SPE-185401-MS

Oil Spill Cleanup Using Aerographene

Rajat Wadhwani, Shell India Markets Private Limited

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Oil and Gas India Conference and Exhibition held in Mumbai, India, 4–6 April 2017.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Even in the 21st century, the oil industry is yet to overcome some major problems it faces related to oil spill
cleanup. Oil spills can cause a multitude of problems for the environment which may even last for decades
after the spill occurs. This paper discusses a novel approach that may provide a complete solution to combat
oil spills. Conventional techniques are not adequate to solve the problems of massive oil spills. Graphene
based aerogels or Aerographene have attracted widespread attention due to its excellent oleophilicity,
hydrophobicity, reusability, high uptake rate of oil, high uptake capacity and recovery of oil. Although
the application of graphene aerogel for an oil spill is still in its nascent stage, it offers great promise for
the future. It is believed to have potential to replace present sorbents which are used commercially. This
paper briefly outlines present oil spill cleanup techniques and problems associated with each technique. A
major part of this paper will be on the evaluation of aerographene properties and how it overcomes major
problems related to conventional techniques. Many properties of aerographene have been studied which
makes aerographene stand a chance of replacing the present oil spill cleanup methods. This paper presents a
novel idea by which cleaning up oil spills with the help of aerographene will become much simpler, easier,
cheaper and will prevent the environment from degrading at a massive scale due to oil spills.

Introduction
The nature needs to pay for every single mistake made by the human. With rising global energy demand, the
oil and gas has a wide range of challenges and opportunities across the upstream, midstream, downstream
and oilfield services sectors. One of the greatest mistakes in humankind history is an oceanic oil spill. It
has become a major environmental problem that the world is facing right now. History has shown how this
problem could go. From the first major commercial spill of 1967 in the United Kingdom, up to the most
recent one, at BP Deepwater Horizon Oil Rig, that leaked thousands barrel of oil into the Gulf of Mexico
since April 2010. Most large-scale oil spills have been disastrous and the marine wildlife is still recovering.
Hence, the tension for a better cleanup technology increases.
In the last thirty-odd years, the issue of oil spills and their effects has taken on much importance. The very
reason for this is the pollution caused by an oil spill has tremendous effects on our ecosystem, environment,
economy, and the society as a whole (Aziz, 2012). Some of the environmental damage caused by an oil
spill can last for decades after the spill occurs. Oil undergoes a wide variety of weathering processes, which
include evaporation, dissolution, dispersion, tar ball formation, microbial degradation, spreading, adsorption
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onto suspended materials, photo-oxidation, sinking, with time. These physicochemical changes enhance oil
dissolution in seawater. Seawater can contain oil in three major forms: 1. free oil larger than 20 microns
in diameter, 2. emulsified oil that have been mechanically or chemically rduced in size to smaller than
20 microns in diameter, and 3. dissolved oil as molecular-scale particles capable of dissolving in water.
Therefore, the extent of the damage and destruction caused by an oil spill and the ease of cleanup depend
on how quick the cleanup process takes effect.
There is an urgent need to comply the environmental rules and regulations so as the oil spill response and
cleanup performance can be improved. The oil spill control methods that are used currently have drastically
failed to ensure environmental safety, economy stability and ecosystem integrity. Cleanup techniques often
lead to hazards in one way or the other which causes public outcry for alternate source of energy. Since
hydrocarbon driven energy demand is in huge demand and is expected to rise in the foreseeable future, the
need of the hour is to work towards sustainable oil spill cleanup operations. The most affected ecosystems
are those of ocean and coastal area which are subjected to severe damages followed by economical charges.
Therefore, the main focus of this study is to control the spillage of oil in a sustainable fashion.

Cleanup Practices
The oil spill cleanup techniques that have been used to control or reduce the immediate effects of an oil
spill include- in-situ burning of oil on water, bioremediation, mechanical equipment (booms and skimmers),
spraying of chemical dispersants and oil sorbents. But these techniques help in the cleanup actions only to
some extent. In order to deal with their limitations and impact there is a need of a more novel technique for
oil spill cleanups. The impacts and limitations of oil spill cleanup methods are discussed as follow:

In-situ burning of oil slick

One of the techniques which have been used in many huge oil spills is by burning a very thick oil slick on
the surface of water. It is able to remove 600-1800 bbl (100-300 tons) of oil per hour (Allen, 1988). To ignite
an oil spill a device is used such as Helitorch, which is a sort of flame-thrower that is mounted beneath
a chopper or dropped from the helicopter as a diesel soaked rag (Aziz, 2012). It has a fireproof U-shaped
boom (a mechanical tool for oil spill control) which is initially used so as to contain a large and thick oil slick
in place which can later be carefully set ablaze and continuously monitored. In reality, there are numerous
problems which limit the viability of this technique (Aziz, 2012). A large amount of smoke generated due
to burning can result in oil rain which contaminates land, crops, water table and animals. Also, it leads to
the formation and possible sinking of the viscous and dense residues that causes immense damage to the
seabed and its inhabitants. Moreover, airborne diseases are also source of concern when combustion is to
be carried out near commercial and residential localities. Carbon monoxide and sulfur dioxide are the most
common toxic compounds which are liberated when oil is burnt on water surface. Also, polycyclic aromatic
hydrocarbons (PAHs) is emitted which causes huge problem to deal with.

Booms
Booms are mechanical barriers which are used to contain and concentrate spilled oil. They are available
in numerous sizes and shapes to encircle a spill, floating both with a portion above and below the water
surface to keep oil from splashing over or escaping beneath. Booms are used mainly for containment and
do not sufficiently contribute to the recovery and cleanup of the spilled oil. Moreover, since booms serve as
containment systems, a major part of the spilled oil sinks to the bottom, precluding recovery, disturbing and
damaging undersea life, and leading of tar balls which wash up on shore. Fig.1 shows the use of boomers
to contain and concentrate spilled oil.
SPE-185401-MS 3

Figure 1—Synthetic boomers method

Dispersants
Dispersants are chemicals (liquid in nature) which if applied to the surface of the spill accelerate the dispersal
of the oil as it reduces the surface tension between oil and water. However, judicious use of these chemicals is
important as they might be toxic. Also, these dispersants are often inflammable and cause potential damage
to fowl, fish and marine mammals and health hazards to the operators. Besides fouling of shorelines, they
can also lead to contamination of drinking water sources. Even if the concentrated spill has been dispersed,
the oil still remains in the water (Charles, 1995). Also, ecological considerations, experience, and recent
technological developments in the handling of oil spills have pushed the chemical dispersant very much
out of the picture. They are very expensive and also contain extremely toxic compounds harmful to both
aquatic fauna and flora. For example, a research was conducted to examine the fish health after the Exxon
Valdez Spill of 1989 which revealed that PAHs liberated due to spill affected the developing hearts of pacific
herring and Pink Salmon embryos, because of which the food industry were hit the most. Fig. 2- shows
dispersants sprayed on the oil spill to accelerate the dispersal of the oil.

Figure 2—Dispersant of chemical

Thickeners
Thickeners also known as herding agents help to thicken the oil quickly by increasing the surface tension
between the oil and the water, which makes the oil spill difficult to spread (keeps it intact) and permits
easier cleanup, however, thickeners are extremely expensive, and many of them are toxic (Charles, 1995).
In addition, the oil which is thickened will sink sooner than the oil that is yet to be treated or has not been
treated. And if the oil sinks, any cleanup technique at the surface is precluded.
4 SPE-185401-MS

Skimmers
Skimmers remove spilled oil mechanically from the surface of the water. They take advantage of the
adhesive nature of the oil, which clings to any surface that it comes in contact with. Initially oil sticks to
the rope and is later carried back to the drive unit for removal. The basic types of skimmers are vacuum,
gravity, oleophilic, and centrifugal skimmers. Skimmers operate to separate the oil from the water however
most skimmers are not very efficient and hence leave much of the recovered oil mixed with water, thereby
making oil recycling expensive and economically impractical (Charles, 1995).

Bioremediation
Its application in oil cleanup involves the introduction of biological agents artificially such as fertilizers
– which act as nutrients to native microorganism in the contaminated site so as to proliferate them (bio-
stimulation) or the introduction of non-native micro-organisms (bio-augmentation) so as to speed up the
natural process of biodegradation which helps to protect the environment mainly shorelines, wetland and
other marshy areas covered by spill from any further damages (Aziz 2012). Bioremediation is not effective
when it comes to remove oil spills that consist of coherent masses and for sunken oil. It is also limited by
abiotic environmental factors which are low level of nutrients that includes phosphate and fixed forms of
nitrogen, very low temperature and insufficient oxygen (Atlas and Cerniglia, 1995).

Sorbents
Sorption is a popular technique applied for treatment of oil spillage. The sorbent is an insoluble material or
mixture of materials which are used to soak up oil from water. The sorbents help to recover the spilled oil
from water by either adsorption, in which the oil is first attracted to the sorbent surface and then later adhered
to it, or absorption, in which the oil penetrates the pores of the sorbent material, or both. Numerous sorbent
materials have been tested and also investigated and has been considered as most effective in oil removal
application. These oil sorbent materials can be grouped into three major class namely inorganic mineral
materials, synthetic organic polymers and organic natural materials. Inorganic mineral materials include
graphite, perlite, silica, vermiculite, fly ash, organic clay and zeolites whereby the examples of synthetic
organic polymers materials is polyethylene, polypropylene and polyacrylate. Organic natural materials used
as sorbent include straw, wool fiber, sawdust cotton fiber, corn cob, coco-nut husk and kapok fibers.
Inorganic mineral materials. Inorganic mineral materials or sinking absorbents which are highly dense
and very fine grained, either natural or processed is used to sink floating oil. Examples of inorganic mineral
materials include fly ash, zeolites, graphite, activated carbon, silica (sand) and silica gel. They are generally
not used due to their numerous shortcomings such as they contaminate the sea beds and their harmful effects
to flora and fauna. They also tend to release large amount of absorbed oil while sinking as they have very
low retention capacity. Another vital limitation of mineral absorbents is the cost of the absorbents which
makes it economically unviable to use as an absorbent.
Synthetic organic sorbents. They are the most effective and efficient in recovering oil. The most widely
used sorbents made from high molecular weight polymers are polyurethane and polypropylene. They
possess very good hydrophobic and oleophilic properties and also high absorption capacity. For example,
ultra light, open-cell polyurethane foams can absorb 100 times their weight of oil from oil-water mixtures. In
some cases a ratio by weight of oil to sorbent of 40:1 can be achieved compared to 10:1 for organic products
and as little as 2:1 for inorganic materials (Use of sorbent materials in oil spill response). But sorbents which
are made from synthetic high-molecular substances have a fundamental defect that they lack in resistance
to oils. They have another disadvantage that the materials, when disposed of by incineration in conjunction
with adsorbed oils, give rise to molten polymers which will do damage to incinerators and issue noxious
gases (Kobayashi, et al, 1977). In addition, the oil-adsorbing materials made of synthetic high-molecular
substances have a fatal drawback that they fail to exhibit any adsorbing activity on the so-called chocolate
SPE-185401-MS 5

mousse which is formed when the waste oil, rolled and pitched on waves, forms balls in consequence of the
emulsification caused thereon by a small proportion of entrapped sea water (Kobayashi, et al, 1977). The
oil-adsorbing materials made of synthetic high-molecular substances also have the disadvantage that they
themselves may cause serious ecological problems if not recovered after use on seas or oceans.
Organic natural sorbent. Organic natural sorbent materials are attractive as they often either abundant in
nature or are the waste by-product of an industrial process and can be purchased readily at low cost or are
freely available. They do not cause harm to the environment and its habitats. It is well known that every
technology has its own limitations. The limitation of natural sorbent is its cost involved in recovering the oil
soaked sorbent then removing the oil and later re-dispensing the sorbent. For example, a million gallon of
oil spilled will require 210 tons of straw to absorb the oil. This means that after use and recovering, vessels
on location must be able to store 20 times the original weight of straw since the straws are now soaked with
oil, and water (Aziz, 2012). Corncobs, straw and other absorbents can hold up only about five times their
own weight and pick up water, as well as oil. Those materials then become industrial waste that must be
disposed in special landfills or burned. Organic natural fibers have a disadvantage that they exhibit a high
water soaking capacity. To be freed from this disadvantage, these materials must undergo a preliminary
treatment designed to impart water repellency or waterproofness thereto. Owing to their generally high
levels of specific gravity (when oil is soaked); they fail to remain afloat on water and tend to sink under
water. They also suffer from the disadvantage that they have rather limited capacities for absorbing and
retaining oils.

Table 1—The benefits and disadvantages of available types of sorbent material.

Proposed Solution
Conventional techniques are not adequate to solve the problem of massive oil spills. In recent years,
graphene aerogel or aerographene has emerged as a potential source of novel solutions to many of the world's
outstanding problems. Although the application of aerographene for oil spill cleanup is still in its nascent
6 SPE-185401-MS

stage, it offers great promise for the future. In the last couple of years, there has been particularly growing
interest worldwide in exploring ways of finding suitable solutions to clean up oil spills through the use
of carbon nanotubes (Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure.
Nanotubes have been constructed with length-to-diameter ratio of up to 132,000,000:1 significantly larger
than for any other material). The characteristics of an ideal sorbent material used for oil spill cleanup include
hydrophobicity or oleophilicity, high uptake capacity and high rate of uptake of oil, buoyancy, and retention
over time, durability in aqueous media, reusability, biodegradability and recovery of oil. However, it is
almost impossible to find a material that has all the properties as mentioned. Hence, the materials which
perform high oil sorption capacity, with good reusability and oil recovery with will be chosen. This paper is
aimed at highlighting a new sorbent material that can be used for oil spill cleanup eliminating disadvantages
and also downplaying advantages of other sorbent materials.

Aerographene
Aerographene or graphene aerogel is the least dense solid known today, at 160g/m3 (0.0100 lb/ft3), less
than helium. It is approximately 7.5 times less dense than air. The graphene aerogel is so light that a cube
inch of the stuff can be balanced on a fluffy seed head of a dandelion, the stamen of a flower (as shown
in Fig. 3), or a blade of grass. Aerographene contains CNTs supports on the inside. These are surrounded
by a graphene exterior. "It's somewhat like large space structures such as big stadiums, with steel bars as
supports and high strength film as walls to achieve both lightness and strength. Here, CNTs are supports
and graphene is the wall."

Figure 3—Aerographene resting on petals of a flower

Synthesis
The synthesis of aerographene is achieved by the process of freeze drying (Freeze-drying, or lyophilization
or also known as cryodesiccation, is a dehydration process which is used to preserve a perishable material or
help to make the material more convenient for transport. It works by initially freezing the material and then
later reducing the surrounding pressure to allow the frozen water present in the material to sublimate from
the solid phase to directly into the gas phase). In case of producing aerographene, a solution of graphene
and CNTs is created and later it is poured into a mold which is then freeze-dried. Freeze drying helps to
dehydrate the solution, leaving single-atom-thick layers of graphene, supported by CNTs. Residual oxygen
is finally removed chemically. With no need for templates, its size only depends on that of the container. A
bigger container helps to produce the aerogel in bigger size, even as much as thousands of cubic centimeters
or larger (as shown in Fig. 5 (B)).
Also, a method proposed is based on the sol-gel polymerization of resorcinol (R) and formaldehyde (F)
with sodium carbonate as a catalyst (C) in an aqueous suspension of Graphene Oxide (GO). The GO is
produced by the Hummers method and the suspension is prepared by ultra sonification. The molar ratio of
R/F is 1:2, the reactant concentration in the starting mixture is 4 wt% RF solids, and the concentration of
SPE-185401-MS 7

GO in suspension is 1 wt%. The molar ratio of R/C is 200:1. The sol-gel mixture is cured in sealed glass
vials at 85°C. After gelation, the wet GO-RF gels are removed from the glass vials and washed in acetone
to remove water from the pores. Supercritical CO2 is used to dry the GO-RF gels, and pyrolysis at 1050°C
under nitrogen yielded the final graphene aerogel (as shown in Fig. 4).

Figure 4—Synthesis of graphene aerogel

Properties
The end result is a graphene aerogel that weighs just 0.16 mg/cm3 and has truly superb elasticity and
absorption. The graphene aerogel can recover completely after more than 90% compression, and absorb
up to 900 times its own weight in oil, at a rate of 68.8 g/sec - only oil, not water (a water contact angle
(CA) measurement was performed to investigate the surface wettability of the graphene aerogel; it exhibited
surface hydrophobicity with a water CA of 135.8°. In contrast to hydrophobic wettability to water, the
graphene aerogel showed excellent oleophilic property) and also remains afloat when saturated with oil for
months. With these two features combined, the material has massive potential to be used to mop up oil spills,
squeezed to reclaim the oil, and then thrown back in the ocean to mop up more oil. "Due to its elasticity,
both the oil absorbed and graphene aerogel can be recycled".
Apart from above advantages, aerographene essential attributes are many: buoyant, resilient, moisture
resistant, and durable. It's said that aerographene repels water like rain on a ducks back. When a substance
does this we call it, hydrophobic. This hydrophobic nature results in the quick-drying, buoyant (also upon
oil saturation) and moisture-resistant properties, which makes aerographene remarkable among synthetic
fibers. Additionally, because the oil is contained within the inner core and not allowed to return to the water,
it is protected from evaporation, emulsification, and contamination for long periods. The oil will remain
unemulsified and uncontaminated for many months after absorption. It has been constructed to be highly
reusable, to be effective even in the roughest water, to recover the greatest amount of oil and permit the
recycling of recovered oil.
Another advantage of the present invention is its ability to retain oil. Besides the oil sorption capacity,
absorbent retention time is another important parameter to be considered. The weight of recovered oil can
cause a sorbent structure to sag and deform, and when it is lifted out, it can release oil that is trapped inside
it causing secondary contamination. The retention capacity (an evaluation of the ability of sorbents to retain
the absorbed oil during transfer and handling operations) of aerographene although variable to a slight extent
with the kind of oil involved, the temperature of water on which the oil is floating and the conditions of the
fibers is more than twice as high as that of the fibers, identical in size, of kapok fibers.
8 SPE-185401-MS

An additional feature of aerographene is that it is robust, highly flexible, can be rolled for storage and
capable of withstanding a number of large strain compressive cycles without affecting their properties
(as shown in Fig. 5(c)). These attributes are highly beneficial for recovery of oil as well as regeneration
and reuse of the material. Aerographene works effectively under harsh conditions, such as high or low
temperatures. Traditional sorbents (such as polyurethane-based and polyethylene-based materials) cannot
be used at temperatures above 200°C, and others will become very brittle at low temperatures. In this regard,
graphene aerogel exhibits exceptional features. When exposed to an ethanol flame, the graphene aerogel did
not support any burning and remained inert. After 30 seconds of such extreme heating, it was immediately
immersed into liquid nitrogen (LN2). No decomposition or material change occurred; even upon repetition
of this treatment for several times, the shape, volume, and inherent 3D porous structure of graphene aerogel
remained unchanged, demonstrating that the graphene aerogel can withstand extreme temperatures and rapid
temperature change. This also helps to recycle and reuse Aerographene multiple times without worrying
about its decomposition.

Figure 5—(A) Graphene aerogel balanced on the spine of a plant. (B) 1000 cm3 aerographene (21 cm in diameter and 3
cm in thickness). (C) Stress-strain curves of several selected cycles on aerographene during repeated compression.

As these are mainly based on CNTs and graphene, economics is certain to play a major role in determining
their commercial viability. Currently, CNTs are priced at around USD 130/kg and expected to reduce to
USD 15/kg in the near future. The present price of graphene nanoplatelets is around USD 435/kg and it is
predicted that nanoplatelets could be produced at USD 11/kg. Therefore, it is likely that these technologies
could become commercially viable solutions for oil spill cleanup in the future. Apart from the production
costs, the economic viability of a technology for oil spill cleanup also depends on other performance factors
such as sorption capacity, rate of sorption of crude oil, regeneration factor, recyclability, costs of disposal
of the material.

Conclusion and Recommendation

This paper reviews the state-of-the-art on various oil spill cleanup methods and their limitations with
environmental impact. This work was done to assist the oil spill cleanup technology and provide the best
solutions and sorption parameters of aerographene. It is quite evident from the foregoing discussion that
nanomaterial's have enormous potential to provide innovative solutions for oil spill cleanup by virtue of
their unique structure, superior properties and outstanding performance. "Maybe one day when an oil spill
occurs we can scatter them on the sea and absorb oil quickly without damaging the environment". However,
for their successful implementation as commercially viable technologies, one needs to carry out a thorough
study on environmental issues, scalability and cost analysis.
At the same time, materials at the nanoscale may pose new toxicological risks due to their greater
biological activity and may have negative impact on human health when these nanoparticles are inhaled,
absorbed through skin, or ingested. There is also some scientific evidence, showing that the nanoparticles
can travel through the food chain from smaller to larger organisms. In addition, they could damage important
SPE-185401-MS 9

microbes in the environment. The oil absorbing materials made of synthetic high-molecular substances
may cause serious ecological problems if not recovered after use on seas or oceans. In view of these
environmental concerns, there is a clear need to carry detailed studies and generate requisite data on
toxicological effects of nanomaterials.

Disclaimer
This paper includes forward-looking statements. This paper is prepared for presentation at the SPE Oil
and Gas India Conference and Exhibition. I hope that the idea discussed will revolutionize the oil and gas
industry, by improving the oil spills cleanup.

Acknowledgment
I would like to thank University of Petroleum and Energy Studies, India for their support to accomplish
this project.
I am as ever, especially indebted to my family for their support and trust throughout my life.

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Authors’ Biography
Rajat Wadhwani has completed B. Tech in Applied Petroleum Engineering with specialization in Gas
from University of Petroleum and Energy Studies and is currently working in Shell India Markets Private
Limited, Chennai as Process Data Engineer (Subsurface and Wells).