Journal Pre-proof

Application of coagulation/flocculation in oily wastewater

treatment: A review

Chuanliang Zhao, Junyuan Zhou, Yi Yan, Liwei Yang, Guohua

Xing, Huanyu Li, Pei Wu, Mingyuan Wang, Huaili Zheng

PII: S0048-9697(20)36324-5
DOI: https://doi.org/10.1016/j.scitotenv.2020.142795
Reference: STOTEN 142795

To appear in: Science of the Total Environment

Received date: 3 August 2020

Revised date: 16 September 2020
Accepted date: 29 September 2020

Please cite this article as: C. Zhao, J. Zhou, Y. Yan, et al., Application of coagulation/
flocculation in oily wastewater treatment: A review, Science of the Total Environment
(2020), https://doi.org/10.1016/j.scitotenv.2020.142795

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© 2020 Published by Elsevier.

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Application of coagulation/flocculation in oily wastewater

treatment: A review

a, b
Chuanliang Zhao , Junyuan Zhou a, Yi Yan a, Liwei Yang a, *
, Guohua

Xing a, Huanyu Li a, Pei Wu a, Mingyuan Wang a, Huaili Zheng c, **

a
School of Civil Engineering, Chang’ an University, Xi'an 710061,

of
China;
b
State Key Laboratory of Environmental Aquatic Chemistry, Research

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Center for Eco-Environmental Sciences, Chinese Academy of Sciences,
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Beijing 100085, China
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c
State Key Laboratory of Coal Mine Disaster Dynamics and Control,
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Chongqing University, Chongqing 400044, China

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*Corresponding author: Liwei Yang, Email: yanglw@chd.edu.cn

**Corresponding author: Huaili Zheng, Email: zhl6512@126.com

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Abstract

Volumes of oily wastewater are inevitably generated by every walk of

life. The removal of oil particles from oil-contaminated wastewater which

is characterized as huge amounts, intricate composition, and great threats

to human health and the ecological environment is a research hotspot in

water treatment fields. Due to high treatment costs and undesirable

treatment efficiencies, oily wastewater treatment remains a topical and

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urgent issue. At present, coagulation/flocculation as an indispensable oily

wastewater treatment technology receives much attention because it is

very well established, economical, practical and relatively efficient. The

influencing factors of oil wastewater treatment by

coagulation/flocculation have also been summarized in-depth, like dosage,

pH, etc. In consideration of its complex composition and treatment

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difficulty, this paper will also compare the treatment effects of different

coagulants/flocculants used alone and combined effects in oily

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wastewater treatment: inorganic coagulants, organic synthetic polymeric
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flocculants, natural flocculants and modified polymeric flocculants.
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Additionally, in this review, the mechanisms of removing oily substance

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by coagulation/flocculation are emphasized. Given strict emission

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standards and the refractory nature of oily wastewater, the combination

process with coagulation/flocculation, such as electrocoagulation,

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coagulation-membrane filtration hybrid process, and

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coagulation/flocculation-flotation can present better application potential

and are discussed in this review. To provide a proper choice in practical

application, the operating cost of coagulation and several conventional

technologies are also compared. Finally, the existing challenges in the

treatment of oily wastewater by coagulation are analyzed, and the feasible

research direction is proposed.

Keywords: coagulants/flocculants, coagulation mechanism,

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demulsification, cost estimation, combined technology

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Abbreviations
United States Environmental Protection
USEPA BA Butyl acrylate
Agency
MW Molecular weight TSS Total suspended solids
PZSS Poly-zinc silicate CMC Cellulose
Dimethyl acryloyloxyethyl benzyl Polyacrylamide on
DBC PAM-G-Magcell
ammonium chloride magnetic cellulose
CS Chitosan H2 Hydrogen
Chitosan-graft- Dimethyl acryloyloxyethyl
CS-g-PDBC DAF Dissolved air flotation
benzyl ammonium chloride
COD Chemical oxidation oxygen TOC Total organic carbon
PAFSi Poly-aluminum ferric silicate A/S Air/solid ratio

of
Sequential batch
OH- Hydroxide SBR
membrane bioreactor

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Upflow anaerobic sludge
CPAM Cationic polyacrylamide UASB
-p blanket
CD Charge density JF Jet flotation
APAM Anionic polyacrylamide NOM Natural organic matter
re
Mullite-Zeolite
PAA polyacrylic acid MZ
membrane
Mullite-Alumina-Zeolite
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PDMDAAC Poly-dimethyl-diallyl-ammonium chloride MAZ

membrane
Oxidation-reduction
IPCs Inorganic polymeric coagulants ORP
potential
na

PAC Poly aluminium chloride PF Permeation flux

PAFSi Poly-aluminum ferric silicate NOM Natural organic matter
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PAMP Polyacrylamide NF Nanofiltration

PSAFS Poly-silicate-aluminum fessic sulfate RO Reverse osmosis
PAZFC Poly-aluminum zinc silicate chloride UF Ultrafiltration
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PAMP Hydrophobically modified polyacrylamide OC Operating costs

Electrode material
AM Acrylamide EMC
consumption
Electric energy
DMDAAC Dimethyl diallyl ammonium chloride EEC
consumption
Poly-acrylamide-dimethyldiallyammonium
P(AM-DMDAAC-BA)
chloride-butylacrylate

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1 Introduction

The past decades have witnessed the rapid development of varieties

of industry which generated a large amount of oily wastewater (Suzuki

and Maruyama, 2005). As the irreplaceable resource together with

increasing energy demands at the present today, fossil fuels such as

petroleum and natural gas are the most important hydrocarbon products in

of
the modern world (Hildenbrand et al., 2016). Undoubtfully, their

extraction, processing and transportation, are well-known contributors to

ro
oily wastewater. Besides, oily wastewater can come from metal smelting,
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food processing, dyeing, municipal sources and other industries (An et al.,
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2017). Statistically, the total amount of oily wastewater in the world

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reached 10-15 billion m3 in 2013, and this number would continue to

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increase significantly in recent years (Cai et al., 2017). When discharged

to the environment, oily wastewater can deteriorate ecological resources

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and function (Noh et al., 2015), endanger the aquatic system and affect
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human health (Fox et al., 2016). Considering the water resources scarcity,

serious environmental pollution and increasingly stringent sewage

discharge standards, how to treat and recycle oily wastewater has become

an urgent topic in the environmental engineering field (An et al., 2017).

Currently, to a certain extent, the environmental issues created by

oily wastewater have been addressed by different approaches. As shown

in Figure 1, the most commonly used are flotation,

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coagulation/flocculation, biological treatment, membrane separation (Liu,

2016), hydro cyclones, sorption (Doshi et al., 2018), mechanical method

and advanced oxidation process. However, biological treatment needs a

long residence time and a large area, and activated sludge

microorganisms might be intolerant to aromatic hydrocarbons and heavy

metals (An et al., 2017) in oily wastewater. The gravity method can only

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remove floating and dispersed oil. Although the membrane separation

method has a good oil removal effect and brief operation characteristics,

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membrane fouling is the unsolved technical difficulty. By contrast,
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coagulation/flocculation is an economical and environmentally friendly
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method and can be an attractive alternative (Wei et al., 2018), because of

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its low-cost, simple operation, and sable effect (Kayvani Fard et al.,
na

2016).
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Figure 1 Various treatment methods for oily wastewater.

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Removing oil from wastewater through coagulation is a physical and

chemical method, including aggregation and flocculation two processes

(Wen et al., 2018). The oil removal process is shown in Figure 2. First of

all, the coagulants can neutralize negative charges of oil particles and

reduce the electrostatic repulsion of the electric double-layer. This

process is regarded as destabilization. Next, the destabilized particles

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begin to develop and gradually aggregate into large flocs. Under free

precipitation or air flotation, the separation of flocs from water phase

occurs. Water recovery and reuse from oily wastewater by

coagulation/flocculation are of huge economic, social and environmental

value for the protection of the ecological system and development of

humans. However, to the best of our knowledge, as a promising

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technology for water sustainable management, there is no detailed review

of oily wastewater treatment by coagulation/flocculation. Therefore, there

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is a growing demand for a deeper insight into coagulation/flocculation
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technology used in oily wastewater. Besides, the purpose of this article is
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to present a full-scale review of recent efforts in this field.

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Figure 2 Most common coagulation/flocculation process in oily

wastewater: creaming, coagulation/flocculation, coalescence and

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sedimentation.
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In this review, the characteristics of oily wastewater, which is

intrinsically decisive to the effect of wastewater treatment, is first

introduced. Secondly, we also summarize the factors that affect the

coagulation/flocculation process, including dosage, pH, initial

concentration and temperature. Third, the treatment properties of different

coagulants/flocculants will be systematically discussed, including

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inorganic coagulants, organic synthetic flocculants and natural polymeric

flocculants. In order to deal with a variety of oily wastewater and obtain

an ideal treatment effect, the coagulation/flocculation process can be

combined with other treatment technologies like membrane filtration

process, electrocoagulation, etc, and the cost estimation is provided.

Lastly, the current challenge and future direction of

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coagulation/flocculation technology in oil-contaminated wastewater

treatment will be presented.

2 Characteristics of oily wastewater

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Oily wastewater comes from various sources, for instance,
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petroleum extraction, refining, processing, printing and dyeing, food

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processing, and other industries (Al-Futaisi et al., 2007). Therefore, the

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characteristics of oily wastewater vary greatly, mainly depending on the

relevant source industry, the process of work and treatment. Sewage, for
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example, has an oil content and a grease content between 50 and 100
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mg/L. By contrast, the most significant proportion of oily wastewater,

with the concentration of oil up to 4000-6000mg/L, is generated by

petroleum extraction and smelting (Ahmad et al., 2005). Still, the typical

characteristics of conventional oily wastewater are mainly summarized in

the following points:

2.1 Extensive sources.

As the economy booms, petroleum remains the primary fossil fuel for
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energy. There are countless products processed from petroleum, including

fuel, lubricating oil, paraffin and other oils; synthetic resin, synthetic fiber,

synthetic rubber and other petrochemical products; surfactants, additives,

adhesives, coatings, spices, pharmaceuticals, pesticides and other fine

chemical products. The oil and relative industries inevitably produce a

large number of oily wastewater (Yu et al., 2017). According to the 2017

United Nations (UN) report, global freshwater consumption is 3,928km3

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per year, 56 percent of which (2,212 km3 per year) is discharged into the

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environment via a range of means. One of the main relevant categories
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that polluted rivers are oily wastewater from various industries,
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residential buildings and catering services (Putatunda et al., 2019). Also,

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with the speedy development of the catering industry, increasing volumes

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of oily wastewater without treatment are discharged into defective

municipal pipelines, which aggravates the burden of water treatment. It

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can be pointed out that the sources of oily wastewater are so extensive,
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which are mainly divided into the following sources: (1) Industry and

agriculture. Oil extraction, purification, smelting, mechanical processing,

steel manufacturing, and other industries have been produced a large

number of oily wastewater. Agricultural oily wastewater sources include

edible oil processing plants, pesticide processing plants, agricultural

machinery, agricultural vehicles, and other production wastewater; (2)

The transportation industry. Oily wastewater mainly consists of ships oily

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ballast and diesel locomotive wastewater; (3) Catering industry. The

domestic sewage from the residential area and catering industry is

discharged into municipal pipelines, containing a large number of

cooking oil.

2.2 Environmental harm.

As is well known, oily wastewater is the first of "three wastes"

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(wastewater, industrial residue and waste gas), whose adverse effects

cannot be underestimated. A large amount of substandard oily wastewater

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is randomly discharged into water bodies, which will cause the following
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harms to the environment (Sun et al., 2017a):
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①When directly discharged into the river or the ocean in large

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numbers, oil and grease will form an oil film on the surface of the water
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that can block sunlight and air, making the water body appear anoxic state.

Accordingly, the growth of plants and animals in the water is further

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affected (Walker and H., 2017). Besides, oily wastewater contains a host
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of soluble aromatic hydrocarbons, heavy metals and even radioactive

materials, which can cause toxic effects on some microorganisms

responsible for water purification and biological treatment (Rengasamy et

al., 2011; Srinivasan and Viraraghavan, 2010).

② Oily wastewater used for irrigation or accidentally infiltrated into

the ground will make the soil hardened, hinder the respiration of

microorganisms and plants. Therefore, the degradation speed of

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microorganisms becomes slow, and then the growth and yields of plants

will be affected (Poulopoulos et al., 2005; Yu et al., 2017).

③ Under the circumstances of discharge directly, the contaminants in

oily wastewater are transferred along the food chain via polluted foods.

Thus, human health will be seriously harmed on account of enrichment

effect (Santos et al., 2017).

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2.3 Complicated components.

In the course of wastewater treatment, oily wastewater was regarded

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as one of the most refractory by the United States Environmental
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Protection Agency (USEPA) (Sheikhi et al., 2019). The main reason is
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that the composition of oily wastewater is exceedingly complex. The

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characteristics and types of oily wastewater vary greatly from different

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resources.

According to the existence of the form, oily wastewater can be

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divided into suspended oil, dissolved oil, emulsified oil, dispersed oil and
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oil solids. The chemical composition, existing species and removal

methods of oily wastewater that are mainly composed of diesel oil, crude

oil, lubricating oil and edible oil were studied (Qu, 2018). Since the

characteristics of diesel oil and crude oil are similar, whose main

components were alkanes, cycloalkanes and aromatic hydrocarbons, there

is little difference in their removal methods. The lubricating oil is mainly

made of cycloalkanes, supplemented by alkanes. The main ingredient of

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edible oil is triglycerides. The lubricating oil and edible oil have a low

degree of emulsification and are largely insoluble in water (Qu, 2018).

The dispersed oil has the same characteristics as suspended oil when it is

stationary. Thus, both suspended oil and dispersed oil can be removed by

physical means such as oil skimmer and hydrophobic linoleum or

coagulation/flocculation. Coagulation/flocculation can effectively remove

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most suspended oil and emulsified oil since aluminum or iron salts have a

good coagulation effect on negatively charged oil droplets (Kayvani Fard

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et al., 2016). However, for dissolved oil, the particle size of oil droplets is
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just a few nanometers, much smaller than that of emulsified oil and the
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main components are stable aromatic hydrocarbons. Therefore,

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purification of dissolved oil is always a great challenge for oily

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wastewater treatment and it is necessary to consider targeted and

comprehensive techniques to remove them.

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Also, according to the composition, oily wastewater usually includes

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the following categories (An et al., 2017):

①Suspended particles. Suspended particles mainly include sediments,

clay, corrosion products and suspended solids that produce in the

production process. They act as a carrier for oil components, affecting oil

droplets migration and transformation in environmental media. Whether

it is promoting or inhibiting the degreasing effect remains unclear and

research in this area is still inadequate.

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②Dissolved salt. During the production process, high temperature and

pressure could dissolve mineral salts, and various additives are added for

oil and gas gathering and transportation, resulting in a large number of

inorganic salts in the oil recovery wastewater. Besides, the oily

wastewater produced by the food processing and catering industry can

also rise the salinity of municipal sewage greatly. Excessive salts will

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inhibit the growth of microorganisms, aquatic animals and plants in water,

affect the self-purification of water and biochemical treatment. When

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directly discharged, it will aggravate land salinization and pollute
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groundwater. In addition, the wastewater usually includes heavy metal
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ions, which adds extra toxicity (An et al., 2017). Resulting from their
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danger, the presence of them will militate against the re-utilization of

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wastewater (Jamaly et al., 2015). If they are directly discharged into the

environment, the natural water even becomes more deleterious. In general,

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removing or recovering heavy metals from oily wastewater requires more

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work to reduce its toxicity, which will deserve more attention in the

future.

③Dissolved or insoluble organics. Such as organic acids, polycyclic

aromatic hydrocarbons, phenols and petroleum hydrocarbon, etc., are

considered to be inhibitors for the growth of animals and plants

(Putatunda et al., 2019). These hydrocarbon compounds often lead to the

increased toxicity of oily wastewater and they are difficult to biodegrade

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and handle with traditional methods because of their durability. Further,

they are mutagenic and carcinogenic to humans (Putatunda et al., 2019).

In addition, the solubility of some hydrocarbons is very limited, thus, they

can form oil droplets. No doubt that these nonbiodegradable pollutants

would be a tough call to the water treatment process.

In short, oily wastewater’s origin, composition and forms of existence

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largely determine whether it can be treated properly. Given the difficulties

during oily wastewater treatment and potential threats to the environment,

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how to reach the emission and recycling standard is a thorny problem to
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be solved.
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3 Coagulation/flocculation in treating oily wastewater

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The coagulation/flocculation is known as one of the most mature and

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effective process, which can remove most of the colloids in the oily

wastewater by forming flocs. Generally, the coagulation/flocculation

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mechanisms can be categorized as the following kinds (Yang et al., 2016):

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(1) Simple charge neutralization. Colloids surfaces are evenly covered

with negative charges. They can be completely neutralized in a specific

dosage of coagulants, at this time, the optimal amounts of

coagulants/flocculants will add proportionally with increasing the initial

concentration of the oily wastewater. (2) Charge patching. Hetero-charges

are unevenly distributed and directly generate electrostatic attraction

between oil particles. Thus, the zeta potential does not equate to zero at
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optimal dosage, forming a broad “flocculation window.” (3) Bridging.

The large molecular weight (MW) and long-chain flocculants connect the

fine flocs to aggregate into the large one. Unusually, high MW of

flocculants bring about larger floc size and better bridging effects. (4)

Sweeping. The sweeping mechanism is based on inorganic coagulants

(Yang et al., 2016). However, some flocculants with lower solubility can

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also form large-sized flocs. The dominant mechanism and treatment

efficiency to a large extent depends on process conditions (including

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coagulant/flocculant dosage, pH, initial concentration and temperature,
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etc.) and the type of coagulants/flocculants (Rojas-Reyna et al., 2010).
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Therefore, the effect of different factors will be detailly discussed as

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follows.
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3.1 Process conditions

3.1.1 Coagulant/flocculant dosage

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The dosage significantly influences the effects of oily wastewater

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treatment of coagulation/flocculation. It has been reported that the oil

removal rate has a close relationship with the coagulant/flocculant dosage

(Zeng et al., 2007). When simple charge neutralization plays a leading

role, the low dosage of coagulants/flocculants is not enough to destabilize

all the colloidal particles (Welz et al., 2007; Yang et al., 2016).

Nevertheless, with excessive coagulants/flocculants, the suspended

particles re-stabilize again and the zeta potential thus deviates from zero.
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It seems that such a phenomenon will lead to a reduction of the treatment

efficiency (Ahmad et al., 2006). Zeng et al. (2007) studied the oil removal

effects of PZSS (poly-zinc silicate). The relationship between coagulant

dose and oil removal efficiency indicated that with the increase of PZSS,

oil-containing wastewater achieved the highest oil removal effect of 99%.

However, it was worth noting that when the dose of PZSS was up to

of
300mg/L, the removal effect of oil exhibited a slight downward trend.

Conversely, when a charge patching mechanism prevails,

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overdosage of the flocculants usually doesn’t make flocculation
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efficiency reduce immediately owing to the wide flocculation window
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(Yang et al., 2016). Thus, the zeta potential at optimal dosage is not zero
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and re-stability is prolonged (Pinotti and Zaritzky, 2001). CS-g-PDBC

na

was synthesized through grafting a cationic monomer, dimethyl

acryloyloxyethyl benzyl ammonium chloride (DBC) onto chitosan and

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the oil removal performance of chitosan (CS) was studied (Lv et al.,
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2015). It was found that the residual turbidity added when chitosan was

increased over optimal dosage 75mg/L, indicating the re-stabilization of

the aggregated particles. In other words, the flocculation window for

chitosan was narrow. In a relatively broad dosage range from 50mg/L to

the highest 180mg/L, CS-g-PDBC exhibited a more excellent efficiency

compared to chitosan, implying a large flocculation window. In addition,

during bridging flocculation, the essential requirement for bridging is

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sufficient unoccupied sites on oil colloids (Oladoja, 2016).

Therefore, oil removal efficiency increases to a certain extent,

with coagulants/flocculants augment. Following is the reduction of

efficiency with dosage further adds when simple charge neutralization is

the dominant mechanism. Instead, oil removal efficiency exhibits a

relatively stable trend owing to the flocculation window in charge

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patching. Besides, the dosage of inorganic salts is usually less than that of

polymer flocculants due to the higher electron density of inorganic salts.

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Therefore, less dose is required for charge neutralization.
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3.1.2 pH
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The pH is another critical factor affecting the

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coagulation/flocculation effects. For the treatment performance of oily

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wastewater, different coagulants/flocculants usually present different pH

dependency. Compared to nonionic flocculants, the charges on the surface

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of the colloids in oily wastewater and ionic coagulants/flocculants are

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significantly affected by the pH (Yang et al., 2016).

For inorganic coagulants/flocculants like aluminum salts, iron

salts and inorganic polymers, the pH directly affects the hydrolysis and

polymerization reaction of aluminum, iron ions and charge density (CD),

deciding the existing species of hydrolysis products. Figure 3 presented

the existing species of Al3+ and Fe3+ at different pH. The forms of

aluminum ions in water don’t depend on other elements, but only on the
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dosage of aluminum salts and pH (Cañizares et al., 2008). In this case, it

is advisable to consider that the hydrochemistry of aluminum is

particularly complicated, since it is connected with the formation of

monomers, polymerized hydroxyl aluminum ions, as well as aluminum

hydroxide precipitation. Aluminum ions are the main species in the acidic

range (Zhao et al., 2016). When pH is less than 3.0, 〔Al(H2O)6〕3+ can

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play the role of double compression layer. With increasing pH, positively

charged polynuclear hydrolysis products form. The best known of these is

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〔Al13(OH)32〕7+ at pH 5.0, which has high molecular weight and positive
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electricity price. They will preferentially adsorb to the adsorption layer of
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the colloids and neutralize zeta potential. Zouboulis et al. (2008) pointed
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out that the low pH would accelerate hydrolysis of coagulants into Al3+
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and Fe3+ , which was conducive to coagulation. When pH is

approximately equal to neutrality, aluminum hydroxide precipitates are

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the primary species that play a sweeping mechanism. Therefore, charge

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neutralization or sweeping can be achieved when pH is below the

isoelectric point, where the surface charge of colloids is zero in this range

of pH. However, at high pH, hydroxide (OH-) increase negative charges

of oily wastewater system, which directly affects the structure of

subsequent hydrolysis products of metal irons, the reaction of continuing

polymerization and eventually deteriorates coagulation performance

(Duan and Gregory, 2003). Sun et al. (2017b) reported that under optimal
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G values and dosage, the satisfactory removal effects of COD (chemical

oxygen demand) and turbidity by PAFSi ((poly-aluminum chloride

silicate) were 94.4% and 94.1% at pH 7. Accordingly, oily wastewater

should be kept in the range of alkalescence as mentioned above, just

being helpful for coagulation.

Figure 3 Al3+ and Fe3+ existing formations in different pH (M3+ = Al3+or

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Fe3+) (Johnson and Amirtharajah, 1983).

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For polymers flocculants, the influence of pH on oil removal
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efficiency rests with the species of flocculants. For cationic polymer

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flocculants such as cationic polyacrylamide (CPAM) and chitosan, they

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can aggregate negatively charged oil droplets (by electrostatic action) and

connect particulate matters via an interparticle bridging mechanism. The

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charge density of the flocculants is also greatly affected by pH (Bolto,

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1995). For anionic polymer flocculants, the negative sites on the chain are

theoretically affected by pH (Bolto and Gregory, 2007; Lapointe and

Barbeau, 2020). Under acidic conditions, anionic polyelectrolytes are

considered non-ionic. When the pH is below 4.5, anionic PAM(APAM) is

generally nonionic. For polyacrylic acid (PAA), it is 4.5. The adsorption

action will be realized by hydrogen bonding because electrostatic

interaction between the polymer chains and particles will be considered

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weak at this time. Based on the pH, anionic polymer flocculants can play

a role of bridging mechanism under the aid of iron salts, aluminum salts,

or in dual polymers system (Das and Somasundaran, 2003). In contrast,

nonionic polymer flocculants exhibit not heavy pH dependence due to

their unique molecular structure and charge properties (Shan et al., 2014).

Consequently, too much acid or alkali is not beneficial to oily

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wastewater treatment. The improved coagulation/flocculation and higher

oil removal efficiency can be obtained by adding calcium hydroxide and

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other alkali compounds to a suitable range, which should be based on the
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removal efficiency and cost.
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3.1.3 Initial concentration

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The practical experience on the coagulation/flocculation process

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denotes that initial concentration of oil also exerts significant impacts on

the oil removal efficiency, and the appropriate initial concentration range
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is of importance. Because the characteristics of oily wastewater

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continuously fluctuate greatly, the removal efficiency during the

coagulation process under different influent conditions also varies

dramatically. The traditional coagulants could effectively treat low

concentration oily wastewater (oil concentration of less than 5000 mg/L).

But when these coagulants were used to treat high concentration oily

wastewater (more than 6000 mg/L), satisfactory results could hardly

achieve, even if more coagulants/flocculants were dosed (Nogueira et al.,

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2016). It seems that when coagulants/flocculants react with the oil at high

concentration, saturation speed is faster, leaving a large amount of

stabilized oil. Daud et al. (2015) reported the influence of COD value on

the treatment of oily wastewater. Under 2680mg/L oily wastewater, the

result indicated that the oil removal rate could reach 97% when the

dosage of aluminum polychloride was 300mg/L. Nonetheless, when inlet

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oil concentration was up to 5000mg/L, a similar removal efficiency could

hardly be obtained (You et al., 2018). The phenomenon suggests that high

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oil concentration is not conducive to oily wastewater treatment, and
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satisfactory results often require more coagulants/flocculants or more
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complicated processes which will be discussed in the section of 3.3.

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3.1.4 Temperature
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It is well known that ambient temperature has apparent effects on

the coagulation/flocculation treatment. Generally, the optimal dosage of

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coagulants/flocculants decreases as the temperature increases within a

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suitable range. In cold areas, the water temperature sometimes reaches

0°C, and it is challenging to achieve the ideal coagulation/flocculation

effects although adding a large number of coagulants. Under the

circumstances, the formation speed of flocs is extremely slow and

particles with loose structures are easily broken. The influence of low

temperature on coagulation effects mainly included the following points:

(1) Hydrolysis of inorganic salt coagulants is an endothermic reaction,

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thereby hydrolysis is difficult at a low temperature, especially for

aluminum sulfate (He et al., 2011). (2) The lower the temperature, the

higher the viscosity of water. The shearing force of water flow will also

increase with the increasing viscosity, which is not beneficial to the

formation of flocs (Zhang et al., 2010). (3) Collision frequency of

colloidal particles is weakened at a lower temperature by low Brownian

of
motion intensity (Lu et al., 2014). Therefore, small flocs are formed. This

phenomenon can be explained by the flocculation kinetics described in

ro
the Eq: K1∝α×β where K1 is the aggregation rate, α denotes the collision
-p
efficiency, and β is the collision frequency (Yang et al., 2016). (4) When
re

the water temperature is low, the colloidal hydration is enhanced. Thereby,

lP

the adhesion between particles and colloidal aggregation is reduced. From

na

another aspect, the solubility and activity of polymer flocculants can

usually be improved when the temperature increases, which leads to high

ur

malleability of the polymer and helps the bridging effect. Furthermore,

Jo

the hydrolysis of aluminum and iron coagulants is also promoted.

However, the too high or too low temperature is not conducive to

coagulation effects (Lu et al., 2005). The flocs become unstable when the

temperature is excessively high. Thus, the solid precipitated before is

easy to expand. Meanwhile, the natural flocculants will be partly

denaturation in high temperatures, leading to a waste of resources

ultimately.
22
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The effects of temperature on the oily wastewater treatment can

also be interpreted by the principles above. Lu et al. (2014) studied the

effect of temperature on oil removal efficiency by

poly-dimethyl-diallyl-ammonium chloride (PDMDAAC). The results

showed that as a certain amount of PDMDAAC was added, residual

turbidity and COD decreased significantly with the increase of

temperature before 60 ℃. When the temperature was higher than 60 ℃,

of
the coagulation performance deteriorated obviously. Zhang. (2017) also

ro
reached similar results. Therefore, in oily water treatment, the dosage of
-p
coagulants should be adjusted dynamically according to seasons.
re

3.2 Chemical coagulants/flocculants

lP

The commonly used coagulants/flocculants according to their

na

chemical composition are divided into three categories: inorganic salts

such as iron salts and aluminum salts; organic synthetic flocculants

ur

mainly including PAA, PAM and its derivatives; and natural polymeric
Jo

flocculants. Through charge neutralization, bridging and sweeping action,

these chemicals facilitate the destabilization and aggregation of fine oil

droplets and suspended colloids. Several natural polymeric flocculants

and several combinations with other modified flocculants are also

reported to improve the coagulation/flocculation performance. Given the

biodegradability and high molecular weight, these natural flocculants are

promising to be substituted for the conventional (Lapointe and Barbeau,

23
 Journal Pre-proof

2020).

3.2.1 Inorganic salt coagulants

Inorganic salt coagulants can be further classified into

small-molecule inorganic coagulants and inorganic polymeric coagulants

(IPCs). The most typical small molecule inorganic salt coagulants are iron

and aluminum salts. By contrast, IPCs have a higher charge density and

of
molecular weight. Thus, they show more advantages in practical

application in oily wastewater. The usage of various inorganic coagulants

in oil-containing wastewater treatment processes has been reviewed in

ro
-p
Table 1.
re

Table 1 Applications of various inorganic coagulants in oily wastewater.

lP

Oil
COD Suspended solids Turbidity
Oily concentration
Dosage
na

Coagulant wastewater pH Refs

(mg/L) Removal Initial Removal Initial Removal Removal
type Influent Initial
rate (mg/L rate (mg/L rate rate
(mg/L) (NTU)
ur

(%) ) (%) ) (%) (%)

Oilfield 1.5-2. (Zeng and

PZSS+APAM 250 763 / 782.5 / 96.5 4.8 196 7.2
Jo

wastewater 5 Park, 2009)

Mn-Poly-silic Synthetic

ate aluminum ship (You et al.,

/ 500 5000 99.89 / / / / / /
ferric sulfate oil-contamin 2018)

(PSAFS) ated water

Poly-aluminu

m zinc
Oily (Cong et al.,
silicate 7-8 / / / / 71.8 / / / 98.9
wastewater 2011)
chloride

PAZFC

PAC+diatomi Oilfield 3000± 280± (Shan et al.,

7-10 50 / 73.62 / / 81±4 91.6
te wastewater 120 12 2014)

24
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The performance of aluminum and iron salts is mainly related to

the existence forms of the metal ions in oily wastewater. Inorganic metal

salt coagulants with suitable polymerization can improve oil removal

efficiency. As mentioned above, species of aluminum are generally

divided into monomer aluminum and polymer forms of aluminum-based

on polymerization degree. Polymer forms of aluminum are more

of
positively charged and stable than monomer aluminum (Duan and

Gregory, 2003). Therefore, oil particles treated by polymer forms of

ro
aluminum are smaller but more compact than those disposed of via
-p
monomer aluminum. According to the experiment, the amounts of flocs
re

are large and the size is large and loose when aluminum sulfate is used as
lP

a coagulant (Yue et al., 2018). Ferric salt is another significant inorganic

na

salt coagulant, which is suitable for a wide range of pH when compared

to alum. When FeCl3 was used as a coagulant, dense flocs were produced
ur

during agitation and coagulation while settling time was slow (Yue et al.,
Jo

2018). At the same condition, the optimal dose of FeCl3 was 500mg/L,

which was more than twice the dosage required for aluminum salts, and

the oil removal effect was worse than aluminum salt (You et al., 2018). If

the treatment of oily wastewater with iron salts, the treated water will

have color especially when iron ions react with colored colloids and a

darker color will produce in the dissolved matter. Besides, as reported,

inorganic salt coagulants in oily water treatment applications are greatly

25
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limited by high dosage required for high concentration oily wastewater.

Other drawbacks include high sensitivity to pH, ineffectiveness on tiny

particles in low temperatures, etc. Moreover, the use of metal salts

produces a large amount of sludge containing metal hydroxide (Lee et al.,

2014a).

Apart from these traditional inorganic coagulants, polyaluminium

of
chloride (PAC), PAZFC, PSAFS and other synthetic inorganic polymer

agents are the most widely used coagulants in oil-contaminated water

ro
treatment (Cong et al., 2011; You et al., 2018; Zeng and Park, 2009). PAC
-p
has higher stability compared with aluminum sulfate coagulants. In
re

addition, the charge density of PAC is higher than that of PAM, CPAM,
lP

chitosan and other conventional coagulants. Thus, PAC and its modified
na

polymers exhibits excellent characters in the oily wastewater treatment.

When a small amount of PAC was added to treat oily wastewater, the
ur

flocs were large and dense, and the oil content of scum was high (Sun et
Jo

al., 2018). Although both polymeric iron and polymeric aluminum belong

to large molecular coagulants, their degree of polymerization is not

significant and far less than that of organic polymeric flocculants. For the

sake of enhancing the degree of polymerization, two or more coagulant

components such as aluminum, iron, silicon and their properties are

usually concentrated in a kind of coagulant. When the elements allocation

is appropriate, different components will produce complementary

26
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advantages. It has been proved that iron and aluminum inorganic

composite coagulants outperform other single component coagulants. Sun

et al. (2017c) prepared a composite coagulant PAFS that could deal with

5000 mg/L high concentrations of oily wastewater using PAM as a

coagulant aid. Experiment results suggested that higher efficiency was

achieved at a dosage of 120 mg/L. Compared with the above inorganic

of
salts, the removal efficiency by PAFS was better. Activated silicic acid is

a kind of anionic polymer with a high degree of polymerization, which

ro
only acts as a bridge for negatively charged colloids in oil-contaminated
-p
water, often being used as a coagulant aid for aluminum or iron salts.
re

When aluminum or iron ion is introduced into silicic acid, it can play the
lP

role of electro-neutralization and adsorption bridging (Moussas and

na

Zouboulis, 2008). Meanwhile, the stability of activated silicic acid is

much improved.
ur

3.2.2 Organic synthetic polymeric flocculants

Jo

In comprehensive consideration of oil removal efficiency,

polymeric flocculants exhibit good treatment effects due to their large

MW. Polymer flocculants vary in MW, structure (linear and branching),

composition, CD and type of charge, but generally synthetic polymers

come in four forms: cationic, anion, amphoteric, and nonionic polmers

(Lee et al., 2014a). The nature of charges is one of the primary parameters

that have significant effects on the performance of

27
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coagulation/flocculation. Generally, they show better stability, less

biodegradability and better bridging performance and lower dosage for

required treatment effects than natural polymers (Lapointe and Barbeau,

2020). Their structure could be modified for specific applications by

introducing various functional groups like hydrophobic functional groups

(Lu et al., 2011; Zhu et al., 2018).

of
Figure 4 The molecular structure of cationic (a) and anionic (b)

ro
polyacrylamide (PAM), chitosan (c), starch-g-PAM (d), starch-g-PAA (e)
-p
(Lapointe and Barbeau, 2020; Shogren et al., 2009).
re
lP

The cationic polymer flocculants have the dual functions of

na

aggregation and flocculation. The structural formula of CPAM is as

follows in Figure 4 (a). The effectiveness of CPAM is attributed to high

ur

CD, MW and long molecular chain (Lapointe and Barbeau, 2020). It has
Jo

been found that polymer adsorption capacity enhances with the increase

of polymer charge density (Norulaini et al., 2005). Compared with 161.7,

355 and 425 C/g charge density, cationic polyacrylamide with 485 C/g

obtained best grease removal efficiency at 30mg/L dosage. Typically,

CPAM is used as an aid of metal salts coagulants to increase

sedimentation rate and floc size. However, with increasing the

aggregation time, the size of flocs can reduce. Moreover, residual

28
 Journal Pre-proof

unreacted monomers will cause secondary pollution and severely

neurotoxic effects on humans (Lapointe and Barbeau, 2020). In addition,

other modified PAM has also received considerable attention. Ma et al.

(2018) prepared hydrophobically modified polyacrylamide (PAMP) by

grafting the cationic groups and hydrophobic monomers onto the PAM

chain successfully. Results showed the adhesion among the fine

of
oil-containing flocs was remarkably improved and PAMP presented

satisfactory demulsification, eventually achieved the best oil and turbidity

ro
removal efficiency 94.5-98.6% and 95.1-98.9% respectively. In this case,
-p
the flocculant can make full use of its function through charge
re

neutralization and bridging effect. With acrylamide (AM), dimethyl

lP

diallyl ammonium chloride (DMDAAC) and butyl acrylate (BA) as raw

na

materials, Yang et al. (2010) adopted a micelle free radical

copolymerization technology to synthesize a cationic hydrophobic

ur

association poly (AM-DMDAAC-BA). After treatment by 50mg/L

Jo

P(AM-DMDAAC-BA), the oil removal efficiency could reach 93.4%.

Anionic polymers such as APAM in Figure 4 (b) can be prepared

by the polymerization and partial hydrolysis of acrylamide, or

copolymerization of acrylic acid and acrylamide. Compared with CPAM

and non-ionic PAM, it has poor coagulation ability because of

electrostatic repulsion between the APAM and negatively charged oil

particles. Similar to APAM, anionic sites of PAA could also be attributed

29
 Journal Pre-proof

to the presence of carboxyl groups. As mentioned above, PAA and APAM

are considered as neutral polymer under acidic conditions, where the

electrostatic interaction of the polymer particles is constrained, which

makes it possible to apply APAM in oily wastewater (Zeng et al., 2007).

Zinatizadeh et al. (2017) used C-PAMs and A-PAMs (as the flocculant) at

dosages of 300 and 50 mg/L, respectively, which showed the best

of
effectiveness in removing total suspended solids (TSS) and COD (96.4

and 70.9%, respectively).

ro
With both cationic and anionic functional groups, such ionic
-p
polymers are called amphoteric polymers and the processing range of
re

amphoteric polymers is significantly improved over a wide range of pH

lP

values (Dao et al., 2016; Yang et al., 2016). Non-ionic polymers can avoid
na

powerful electrostatic repulsion in an alkaline environment and exhibit

high bridging possibility owing to the high MW. In oily wastewater

ur

treatment, non-ionic flocculants are generally used as an aid for cationic

Jo

coagulants/flocculants, the most typical of which is PAM. Although

several flocculants, including synthetic and natural flocculants, has been

studied in the field of wastewater treatment, their practical applications

are still few.

3.2.3 Natural polymeric flocculants

As mentioned above, inorganic salt coagulants and organic

synthetic flocculants have been proved to be effective in the treatment of

30
 Journal Pre-proof

oily wastewater, but they may cause additional pollution. They also pose

many threats to human health due to the release of residual metal ions or

harmful polymer monomers. Therefore, natural polymeric flocculants as

the green agents possess high potential to be a hopeful substitute for other

inorganic coagulants and flocculants in recent years (Lee et al., 2014b).

Natural flocculants mainly come from starch, chitosan, cellulose and

of
other polysaccharide materials (Zhang et al., 2010). Compared with

traditional flocculants, natural organic flocculants are easily obtained

ro
from renewable resources, resulting in their biodegradability, high
-p
efficiency and low costs (Wei et al., 2018). These natural flocculants also
re

have macromolecular structures and some functional groups, which can

lP

neutralize negative charge particles and reduce zeta potential to compress

na

the double electric layer (Zacar and L, 2000). Moreover, natural

saccharide-based polymers are composed of hexagonal sugar rings with a

ur

rigid rod structure, which may improve the compactness of flocs.

Jo

Whereas in many cases, achieving the same flocculation performance

requires a higher dose. Furthermore, they have a short storage time due to

their instability and possible biodegradability, which limits their

application in oily wastewater treatment to a great extent.

Compared to other natural flocculants, chitosan in Figure 4 (c)

and its composites acquire the most extensive application in oily

wastewater treatment due to cationic behavior. In an acidic environment

31
 Journal Pre-proof

(below 5), chitosan becomes a cationic polymer with relatively high

charge density. With high CD and long molecular chains, chitosan

flocculants show excellent performance. Ahmad et al. (2006) compared

chitosan, alum and PAC to treat palm oil mill effluent containing

2000mg/L oil, the results proved that chitosan was more efficient,

economic and environmental than PAC and alum. In addition to chitosan,

of
chitosan derivatives got more attention by grafting hydrophobic or

cationic groups in oily wastewater treatment (Lü et al., 2019; Lu et al.,

ro
2018; Peng et al., 2018). A study reported a novel flocculant CS-g-PDBC
-p
with amphiphilic and cationic groups. In comparison to chitosan, CAPM
re

and PAC, CS-g-PDBC with a significantly broadened flocculation

lP

window, thus can achieve enhanced efficiency in the oily wastewater

na

treatment. With 100mg/L dosage, the residual turbidity was reduced to

almost 10% at a suitable pH 7 (Hoseini et al., 2015).

ur

Starch is the most abundant and lowest-cost natural polymeric

Jo

flocculant. The molecular weight of amylopectin can reach 5.7×10 9g/mol,

which is larger than that of traditional coagulants PAM, PAC and amylose.

Generally, starch required a higher dosage than synthetic polymers such

as CPAM or PAM to obtain the same turbidity removal effect (Lapointe

and Barbeau, 2020). Teh et al. (2014) employed rice starch to palm oily

wastewater. Although TSS was removed up to 84%, the dosage of rice

starch was 2000mg/L. However, compared to that forming by alum alone

32
 Journal Pre-proof

and alum plus rice starch, larger and more compact flocs forming by rice

starch indicated a better setting performance. In addition, it was reported

that starch had synergistic effects when combined with polyacrylamide

(Lapointe and Barbeau, 2017). About 70% of PAM dosage could be

replaced by starch without decreasing the turbidity removal rate.

Cellulose (CMC), sodium alginate and tannic acid are anionic

of
natural flocculants (Lee et al., 2014a). Various functional applications of

cellulose based materials have been studied (Peng et al., 2020). Cellulose

ro
based materials could flocculate suspended solids, adsorb heavy metals or
-p
chemicals and achieve oil/water separation of oily wastewater by
re

cellulose film. Wang et al. (2016) prepared a silanized cellulose adsorbent

lP

for the treatment of vegetable oil wastewater. The separation efficiency

na

was 99.93%, and the adsorption effect decreased by less than 1% even

after ten uses. Polyacrylamide on magnetic cellulose (PAM-G-Magcell)

ur

was prepared by microwave assisted synthesis (Noor et al., 2020). Under

Jo

the best conditions, the removal rates of TSS, turbidity and color were

82.97%, 88.62% and 91.76%, respectively. As a renewable material,

functional cellulose provides a more environmentally friendly alternative.

However, the future development of these bio-flocculants is

refined by some disadvantages. Firstly, they all have a shorter shelf life

because of easy biodegradability. Furthermore, flocs formed by

bio-flocculants are inclined to lose stability and strength. Eventually, they

33
 Journal Pre-proof

are used in such a high dosage that equivalent effects can be achieved and

they are only utilized as coagulants aids. Accordingly, the subject of

researches in recent years is to improve their property and application

potential by modifying their physical and chemical structure (Das et al.,

2012). A novel generation of polymeric flocculants can also be suitably

designed by grafting synthetic flocculants chains onto purified

of
polysaccharide skeleton (Pal et al., 2012). The application of natural

flocculants in oily wastewater has been summarized as follows in Table 2.

ro
Table 2 Applications of various natural polymeric flocculants in oily
-p
wastewater treatment.
re
Oily Oil concentration COD Suspended solids Turbidity
Dosage
Flocculant wastewater pH Refs
lP

Influent Removal Initial Removal Initial Removal Initial Removal

(mg/L)
type (mg/L) rate (%) (mg/L) rate (%) (mg/L) rate (%) NTU rate (%)

(Ahmad
Palm oily
na

Chitosan 4 500 2000 >99 50000 / 990 97.7 550 / et al.,

wastewater
2006)

Petrochemic (Lü et
CS(56%)-g-
ur

al oily 7.3 500 2954 99.58 8400 82.1 2675 95.4 2755 98.5 al.,
PDBC(44%)
wastewater 2019)
Jo

amphoteric

chitosan-bas

ed grafting (Peng et
oil recovery
flocculants 7.2 2.8 / / 3162 98.88 154 99.3 / / al.,
wastewater
(CM-chi)-g- 2018)

PDMDAAC

(5)

Quaternized

chitosan-gra
(Lu et
fted Diesel-in-wa 4,7
17,17,19 2000 >95 / / / / / / al.,
magnetic ter emulsion ,10
2018)
nanoparticle

Starch-acryl Grease 5.5 8 / / 2840 45.64 / / / / (Zheng

34
 Journal Pre-proof

amide(1:3) wastewater et al.,

2008)

Simulating (Chi et
Modified
oily 9 22.4 1200 88.2 3775 95.7 / / 400 97.1 al.,
starch
wastewater 2009)

3.2.4 Evaluation of coagulants/flocculants

Table 3 presents a comparison of diverse coagulants and

flocculants in oil removal efficiency. At present, inorganic coagulants and

organic synthetic flocculants are still the most crucial agents in the

of
treatment of oily wastewater, which mainly include aluminum salts, iron

ro
salts, PAC, PAM and their derivates. Although inorganic coagulants are
-p
cheap and relatively effective at treating oily wastewater, they have many
re
disadvantages including high dosage, being sensitive to pH and the
lP

generation of residual metal ions (Lee et al., 2014a). By contrast, organic

synthetic polymeric flocculants are preferable in dosage, floc structure

na

and oil-removing performance, among which PAM and its derivatives are
ur

the most widely used, but their costs are that high. Moreover, the addition
Jo

of PAM may bring pollution and toxicity risks due to the release of

residual monomers. Recently, the natural macromolecule flocculants

draw more and more attention because of their environmental friendliness,

high molecular weight, biodegradability, low price and easy accessibility

(Lapointe and Barbeau, 2020). However, they still lack practical

applications and the disadvantages listed above require further study.

Therefore, cheaper, more efficient and green coagulants/flocculants ought

35
 Journal Pre-proof

to be designed and prepared (Lee et al., 2014a).

Table 3 A summary of diverse coagulants/flocculants in oily wastewater

treatment.
Floc properties
Coagulants/flocculants Representatives Dose(mg/L) pH range Temperature Efficiency Price Toxicity
Size Compactness

FeCl3, Al2(SO4)3, Moderate High

Inorganic coagulants High Sensitive Moderate Denser Moderate Low
PAC (5-9) (Al3+)

Synthetic polymeric PAM, CPAM, High

Moderate Wide (2-12) Insensitive Big Moderate Good High
flocculants PAA (AM-)

Natural polymeric Chitosan, starch,

of
Moderate Wide (2-12) Insensitive Big Moderate Good Low Low
flocculants cellulose

ro
To improve their application potential, polymer flocculants can be

modified by chemical or physical approaches (Das et al., 2012). Grafting

-p
natural polysaccharides or synthetic polymers is the most commonly used
re

modification method in the field of water treatment (Umar et al., 2014;

lP

Wang et al., 2012). Given economic factors and treatment efficiency,

na

other simple modified methods such as etherification, esterification,

oxidation, etc., also deserve to be adopted. Through these approaches,

ur

target functional groups can be conveniently introduced into the polymer

Jo

backbone for various purposes, further enhancing the charge density,

hydrophobicity of the polymer. Thus, the effect of electrical neutralization

and hydrophobicity association can be greatly improved. A study

exhibited that many advantages could be obtained by grafting

copolymerization: strong solubility, stability, higher molecular weight and

good flocculation performance (Yang et al., 2013). In addition, polymer

molecular structure could be modified by grafting and appropriate

36
 Journal Pre-proof

chemical crosslinking, further enhancing the bridging effects of

flocculants (Wei et al., 2018). Some natural-synthetic polymer flocculants

by grafting PAM and PAA onto starch in Figure 4 (d) and (e) will provide

favorable options for oily wastewater industry if their preparation costs

are acceptable (Yang et al., 2010).

Accordingly, a proper flocculant can be selected or designed

of
according to the targeted wastewater by precise control and sophisticated

design (Wei et al., 2018). The effect of the molecular structure of

ro
coagulant/flocculants on treatment efficiency is summarized in Figure 5.
-p
Hopefully, more research is needed to focus on modified methods and
re

combination usage of coagulants/flocculants to achieve the satisfying

lP

coagulation/flocculation performance in oily wastewater treatment.

na

Figure 5 Effects of the molecular structure of coagulant/flocculant

ur

on the treatment efficiency.

Jo

3.3 Combined technologies

Oily wastewater often has the characteristics of complicated

components, poor biodegradability and dramatic fluctuation. The

coagulation/flocculation has striking treatment efficiency, but it is

difficult to achieve the discharge standard by a single technology

(Jaruwat et al., 2010). In recent years, in addition to

37
 Journal Pre-proof

coagulation/flocculation, other techniques have also been confirmed to

improve oil removal performance effectively, including flotation, hydro

cyclones, adsorption, biological treatment, membrane separation,

mechanical method and advanced oxidation process (An et al., 2017).

However, after being treated with gravity separation, hydro cyclones or

adsorption, many fine even submicron-sized residual oil droplets still

of
exist in the wastewater. Although flotation can remove fine oil droplets, it

still produces a large amount of scum, and the processing time is

ro
relatively long. For membrane treatment, chemical oxidation and
-p
biodegradation, they have high requirements for characteristics of
re

influent water and need to be combined with other pretreatment methods

lP

to a certain extent. In order to directly discharge or recycle oily

na

wastewater, it is expedient to take full advantage of different treatment

methods. The optimal hybrid technology should be designed according to

ur

water characteristics, cost and discharge standards for oily wastewater.

Jo

Eventually, it is possible to maximize the advantages of various methods,

reduce operating costs, achieve sustainable water resources and avoid the

limitations of multiple technologies.

3.3.1 Electrocoagulation

Electrocoagulation mainly includes two crucial chemical

processes: metal is oxidized at the anode to form metal ions. At the same

time, water molecules ionize in the cathode to form OH- and hydrogen
38
 Journal Pre-proof

(H2) as presented in Figure 6. On the one hand, cations (Al3+, Fe2+, etc.)

that produce in the anode can form polymetallic hydroxide deposits

(Pablo et al., 2006). On the other hand, many tiny bubbles forming by

hydrogen gas adhere to the surface of solid particles and form flocs to be

removed. In addition, the residual hydrogen can be collected as fuel to

realize secondary utilization (Al Aji et al., 2012). It has been

of
demonstrated that electrocoagulation has the advantages of simple

equipment, effortless operation, short reaction time, less or no use of

ro
chemicals and low sludge production (Un et al., 2009). Therefore, the
-p
comprehensive application of electrocoagulation shows its potential in the
re

efficient treatment of oily wastewater.

lP
na

Figure 6 Mechanism of electrocoagulation (An et al., 2017).

ur

With perforated aluminum electrode, Bande et al. (2008) reported

Jo

that finely dispersed oil droplets were separated from petroleum

wastewater in an electrocoagulation tank. The results showed that at the

initial oil concentration of 50-100mg/L, the oil removal rate was more

than 90% and the salt content was greatly reduced. Another study

demonstrated the feasibility of electrocoagulation as an available and

reliable technology for the pretreatment of heavily oil-polluted

wastewater. Still, the COD removal effect was not obvious (El-Naas et al.,
39
 Journal Pre-proof

2009). Bensadok et al. (2008) and Kobya et al. (2008) studied that when

initial COD was 596mg/L, the oil removal rate increased to 63%. With

the initial COD concentration increasing up to 17312mg/L, the removal

efficiency of COD and turbidity could reach above 90% and 99%

respectively under optimal conditions. Chen et al. (2007) reported that the

electrocoagulation technology was used to treat catering oily wastewater

of
with an oil content of 120-1500mg/L. The experiment showed that the oil

removal efficiency in all tested samples of oil-contaminated wastewater

exceeded 94%. Some other applications with similar results of

ro
-p
electrocoagulation in oily wastewater are summarized in the following
re

Table 4.
lP

Table 4 Applications of electrocoagulation in oily wastewater.

Removal Energy and
na

Oily water Oil Current Reaction

Electrode efficiency cost analysis Refs
source concentration(mg/L) density(A/m2) time(min)
3
(%) (kWh/m )
ur

Biodiesel 0.43kWh/g
6412 Iron 100 25 82 (Ahmadi et al., 2013)
wastewater oil and grease

Slaughterhouse
Jo

143.1 Aluminum 10 20 85(COD) 2.14 (Bayar et al., 2014)

wastewater

Produced Aluminum (Esmaeilirad et al.,

>2400 1343 6.8L/min 0-60 /
water and iron 2015)

Leachate of
(Ighilahriz et al.,
oil-drilling 303(COD) Aluminum 286 60 95 /
2014)
mud

Restaurant Aluminum
180-280 43 34 99 / (Ji et al., 2015)
wastewater and iron

Iron and (Rincon and La Motta,

Bilge water 5000 6 1L/min >99 /
aluminum 2014)

(Thirugnanasambandh
Tannery
1574 Iron 200 40 95 6 am and Sivakumar,
wastewater
2016)

40
 Journal Pre-proof

To better utilize advantages of various oily wastewater treatment,

coupling treatment processes have been employed in engineering fields.

Considerable efforts have been made in the use of electrocoagulation and

other technologies. For example, electrocoagulation can be adopted

effectively in combination with membrane technology to reduce

membrane fouling and enhance oil removal efficiency. Yang et al. (2015)

of
combined electrocoagulation and kaolin dynamic membrane to reduce

reversible resistance. The maximal removal rates and permeates at 65%

ro
and 85% were observed, respectively. Electrocoagulation can also be
-p
combined with physiochemical technologies such as acid cracking,
re

anaerobic co-digestion, etc. Arslan-Alaton et al. (2014) reported that the

lP

integration process of electrocoagulation and acid cracking to handle with

na

olive oil mill wastewater. Acid cracking was achieved by adjusting pH to

2 and heating wastewater samples to 70°C. After electrocoagulation

ur

treatment, 96% oil and grease could be removed. Shahriari et al. (2018)
Jo

employed electrocoagulation-flocculation method to treat Shazand oil

refinery wastewater. Compared to aluminum electrodes, iron electrodes

demonstrated a better efficiency. Hernández-Francisco et al. (2017)

observed significant effects on the oil refining industry wastewater with

presence of H2O2 using electrocoagulation.

Above all, electric-coagulation technology has an excellent

removal effect in treating oily wastewater. The in-depth research on the

41
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application of electrocoagulation in oil wastewater treatment would

become more and more significant (An et al., 2017). However, the

drawbacks of electrocoagulation lie in large electricity consumption and

electrodes materials, which to some degree limit the large-scale

application. Thus, the development of advanced electrode materials and

the optimization design of the reactor are of considerable significance to

of
improve the large-scale application of electrocoagulation treatment.

3.3.2 Coagulation/flocculation-flotation treatment

ro
The flotation process can not effectively treat oil emulsion
-p
containing micelles unless the emulsion was unstable (Yang, 2007).
re

Therefore, flotation is widely employed in the removal of emulsified oily

lP

wastewater, after being destabilized by coagulation/flocculation. The

na

combination of coagulation-flotation can make full use of their

advantages and the condensed oil droplets can more easily absorb bubbles.
ur

In comparison with coagulation/flocculation or air flotation alone,

Jo

emulsified oil droplets can be better separated since the destabilization of

coagulants/flocculants (Hoseini et al., 2015). Some applications of the

coagulation-flotation process have been summarized under the Table 5.

Figure 7 Conventional DAF unite schematic diagram.

During flotation-coagulation/flocculation, oil removal efficiency

42
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depends on several factors, such as the adhesion between oil droplets and

bubble, the characteristics of aggregates and bubbles size (Etchepare et al.,

2017). However, the droplet size and bubble size are the usually decisive

factors in achieving higher oil removal efficiency (Santander et al., 2011a;

Saththasivam et al., 2016). Compared to the traditional flotation process,

DAF as shown in Figure 7 has been the most widely used flotation

of
technology by far, the distinguishing feature of which is that it produces a

large number of bubbles with a diameter of 30-100 microns (Rubio et al.,

ro
2002). Santo et al. (2012) selected PAX18 (17% Al2O3), aluminum sulfate
-p
and ferric sulfate as a coagulant, the removal rate of COD, total organic
re

carbon (TOC) and turbidity was 97%, 90% and 88% respectively. With
lP

continuous mode operation, flotation tests showed that 95% of

na

hydrocarbons could be removed at an air/solid ratio (A/S) of 0.6kg/kg.

This shows that coagulation/flocculation-DAF has great advantages in the

ur

removal of emulsified oil under optimal coagulants/flocculants dosage

Jo

and species, suitable A/S and other operating parameters. Besides, apart

from selecting a proper coagulant/flocculant, oil removal probability can

be increased by reducing the size of the gas bubble. Etchepare et al. (2017)

studied that after flocculation, the nanobubbles (D32=150-350nm)

conditioning stage ahead of flotation resulted in an increase in flotation

efficiency from 73% to 84%. Flotation with isolated nanobubbles

achieved oil removal efficiency up to 90%. The result clearly

43
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demonstrated that nanobubbles played a role in facilitating

hydrophobicity and adhesion between bubbles and aggregates, improving

aggregation and stabilization. Other than DAF, the combination of

coagulation-jet flotation or electroflotation exhibited great treatment

efficiency (Hmidi et al., 2017; Santander et al., 2011b). Ke-Yong et al.

(2016) also observed that microbubble flotation was more efficient than

of
macrobubble flotation in a novel integration of coagulation/microbubble

flotation, catalytic ozonation and Sequential batch membrane bioreactor

ro
(SBR) to treat heavy oil wastewater treatment. The results showed that oil,
-p
COD and NH3-N decreased by 97%, 88%, 91% respectively. In the oil
re

wastewater treatment engineering, the combination of physicochemical

lP

and biological processes can usually achieve a relatively ideal treatment

na

effect. Rong-wei et al. (2019) combined coagulation air flotation/upflow

anaerobic sludge blanket (UASB)/biological contact

ur

oxidation/coagulation sedimentation process to treat oil production

Jo

wastewater with 2500 mg/L COD. Eventually, the effluent COD, BOD5

and oil removal was 89mg/L, 19mg/L and 10mg/L respectively.

Although flotation-coagulation has a good removal effect on the

suspended oil and emulsified oil, it has a mediocre effect on dissolved oil.

Qu, (2018) studied that to the exclusion of emulsified oil with alkane as

the main component, the removal rate of each dissolved components were

obviously improved by aeration flotation, but naphthalene and dimethyl

44
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naphthalene were still difficult to be removed.

Table 5 Reported studies on coagulation-flotation in oily wastewater.

Oil
Oil-water Reaction Dosage Removal Airflow
Type of technology Coagulant/flocculant concentration pH Refs
resource time (mg/L) rate (%) Rate
(mg/L)

Coagulation-DAF Petroleum (Hoseini et

Aluminum sulfate 500 4 10 50 93 4.51(/min）
wastewater al., 2015)

(Santander
Petroleum
Jet flotation -flocculation Polyvinyl alcohol 100-400 / / 3 81 5m³/h et al.,
emulsion.
2011b)

Ship

of
Poly-aluminum
emulsified (You et al.,
Coagulation-flotation ferric chloride 3000-5000 6.5-6.9 / 300 <15ppm 0.25m³/h
oily 2018)

ro
(PAFC)
wastewater

Ternary
(Wang et
Coagulation-floatation flooding Al2(SO4)3+PAM 320-340
-p 9.5 / 5.5 97.5 /
al., 2018)
wastewater
re
The refinery

wastewater 205A/㎡
(Hmidi et
Electro-flotation-coagulation of Al2(SO4)3 9200(COD) 5.9 25 1400 92.4(COD) (Charge
lP

al., 2017)
residual-olive density)

oils
na

3.3.3 Coagulation-membrane filtration hybrid process

The membrane separation process is an emerging technology for

ur

the treatment of oily wastewater due to high oil removal efficiency and
Jo

relatively convenient operational process. However, direct filtration

would cause serious membrane fouling (Alpatova et al., 2014). By

contrast, the permeability of membrane ability after

coagulation/flocculation is partly restored. It has been reported that large

flocs are produced under effective coagulation/flocculation conditions,

which is beneficial for reducing membrane fouling and increasing dirt

transfer from the membrane surface (Almojjly et al., 2018; Kim et al.,
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2011). Some studies show that polymer flocculants can not remove the

natural organic matter (NOM) components that cause fouling because of

the high resistance of concentration polarization, filter cake layer and

adsorption layer (Rasouli et al., 2017). Moreover, compared to that

produced by sweeping, flocs produced by charge neutralization can

generate lower hydraulic resistance (Choi and Dempsey, 2004). Thus, iron

of
salts and aluminum salts are generally selected as coagulants in the

coagulation-membrane process (Rasouli et al., 2017).

ro
The in-line coagulation-microfiltration process is the process of
-p
adding coagulants/flocculants into the feed and then directly into the
re

membrane components, thus eliminating the precipitation stage or

lP

pre-filtration step (Choi and Dempsey, 2004). Two types of ceramic

na

membranes MZ (Mullite-Zeolite membrane) and MAZ

(Mullite-Alumina-Zeolite membrane) were employed to treat oily

ur

wastewater in an in-line coagulation-MF hybrid process (Rasouli et al.,

Jo

2017). The experimental results indicated that compared with other

coagulants, Al2(SO4)3 had superior performance in improving membrane

flux and reducing membrane pollution, so that the oxidation-reduction

potential (ORP) in MAZ increased from 96.2% to 99%, and the ORP in

MZ increased to 96.6% to 98.8%. Their results showed that the TOC

removal rate was as high as 90% under the dosage of iron salts from 50 to

200mg/L. Moreover, these two membranes were easily accessible and had
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high ORP from 95% to 99% and permeation flux (PF). This process

vastly improved turbidity and UV254 removal rates, providing the

possibility for the successful treatment of oily wastewater and the

production of cleaner wastewater for suitable discharge (Almojjly et al.,

2019). Almojjly et al. (2018) studied that it was more desirable to

combine coagulation/sand filter–microfiltration for oil-water emulsions

of
treatment, comparing to sand filter/microfiltration, direct ceramic

membrane and sand filter alone, respectively. The process not only led to

ro
a reduction of membrane fouling but also significantly improved oil
-p
removal efficiency.
re

The coagulation process can also be combined with ultra filtration

lP

(UF), nanofiltration (NF), reverse osmosis (RO) and other membrane

na

processes to completely treat oily wastewater, thus reducing energy

consumption and costs (Rasouli et al., 2017). Ozbey-Unal et al. (2018)

ur

investigated the treatability of olive oil wastewater by coagulation with

Jo

PAC-s and further UF, NF and RO at pH 3. In the course of coagulation,

the COD of sample wastewater was only decreased by 35.5% when the

removal rate of suspended solids was 29.7%. In the coagulation-UF

process, the COD removal rate increased from 35.5% to 65.6%. Under

this condition, UF was preferable to NF and RO. Therefore, it’s desirable

to treat dissolved oil particles and deal with a tough call in oily

wastewater treatment via coagulation/flocculation-UF.

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Coagulation-membrane filtration technology can shorten filtration time,

improve ORP and control pollution.

Due to complex matrices of oil-contaminated wastewater,

coupling different processes such as advanced oxidation can be an

alternative for highly effective oily wastewater treatment. Goncalves et al.

(2016) applied coagulation-membrane at first stage to reduce turbidity,

of
color, oil&fats. Following was Fenton/photo-Fenton reactions to remove

organic matters. Under optimal conditions, 90% dissolved organic carbon

ro
and 90% COD was removed. Mazumder et al. (2020) proposed a type of
-p
hybrid electrocoagulation and electroflotation enhanced membrane
re

process module. The synergistic effects facilitated demulsification and

lP

greatly eliminated membrane fouling. Results showed that oil rejection

na

reached 94%-96%. And electricity energy cost ranged from 20 to 218

INR/m3 (about 0.27 to 2.97 $/m3). These facts demonstrate the synthetic
ur

effectiveness and great prospects of different process with coagulation to

Jo

enhance oily wastewater treatment.

3.3.4 Coagulation/flocculation-adsorption treatment

The adsorption process is simple and effective in oily wastewater

treatment. If it is used to remove soluble and dispersed oils and recover

other organic materials in oily wastewater under proper treatment

conditions, certain economic and environmental benefits can be obtained.

The combination of coagulation and adsorption method will reduce

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sorbents pollution and improve the treatment effect of dissolved oil.

Different types of pollutants can be removed by adsorption and

coagulation processes, which can play a good complementary role.

Therefore, the great potential of this joint technology lied in the

feasibility of the complete removal of organic pollutants (Wang et al.,

2017).

of
Qu, (2018) compared the removal of emulsified oil from diesel

wastewater by activated carbon adsorption and PAC coagulation. Most

ro
alkanes in emulsified oil could be removed by coagulation/flocculation
-p
method, but the removal effect of aromatic hydrocarbon was not obvious.
re

When emulsified oil was removed by activated carbon, the equilibrium

lP

adsorption amount of each substance was very low. Therefore, the main
na

strategy is to remove emulsified oil by coagulation/flocculation anterior

to adsorption. After removing the emulsified oil by coagulation, the diesel

ur

wastewater was treated by activated carbon (Qu, 2018). It was found that
Jo

after the interference of emulsified oil was eliminated, the equilibrium

adsorption amount of various aromatic components by activated carbon

was significantly increased when compared with that before. Therefore,

adsorption is one of the promising choices for the dissolved oil removal.

Wang et al. (2017) evaluated the effectiveness of combined

adsorption-coagulation process in treating petroleum refinery effluent, the

results showed that the adsorption method had a better removal effect on
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phenols and iso-alkanes, while the coagulation method had a better

removal effect on esters and n-alkanes. Most of alkanes and phenols were

efficiently eliminated and kinds of typical pollutants decreased from 36 to

5. Wu et al. (2018) studied the coagulation-adsorption emergency

treatment of petroleum wastewater. The optimal process conditions were

PSAF and linoleum as coagulants and sorbent respectively, with a pH of

of
8, a dosage of 80mg/L, and a resting time of 30min. The results showed

that the oil removal rate can reach 99% after adsorption and secondary

ro
coagulation, and the treated effluent water quality is suitable for industrial
-p
water and recreational water that is not in direct contact with human body.
re

Therefore, the combination of these two processes means a promising

lP

technique for the purification and treatment of oily wastewater.

na

The selection of appropriate adsorbents and coagulants was the

key to the effective treatment of oily wastewater (Wang et al., 2017).

ur

Adsorption method often employs activated carbon as an adsorbent.

Jo

Possessing a porous structure and large specific surface area, activated

carbon can remove dissolved oil and other organic matter in oily

wastewater. Wang et al. (2017) compared adsorption efficiency of five

different sorbents: wooden activated carbon, diatomite, sodium bentonite,

calcium bentonite and zeolite, showing that wooden activated carbon had

a greater advantage in COD removal, up to 68.67%. Meanwhile, the

removal efficiencies for COD and TOC increased to 89.27% and 85.18%
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with polymeric magnesium ferric sulfate and wooden activated carbon,

due to the synergistic effect between coagulation and adsorption. In

addition to activated carbon, other chemical adsorbents and natural

adsorbents have also received great attention in oily wastewater. Rice

husk was chosen as a natural substitute for chemical adsorbent (Cercado.,

2019). After adsorption, the turbidity decreased from 454 to 93 NTU, and

of
the removal rate was 80.39%. Subsequently, the coagulation method was

used to remove the rice husk. the total removal rate of COD was 99.55%.

ro
Therefore, rice husk can be a high-value product as an option for the
-p
treatment of high concentration oily wastewater.
re

The exploration of efficient and convenient natural adsorbent

lP

and the development of green and low-cost chemical adsorbents may

na

become the focus of research on the treatment of oily wastewater by

adsorption. In addition, the recovery of oil and the regeneration of

ur

adsorbent are of great significance for the treatment of oily wastewater.

Jo

The regeneration method of adsorbent depends on the type and property

of adsorbate. Desorption can be roughly divided into the following:

thermal regenerative method, ultrasonic regenerative method,

electrochemical regenerative method, solvent regenerative method,

biological regenerative method, mechanical regenerative method, etc.

Different desorption methods may be combined to meet the requirements

for the extremely complex composition of oily wastewater.

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4 Cost estimation and comparison

According to the above discussion, each method has its advantages

to reduce the environmental impacts of oily wastewater. However, energy

consumption and cost are also valid parameters for oily wastewater

treatment. Therefore, this paper also compares coagulation/flocculation

with other treatment methods in terms of economy and energy, aiming at

of
providing reference for process selection.

The operating costs (OC, $/m3) of chemical coagulation/flocculation

ro
mainly include chemical agents, power consumption and sludge treatment.
-p
The OC of electrocoagulation treatment mainly includes electrode
re

material consumption (EMC) and electric energy consumption (EEC).

lP

Market prices used to calculate electrode materials and electricity bills

na

have been fluctuating, depending on regions and financial conditions.

Coagulation/flocculation with low cost and energy consumption

ur

possesses high interests in oily wastewater treatment. Ngamlerdpokin et

Jo

al. (2011) compared efficiency of biodiesel wastewater by coagulation

and electrocoagulation. It has been demonstrated that both methods

achieved similar treatment effects. Although the cost of remaining sludge

for coagulation was higher, coagulation consumed less electricity than

electrocoagulation. The operating costs of coagulation and

electrocoagulation were 1.11 $/m3 and 1.78 $/m3, respectively. Another

study also obtained similar results. Demirbas and Kobya. (2017)

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compared treatment performance and operating costs of coagulation and

electrocoagulation in real metalworking fluid wastewater. Coagulation

provided optimal removal efficiencies of 97% for COD and 81% for TOC

and OC was 0.12 $/m3. However, the highest removal rates of 94% for

COD and 83% for TOC with Al electrode for electrocoagulation were

observed. OC was calculated as 0.313-1.547 $/m3 at reaction time of 0-30

of
min. There are also some literatures evaluating the economics of

electrocoagulation in oily wastewater. Bilgili et al. (2016) investigated

ro
batch and continuous operations of electrocoagulation in bilge wastewater.
-p
In continuous operations under optimal conditions, TSS, oil&grease and
re

COD removal efficiency were approximately 80%, 90% and 77%

lP

respectively. Total costs were calculated as 1.4$/m3. Mohamud et al.

na

(2018) studied shipyard oily wastewater treatment and 88.83% COD was

removed at 3mA/cm2. The energy and electrodes consumptions were

ur

calculated as 6.15 kWh/m3 and 0.088kg/m3 respectively. The total cost

Jo

was evaluated as 0.88 $/m3. Similarly, another experiment investigated

electrocoagulation with Al and Fe electrodes for oily car washing

wastewater. Under optimal conditions, the total costs were calculated as

0.6 and 0.3$/m3 for Fe and Al electrodes respectively (Gonder et al., 2017).

Genc et al. (2017) studied high concentration COD and oil&grease

wastewater using horizontal and vertical electrochemical cells, and

eventually, EEC was 14.64 and 12.95 kWh/m3 for the horizontal and
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vertical cells at a continuous experiment, which were converted into 1.76

and 1.55 $/m3. Evidently, the treatment efficiency of coagulation and

electrocoagulation are about the same, while coagulation has a serious

advantage in the energy consumption and costs.

The total cost of membrane technology is divided into annual cost

and operation&maintenance costs. The former mainly includes membrane

of
cost, construction, installation, electrical, instrument, control and indirect

costs (Valizadeh et al., 2015). In comparison to the conventional,

ro
membrane technology possesses higher capital costs which mainly rely
-p
on the materials of membrane and the characteristics of oily wastewater
re

(Valizadeh et al., 2015). For example, the costs for oily wastewater from
lP

the fatty acid industry and metalworking by UF were 2.65$/m3 and

na

2.8$/m3, respectively (Cheryan, 1998; Dangel et al., 1995). Drewes and

Debroux. (2009) applied chemical oxidation to treat oily wastewater and

ur

the capital costs and operating as well as maintenance cost were 2.64
Jo

$/m3 and 0.063 $/m3 respectively. Pelendridou et al. (2013) examined the

feasibility of coagulation-flocculation not only as a single step but as a

second stage following biological treatment. In a single step, the OC of

coagulation was just 0.36-1.7€/m3(about 0.43-2.0$/m3). When biological

treatment and coagulation/flocculation were combined, removal

efficiency was improved and the OC was relatively low(0.36-2.03€/m3,

about 0.43-2.40 $/m3). In addition, it was also reported that the cost of
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oily wastewater using DAF was ~3.65$/m3 (Cheryan, 1998). It’s evident

that coagulation method has not only great environmental value but also

economical advantages. Based on the cost estimation in the above

literature, the cost of coagulation is relatively lower when compared with

electrocoagulation, membrane treatment, DAF, etc, as it is observed in

Supplementary Text S1, which shows that coagulation plays an important

of
role in practical engineering application and has a low operating cost.

Therefore, coagulation/flocculation technology still possesses

ro
considerable prospects in commercial application of oily wastewater.
-p
5 Current challenges and future directions
re

With the improvement of wastewater discharge standards and

lP

increasing awareness for environmental protection, the greatest

na

challenges of employing coagulation/flocculation to treat oily wastewater

lie in how to deal with complex water quality not only including
ur

suspended oil and emulsified oil but also having a better effect in
Jo

removing dissolved oil. Considering the future of oily wastewater

treatment, we should pay attention to the following points.

 As a kind of mixture, oily wastewater contains different components

such as an alkane, aromatic hydrocarbon and cycloalkane. In addition,

oil particles also exist in the water in different forms. The properties

of different components and different species of oily wastewater vary

greatly. Considering these points, it is suggested to carry out a more

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detailed study on characteristics and components of oily wastewater,

formulate the corresponding treatment scheme and provide theoretical

support for future water treatment. In the process of oily wastewater

treatment, it is not advisable to mix oily wastewater from different

production processes, which increases the complexity and difficulty

of treatment. Therefore, separating treatments of various oily

of
wastewater should be considered.

 At present, the treatment of oily wastewater is mainly aimed at

ro
removing oil contaminants as a whole or focused on the treatment of
-p
suspended oil, emulsified oil and dispersed oil. However, there are
re

few researches and treatment standards for the removal of dissolved

lP

oil and specific toxic components, though the removal of dissolved oil
na

is the bottleneck of oily wastewater treatment and

coagulation/flocculation technology. Dissolved oil can be mainly

ur

removed by adsorption, aeration, membrane separation, ozone

Jo

oxidation and biological treatment. Therefore,

coagulation/flocculation can be scientifically combined with the

above methods to enhance the removal effects of various oil

substances especially dissolved oil. It is suggested that more studies

should be carried out to investigate the cooperation and compensation

mechanism, optimize the reaction conditions and reduce the input cost

under the best treatment effects. Besides, it should be pointed out that
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a lot of current researches take laboratory simulated water as the

research object, resulting in a large deviation between the actual

effects and the laboratory results. Future studies should take simulated

water as the object to analyze the mechanism, and actual oily

wastewater as the object to verify the treatment effects, to improve the

practical application potential of coagulation/flocculation technology.

 In addition, it must be pointed out that one of the shortcomings of

of
coagulation/flocculation is the release of hazardous monomers and

ro
residue of coagulants/flocculants in the effluents, exerting adverse
-p
effects on human health and the environment. To reduce pollution of
re

coagulants/flocculants to natural water, developing green and

lP

effective coagulants/flocculants becomes a research hotspot.

na

Coagulants/flocculants made from biomaterials are usually low-cost

and environmentally friendly due to their abundant resources and

ur

biological sources. To achieve large-scale application of efficient

Jo

flocculants and improve the stability of natural flocculants, the

additional modification should be considered based on a

well-established structure-activity relationship. Understanding the

physicochemical interaction between oil particles and

coagulants/flocculants is a significant beginning of

coagulation/flocculation. The influence of the structural

characteristics, including various types of functional groups and their

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distribution, molecular weight, diverse chain structures and charge

density of diverse coagulants/flocculants should be investigated

in-depth in the future. In addition, it should be noticed that coupling

some adsorption groups in the flocculants can endue the flocculants

with the dual functions of coagulation/flocculation and adsorption,

and enhance the treatment efficiency.

of
6 Conclusion

In this paper, the treatment of oily wastewater by

ro
coagulation/flocculation method is reviewed at length. In conclusion,
-p
coagulation/flocculation is a promising and indispensable technology for
re

removing oil from oil-contaminated wastewater. This method has been

lP

successfully used to remove oil from a wide range of oily wastewater.

na

The characteristics of oily wastewater have been summarized in this

review in detail. The performance of the coagulation/flocculation process

ur

is closely related to many other system characteristics and operating

Jo

factors like properties of coagulants/flocculants, dosage, pH value,

temperature, initial oil concentration, type and characteristics of oily

wastewater. The advantages of coagulation/flocculation lie in

well-established technology, low cost, relatively efficient removal of

floating oil, emulsified oil and colloidal particles. Each method has its

advantages and disadvantages. There is no exception for

coagulation/flocculation, which cannot obtain desirable results for the

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removal of dissolved oils and specific toxic pollutants. However,

compared to other treatment technologies, coagulation/flocculation has

more advantages in economic aspects. To meet with increasingly

stringent emission standards and environmental requirements, the

development of efficient green natural coagulants/flocculants,

determination of components of different oily wastewater and study of

of
dissolved oil treatment are expected to improve the treatment efficiency.

However, the application of large-scale natural coagulants/flocculants

ro
needs further study. In addition, it is also of great practical significance to
-p
combine coagulation/flocculation and other treatments like sorption,
re

biological treatment to bring their respective advantages into full play and
lP

finally achieve better oil removal performance. Further researches on the

na

mechanism of oil removal under these conditions also provide a solid

theoretical basis. According to the characteristics of the

ur

coagulation/flocculation process, when using coagulation/flocculation to

Jo

treat oily wastewater in practical projects, it shall precisely control the

reaction conditions, determine the type and amounts of

coagulants/flocculants according to the different inlet water

characteristics of oily wastewater.

Acknowledgements

This work was supported by the National Key R&D Program of China
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(Grant No.2018YFE0103800), Science and Technology Project of

Shaanxi Province, China (Project No. 2019JQ-443), and National

Undergraduate Innovation Training Program of Chang’ an University

(Project No. 201910710116).

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Figure 1 Various treatment methods for oily wastewater.

Figure 2 Most common coagulation/flocculation process in oily

wastewater: creaming, coagulation/flocculation, coalescence and

sedimentation.

Figure 3 Al3+ and Fe3+ existing formations in different pH (M3+ = Al3+or

Fe3+).

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Figure 4 The molecular structure of cationic (a) and anion (b)

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polyacrylamide (PAM), chitosan (c), starch-g-PAM (d), starch-g-PAA (e)
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Figure 5 Effects of molecular structure of coagulant/flocculant on the
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treatment efficiency.
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Figure 6 Mechanism of electrocoagulation.

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Figure 7 Conventional DAF unite schematic diagram.

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Declaration of competing interest

The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

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Highlights
 Few articles focus on the technology of

coagulation/flocculation in oily wastewater.

 The mechanisms, influencing factors, challenges and feasible

research direction of coagulation/flocculation in the treatment

of oily wastewater are discussed.

 Coagulation/flocculation

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presents an excellent removal

efficiency on oily wastewater.

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 Combined technologies for oil removal can meet strict
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effluent guidelines.
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