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Review
Oil Removal from Aqueous State by Natural Fibrous Sorbent: An Overview
Rafeah Wahi, Luqman Chuah Abdullah, Thomas Choong Shean Yaw, Zainab
Ngaini, Mohsen Nourouzi Mobarekeh
PII:
DOI:
Reference:

S1383-5866(13)00221-9
http://dx.doi.org/10.1016/j.seppur.2013.04.015
SEPPUR 11151

To appear in:

Separation and Purification Technology

Received Date:
Revised Date:
Accepted Date:

25 February 2013
10 April 2013
11 April 2013

Please cite this article as: R. Wahi, L.C. Abdullah, T.C.S. Yaw, Z. Ngaini, M.N. Mobarekeh, Oil Removal from
Aqueous State by Natural Fibrous Sorbent: An Overview, Separation and Purification Technology (2013), doi:
http://dx.doi.org/10.1016/j.seppur.2013.04.015

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Oil Removal from Aqueous State by Natural Fibrous Sorbent: An Overview

Rafeah Wahia,b, Luqman Chuah Abdullaha, Thomas Choong Shean Yawa, Zainab Ngainib,
and Mohsen Nourouzi Mobarekeha
a

Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400

UPM Serdang, Selangor, Malaysia


b

Department of Chemistry, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak,

Malaysia

Corresponding author:

Rafeah Wahia,b
a

Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400

UPM Serdang, Selangor, Malaysia


b

Department of Chemistry, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak,

Malaysia
Email: wrafeah@frst.unimas.my
Tel.: +6082-671000
Fax: +6082-673160
1

Abstract

The threat of oil pollution increases with the expansion of oil exploration and production
activities, as well as the industrial growth around the world. The study on the treatment of
oily wastewater is a critical issue to the environmental protection as oil caused problems to
the wastewater treatment facilities. Although oil particles can efficiently be removed by
advanced technologies, the treatments are usually expensive and difficult to maintain.
Adsorption and coalescence filtration are promising choice of treatment for its simplicity,
effectiveness, and feasibility when appropriate sorbent is used. This review discusses the
recent papers on the use of natural fibrous sorbent for removal of oil from wastewater, and its
current development. With their excellent oil removal properties, environmental friendliness,
easy availability, and feasibility, natural fibrous sorbents are an attractive alternative for oily
wastewater treatment.

Keywords: Oily wastewater, natural fibre, adsorption, coalescence

1. Introduction
Oily wastewater is one of the environmental concerns nowadays. The seriousness of oil
pollution problem comes in sync with the expansion of oil exploration and production
activities, as well as industrial growth around the world. For instance, annual worldwide use
of petroleum-based products and vegetables oils are approximated to exceed 100 and 92
million tonnes, respectively [1], [2]. It is estimated that between 2000 and 2011 alone,
224,000 tonnes of petroleum oil polluted the worldwide marine due to oil tanker spill [3].

Oils in wastewater can be found in various forms such as fats, lubricants, cutting oils, heavy
hydrocarbons, and light hydrocarbons [4]. These oils can be further divided into two
categories, namely free and emulsified oils. The free oil fraction of the wastewater is easier to
treat by physical techniques such as gravity separation and skimming [5], [6]. In contrast,
emulsions or the oil droplets dispersed in water phase, are more difficult to treat due to their
high stability in aqueous phase [7], [8]. Emulsions can be further divided into two groups:
simple emulsions and multiple emulsions (Figure 1). In simple emulsions, oil droplets are
dispersed in immiscible oil-water phase. Meanwhile, in multiple emulsions, additional
emulsions occur in an emulsion itself, in which one or more smaller droplets can be found
inside globule of a multiple emulsion [9].

(b)

(a)

Figure 1: Emulsions in oily wastewater: (a) single emulsions and (b) multiple emulsions [10]

Moreover, oily wastewater originates from various sources such as the food, vegetable oil,
metal, textile and leather industries, oil and gas production, domestic sewage, kitchens, and
vehicles [11], [12]. Environmental contamination occurs during oil and gas production as oil
is transferred to the environment by transportation, refining, and use [13], [14]. It is estimated
that the total annual oil pollution through transportation of petroleum hydrocarbons alone
could reach up to 10 million metric tonnes [14]. Oily wastewater concentration generated by
industrial activities could reach as high as 40,000 mg/l [15]. Oil is usually removed from
wastewater prior to discharge to the environment to meet the maximum allowable limit of oil
and grease in water as required by local enforcing agency. However, oily wastewater from
kitchens and small enterprises is commonly discharged without any prior treatment and hard
to control.

Unlike other water contaminants, not all countries have set maximum allowable limit for oil
and grease in water. For example, the maximum limit for oil and grease in drinking water is
not mentioned in World Health Organisation (WHO) drinking water guidelines (2011) [16]
and European Communities (Drinking Water) (No. 2) Regulations 2007 [17]. The United
States Environmental Protection Agency (USEPA) limits oil grease content in drinking water
to 0.3 mg/l [5]. In Malaysia, the maximum allowable limit set by the Department of
Environment for oil and grease in water is 50 mg/l.

The main purpose of this review is to:


(1) present general description on the use of fibrous natural sorbent for oil removal from
wastewater by adsorption and filtration techniques,
(2) discuss in general, other available techniques for oily wastewater treatment,
(3) highlight the factors influencing oil removal efficiency of natural fibrous sorbent.

2. Effect of oily wastewater on health and environment


Oily wastewater, both from the natural and synthetic sources, are persistent environmental
pollutants [6]. Oily wastewater could cause health hazards if it is not appropriately treated.
High oil contamination in water bodies gives adverse effect on aquatic organisms, human
economy, and tourism activities due to its coating properties as well as unpleasant view and
odour [11]. Many studies have been conducted on the effect of oily wastewater on human
health and environment. Most of the studies focused on oil wastewater caused by
hydrocarbon oil spill in marine environment.

A review by Aguilera et al. [18] suggested that oil compounds have the ability for
bioaccumulation as they are transferable along the food chain via oil-contaminated marine
food. In vitro studies on fuel extract from Erika oil spill showed that consumption of oilcontaminated marine food could cause detrimental effects on human health (Table 1). Some
examples are the induction of metabolic enzymes involved in carcinogenic processes [19] and
genotoxic damage in consumers [20], [21].

Aguilera et al. [18] also summarizes the acute effects and psychological symptoms reported
by previous researchers who studied the effect of hydrocarbon oil spill. They found that
hydrocarbon oily wastewater did give impact on human health, especially to those who had
direct bare-hand contact with the oil. Studies also found that the urinary volatile organic
compounds (VOC) and polycyclic aromatic hydrocarbons (PAH) metabolite levels in oil spill
cleanup volunteers are found increased after cleanup [21]. Long term bare-handed contact
with hydrocarbon oil wastewater lead to an increased risk of developing skin tumours, due to
exposure to carcinogenic properties of hydrocarbon oil [22].

Excessive amount of vegetable oil in water stream could cause the formation of oil layer
which limits the oxygen penetration into water and thus, is harmful to aquatic organisms [23].
The ability of oily water to cause toxic effects could harm aquatic plants and coral reefs [24
27]. In addition, oil could also cause toxic effects on microorganisms responsible for
biological treatment of wastewater [2830].

Table 1: In vitro studies and studies on the effects caused by transference to the food chain
(in order of the chronology of the spills) [18]
Accidentreference
Erika [19]

Study characteristics

Methods

Results

In vitro genotoxicity of an Erika


fuel extract in human epithelial
bronchial cells and human
hepatoma cells

DNA adducts.
CYP 1A1, 1A2, 1B1,
2C9, COX1, COX2
AND 5-LOX protein
expression.
LT B4 and PG E2
detection

Adducts formation and


induction of CYP 1A2,
COX2 and 5-LOX in
hepatoma cells,
formation of LT B4 in
bronchial cells

Erika [20]

Genotoxicity associated with


Comet assay in hepatic
Erika oil-contaminated mussels cells, bone marrow and
consumption in rats fed daily for blood cells
2 and 4 weeks

Dose-effect-time
relationship in hepatic
and bone marrow cells.
No effect in blood
cells.

Erika [31]

CYP 1A1 induction associated


with Erika oil-contaminated
mussels consumption in rats fed
for 2 days

CYP 1A1 mRNA and


EROD activity
transient induction

CYP 1A1 mRNA


expression and EROD
catalytic activity in
liver

Note: COX, cyclooxygenase; CYP, cytochrome P450; ethoxyresorufin-O-de-ethylase; LOX,


lipooxygenase; LT, leuctriene; PG, prostaglandine.
3. Oil removal from wastewater

As one of the most important global sources of energy and raw material for industries, oil is
regarded as a precious commodity. Any spillage or inefficient extraction implies economic
loss and in some cases, environmental issues. Thus, an efficient system is greatly important
for the recovery of the spilled or residue oil. Oil removal and recovery technologies are
classified into several categories: physical, mechanical, biological and photochemical
recovery, filtration, and the most commonly used, adsorption [7]. These technologies are used
either separately or in combination with each other.

Table 2 shows the advantages and limitations of each treatment method. Examples of
physical and mechanical methods are skimmer, gravity separation, micro and ultrafiltration,
and membrane filtration. Biological method includes the use of microorganisms to remove oil
[30]. Chemical treatment can be realised by coagulation and flocculation, electrocoagulation,
and flotation techniques [3234]. Surface and depth filtration method is commonly done
using granular or fibrous filter material [35], [36]. Meanwhile, adsorption method utilises
booms, dispersants, and sorbents to remove oil [14].

Among all the methods, adsorption and coalescence (via depth filtration) by natural fibrous
sorbent seem to be the two most attractive methods due to their feasibility and effectiveness,
if appropriate media are used. In adsorption and coalescence mechanisms, no additional
chemicals are required to demulsify oil in water and high removal efficiencies of chemical
oxygen demand (COD) from wastewater are demonstrated [23]. In general, natural fibrous oil
sorbents contain micro and macroporous structures that permits oil attachment and
entrapment inter and intra-fibre structures [2]. Adsorption and coalescence of mechanisms are
often separately studied, although there is a very high probability that both mechanisms occur
simultaneously. In both mechanisms, oil adsorption performance is normally measured in
terms of oil removal efficiency (% removal) and sorption capacity (mass of oil sorbed per
gram sorbent).

Table 2: Methods for treating oily wastewater


Methods
Adsorption

Advantages
Good oil removal
efficiency
Simple operation
Low processing cost

Disadvantages
Labour intensive
Poor removal of fine
emulsions (<100 m)

Researchers
[3741]

Coagulation &
flocculation

Good oil removal


efficiency

High initial and operating


cost
Labour intensive
Generation of secondary
pollutant

Electrocoagulation

High oil removal efficiency High initial cost


Low operating cost

[32], [44]

Flotation

High oil removal efficiency Complex operation (involves


coagulants/flocculants)
Poor removal of fine oil
droplets (<50 m)
High operating cost

[34], [4547]

Coalescences
(depth filtration)

Good oil removal


efficiency
Simple operation
Low initial and operating
cost

[24], [28], [35],


[36], [4850]

Membrane
filtration

High oil removal efficiency Requires pre-treatment of


wastewater
High initial and operating
cost
Premature membrane fouling

[5], [51], [52]

Biological
treatment

Good oil removal


efficiency
Low operating cost

[30]

Oil removal efficiency highly


depends on the quality of
filter bed media
Slow oil removal process

Extremely temperature and


pH sensitive
Requires skilled operator
Requires wide space

[33], [42], [43]

3.1 Oil removal by adsorption

Adsorption is the attraction between the outer surface of a sorbent and a sorbate. In
adsorption process, molecules of the sorbate accumulate on the sorbent surface without
penetrating into the sorbent (Figure 2). In general, oil adsorption occurs in three steps:
diffusion of oil molecules into the sorbent surface, entrapment of oil into the sorbent structure
by capillary action, and finally agglomeration of oil droplets in porous and rough structures
of the sorbent [34].

Studies have shown that oil adsorption is closely related to functional group properties of the
sorbent [2], [30], [53]. Important functional groups responsible for oil adsorption include OH, C=O, and C-O [5456]. Another important characteristic is the surface morphology of the
sorbent. For example, many excellent natural sorbents like kapok fibre and populous seed
contain hollow structures that give rise to higher surface area available for adsorption[57],
[58].

Figure 2: In adsorption process, molecules of the sorbate accumulate on the sorbent surface
without penetrating into the sorbent

10

Adsorption is a preferred oil removal technology due to its simplicity and relatively lower
processing cost in comparison to other oil removal technologies [59]. Oil adsorption can be
defined as attraction of oil to the surface of a sorbent. In order for adsorption phenomenon to
occur, various types of attractive forces act together; some forces act more significantly
compared to others, depending on the situation. The attractive forces can be grouped into the
chemical (covalent or hydrogen bonds), electrostatic (ionion, iondipole), and physical
(Coulombic, Kiesom energy, Debye energy, London dispersion energy) forces [58].

Natural oil sorbents are among the alternatives for oil removal from wastewater. Unlike
synthetic sorbents, natural sorbents are derived either from plant and animal residues (organic
sorbent) or minerals (inorganic sorbent). Natural organic and inorganic sorbents can absorb
oil between 3-15 and 4-20 times of their weight, respectively [60]. However, inorganic
sorbents are less preferred due to their low oil sorption capacities and low buoyancy [61]. On
the other hand, organic fibrous sorbents have relatively higher sorption capacity. Organic
fibrous sorbents also have equal or sometimes lower density compared to inorganic and
synthetic sorbents. Moreover, organic fibrous sorbents are also environmental friendly and
cost effective [62]. Other advantages of natural organic sorbent are possibility of sorbent
collection, and higher oil recovery and relatively easy disposal compared to other types of
sorbent [2].

There are a large volume of published studies describing oil removal by natural fibres. Most
common natural oil sorbents are kapok fibre, sugarcane bagasse, rice husk, barley straw,
cotton, wool, wood residues, and various plant and animal materials (Table 3). These
sorbents are either used as received [63] or formed into sheets, booms, pads, [38,50], filter
11

[65], and fibre assemblies [29]. Raw natural sorbents generally have excellent sorption
capacity, comparable density with synthetic sorbent, chemical-free, and highly biodegradable
[8].

Despite of their advantages, many natural sorbents suffer drawbacks in terms of high water
uptake [66], which is associated with low hydrophobicity or water repelling ability of the
sorbents. Lack of hydrophobicity will reduce the effectiveness of sorbent microporous
structure to absorb oil due to high water uptake [57]. Presence of waxy coatings on surface of
natural sorbents contributes to high hydrophobicity and oil sorption capacity, as observed in
kapok fibre [2], [53]. Other closely related characteristics of a natural sorbents to
hydrophobicity are their functional group content, surface morphology, active surface area,
pore size and surface interaction. Thus, many works on increasing hydrophobicity of natural
fibrous sorbent to increase oil removal efficiency have been conducted, as shown in Table 3.

Table 3: Reported natural organic fibrous oil sorbents


Sorbent

Sorbent treatment

Water
uptake
(g water/g
fibre, unless
specified)
3

Sorbate and sorption


capacity (g oil/g
fibre, unless
specified)

Researchers

Barley straw

Drying

Gas oil:
78.5

[64]

Carbonisation (T: 400 C,


0.53h)

1.93.5

Gas oil:
8.59

[64]

Chemical treatment by
NaOH &
hexadecylpyridinium chloride
monohydrate (CPC)

Canola oil: 0.576

[13]

Chemical treatment by
NaOH &
hexadecylpyridinium chloride

Canola oil: 0.613


Mineral oil: 0.584

[59]

12

Sorbent

Sorbent treatment

Water
uptake
(g water/g
fibre, unless
specified)

Sorbate and sorption


capacity (g oil/g
fibre, unless
specified)

Researchers

Raw fibre

Petrol: 1420
Diesel oil: 920.5
Engine Oil: 1222
Mineral oil: 1518

[67]

Mixed with 20% polyester

Petrol: 17
Diesel oil: 20
Engine Oil: 21.5
Mineral oil: 20.5

[67]

Mixed with 20% polyester,


heated

Petrol: 16.5
Diesel oil: 19
Engine Oil: 15.5
Mineral oil: 18

Cellulose

Raw fibre

Isooctane: 75100%

[35]

Kapok

Raw fibre

Diesel oil: 36.7


Engine oil: 47.4
Used engine oil:
50.8

[2]

Sun-drying

0.30

Diesel oil: 19.35


Crude oil: 25.71
Engine oil: 60.51
Used engine oil:
49.94

[66]

Oven drying at 60 C, 24 h

Engine oil: 0.827

[54]

Thermal bonding at 200 C,


36s, 1050 bar

HD oil: 1212.6
Diesel oil: 10.6
11.8

[29]

Co-blending with 30%


polypropylene, thermal
bonding at 200 C, 36 s, 1050 bar

HD oil: 10.226
Diesel oil: 9.610.4

[29]

Raw fibre

01.9

Diesel oil: 2.59

[63]

Raw fibre

Toluene: 30
Chloroform: 40
Xylene: 28
n-hexane: 22

[53]

Solvent treatment (water)

Toluene: 34
Chloroform: 50

[53]

monohydrate (CPC)
Cotton grass

13

[67]

Sorbent

Sorbent treatment

Water
uptake
(g water/g
fibre, unless
specified)

Sorbate and sorption


capacity (g oil/g
fibre, unless
specified)

Researchers

Xylene: 34
n-hexane: 26

Solvent treatment (HCl)

Toluene: 35
Chloroform: 51
Xylene: 34.5
n-hexane: 26

[53]

Solvent treatment (NaOH)

Toluene: 32
Chloroform: 42
Xylene: 33.5
n-hexane: 24

[53]

Solvent treatment (NaClO2)

Toluene: 36
Chloroform: 52
Xylene: 36
n-hexane: 26

[53]

Solvent treatment
(Chloroform)

Toluene: 24
Chloroform: 36
Xylene: 28
n-hexane: 20

[53]

Sun-drying

3.44

Diesel oil: 2.60


Crude oil: 2.56
Engine oil: 9.26
Used engine oil:
7.59

[66]

Oven drying, 60 C, 24 h

Engine oil: 0.298

[54]

Pyrolysis (T:480 C, t: 3 h,
under vacuum)

1.1

Gasoline: 3.7
Diesel oil: 5.5
Light crude oil: 6.0
Engine oil: 7.5
Heavy crude oil: 9.2

[7]

Coconut husk

Oven drying, 60 C, 24 h

Engine oil: 0.058

[54]

Salvinia
cucullata Roxb.

Oven drying, 60 C, 24 h

Engine oil: 0.944

[54]

Oven drying, 60 C, size <4


mm

Vaseline: 3.67.3
Nujol: 4.78.6
Marlin oil: 4.811.6

[55]

Oven drying 110 reduced to


60 C, milling

Motor oil: 4252


Vegetable oil: 37
60

[68]

Rice husks

Silk worm
cocoon waste

14

Sorbent

Sorbent treatment

Water
uptake
(g water/g
fibre, unless
specified)

Sorbate and sorption


capacity (g oil/g
fibre, unless
specified)

Researchers

Sugarcane
bagasse

Sun-drying

8.45

Diesel oil: 10.51


Crude oil: 13.27
Engine oil: 19.95
Used engine oil:
18.01

[66]

Oven drying, 60 C, 24 h

Engine oil: 0.019

[54]

Oven drying

3.8

Engine oil: 3.25.3

[56]

Esterification with stearic


acid

Engine oil 1.33.2

[56]

Machine oil: 20.2

[69]

Mixed sawdust

Esterification with Nbromosuccinimide (NBS)


Drying

2127%

Crude oil: 56

[8]

Pine sawdust

Drying

[70]

Sawdust

Mixing with CaSO4

Olive oil mill


wastewater
Cutting oil: 99%

Wood chips

Oven drying, 60 C, 24 h

Engine oil: 0.343

[54]

Wood chips

Not specified

Light cycle oil: 2.5


(dry), 22.7 (wet)
Heavy oil: 3.5 (dry),
5 (wet)
Light gas oil: 2.3
(dry), 3.23.7 (wet)

[71]

Fir fibres

Delignification, carbonisation
at 380 or 900 C, 1 h

Heavy oil
Grade A: 1020
(low bulk density
carbon) and 6080
(higher bulk density
carbon)
Grade C: 15

[72]

Walnut shell

Drying

[4]

Palm oil shell

Carbonisation & magnetic


composite
Drying

Mineral oil: 0.6


Canola oil: 0.6
Cutting oil: 0.8
-

2731%

Crude oil:67

[8]

4245%

Crude oil: 3.56

[8]

Sisal leaves
(Agave sisalana)

Coconut coir
Drying
(Cocos nucifera)

15

[24]

[73]

Sorbent

Sorbent treatment

Sorbate and sorption


capacity (g oil/g
fibre, unless
specified)

Researchers

Drying

Water
uptake
(g water/g
fibre, unless
specified)
5051%

Sponge gourd
(Luffa
cylindrica)

Crude oil: 3.54

[8]

Silk-floss fibre
(Chorisia
speciosa)

Drying

2.55%

Crude oil: 6885

[8]

Reed canary
grass (Phalaris
arundinacea)

Co-milling & screening with


Flax (Linum usitatissimum
L.) & Hemp fibre (Cannabis
sativa L.)

311

Engine oil: 1

[65]

Cattail fibre

Oven drying, 60 C, 24 h

Engine oil: 1.107

[54]

Recycled wool
based nonwoven
material

Drying

Diesel oil: 9.610.6


Crude oil: 11.112.5
Base oil: 1314.8
Vegetable oil: 13.2
14.5
Engine oil: 15.8

[74]

Drying

Motor oil: 5.56

[75]

Drying

Motor oil (real)


a) 0.225
b) 5.56

[75]

Drying

Motor oil
(synthetic): 3343

[76]

Wool fibres

Several previous studies used Langmuir or Freundlich isotherm models to describe oil
adsorption behaviour of the fibrous sorbent (Table 4 and 5). The relative coefficient of this
model is calculated using linear least-square fitting. The Langmuir adsorption isotherm
represents monolayer oil adsorption on homogenous surface of the sorbent. The Langmuir
equation is

16

(Equation 1)
where qe is the equilibrium concentration of oil in the adsorbed phase (mg/g), Qm is the
maximum adsorption capacity (mg/g), b is a constant related to energy of adsorption, and Ce
is the equilibrium concentration of oil in liquid phase (mg/l). On linearisation, this equation
becomes

(Equation 2)
Qm and b can be calculated from the intercept and slope of the linear plot, Ce/qe vs. Ce.

Meanwhile, the Freundlich isotherm model is applied to describe the multilayer adsorption on
heterogeneous surface of the sorbent. The Freundlich equation is

(Equation 3)
where, Ce is the equilibrium concentration (mg/l), qe is the amount of oil and grease group
adsorbed (mg/g) at equilibrium time, n and Kf are Freundlich constants with n giving an
indication of how favourable the adsorption process and Kf (mg/g (l mg-1)n) is the adsorption
capacity of the adsorbent. Linear plots of log qe vs. log10 Ce show that the adsorption of oil
and grease onto studied sorbent follows the Freundlich isotherm model. The values of n and
Kf can be calculated from the slope and intercept of the plots.

However, there is a very important point to ponder regarding the use of Langmuir and
Freundlich isotherm for multisolutes adsorption as in oil system. The Langmuir or Freundlich
17

multicomponent isotherms can only be applied if all the studied solutes individually obey
these isotherms. However, not all organics obey these isotherms as single solutes [77]. In a
complex system such as oil, many organic components are involved, thus even making the
use of the Langmuir or Freundlich multicomponent isotherms is difficult. This is due to the
need to know the adsorption coefficient of each single solute prior to the isotherms
application [77].

Table 4: Reported Langmuir isotherms on oil adsorption by natural fibrous sorbent from
previous studies
Sorbent

Oil type

Langmuir
constant, b (l/g)

Researchers

Crude oil

Maximum sorption
capacity at
equilibrium, Qm
(mg/g)
2000

Chitosan

5.96

[41]

Chitosan

Palm oil mill


effluent

Powder: 3420
Flake: 1970

Powder: 2.18
Flake: 1.20

[39]

Barley straw (surfactantmodified)

Canola oil

576

3.78

[13]

Barley straw (surfactantmodified)

Canola oil

613.3

5.2

[59]

Barley straw (surfactantmodified)

Mineral oil

584.2

14

[59]

Table 5: Reported Freundlich isotherms on oil adsorption by natural fibrous sorbent from
previous studies
Sorbent

Oil type

Adsorption
intensity (1/n)

Kf

Researchers

Chitosan

Crude oil

0.27

1.4 g/g(l/g)1/n

[41]

Chitosan

Palm oil mill

Powder: 0.388

Powder: 2.31

[39]

18

effluent

Flake: 0.457

Flake: 2.08

Barley straw
(surfactantmodified)

Canola oil

0.235

84.4 l/mg

[13]

Barley straw
(surfactantmodified)

Canola oil

0.210

112.1 l/mg

[59]

Barley straw
(surfactantmodified)

Mineral oil

0.168

165.0 l/mg

[59]

3.2 Oil removal by coalescence

There are two crucial emulsions separation mechanisms in porous, fibrous media filtration
system: separation through surface filtration and coalescence through depth filter [35]. In
surface filter, oil loads only on the surface of media, while in depth filter, oil penetrates
through the depth of the media. In depth filtration, coalescence or the merger of two or more
oil droplets during contact to form a single droplet is highly anticipated [48].

Bansal et al. [35] identified that oil removal by coalescence in depth filter could give
relatively better removal of lighter emulsions (<100 m) in oily wastewater than adsorption.
This is because, in adsorption process, removal of lighter emulsions by buoyancy and
gravitational forces alone are difficult due to low settling velocity of the emulsions. In
contrast, in depth filtration, more oil in water droplets is allowed to adhere, combine, and
deform at filter media due to shear forces prior to permanent removal from the wastewater
(Figure 3).

19

Figure 3: Oil in water emulsion separation mechanism at a (a) hydrophobic surface and (b)
hydrophilic surface: (1) droplet adhesion and coalescence at filter; (2) droplet deformation at
the pore due to shear forces; and (3) droplet escape from the pore and coalescence in the flow
stream [35].

Coalescence is important as it affects the oil droplets size and buoyancy. In depth filtration
method, a highly efficient coalescing medium enables the formation of larger oil droplets.
This will in turn reduce the oil buoyancy and increase the oil droplets rise time, thus
increasing the oil-water separation [50]. In coalescence process, smaller oil droplets in the
form of immiscibles are first transported into the filter and attached to the fibre surfaces prior
to coalescence. This is followed by agglomeration and transport of larger droplets on the
fibre, and finally removal of oil droplets from the filter as oil residence time is prolonged
(Figure 3b) [35].

Huang & Lim [78] described four stages involved in fibrous depth filtration of oily
wastewater, namely infiltration, separation, displacement, and equilibrium. During infiltration
stage, oily wastewater flows downwards the filter bed at constant rate. The hydrophobicity of
20

the filter media will determine its wettability by oil or water. In the separation stage, oil and
water flow separately. In hydrophobic-oleophilic media, water will begin to flow faster that
oil due to coalescence process. The displacement stage is marked with the appearance of
water at the outlet of the filter column. Finally, the equilibrium stage occurs once the first oil
droplet emerges at the outlet of the filter column. At equilibrium, the filter media reach their
maximum coalescence capacity, and no further oil retention in the media is possible.

Among all chemical and physical methods available for treating oily wastewater, depth
filtration is found to be highly feasible and effective [24], [65], [78]. Bansal et al. [35]
identified that depth filtration could give relatively better removal of lighter emulsions (<100
m) in oily wastewater than adsorption. This is because in adsorption process, removal of
lighter emulsions by buoyancy and gravitational forces alone are difficult due to low settling
velocity of the emulsions. In contrast, in depth filtration, more oil in water droplets are
allowed to adhere, combine, and deform at filter media due to shear forces prior to permanent
removal from the wastewater.

Depth filtration works best with appropriate filtration media. In recent years, most related,
published studies focused on investigation of feasible, efficient, and environmentally
acceptable filtration media [24]. At the same time, the use of natural fibre as filtration media
is gaining more attention. This is due to its acceptable density range, high sorption capacity,
feasibility, and environmental friendly characteristic [2], [76]. Several attempts have been
made to use natural fibres as filter media made for depth filtration of oily wastewater. Among
the natural fibres are reed canary grass [65], sawdust [24], kapok fibre [78], dried salvinia
[55], wool fibre [75], carbonised rice husk [7] and cellulose [35].
21

Pasila [65] studied the oil adsorption performance of reed canary grass, flax, and hemp fibres
separately by means of depth filtration. Adsorption study was conducted on synthetic
wastewater (fuel oil No. 2 and lubrication oil). The author found strong correlation between
ash content and oil adsorption. It was taught that the high ash content caused the fine fibres to
be easily detachable, resulting in higher viscosity of the flowing oil. The results also showed
that finer filter material gives higher oil adsorption. The oil sorption capacities of the studied
fibres were 2-4 g/g, while the water uptake ranged between 1-3 g/g.

Cambiella et al. [24] investigated the oil adsorption performance of sawdust mixed with
CaSO4 as coagulant on the treatment of synthetic cutting oil wastewater. It was demonstrated
that coagulant played important role to increase oil sorption capacity by promoting
coalescence of oil droplets. The authors also pointed out four possible processes, namely
coagulation, coalescence, adsorption, and straining, involved in the removal of emulsified oil
by means of depth filtration with the aid of coagulant. The oil adsorption study revealed that
99% of oil in water was successfully removed by the system.

Huang & Lim [78] examined the effect of kapok fibre packing density, oil concentration, and
oil viscosity on depth filtration of synthetic oily wastewater (diesel and hydraulic oil).
Experimental results showed that hydraulic conductivity or the ability of oily wastewater to
flow through the filter material decreased with higher packing density and oil concentration.
In addition, highly viscous oil had slower flow but did not affect the volume of oil captured
by the kapok fibre.

22

A study on dried salvinia as filter media by Ribeiro et al. [55] demonstrated up to 90%
removal of heavy crude oil, nujol, and vaseline USP from wastewater. On the other hand, the
oil sorption capacity was 1.33 g/g, which was considerably low compared to oil sorption
capacity in dry system (11.6 g/g). This might be due to the occurrence of free oil available for
oil-sorbent interaction in dry system, and water flew faster than the oil and wetted the sorbent
surfaces before oil in wet system [67], [72]. However, high hydrophobicity and hair-like
structure of the salvinia surface were believed to prevent high water uptake, leading to
excellent oil adsorption performance [55].

The efficiency of oil removal from natural and recycled wool fibre was investigated by
Rajakovic et al. [75] on real motor oil wastewater. Adsorption was conducted in a filter bed at
sorbent mass of 5 g, wastewater flow rate of 2 cm3/min, temperature of 20 C, contact time
25 min, and oil concentration of 1511 mg/l. The authors found that oil removal efficiency
was highly influenced by volume of oily wastewater. As higher wastewater volume was
introduced to the filter bed, the percentage removal decreased. This was due to significant
drop of free oil content in wastewater after contact with filter media. In addition, when higher
wastewater volume entered the filter bed, the emulsified oil-sorbent contact time was being
shortened, leading to weak interactions between them.

Angelova et al. [7] conducted a similar series of experiments using carbonised rice husk as
filter media to investigate the effect of sorbent bulk density and oil density on sorption
capacity. The authors highlighted that the sorbent bulk density and oil density were inversely

23

proportional to the oil penetration level. There was also steady decrease of oil adsorption rate
with increasing contact time. GCMS analysis showed that the carbonised rice husk surface
contained oleophilic high molecular alkanes, which were believed to be responsible for high
oil sorption capacity. In addition, the mesoporous structure of the carbonised rice husk
enabled good oil retention of up to 10 days.

Bansal et al. [35] examined the mechanisms of secondary emulsions separation in fibrous
depth filter. Cellulose was chosen as one of the filter media and isooctane in water emulsion
was the studied wastewater. The study showed that an increase in fibre surface energy led to
increased dispersed oil droplet size in wastewater and higher oil-water separation efficiency.
In addition, increasing fibre pore size would reduce the oil droplets capturing, thus reduced
the separation efficiency. Another important finding was that filter media could be activated
to capture more oil by wetting it with the studied oil. The approach successfully addressed the
water wetting problem encountered in previous studies [56], [67], [72].

4. Properties of natural fibrous oil sorbent


4.1 Hydrophobicity
Hydrophobicity is the ability of a material to repel water. Oil adsorption occurs as a result of
hydrophobic interaction between the sorbent and sorbate [55]. In addition, low
hydrophobicity contributes to sorbents low water uptake even in a turbulence oil-in-water
condition[8], [78]. Lack of hydrophobicity may also cause collapse in sorbent microstructure
due to water adsorption [57].

24

4.2 Functional group


Certain functional groups determine oil removal efficiency of natural sorbent. For example,
several studies found that important functional groups are the asymmetric and symmetric
aliphatic CH2 and CH3 stretching associated to n-alkanes, alcohols, fatty acids, aldehydes,
ketones and n-alkyl esters [2], [30], [53].

4.3 Surface morphology


Another important factor governing oil adsorption by natural sorbent is the morphological
structure of the sorbent. For example, excellent sorption capacity of kapok fibre and populous
seed in comparison to other natural oil sorbent is ascribed to their microtube or hollow
structure (Figure 4) [57]. This kind of structure enables maximum oil entrapment within their
empty lumens[2], [57]. Other highly potential oil sorbents such as cotton [62], [79], fir fibre
[72], and wool [74] have been observed to have either rope or twisted ribbon with entangled
structure with micropores. Rough surface morphology and entangled pore structure of sorbent
surfaces are also desirable and linked to high sorption capacity. Such morphology and
structure provide more active sites for oil adsorption rather than smooth surfaces.

25

Figure 4: SEM images of (A) poplar seed fibres, (B) kapok fibres, (C) cotton, and (D)
expanded polypropylene fibres (magnification 500) [57]

4.4 Surface area


Oil adsorptivity of a natural sorbent is dependent to its active surface area. Generally,
increase in active surface area increases sorption capacity [7]. However, in a sorbent that has
low hydrophobicity, high active surface area could also cause undesirably high water uptake
[75]. Active surface area of a sorbent can be improved by increasing the microporous,
mesoporous, rough, expanded, and hollow structures in the sorbent by means of carbonisation
and chemical modification of the natural sorbent [8], [11], [80]. Surface area of natural
fibrous oil sorbent from previous studies is summarised in Table 6.

26

Table 6: Reported surface area of natural fibrous oil sorbent from previous studies
Sorbent

Surface
area (m2/g)

Oil removal efficiency


(%)

Sorption capacity
(g oil/g sorbent)

Researchers

Salvinia cucullata
Roxb.

218

Marlin oil: 8085

Vaseline: 3.67.3
Nujol: 4.78.6
Marlin oil: 4.8
11.6

[55]

Walnut shell

0.1713

3651334

Mineral oil: 0.6


Canola oil: 0.6
Cutting oil: 0.8
-

[4]

Palm oil shell


(carbonised)
Chitosan

Mineral oil: 45
Canola oil: 60
Cutting oil: 70
POME: 6290

Powder:
2030
Flake:
510

POME: 99%

Powder: 0.55
Flake: 0.45

[39]

Rice husk
(carbonised)

240

Gasoline: 3.7
Diesel oil: 5.5
Light crude oil:
6.0
Engine oil: 7.5
Heavy crude oil:
9.2

[7]

Barley straw
(surfactantmodified)

63.2

Canola oil: 3090


Mineral oil: 1595

Canola oil: 0.613


Mineral oil: 0.584

[59]

Barley straw
(surfactantmodified)

75.70

Canola oil: 0.576

[13]

[73]

4.5 Pore size


A number of studies have also established the effects of sorbent pore size in oil adsorption.
Increase in sorbent pore size decreases oil adsorption efficiency, and reduced pore size allows
complete oil droplets capture [35]. In addition, low inter fibre pore diameter permits higher
oil adsorption when the oil capillarity is low and gravitational force rules adsorption [29]. In
hollow-structured sorbent, high sorption capacity is possible despite of the high inter fibre
pore diameter if entangled structures are present [2]. Study showed that micropores allow

27

only oil flow while macropores allow penetrations of both oil and water [78]. Furthermore,
wide pore size distribution will cause slow adsorption of heavy oil [12].

4.6 Surface interaction


Surface interaction, namely the surface tension and surface energy, is another important
factor in determining the sorption capacity of a sorbent. Previous findings (Table 3) showed
that sorption capacity differs among different sorbent and type of oil sorbed due to difference
in oil surface tension and sorbent surface energy [63]. Sorbent with low surface energy has
higher wetting capability by oil rather than water. This implies that the sorbent-oil adhesive
forces are higher than that of sorbent-water despite of higher polarity of water [35]. In
addition, high liquid-to-air surface tension causes the liquid to remain in droplet condition
due to presence of pore air, thus decreasing wetting capability on the sorbent surface [78].

4.7 Buoyancy
Finally, buoyancy also influences the oil adsorption performance of a sorbent. Good
buoyancy enables sorbent-oil conglomerate to stay afloat on water surface up to 10 days [7].
However, many natural sorbents have poor buoyancy and tend to sink in water environment
[66]. In some natural sorbents with high buoyancy including kapok [2], milkweed [29], ad
silkworm cocoon [68], high hydrophobicity is also observed. Previous works suggested that
the coexistence of buoyancy and hydrophobicity in these sorbents is due to their wax content
[4], [54], [57]. On the other hand, Abdullah et al. [2] pointed out that although wax content
influences the buoyancy and hydrophobicity, it is not the main factor influencing oil sorption
and retention capacity. In addition, the presence of long and branched hydrocarbon chains in
the sorbents is identified as a contributing factor to buoyancy and hydrophobicity [57].
28

5. Factors affecting oil removal efficiency of natural sorbent


5.1 Sorbent dosage
If sorbent dosage increases, oil removal efficiency increases. The phenomenon is associated
with an increase in available binding sites for adsorption in higher sorbent dosage [39].
However, sorption capacity decreases with an increase in sorbent dosage, mainly due to the
increase of unsaturated oil binding sites [13]. In addition, saturation effect also causes a
decrease in oil removal efficiency when maximum sorption capacity has been reached [76].

5.2 Sorbent bed height


In column adsorption system, sorbent bed height plays an important role. Sorbent bed height
is directly related to sorbent mass or dosage [24], which means higher bed height gives rise to
higher oil removal efficiency[2], [24]. This is due to an increase in available binding sites for
adsorption in higher sorbent dosage [39]; however, this is only true for oil removal of below
critical bed height [24]. Beyond the critical bed height, there is a decrease in coalescence
efficiency [36]. It is also suggested that, at higher bed height, the coalesced oil droplets are
redispersed and recoalesced several times as they flow downwards the sorbent bed [28].
Thus, there is no improvement of oil removal beyond the critical bed height.

5.3 Sorbent particle size


At the initial stage of oil removal, higher oil removal efficiency is demonstrated by sorbent
with smaller particle size. In fact, smaller particles contain more available surface area as oil
binding sites and therefore increase adsorption [59]. Although more oil can be captured on
29

larger particles due to increase in oil-sorbent collision, its greater shear forces reduce
possibility of oil retention [43]. After equilibrium, oil removal efficiency is independent of
particle size due to wetting of sorbent active surfaces [7]. It is predicted that oil adsorption at
this stage is mainly determined by the surface morphology and by the oleophilicity of the
adsorbent, rather than the particle size [7].

5.4 Flow rate


Influent or sorbate flow rate is an important factor with regards to oil removal from
wastewater by column technique. In specific, flow rate influences the coalescence
performance and migration behaviour of the oil-in-water droplets [36]. Oil removal is
observed high at low flow rate due to long oil residence time in the sorbent bed [6].
Consequently, coalescence of smaller oil droplets into droplet large enough for entrapment is
allowed to occur [24]. High flow rate also causes large pressure drop across the sorbent bed
and production of small droplets in the upstream of the column [36]. Thus, low oil removal
efficiency will be observed at high flow rate.

5.5 Initial concentration


Oil initial concentration affects oil removal from wastewater as the oil initial concentration
influences the oil adsorption kinetics [39] and inhibits hydraulic conductivity [78]. In a study
on oil removal from palm oil mill effluent (POME) by chitosan, it was found that the same
dosage of chitosan was able to give high oil removal efficiency in POME of low oil
concentration compared to POME of higher oil concentration [81]. It seems that, at high oil
concentration, oil occupies the sorbent surface thus saturation is reached much faster and high
amount of unattached oil is left. In terms of filtration mechanism, this phenomenon can be
30

explained by the occupation of spaces between sorbent particles (macropores) by oil, hence
hindering more oil to infiltrate into the sorbent micropores [78].

5.6 pH
Influent pH is another important factor in determining oil removal. This is because the
changes in pH affect surface properties and binding sites of sorbent [59], and emulsion
breaking [41]. Several attempts have been made to investigate the influence of pH on oil
removal from wastewater. It is found that different sorbent behaves differently towards
changes in sorbate pH.

A number of studies reported the increase of oil removal in acidic and basic conditions.
Studies on chitosans showed that palm oil and crude oil removal efficiency was increased at
strongly acidic and basic pH [39], [41]. In both studies, oil removal efficiency increased in
the order of neutral condition < strongly basic condition < strongly acidic condition. Similar
pattern was demonstrated by recycled wool-based nonwoven material in removal of motor oil
[76].

High removal efficiency at extremely low and high pH can be explained in terms of filtration
and adsorption mechanism. During filtration, strongly acidic condition promotes
destabilisation of oil droplets thus resulting in demulsification and formation of larger oil
droplets [39]. Oil removal efficiency could be enhanced by formation of larger oil droplets
[35]. In adsorption mechanism, acidic condition is believed to encourage reaction between oil
molecules and NH2 functional group in sorbent [41]. Meanwhile, high removal efficiency at
31

strongly basic condition is associated to saponification process whereby hydrolysis of oil in


sorbate occurs [39]. This results in solvent non-extractable hydrolysed oil, which contributes
to inaccurate, high removal efficiency reading.

Several studies demonstrated an increase in oil removal efficiency with the increase of
sorbate pH. For instance, motor oil removal using natural wool fibre showed maximum
removal efficiency at pH 10, and minimum removal efficiency at pH 5 [76]. In addition, the
use of surfactant-modified barley straw showed the lowest removal efficiency for canola oil
and mineral oil at strongly acidic condition (pH 2), with an increase in removal efficiency in
parallel to increasing pH. Nevertheless, no significant difference in oil removal efficiency
was shown at pH between 6 to 10 [6,9]. Low oil adsorption at extremely low pH was
suggested to occur due to ionisation of the sorbate, which caused lower favourability of oil
adsorption [59]. However, this view was in disagreement with Aranelovi et al. [6], who
pointed out the absence of ionisable molecules in heavier oil.

In some other studies, however, changes in pH showed no significant effect on oil removal
efficiency. For example, removal of mineral oil at pH between 3 and 10.5 gave difference of
less than 15%. It was suggested that heavy oil containing mainly alkanes were less affected
by pH. This was due to their chemical stability and absence of ionisable or hydrophilic
groups, which could be influenced by pH [6].

32

5.7 Temperature
At higher temperature of more than 80 C, adsorption of oil will be reduced. The
phenomenon can also be explained in terms of oil adsorption and filtration mechanism. When
the sorbate temperature increases, the speed of its Brownian motion will also increase. Thus,
more energy is required to adhere the oil molecule onto the sorbent surface [6]. In addition, at
such temperature of higher than 80 C, the randomness of oil adsorption-desorption
increases, which may cause less probability of oil attachment on sorbent surface [82]. Next,
in filtration mechanism, increase in sorbate temperature causes decrease in oil viscosity,
increase in oil solubility in wastewater, and increase in oil drainage from sorbent surface
[24].

5.8 Contact time


Sorbent-sorbate contact time is often studied in batch or batch-flow adsorption processes.
Basically, increase in contact time results in increased oil-sorbent interaction, thus increasing
the oil removal efficiency [39]. However, contact time plays important roles only at the
beginning of oil adsorption, and is less important near equilibrium [39], [41], [59]. Near
equilibrium, only small increase in oil removal is observed due to limited availability of
sorbent surfaces for oil entrapment [41]. In several previous studies on oil removal,
significant removal of oil occurs before 30-60 min, depending on the type and dosage of
sorbent. In a batch-flow column adsorption study (0-1400 min), contact time was found to
give only significant influence on oil removal during the first 60 minutes, with removal
efficiency of 99% [6]. Similar findings were obtained in other studies on batch oil adsorption
by plant fibres conducted between 0-140 min [59] and 0-1500 min [8]. However, in a batch
study using chitosan for removing oil from palm oil mill effluent, significant increase in
removal efficiency occurred only during the first 30 min [39].
33

6. Chemically modified natural fibre


Two major problems of many natural oil sorbents are low hydrophobicity and low buoyancy
[66] that could lead to low oil removal efficiency and oil sorption capacity. Therefore,
numerous attempts have been made to improve oil removal efficiency and oil sorption
capacity through physical, chemical, and thermal modifications to increase oil removal
efficiency of sorbent material.

Physical treatments such as grinding and mechanical pressing have no effect on hydrophobic
characteristics of natural sorbent [2], [8]. However, physical treatments do affect the oil
removal efficiency of natural sorbent. For example, grinded natural sorbent exhibits high oil
sorption capacity [78] due to the fact that more oil-sorbent contact surfaces and binding sites
are available on finer sorbent particles [13]. Mechanically pressed natural sorbent has higher
packing density. Sorbent with higher packing density has higher dynamic oil retention
capacity, but lower oil sorption capacity in comparison with sorbent of low packing density
[2], [78].

Thermal treatments at low temperature such as drying and thermal bonding give no
significant increase in hydrophobicity and oil sorption capacity of natural sorbent as
compared to raw fibre [29]. On the other hand, high temperature thermal treatment such as
carbonisation is very effective in increasing the oil sorption capacity of natural fibre [7], [72],
[73]. However, carbonisation is a costly and time-consuming process.

34

Chemical modification demonstrates potential application to increase oil removal efficiency


of natural sorbent due to its promising outcomes, simplicity, and relatively lower cost than
carbonisation. Several approaches have been used in previous attempts to improve oil
removal efficiency of natural sorbent through chemical modification. Among the approaches
are acid treatment [53], [83], alkali treatment [2], [53], salt treatment [53], surfactant
treatment [13], [59], esterification [14], [56], and acetylation [62], [69]. In these studies,
however, no empirical data were provided on the effect of the above-mentioned treatments on
the hydrophobicity of the studied natural sorbent.

To determine the effect of acid treatment on oil sorption capacity of natural sorbent, Sayed &
Zayed [83] used dodecyl benzene sulphonic acid to treat garlic and onion peels. Results
showed that dodecyl benzene sulphonic acid treatment caused a decrease in oil sorption
capacity of these sorbents. This was because dodecyl benzene sulphonic acid was slowly
adsorbed into these sorbents and had the tendency to disperse on oil surface. Another attempt
on acid treatment of natural sorbent was by using hydrochloric acid (HCl) on kapok fibre
[53]. In the study, it was found that the HCl treatment resulted in removal of wax content and
an increase in cellulose hydroxyl groups in kapok fibre walls. In the study, oil sorption
capacities of HCl-treated kapok were found 11-27% higher than raw kapok fibre.

Alkali treatment or alkalisation of natural fibre is originally used to remove lignin, pectin,
wax and natural oils covering the outer surface of the fibre, which consequently improve its
surface and mechanical properties for polymer application [84]. While alkalisation removes
the coatings on the outer surfaces, it exposes the inner surfaces of natural fibre, resulting a
rough surface topography of the fibre [84]. The exposure of the inner surfaces is believed to
35

contribute to oil entrapment. However, experimental investigation on the impact of


alkalisation on oil sorption capacity [2] found that alkalisation could instead, cause reduced
oil sorption capacity. This is due to de-esterification process which removed the waxy
coatings of the kapok fibre. This finding was consistent with Wang et al. [53] who found that
alkalisation caused wax removal from the fibre, with reduction of C=O, C-H, and C-O
functional groups. The results also indicate the importance of waxy coatings on natural
sorbent in oil removal.

Esterification is another technique to increase oil removal efficiency of natural sorbent. In the
study by Banerjee et al. [14], esterification was conducted on sawdust using oleic acid, stearic
acid, and decanoic acid. Treatment was conducted in n-hexane with H2SO4 as catalyst, at 65
C for 6 h. FTIR results showed that OH functional group in sawdust was replaced by C=O
and CO group after esterification. The results also showed that esterification increased the
oil sorption capacity of oleic acid-treated sawdust, from 3.5 g/g (non-treated) to 6 g/g of
crude oil. Said et al. [56] studied esterification of sugarcane bagasse by mixing stearic acid,
basic compounds, and water in excess for 2 h, followed by vacuum drying at 60 C for 20 h.
Results from this study showed that the esterified sugarcane bagasse had lower water uptake
and higher oil sorption capacity in comparison with untreated bagasse.

Acetylation of natural fibres to increase oil removal efficiency through hydrophobisation of


natural fibre was first studied by Sun & Sun [85] based on the fact that acetyl group has
higher hydrophobicity than the hydroxyl group. In this study, the hydroxyl (OH) group in
rice, wheat, rye, barley straws, and poplar wood fibre was successfully replaced with acetyl
groups. However, study on the oil sorption ability of the acetylated fibre was not performed.
36

Further attempt by Sun [69] was on sugarcane bagasse through N-bromosuccinimide (NBS)assisted acetylation. Data of the oil adsorption study showed that acetylated sugarcane
bagasse had sorption capacity of 13.520.2 g/g on machine oil. Adebajo & Frost [62]
investigated on acetylation of cotton performed at 140 C (110 h) under reflux at
atmospheric pressure, while Ren et al. [86] studied acetylation of wheat straw in ionic liquid.
Both treatments successfully reduced OH group and enhanced the three ester bands
associated with successful acetylation, namely the carbonyl C=O stretching of ester (at 1740
1745 cm1), CH in O(C=O)CH3 (at 1369 cm1), and CO stretching of acetyl group (at
1234 cm1). On the other hand, these studies did not cover oil adsorption performance of the
acetylated fibres.

Other chemical approaches used to increase oil removal efficiency include salt treatment
[53], surfactant treatment [13], [59], and combination of chemical-biotechnological treatment
[87]. For example, a study showed that NaClO2 treatment of kapok caused cleavage of the
aromatic ring in lignin, implying the removal of wax coating of kapok [53] and consequently
cause low oil sorption capacity. In contrast, the oil sorption capacity of NaClO2-treated kapok
significantly increased as compared to untreated kapok. Barley straw treated with
hexadecylpyridinium chloride monohydrate (CPC, C21H38NCl), a cationic surfactant, caused
the studied oil to be strongly bonded to the sorbent. This was due to the increase in the
hyrophobicity of the surfactant-modified barley straw [13], [59]. Maximum oil sorption
capacities based on Langmuir isotherm for canola oil and mineral oil were 0.61 and 0.58 g/g,
respectively. In other study, the use of lauryl gallate in combination of laccase significantly
decreased the water uptake by cellulose fibre [87]. However, no study was conducted on the
oil adsorption performance of the modified cellulose fibre.

37

7. Conclusion
This review article explored the origin and characteristics of oil particles in the wastewater.
Various existing methods for its treatment and removal were discussed. In the oily
wastewater treatment, choice of the best technology is based on wastewater chemistry, costeffectiveness, space availability and discharge plans. Natural fibres are among the
alternatives for oily wastewater treatment for their simplicity, excellent oil removal
properties, environmentally friendly characteristic and easy availability and feasibility.
Upgrading of these fibres through chemical modifications could further enhance their oil
adsorption capability.

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44

Oil Removal from Aqueous State by Natural Fibrous Sorbent: An Overview

Rafeah Wahia,b, Luqman Chuah Abdullaha, Thomas Choong Shean Yawa, Zainab Ngainib, and
Mohsen Nourouzi Mobarekeha
a

Department of Chemical and Environmental Engineering, Universiti Putra Malaysia, 43400


UPM Serdang, Selangor, Malaysia

Department of Chemistry, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak,


Malaysia

HIGHLIGHTS

Many natural fibrous sorbents suffer lack of hydrophobicity and buoyancy.

Oil removal mechanisms by fibrous sorbent are via adsorption or/and coalescence.

Langmuir/Freundlich isotherms must be used with caution to describe oil adsorption.

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