Sohar University: Oilfield Produced Water Treatment Using Membrane Technology

Sohar University
Oilfield Produced Water Treatment

Using Membrane Technology
Done By
Sadegh Asadzadeh, Maroa Al-Jahwari, Yasmine Al-Senaidi
A Final Year Report
Submitted to Sohar University
in partial fulfilment of the
requirements for the degree of
Bachelor of Engineering
in
Chemical Engineering
Sohar, Sultanate of Oman, June 2015
Supervised by: Dr. Ahmed Jawad Ali Al-Dallal

Declaration
We hereby declare that this report is based on our original work. We also declare that it
has not been previously and concurrently submitted for any other degree or award.
Signatures
We further permit Sohar University to reproduce this thesis by repetition or by other

means, in total or in part, at the request of other institutions or individuals for the purpose
of scholarly research.
Signatures
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Acknowledgment
The project group would like to thank their supervisor Dr Ahmed Al-Dallal for his
assistance, valuable advice, and support along the project. They also appreciate Mr
Ibrahim Al-Ajmi and Mr Rashid for their support and their continuous help during the
fabrication of the experimental set-up.
We thank our beloved Prof. Ehab Alellobody, Assistant Dean, Faculty of Engineering,
for all his encouragement and support which helped us to complete the experimental
study successfully.
Our appreciations and great thanks to all staff in the department of Chemical
Engineering especially Dr Yusuf Touhami, Dr Nitin Raut, Dr Rajmohan Natarajan,
Mrs. Ohood AL-Hamdani, Mrs. Muna AL-Ajmi, Mrs. Fatma Al Qasmi, Mrs. Fatma
Abdelamir and Mrs. Saud AbuHour for their kind, helpful and honest advices and their
great cooperation.
Furthermore, the authors would also like to express their gratitude to their loving parents
and friends who had helped and encouraged them.
Finally we offer our sincere thanks to The Research Council for providing us with the
financial support to create the infrastructure for conducting of our experiments. Without
the mentioned parties, it was impossible to complete this final year project.
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Executive summary
More and more oily wastewater has been generated from the development of oilfields,
especially for that using water injection technology. It is necessary to purify this water so
that it can be reused to save water resources and to protect the environment. One of that
methods using in the treatment of oily wastewater is membrane technology.
For the experimental investigation, a membrane technology for the synthetic oily
wastewater treatment was selected. This membrane unit is consists of a feed tank (40 L)
where oil-water emulsion fed by a centrifugal pump through the microfiltration
membrane. The membrane discharge streams are permeate and retentate streams. There is
a cooling system to avoid the temperature elevation due to pump circulation.
The permeate flow rate and NTU is recorded each five minutes during one hour for each
experiment at retentate flow rate (2, 1.5 and 1 m3/hr) with corresponding TMP (1, 1.5
and 1 Bar) by using 200 nm and 100 nm pore size ultrafiltration membrane.
The large pore size of the membrane generates high permeate flux. Secondly, the
permeate flux depends strongly on the applied TMP. When the feed solution is the pure
water, the filtration resistance is only the membrane resistance. The permeate flux
increased linearly with increase of TMP.
Membrane fouling is predominantly responsible for the decline of the permeate flux.
Effective membrane cleaning is necessary to maintain large permeate flux. The procedure
of membrane cleaning proposed here was sodium hydroxide solution washing and results
showed this method was not sufficient , in order to restored the initial efficiency of
membranes washing with hot water should be added to cleaning procedure.
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Nomenclature
COD Chemical oxygen demand
TMP Transmembrane pressure (bar)
CFV cross-flow velocity (m/s)
UF Ultrafiltration
NF Nanofiltration
RO Reverse osmosis
MF Microfiltration
PPI Parallel plate interceptors
CPI Corrugated plate interceptors
DAF Dissolved air flotation
TOC Total organic carbon (mg/l)
O&G Oil and gas (ppm)
MWCO Molecular weight cut-off
NTU Turbidity (dimensionless)
T Temperature (℃)
TSS Total suspended solid (mg/l)
TDS Total dissolved solid (mg/l)
Ji Initial pure water permeate flux (m3/ (m2 s))
Jf Distilled water permeate flux after cleaning operation (m3/ (m2 s))
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J Permeate flux (m3/ (m2 s))
WFR Water flux recovery
n Number of channels in the membrane
r Radius of the circular membrane channel (m)
Qf Permeate flow rate (m3/s)
Ra Rejection
Rr Real rejection
CP Instantaneous solute concentration in the feed
CF Instantaneous solute concentration in the permeate stream
Cg Solute concentration on the membrane surface
Rm Membrane resistance
µ Dynamic viscosity
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Table of Contents
Declaration...........................................................................................................................I
Acknowledgment...............................................................................................................II
Executive summary.........................................................................................................III
Nomenclature...................................................................................................................IV
List of Figures..................................................................................................................IX
List of Tables....................................................................................................................XII
Chapter 1 : Introduction.......................................................................................................1
1.1 Background................................................................................................................1
1.2 Objective of the thesis...............................................................................................2
Chapter 2 Literature Survey.................................................................................................3
2.1 Produced water management.....................................................................................3
2.1.1 Produced water source........................................................................................3
2.1.2 Conventional treatment of produced water.........................................................4
2.2 Membrane..................................................................................................................9
2.2.1 Classification......................................................................................................9
2.2.2 Membrane material...........................................................................................11
2.2.3 Pressure driven processes.................................................................................12
2.2.4 Membrane module............................................................................................12
2.2.5 Membrane operation.........................................................................................16
2.3 Advantages of using membrane technology............................................................17
2.4 Membrane treatment of oily wastewater.................................................................18
2.5 Membrane fouling...................................................................................................21
2.6 Membrane cleaning.................................................................................................21
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2.7 Membrane theory.....................................................................................................22
2.7.1 Transmembrane pressure (TMP)......................................................................22
2.7.2 Cross-flow velocity (CFV)...............................................................................23
2.7.3 Flux...................................................................................................................23
2.7.4 Rejection (R).....................................................................................................23
2.7.5 Membrane filtration resistance.........................................................................24
Chapter 3 : Experimental work.........................................................................................25
3.1 Design of Equipment...............................................................................................25
3.2 Experimental set-up.................................................................................................26
3.3 Chemicals................................................................................................................28
3.4 LaMotte (2020we) waterproof portable turbidity meter..........................................29
3.5 Membrane selection.................................................................................................30
3.6 Experimental procedures.........................................................................................30
3.6.1 Preparation of feed solution..............................................................................31
3.6.2 Operation of MF process..................................................................................31
3.6.3 Cleaning procedure...........................................................................................32
3.7 Calibration curve.....................................................................................................32
Chapter 4 : Results and Discussion...................................................................................34
4.1 Effect of change TMP at fixed retentate flow rate on permeate flux and NTU......34
4.1.1 Experiments of set one (200nm )......................................................................34
4.1.2 Experiments of set two (100nm).......................................................................42
4.2 Comparison of characteristics of the two membrane..............................................50
4.3 Effect of CFV..........................................................................................................53
4.4 Effect of TMP..........................................................................................................53
4.5 Effect of cleaning.....................................................................................................54
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Chapter 5 : Conclusion and Recommendations for Future Work......................................56
5.1 conclusion................................................................................................................56
5.2 recommendation for future work.............................................................................57
REFERENCES................................................................................................................58
Appendicies……………………………………………………………………………...63
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List of Figures
Figure 2.1: Typical reservoir
Figure 2.2: oil/water conventional treatment system
Figure 2.3: schematic of gas flotation unit
Figure 2.4: Corrugated Plate (CPI) packing separates oil and solids from produced water
Figure 2.5: Schematic illustration of membrane separation
Figure 2.6: Schematic of a plate and frame membrane
Figure 2.7: Schematic of a hollow fibre membrane
Figure 2.8: Typical tubular membrane modules
Figure 2.9: Cut-up diagram of a typical spiral-wound RO membrane element
Figure 2.10: (a) Dead-end filtration, (b) Cross-flow filtration.
Figure 2.11: Types of resistances during filtration process
Figure 3.1: Drawing of the setup for membrane unit
Figure 3.2: apparatus of membrane filtration
Figure3.3: The ceramic membrane outlook
Figure 3.4: calibration curve between NTU and ppm of solution
Figure 4.1: permeate flux vs. time (the top) and NTU vs time (the middle) and CFV vs
time (the bottom) for retentate flow rate=1m3/hr and TMP=2 Bar, 200 nm pore size
ultrafiltration membrane
time (the bottom) for retentate flow rate=1m3/hr and TMP=1.5 Bar, 200 nm pore size
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Figure 4.3: permeate flux vs. time (the top) and NTU vs time (the bottom) for retentate
flow rate=1m3/hr and TMP=1 Bar, 200 nm pore size ultrafiltration membrane
time (the bottom) for retentate flow rate=1.5 m3/hr and TMP=1.5 Bar, 200 nm pore size
time (the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1Bar, 200 nm pore size
flow rate=2 m3/hr and TMP= 1 Bar, 200 nm pore size ultrafiltration membrane
Figure 4.7: NTU vs Time for 200 nm membrane
Figure 4.8: NTU vs Time for distilled water
Figure 4.9: permeate flux vs. time (the top), NTU vs time (the middle) and CFV vs time
(the bottom) for retentate flow rate=1 m3/hr and TMP= 2 Bar, 100 nm pore size
Figure 4.10: permeate flux vs. time (the top), NTU vs time (the bottom) and CFV vs
time(the bottom) for retentate flow rate=1 m3/hr and TMP= 1.5 Bar, 100 nm pore size
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(the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1.5 Bar, 100 nm pore size
Figure 4.13: permeate flux vs. time (the top), NTU Vs time (the middle) and CFV vs time
(the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1 Bar, 100 nm pore size
Figure 4.15: NTU vs Time for 100 nm membrane
Figure 4.17: permeate flux vs. time (the top) and NTU vs time (the bottom) for
retentateflow rate=2, 1.5 and 1 m3/hr and TMP= 1, 1.5 and 1 Bar, for 200 nm pore size
Figure 4.18: permeate flux vs. time (the top) and NTU vs time (the bottom) for
retentateflow rate=2, 1.5 and 1 m3/hr and TMP= 1, 1.5 and 1 Bar, for 100 nm pore size
Figure 4.19: distilled water at 1.5m3/h and 1.5 bar for 200 nm membrane
Figure 4.20: distilled water at 1.5m3/h and 1 bar for 100 nm membrane
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List of Tables
Table 2.1: Technologies have been used for Oil and grease removal based on size of
removable particles
Table 2.2: Advantages and disadvantages of the current treatment process [20]
Table 2.3: Characteristics of membrane filtration process
Table 2.4: Studies and researches on different membrane’s technology
Table 3.1: Operating condition for the membrane unit from manufacturer
Table 3.2: Properties of chemicals have been used
Table 3.3: Composition by weight of oily chemical elements
Table 3.4: Ceramic membrane dimensions
Table 4.1: recorded data of permeate flow rate and NTU with time for a retentate flow
rate=1.5 m3/hr and TMP=1.5 Bar, 200 nm pore size ultrafiltration membrane
Table 4.2: recorded data of pressure from pressure gauges (pressure gauge of feed PG1
and retentate pressure gauge PG2) for a retentate flow rate=1, 1.5 and 2 m3/hr for 200 nm
pore size ultrafiltration membrane
Table 4.3: recorded data of pressure from pressure gauges (pressure gauge of feed PG1
Table 4.4: recorded data of permeate flow rate and NTU and corresponding ppm by using
calibration curve with time at retentate flow rate= 1.5 m3/hr and TMP= 1 Bar, for 100 nm
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Chapter 1 : Introduction
1.1 Background
Currently, regulations limiting the oil content of produced waters often govern the
methods for treatment and disposal of these waters. In the oil and gas industry, oil is a
general term used to describe organic matter which, in produced waters, can include
aliphatic and aromatic hydrocarbons, phenols, and carboxylic acids [1]. These organic
compounds are present in produced waters either in a dispersed (emulsified and free oil)
or a dissolved form, and appear to be key factors affecting toxicity to fish and wildlife
when produced waters are discharged to surface water environments [2][3].
The methods of treatment and disposal of produced waters depend on many factors,
including volume of water, type of water, location of the oil or gas field, and site-specific
regulatory considerations. There is a need for produced water treatment methods that can
lower the oil and grease and the suspended solids concentrations to minimize reinjection
problems and meet regulatory limits [4].
More and more oily wastewater has been generated from the development of oilfields,
especially for that using water injection technology. It is necessary to purify this water so
that it can be reused to save water resources and to protect the environment .Conventional
oily wastewater treatment methods include gravity separation and skimming, dissolved
air flotation, de-emulsification, coagulation and flocculation, which have several
disadvantages such as low efficiency, high operation costs, corrosion and
recontamination problems. Also, these methods are not effective in removing smaller oil
droplets and emulsions as their diameters are less than 20µm. All of these disadvantages
have encouraged the development of new processes for oily wastewater treatment [5].
One oilfield in the Nimr area of Oman produces 12 million gallons per day (mgd) of
oilfield wastewater. The wastewater is treated initially using dissolved air flotation so that
the oil content is down to about several hundred milligrams per litre. The shallow water
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disposal requirement in Oman specifies oil content allowable in disposal water is up to a
maximum of 5.0 mg/L [6].
Membrane filtration is playing a more prominent role in the treatment of oily wastewater
due to its advantages: no chemical additives are needed to break the emulsion, high
chemical oxygen demand (COD) removal efficiencies are achieved, and treatment
facilities are quite compact and fully automated. Many studies have been done on the oily
wastewater treatment with different membranes [7].
1.2 Objective of the thesis

In this thesis, it is intended to study:
1- To understand characteristics of membrane filtration process.
2- To conduct synthetic oily wastewater treatment by MF ceramic membranes.
3- To identify the effect of transmembrane pressure (TMP), cross-flow velocity
(CFV) and oil content on the permeate flux.
4- The effect of membrane fouling on the flux decline.
5- To design membrane cleaning method.
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Chapter 2 Literature Survey
2.1 Produced water management
2.1.1 Produced water source

Produced water is any fossil water that is brought to the surface along with crude oil or
natural gas. Natural water or formation water is always found together with petroleum in
reservoirs. It is slightly acidic and sits below the hydrocarbons in porous reservoir media
and Figure 2.1 shows that.
Figure 2.1: Typical reservoir

Extraction of oil and gas leads to a reduction in reservoir pressure, and additional water is
usually injected into the reservoir water layer to maintain hydraulic pressure and enhance
oil recovery. In addition to injected water, there can be water breakthrough from outside
the reservoir area, and as oil and gas production continues, the time comes when
formation water reaches production well, and production of water begins alongside the
hydrocarbons. This water is known as produced water or oilfield brine, accounting for the
largest volume of byproduct generated during oil and gas recovery operations [8]. It is a
mixture of injected water, formation water, hydrocarbons and treating chemicals [9],
generally classified as oilfield produced water, natural gas produced water and coal bed
methane (CBM) produced water depending on the source.
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2.1.2 Conventional treatment of produced water
Treatment methods for oily wastewater can be classified into three categories namely,
primary or gravity treatment units, secondary processes and tertiary processes. Figure 2.2
illustrates the categories of oily wastewater conventional treatment system.
Figure 2.2: oil/water conventional treatment system

The primary treatment of oily wastewater is usually conducted by the API separator
which treats the free oil effectively by gravity force. Modifications of the API separator
include the use of parallel plate interceptors (PPI) or corrugated plate interceptors (CPI).
These modifications are to improve the removal efficiency and reduce the space
requirement of API separator. However, the API separator and its modifications have no
effect on the soluble fraction of the oil and on the oil/water emulsion. Because the
densities of the oil/water emulsion and water are approximate, the oil/water emulsion
cannot be removed by simple gravity separation. Therefore, a variety of secondary and
tertiary treatment methods have been applied to treat the soluble fraction and the
oil/water emulsion of the oily wastewater.
Among the physical-chemical processes, dissolved air flotation (DAF) is the one of the
most common processes used to treat the oily wastewater after gravity separation. The
DAF process includes two different stages:
1. The chemical stage, which consists of emulsion breaking and creation of
solid aggregates (coagulation and flocculation) by chemical addition.
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2. The physical stage, which separates the aggregates from the liquid phase
using air bubbles released under pressure.
This process has been reported to achieve oil removal of 80% to 90% [10, 11, and 12].
Galil and Wolf [13] also reported the removal efficiency of dissolved organic matter at
40% of the DAF process.
Coalescence, filtration and adsorption are the other alternatives for oily wastewater
treatment. Coalescence method, which create the microdroplet coalesce to form large
droplet size to be easily separated by decantation [14], is normally suitable for oil
emulsion with low concentration of emulsion. Filtration process can be carried out by
various types of filter media ranging from coarse granular to fine filtration such as sand,
anthrasilt and diatomaceous earth. It has been reported that the influent oil concentrations
of 130 mg/L to 500 mg/L can be reduced to the range of 12 mg/L to 77mg/L by filtration
system [15]. Campos et al. [16] used microfiltration as pretreatment of oilfield
wastewater before biological process. The removals of 35%, 25%, 92% and 35% were
reported for COD, TOC, O&G and phenols respectively.
Adsorption process is normally used as tertiary treatment to remove trace amount of oil
and emulsifier. Among the adsorbents used are silica base material, organic polymer,
bentonite, activated carbon etc. Most of the physical-chemical treatment methods for oily
wastewater require intensive washing and replacement of filtration or adsorption
materials that lead to difficulty in operation and increase in treatment cost. Moreover, the
common disadvantage of all physical-chemical treatment methods is that they do not
remove the oil completely but just transfer them to a more concentrated waste. Therefore,
waste disposal is always problematic for physical-chemical treatment of oily wastewater
because the oily waste is considered as hazardous waste.
Biological processes have also been applied in oily wastewater treatment. These
processes are mainly to remove soluble organic matters remaining after physico-chemical
treatment. Biological treatment is only effective for highly diluted oily wastewater since
oil components are adsorbed on microorganism faster than they can be metabolized.
Subsequently the adsorbed oil tends to damage sludge settling characteristics and cause
system failure [17].
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Table 2.1 shows typical performance for oil removal treatment as expressed by size of oil
particle [18].
Table 2.1: Technologies have been used for Oil and grease removal based on size of
removable particles.
Minimum size of particles removed
Oil Removal Technology (microns)
API gravity separator 150
Corrugated plate separator 40
Induced gas floatation (no flocculants) 25
Induced gas floatation (with flocculants) 3-5
Hydrocyclones 10-15
Mesh coalesce 5
Media filter 5
Centrifuge 2
Membrane filter 0.01
2.1.2.1 Gas flotation

Gas floatation units use air/gas to float out oil more rapidly from the produced water. The
density of oil particles reduce as they attach to gas bubbles. Reduced density improves
the speed of oil floatation to the surface. The oil lumps on the surface are skimmed off.
There are two types of floatation systems; dissolved air floatation and induced gas
floatation. Dissolved air floatation uses an air compressor to inject and dissolve air into
the produced water steam.
Induced gas floatation as shown in Figure 2.3 creates fine gas bubbles through
mechanical, hydraulic or sparging systems. The induced gas bubbles adhere to the oil
droplets as they move upward to the surface. It provides high oil removal efficiency at
larger throughput or lesser retention time for a given rate. Efficient performance is
limited to oil droplet size of greater than 25 microns. To achieve higher efficiency if
smaller droplets are present, flocculants and coagulants are added to improve the
performance. Produced water treatment systems based on micro-bubble floatation system
have been developed which use 5-50 micrometer bubbles through the reactor [19].
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Smaller bubbles more effectively separate oil from the produced water which results in
low skim volume.
Figure 2.3: schematic of gas flotation unit
2.1.2.2
Corrugated plates
Corrugated plates are packed to enhance the performance of gravity separation tanks and
it’s shown in Figure 2.4. The oil droplets coalesce and form larger oil droplets as the
corrugated plates provide a longer path for the oil droplets to travel to the top of the tank.
It is a simple operation that allows the compact design of the API separation tank;
however, the efficient oil removal limits the oil droplet size of 40 microns and larger.
Removal of smaller oil droplets is difficult with corrugated plate separator [19].
Figure 2.4: Corrugated
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Table 2.2 illustrates deferent types of treatment method.
Table 2.2: Advantages and disadvantages of the current treatment process [20]
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2.2 Membrane
The membrane is a physical barrier that allows certain compounds to pass through,
depending on their physical and/or chemical properties. Membranes commonly consist of
a porous support layer with a thin dense layer on top that forms the actual membrane.
Figure 2.5: Schematic illustration of membrane separation
Figure 2.5 illustrates the process of a semi-permeable barrier: one component (permeate)
of the mixture to be separated (feed) passes through such barrier easier than the other. In
general, the rate at which a particular component moves through the membrane is
determined by the size of the molecule, the concentration, the pressure difference across
the membrane and the affinity of the component for the membrane material [21, 22].
2.2.1 Classification
Membranes are classified into different types based on their nominal size or molecular
weight cut-off (MWCO) including:
 Microfiltration (MF)
 Ultrafiltration (UF)
 Nanofiltration (NF)
 Reverse osmosis (RO)
Microfiltration membrane rejects suspended solids in the size range of 0.10 to
100 µm. Ultrafiltration membrane rejects macromolecules and suspended solids in the
size of 0.001 to 0.02 µm (or 1000 to 100000 MWCO) [23]. Because some UF
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membranes have the ability to retain larger organic macromolecules, they have been
historically characterized by a molecular weight cut-off (MWCO) rather than by a
particular pore size. The concept of the MWCO (expressed in Daltons – a unit of mass)
is a measure of the removal characteristic of a membrane in terms of atomic weight (or
mass) rather than size [24]. Typically, ultrafiltration membranes will remove high
molecular-weight sub-stances, colloidal materials, and organic and inorganic polymeric
molecules, while low molecular-weight organics and ions are not removed. Because only
high-molecular weight species are removed, ultrafiltration achieves high flux rates at low
applied pressure. This makes ultrafiltration the ideal filtration method to introduce the
basic principles of filtration such as flux, permeability and rejection [22]. Nanofiltration
membrane rejects divalent salts and dissociated acids with size lower than 1000 MWCO.
Reverse osmosis membrane can be used to reject all the remaining ions except water
[23]. Table 2.3 shows the classification of membrane based on their sizes and MWCO.
Table 2.3: Characteristics of membrane filtration process

Process Separation Size Range MWCO Objective
Technolog Principle
y
MF Size 0.05 – 10 μm - Removal of suspended solids,
bacteria, cysts and spores
etc.
UF Size, 1-50 nm > 1000 Removal of both large
Charge dissolved solute molecules and
suspended colloidal particles
including protein, viruses etc.
NF Size, ~ 1 nm 200-1000 Removal of multivalent ions
Charge, and certain charged or polar
Affinity molecules such as sugars,
pesticides etc.
RO Size, <1 nm <200 Removal of inorganic ions,

Charge salts and sugars
, Affinity
2.2.2 Membrane material

The membrane material refers to the substance from which the membrane itself is made.
Normally, the membrane material is manufactured from a synthetic polymer, although
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other forms, including ceramic and metallic membranes. The material properties of the
membrane may significantly impact the design and operation of the filtration system.
Mechanical strength is another consideration, since a membrane with greater strength can
withstand larger transmembrane pressure (TMP) levels allowing for greater operational
flexibility [21, 25].
2.2.2.1 Polymeric membranes

Cellulose acetate is a common membrane material used at the onset of modern membrane
technology. Cellulose is a polymer of β-1,4 linked glucose units with one primary and
two secondary hydroxyl groups and the β- glucosidic oxygen in the equatorial position.
Cellulose acetate membranes are widely used for reverse osmosis and ultrafiltration
applications, they have high hydrophilicity which is essential in minimizing membrane
fouling, low production and manufacture cost and they can be produced with a wide
range of pore sizes. Disadvantages are narrow temperature and pH ranges, low chemical
resistance and they are highly biodegradable. Notable membrane polymeric materials that
have excellent properties such as the polysulfone membranes include polyvinylidene
fluoride (PVDF), polyetrafluororthylene (PTFE), polypropylene (PP), polystyrene (PS)
and polyvinyl chloride (PVC), polyolefin (P) just mentioning a few. These materials
confer on the membrane unique characteristics and additional tolerance to exacting
operating conditions [21, 25].
2.2.2.2 Inorganic membranes

Inorganic membranes also called ceramic membranes spearheaded the latest revolution in
membrane technology starting from the 80s. Ceramic membranes are made from a wide
range of inorganic materials and the more common ones are made from alumina, titania,
zirconia and silicon oxides. In their manufacture they are often formed into asymmetric,
multi-channel elements and normally have an asymmetrical structure composed of at
least two, mostly three, different porosity levels. They are a vast improvement both in
material characteristics and in the technology dividend to membrane filtration over
polymeric membranes. They are inert to common chemicals and solvents, can withstand
high acidity and alkalinity, have wide temperature, pH, and pressure limits, and their long
life and durability increasing their appeal significantly. Limitations common to them
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include brittleness, relatively large energy consumption in running them and pore size
limitation in the lower micron range [21, 25].
2.2.3 Pressure driven processes

Separation with membranes occurs because of the existence of a gradient across the
membrane, and membrane processes may be divided into groups based on the specific
type of gradient. The most common way of categorising membrane is to divide them into
two groups: pressure driven and non-pressure driven .In pressure driven membrane
process, the filtration occurs because a pressure gradient is created across the membrane.
The pressure gradient is called transmembrane pressure (TMP), and as the driving force
of the pressure-driven membrane processes, it plays a crucial role in membrane filtration.
There are four pressure driven membrane processes namely microfiltration (MF),
ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) [25, 26].
2.2.4 Membrane module

A useful membrane process requires the development of a membrane module containing
large surface areas of membrane. In much of the early laboratory work membranes we
reused in the form of flat sheets, but for industrial applications of any scale the membrane
has to be suitably housed in a manageable unit. The structure of such a device has been a
continual challenge, which requires balancing the economic costs of a unit versus
performance factors and operational factors, e.g. cleaning, replacement. There are four
types of membrane modules [27]: plate and frame, spiral-wound, hollow-fibre, and
tubular.
2.2.4.1 Plate and frame

Plate and frame type membranes are amongst the earliest membrane module type. It
consists of a rigid, flat plate on which a flat sheet of membrane is placed and a spacer is
put between the membrane and the flat plate. The spacer a netlike material is placed
between the membrane sheets and provides channel for permeate flow and this sheet is
sealed around the edges with a passage for permeate collection. This “unit” (membrane-
spacer-membrane) is then stacked on top of each other or adjacent to one another
depending on the decided orientation of the stack. The operation of the plate and frame
module involves passing the feed through the plates and the permeate flows though
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spacer to the collection tube, the retention goes through the module to the exit. Figure 2.6
illustrates the structure of plate and frame membrane.
Figure 2.6: Schematic of a plate and frame membrane
Advantages of the plate and frame include the ability for easy maintenance of the
membrane module as replacement of the stack is easy and the cleaning equally easier and
straightforward. The plate and frame module have intermediate energy consumption and
packing density when compared against the spectrum of the tubular and spiral wound
modules. Plate and frame modules find wide application in food and beverage industries
and some chemical process lines [28].
2.2.4.2 Hollow fiber

Hollow fibre membranes are basically made up of “spaghetti” like fibers bundled
together and sealed by an epoxy resin plug encased in PVC, or acrylic tube or a fibre
plastic. They are made in a wide array of diameters from 100 micron to about 2 mm, their
fibers have a cross-sectional thickness of about 100 -400 microns with bundles containing
about 50 - 3000 individual fibers sealed into hydraulically symmetrical housings in a
shell-and tube arrangement bonded by epoxy at their end, as shown in Figure 2.7.
Advantages of the hollow fibre membrane include a high surface area to volume ratio,
they have very low pressure rating with their maximum pressures hovering around 1.8
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bar (25 psig), and also their energy consumption is relatively low when compared to
other membrane modules [28].
Figure 2.7: Schematic of a hollow fibre membrane
2.2.4.3 Tubular modules

Tubular membranes are suitable for handling large size particles and high flow rates,
and they have easier cleaning-in-place methods but the surface area to volume ratios of
these membranes are low [29]. Tubular membranes have the largest diameter of all
membrane module types with internal diameters ranging from 12.5 to 25mm with lengths
varying from the 0.6 to 6.4m. The difference from hollow fiber membranes in that they
are supported along its length and cannot stand alone. Tubular membranes generally
operate with the flow going through the internal diameter or lumen of the membranes and
the permeate flowing outward from the skin of the membrane collecting in the housing
where the membrane in fitted to a permeate collection outlet.
Tubular membranes have low membrane densities, and a high flow demand when
compared to other modules. They are known to handle high solids feed more than any
other membrane module type. They are also easily cleaned and have excellent backwash
or back flush capacity like the hollow fibre, thus their tendency to fouling is lowest
amongst the membrane modules. They have the lowest surface to volume ratio of all
14 | P a g e
membrane modules and require more energy in their operation due to the high
recirculation rates during operation. They are also relatively expensive as ceramic,
polymeric and other tubular membrane modules cost more than other modules of the
same material. Tubular membranes find wide application in a host of challenging
rheological feed streams usually those with high suspended solids or with challenging
chemicals such as solvents[30]. Figure 2.8 illustrates tubular membrane modules.
Figure 2.8: Typical tubular membrane modules.
2.2.4.4 Spiral-wound module

Compared to other membrane packages, the most noticeable difference is the complexity
of the design. A typical element is made from up to 11 different materials. Until fairly
recently each element had to be handmade. The spiral-wound module is one of the most
favoured for the applications of gas separation and RO. Despite its complex internal
design, it is easy to use, and is available in a large number of formats with different
materials. In addition, spirals have a reasonably high membrane area per unit volume
which means the size of the pressure vessels and associated pipework and frames are less,
giving an additional economic and practical benefit. The major disadvantage of the spiral
device is a thicker feed spacer when the spiral device is applied in ultrafiltration, this
means there is a reduction in membrane area for a given size device [31]. Figure 2.9
shows cut-up of spiral-wound membrane module.
15 | P a g e
Figure 2.9: Cut-up diagram of a typical spiral-wound RO membrane element.
2.2.5 Membrane operation

There are two operating modes for membranes as shown in figure 2.10, the dead end
filtration mode and the cross-flow filtration mode. In the dead end mode the feed stream
is pumped directly through the membrane. During dead-end filtration all the solvent that
enters the membrane surface passes through the membrane while the solid particles or
retentate stay behind on the membrane. Inevitably the solvent will experience greater
flow resistance as the retentate builds up on the surface of the membrane resulting in flux
decrease. Dead end filtration is common in low solids feed such as cartridge filtration of
boiler feed or ultrafiltration of apyrogenic pure water production [30].
The second operating mode is called the cross flow operating mode, It involves moving
the feed stream tangentially across the membrane surface while the permeate flows
normal to the surface. In this operation mode there is one stream entering the membrane
(feed stream) and two streams leaving the membrane (the permeate stream and the
retentate stream). Cross flow filtration is effective against filter cake build up as the
suspended solids that would have otherwise accumulated at the membrane surface are
removed by the shear caused by cross flow at the membrane surface. Cross flow filtration
finds wide use in streams with high solids, though it operation requires more energy. It is
16 | P a g e
effective in filtration of a lot of streams. This thesis is confined to investigations
concerning cross flow filtration [32].
Figure 2.10:
(a) Dead- end
filtration, (b) Cross-flow filtration.
2.3 Advantages of using membrane technology

Membrane technologies have some advantages that make them popular for produced
water treatment processes:
 sludge reduction
 high quality of permeate
 smaller space needed
 ease of operation
 possibility for recycling of waste streams
 possibility for having an automated plant
 moderate capital costs
 low energy consumption
 continuous separation
 little or no chemicals required
 minimal impact on permeate quality with variation in feed water quality
17 | P a g e
But there may be some drawbacks for using membrane processes including
concentration, polarization/membrane fouling, low selectivity or low flux and low
membrane lifetime [33].
2.4 Membrane treatment of oily wastewater

Several common techniques are used in oil–water separation and treatment. The gravity
settling separation and mechanical coalescence methods are the well-known traditional
treatment processes, the efficiency of which depends on the size of the oil droplets in
wastewater. Chemical emulsion breaking is an effective way under proper application
[34, 35]. The coagulation and air flotation electrostatic and electrocoagulation separation
methods were also applied in the oily wastewater separation processes. However, these
methods would lead to a huge production of sludge and complicated operation problems.
Other methods such as microwave treatment ultrasonic wave treatment, thaw and heat
treatment [36] have been occasionally applied in special oily water (sludge) treatment in
recent years. Membrane separation has enjoyed great popularity over the last 30 years
and is becoming a promising technology. This technology has several advantages
including stable effluent quality and small area requirement. Moreover, no chemicals
addition is required. Many studies of membrane separation for oily wastewater treatment
have been reported, particularly in ultrafiltration (UF) and reverse osmosis (RO) with
organic membranes.
After a primary process of separation from the oil, the water still contains drops of oil in
emulsion in concentrations as high as 2000 mg/L, necessitating further treatment before it
may be discharged. Consequently, the international standards require more efficient
separation systems [37]. Hence operators have turned to membrane filtration schemes due
to their potential to minimize additional costs and disposal issues associated with current
technologies. Both, polymeric and ceramic membranes have been investigated under
various field conditions. These membranes are effective in separating the oils, emulsions,
and silts. However, they tend to foul through waxes and asphaltenes. Hence, to reduce
fouling, modification of the waxes and asphaltenes, and, to increase membrane
regeneration post-usage, the provision of an expedient, cost effective, and non-hazardous
procedure of membrane cleaning may be addressed. The key technical obstacles for the
18 | P a g e
integration of MF/UF/NF membrane filtration into the oil-field water treatment process
have been reviewed [38]. However, membrane fouling remains a major obstacle to the
application of membrane-based treatment of produced water for beneficial use.
Previous studies and researches on oily waste water treatment by using membrane have
been collected and summarised in table 2.4
Table 2.4: Studies and researches on different membrane’s technology
Ref Type of Influent Effluent Technology Notes

wastewater property property used
and operating
condition
Reyhania real produced Oil and grease : 42 Oil and two-stage A rectangular-sheet polymeric
et al. water ppm grease : ultrafiltration membrane Polyacrylonitrile
(2013) TSS: 108 ppm <1.5ppm process (PAN350) with a surface area
[39] Turbidity: 90 TSS : Trace of 66.15 cm2, purchased from
TOC: 109 ppm Turbidity:0.5 Sepro Company (America).
TMP: (1.5,3,5) bar TOC:35ppm
T: (25,40,50) ℃
CFV:
(0.5,0.75,1) m/s
Salahi et Synthetic and The oil UF membrane Five different Oil-in-water emulsions were
al. (2010) industrial oily concentration of was effective membranes were prepared by mixing
[40] wastewaters synthetic feed was and suitable used including: commercial grade gas–oil
treatment 0.1% for all for treatment two (Tehran refinery, IRAN),
from refinery experiments of the oily microfiltration deionized water and surfactant
wastewater to (MF) PS (0.1 μm) (Triton X-100 from
achieve up to and PS (0.2 μm) Merck).The surfactant was
94.1%, 31.6%, membranes and dissolved in water 10 min
96.4%, and three ultra- before addition of gas–oil.
97.2% removal filtration (UF) Surfactant was added as
of TSS, TDS, PAN (20 kDa), PS emulsifier to the mixture to
turbidity and (30 kDa) and stabilize the emulsions. A
oil-grease PAN (100 kDa) blender was used to mix the
content membranes. mixtures at high shear rates
(6000 rpm) for 30 min.
Santos Produced TOC: Oil and grease: Ultrafiltration , 300 L/h laboratory scale unit,
and water 52.9-354ppm 2-5 ppm two tubular supplied by Zenon
Wiesner Oil and grease: 16- Permeate flux: organic polymeric Environmental Inc. was
(1997) 485 pmm 100-200 operated in total recycle mode
[41] NTU: 4-86 L/m2.h using tubular, ultrafiltration
CFV: 3.53m/s membrane with surface area of
TMP: 350 kPa (306-327 cm2)
19 | P a g e
Sarakulski Oily UF Oil: 5000 Oil: 2- 4.2 Combination of Ultrafiltration experiments
et al. wastewater ppm ppm ultrafiltration/ were carried out on the
(1995) TDS: 520 TDS: 455-477 reverse osmosis tubular membranes made of
[42] mg/L mg/L processes. polyvinyl chloride (PVC),
TMP: Ultrafiltration polyacrylonitrile (PAN) and
0.2MPa system using cellulose acetate (CA),
T: 298K cellulosic and manufactured in laboratory
RO Oil:3.7ppm Oil: 0.2 ppm non-cellulosic
TDS: TDS: membranes
469mg/L 34mg/L
TMP:
0.2MPa
T: 298K
Anggun synthetic oil content: NTU: - The purposes are to determine
and produced 100ppm 0.96-1.13 microfiltration membrane
Ahmad water NTU: 1.4-3.6 cleaning effect by using NaOH
(2011) as cleaning solution, to
[43] determine concentration effect
of chemical cleaning agent in
membrane cleaning process as

well as period of cleaning.
Feng lin Oily TOC: 284ppm TOC: 13ppm MF multiple stage Total recycle model (permeate
wastewater Feed flow rate: Steady ceramic returned to feed tank)
(2006) 500L/hr permeate flux: membrane Membrane area: 4m2
[44] CFV: 1.64m/s 184 L/m2.hr
Pressure: 0.2MPa
Mueller et Oily water Concentration: Oil removal Two Crude oil from Hueneme field
al. (1997) 250-1000 ppm reach 99.9% microfiltration in California,
[45] ceramic Surface area: 45.3cm2
membrane
Hua et al. Oily TOC: 500 ppm Permeate flux: Cross-flow Aims:
(2007) wastewater TMP:0.05-0.2 MPa 30-170 L/m2.h microfiltration 1-study the effect of TMP on
[46] CFV: 0.17-1.7 m/s (MF) ceramic permeate flux
membrane with 2-study the effect of CFV on
50nm pore size permeate flux
Gilbert et Oil and grease: Oil and grease: Activated sludge removal efficiencies of 99 %
al. (2005) 147 mg/L 3.6 mg/L process. The were observed
[47] Total dissolved COD: 35 mg/L field-scale
solids: 35,023 Total produced water-
mg/L dissolved treatment process
COD: 431 mg/L solids: 34 consisted of:453-
mg/L L skimming and
20 | P a g e
preaeration unit
followed by a
945-L activated
sludge treatment
unit
SCHOLZ Synthetic 0.05-0.7 mg/L External During the different loading
and W. wastewater membrane stages of the MBR operation a
FUCHS containing fuel oil bioreactor (MBR) removal rate of 99.99% could
(2000) or lubricating oils be achieved for fuel-oil as well
[48] plus surfactants as lubricating oil at a hydraulic
with oil retention time of 13.3 h.
concentration
800-13000 mg/L
2.5 Membrane fouling

The use of membrane filtration in produced water process can be cause fouling in
membrane. Fouling is a process resulting in loss of performance of a membrane due to
deposition of suspended or dissolved. The effect of fouling is decrease of permeate rat e
and increase of pressure drop. There are 3 kinds of foulant: organic foulant, inorganic
foulant and biology foulant. Membrane fouling occurs through one or more of the
following mechanisms:
 Accumulation of solute and gradual irreversible changes in the polarized layer

(such as cake formation).
 Surface adsorption: deposition of solutes.
 Adsorption: deposition of solute within the membrane.
There are many factors contributing to fouling including surface properties (chemistry,
morphology, etc.), hydrodynamic conditions, ionic strength and solute concentration [49].
2.6 Membrane cleaning

Regularly scheduled cleaning of the membranes increases ceramic membrane life and
ensures thorough membrane performance. Cross-flow filtration is helpful in slowing
down membrane fouling but does not eliminate it. Therefore, all membrane-based
filtration processes require some form of periodic cleaning to remove the foulants.
Membrane cleaning may involve the removal of external foulants deposited on the
membrane surface as well as foulants embedded within the membrane pore [50].
21 | P a g e
The initial pure water permeate flux (Ji) of the membrane was first determined before
membrane separation. Then, membrane filtration of oily wastewater was conducted.
Periodic permeate flux (Jw) measurements were made until it reached a steady state. In
the next step, the procedure of membrane cleaning was conducted.
Membrane cleaning was carried out by using five different chemicals. They were: acidic
solution (HNO3, 0.2 mol/L), alkaline solution (NaOH, 0.5 mol/L), oxidant agent (NaOCl,
0.01 mol/L), chelating agent (EDTA, 0.2 mol/L) and surfactant (tween-80). The
membrane cleaning procedure was adapted from a previous study [51]. Firstly, the oily
wastewater was drained from the system. The membrane was then washed by circulating
a solution of chemical agent for 1 hour in order to restore the membrane permeability.
Finally, the system was rinsed using tap water and the washing procedure was completed
by rinsing with deionized water until the permeation reached neutral. The permeate flux
(Jf) was measured using distilled water after every cleaning operation. The cleaning
efficiency was evaluated with water flux recovery (WFR) [52].
WFR was defined as:
J f −J w
WFR= ∗100 (2.1)
J i−J w
2.7 Membrane theory
2.7.1 Transmembrane pressure (TMP)

The average transmembrane pressure was approximated as the average of the pressure
readings upstream and downstream of the membrane since permeate was discharged to
atmospheric pressure [53].
The calculation of TMP uses the formula:
( Inlet pressure of feed+ outlet pressure of retenate )

TMP= (2.2)
2
22 | P a g e
2.7.2 Cross-flow velocity (CFV)
For cross-flow velocity the following equation will be used [54]:
(Q f )
CFV =
[ ( π∗r 2)∗n ] (2.3)
Where, CFV: cross-flow velocity (m/s), n: number of channels in the membrane, r: radius
of the circular membrane channel (m), π: mathematical constant (3.14159), Q f: flow rate
(m3/s).
2.7.3 Flux
The permeate flux (J) is calculated by dividing the permeation volume by the product of
effective membrane area and the sampling time.
permeate volume collected

permeat flux= (2.4)
membrane area∗time
It takes SI units of m3/ (m2 s) or simply m/s.
2.7.4 Rejection (R)

Rejection relates to the solute quantity that permeates or is retained by a membrane.
Solute rejection by a membrane is usually defined as the reduction in the feed
concentration across the membrane. At any point in the filtration process, the apparent
rejection (instantaneous rejection), Ra, of a membrane is given by:
Cp
Ra =1− (2.5)
Cf
Where, CF is instantaneous solute concentration in the permeate stream; CP is

instantaneous solute concentration in the feed or retentate stream. Actually, the
concentration of the solute will be higher near the membrane surface compared to the
bulk of the liquid because of concentration polarization and cake fouling. Hence, the real
value of rejection, R , should be calculated a s shown below [55]:
r
Cp
Rr =1− (2.6)
Cg
Where, Cg : the solute concentration on the membrane surface.
23 | P a g e
2.7.5 Membrane filtration resistance
During the operation of membrane filtration processes, Flux decline under constant
operating conditions (TMP, CFV, etc.) occurred. This is because besides the membrane
resistance, the process still affected by concentration polarization, adsorption, gel-layer
formation and plugging of the pores. All these factors induce additional resistances on the
feed side to the transport across the membrane. Figure 2.11 shows types of resistance that
exerted at membrane.
Figure 2.11: Types of resistances during filtration process
The flow of solvent through the membrane can be described as being proportional to a
driving force ∆P, and inversely proportional to the membrane resistance Rm, and the
dynamic viscosity µ
∆P
Rm = (2.7)
µ∗J i
∆P
J= (2.8)
μ ( Rm + R cp + Rc + Ra + R p )
Where, Rm : membrane resistance, RP: pore-blocking, Ra: adsorption, Rc: cake layer
formation, Rcp: concentration polarization , ∆ P : driving force, µ : dynamic viscosity and
J i : pure water permeability, J: flux [56].
Chapter 3 : Experimental work
24 | P a g e
3.1 Design of Equipment
The membrane unit used in this experiment was manufactured by ZIBO DONGQIANG
environmental protection equipment Co. Ltd. (china). It consists of a feed tank (40 L),
ball valves, regulatory valves, centrifugal pump, pressure gauges, temperature meter,
rotameters, contacting junctions and control panel. Cooling system was added to the unit
to maintain a constant temperature during experimentation. Figure 3.1 shows the
flowsheet of the membrane filtration process.
Figure 3.1: Drawing of the setup for membrane unit
Table 3.1 illustrates the operating parameters of membrane filtration unit as it

recommended from manufacturer:
Table 3.1: Operating condition for the membrane unit from manufacturer
25 | P a g e
Operating parameter Range Unit
Flow for the pump m3

1-3
hr
Working pressure 0.2-0.4 MPa
2-4 bar
Maximum pressure 1 MPa
TMP 1 bar
100 kPa
Rotameter of permeate L
16-160
hr
Rotameter of retentate m3
1-6
hr
3.2 Experimental set-up

The feed tank was filled with total 24 litres of oily emulsion. The feed solution was
pumped by means of a circulation pump through the ceramic module. Then, by throttling
the pump motor-power adjustor and control valve, TMP and CFV were independent
regulated from 0.10 to 0.30 MPa and from 1.5 to 2.5 m/s, respectively. The permeation
sample was collected each 5 min interval, and the flowrate was measured by the permeate
flowmeter or by measuring the volume collected with time.A sample was also taken
from the permeate to measure the NTU value. A water cooling system was used to
prevent the change of temperature due to cycling of feed solution through pump. Figure
3.2 shows an apparatus of membrane filtration.
26 | P a g e
Figure 3.2: apparatus of membrane filtration.
Before each filtration performance experiment, the equipment was rinsed with distilled
water. After each test the membrane was first cleaned with NaOH solution, and then
rinsed with distilled water.
27 | P a g e
3.3 Chemicals
The chemicals used in the experiment were tap water, crude oil, salt and detergent. Table
3.2 shows some properties of the chemicals have been used at normal temperature and
pressure:
Table 3.2: Properties of chemicals have been used
Molecula
Chemical Density Dynamic viscosity
Formula r weight
name (kg/m3) (Pa.s)
(g/mole)
Tap water H2O 18 1000 0.001
Salt NaCl 58.44 2.165
Triton X-100 C 14 H 22 O ( C 2 H 4 O )(nn=9−10) 674 1.07 270*10-3(at 125 ℃ ¿
Crude Oil or Petroleum is simply unprocessed oil found deep beneath the earth’s surface.
It can range in colour from clear to black and can be found as a liquid or solid. Overall
properties of crude oils are dependent upon their chemical composition and structure. The
exact molecular composition varies widely from formation to formation but the chemical
element’s proportion varies over fairly narrow limits as table 3.3 illustrate:
Table 3.3: Composition by weight of oily chemical elements
Elements Percent range

Carbon 83 to 85%
Hydrogen 10 to 14%
Nitrogen 0.1 to 2%
Oxygen 0.05 to 1.5%
Sulfur 0.05 to 6.0%
Metals <0.1%
28 | P a g e
3.4 LaMotte (2020we) waterproof portable turbidity meter
Turbidity is an aggregate property of the solution, which is water in most cases. Turbidity
is not specific to the types of particles in the water. The particles could be suspended or
colloidal matter, and they can be inorganic, organic or biological. At high concentrations,
turbidity is perceived as cloudiness, haze or an absence of clarity in the water. Turbidity
is an optical property that results when light passing through a liquid sample is scattered.
The scattering of light results in a change in the direction of the light passing through the
liquid. This is most often caused when the light strikes particles in solution and is
scattered backward, sideways and forward. If the turbidity is low, much of the light will
continue in the original direction. Light scattered by the particles allows the particle to be
”seen” or detected in solution just as sunlight allows dust particles in the air to be seen.
The meter also allows the user to choose the units of measure for expressing turbidity.
Nephelometric turbidity unit (NTU) has been the standard for years [59]. Figure 3.2
shows turbidity meter that has been used.
Figure3.2: 2020we Portable turbidity meter
29 | P a g e
3.5 Membrane selection
The ceramic membrane used in this research was supplied by Zibo Dongqiang
environmental protection equipment Limited Company. It was an aluminium oxide (α-
Al2O3) membrane. Two kinds of pore size of membranes with average pore sizes of 100
nm and 200 nm were chosen in order to have MF process. According to the purpose of
acquirement (high permeate flux and acceptable permeate quality) of the oily wastewater
separation. The dimensions of the ceramic membrane are 1178 mm length, 25.4 mm
diameter with 7 lumens which with 6 mm diameter. Thus, the effective surface area was
0.16 m2. The membrane outlook is shown in Figure 3.3.
Figure3.3: The ceramic membrane outlook.
Table 3.4 The dimensions of membranes

used.
Table 3.4: Ceramic membrane dimensions

Length(mm) Diameter(mm) lumens Pore size Type of
membrane
1178 25.4 7 100 nm
1178 25.4 7 200 nm MF
3.6 Experimental procedures

Membrane characterizations were determined with water under various conditions of
TMP and fixed temperature. Then, the influences of variables such as TMP and CFV on
membrane filtration of oily wastewater were studied. Finally, membrane cleaning was
carried out.
3.6.1 Preparation of feed solution

The feed solution consists of water, detergent, crude oil and salt. Eight litters of water
was poured into the container, then 0.3 ml of detergent (Triton-X 100) and 0.5 g of salt
was added to the water, and finally 4 ml of crude oil was added to the solution in order to
have 500 ppm of crude oil in the solution. The feed was stirred at speed of 6000 rpm
30 | P a g e
using high speed shear mixer to be sure that the oil is well dispersed into solution. Three
batches was prepared for each set of experiments.
3.6.2 Operation of MF process

1. The experimental setup was rinsed with distilled water. The initial pure water
permeate flux (Ji) of the membrane was first determined before membrane
separation.
2. After connecting the membrane unit to the power, the feed tank was filled with a
total of 40 liters of oil emulsion and by opening the ball valve (V-1) under the
feed tank, the feed solution will go into the pipe.
3. By turning on the power (the green button), the feed solution was pumped by
means of a circulatory pump (P-1) through the ceramic module.
4. By controlling valves (V-4) and (V-5), TMP and CFV were independent regulated
from 0.10 to 0.30 MPa and from 1.5 to 2.5 m/s, respectively.
5. The permeation sample was collected each 5 min interval, and the sample volume
was measured. Several millimeters of permeation was remained for determination
of NTU later, the rest sample was returned to the feed tank.
6. A water cooler was used to prevent the fluctuation of temperature due to cycling
of feed solution using a pump. The cooling water is introduced through the jacket
of the feed vessel.
7. Before each filtration performance, the experimental setup was rinsed with
distilled water. And After each test the membrane cleaned.
8. Periodic permeate flux (J) measurements were made until it reached

approximately steady state.
9. The permeate flux (J) is calculated by dividing the permeation volume by the
product of effective membrane area and the sampling time.
31 | P a g e
10. After the filtration is finished, the liquid is drained by opening the draining
valves, then the power was turned off (the red button).
3.6.3 Cleaning procedure

After each operation of membrane process the membranes should be cleaned. Follow the
below procedure:
1. Drain the oily wastewater from the system.
2. Wash the system by circulating 2% NaOH solution for 2 hours in order to restore
the membrane permeability.
3. Rinse the system by using tap water until neutral permeates reaches.
4. Check the water flux of membrane after cleaning to ensure a difference of less
than 10% to the water flux before next filtration.
Note: Although the pure water permeate flux after membrane cleaning changes from time
to time for a used membrane, a difference of less than 10% of the water flux is ensured
for each group test.
3.7 Calibration curve

The calibration curve between oil concentration of solution and NTU (Figure 3.4) was
done for the range that can be read by turbidity meter with positive results. When the oil
content is high in the sample the reading gives negative numbers so we have to dilute the
samples by adding water.
32 | P a g e
Calibration curve
20
18
f(x) = 4.52 x
16
14
12
NTU
10
8
6
4
2
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5
Concentration (ppm)
Figure 3.4: calibration curve between NTU and ppm of solution
33 | P a g e
Chapter 4 : Results and Discussion
4.1 Effect of change TMP at fixed retentate flow rate on permeate

flux and NTU
m3 m3 m3
The effects of change in TMP at retentate flow rate (1 , 1.5 ∧2 ¿ on the permeate
h h h
flux were studied by using two types of microfiltration membrane 200 nm and 100nm .
The results obtained for the two sets of experiments are shown in the figures below.
4.1.1 Experiments of set one (200nm )

All experiment on set one were done by using 200 nm pore size membrane, permeate
flowrate and NTU were recorded for each 5 min during 60 min interval, retentate
flowrate was adjusted for each experiment, TMP were found by taking the average of
pressure gauge readings before and after the membrane module. The permeate flux and
CFV were calculated.
4.1.1.1 Experiment one at retentate flowrate=1m3/hr and TMP=2 Bar

The permeate flux, NTU and CFV change with time are shown in Figure 4.1.
34 | P a g e
Permeate flux vs Time
0
F lu x ( m 3 / m 2 .s) 0
0
0 10 20 30 40 50 60
Time ( min )
NTU vs Time
14
12
10
8
N TU
6
4
2
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.18
0.16
0.14
C F V (m / s)
0.12
0.1
0.08
0.06
0.04
0.02
0
0 10 20 30 40 50 60
Time ( min )
Figure 4.1: permeate flux vs. time (the top) , NTU vs time (the middle) and CFV vs time
(the bottom) for retentate flow rate=1m3/hr and TMP=2 Bar, 200 nm pore size membrane.
35 | P a g e
4.1.1.2 Experiment two at retentate flowrate=1m3/hr and TMP=1.5 Bar

0
0
F lu x ( m 3 / m 2 .s )
0
0 10 20 30 40 50
Time ( min)
NTU vs Time
25
20
15
N TU
10
0
0 10 20 30 40 50
Time ( min)
CFV vs Time
0.06
0.05
C F V (m / s)
0.04
0.03
0.02
0.01
0
0 10 20 30 40 50
Time ( min)
36 | P a g e
Figure 4.2: Permeate flux vs. time (the top) , NTU vs time (the middle) and CFV vs
time (the bottom) for retentate flow rate=1m3/hr and TMP=1.5 Bar, 200 nm pore size
membrane
4.1.1.3 Experiment three at retentate flowrate=1m3/hr and TMP=1 Bar

NTU vs Time
3
2.5
2
N TU
1.5
0.5
0
0 10 20 30 40 50 60
Time ( min )

0
0
F lu x ( m 3 / m 2 .s )
0
0
0
0
0
0
0
0
0 10 20 30 40 50 60
Time ( min )
37 | P a g e
CFV vs Time
0.01
0.01
0.01
C V F (m / s)
0.01
0
0
0
0
0
0 10 20 30 40 50 60
Time ( min )
Figure 4.3: Permeate flux vs. time (the top) , NTU vs time (the bottom) for retentate flow
rate=1m3/hr and TMP=1 Bar, 200 nm pore size membrane.
4.1.1.4 Experiment four at retentate flowrate=1.5m3/hr and TMP=1.5 Bar

38 | P a g e
NTU vs Time
35
30
25
20
N TU
15
10
0
0 10 20 30 40 50 60
Time ( min )

0
0
F lu x ( m 3 / m 2 .s)
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.01
0.01
0.01
C F V (m / s)
0.01
0.01
0
0
0
0
0
0 10 20 30 40 50 60
Time ( min )
39 | P a g e
(the bottom) for retentate flow rate=1.5 m3/hr and TMP=1.5 Bar, 200 nm pore size
membrane.
4.1.1.5 Experiment five at retentate flowrate=1.5m3/hr and TMP=1 Bar

NTU vs Time
2.5
1.5
N TU
0.5
0
0 10 20 30 40 50 60
Time ( min )

0
0
F lu x ( m 3 / m 2 .s)
0
0
0
0
0
0
0
0
0 10 20 30 40 50 60
Time ( min )
40 | P a g e
CFV vs Time
0.02
0.01
0.01
C F V (m / s)
0.01
0.01
0.01
0
0
0
0 10 20 30 40 50 60
Time ( min )
.
(the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1Bar, 200 nm pore size
membrane
4.1.1.6 Experiment six at retentate flowrate=2 m3/hr and TMP=1 Bar

41 | P a g e
NTU vs Time
20
18
16
14
12
N TU
10
8
6
4
2
0
0 10 20 30 40 50 60
Time ( min )
0
F lu x ( m 3 / m 2 .s )
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.01
0.01
0.01
C F V (m / s)
0.01
0.01
0
0
0
0
0
0 10 20 30 40 50 60
Time ( min )
Figure 4.6: permeate flux vs. time (the top) , NTU vs time (the bottom) and CFV vs time
for retentate flow rate=2 m3/hr and TMP= 1 Bar, 200 nm pore size membrane.
42 | P a g e
4.1.1.7 Analysis of NTU for 200 nm membrane
By using turbidity meter to measure NTU, the trend values of NTU are not fixed for one
pattern. Figures 4.1, 4.2 and 4.4 shows that, the NTU values increase with time (direct
proportional), while figures 4.3, 4.5 and 4.6 show inversely proportional between NTU
values and time. The NTU value for distilled water was 0.16 but the values of NTU for
oily water (Figure 4.7) emulsion are fluctuating, the maximum value reached was 40 and
the minimum was 0.67.
NTU vs Time 2 Bar :1m3/hr

45
1.5 Bar :1m3/hr
40
35 1 Bar :1m3/hr
30
1.5 Bar :1.5m3/hr
25
N TU
20 1 Bar :1.5m3/hr
15 1 Bar :2m3/hr
10
5
0
0 10 20 30 40 50 60 70
Time (min)
Figure 4.7 : NTU vs Time for 200 nm membrane
0.09 NTU vs Time

0.08
0.07
0.06
0.05
N TU
0.04
0.03
0.02
0.01
0
0 10 20 30 40 50 60 70
Time (min)
Figure 4.8 : NTU vs Time for distilled water
43 | P a g e
Normally the NTU should decrease during the process, but here at some experiments is
not so, when the results of NTU for 200 nm membrane is compared to the results of
distilled water it can be noticed that the NTU of operation conditions of 1 bar : 1.5 m 3/hr
was the best the result that 200 nm membrane could achieve because its range of NTU
values are less than 0.5 and it is closet results to the range of NTU distilled water.
4.1.2 Experiments of set two (100nm)

All experiment on set two were done by using 100 nm pore size membrane, permeate
flowrate and NTU were recorded for each 5 min during 60 min interval, retentate
flowrate was adjusted for each experiment, TMP were found by taking the average of
pressure gauge readings before and after the membrane module. The permeate flux and
CFV were calculated.
4.1.2.5 Experiment one at retentate flowrate=1m3/hr and TMP=2 Bar

44 | P a g e
0
F lu x (m 3 / m 2 .s )
0
0
0 10 20 30 40 50 60
Time ( min )
NTU vs Time
14
12
10
8
N TU
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.1
0.09
0.08
C F V (m / s)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0 10 20 30 40 50 60
Time ( min )
membrane
45 | P a g e
4.1.1.5 Experiment two at retentate flowrate=1m3/hr and TMP=1.5 Bar

0
0
F lu x (m 3 / m 2 .s)
0
0 10 20 30 40 50 60
Time ( min )
NTU vs Time
3.5
2.5
2
N TU
1.5
0.5
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.06
0.05
C F V (m / s)
0.04
0.03
0.02
0.01
0
0 10 20 30 40 50 60
Time ( min )
Figure 4.10: permeate flux vs. time (the top), NTU vs time (the bottom) and CFV vs
time (the bottom) for retentate flow rate=1 m3/hr and TMP= 1.5 Bar, 100 nm pore size
membrane.
46 | P a g e
4.1.1.6 Experiment three at retentate flowrate=1m3/hr and TMP=1 Bar

0
0
F lu x (m 3 / m 2 .s )
0
0 10 20 30 40 50 60
Time ( min )
NTU vs Time
2.5
1.5
N TU
0.5
0
0 10 20 30 40 50 60
Time ( min )
CFV vs Time
0.04
0.04
0.04
C F V (m / s )
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0.04
0 10 20 30 40 50 60
Time ( min )
membrane
47 | P a g e
4.1.2.4 Experiment four at retentate flowrate=1.5m3/hr and TMP=1.5 Bar
0
0
F lu x (m 3 / m 2 .s)
0
0
0
0
0
0
0
0
0 10 20 30 40 50 60
Time (min)
NTU vs Time
2.5
1.5
N TU
0.5
0
0 10 20 30 40 50 60
Time (min)
0.01
CFV vs Time
0.01
0.01
C F V (m / s )
0.01
0.01
0.01
0.01
0.01
0 10 20 30 40 50 60
Time (min)
(the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1.5 Bar, 100 nm pore size
membrane
48 | P a g e
4.1.2.5 Experiment five at retentate flowrate=1.5m3/hr and TMP=1 Bar
0
F lu x (m 3 / m 2 . s )
0
0 10 20 30 40 50 60
Time (min)
NTU vs Time
2
1.8
1.6
1.4
1.2
N TU
1
0.8
0.6
0.4
0.2
0
0 10 20 30 40 50 60
Time (min)
0.02 CFV vs time

0.02
0.02
0.01
C F V (m / s)
0.01
0.01
0.01
0.01
0
0
0
0 10 20 30 40 50 60
Time (min)
Figure 4.13: permeate flux vs. time (the top), NTU Vs time (the middle) and CFV vs
time (the bottom) for retentate flow rate=1.5 m3/hr and TMP= 1 Bar, 100 nm pore size
membrane.
49 | P a g e
4.1.2.6 Experiment six at retentate flowrate=2 m3/hr and TMP=1 Bar

0
0
F lu x (m 3 / m 2 .s)
0
0 10 20 30 40 50 60
Time (min)
NTU vs Time
3.5
3
2.5
2
N TU
1.5
1
0.5
0
0 10 20 30 40 50 60
Time (min)
0.01
CFV vs time
0.01
C F V (m / s )
0
0 10 20 30 40 50 60 70
Time (min)
membrane.
50 | P a g e
4.1.2.7 Analysis of NTU for 100 nm membrane
By using turbidity meter to measure NTU, the values of NTU are not fixed for one
pattern. Figures 4.15 shows that the NTU values increase with time (direct proportional),
while other figures have steady relation of NTU during the experiment. The NTU value
for distilled water was 0.16 (Figure 4.16) but the values of NTU for oily water emulsion
are fluctuating, the maximum value reached was 13.33 and the minimum was 0.71.
14 NTU vs Time
2 Bar :1m3/hr
12
1.5 Bar :1m3/hr
10
1 Bar :1m3/hr
8
NTU
1.5 Bar :
6 1.5m3/hr
4 1 Bar :1.5m3/hr
1 Bar :2m3/hr
2
0
0 10 20 30 40 50 60 70
Time (min)
Figure 4.15 : NTU vs Time for 100 nm membrane
0.7 NTU vs Time

0.6
0.5
0.4
N TU
0.3
0.2
0.1
0
0 10 20 30 40 50 60 70
Time (min)
51 | P a g e
It can be observed from the figure () that NTU at condition of 2 bar : 1 m3/hr increases
from 8 to 13.31 but NTU at the other conditions does not fluctuate and remains steady.
The values of NTU at 1 bar : 1.5 m3/hr are closet to the range of NTU in distilled water.
By comparing of the values of NTU of the two membrane it can be concluded that values
of this parameter for 100 nm membrane was more reasonable and reliable (expect at 2 bar
: 1 m3/hr) and it shows that 100 nm membrane was more effective to reduce the amount
of oil concentration and therefore the NTU.
4.2 Comparison of characteristics of the two membrane

The permeate flux, and CFV change with time for the two membranes are shown in
Figures 4.17 and 4.18.
52 | P a g e
0 Permeate flux vs Time (200 nm) 2 Bar :1m3/hr
0 1.5 Bar :1m3/hr

Permeate flux (L/m2 s)
1 Bar :1m3/hr
0 1.5 Bar :
1.5m3/hr
0 1 Bar :1.5 m3/hr
1 Bar :2m3/hr
0
0
0 10 20 30 40 50 60
Time (min)
0.18 CFV vs Time (200 nm)

0.16
0.14
2 Bar :1m3/hr
0.12 1.5 Bar :1m3/hr
0.1
CFV (m/s)
1 Bar :1m3/hr
0.08 1.5 Bar :1.5 m3/hr
0.06 1 Bar :1.5m3/hr
0.04 1 Bar :2m3/hr
0.02
0
0 10 20 30 40 50 60
Time (min)
flow rate=2, 1.5 and 1 m3/hr and TMP= 1, 1.5 and 1 Bar, for 200 nm pore size
53 | P a g e
0 Permeate flux vs Time 1 Bar :1m3/hr
0 1.5 Bar :1m3/hr
2 Bar :1m3/hr
0
Permeate Flux (L/m2 s)
1.5 Bar :
1.5m3/hr
0
1 Bar :1.5m3/hr
0 1 Bar :2m3/hr
0
0 10 20 30 40 50 60 70
Time (min)
0.1 CFV vs Time

0.09 1 Bar :1m3/hr
0.08 1.5 Bar :1m3/hr
0.07 2 Bar :1m3/hr
0.06 1.5 Bar :

CFV (m/s)
1.5m3/hr
0.05
1 Bar :1.5m3/hr
0.04
1 Bar :2m3/hr
0.03
0.02
0.01
0
0 10 20 30 40 50 60
Time (min)
flow rate=2, 1.5 and 1 m3/hr and TMP= 1, 1.5 and 1 Bar, for 100 nm pore size
54 | P a g e
4.3 Effect of CFV
To study the effect of CFV on the permeate flux, experiments were carried out under
CFV range of 0.009 – 0.16 m/s. The initial permeate flux of membranes with pore sizes
of 200 nm and 100 nm were 0.000197917 L/(m 2 .s) and 0.00011458 L/(m2 . S),
respectively.
The permeate fluxes decreased significantly in the early stage of filtration. However
higher CFV produced higher permeate flux. The largest permeate fluxes reached
0.000112847 L/(m2 s) and 0.00010069 L/(m2 s) with pore size of 200 nm and 100 nm,
respectively. The permeate flux at steady state of 200 nm membrane was not much larger
as expected than that of 100 nm membrane. Although CFV does not impose any
influence on permeate flux when pure water is used as feed solution, however, CFV can
influence the deposition of solute on the membrane surface.
High CFV value can increase permeate flux of membrane filtration, however, several
cautions must be paid. Turbulent flow may consume TMP of the system, which is likely
to result in the decline of permeate flux. Forceful turbulent is not recommended in the
MF membrane process. Koltuniewicz et al. [57] reported that CFV exerted a greater
effect for the high TMP than that at the low pressure. At lower pressure, the flux was
almost independent of CFV changes. Besides, increasing CFV needs to increase power
cost. The cost-effectiveness of system must be evaluated.
4.4 Effect of TMP

To study the effect of TMP on the permeate flux, experiments were carried out under
TMP range of 1 – 2 bar. As could be observed for each membrane, the initial permeate
flux had a high value. The permeate fluxes decreased sharply in the early stage of
filtration and then decreased slowly to a constant value. The permeate flux value was
strongly dependent on TMP conditions. Higher TMP resulted in higher permeate flux for
both membranes.
The largest permeate fluxes reached are 0.000112847 L/(m2 s) and 0.00048611 L/(m2 s)
under the highest TMP conditions for the membranes with its pore diameter of 200 nm,
100 nm, respectively.
55 | P a g e
The permeate flux at steady state of 200 nm membrane was not much larger as expected
than that of 100 nm membrane,. When solute is presented in the feed stream, the
influence of TMP on the permeate flux has both positive and negative effect. The positive
effect was that under higher TMP the droplets (both solvent and solute) passed through
the membrane pores rapidly, while the negative effect was that more and more oil droplet
accumulated both on the membrane surface and in the membrane pore, which resulted in
membrane fouling and decrease of permeate flux.
4.2 Effect of cleaning

Fouling is a major problem in all membrane operations. Fouling can be defined as the
irreversible deposition of retained particles, colloids, macromolecules, salts, etc., at the
membrane surface or inside the membrane at the pore wall, which causes a continuous
flux decline.Cross-flow filtration is often helpful in slowing down membrane fouling but
does not completely eliminate it [58]. Therefore, membrane cleaning is necessary.
In this study, membrane cleaning protocol was as follows. Firstly, the fouled 200 nm and
100 nm membranes were cleaned with chemical cleaner (sodium hydroxide (2% w/w).)
for 2 hours at TMP of 2 bar and retantate flow rate of 1 m 3/hr, then the system was rinsed
tap water until the permeate reached neutral. At last, the permeate flux was measured
again using distilled water to identity effect of membrane cleaning.
Figures 4.19 and 4.20 represent the permeate flux before and after of the cleaning:
56 | P a g e
Permeate flux vs Time (200 nm)
0
0
Flux (m3/m2.s)
before
0
after
0
3 5 7 9 11 13 15
Time (min)
Figure 4.19: distilled water at 1.5m3/h and 1.5 bar for 200 nm membrane
Permeate flux vs Time (100 nm)

0
0
Flux (m3/m2.s)
0 before
after
0
0
3 5 7 9 11 13 15
Time (min)
Figure 4.20: distilled water at 1.5m3/h and 1 bar for 100 nm membrane
The results of Figures 4.19 and 4-20 shows that flux was declined remarkably after we
tested after cleaning which means chemical cleaner had its influence and has cleaned
some oil drops in the pores but this amount is not sufficient and washing with hot water
before using NaOH solution should be used in order to have good cleaning and the initial
efficiency for membrane can be restored.
57 | P a g e
apter 5 : Conclusions and Recommendations for Future Work
5.1 Conclusions
In this study, two micro filter membranes with pore sizes of 200 nm and 100 nm was
selected to conduct the experiments and observe the effect of parameters such as CFV
and TMP on permeate flux and NTU. Totally 12 experiments were done (6 experiments
for each membrane) and the operation conditions were : 2 bar - 1 m 3/hr , 1.5 bar – 1 m3/hr
, 1 bar – 1 m3/hr , 1.5 bar – 1.5 m3/hr , 1 bar – 1.5m3/hr and 1 bar – 2 m3/hr. Membrane
filtration process is influenced by the characteristics of membrane material, the nature of
solution environment, and operating conditions.
By observing the results it was noticed that The permeate fluxes decreased sharply in the
early stage of filtration and then decreased slowly to a constant value. Higher CFV
produced higher permeate flux. The largest permeate fluxes reached 0.000112847 L/(m 2
s) and 0.00010069 L/(m2 s) with pore size of 200 nm and 100 nm, respectively. The
permeate flux value was strongly dependent on TMP conditions. Higher TMP resulted in
higher permeate flux for both membranes. The largest permeate fluxes reached
0.000112847 L/(m s) and 0.00048611 L/(m s) under the highest TMP conditions for the
2 2
membranes with its pore diameter of 200 nm, 100 nm, respectively.
Normally the NTU should decrease during the experiment but in some of experiments
such as : 2 bar - 1 m3/hr , 1.5 bar – 1 m3/hr for 200 nm membrane the results show NTU
increases with time which should not be, actually we were not able to find out effect of
CFV and TMP on the NTU.
Membrane fouling is predominantly responsible for the decline of the permeate flux.
Effective membrane cleaning is necessary to maintain large permeate flux. The procedure
of membrane cleaning proposed here was sodium hydroxide solution washing and results
showed this method was not sufficient , in order to restored the initial efficiency of
membranes washing with hot water should be added to cleaning procedure.
58 | P a g e
5.2 Recommendations for future work
This study shows the characteristics of membrane process effect of the TMP and CFV
parameters , but for better understanding the concepts and in order to reach eventual goal
of optimizing the process and reducing the energy consumption further study is required.
The following points should discussed in more details in future work:
 UF membrane: in this study only micro filtration membranes were used, by using
the UF membranes we would have more clear ideas about the membrane process.
 The relation of NTU with changes in TMP and CFV : further study should be
assess to find out of the relation on NTU to TMP and CFV.
 Cleaning: in this thesis only one method (washing with sodium hydroxide
solution) was used, further field tests are needed to modify the process including
when and how long the ceramic membrane should be cleaned and effect of
washing with hot water .
 Resistance models: this report mainly focused on CFV , TMP and permeate flux
but there are other factors such as resistance models which are necessary to know.
.
59 | P a g e
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WASTEWATER IN A MEMBRANE BIOREACTOR”, Wat. Res. Vol. 34, No. 14,
pp. 3621-3629, 2000
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membranes in the ultrafiltration of the aqueous extract of soy flour, J. Membr. Sci.,
114, 93-104.
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64 | P a g e
APPENDECES
Appendix A :Sample calculations

Here are some calculations which were done to conduct the results:
Table A.1: recorded data of permeate flow rate and NTU with time for a retentate flow
rate=1.5 m3/hr and TMP=1.5 Bar, 200 nm pore size ultrafiltration membrane
Permeate
Permeate Cross- CFV
Time flow rate surface
m3 section area m
(min) m3 area (m 2) flux ( 2 ) (s¿
( )
s
m .s (m2)
5 1.67E-06 0.16 1E-05 0.000198 0.008425

10 1.53E-06 0.16 9.6E-06 0.000198 0.007751
15 1.5E-06 0.16 9.4E-06 0.000198 0.007583
20 1.5E-06 0.16 9.4E-06 0.000198 0.007583
25 1.48E-06 0.16 9.3E-06 0.000198 0.007498
30 1.5E-06 0.16 9.4E-06 0.000198 0.007583
35 1.5E-06 0.16 9.4E-06 0.000198 0.007583
40 1.5E-06 0.16 9.4E-06 0.000198 0.007583
45 1.57E-06 0.16 9.8E-06 0.000198 0.00792
50 1.6E-06 0.16 0.00001 0.000198 0.008088
55 1.6E-06 0.16 0.00001 0.000198 0.008088
60 1.63E-06 0.16 1E-05 0.000198 0.008257
Surface area of membrane = 0.16 m2
6 mm 2
Cross-sectional area = π D2
× number of channels=
π× ( 1000) ×7
4 4
¿ 0.00019782 m2
m3
In experiment set 1(200 nm): at retentate flowrate=1.5 and TMP=1.5 bar
h
65 | P a g e
m3
1.6667 ×10−6
permeate flow rate s m
CFV = = 2
=0.008425
Cross−sectional area 0.00019782 m s
m3
1.6667 ×10−6
permeate flow rate s −5 m3
permeate flux= = =1.0416 ×10
surface area 0.16 m2 m2 . s
m3
In experiment set 2(100 nm): at retentate flowrate=1 and TMP=1.5 bar
h
m3
0.00001
permeate flow rate s m
CFV = = =0.05055
Cross−sectional area 0.00019782 m2 s
m3
0.00001 3
permeate flow rate s −3 m
permeate flux= = =0.0625 ×10
surface area 0.16 m2 m2 . s
Table A.2: recorded data of pressure from pressure gauges (pressure gauge of feed PG1
Set 1(200 nm )
Retentat
Needed
e PG1 PG2 TMP
TMP
Flow (bar) (bar) (bar)
(bar)
rate
2 2 2 2
m3 1.5 1.5 1.5 1.5
1
h
1 1 0.9 0.95
1.5 1.5 1.4 1.45
m3
1.5
h 1 1.2 0.95 1.075
66 | P a g e
m3
2 1 1 0.5 0.75
h
m3
To find TMP: For example in Set 1(200 nm) at 1
h
Pressure gauge 1 reading (before membrane) = 2 bar
Pressure gauge 2 reading (after membrane) = 2 bar

TMP=
2
( 2+ 2 ) ¯
¿ =2 ¿
2
Table A.3: recorded data of pressure from pressure gauges (pressure gauge of feed PG1
and retentate pressure
Set 2(100 nm )
gauge PG2) for a
Retentat
Needed retentate flow
e PG1 PG2 TMP
TMP
Flow (bar) (bar) (bar) rate=1, 1.5 and 2
(bar)
rate
m3/hr for 100 nm pore
2 1.9 1.75 1.825
size m3 ultrafiltration
1 1.5 1.5 1.3 1.4
h membrane
1 1 0.8 0.9
1.5 1.5 1 1.25
m3
1.5
h 1 1 0.2 0.6
m3
2 1 1 0.5 0.75
h
67 | P a g e
m3
To find TMP: For example in Set 2(100 nm) at 2
h
Pressure gauge 1 reading (before membrane) = 1 bar
Pressure gauge 2 reading (after membrane) = 0.5 bar

TMP=
2
(1+ 0.5 )
¿ =0.75 ¯¿
2
Appendix B
Table A.4: recorded data of permeate flow rate and NTU and corresponding
ppm by using calibration curve with time at retentate flow rate= 1.5 m3/hr
and TMP= 1 Bar, for 100 nm pore size ultrafiltration membrane
Time (min) permeate flowrate (L/h) NTU ppm
5 12.96 1.87 18.83182
10 12.12 1.19 11.98389
15 10.2 1.04 10.47331
20 9.48 1.01 10.1712
25 8.4 0.99 9.969789
30 7.8 0.97 9.768379
35 7.08 0.93 9.365559
40 6.72 0.81 8.1571
45 6.12 0.8 8.056395
68 | P a g e
50 5.88 0.77 7.75428
55 5.76 0.75 7.55287
60 5.64 0.71 7.15005
69 | P a g e

Sohar University: Oilfield Produced Water Treatment Using Membrane Technology

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Sohar University

Oilfield Produced Water Treatment

Sadegh Asadzadeh, Maroa Al-Jahwari, Yasmine Al-Senaidi

A Final Year Report

Submitted to Sohar University

in partial fulfilment of the

requirements for the degree of

Sohar, Sultanate of Oman, June 2015

Supervised by: Dr. Ahmed Jawad Ali Al-Dallal

We further permit Sohar University to reproduce this thesis by repetition or by other

TMP Transmembrane pressure (bar)

CFV cross-flow velocity (m/s)

PPI Parallel plate interceptors

CPI Corrugated plate interceptors

DAF Dissolved air flotation

TOC Total organic carbon (mg/l)

O&G Oil and gas (ppm)

MWCO Molecular weight cut-off

NTU Turbidity (dimensionless)

TSS Total suspended solid (mg/l)

TDS Total dissolved solid (mg/l)

Ji Initial pure water permeate flux (m3/ (m2 s))

WFR Water flux recovery

n Number of channels in the membrane

r Radius of the circular membrane channel (m)

Qf Permeate flow rate (m3/s)

CP Instantaneous solute concentration in the feed

CF Instantaneous solute concentration in the permeate stream

Cg Solute concentration on the membrane surface

1.2 Objective of the thesis...............................................................................................2

Chapter 2 Literature Survey.................................................................................................3

2.1 Produced water management.....................................................................................3

2.1.1 Produced water source........................................................................................3

2.1.2 Conventional treatment of produced water.........................................................4

2.2.2 Membrane material...........................................................................................11

2.2.3 Pressure driven processes.................................................................................12

2.2.4 Membrane module............................................................................................12

2.2.5 Membrane operation.........................................................................................16

2.3 Advantages of using membrane technology............................................................17

2.4 Membrane treatment of oily wastewater.................................................................18

2.5 Membrane fouling...................................................................................................21

2.6 Membrane cleaning.................................................................................................21

2.7.1 Transmembrane pressure (TMP)......................................................................22

2.7.2 Cross-flow velocity (CFV)...............................................................................23

2.7.4 Rejection (R).....................................................................................................23

2.7.5 Membrane filtration resistance.........................................................................24

Chapter 3 : Experimental work.........................................................................................25

3.1 Design of Equipment...............................................................................................25

3.2 Experimental set-up.................................................................................................26

3.4 LaMotte (2020we) waterproof portable turbidity meter..........................................29

3.5 Membrane selection.................................................................................................30

3.6 Experimental procedures.........................................................................................30

3.6.1 Preparation of feed solution..............................................................................31

3.6.2 Operation of MF process..................................................................................31

3.6.3 Cleaning procedure...........................................................................................32

3.7 Calibration curve.....................................................................................................32

Chapter 4 : Results and Discussion...................................................................................34

4.1.1 Experiments of set one (200nm )......................................................................34

4.1.2 Experiments of set two (100nm).......................................................................42

4.2 Comparison of characteristics of the two membrane..............................................50

4.3 Effect of CFV..........................................................................................................53

4.4 Effect of TMP..........................................................................................................53

4.5 Effect of cleaning.....................................................................................................54