to a value added synthetic crude oil of 18–23° API
gravity. The process consists of two stages: solvent de-asphalting fol-
lowed by distillation. The innovation associated with the Petrosonic
upgrading process, lies in the rapid de-asphalting achieved by using
ultrasound cavitation in the patented Petrosonic reactor. The process
anticipates that 15–20% of the asphalt byproduct, can be sold in the
asphalt market. The Sonoprocess™ filters the DAO (de-asphalted oil)
from the hydrocarbon asphaltene and reduces the de-asphalting time
from 6 to 10+ h to 2 min, i.e., 50 orders of conversion rate improve-
ment. Given the significant difference in boiling points between the
upgraded oil and the solvent for recovery, they are easily and eco-
nomically separated with only a solvent residual of less than 4% re-
maining in the oil. Such a small solvent residual in the oil is well within
the quality parameters for pipeline and refinery specifications. The
process requires much lower capital expenditures, operational costs and
it also lowers the transportation cost of the refined oil.
5. Crude oil viscosity reduction using cavitation
Heavy crude oil and bitumen exploration is faced with technical
challenges at all stages from recovery/production from the reservoir to
transportation and refining. Transporting heavy crude oil and bitumen
via pipeline to storage or refinery for downstream processing is usually
challenging due to their high density and viscosity (1000 cP). Further,
asphaltene deposition, heavy metals, sulphur and brine or salt content
in crude oil makes it difficult to transport [77–79]. Asphaltene are
heavy complex molecules which are soluble in aromatics and not so-
luble in paraffin. They are the heaviest and the most polar fraction of
crude oil. Canada and Venezuela are the countries presently exploiting
heavy crude oil reserves and pipelines are used to transport 95% of the
heavy oil produced by them. The asphaltene portion of the heavy oils is
known to be insoluble in straight chain hydrocarbons such as pentane
and heptane. Therefore, problems due to asphaltene precipitation due
to depressurisation (below asphaltene precipitation onset pressure) may
occur when transporting the heavy crude oil. High pressure drop along
Table 3
Viscosity reduction of petroleum oils under ultrasound cavitation conditions.
Crude oil details Time (min)
Crude oil 30–60
Asphaltenic crude oil (bitumen) 50
Athabasca bitumen 50
Extra heavy oil 2 24
Liquid paraffin oil 2 10
Binnan oil well of Shengli oil field 30
Crude oil from Samara region 240
Liaohe heavy oil 30
Residual fuel oil 5 45
Synthetic oil, Paraffin oil & Kerosene 60
Residual oil 14
Ultrasonics - Sonochemistry 42 (2018) 493–507
the pipeline due to high viscosity of the heavy oil makes it cost and
energy intensive to transport via pipeline [80]. Improved way of
transporting the heavy crude and bitumen using pipelines can be
achieved through pre-heating of the heavy crude alongside heating of
the pipeline, blending or dilution with light hydrocarbon fluids, as well
as emulsification of heavy oil with water and reduction of viscosity of
the oil by core-annular flow [81–84]. Another set of processes rely on
the reduction of heavy crude oil viscosity by heating the crude oil by
partial upgrading were reported [85,86].
High energy ultrasound can induce cavitation effect in extra heavy
oil. This can change large molecules in extra heavy oil into light hy-
drocarbon molecules. The earliest work on viscosity reduction of heavy
oils was reported by Sokolov et al. [87], who observed that viscosity is
reduced by 20–25% for 30–60 min of operation. Islam et al. [88] car-
ried out experiments to ascertain the relationship between asphaltene
content (molecular weight) and bitumen viscosity. They showed that
high oil viscosity was due to the presence of more asphaltene heavy
components. Using ultrasound cavitation they cracked the asphaltene
molecular chains, and consequently reduced the viscosity of oil.
Chakma and Berruti [89] reported 15% viscosity reduction of heavy
asphaltene oil samples after irradiating with ultrasonic waves. In 1993,
Xianghong and Yaping [90] showed that the viscosity of 20 ml extra
heavy oil is reduced by 24% after 2 min of ultrasonic treatment. Espe-
cially for extra heavy oil mixed with water, its viscosity can be greatly
reduced after ultrasonic treatment. In 2004, Bjorndalen and Islam [91]
found that the relative viscosity of liquid paraffin is reduced by 10%
after 2 min of ultrasonic treatment. Xianyong and Ping [92] and Jihui
et al. [93] studied the influence of ultrasound frequency, treatment
time, temperature and sound intensity on the viscosity reduction of
Binnan oil well of Shengli oil field in China. Experimental results have
shown that the optimum values of ultrasonic frequency, treatment time,
temperature and sound intensity for reducing the viscosity of crude oil
is 18.5 kHz, 30 min, 40 °C and 52 W/cm2 respectively. Abramov et al.
[94] have conducted field experiments to show that a viscosity reduc-
tion by 16% after 4 h of treatment was observed and this simulta-
neously increased the oil production rate by 26.5%. After its recovery
when the same oil is treated in a special type of ultrasonic hydro-
dynamic treatment reactor, causes not only further reduction of visc-
osity by 30% but also changes the fractional composition of the oil. Shi
et al. [95] have reported a viscosity reduction of 57% on Liaohe heavy
oil using ultrasonic static mixer at 360 °C temperature, with 1.8 kW
power and 30 min. operating conditions. They reported ultrasonic
treatment requires 43% less energy compared to conventional vis-
breaking technology. Viscosity reduction of various petroleum crude
oils under ultrasonic cavitation treatment is shown in the Table 3.
Right now, ultrasonic viscosity reduction techniques in many
countries emphasize field tests, with the research on theoretical models
still in its infancy, the basic theory for ultrasonic viscosity reduction
technique has still not been established. In petroleum chemistry it is
predominantly accepted that asphaltenes are suspended in micelle form
in petroleum and are stabilized by adsorbed resins in solutions [99].
% Reduction Reason for viscosity reduction Reference
20–25 Temperature increase [87]
– Reduction of asphaltene content [88]
15 Reduction of asphaltene content [89]
Cracking of heavy molecule [90]
Cracking of heavy molecule [91]
30–40 – [92,93]
16 Craking of heavy molecules [94]
57 Craking of heavy molecules [95]
Cracking of heavy fuel oil [96]
3.2, 3.8 & 4.0 Heat effects & cavitation [97]
63.94 Cracking of heavy fuel oil [98]
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time. At this optimum time of irradiation the rate of asphaltene disin-

tegration is equal to rate of asphaltene formation through a free radical
mechanism generated through ultrasound cavitation. However, by
providing the conditions favourable to free radical formation (such as
hydrogen donor solvent/hydrogen gas) heavy asphaltene can be con-
verted to gas oils and resins, which further causes reduction in visc-
osity.

6. Ultrasound assisted demulsification of water-crude oil

emulsions

Crude oil after reaching the refinery, undergoes removal of dis-

solved metal salts such as NaCl, CaCl2 and MgCl2 [103]. If not removed,
these dissolved chlorides could get hydrolysed in presence of water and
deactivate the refinery catalysts besides causing further corrosion in
Fig. 3. Crude oil viscosity variation with ultrasound irradiation Region 1: Dissolution of
overhead distillation columns [104,105]. Hence it is required to limit
unsolved suspended particles in the crude oil Region 2: Disintegration of asphaltenes due
the salt concentration below 5.0 mg/L and water content below 0.3%
to free radical reactions Region 3: Disintegration and integration of asphaltenes due to
free radical reactions. (v/v) of the crude oil before further processing [106]. In this desalting
process, (1–20%) water is mixed with the crude to dissolve the metal
chloride salts. Unfortunately, naturally occurring polar substances in
The ratios of resin to asphaltene and aromatic content to saturate are
the crude such as resins and asphaltene assist the formation of water-in-
the key parameters that control the stability of asphaltene micelles in
oil (w/o) type emulsions [107]. In case of heavy/extra heavy crude oils
crude oil. When these ratios decrease, asphaltene micelles flocculate
the presence of highly poly aromatic asphaltene makes them very dif-
and form larger aggregates, these events may increase the viscosity of
ficult to desalt by conventional methods such as electric desalting and
the oil [100].
dewatering methods [108]. Therefore, for heavier crude oil which
Based on a series of experiments on rheological properties and as-
contains more salt concentration, the commonly used electrostatic
phaltene flocculation of crude oils using confocal microscopy analysis,
method is undesirable and non-efficient [109]. Various techniques are
Najafi et al. [101] reported the existence of an optimum irradiation
used to destabilise these emulsions, among which the most widely used
time at which asphaltenic crude oils reach the minimum kinematic
method consists of adding small amounts of demulsifiers. These surface-
viscosity. Accordingly, they proposed the idea of asphaltene floccula-
active molecules adsorb at the oil-water interface, displaces the as-
tion inhibition due to ultrasonic irradiation. Ultrasonic wave irradiation
phaltene and accelerates phase separation by destabilising the emul-
on the crude oil having API gravity 20°, whose viscosity variations have
sions. For these extra heavy crude oils various methods like multi-stage
shown three different regimes with ultrasonic irradiation. As is shown
desalting processes, cross flow membrane, microwave assisted de-
in Fig. 3, there is an optimum irradiation time at which the value of
mulsification techniques [110,111] were developed. However, even
viscosity has been observed to be minimum. This time was recorded to
with three stages of electrostatic desalting operation, the crude oil
be between 10 and 25 min for crude oil having API gravity 20°, and this
specification cannot meet the desired level of quality suitable for fur-
optimum irradiation time increases with decreasing API gravity. At
ther processing. Hence the need of demulsification and the impetus for
each stage one or two of the mechanisms are dominant. Previously,
developing new methods for effective treatment of oil became more
Argillier et al. [102] mentioned the concept of critical concentration of
important.
asphaltene above which the overlap between asphaltene particles
The effect of ultrasonic waves were studied on suspended particles,
would lead to an increase in viscosity. Recently similar set of experi-
droplets and bubbles by various researchers [112–114]. It has been
ments on south Iranian oil field conducted by Salehzadeh et al. [28]
understood that emulsion breaking happens as a result of the combi-
confirm the results of optimum time and power of ultrasonic irradia-
nation of three basic processes such as creaming, coagulation, coales-
tion. They showed that ultrasound cavitation may inhibit the asphal-
cence and followed by sedimentation. In ultrasound irradiation, the
tene flocculation at the near well region and causes improvement in the
reverberation of ultrasonic field causes the formation of standing wave
oil well production. The rheological behaviours at each of these ranges
field which in turn causes the coagulation and coalescence of droplets.
has been explained as:
When the standing wave of ultrasound spreads in a continuous medium
Region 1: In this range the main role is played by dissolution of
having scattered drops, the displacement effect happens on the dro-
unsolved suspended particles in crude oil which leads to an increase in
plets. The ultrasound standing wave pushes the water drop to wave
viscosity.
nodes and causing them to coagulate. The externally added demulsifiers
Region 2: The main reasons for viscosity reduction in this range are
may assist them to coalesce and subsequently separation occurs due to
temperature increase and asphaltene molecules disintegration takes
sedimentation. The distance between the transducer surface and the
place. Ultrasonic wave forms the free radicals and cracks the long chain
reflection surface was determined strictly in order to form a standing
and heavy molecules which leads to a reduction in viscosity.
wave field in the device. The wave reflection at the opposite end of the
Region 3: In all periods of sonication two mechanisms are active in
transducer takes place only when the acoustic impedance (Zs) of the
crude oil system. These mechanisms causes the disintegration of mo-
medium is greater than the acoustic impedance of the air in which wave
lecules into free radicals and hydrocarbons with shorter chain length
is travelling, otherwise it may absorb completely, and it neither gets
and integration of free radicals causes the formation of heavy mole-
reflected nor forms a standing wave [115]. In a recent review [116], the
cules. This means that sonication can change the composition of crude
opportunities and developments to use ultrasonic standing waves for
oil. Based on the viscosity curves shown in Fig. 3, after the local visc-
the separations of suspensions and emulsions for applications in food
osity minimum point, named the optimum irradiation time, the domi-
and other material processing industries have been well explained.
nant factor is reintegration of free radicals to each other and formation
However, recently published literature suggests that low frequency
of heavy molecules.
ultrasound also causes demulsification of water-in-oil crude oil emul-
Based on the experiments [28,101], ultrasonic irradiation before the
sions [117,118]. Authors have observed better demulsification effi-
optimum time can reduce the asphaltene content of the crude oil, and
ciency at lower frequencies (25, 35 and 45 kHz) and no demulsification
thereafter the asphaltene content increases with increase of irradiation
at higher frequencies (> 135 kHz). They claimed that cavitation effects

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such as micro-streaming and turbulence are responsible for the

breaking of interfacial films that stabilises the emulsions, which may
lead to coalescence of the droplets and causing better oil water se-
paration. These cavitation effects should be sufficient enough to break
these interfacial films otherwise high intense cavitation may lead to
further emulsification. In case of higher frequencies (> 135 kHz) nei-
ther cavitation effects are intense enough to break these interfacial
films nor is the condition for formation of standing wave was estab-
lished.
Ye et al. [119] pre-treated the crude oil for 5 min at 80 °C in a
standing wave field with frequency of 10 kHz and ultrasonic intensity of
0.38 Wcm−2. After the pre-treatment, the dewatering rate and desalting
rate were up to 92.6% and 87.9% (v/v), respectively after 90 min of
settling the emulsion. They also reported that by adding 30 ppm of
demulsifier, the final salt and water contents were decreased to
3.851 mg/L and 0.37% respectively. Check and Mowla [120] reported,
under optimal ultrasonic parameters such as irradiation time of 6.2 min,
power of 57.7 W, temperature of 100 °C, with water content of 7 vol%
and chemical demulsifier of 2 ppm the removal efficiencies of the de-
salting/dehydration were 84% and 99.8%, respectively after 60 min of
settling the emulsion. Wei et al. [121] suggested that the water content
Fig. 4. Hydrogenation reaction rate with various sulphur compounds.
can be reduced to 0.13% under optimum experimental conditions by
ultrasound combined with electrical desalting. The factors effecting the
dehydration by ultrasound such as power of ultrasound, operation gasoline fuel could lead to the emission of SO2 and sulfate particulate
temperature, demulsifying agent and voltage of desalting tank were matter (PM), which could cause acid rains and endanger public health
studied. The effect of standing wave field combined with demulsifier & welfare besides polluting the environment [128,129]. The sulphur is
was synergistically showing better results compared with each tech- present in heavy crude oil in the form of thiophenes, benzo thiophenes
nique alone. Efficiency of demulsification of various studies under ul- (BT), di-benzo thiophenes (DBT) such as 4 methyl di-benzo thiophene
trasound conditions was shown in the Table 4. (4 MDBT) and 4, 6 di-methyl di-benzo thiophene (4, 6 DMDBT). These
Various parameters need to be taken into account while designing sulphur compounds have very low reactivity for hydrodesulphurisation
the industrial scale ultrasonic desalter [125]. However, the crude oil (HDS), which can be explained by combinations of electronic density,
itself is a complex mix of various hydrocarbons which makes the op- bond order, spatial geometry and steric hindrance around the sulphur
eration of the ultrasonic desalter more troublesome. The intensity of the atom [130–132]. Hydrodesulphurisation reaction kinetics of di-
ultrasound in this process needs to be controlled as otherwise after benzothiophene and benzothiophene in coal derived liquid fuels are
certain optimum intensity of ultrasound, the demulsification efficiency well explained by Katti et al. [133]. The relative reaction rate/hydro-
can decrease. In fact high intensity cavitation is known to increase the genation rate of the typical sulphur compounds present in the crude oil
emulsification process for many industrial applications [126]. Ultra- is shown in Fig. 4. It is very difficult to hydrogenate these compounds
sound parameters need to be highly accurate in the design of desalter with conventional technology like hydrodesulphurisation (HDS) unless
for real plant scale application. A few consulting companies have it is done at high temperature, pressure and with special type of cata-
mentioned the application of this technology for industrial scale de- lyst. The need to desulfurize the cracked stocks in addition to the
salter application [127]. However no report has been mentioned on straight run streams is forcing the refiners to choose the most cost-ef-
usage of the technology for commercial refining operation. fective technologies [134,135].
In the past four decades, alternatives to hydrodesulphurisation have
been investigated extensively such as bio-desulphurisation, adsorptive
7. Ultrasonic assisted oxidative desulphurisation (UAOD) desulphurisation, extractive desulphurisation, ionic liquid catalysis and
oxidative desulphurisation [136–144]. Among these, oxidative desul-
Catalytic hydrotreating is an important process in petroleum re- phurisation (ODS) is a promising technology to remove the high mo-
fining, to remove about 90% of contaminants such as sulphur, nitrogen, lecular weight sulphur containing compounds from the petroleum
oxygen, and metals from liquid petroleum fractions. These con- crude at relatively low temperature (50–60 °C) and pressure. In ODS
taminants can have detrimental effects on the equipment, the catalysts, heavier sulphur compounds are oxidised by using an oxidant without
and the quality of the finished product. Typically, hydrotreating is done breaking the C–S bond to their respective sulphoxide and sulphone.
prior to processes such as catalytic cracking and/or reforming so that These two forms of compounds were having high polarity compared to
the catalyst is not contaminated with sulphur compounds that may be its un-oxidised sulphur form (e.g. thiophene, benzothiophene etc.), and
present in crude oil. If not removed sulphur present in the diesel/

Table 4
Dehydration/desalting efficiency of water in oil emulsions under ultrasonic conditions.

Emulsion system Ultrasonic irradiation time (min.) T (°C) Efficiency (%) Reference

Dehydration Desalting

Water in crude oil emulsions 15 45 65 87.9 [118]

Water in crude oil emulsions 5 80 92.6 – [119]
Water in crude oil emulsions 6.2 100 99.8 84 [120]
Water in olive oil emulsions 2.8 25 99.9 – [122]
Water in heavy crude oil emulsions 4 90 80 – [123]
Saline water in crude oil emulsions 15 50 93 – [124]

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Table 5 (model compound used quinoline) on UAOD process has impaired the
Companies engaged in ODS process technology during 20 years [145]. sulphur removal efficiency, however same oxidative conditions can be
used simultaneously for denitrogenation (UAODN) [156]. The opti-
Company Country Oxidant Patents
mised conditions from the batch UAOD and UAODN processes were
BP, corp., AMOCO USA H2O2 2 used to design the continuous flow reactors for energy efficient UAOD/
Exxon corp. USA H2O2 1 UAODN process [157–159].
DS2Tech ., Inc. USA H2O2 1
Carnegie-Mellon Univ. USA H2O2 2
Gul Oil corp., R&D USA HNO3 1 7.1. History of UAOD
Lyondell Chem. Comp. USA TBHP 2
Oxochem techn. Inc. USA H2O2 3 Oxidative desulphurisation process using ultrasound has been under
Petrobras Brazil H2O2 2 development since 1990. Desulfurization was carried out in basic or
PetroStar Inc. USA H2O2 3
acidic conditions by applying ultrasound frequency of 20 kHz to crude
UOP USA HCHP 4
Stanciulescu USA H2O2 1 oil. Use of transition metals, nickel and vanadium, as catalysts along
SulphCo. USA H2O2 3 with hydrogen peroxide as a chemical oxidant, assisted with ultrasound
TotalFinaElf. Corp. France H2O2 2 was developed by authors [160,161]. In the UAOD process, the Ven-
UniPureenergy Corp. USA H2O2 4
turella type of transition metal catalysts (TMC), or polyoxometalates
with Keggin structure such as phosphotungstic acid, and a quaternary
ammonium salt, tetraoctylammonium bromide, as phase transfer cata-
lyst (PTC) were introduced so as to produce highly effective and se-
lective oxidation with hydrogen peroxide to improve desulfurization
[148]. Higher than 98% desulfurization efficiency has been achieved
for diesel fuels in 10 min of ultrasonic cavitation with 30% wt hydrogen
peroxide as oxidant. However, this process has a low conversion of
benzothiophene (BT) and its derivatives and forms the brominated by-
products. Changing to phase transfer catalyst (second generation
UAOD) such as quaternary ammonium salt with fluoride instead of
bromide as anion in the catalyst eliminated the formation of by-pro-
duct, and also increased the overall desulfurization efficiency to 95%
[162]. Based on the second generation UAOD, a customized continuous
Fig. 5. Oxidation process route of various sulphur compounds. desulfurization system of 24 kg of diesel per day gave 92% desulphur-
isation efficiency [163]. To reduce hydrocarbon loss, alumina adsorp-
hence easily extractable using a suitable polar solvent. Thus basically tion was used to remove sulfones instead of liquid-liquid extraction
ODS is a two-step process, oxidation followed by either solvent ex- [164].
traction or solid adsorption. Many companies are actively engaged in The recent development of the third generation of UAOD using
ODS process development because of its attractive cost benefits as an room temperature ionic liquids (RTIL) as phase transfer catalyst and
alternative to conventional HDS process. During the past 20 years alone extracting solvent, has achieved greater than 99.9% desulfurization in
more than 30 process patents have been issued to the companies various diesel samples with 10 min of ultrasonic cavitation [165]. Ultra
working in the ODS technology as shown in Table 5 [145]. The oxi- low sulphur diesel (ULSD) with sulphur content less than 15 ppm can be
dation process route of the sulphide/thiophene/benzothiophene/di- produced from various diesels by this third generation UAOD process.
benzo thiophene to higher polarity (sulphone and sulphoxide) is shown Ionic liquids with alkylsulfate as anion that are relatively more stable,
in Fig. 5 [146]. With the advent of ultrasound cavitation technology the and produce non-corrosive byproducts upon degradation were used for
critical drawback associated with the slow/sluggish heterogeneous re- UAOD [166,167]. As shown in Table 6, the efficiency of sulphur re-
action between the oil phase and aqueous phase oxidant can be elimi- moval can be significantly improved by using ultrasound compared
nated, and the reaction can be carried out faster and at relatively low with stirring under identical oxidative system.
temperature and pressure. Ultrasound assisted oxidative desulphurisa-
tion (UAOD) has potential to replace the HDS to process the heavy and 7.2. Reaction conditions for UAOD
extra heavy crude oils in near future [147–150]. The extreme condi-
tions of temperature and pressure during acoustic cavitation causes the In presence of ultrasound various oxidants such as concentrated
formation of free radicals such as H% and OH% (among these OH% radi- nitric acid, peroxyacids, ozone, hydrogen peroxide, oxygen, organic
cals are strong oxidising agents) [151]. It is also reported that atomic hydro peroxides and permanganate have been used for ODS processes
oxygen can be generated from dissolved oxygen in aqueous solution [175–180]. Among them, the oxidant H2O2 is considered most pro-
upon ultrasound irradiation [152]. These radicals and atomic oxygen mising in terms of selectivity, availability, safety, cost effectiveness and
would further react with dissolved oxygen, water molecules, or other environmental friendliness [181]. Fenton's reagent is also a strong
radicals to form hydrogen peroxide and oxygen eventually. Moreover, oxidising agent, improves the hydrotreated diesel desulfurization rate
the volatile and semi-volatile thioethers and thiophenes can also di- probably by increasing the concentration of available %OH (free radi-
rectly be decomposed by sonication in aqueous solutions [153]. Bolla cals) [147]. Similar to hydrogen peroxide, superoxide anion is also
et al. [154] carried out experiments for studying the mechanism of considered as a reactive oxygen species. Callahan et al. [182] have
UAOD. Ultrasound cavitation works by creating the micro turbulence found hydrogen peroxide, the superoxide anion radical, and the hy-
which enhances the oxidation reaction between hydrocarbons such as droxyl radical are the most important reactive oxygen species. How-
thiophenes and its derivatives with the aqueous H2O2. While the exact ever, oxidising agent (H2O2) alone is not sufficient in giving the good
reaction mechanism is still under debate, the overall oxidation reaction reaction rate and requires a catalyst to work in mild temperature,
rate can be improved by ultrasound cavitation to several folds. Few pressure conditions ranging from 25 °C to less than 100 °C under am-
studies [155] mapped the acoustic field intensity with desulfurization bient pressure. Various types of ODS catalysts found include carboxylic
efficiency, suggesting that high intensity acoustic regions were giving acids, poly-oxometalate acids, aldehydes and transition metal salts
high desulfurization efficiency. The presence of nitrogen compound [183–187]. Basically, poly-oxometalate anions are capable of reversible
redox reactions to actively transfer oxygen to the targeted compounds

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Table 6
Effectiveness of ultrasound cavitation over normal stirring conditions for ODS.

Oxidative system Time (min) T (°C) Sulphur removal (%) Reference

US Stirring

Diesel, Fenton’s reagent 15 27 93 53 [147]

DBT in toluene, H2O2-Phosphotungstic acid-tetraoctylammonium bromide 3 75 95 50 [148]
Diesel, H2O2-CH3COOH 15 27–70 43–95 29–68 [149]
VGO or Diesel, H2O2-CH3COOH 10–16 70 83–90 20–60 [168]
DBT in petroleum feed stock, H2O2-CH3COOH 9 27–30 95 50 [169]
BT/DBT/DMDBT in petroleum feed stock, H2O2-CH3COOH 9 90 99 < 82 [170]
BT/DBT/DMDBT in diesel oil, H2O2-CH3COOH 9 90 > 75 < 55 [170]
DBT in Fuel oil, H2O2-Phosphotungstic acid 90 80 35 19 [171]
DBT in Diesel oil, H2O2, MoO3/Al2O3 9 70 100 40 [172]
DBT in Bunker-C oil, TBHP/MoO3 30 45 98 55 [173]
DBT in model oil, H2O2-phosphotungstic acid encapsulated into Amino-Functionalised MOF 15 27–30 98 – [174]

for selective oxidation [188,189].
It has been demonstrated that ionic liquids, especially room tem-
perature ionic liquids (RTILs) could be used for desulfurization.
Extractive desulfurization using ionic liquids are of particular interest
wherein specific ionic liquids could form relatively strong π complex
with organic sulphur compounds (OSC) such as thiophene as compared
to benzene and paraffin [190]. Another use of RTILs is a combination of
oxidative and extractive desulfurization process. With water miscible
RTILs, OSCs can be extracted from fuel and become oxidized by oxidant
such as hydrogen peroxide to the corresponding sulfones in RTIL phase
[191]. In modified UAOD process, ionic liquid imidazolium alkylsulfate
is utilised as multi-phase transfer catalyst to transfer active oxygen
species from aqueous phase to organic phase. The same ionic liquid
could also extract OSCs or oxidized OSCs from the fuel. In combination
with RTILs, UAOD process can achieve more than 99% desulfurization
with various types of diesel fuel oils [165,192–194].
A right combination of the oxidant, catalyst and phase transfer
catalyst needs to be found out for each petroleum feedstock of its
characteristic sulphur compounds or oil stream to make the UAOD
successful at the commercial scale. Also the advent of magneto-striction
based transducers that can work for 24 h without much intermittent
stoppages, the UAOD technology is now ready to serve the industrial
needs.
7.3. SulphCo process
The first commercial ultrasonic desulfurization unit has been in-
stalled at the IPLOM petroleum refinery near Genoa in Italy with con-
tinuous desulfurization of diesel fuel up to 350 bbl per day [195]. The
proposed technology meets the 10 ppm of sulphur requirement in hy-
drocarbon streams. In accordance with the preliminary estimation of
Betchel Corp. Scientists, the SulphCo unit will cost about 50% of what
an equivalent hydrotreater would cost. The application of SulphCo’s
technology for crude oil upgrading has also been studied, API gravity
increase up to 3 points and viscosity reduction up to 15% has been
reported [196–198].
A short coming of ultrasound (acoustic) cavitation is that it occurs
only in the close vicinity of the surface of the ultrasonic probe and this
severely limits the active volume of the reactor and leads to poor per-
formance in industrial scale operations. Hydrodynamic cavitation is an
alternative to ultrasound (acoustic) cavitation. The technique in prin-
ciple can be used to process a large volume of materials for industrial
scale applications [199]. Hydrodynamic cavitation reactors powered by
5–200 kW electric motors these devices can generate sound energy in-
tensity in excess of 1 MW/m2. Sparse patent literature is available for
desulphurisation of transportation fuels by hydrodynamic cavitational
reactors [200–202]. In order to commercialise the oxidative desul-
phurisation for ultralow sulphur diesel (ULSD), hydrodynamic cavita-
tion along with some synergistic process aids like using ionic liquids can
help.
8. De-Metallization using ultrasound cavitation
The amount of metals in petroleum crude oil varies from a few ppm
to more than 1000 ppm. The metals typically found are sodium, po-
tassium, lithium, calcium, strontium, copper, silver, vanadium, man-
ganese, tin, lead, cobalt, titanium, gold, chromium and nickel. The
metals are usually present as soaps (in combination with naphthenic
acids) or complex organometallic compounds such as ‘metallopor-
phyrins’ or ‘petroporphyrins’ [203–205]. Among these metals the most
abundant and undesirable are vanadium and nickel. These metals are
thought to occur in petroleum in two forms; ‘metalloporphyrinic’ and
‘metalnonporphyrinic’. Metalloporphyrins are typical metal complexes
of porphyrin ligands shown in the Fig. 6. Metalloporphyrins (Ni and V)

Fig. 6. Ni and V metal porphyrins structures, typically

found in crude oil.

501
B. Avvaru et al.
are concentrated in the high molecular weight fraction of the asphal-
tenes. Ni and V increase with the asphaltic content of the crude oil.
Removal of Ni and V from metalloporphyrins requires a very strong
acid, such as methanesulfonic acid or tri-fluoroacetic acid, but also
produces a free base porphyrin where two hydrogen ions displace one
central metal atom. Although a variety of physical and chemical
methods were investigated with the intention to remove metals [205],
yet no industrially viable pre-treatment process of demetallization is
available. Currently in catalytic hydroprocessing, hydrogenation is used
to remove the metals from liquid petroleum fractions. One of the most
practical and effective methods of feedstock demetallization is the use
of hydro demetallisation (HDM) catalysts, which requires expensive
capital investment and hydrogen gas as operating cost [206].
There is literature on effective decomposition of metalloporphyrins
using radical induced decomposition produced by ultrasound cavita-
tion. The use of additives such as hydrogen peroxide (initiator of hy-
droxyl free radicals) and surfactant can enhance the efficiency in which
the surfactants act as phase transfer agents between the oxidants in
aqueous phase and the metalloporphyrins in organic phase. A pre-
liminary mechanism and kinetics for the decomposition of model me-
talloporphyrins is available [207]. It has been mentioned that me-
talloporphyrin undergoes oxidation with hydroxyl radicals forming π-
cation radical of porphyrin before decomposing to model paraffinics,
naphthenics, aromatics and metal ions [207–209]. Literature published
elsewhere [210] reported the effect of ultrasound assisted demetalli-
zation and the amount of demetallation agent, reaction time on de-
metallization of gasoline stream coming from coker unit that processes
the oil from Liaohe oil field. The ultrasound cavitation results show that
high metal removal efficiency was obtained in a short time. The opti-
mised parameters are demetallation agent mass fraction of 1500 μg/g,
ultrasound irradiation time of 15 min and ultrasound intensity of 8 W/
cm2. The removal rate of Zn is 90% and above 80% for Ca and Ni. These
studies were conducted on model metalloporphyrins (VoTPP and
NiTPP) compounds in various chlorinated solvents. No studies have
been reported with real asphaltene hydrocarbons. The complex nature
of crude oil may decrease the decomposition rate of metalloporphyrins,
but decomposition mechanism remains same under the cavitation
conditions.
A review paper on this subject [204,205,211] revealed various
academic labs, oil companies and individual researchers are exploring
non-conventional options for metal removal from crude and residual
oils. These methods include chemical treatment with acids and alkali,
selective oxidation/solvent extraction, the photo catalytic methods,
electrochemical treatment, novel thermal and catalytic methods. In
general, these efforts are at the laboratory to small pilot plant stage and
no information is available at commercial stage. However, even if the
ultrasonic treatment benefits heavy oil upgrading or desulphurisation
processes, the in situ demetallation can be expected to improve.
9. Upgrading of heavy crude oils using cavitation
Number of technologies have been developed over the years for
heavy crude and residue oil upgrading, which provide an opportunity
for those refineries which can process low grade crude oils. These
technologies include processes that are based on carbon rejection, hy-
drogen addition and combination of both, most of them with some
commercial success [212–217]. Another new group of technologies also
are emerging as a promising solution of the problem. These technolo-
gies are focused on the upgrading the properties of the heavy crudes,
i.e. improvement in API gravity/reduction of viscosity and impurities
content such as sulphur, nitrogen and metals to feed the refineries.
Ultrasound cavitation technology is among one such technologies has
been showing improved applications in the crude oil upgrading.
The paper presented in 1960 at the All Union Scientific and
Technical conference, was probably a pioneering one concerning the
possibility of using cavitation for enhancing the cracking of petroleum
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Ultrasonics - Sonochemistry 42 (2018) 493–507
feedstock [218]. The author studied the effect of ultrasonic vibrations
on cracking of heavy petroleum residues at high pressure. The thermal
cracking was conducted on a continuous laboratory setup at a tem-
perature of 430–470 °C and pressures 20–40 MPa [218]. Ultrasonic
energy is used in association with various agents, such as diluents and
other emulsifying agents to facilitate the scission of carbon-carbon
bonds in various petroleum mixtures by controlling the cavitation
phenomena. The reactions pertaining to the cracking of heavy oils in
presence of ultrasound cavitation can be elucidated by Rice mechanism
[219]. The cracking of asphaltenes into gas oil and resins can be clas-
sified as free radical reactions. The bond cleavages of the asphaltenes
(RR’) under ultrasound result into R and R’, both hydrogen and hy-
droxyl radicals are generated during the homolytic dissociation of
water molecules under ultrasound cavitation conditions producing the
high temperature and pressure. Thus, the hydrogen radicals may either
come from dissociation of water or desorption of dissolved hydrogen
molecules from crude oil by ultrasonic irradiation. Chain propagation
(addition) reaction (i.e. polymerization and/or polycondensation) may
occur, the addition reaction can form compounds with higher mole-
cular weight (preasphaltene).
Asphaltene aggregates carry negative charge, since the thickness of
the double layer around the particles will affect the repulsive force
among particles, the addition of anionic surfactant will improve the
quality of asphaltenes suspension more than non-ionic or cationic sur-
factant [160]. However they have found with limited set of surfactant
system, under ultrasound cavitation conditions the non-ionic surfactant
works better than the anionic and followed by cationic surfactant in
presence of reducing agent (hydrogen) environment. It is proposed that
both gas-oil and resin fraction can be derived by cracking the asphal-
tenes. Likewise, the resin can be converted to gas-oils. The type of
surfactant used affects the selectivity of these two reactions. The hy-
droxyl functional group is a polar group and the termination of free-
radical reactions by hydroxyl groups will increase the polarity of the
final compound, but with hydrogen radicals it will not. The polarity of
compound (either gas oil or resins) will enhance the aggregation in the
asphalt system. Thus, the H% (free radical) terminator is superior to the
OH% (free radical) terminator for disintegration of asphaltenes. Another
study by the Dunn and Yen [220], has indicated that the asphaltenes
under ultrasound cavitation undergoes simultaneously both dehy-
drogenation and cracking reactions. In their study, conversion by ul-
trasound without hydrogen sources is mostly dehydrogenation i.e., 82%
of dehydrogenation and 18% of cracking. In presence of hydrogen
source, this condition is almost equally for both dehydrogenation and
cracking i.e., 57% for dehydrogenation and 43% for cracking reaction.
In a complete summary of previous literature results, Sawarker et al.
[221] mentioned the effect of ultrasound cavitation for the upgrading of
vacuum residue is high when the vacuum residue is emulsified in water
with surfactants. A kinetic model has been developed based on the
constituents of the vacuum residue to get an insight into the reaction
mechanism. Gopinath et al. [222] treated the heavy gas oil using ul-
trasound energy without the use of any additives at atmospheric pres-
sure. They obtained lighter gas hydrocarbons such as methane, ethane,
ethylene and propylene. Wang et al. [223] have studied the effect of
ultrasound treatment on the properties of petroleum coke oil slurry.
They found that the apparent viscosity decreased with the duration of
ultrasound treatment increased. Kaushik et al. [224] studied the up-
grading of vacuum residue including the effect of surfactant, irradiation
time and probe diameters of the ultrasound horn reactor. With and
without surfactant, they found reduction by 48% and 40% of asphal-
tene content respectively leading to lower viscosity and converting the
residue into more useful products. Asphaltene content reduced sharply
within 30 min of irradiation time and beyond that time it reduced very
slowly. Several researchers [225–227] have proposed use of hydrogen
donors like cyclohexane, methylcyclohexane, tetralin etc. for upgrading
heavy oils and natural bitumens during pyrolysis. The hydrogen donor
forms hydrogen free radicals that react with radicals in the crude
B. Avvaru et al.
leading to viscosity reduction in the products by blocking polymeriza-
tion reactions. Yang et al. [228] have proposed combination of ultra-
sonic cavitation and introduction of hydrogen donor into the reaction
mixture as a promising technology for refining heavy oil residues.
Combined treatment with a hydrogen donor i.e., tetralin and ultrasound
cavitation results in synergistic effects for the reduction of viscosity,
density, and pour point of Beijing Yanshan refinery vacuum residue.
Quite a few companies are offering this technology for the pilot and
commercial scale production. NexGen technology [229] sends the
heavy crude oil through a membrane separation process where the
asphaltenes are separated from the lighter crude oil. Once the asphal-
tenes and heavy oil have been partially cracked by the process, they are
sent to the next cracking process which has great control on the type of
hydrocarbon formed. The key points of this process is that it converts
low cost heavy oil into valuable light oil, the process operates at a low
temperature and pressure, without any catalyst and the foot print is
small as compared to any other current method of refining or heavy oil
upgrading today. The technology can process feedstock such as bot-
toms, heavy oil and extra-heavy oil (bitumen). It considerably improves
oil quality before the oil refining takes place; significantly improves
yields and reduces coking reactions.
SulphCo was founded in 1999, has developed an economic process
employing ultra-sound technology for desulfurization, hydrogenation of
crude oil and other oil related products. The technology upgrades sour
heavy crude oils into sweeter, lighter crudes, producing more gallons of
oil per barrel. SulphCo has conducted four separate series of sono-
cracking trials since 2002, and has five U.S. patents issued for their high
powered ultrasound technology [196–198,230–232]. SulphCo’s Sono-
cracking technology has lower cost and low environmental impact than
conventional HDS (Hydro-Desulphurization) units, which allows the
refinery to optimize its crude and feedstock mix for greatest economic
gain. The hydrogen addition technologies have higher investment and
operating costs. Ultrasound cavitation technologies have definitively
attracted the attention of the refiners. Feasibility studies are being
carried out by many petroleum companies to make proper decision to
adopt these technologies.
10. Industrial scale cavitation reactors
In 2001, the US department of energy successfully developed a vi-
brational transducer particularly for enhanced oil production, but it has
lower ultrasonic frequency and lower energy density [233]. In 2007,
Germany’s Hielscher company successfully operated high power cy-
lindrical transducer [234], the most notable feature is that it can work
continuously under humid and high pressure conditions. Various de-
signs with different rated power capacities are available for various
physico-chemical operations, but they cannot work at high tempera-
tures. Edward H. Phillips proposed in their patent that piezoelectric
elastomer can be used to generate high power ultrasound for enhanced
oil production [235]. In 2006, China has developed first generation
high power transducer based on piezoelectric ceramic material. This
design further modified in 2013 and named it as second generation high
power transducer [236]. The successful development of the second
generation transducer has greater strategic significance and this light
weight transducer was successfully tested in Daqing oil field, Changqing
oil field, Shengli oil field and Liaohe oil fields for enhanced oil recovery.
Recently, the research teams working on improving the ultrasonic oil
production technique have developed a new high power ultrasonic
transducer, the piezoelectric vibrator made of a new piezoelectric ma-
terial lithium-niobate crystal [237–239]. One transducer has many li-
thium niobate piezoelectric vibrators, and are all having same emission
frequency and vibration phase, ultrasound field emitted by these li-
thium niobate piezoelectric vibrators are coherent wave fields. Lithium
niobate has good mechanical performance and chemical stability, its
mechanical quality factor (about 105 magnitude) is much higher than
common piezo electric transducer. These lithium niobate transducers
503
Ultrasonics - Sonochemistry 42 (2018) 493–507
have been particularly used for enhanced oil recovery technique. All
these improved designs can work up to temperature and pressure more
than 1200 °C, 9 MPa respectively. For batch mode operation, these high
power transducers can be directly immersed into the reactor for desired
physico-chemical transformation. However industrial processes are
continuous type, these batch mode operations can be converted into
continuous mode with the help of flow cell arrangements. In this design
an external pump is used for pumping the reaction mass to ultrasonic
chamber, depending on the reaction rate residence time can be fixed by
varying the flow rate of the pump.
Researchers [240–243] working on hydrodynamic cavitation tech-
nology, developed the most economical way of producing the cavitation
by hydrodynamic means. Researchers [244–246] have proved the hy-
drodynamic cavitation is more energy efficient in the generation of
cavities whereas cavity collapse in ultrasound cavitation was much
more violent. The combination of the above two techniques yields sy-
nergistic cavitation effects, the operating parameters for the optimised
design have been proposed.
Another successful design of hydrodynamic cavitation reactor is
shockwave power reactorTM (SPR) system that was constructed by
Hydrodynamics Inc., [247]. The unit consists of concentric cylinders
with an annular space separating the stationary outer cylinder from the
inner, rotating cylinder. The rotating cylinder is driven by a motor and
generates cavitation in the fluid in the annular space when fluid enters
and exit cavities on the surface of the spinning cylinder. The inner,
rotating cylinder houses multiple cavities where fluid is pressurized and
depressurized many times, causing hydrodynamic cavitation to occur.
As cavitation occurs, the fluid bulk receives energy dissipated by the
bubbles in the vapor phase as the bubble collapses. This type of cavi-
tation is deemed to be ‘vortex’ cavitation and occurs in the cavities of
the inner rotor. This novel design allows for a continuous flow of fluid
to replenish multiple cavities as the rotor spins, facilitating cavitation
and product flow through the system. Pressurizing the system during
operation ensures continuous product contact with the inner rotor re-
sulting in the fluid undergoing controlled cavitation. As product enters
the SPR annular space with the rotor set at a specified operational
speed, the mass flow rate of product dictates the frequency of cavitation
events and ultimately the exit temperature.
11. Concluding remarks
Since the first application of cavitation technology for petroleum
crude oil recovery (1930), the subject of ultrasonic application to pet-
roleum refinery processes has moved a long way from academic re-
search to industrial applications. For EOR, the technology has got more
attention due to its simplicity, lower expenses, good applicability and
no reservoir pollution. The technology has shown improvement in all of
the sites operated at Western Siberia, Samara regions and as well as in
China. With continuous improvement, it is likely to have more success
in all of the wells it is applied.
The promise shown by oil shale extraction processes at the labora-
tory scale is not replicated at industrial scale. The economic viability of
these processes at industrial scale needs to be established. The advent of
recent high power transducers such as Lithium niobate piezo-electric
transducers may improve the economic feasibility at industrial scale
operations.
As per literature, ultrasonic demulsification and dehydration were
mainly reported in China compared to other parts of world. The de-
mulsification of water-in-oil type emulsified crudes, the combined ul-
trasonic and chemical demulsification methods show better perfor-
mance when they are applied together compared to each alone.
However comparison should be made with the present conventional
technology of high voltage electric desalting techniques generally
practised at the refinery site, if not at industrial scale level but at least at
the pilot scale operations. A complete report of the same in terms of
economic feasibility and ease of operation, definitely enable the refiners
B. Avvaru et al.
to choose this technology at commercial scale.
Ultrasound assisted oxidative desulphurisation technology (UAOD)
has shown great success at laboratory and pilot scale experiments, but it
has not progressed to industrial scale production. Definitely, UAOD has
great potential to replace HDS in near future it is a matter of time for
refineries to realise, if not for whole stream of petroleum fuels but
definitely for sour crudes having high percentage of refractory type
compounds. Given the stringent regulatory emission standards for
transportation fuels (within 10–15 ppm), and with need for ever hy-
drogen fuel consumption in HDS, UAOD looks to be a promising option
for refiners.
Cavitation technology has definitively attracted the attention of the
refiners for crude upgrading, by cracking the asphaltene molecules and
thereby reducing the viscosity of the extra heavy crude oil. Feasibility
studies are being carried out by many petroleum companies to make
proper decision to invest in this technology. Cavitation cracking tech-
nology is more advantageous compared to hydrogen addition technol-
ogies due to lower investment and operating costs associated with it.
Recent joint venture agreement [248,249] between cavitation tech-
nology offering companies with petroleum industries such as Exxon
Mobil and CNPC (China National Petroleum Corporation) has enabled
this technology not only pertaining to academic interest but also ac-
cepting the same at industrial scale operations.
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