4th semester Internship Report on

MEMBRANE PROCESSES FOR REMOVING OF OIL AND

ARSENIC FROM WATER

Submitted to

DEPARTMENT OF CHEMICAL ENGINEERING

By

Uddipta Jyoti Bhuyan(18/329), Bishal Deep nath(19/532),

Dibendu Das(18/296),Ronit Dutta(18/129)

DEPARTMENT OF CHEMICAL ENGINEERING

Assam Engineering College,Jalukbari

Session 2020
 CERTIFICATE

It is to certify that MR. Bishal Deep Nath, Mr. Ronit Dutta, Mr.
Uddipta Jyoti Bhuyan, and Mr. Dibendu Das of 4th semester,
Chemical Engineering, Assam Engineering college have successfully
completed their internship report on the topic “MEMBRANE
PROCESSES FOR REMOVING OF OIL AND ARSENIC
FROM WATER” under the guidance of Mr. Souradip Choudhury
during the academic session of 2019-2020.

___________ _______
Souradip Choudhury Date
M.Tech IIT Guwahati
Faculty Dept Of Chem Engg
Assam Engineering college.
 ACKNOWLEDMENT

We take the opportunity to express our sincere gratitude and heartiest

thanks to our honorable guide Mr. Souradip Choudhury, Faculty of Chemical
Engineering Department Assam Engineering College for his guidance and
supervision as well as for providing necessary information regarding the
internship and also for his support in completing the work.

Yours sincerely,

SRI BISHAL DEEP NATH 19/532

SRI UDDIPTA JYOTI BHUYAN 18/329
SRI RONIT DUTTA 18/129
SRI DIBENDU DAS 18/296
 ABSTRACT

Water contamination by heavy metals, cyanides and dyes is

increasing globally and needs to be addressed as this will lead to water
scarcity as well as water quality. Different techniques have been used to
clean and renew water for human consumption and agricultural purposes
but they each have limitations. Among those techniques, membrane
technology is promising to solve the issues. Nanotechnology present a
great potential in wastewater treatment to improve treatment efficiency of
wastewater treatment plants. In addition, nanotechnology supplement
water supply through safe use of modern water sources. This chapter
reviews recent development in membrane technology for wastewater
treatment mainly for pollutant ARSENIC and OIL. Different types of
membrane technologies, their properties, mechanisms advantages,
limitations and promising solutions have been discussed.
 CONTENTS

CHAPTER CONTENTS PAGE-NO

1 INTRODUCTION 1-2

2 TYPES OF MEMBRANE 3-5

PROCESSES

3 ADVANTAGES AND 6-7

LIMITATIONS

4 PROCESS DESCRIPTION 8-14

5 CONCLUSION 15

4
 CHAPTER = 1

INTRODUTION

1.1 MEMBRANE PROCESS

Clean water is important for every living organism to withstand life, but
due to rapid increase in growth population and industrialization, there is more
demand for clean, safe and drinkable water. About 97% of water is stored in
oceans as salty water which is not good for human consumption or agricultural
use, only less than 3% water on planet available for drinking and agricultural
use. Most available water is highly contaminated by effluent from agricultural
and industrial activity and cannot be consumed therefore water quality and
quantity are the main problems that need to be solved. Removal of
contaminants/water pollutants is required as to avoid negative effects on the
environment as well as human health.

Membrane water treatment is a process that removes unwanted

constituents from water. A membrane is a barrier that allows certain substances
to pass through while blocking others. Water treatment facilities use various
types of membrane and processes to clean surface water, ground water, and
waste water to produce water for domestic and industrial and drinking purpose.

There are several different types of membrane that can be used to treat
water depending on the contaminants that need to be removed and the end-users
desired product water quality.

Membrane filtration uses membrane to remove particles from water. The

process is similar to conventional sand or media filters in that suspended solids
are removed, but generally dissolved solids are not removed. Membrane
filtration processes can operate under pressure or vacuum. Membrane filtration
is commonly used to treat wastewater to remove bacteria and some virus.

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1.2 PROPERTIES

Properties of water treatment membrane are,

 Compactness
 Low tangential flow resistance
 Uniform velocity distribution without dead regions
 Easy maintenance and cleaning
 Low unit coast

1.3 OIL AS A POLLUTANT

Oil cannot dissolve in water and forms a thick sludge in water. This
suffocates fish, gets caught in the feathers of marine birds and sea otters. Oil is
toxic and harmful to plants and animals and threat to their habitats. Oil can
make drinking water sources unfit for use. Oil contamination can make water
unsuitable for irrigation.

1.4 ARSENIC AS A POLLUTANT

Arsenic is naturally present at high levels in the groundwater of a number

of countries. Arsenic is highly toxic in its inorganic form. Contaminated water
used for drinking, food preparation and irrigation of food crops poses the
greatest threat to public health from arsenic. Long-term exposure to arsenic
from drinking water and food can cause cancer and skin lesions. It has also been
associated with cardiovascular diseases and diabetes. In utero and early
childhood exposure has been linked to negative impacts on cognitive
development and increased deaths in young adults. The most important action
in affected communities is the preventions of further exposure to arsenic by
provision of a safe water supply.
CHAPTER = 2

2
 TYPES OF MEMBRANE PROCESSES

2.1. MICROFILTRATION

Microfiltration is a pressure driven process where separated compounds

are 0.1–0.2 um such as nanoparticles. It is regarded as the first pre-treatment of
NF and RO membrane processes. MF removes little or no organic matter;
however, when pre-treatment is applied, increased removal of organic material
can occur. MF can be used as a pre-treatment to RO or NF to reduce fouling
potential. The main disadvantages of MF is that it cannot eliminate
contaminants (dissolved solids) that are <1 mm in size. In addition, MF is not
an absolute barrier to viruses. However, when used in combination with
disinfection, MF appears to control these microorganisms in water.

2.2. ULTRAFILTRATION

Ultrafiltration membrane process can separate compounds between 0.005

≈ 10 um which is between MF and RO. UF membranes are highly prominent
water filters with low energy consumption in removal of pathogenic
microorganisms, macromolecules and suspended maters among
others .However, UF has some limitations including its inability to remove any
dissolved inorganic substances from water and regular cleaning to maintain
high pressure water flow. A synthetic procedure for hybrid ultrafiltration
membrane for water treatment was developed. It used wet-phase inversion
method with polysulfone and graphene nanoplatelets modified with poly
(styrene) to obtain their membranes. ZnO was deposited on one surface of the
membrane with polymers that are soluble in water. In a certain, the modified
GO-membrane showed 2.6 times better flux recovery compared to the
unmodified membrane and this shows that it is wise to modify membrane with
GO to increase flux recovery. It used a simple method known as UV induced
amination which has high flux UF membrane found to be resistant to organic
fouling, and the resulting membrane can be applied in waste water treatment
application. Incorporating hydrophilic materials onto the surface of these
polymers will lead to more hydrophilic surface membrane.

3
2.3. NANOFILTRATION

NF is capable of removing ions that contribute significantly to the

osmotic pressure hence allows operation pressures that are lower than those RO.
For NF to be effective pre-treatment is needed for some heavily polluted waters;
Membranes are sensitive to free chlorine. Soluble elements cannot be separated
from water. In a study, PMIA/GO composite nanofiltration membranes were used
for water treatment. The prepared composite membrane had greater hydrophilic
surface which gave rise to high pure water flux compared to that of the pure
polymer (PMIA). The results obtained showed high dye rejection and enhanced
fouling resistance to bovine serum albumin (BSA). On reporting NF membrane
for textile waste water treatment, the prepared membrane displayed good
removal of heavy metal ions, common salts and dyes, showing high removal
efficiency toward metal ions and cationic dyes. On reporting of nanofiltration
membranes for dye (Congo red and direct red) and salt rejection, the results
showed high dye rejection and low salt rejection which shows the possibility of
the salt reuse in FO.

2.4. FORWARD OSMOSIS

FO is a natural occurrence where the solvent moves from a region of

lower concentration to the region of higher concentration across a permeable
membrane. This method is found to be highly efficient with low rate production
of brine and is well studied as it promises to solve water problems worldwide,
however regeneration of the draw solution is highly expensive for desalination
processes hence the use of nanofiltration or reverse osmosis for regeneration of
draw solution.

2.5. REVERSE OSMOSIS

4
 RO is pressure driven technique used to remove dissolved solids and
smaller particles; RO is only permeable to water molecules. The applied
pressure on RO must be enough so that water can be able to overcome the
osmotic pressure. The pore structure of RO membranes is much tighter than
UF, they convert hard water to soft water, and they are practically capable of
removing all particles, bacteria and organics, it requires less maintenance. Some
disadvantages include the use of high pressure, RO membranes are expensive
compared to other membrane processes and are also prone to fouling. In some
cases, high level of pre-treatment is required. RO has extremely small pores and
able to remove particles smaller than 0.1 nm. On reporting of RO membranes
coated with azide functionalized graphene oxide hence created smooth,
antibacterial and hydrophilic membrane, which removed Escherichia coli and
reduced BSA fouling.

5
 CHAPTER = 3
ADVANTAGES AND LIMITATIONS

Compares the advantages and limitations of various membrane technologies

3.1 Reverse Osmosis

Advantages:
* Higher oil removal (>99%) e.g., treat saline oily waste.
* Removes dissolved contaminants.
* Higher quality effluent.
Limitations:
* High pressure requirements.
* Membrane fouling issued caused by the trace amount of oil & grease.

2. Forward Osmosis (FO):

Advantages:
* Higher oil removal.
* Low membrane fouling comparison with other pressure driven membrane
process.
* Low or no hydraulic pressures requirement.
* The equipment used is very simple and membrane support is less of a
problem
Limitations:
* Concentration polarization (CP) issues.
3. Nanofiltration (NF):
Advantages:
* Higher oil removal, large organic molecule (e.g., surfactant), hardness
removal and divalent salts removal.

6
 * Consumes lower energy in comparison with RO processes.
* Compact module.
Limitations:
* Higher energy consumption than FO.
4. Microfiltration (MF):
Advantages:
* Micron and nano-sized particulates (e.g., emulsified oil/grease).
* Compact modules.
* Low energy cost.
* No degradation due to heating.
* No extra safety considerations as in high voltage demulsification.
Limitation:
* High energy consumption.
* Membrane fouling of low molecular-weight MW organic.
5. Ultrafiltration (UF):
Advantages:
* Effective in the removal of oily microemulsions.
* Superiority of low energy consumption and high efficiency.
* No chemical preparation involved.
Limitations:
* Low flux.
* Membrane fouling by property of extremely hydrophobicity

7
 CHAPTER = 4

PROCESS DESCRIPTION

4.1 REMOVAL OF ARSENIC FROM WATER BY

MEMBRANE PROCESSES

The maximum contaminant level (MCL) of arsenic in drinking water has

been reduced to 10ppb by European legislation as well as by international
organizations. To meet these strict standards, conventional technologies for
removing arsenic from drinking water have been reconsidered and advanced
ones have been under development in recent years. These methods
have been examined in this study in order to understand the
mechanism of arsenic removal, to identify the main factors influencing
process performance and to assess their overall effectiveness.
Bench-type experiments have also been carried out, using NF
and RO membranes, over a range of arsenic concentration in the feed
water of practical interest. It is concluded that RO membranes are
suitable for meeting the stringent maximum contaminant level
(MCL), although some process of membrane process design still
need attention.

Pressure-driven membrane processes

microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse
osmosis (RO). NF and RO primarily remove constituents through chemical
diffusion. MF and UF primarily remove constituents through physical sieving.
Membrane processes can remove arsenic through filtration, electric charge
repulsion, and adsorption of arsenic-bearing compounds. MF efficiency for
arsenic removal is highly dependent on size distribution of arsenic-bearing
particles in the source water. MF pore size is too large to substantially remove
dissolved or colloidal arsenic. To increase removal efficiency in source waters
with a low percentage of particulate arsenic content, MF can be combined with
coagulation processes. Ultrafiltration processes are generally capable of
removing some colloidal and particulate constituents. However, if the
membrane is charged, the mechanism of as removal changes and the rejection

8
increases. Developments in membrane technology have produced nanofiltration
membranes (NF) with higher selectivity and increased water flux at much lower
operating pressure. In addition, because arsenic is typically present in natural
waters as a divalent oxyanion there has been much interest in the use of NF
membranes, which are known to be quite effective at removing divalent ions.
To apply the NF membrane process to arsenite-contaminated groundwater, the
pre-oxidation of arsenite to arsenate must be considered. A high concentration
of iron in ground water is expected to help the oxidation. If arsenite is
predominant in water, the NF processes cannot satisfy the recent MCL for
potable water because its removal is relatively low. A solution to this problem is
the oxidation of as (III) to as(V) or the use of RO membrane processes.RO

produces nearly pure water by maintaining a pressure gradient across the

membrane greater than the osmotic pressure of the feed water [11]. Overall, RO
is capable of achieving finished water arsenic concentrations below 0.002 mg/L
when arsenic is present as as(V) Research has shown that the rejection of as[V]
can be 94-100% and the rejection of As [III] 65-99% for neutral pH and without
pre-chlorination. The rejection of total Arsenic tends to be greater for low feed-
water concentrations. The wastewater (concentrate) from the reverse osmosis is
reportedly close to 10% of feed water. The arsenic removed is concentrated in
the wastewater; there is no solid waste (sludge) produced by the RO process
itself. RO processes tend to remove useful substances from water (water pure in
salt). Thus, in a unit producing potable water, a further treatment may be
necessary.

4.2 STEPS FOR EXPERIMENT

The initial solutions of arsenic are prepared by dissolving NaHAsO4.7H2O in

deionized water. A high-pressure stirred cell is employed, using membranes
with
effective surface area of approx. 20 square cm. The cell is made of stainless
steel and its capacity is approx. 200ml. The solution in the cell is agitated using
a magnetic stirrer. High-pressure nitrogen is used to adjust the pressure at the
desired level. In RO experiments a TFC-HR (thin-film-composite-high-
rejection) low-pressure aromatic polyamide membrane by Koch was used. This
membrane is employed for brackish water desalination with a typical rejection
in NaCl 91% and operating pressure of 10 bar. In NF experiments a TFCS (thin-
film-composite-high-rejection) low-pressure aromatic polyamide membrane by
Fluid systems was used. This membrane is usually employed for water

9
softening with an operating pressure of 7 bar. Arsenate can be measured by a
slight modification of a phosphate determination method. Arsenate like
phosphate forms a blue complex with molybdate, which allows
spectrophotometric determination. Before the experiments, the membrane was
immersed in deionised water for approx. 24hrs. Solutions with various initial
concentrations were prepared. 150ml of the solution was placed in the cell and
10 bar pressure was applied. Samples of the permeate were collected every 20
min and their volume, pH, conductivity and concentration were measured.
Before the experiments using NF membranes, 250 ml of deionised water was
filtered through the membrane in the cell. The following steps were similar to
those with RO membranes.

The experiments with NF and RO membranes were conducted in the

dead-end mode of operation. Consequently, the salts concentration in the
concentrate tends to increase with time. Experiments using NF membranes
showed that the concentration of the permeate increased during the test. On the
contrary, when RO membranes were used the concentration of the permeate
remained nearly stable and very low. Two examples of Experiments using NF
membranes show that as the bulk concentration increases, the rejection of
arsenic is reduced. On the contrary, the as rejection of the RO membranes,
despite the scatter, is very high, in the range of 80% to 97% regardless of the
initial concentration in the feed water. Although arsenic rejection is high by
using the RO membrane, for balk concentrations greater than 200ppb the as
concentration in permeate is greater than 10ppb (MCL). On the contrary, for
lower balk concentrations (but yet far greater than the MCL), the concentration
of the permeate is lower than 10 ppb. Therefore, we can conclude that RO
filtration can be used as a final step of arsenic-polluted-water treatment. During
the tests, the pH of permeate was reduced, which was attributed to the
dissociation of arsenate salts in the feed water and the high rejection of hydrated
arsenate ions. Using RO membranes, the permeate conductivity stabilizes to
values near conductivity of the feed water. Indeed, low-pressure RO membranes
do not produce water with very low conductivity, permitting a significant
amount of salts from feedwater to pass through. The increase of salt
concentration in the cell leads to a reduction of permeation rate (as expected. In
conclusion, low-pressure RO membranes are suitable for meeting the stringent
maximum contaminant level (MCL) for feedwater with relatively low arsenic
concentration

10
4.3 Membrane technology enhancement in oil
Membrane separation processes have become an emerging technology for the
treatment of oily wastewater due to high oil removal efficiency and relatively
facile operational process
With the advent of modern drilling technology namely sand-tar, hydraulic
fracturing and enhanced oil recovery, the amount of waste water to be treated
before reuse and/or discharge to the environment has increased manifold in
recent time. The treatment of produced water and refinery waste water from the
oil industry has been traditionally done by physical as well as chemical
processes. The use of membrane technology for the produced and refinery
waste water treatment has been recent phenomenon and active research has
been focused to enhance the efficiency and life time of the membrane during the
operation of the waste water treatment. In this review we briefly focus on the
produced and refinery waste water treatment by primary and secondary
treatment in historical perspective followed by focusing on various membrane
technologies starting from microfiltration (MF), ultrafiltration (UF),
nanofiltration (NF) and reverse osmosis (RO). Finally, we also focus on the
membrane distillation (MD) in combination with forward osmosis (FO) as
potential future technology.

Pollution by oily waste water, which is also known as produced water, has
become one of the major worldwide issues as the consequences of rapid
industrialization in oil and gas, petrochemical and metallurgical industries.
Serious oil spill accidents due to oil exploration and transportation has also
further exacerbated problems. Other than oil and grease, typical oily wastewater
also contains highly toxic substances, hydrocarbon compounds, heavy metals
and suspended solid particles. Hence, the generation, discharge and leakage of
oily waste from these industries have severely threatened public health and
affected the marine ecosystem. Additionally, the presence of wastewater has
also caused the deterioration of crop production and devastation of natural
landscape. With the booming of oil and gas production, the water community
has urgently called for promising approaches for oily wastewater treatment. As
the management of oily wastewater has imposed. considerable costs and
challenges to the oil and gas industry, there is an urgent need to explore more
cost-effective and energy-efficient technique to treat oily wastewater. Among
the wide range of contaminants found in oily waste water, the separation of oil
and grease presents the most challenge task. These oil constituents exist in the
form of dispersed oil with size ranges from 20 to 150 µm, stable emulsified oil

11
with droplet size <20 µm and free-floating oil with size >150 µm . Commonly,
oily wastewater has been treated in a number of conventional processes that
involve the separation of oil/water emulsion, which is mostly based on physical
processes such as adsorption, flotation, and coagulation.

The oily waste water discharge from industries such as metallurgical,

transportation, petrochemical, and petroleum refineries has cumulatively
contributed to the significant amount of waste o the water body. The typical oily
wastewater normally consists of 50–1000 mg/L of oil and grease contents,
depending on the nature and origins of the crude oil as well as their
demulsification efficiency in the water. The conventional disposal practices
have led to serious environmental pollution that has consequently posed severe
hazards and threats to the aquatic ecosystem. Hence, treatment and removal of
oily substances has become a critical aspect for the pollution control. Generally,
the total oil and grease found in the oily wastewater discharged should be
controlled in the range of 10–15 mg/L based on the environmental regulations
set by most of the countries. Unfortunately, traditionally applied approaches for
oily waste water treatment have been found in adequate to fulfil the requirement
of various process industries to comply the discharge and reuse standards. In the
recent decade, membrane technology has been recognized as an attractive
alternative for oily wastewater treatment due to their efficiency in removing
small oil droplets and offer treated water with a higher quality for reuse. For
years, polymeric and ceramic membranes have been feasibly applied in various
membrane processes to treat oily waste water. Depending on the size, charge,
and other water chemistries of the discharge components, membrane
technologies with different driving forces have been used for the oil-water
separation.
MF and UF are two commonly applied membrane processes to separate
the oil/water mixture. Despite the advantage of high water flux, asymmetric
MF, and UF membranes that consist of relatively loose and large pores are
inadequate to effectively reject smaller and stable emulsified oil particles.
Current advancement in UF for oily wastewater mainly focuses on the design of
anti-fouling membranes through the accomplishment of novel strategies that
involve the use of nanomaterials and other functional materials.
RO is a very promising separation technology to yield high quality treated water
owing to the almost complete rejection of most of the components found in oily
wastewater. Over the past decade, a considerable amount of studies has
evidenced the possibility of using RO to treat produce water. RO has been

12
prevailingly used for produced water desalination to generate fresh water to be
reused at the oil and gas industries. Due to the high susceptibility towards oil
and hydrocarbon fouling, RO process normally requires effective pre-treatment
for oil and grease removal. Infect, the oil and grease contents in the RO feed
should be reduced to <0.1 mg/L, as recommended by most of the membrane
manufacturers.
One attractive alternative of conventionally pressure driven processes is FO.
Compared to commonly used UF, this osmotically driven process is less energy
intensive, while demonstrating better oil rejection and lower fouling tendency.
In order to be competitively used in both bench and industry scales, the
challenges deal with the membrane performance and economic viability of draw
solution regeneration must be resolved. Currently, the FO membrane
improvement is focused on the design of TFC and thin film nanocomposite
(TFN) with desired characteristics. As a rule of thumb, a technological feasible
draw solution should allow high water flux and low reverse salt flux to
minimize the salt leakage as being easily recovered to improve energy
efficiency. Currently, a broad range of draw solutions with a promising FO
performance and easy regeneration features has been explored.

In the integrated system that consists of several stages of membrane processes,

loose membranes such as UF and MF are used in the pre-treatment unit to
remove large oil droplets before subjected to more selective RO or MD
processes. While trace amounts of oil can still be detected in the permeate of
MF and UF processes, RO and MD worked as an enhanced treatment process to
further remove the small oil droplets in order to achieve almost complete oil
removal and obtain high-quality water. A recently developed FO-RO pilot
system for produced water treatment has evidenced the production of high
quality permeate. In this hybrid system, commercial cellulose triacetate spiral-
wound FO membranes were used as pre-treatment unit of raw produced water.
The diluted draw solution was re-concentrated by the downstream RO system
and returned to the FO system in a closed loop. Rejection of above 99% was
observed for the major components found in the produced water such as salt
ions, n-alkanes and fatty acids. Integrated UF-FO-MD system has also been
reported to treat oily wastewater. The osmotic pressure difference and vapor
pressure difference rendered by high salinity and temperature oily wastewater
was used as the driving forces of the FO process and MD process, respectively.
Further treatment using MD also allows the continuous regeneration and reuse
of the draw solution. Such an integrated system can be promisingly utilized to

13
realize simultaneous oil recovery and energy utilization while achieving high
quality water regeneration.

14
 CHAPTER= 5

CONCLUSION

RO appears to be the most effective and reliable process to be employed

as a final stage of potable water treatment. However, some issues of membrane
process design still need attention, such as optimization of applied pressure
leading to reduced energy requirements, as well as overall economic appraisal.
Membrane separation technology is one of the promising separation
technologies in the treatment of oily wastewater. The necessity of water for
living organisms increases the responsibility of the researcher to provide pure
water as much as less cost. Membrane separation process is economically
effective as compared to other commercial methods. The continuous and
increasing efforts in development of efficient membranes provide an effective
and economically feasible process for oily wastewater treatment.

15
 REFERENCES

[1] Researchgate.net/publication

[2] Desline.com

[3] CEN Online, sup membrane separates oil and water, YouTube video

[4] Intech Open

[5] Res.mdpi.com

[6] sciencedirect.com

[7] colloid.ch

[8] Indian Journal of Chemical Technology Vol 14, September 2007, pp 441-
450

[9] Researchgate.net

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