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Water Research 135 (2018) 262 e 277 Contents lists available at ScienceDirect Water Research journal homepage:

Contents lists available at ScienceDirect

Water Research

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

Research journal homepage: www.elsevier.com/locate/watres A review of bio-based materials for oil spill treatment

A review of bio-based materials for oil spill treatment

Bhairavi Doshi a , * , Mika Sillanp a a , b , Simo Kalliola a

a

Mika Sillanp a a , b , Simo Kalliola a € a € a Laboratory of

a Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, Mikkeli, 50130, Finland b Department of Civil and Environmental Engineering, Florida International University, Miami, FL, 33174, USA

article info

Article history:

Available online 15 February 2018

Keywords:

Oil spill

Sorbent

Particle

Surfactant

Aerogel

Gelator

Separator

abstract

Being cost-effective, synthetic materials were initially used abundantly for the removal of oil. Gradually, however, awareness of the use of dispersants like Corexit, which makes water resources more toxic than oil, has changed the scenario for the treatment of spilled oil. The removal of spilled oil from water re- sources is still a very topical issue. An eco-friendly and sustainable approach towards the environment has introduced many low-cost, non-toxic and biodegradable materials along with different biomasses to make micro-to nano-sized materials, membranes, sponges/aerogel, etc. for the removal and recovery of oil from water resources. Additionally, the reusability of these materials after the recovery of oils has added one more step towards sustainability. This review comprises the work conducted by various re- searchers in the eld of the removal and recovery of spilled oils using various biomasses and polymers, either in the form of sorbents or separators. © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ).

Contents

1.

Introduction

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2. Statistical trend of sorbents used in oil spill response

 

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3. Materials for oil removal, dispersion and biodegradation

 

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3.1.

Biomass sorbents

 

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3.2. Particles

 

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3.3. Surfactants

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4.

Materials for oil recovery

 

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4.1.

Conventional sorbents

 

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4.2. Separators

 

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Aerogels

4.3. .

 

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Gelators

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5. Outlook and challenges

 

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6. Conclusions

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Acknowledgement

 

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References

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1. Introduction

Currently, the challenge is to clean water resources, which are being polluted by oil either in the form of routine shipping, run-offs

* Corresponding author. E-mail address: Bhairavi.doshi@lut. (B. Doshi).

from industry, dumping, or oil spills ( NOAA, 2017a ). An oil spill is the accidental or intentional discharge of petroleum hydrocarbons into the environment, especially the marine ecosystem. An oil spill on water can be transported by wind and current, and the distributed oil either evaporates or forms a surface slick, disperses in water, or submerges and accumulates in the sediments ( Reddy et al., 2002; Liu et al., 2012 ). Additionally, temperature, salinity, and waves also increase oil transportation and weathering rates.

0043-1354/ © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ).

B. Doshi et al. / Water Research 135 (2018) 262e 277

263

Moreover, oil spill from tankers such as Exxon Valdex in 1987 (11 million gallons) ( Carson et al., 2003 ) and Deep Horizon in 2010 (4.9 million barrels) ( Brody et al., 2010 ) were marked as the greatest disasters for the marine environment. Since most oils oat on the water surface, seabirds and marine animals are mainly affected ( Barron, 2012 ), and other creatures and terrestrial animals are

harmed if the oil comes ashore ( Brody et al., 2010 ). Such spilled oils also affect humans through inhalation, skin and eye irritation. Many researchers have reviewed the aspects and impacts of these

spills on the ecosystem over time ( Jernel ov, 2010; Henkel et al., 2012; Chang et al., 2014 ) and developed various methods and chemicals for oil spill response ( Michel et al., 1992; ITOPF, 2014a ). However, the spill intensity and location determine the clean-up technology that needs to be applied. Oil spill treatment methods can be classi ed as physical/me- chanical, chemical, or biological ( EPA, 2017 ). Physical/mechanical methods include booms that are stationary oating devices to prevent the movement of the oil slick. Using high-temperature booms enables the burning of the oil in-situ ( Evans et al., 2001 ; Fingas, 2011 ; IOGP, 2016 ). Skimmers are stationary or mobile de- vices, that were used to remove oating and/or emulsi ed oil from the water surface ( Michel et al., 1992 ). Hydrophobic meshes that repel water but allow oil to pass through can be utilized in skim- mers for enhanced oil recovery. Chemical methods include dis- persants ( IPIECA, 2001 ; ITOPF, 2014b; Graham et al., 2016 ) sprayed on the oil spill to break it up into small droplets ( NOAA, 2017b ). In addition, sorbent materials may be used in small-scale oil spills. Biological methods include the addition of microbes and/or nutri- ents and/or oxygen to stimulate bacterial growth and the resultant biodegradation of the spilled oil ( Azubuike et al., 2016 ). However, physiochemical methods have limitations in terms of crude oil clean-up, so recently biological methods have held sway ( Das and Preethy, 2011 ; Dave and Ghaly, 2011 ). However, the selection of sorbent materials is dependent on the nature of the spilled oil ( Teas et al., 2001 ). The rate at which oil can be treated in open waters depends on the treatment method. Dispersants applied from aircrafts are the fastest, followed by skimming and in-situ burning ( Graham et al., 2016 ). In addition, environmental conditions affect the perfor- mance of the treatment methods, such as wind, currents, waves, oil viscosity, and sensitivity to debris. The costs of different oil spill treatment methods from the least to most expensive are as follows:

in-situ burning, dispersants, mechanical recovery, and manual cleanup. Despite cost ef ciency, in-situ burning generates many particulates and carbon dioxide in the environment ( Mullin and Champ, 2003 ). Choosing the oil spill treatment method becomes an optimization task by minimizing both the environmental impact and cost of operation. Local jurisdiction also affects costs, due to possible nes based on the amount of spilled oil, which limits the oil spill. However, some treatment methods leave the oil in the environment, so it may still cause damage to the ecosystem. It was therefore suggested to impose nes based only on the amount of oil left in the environment. In other words, recovering the spilled oil would decrease the amount of the ne. This kind of jurisdiction could make recovery methods more economically viable, depend- ing on the scale of the ne and the oil spill scenario ( Prendergast and Gschwend, 2014 ). Most of the materials reviewed in this paper aim to either recover spilled oil or enhance the biodegradation of the oil. The best solution in the case of an oil spill depends on numerous factors, and the optimal solution from environmental and economic points of view might be a combination of several different methods. There- fore, instead of classifying oil spill treatment methods based on technical aspects, solution-based classi cation of oil recovery or oil biodegradation is proposed. In the case of an oil spill, either the oil

must be left in the environment for biodegradation or it can be recovered from the environment, and to achieve this there are different technical methods and materials. Scheme 1 shows this classi cation. Existing dispersants/chemical herders are chemically stable, but non-biodegradable so remain longer in the marine environment. There is therefore a growing demand for green, facile and eco- friendly, low-cost sorbents from biopolymers for the treatment of

oil spills and chemical leaks. In past few years, advanced materials

such as aerogels, foam membranes, inorganic meshes, and surface- modi ed fabrics have been used extensively for the separation of oil-water mixtures. Meanwhile, the increasing population rate has increased the rate of food consumption, resulting in massive amounts of bio-waste globally. For this reason, the wise way is to use such easily biodegradable bio-waste or biomass to produce low-cost sorbents with higher oil sorption capacity that are simple to scale up for the cleanup of an oil spill, rather than hazardous chemicals. This review addresses the potential and environmentally-friendly bio-based materials in the form of sor- bents, particles, gelators, surfactants and separators for oil spill treatment. These kinds of bio-based materials have recently been the subject of increasing interest in oil spill treatment applications, and reviews have been published on speci c materials or methods ( Sabir, 2015 ; Ifelebuegu and Johnson, 2017 ). The different materials and methods for oil spill treatment are suitable for different kind of conditions. For sustainable and effective oil spill treatment, bio- based materials must be studied extensively, since one material is unlikely to be suitable in all possible oil spill scenarios. Additionally, local legislation has also affected the economic view of the mate- rials, and method design must be considered. Legislation is subject to changes due to increased environmental awareness, which has a direct impact on oil spill treatment methods, so the utilization of bio-based materials in different kind of oil spill treatment methods and materials must be extensively studied and researched, in response to different kinds of oil spill scenarios and possible future legislation. This review highlights a wide range of different bio- based oil spill treatment materials and methods along with their strengths and weaknesses.

2. Statistical trend of sorbents used in oil spill response

The statistical trends based on the Scopus database of various sorbents studied extensively in the past ten years are given below ( Fig. 1 ). This implies that more research is being conducted using these materials as oil sorbents. Statistical data shows a continual increment in the use of nanoparticles and aerogel for oil spill treatment in the past few years.

and aerogel for oil spill treatment in the past few years. Scheme 1. Oil spill treatment

Scheme 1. Oil spill treatment methods based on the oil recovery or oil dispersion.

264

B. Doshi et al. / Water Research 135 (2018) 262e277

600 500 400 300 200 100 0 2007 2009 2011 2013 2015 2017 publica o
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0
2007
2009
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publica o nsAnnual

Year

aerogels

sorbents

gelators

nanopar cles

nanopar cles

surfactants

separators

Fig. 1. Annual publications including words oil AND spill AND materialextracted from Scopus.

3. Materials for oil removal, dispersion and biodegradation

3.1. Biomass sorbents

In adsorption, sorbate molecules accumulate on the surface of the sorbent. In the case of oil adsorption, the oil molecules need to diffuse onto the sorbent surface, the oil molecules then entrapped in the sorbent due to capillary effects, and nally the oil droplets agglomerate in the pores of the sorbent. Oil consists mainly of non- polar hydrocarbons and their adsorption is attributed to physical non-covalent interactions such as van der Waals forces ( Wahi et al., 2013 ). However, for brous sorbent, only adsorption and capillary action processes take place. In this paper, the term oil sorption is used instead of oil adsorption, absorption, separation, or removal, since all these terms are used in literature when discussing oil sorption on various materials. The differences have not usually been discussed in literature and one of the terms is used without further rationalization. Therefore, to avoid confusion, in this paper oil sorption refers to oil removal using sorbents. Surface chemistry and morphology determine the wettability of the surface, which closely relates to the adsorption of oils. Water contact angle is used to measure wettability. If the contact angle of a water droplet on a at surface is less than 90 , it is characterized as hydrophilic, if the contact angle is between 90 and 150 , it is characterized as hydrophobic, and if the contact angle is over 150 , it is characterized as superhydrophobic ( Fig. 2 ). Similar measure- ments can be done for different kinds of oils, and the solid material can be characterized as oleophilic, oleophobic, or superoleophobic, respectively. The hydrophobicity of the sorbent prevents water sorption and therefore enhances the oil sorption capacity due to the lack of competition between water and oil molecules. Natural

materials such as lotus leaves are superhydrophobic but super- hydrophobicity can be also introduced into an otherwise non- superhydrophobic material by increasing the roughness of the surface and decreasing the surface energy. An ideal sorbent for oil sorption has high porosity and surface area, and is selective to oil. For oil spill treatment applications, the sorbent should also be mechanically and chemically stable, recyclable, environmentally- friendly, and have low density and good buoyancy properties ( Gupta and Tai, 2016 ). Natural products, such as cotton, kapok, rice straw, etc. are abundant, low-cost, biodegradable, and non-toxic materials and therefore ideal for oil sorption in oil spill treatment (Refer Table 1 ). The downsides of such materials are poor hydrophobicity, buoy- ancy, and sorption capacity ( Maleki, 2016 ). There were a variety of different kind of modi cations to natural sorbent materials re- ported in literature, which enhanced the properties of the materials such as hydrophobicity and sorption capacity. Ideally, the modi - cation should be minimal and should keep the good properties of the native material while enhancing weaker properties i.e. enhancing oil sorption and buoyancy while not altering the biocompatibility of the materials. Moreover, the sorption capacity

of the oleophilic sorbents prepared via bulk polymerization mainly

depends on the size and molecular weight of the polymer used.

Increasing size from monomer to macromonomer increases the cross-linked structure, but in turn decreases the swelling capacity by blocking the penetration of organic solvents into polymer network. On the other hand, the increasing molecular weight of the dendric structure macromonomer also increase the hydrophobicity

of the sorbent ( Kizil and Sonmez, 2017 ).

Cheaper and readily biodegradable plant biomass such as kapok ber, cattail ber, Salvinia sp., wood chip, rice husk, coconut husk and bagasse are used as inserts to remove oil from the storm water runoff of gas station ef uent, with 70% greater oil removal capacity compared to synthetic polymer ber sorbent, due to the presence

of ample void spaces in their loose ber structure and hydropho-

bicity ( Khan et al., 2004 ). The bio-waste of rice (rice husk) contains

a large amount of silica. The pyrolysis of rice husk causes the

decomposition of organic material and the breaking of bonds be- tween the silicon and organic material present in it. This enhances the hydrophobicity of rice husk, which leads to the puri cation of crude oil ( Vlaev et al., 2011 ). The adsorption of the oils shows a direct dependency on granulometric composition i.e. weight ratio of C/SiO 2 along with the bulk density, surface morphology and oleophilicity of the sorbent. However, an inverse dependency of sorbent bulk density on the height of penetration of the oil in it exists ( Angelova et al., 2011 ). Moreover, alkaline treatment of rice husk produces lignocellulosic sorbent material by removing its silica, which enhances the adsorption capacity of the diesel. Such adsorbed oil along with the sorbent can be used as a solid fuel

oil along with the sorbent can be used as a solid fuel Fig. 2. Wettability of

Fig. 2. Wettability of water on the at surface of the sorbent.

B. Doshi et al. / Water Research 135 (2018) 262e 277

Table 1 Biomass-based sorbent used for the degradation and removal of oils.

265

Sorbent

Method

Oils

Sorption Capacity/

Ref.

 
 

Removal

 

Rice Husks

White Ash (Pyrolysis)

Diesel

5.02 g/g 6.22 g/g 2.78 g/g 2.98 g/g 3.7 kg/kg 5.5 kg/kg 6.0 kg/kg 7.5 kg/kg 9.2 kg/kg 19 g/g 42 e 52 g/g

 

( Vlaev et al., 2011 )

 

Crude

Oil

 
 

Black Ash (Pyrolysis under N 2 or inert atmosphere)

Diesel

 

Crude

Oil

Rice

Husks

Pyrolysis (Carbonized) at 480 C

Gasoline

 

(

Angelova

et al., 2011 )

 

Diesel Light crude oil

 

Motor

oil

Heavy

Crude oil

Rice Husks Silkworm cocoon waste

Alkaline treatment Drying (110 C), Cutting, and Milling

Marine diesel

 

( Bazargan et al., 2014 ) ( Moriwaki et al., 2009 )

Motor oil

(51%)

 

Vegetable oil

37 e 60 g/g (54%)

 

Banana skins Potato peel Luffa (an agricultural

Drying (sunlight and 70 C), crushing and Sieving Drying (70 C) and Crushing Cutting, Sieving, washing and drying (105 )

Crude oil

5 e 7 g/g

 

( Alaa El-Din et al., Article-In-Press ) ( Tontiwachwuthikul et al., 2016 ) ( Abdelwahab, 2014 )

Waste lubricating oil 2.15 g/g

Diesel Oil Heavy Crude Oil Mineral oil Vegetable oil Cutting Oil Mineral oil Vegetable oil Cutting Oil

> 85%

waste) M.Rouxii (32.7% Chitosan) Shaking ask method, Autoclave and drying

>

50%

77.2 mg/g (77%) 95.5 mg/g (93%) 84 mg/g (84%)

( Srinivasan and Viraraghavan, 2010 )

A.Coerulea (10.4% Chitosan)

 

72%

 
 

91%

80%

Hybrid peel waste (Banana Hybridization of peels with NaOH and drying at 70 C Lubricant oil

38%

 

( Abdullah et al., 2016 )

skins + orange peel) Walnut shells

 

Petrol oil

32%

 

Media

Mineral Oil

0.56 g/g

 

( Srinivasan and Viraraghavan, 2008 )

 

Vegetable oil

0.58 g/g

DoALL Bright-Edge

0.74 g/g

 

Oil

( Bazargan et al., 2014 ). Another low-cost sorbent obtained from silkworm cocoon waste removes 30% more motor oil and vegetable oil from marine water than natural wool bers ( Moriwaki et al., 2009 ). Various fruit peels such as banana and orange, being rich in cellulosic content, can remove heavy oil more effectively than lighter oils ( Abdullah et al., 2016 ; Alaa El-Din et al., Article-In- Press). Similarly, Tontiwachwuthikul et al. show the effectiveness of potato peel in the remediation of water from a waste-lubricating oil spill ( Tontiwachwuthikul et al., 2016 ). Cellulosic materials, being uffy and possessing low bulk density, show higher uptake of marine fuel with less treatment. Macroporous agricultural waste called Luffa with low bulk density removed more than 50% of crude oil from water with good reusability ( Abdelwahab, 2014 ).

3.2. Particles

Particle behavior in the presence of oil and water mainly

depends on its functional characteristics together with size and porosity, which either undergoes emulsion and/or adsorption. In an emulsion system, small-volume fraction is classi ed as dispersed phase (oil) and larger as continuous phase (aqueous/water). Strongly hydrophilic particles get wetted only by water and remain dispersed in the aqueous phase of the emulsion whereas strongly hydrophobic particles remain in the oil due to being wetted only by the oil phase. The particle needs to be amphiphilic in order to adsorb at the interface. Oil-in-water (o/w) emulsion is favorable when the three-phased contact angle (CA) between the oil, solid and water is < 90 , whereas water-in-oil (w/o) emulsion when CA is > 90 ( Aveyard et al., 2003 ). Moreover, adsorption-free energy is at maximum when the CA is z 90 i.e. the particle is equally wetted by both the aqueous and oil phases. In this case, other factors such as the wettability of the particles, inter-particle interactions, etc. must be considered, knowing the type of emulsion. Emulsions are therefore stable, if particle adsorption and droplet stabilization by

stable, if particle adsorption and droplet stabilization by Fig. 3. Oil dispersion/degradation using different types of

Fig. 3. Oil dispersion/degradation using different types of particles.

266

B. Doshi et al. / Water Research 135 (2018) 262e277

those particles resist destabilization phenomena such as coagula- tion and coalescence ( Chevalier and Bolzinger, 2013 ). However, Lam et al. in their work emphasized that stable emulsion has also been observed with contact angles 20 e120 ( Lam et al., 2014 ). However, the oil/water emulsion system separates, if the interfacial tension (IFT) between these two phases increases. Moreover, interfacial area had direct in uence on resulting droplet size depending on particle dosage, i.e. a lower number of particles creates a small interfacial area and larger droplets, whereas a higher number of particles forms ne emulsion with smaller droplets. Fig. 3 shows the pictorial form of particles used in the destabilization of oils. Generally, raw natural sorbents have excellent adsorption ca- pacity, biodegradability and non-toxicity in comparison with syn- thetic sorbents, but their low hydrophobicity increases water uptake and lowers oil sorption capacity. Many researchers are therefore working on the enhancement of oil sorption af nity through various modi cations or the addition of hydrophobic moieties to these natural sorbents, as the functional group prop- erties play a signi cant role in the adsorption of oils (Refer Table 2 ). The addition of a hydrophobic chain on the biopolymer enhances

the tensile properties and thermal stability of the polymers ( Amri et al., 2011 ) and forms more stable emulsion due to its amphiphi- licity ( Doshi et al., 2018 ). However, by increasing the hydropho- bicity, the particles get wetter in oil than in water, and form w/o instead of o/w emulsion ( Andresen and Stenius, 2007 ). On the contrary, the formation of stable emulsions is feasible by switching the pH rather than hydrophobic modi cation ( Liu et al., 2012 ). Pickering emulsions are emulsions stabilized by solid particles, with similar properties to classical emulsions stabilized by surfac- tant, which can be either o/w-, w/o- or multiple emulsions ( Chevalier and Bolzinger, 2013 ). Cellulose nanocrystals (CNC) ob- tained using a deep eutectic solvent (DES) of choline chloride with oxalic acid dihydrate, form emulsi ed creaming with marine diesel through Pickering emulsions, which in the case of oil spill can be easily skimmed ( Laitinen et al., 2017a ). Such particles forming Pickering emulsions, are irreversibly adsorbed at the oil-water interface and require high energy for desorption compared to conventional surfactants. So, particles that carry thermo- responsive polymers (copolymers) are used as stabilizers for o/w Pickering emulsion, and the emulsions are destabilized by simple

Table 2 Different particles used in the formation of emulsions, removal and recovery of oils.

Particles

Method

Hydrophobic modi cation

Oil

Type of Emulsion/ Adsorption capacity/ Recovery

Ref.

Chitin

Powder form

Toluene

1.6 mg/g

( Mohamed and Ouki, 2011 ) ( Mohy Eldin et al., 2011 )

Chitosan

2.2 mg/g

Chitosan

Grafting using free radical n-butyl acrylate polymerization

Gasoil Mobil-1 oil Light crude oil Heavy Crude oil Crude Oil Marine Diesel Diesel Neste 2T oil Wastewater of oil extraction Marine Diesel

~45%

~60%

 

~75%

~80%

Oil palm leaves Carboxymethyl chitosan (Micro-sized)

Blending and mixing Partial Carboxymethylation

Lauric acid

1.2 g/g Winsor o/w micro emulsion ( < 100 mm)

( Sidik et al., 2012 ) ( Doshi et al., 2017 )

monochloroacetic acid

(partial)

 

H-Oleoyl-Carboxymethyl chitosan

Carboxymethylation and

Oleoyl chloride

> 95% residual oil adsorption o/w emulsion ( 30 mm);

( Sun et al., 2010 )

acylation

Sodium salt of oleoyl carboxymethyl chitosan (Micro-sized)

Carboxymethylation and

Oleoyl chloride

( Doshi et al., 2018 )

acylation

75

e 85% oil recovered

Chitosan Microspheres

Carboxymethylation and

Sodium tripolyphosphate

Oil in water ef uents

by CaCl 2 90% removal ( Grem et al., 2013 )

cross-linking

of oil industry Toluene, cyclohexane, > 90% removal n-heptane, Chloroform

 

Chitosan-silica hybrid (Nano-sized)

Sol-gel encapsulation

Tetraethyl orthosilicate, 3- (triethoxysilyl)propyl isocyanate Choline chloride and oxalic acid dihydrate n-butylamine

( Soares et al.,

 

2017

)

Cellulose nanocrystals (Nano-sized)

Deep Eutectic Solvents

Marine Diesel

Pickering Emulsion ( < 10 mm)

( Laitinen et al., 2017a )

Bifunctionalized cellulose (Nano-sized) Oxidation and Amination

Marine Diesel

o/w emulsion ( < 20 mm) ( Ojala et al., 2016 )

Blends of poly (vinyl alcohol) nanoparticles with chitosan or starch (Nano-sized) Electrospun Polyvinyl Chloride/ Polystyrene Fibers (Nano bers)

Emulsion polymerization

Toluene

48.7 g/g

( Fouad et al., 2016 )

Kerosene

39.3 g/g 22.7 g/g (Oil absorption) 146 g/g 119 g/g 38 g/g (Oil sorption) ~81 g/g ~75 g/g ~5 g/g 31.7 g/g 33.8 g/g ~32 g/g (Oil absorption;

Hydraulic oil

Electrospinning

Motor oil

( Zhu et al., 2011 )

peanut oil

 

diesel

Eugenol-Based Polymeric microspheres Suspension Polymerization and self-crosslinking

 

Chloroform

( Deng et al., 2015 )

Toluene

 

Gasoline

Diesel

Kerosene

Peanut Oil

 

5

cycles)

Cellulose nano bril and polyvinyl alcohol (Aerogel microspheres) Polyvinylpyrrolidone-coated magnetite nanoparticles (Nano-Sized)

Emulsi cation and Freeze Drying Hydrothermal Method

Span-80

Crude oil

54 e 140 g/g

(Oil

( Zhai et al., 2016 )

MC252 oil

absorption) ~100% (Magnetic oil sorption and separation) ~100% (Magnetic oil sorption and separation)

(

Mirshahghassemi

 

and Lead, 2015 )

Polystyrene coated magnetic hollow Fe3O4 nanoparticles (Nano-Sized)

Hydrothermal synthesis

lubricating oil

( Chen et al., 2013 )

and emulsion

 

polymerization

B. Doshi et al. / Water Research 135 (2018) 262e 277

267

heating ( Zoppe et al., 2012 ). Cellulose consists of long chains of poly- b-(1 / 4)- D -glucosyl residues and these chains unite to form long thread-like bers known as micro brils. Due to the hydro- philic nature of brillated and micro-brillated cellulose (MFC), wettability in water is more than that in oil, to form o/w emulsion. Bifunctionalized cellulose rod-like nanocrystals ( < 120 nm in length) obtained by oxidation of cellulose with sodium periodate and chlorite followed by amination with n-butylamine, were effectively used to stabilized oil-in-water (o/w) emulsion of up to 3.5% sea water salinity ( Ojala et al., 2016 ). Hydrophilic carboxymethyl chitosan (CMC) obtained from crab shells destabilized Marine Diesel, Diesel and Marine-2T oil into small droplets of < 100 mm at sea water alkalinity and salinity ( Doshi et al., 2017 ). In a similar way, our previous work ( Kalliola et al., 2016 ) re ects the applicability of Ca þ 2 cross-linked CMC nano- particles to stabilize dodecane in o/w emulsions. However, chitosan akes have superior adsorption properties to chitosan powder for oil ( Barros et al., 2014 ). Chitosan microspheres produced by ionic gelation of chitosan with sodium tripolyphosphate (STP) separated 90% of the oil from oil industry ef uents using packed columns ( Grem et al., 2013 ). On the other hand, polymeric microspheres derived from eugenol suspension polymerization and self- crosslinking showed higher adsorption of chloroform and toluene than gasoline, diesel, and kerosene, as these lighter oils consists of longer molecular chains, which adsorb on the surf