INDIAN INSTITUTE OF TECHNOLOGY

GUWAHATI

CL 599: SCIENTIFIC COMMUNICATIONS

TERM PAPER: REFINERY WASTEWATER

TREATMENT BY MEMBRANE PROCESSES

Submitted By
Tapas Jyoti Deka, Roll No: - 214107017
Under the Guidance of
Prof. Chandan Das,
Department of Chemical Engineering
CONTENTS

ABSTRACT.........................................................................................................3

INTRODUCTION................................................................................................4

Composition of refinery wastewater..................................................................4

Refinery wastewater treatment..........................................................................5

Membrane technology in wastewater treatment................................................5

LITERATURE REVIEW.....................................................................................7

KNOWLEDGE GAP............................................................................................8

INFERENCE FROM LITERATURE REVIEW AND JUSTIFICATION FOR

PRESENT STUDY...............................................................................................9

CONCLUSION.....................................................................................................9

REFERENCES...................................................................................................10
ABSTRACT

Membrane processes have seen application in a lot of fields due to its sheer versatility.
Membranes can be made to separate solids, liquids and even gases, they can be made for a
single use or even to last a long period of time, they can be made for high efficiency or be
made for cost effectiveness, in short membranes can indeed be customized to account for any
need.
Hence, a lot of studies into application of membrane processes in refinery wastewater
treatment have been done. Research into the different types of membrane processes –
microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and
membrane distillation (MD), types of membranes – ceramic, polymer, nanostructured,
selectivity of membranes for different pollutants and a lot more is done.
In this study, a general overview into the application of various membrane processes for
refinery wastewater treatment is discussed. A number of literatures has been studied and
reviewed, in search for a knowledge gap to facilitate further research in this domain.
INTRODUCTION

Since mid-1950s, oil has been the world’s most important energy source. From power
generation to transportation of goods and people to being used as feedstock for various
industries, oil is the lifeblood of modern society. Although many alternate energies sources
are currently being used and developed, none of them comes anywhere close to replace oil as
the primary energy source, at least in the near foreseeable future.
Oil refineries are large plants that can process up to hundreds of metric tons of oil. Refineries
convert raw crude oil into useful products like petrol, diesel, kerosene, liquified petroleum
gas, asphalt base, fuel oil, naphtha, and lubricants using various processes like distillation,
desalting, catalytic cracking, delayed coking, hydrocracking, etc. Therefore, refineries
generate a lot of waste-water from their process usage and cooling towers. The composition
of the wastewater varies depending on the type of crude oil, the processes and the treatment
methods used. Hence, waste management is a very important subject in an industry operating
at such a large-scale. A proper waste management system can not only control pollution but
also help in increasing the efficiency of the processes.

Composition of refinery wastewater

Refinery wastewater consist of both organic and inorganic pollutants. Organics present in
refinery wastewater may be polar or non-polar, aromatics or aliphatic, small or large. Phenol,
Benzene, Toluene, Ethylbenzene and Xylene are some common organic constituents in
refinery wastewater. Meanwhile, majority of inorganic pollutants exist in the form of anions
and cations. Anions of Chloride (Cl-), Bicarbonates (HCO3-), Sulphites (SO32-), Sulphates
(SO42-), Nitrate (NO3-), Nitrite (NO2-) and metallic cations like calcium (Ca), sodium (Na),
potassium (K), magnesium (Mg), iron (Fe), aluminium (Al), boron (B), barium (Ba), lithium
(Li), zinc (Zn), manganese (Mn), mercury (Hg), chromium (Cr), cadmium (Cd), lead (Pb),
strontium (Sr), beryllium (Be) and arsenic (As) are present in varying amounts in refinery
wastewater. Clay, sand, bacteria and other suspended solids and gases like oxygen (O 2),
carbon dioxide (CO2), Hydrogen sulphide (H2S) and Ammonia (NH3) are also present in
noticeable quantities.
 Units Major Pollutants
Crude Desalting Free Oil, Ammonia, Sulphides and
Suspended solids
Crude Distillation Sulphides, Ammonia, Phenols, Oil,
Chloride, Mercaptans
Thermal Cracking H2S, Ammonia, Phenols
Catalytic Cracking Oil, Sulphides, Phenols, Cyanide, Ammonia
Hydrocracking Sulphides
Polymerization Sulphides, Mercaptans, Ammonia
Alkylation Spent caustic, Oil, Sulphides
Isomerization Low levels of Phenols
Reforming Sulphide
Hydrotreating Ammonia, Sulphide, Phenol

Table: Major wastewater pollutants from different units in a refinery.

Refinery wastewater treatment

Treatment of refinery wastewater can generally be carried out in three steps – Primary,
Secondary and Tertiary treatment. Refinery wastewater containing suspended solids, coarse
particles, grease, and other large impurities first need to treated using physical means before
subjecting to any chemical or biological means. Primary treatment units like screens and grit
chambers are used to remove larger debris, gravels, sand, etc based on their sizes. Then,
processes like primary sedimentation, oil separation and settling is done to remove suspended
solids and larger impurities by using the difference in specific gravities of the components.
Components with higher specific gravity settle down at the bottom, while those with lower
specific gravity float to the top. Secondary and tertiary treatments can be in the form of
chemical methods or biological methods. Chemical processes like coagulation, flocculation
and sedimentation are used to lower the oil content in the wastewater. Use of flocculants and
coagulants with agitation can accelerate the processes greatly. Biological treatments like
trickling filters, activated sludge, oxidation ditch, aerated lagoons and oxidation ponds are
also very effective in removing the organic matter from the wastewater. For further
purification, methods like filtration, ion-exchange, reverse osmosis and carbon adsorption can
be used to remove smaller organics, heavy metals and other ions.

Membrane technology in wastewater treatment

Membrane processes separate components based on their size using a selectively permeable
barrier. Membrane processes like microfiltration (MF), ultrafiltration (UF), nanofiltration
(NF) and reverse osmosis (RO) are very efficient in removal of pollutants from water. The
pore size decreases and selectivity increases in the order of MF to UF, then NF and lastly RO.
The operation pressure for the membranes also increases significantly with the decrease in
pore size. The operation mechanism for MF and UF membranes are based on the Darcy’s law
i.e. convective pore-flow, whereas the RO membrane is based on the Fick’s law, solution
diffusion. The NF membrane operates in between, following both pore-flow and diffusion
mechanism.
Microfiltration is done for pore size in the range of 0.1–10 μm. It can be uses to separate
suspended solids, bacteria, etc from water but it allows virus, divalent ions and other smaller
particles to pass through. MF membranes are mostly used as pre-treatment to increase the
efficiency of UF, NF or RO processes. The pore size for ultrafiltration is between 2–100 nm
and it removes most macromolecules and virus, but it can’t stop most of the dissolved ionic
species from passing through. UF membranes are applicable in removing organic molecules.
these membranes are very effective in low saline and low toxic environments but are
susceptible to membrane fouling in other cases. UF membranes can be used as the ultimate
pre-treatment for any NF or RO process. NF membrane pore size is about 0.5–1 nm this is
where transition from pore-flow to solution-diffusion mechanism occurs. Ideally, NF
membrane should reject divalent and multivalent ions removing most organics, allowing only
monovalent ions like Na+, Cl−, etc. RO membranes operate below 0.1 nm and should reject all
the ionic species and allow only water molecules to pass through. NF and RO membranes
operate at high pressures compared to MF and UF membranes. In most cases, nanofiltration
is sufficient for the treated water to reused in the plant or be used in irrigation. RO can be
used to purify the water enough to be even used as drinking water. However, due to this high
selectivity NF and RO membranes are also very susceptible to membrane fouling. Sufficient
pre-treatment of the wastewater must be done or else, the membranes will degrade very
quicky.

Fig: Types of membranes and their characteristics

LITERATURE REVIEW

Munirasu, Haija, & Banat, 2016 [1] is a study into treatment of produced and refinery waste
water by primary and secondary treatment, and the application of the various available
membrane technologies in water treatment. A general discussion on process and application
of microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) is
done. Then, studies into membrane distillation (MD) in combination with forward osmosis
(FO) as potential technology is discussed. The research concludes that type of membrane to
be used depends on the wastewater source and composition and efficiency of membrane
processes depends a lot on the pre-treatment methods used. In general, MF and UF
membranes can be used in pre-treatment for NF and RO processes. In most cases, such as
reuse in the industry or irrigation NF is sufficient, and RO is only essential if water is to be
treated for drinking. Membrane fouling is also discussed as it leads to difference in
performance with synthetic and real wastewater.
Tanudjaja et al., 2019 [2] is a work on the various aspects related to practical application of
membranes in oily wastewater treatment. The sources and composition of oily wastewater,
the conventional treatment methods and regulations are discussed before studying the
different commercially available membranes, their operation and economics. The challenges
in membrane processes are discussed with regards to membrane fouling and its mitigation.
The study concludes that depending on source and composition, treatment procedure for the
wastewater needs to change. Oily wastewater also influences membrane fouling differently
than other particulates. So, use of complementary conventional treatment methods along with
membranes can help in increasing the efficiency of the process and to control membrane
fouling.
Yang, Shen, He, & Li, 2021 [3] discusses about removal of small organic molecules with
different size and chemistry using single layer nano porous graphene (NPG) membrane with
high water permeability and different selectivity to understand the governing parameters for
common organic pollutants removal. Seven organic molecules are studied - methanol, urea,
ethanol, 2-propanol, n-nitrosodimethylamine (NDMA), pyrrole, and phenol. Molecular
transport dynamics and energetics have been studied for membranes of various pore sizes
functionalized hydrophobically (hydrogenated) or hydrophilically (hydroxylated). The study
found that hydrophilic OH-functionalized NPG membrane offer better perm-selectivity than
hydrophobic H-functionalized NPG membrane. Membrane pore size is the primary
parameter for removal of organic molecules, smaller pore size performs better with
selectivity increasing with increase in molecule size.
Karimzadeh et al., 2006 [4] is a study into removal heavy metal ions using silicon carbide
membranes with varying functional group (N, F, OH). The efficiency in removal of Zn 2+, Pb2+
and Cd2+ ions using reverse osmosis is studied with respect to variation in pressure,
temperature and electric field across the membranes. The results show that functionalization
of pores increased the system's ion rejection efficiency. F- functionalized membranes work
best in this study followed by N- functionalized and OH- functionalized membranes, all of
which outperforms the original silicon carbide membrane. Water flux increases with increase
in pressure and temperature. Another major finding is that electric field can play an important
role in heavy metal ion separation, cations flow along the direction of the electric field and
improves the membrane performance.
Veleva et al., 2021 [5] discusses on the use of membrane distillation (MD) in removing
petrochemical pollutants. The efficiency of Direct Contact Membrane Distillation (DCMD)
for removal of acetate, propionate, and phenol with hydrophobic and oleophobic membranes
with respect to variation in operating parameters is studied to get optimum rejection and
membrane performance. The flux and distillate composition are studied with variation in feed
and distillate temperatures, pH and cross-flow velocity. The study that finds hydrophobic
membrane shows higher flux than oleophobic membranes due to lower porosity of
oleophobic membranes. However, oleophobic membrane has the best results for rejection for
phenol at pH 13.
Urgun-Demirtas et al., 2012 [6] is a study into efficiency of the various membrane processes
in mercury (Hg) removal from refinery wastewater to a target Hg concentration (<1.3 ng/L)
as function of pressure. MF, UF, NF and RO processes are carried out at three different
pressures to check the performance of each process for particulate Hg. The membrane fouling
mechanism and particle size distribution for the processes is also discussed. The results show
that MF and UF membranes with operating pressure under 2.8 bar are highly effective in Hg
removal. Meanwhile, NF and RO processes perform well at lower pressures (20.7 bar) but at
pressures higher than 34.5 bar, the efficiency decreases due to solids deposition on the
membrane surface or breakage of Hg particulate bond and release of the Hg into the
permeate. Correlation between mercury concentration and particle size distribution shows
that the membranes with a pore size of less than 0.45 μm can reject more than 90% of the Hg
particulates in the refinery samples and can fulfil the target Hg concentration (<1.3 ng/L).

KNOWLEDGE GAP

The various studies into refinery wastewater treatment using membrane processes have
discussed a great deal about membranes used in MF, UF, NF and RO and their application
with respect to different feed composition, pressure drop, pH and other operation parameter.
Studies into membrane fouling are also done for different organic and inorganic components
present in the wastewater. However, since membranes are not only exposed to slightly
different wastewater composition in a refinery than the composition simulated in a
laboratory, the studies into synthetic wastewater falls short of accurately predicting
membrane behaviour over long periods of time. Hence, study into improving the membrane
performance, fouling resistance and mechanical strength through modification of the
structure and composition of a membrane that can last over a longer period of time can be
done.
INFERENCE FROM LITERATURE REVIEW AND JUSTIFICATION
FOR PRESENT STUDY

The treatment procedure of refinery wastewater depends a lot on the source and composition
of the wastewater. The units produce different composition as different processes are carried
out to get a wide range of products in a refinery. This leads to a need in optimizing the
treatment procedure for various units separately. Membrane processes can play an important
role since, membranes available in wide variety and can easily be modified to accommodate a
different composition or parameter. Membranes however work best in conjunction with
conventional separation techniques.
Current studies have show that membrane performance can be affected by a number of
factors – pressure, temperature, pH, flow rate, feed composition, presence of electric field,
etc. The membrane itself can also be modified by changing the structure, using coatings or
functionalizing to get hydrophilic, hydrophobic or oleophobic surfaces to improve selectivity
for certain molecules, water flux and fouling resistance of the membrane. This has opened the
door to a wide range of possibilities, as membranes can be custom-made to separate out
certain components and/or be made to withstand certain operating parameters that are
difficult to control.

CONCLUSION

Membrane processes are not meant to replace the conventional treatment methods. Instead,
membranes are best used to supplement existing conventional methods to get the best results.
Membranes can also be modified to selectivity separate certain groups of particles and
perform better under different operating parameters. This versatility of membranes has led to
increased application in a lot of areas including refinery wastewater treatment. However,
membrane technology has not yet reached its peak, a lot more can be done to improve upon
existing membrane processes and development of better future technology.
REFERENCES

1. Munirasu, S., Haija, M. A., & Banat, F. (2016). Use of membrane technology for oil
field and refinery produced water treatment—A review. Process Safety and
Environmental Protection, 100, 183–202. https://doi.org/10.1016/j.psep.2016.01.010
2. Tanudjaja, H. J., Hejase, C. A., Tarabara, V. V., Fane, A. G., & Chew, J. W. (2019).
Membrane-based separation for oily wastewater: A practical perspective. Water
Research, 156, 347–365. https://doi.org/10.1016/j.watres.2019.03.021
3. Yang, J., Shen, Z., He, J., & Li, Y. (2021). Efficient separation of small organic
contaminants in water using functionalized nanoporous graphene membranes: Insights
from molecular dynamics simulations. Journal of Membrane Science, 630, 119331.
https://doi.org/10.1016/j.memsci.2021.119331
4. Karimzadeh, S., Safaei, B., Jen, T.-C., & Oviroh, P. O. (2021). Enhanced removal
efficiency of heavy metal ions from wastewater through functionalized silicon carbide
membrane: A theoretical study. Journal of Water Process Engineering, 44, 102413.
https://doi.org/10.1016/j.jwpe.2021.102413
5. Veleva, I., Vanoppen, M., Hitsov, I., Phukan, R., Wyseure, L., Dejaeger, K., …
Verliefde, A. R. D. (2021). Selection of membranes and operational parameters
aiming for the highest rejection of petrochemical pollutants via membrane distillation.
Separation and Purification Technology, 259, 118143.
https://doi.org/10.1016/j.seppur.2020.118143
6. Urgun-Demirtas, M., Benda, P. L., Gillenwater, P. S., Negri, M. C., Xiong, H., &
Snyder, S. W. (2012). Achieving very low mercury levels in refinery wastewater by
membrane filtration. Journal of Hazardous Materials, 215-216, 98–107.
https://doi.org/10.1016/j.jhazmat.2012.02.040