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McGill University

NANOTECHNOLOGY BASED SOLUTION FOR OIL


SPILL REMEDIATION
CIVE 521: Nanomaterials and aquatic environments
Winter 2017

Tazmir Nahar (260458402)


30th March 31, 2017
Abstract
Oil spill causes great havoc to our ecosystem and the conventional clean up process is not sufficient. The
oil spreads in the ocean water very quickly and it is required to separate the oil from water as soon as
possible. The nanotechnology has great potential in oil spill remediation due to its unique wettability
property. It is possible to engineer nanoparticles with super hydrophobicity and high oleophilicity that can
absorb massive amount of oil. Other properties like fasr dissolution, high reactivity, strong sorption, super
para-magnetism and localized plasma resonance makes nanomaterials very useful in oil-water separation
process. Nanotechnology can be engineered as magnetic nanocomposite, nanowire membrane, TiO2
photocatalytic decomposition or modified CNT mesh. Each ENP has its unique advantages and limitations.
This paper explores those advantages and limitation. The paper concludes that magnetic nanocomposites
are viable option for in-situ remediation where as CNT-SS is more effective choice. It also explores the
toxic effect of these nanoparticle and possible environmental effect.

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Table of Contents
Introduction ................................................................................................................................................... 1

Characteristics for oil-water separation and nanotechnology ....................................................................... 1

Nanowire membrane ..................................................................................................................................... 2

Modified carbon nanotube............................................................................................................................. 3

Nano TiO2 photocatalytic decomposition ..................................................................................................... 4

Magnetic polymer-metal oxide nanocomposites ........................................................................................... 5

Comparison and factors in implementation................................................................................................... 7

Environmental factor ................................................................................................................................. 8

Cost and commercial viability................................................................................................................... 8

Conclusion and Recommendation ................................................................................................................. 8

Reference ....................................................................................................................................................... 8

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Introduction
Oil spill is a serious concern worldwide due to its environmental impact. The histories worst oil spill in the
Gulf of Mexico effected hundreds of species in the marine ecology and nearby costal zones. Since then the
world has seen many accidental oil spills which causes havoc to the ecology and the economy. The cleanup
process is usually dealt using microorganism and mechanical skimmer (Kharisov, Dias, & Kharissova,
2014) which cannot remove all the oil from the water. These traditional methods are not adequate for large
oil spill cleanup hence, requires more effective approach. Recent development in nanoscience has
introduced some promising technology which could solve the oil spill problem (Watlington, August 2005).
The nanotechnology is still in its nascent stage and requires more research and understanding. This paper
allows to explore the available technologies, its effect and outcome in oil spill remediation.
There are two types of remediation process in-situ, remediation process in the contaminated site and ex-
situ, treatment of contaminated water outside of the affected area (J.R. Gallego, 2007). Ex-situ is widely
used for small scale treatment. As nanotechnology based solution is still under progress most of the
literatures used in this paper performs ex-situ remediation with some in-situ experiments for small scale
spills.
Nanomaterials are chemical substances that are manufactured and used at a very small scale. It exhibits
various characteristics like increased strength, chemical reactivity and conductivity compared to the same
material without nanoscale feature (Lahann, 2008). Due to its distinctive properties, it has the potential to
improve health and quality of life. However, it also comes with many risks and safety concern for people
and the environment due to its toxicity.

Characteristics for oil-water separation and nanotechnology


Solid surfaces with super hydrophobicity and superoleophobicity can separate oil and water (Calcagnile et
al., 2012). A super hydrophobic surface can cause water droplets to bead off completely as it has water
contact angle greater that 1050. On the other hand, contact angle less than 50 will cause the substance to
attached to the surface. Using this property, a solid surface with unique wettability can repel water but
attach oil and separate them. It is possible to construct an implement like membrane, filter or sponges that
has surface processing with unique combination of super hydrophobic and superoleophilic property
(Narayan, 2010).
The various approaches employed for oil spill clean up using nanomaterials include MnO nanowire
membrane, Carbon nanotube sponges, magnetic nano-composites, Nano-TiO2 photocatalytic
decomposition. The performance of these technologies depends on the nonporous materials sorption

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capacity, selectivity for organic solvents and oil, sorption rate and tailored surface chemistry (Mahajan,
2011).

Nanowire membrane
MIT researcher has developed such nanowire membrane that is capable of absorbing oil up to 20 times their
weight(Zhang et al., 2017). This super-hydrophobic/oleophilic membrane material is synthesized by
coating MnO nanowires with silicone using vapor deposition technique. This nanowire is thermally stable
and has paper like structure that exhibits controlled wetting behaviour. The membrane is composed of three-
dimensional porous nanostructure exhibiting a super hydrophilic character with wetting time of 0.5s. It is
also coated with a thin layer of super hydrophobic molecules (silicone) giving the surface high water angle
(>1700). At elevated temperature, the coating can be remove and switch the membrane characteristics as
desired. This design flexibility gives the membrane efficient adsorption property and high level of
selectivity for a broad range of organic solvents and oil. Selective adsorption is achieved by forming a net
of open superwetting capillaries with oleophilic fiber like non-woven polypropylene fibres.
Selective adsorption can be confirmed by comparing polypropylene and glass fabric membranes which
absorb both water and toluene whereas nanowire membranes absorb only toluene (Yuan et al., 2008). Figure
2 illustrates the broad range of oil absorption capacity by MnO nanowire. Thermal stability upto 3800C is
another advantage of the MnO nanowire and it can be regenerated by ultrasonic washing and autoclaving
after each use.

Figure 1: Oil uptake studies of Si-coated MnO nanowire mebrane.

However, along with all the advantages MnO shows some risk of toxicity. Bactericidal properties of
nanowires illustrate the toxicity of the MnO nanowires. It reduces cell viability by breaking bacterial cell
membranes. It is observed that MnO NWs disrupt E. coli cell membranes and cause leakage of intracellular
contents in a study that used TEM analysis (Hassan et al., 2012).

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Modified carbon nanotube
Carbon nanotubes (CNTs) has strong SP2 hybridization carbon tubular network with high tensile strength
and thermal conductivity (Lee, Johnson, Drelich, & Yap, 2011). Its unique properties like nanoscale
dimension, chemical inertness and high aspect ratio it is one of the best candidates for super hydrophobic
coating (Gui et al., 2010). A vertically aligned multiwalled CNT synthesized on stainless steel (SS) mesh
is developed by SKKU researchers combining all desired properties of CNT along with super hydrophobic
and superoleophilic properties. A forest of vertically aligned CNTs are deposited on the SS mesh and the
forest height is less than 5m. The outer diameter for CNTs vary from 10 to 30nm. The oil water separation
is examined with 20-50mL gasoline-water emulsion and small current and voltage through CNT-SS mesh.
Figure 3 shows the bottom-up view of CNT-SS mesh and illustrates the super hydrophobicity and
superoleophilicity of the nanotube. Water droplet (top) is in contact with the tip of the tube but due to CNTs
hydrophobic property, it is prevented from wetting the CNT wall or pass through it. However, the oil in the
water wets the CNT walls and travel downwards to the filter due to gravitational force thus separating from
the water.

Figure 2: Hydrophobicity and oleophilicity of CNTs on the Figure 3: Possible mechanisms during the filtration of
SS-CNT mesh. water-in-oil emulsion that led to entrapment and formation
of microscopic water droplets in mesh openings.

The experiment showed that the efficiency of oil-water filtration influenced by water droplet size
distribution in feed emulsion, duration of filtration and height of emulsion column placed on the
mesh. The procedure prevented 80 wt.% of water to pass through the tube. However, it is also seen
that some water droplet was trapped on the CNT-SS mesh and eventually blocking the filtration
process (figure 4).

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Nano TiO2 photocatalytic decomposition
Photocatalytic semiconductor obtains their energy from absorption of light (Beydoun, Amal, Low,
& McEvoy, 1999). TiO2, ZnO, iron oxide and WO3 act as photo-catalysis and due to their UV light
absorption capabilities they show self cleaning and disinfecting properties (Mahajan, 2011).
Moreover, photo-catalyst can oxidize toxic organic substances into harmless compound (Gehrke,
Geiser, & Somborn-Schulz, 2015). The water-soluble crude oil fraction (WSF) of Brazilian crude
oil sample was investigated to understand the effect of UV/TiO2 nanotechnology in oil-water
separation. An average particle of 30nm non-porous TiO2 was used as photo-catalyst (Ziolli &
Jardim, 2002).

Figure 4: Toxicity effect on luminescent bacteria.


Figure 5: Photocatalytic reactor.

1200mL crude oil samples (A richer in organic compound, B more paraffinic) was used and
treated in a photocatalytic reactor (Pyrex reactor) in batch experiment. Hg lamp with high pressure
and 366nm wavelength was used as UV source. The reactor was set as shown in figure 6 and
continues cooling water supply was used to keep the temperature under control. After 7 days, the
samples were tested for oil degradation and toxicity.

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Figure 6:a) WSF of A-Brazilian crude oil in seawater. b) WSF of B-Brazilian crude oil in seawater. Legends : () Only WSF
(control); ()WSF with TiO2 in dark; () WSF during exposure to UVVIS irradiation without TiO2;() WSF with TiO2 during
exposure to UV-VIS.

Figure 7 indicate the oil degradation as a function of time for two different sample. The experiment
shows that the degradation is dependent on the nature oil. There was not any degradation when the
sample was in dark or without TiO2. There was 90% degradation of carbon concentration when
the sample was exposed to UV light and TiO2 nanoparticles (Ziolli & Jardim, 2002). However,
there was by-product of hydrogen peroxide or other toxic species. Figure 5 demonstrates the
toxicity of the process. Toxic unit (TU) higher than 1 means the sample shows acute toxicity.
Generally, TiO2 and ZnO has extensive toxicity measurement due to its use in sunscreen
production.
A study done with two different size of nano-TiO2 particles in rats and mice revealed that the
smaller particles induced greater pulmonary-inflammatory neutrophil response as compared to the
larger particles. Other studies shows that smaller photo-catalyst particle size does not necessarily
indicate a greater level of toxicity (Warheit, Webb, Sayes, Colvin, & Reed, 2006).

Magnetic polymer-metal oxide nanocomposites


Magnetic spheres with high hydrophobic and oleophilic property can be placed on polluted water
and be removed with external magnetic filed (Gomes de Souza, Marins, Rodrigues, & Pinto, 2010).
These spheres will extract the spilled oil from the polluted water (figure 8).

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Figure 7: Illustration of oil-water separation with magnetic properties of metal oxides.

A Chinese research team used highly selective oil absorbent carbon nanoparticle with iron-oxide
core shell (Zhu, Tao, & Pan, 2010). This nanocomposite exhibit high hydrophobic property due
to porous polysiloxane layers on the nanoparticle. Weight of the nanoparticle before and after the
oil absorbent was used to determined the absorption capacity of the modified nanocomposite. The
surface of Fe2O3 particle is coated with a layer of carbon with a thickness of 7-36 nm, forming a
core shell nanocomposite (fig10

Figure 9: TEM image of nanocomposite. a)100000 b) 200000x


Figure 8: oil-absorbed pristine and polysiloxane coated
nanocomposite.

These nanocomposites are unsinkable and can absorb oil 3.8 times of their own weight very
quickly and selectively (Thanikaivelan, Narayanan, Pradhan, & Ajayan, 2012). Figure 9 illustrates
the importance of super hydrophobic property comparing the oil absorption capacity of pristine
and polysiloxane coated nanocomposite where polysiloxane is highly hydrophobic. Moreover,

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these types of nanoparticles can be regenerated by ultrasonic washing in ethanol for 5 min reducing
the operational cost (Mirshahghassemi & Lead, 2015).

Comparison and factors in implementation


Each of the above technology has its own advantages and disadvantages. For successful
implementation of those technologies some important factors should be considers like cost and
commercial viability, environmental impact, engineering aspect like scalability and performance
criteria.
In order to, get maximum benefit from the nanotechnology it is required that the nanomaterial has
broad range selectivity in oil and organic matter absorbance. All four-nanotechnology discussed
in this paper shows a broad range of selectivity. CNT-SS mesh has additional feature with their
robust property and high flexibility high can withstand large strain. These attributes are highly
beneficial for recovery of oil as well as regenerate and reuse the material. Figure 11 shows the
capability of oil absorption for different technology. From the above discussed technologies CNT-
SS mesh gives the highest oil absorption capability followed by polyurethane foam which is a type
of magnetic nanocomposite. The bar chart does not show the oil absorption capacity of TiO2
nanoparticle because it is done in small batch and not sufficient information was found in large
scale remediation.

Figure 10: oil absoption capacity of various nanotechnology with different tyoes of oil.

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Environmental factor
Materials at nanoscale might pose toxicological risk due to high biological activity. Some
nanoparticle has negative effect on human life when inhaled, absorbed through skin or ingested. It
may travel through the food chain and effect ecological system. TiO2 and MnO showed toxicity in
bacterial level and might also effect human cells when inhaled. TiO2 photosynthesis produce
hydrogen peroxide and some other toxic species that is harmful to the environment. Some magnetic
species also shows sign of toxicity. However, the actual toxic effect varied in different cases and
requires extensive research with different dosage for all nanomaterial.

Cost and commercial viability


Commercial viability and cost depends on the raw material, maintenance and scale up possibility.
Magnetic nanocomposite and nanowire membrane can absorb large amount of oil by in-situ
remediation whereas TiO2 photo-catalysis and CNT-SS mesh requires extraction of polluted water
and ex-situ remediation through filtration. The later method increase the cost with additional
transportation and limits the amount of water that can be treated as it is impossible to transport
ocean water in short time. Though CNT-SS can absorb almost 90% of the oil it is not a viable
option to treat massive oil spill in ocean. The best option for oil spill remediation is magnetic
nanocomposite however it does not have huge range of oil absorption selectivity.

Conclusion and Recommendation


Nanotechnology can solve the oil spill cleanup problem and save the environment and marine life.
However, it has some limitations and most of the limitation is due to lack of knowledge and
research on the field. Nanomaterial combined with different functional characteristics can increase
its capability for more efficient removal. There are many ongoing bench scale experiments
showing promising result in oil -water separation. The challenge is to scale up the process like
TiO2 photo-catalysis or CNT-SS mesh and we can have the most effective method of oil spill
remediation.

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