Refinery Wastewater Treatment

• Details of MD and DFT

• MF,UF,NF,RO, FO,MD(membrane distillation)
• Adsorption, Liquid Membrane, MOF
• Heavy metals, Organics, Mixture
• Wastewater treatment, Remediation
• Composition of various effluent
• Suitable method for treatment of individual effluent
Introduction
• Refineries generate a lot of wastewater 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. Some of
the common pollutants in the wastewater are – organic compounds like Phenol, Benzene, Toluene,
Ethylbenzene, Xylene, H2S, NH3, Suspended solids, Chloride, Bicarbonates, Sulphites, Sulphates, Metal ions
like Ca, Na, K, Mg, Fe, Cu, Zn, As, Pb.

• Treatment of refinery wastewater can generally be carried out in steps, Pre-treatment like screening can be
done to remove large debris. Then, primary treatment like sedimentation and settling is done to remove
suspended solids and larger impurities. Secondary treatment is then done for further treatment of the effluent.
Secondary treatment may be in the form of chemical methods or biological methods like bioreactors.
Membrane processes like Microfiltration, Ultrafiltration, Nanofilteration, RO are very efficient in removal of
pollutants from water. Membranes can also be modified to selectivity separate certain groups of particles and
perform better under different operating parameters.
Phenol
• Chemical formula – C6H5OH
• Molar Mass – 94.113g/mol
• Density – 1.07g/cm3
• Melting point – 40.5 C (313.6 K)
• Boiling point – 181.7 C (454.8 K)
• Appearance – Transparent crystalline solid
• Water soluble
Ammonia
• Chemical formula – NH3
• Molar Mass – 17.031 g/mol
• Melting point – -77.73 C (195.42 K)
• Boiling point – -33.34 C (239.81 K)
• Appearance – Colourless Gas
• Pungent smell
• Water soluble
Sl.No Title
Molecular dynamics simulation
for membrane separation and
1 in Membrane separation
porous materials: A current state
of art review
Efficient separation of small
organic contaminants in water
using functionalized nanoporous
2 hydrophobic NPG
graphene membranes: Insights
from molecular dynamics
simulations
Enhanced removal efficiency of
heavy metal ions from wastewater
through functionalized silicon
3 with varying functional
carbide membrane: A theoretical
study
Work Done
Review on MD simulation
process and its application
Removal of 7 small organic
molecules with different
size and chemistry using
NPG membrane
Zn2+, Pb2+ and Cd2+ removal
by siliconcarbide membrane
group (N,F,OH), pressure,
voltage
Conclusion Knowledge Gap
Application as
computational tool is well
established.
Prediction ability can
progress further.
Hydrophillic NPG
Study on other organic
membrane offer better
molecules.
permselectivity than
Type of membrane and
other parameters can be
membrane.
changed
Smaller pore sizes perform
DFT study
better.
Functionalization of pores Study on heavy metal
increased the system's ion ions.
rejection efficiency. Type of membrane and
Electric field can play an other parameters can be
important role in heavy changed
metal ion seperation
Sl.No Title
Investigation of the interaction
between xanthate and kaolinite
based on experiments, molecular
4 electrostatic interactiion
dynamics simulation, and density
functional theory
Selective membranes in water and
5 wastewater treatment: Role of
advanced materials
Work Done Conclusion Knowledge Gap
Xanthate molecules
adsorbed on the Kaolinite
Application of Kaolinite
through H-bonds and
Study of adsorption of as membrane.
xanthate on kaolinite Operatiing parameters
(similar to that between
can be varied
Polyacrylamide and the
Kaolinite surface)
A number of novel
materials have shown
promise as high selectivity
Study on the role of membranes for various
In dept study of the
membrane material in water applications.
various materials
and wastewater treatment Development of novel
membrane materials are
still in their early stages,
further study is required
Sl.No Title Work Done
Membrane-based Sources and composition
separation for oily of oily wastewater,
wastewater: A practical Membrane technology for
6
perspective oily wastewater treatment,
Membrane fouling
Metal-organic MOF membrane , design,
framework membranes structural defects and
for wastewater treatment characterization,
7 and application in membrane
water regeneration filtration, distillation and
pervaporation
Molecular dynamics Characteristics of
simulation of polyamide-based
8 polyamide-based materials using MD
materials – A review simulation. Software
packages and Force fields
Conclusion Knowledge Gap
Depending on source and Molecular study of
composition, treatment differs. membrane fouling by oil
Membrane technology complements MD simulation
conventional technology. DFT
Membrane fouling by oil is different
from particulate foulants
MOF membranes offer good Synthesis of modified
compatibility and highly adjustable MOF membrane
pore structure. Long term stability of
High stability and permeability of MOF in different
water-stable MOF along with environment
modification using structural defects
lead to various application
Study of physical, membrane DFT
permeability, mechanical and Study on modified
thermal properties of polyamide polyamide membranes
using MD simulation confirms to
the experimental results
Sl.No Title Work Done Conclusion Knowledge Gap

Selection of membranes Efficiency of Direct Hydrophobic membrane shows Long term stability of
and operational Contact Membrane higher flux. Oleophobic membrane oleophobic membrane
parameters aiming for Distillation (DCMD) for has better rejection for phenol at pH MD simulation
the highest acetate, propionate, and 13 DFT
9
rejection of phenol with hydrophobic
petrochemical pollutants and oleophobic
via membrane membranes with varying
distillation parameters
Rejection of heavy Study on Cd2+, Pb2+, High rejection (94%) for the Change in operating
metals in acidic Cu2+, Zn2+ rejection using divalent heavy ions in relative acidic parameters and heavy
wastewater by a novel FO by nanoporous thin pH and feed conc. 200mg/L due to metal ions
10 thin-film film inorganic membrane surface potential ( more than pore MD simulation
inorganic forward in acidic condition( pH size). DFT
osmosis membrane 4.5) Higher feed conc. decreases
rejection
Sl.No Title
Effect of modified PVDF
hollow fiber submerged
ultrafiltration membrane for
11 refinery wastewater
treatment
Comprehensive chemical
characterization of
dissolved organic matter in
12 typical point-source
refinery wastewaters
Synthesis of nanocomposite
membrane incorporated
with amino-functionalized
nanocrystalline cellulose
13 for refinery wastewater
treatment
Work Done
Effects of surface properties
on modified PVDF hollow
fiber composite membranes
by LiCl·H2O and TiO2 for
refinery wastewaster
Characterization of refinery
wastewater from electric
desalting, distillation, and
stripping processes
UF treatment of oil in water
emulsion by PSf membrane
with amino-functionalized
nanocrystalline cellulose
(NCs)
Conclusion Knowledge Gap
LiCl·H2O and TiO2 improved membrane Change in
performance with higher flux and rejection. functionalization,
1.95 wt.% of TiO2 nanoparticles resulted membrane type
in smaller nanoparticles which in turn MD simulation
achieved higher hydrophilicity, DFT
small pore size, and high porosity
Electric desalting, distillation, and stripping Study of other units
processes contributed 35.5 % DOC of the Removal of DOM
total wastewater treatment plant. These
units were all dominant by Ox and OxSy
class species. VOCs like benzene in Electric
desalting and OVOCs in distillation, and
stripping processes
NCs contribute improved porosity, Change in
hydrophilicity and anti fouling properties functionalization,
against oil molecules. membrane type
optimum loading of 1 wt% NCs, gives Operating parameters
water flux of 105.2 L/m2.h (43% better) and MD simulation
oil rejection of 98.2% (10% better) DFT
compared to the pristine PSF membrane.
Sl.No Title Work Done Conclusion Knowledge Gap
Achieving very low Efficiency of MF, UF, NF MF and UF membranes Change in operating
mercury levels in and RO in Hg removal with operating pressure under 2.8 parameters and organic
refinery wastewater by from refinery wastewater bar are highly effective molecules and heavy
membrane filtration as function of pressure, NF and RO perform well at lower metal ions
Membrane fouling and pressures (20.7 bar) but at pressures MD simulation
14
particle size distribution higher than 34.5 bar efficiency DFT
decreases due to solids deposition
on the membrane surface or
breakage of Hg particulate bond and
release into the permeate
Use of membrane Composition of refinery Efficiency of membrane processes Further study into
technology for oil field wastewaster, Primary and depends a lot on the pre-treatment membrane fouling with
and refinery produced secondary treatment, methods used. For drinking water real wastewater
water treatment—A MF,UF, NF, RO, Thermal quality RO treatment is necessary, Study of large scale
review desalination (MD) and FO for reuse in the industry or irrigation plants
15 NF is sufficient. Membrane fouling
leads to difference in performance
with synthetic and real wastewater.
Type of membrane to be used
depends on the wastewater
composition.
Sl.No Title
Phenol and ammonia
removal in petroleum
refinery wastewater using a
poly(vinyl) alcohol coated
16 polysulfone nanohybrid
membrane
Ammonium removal from
aqueous solutions by
reverse
osmosis using cellulose
17
acetate membranes
Work Done Conclusion Knowledge Gap
Polysulfone Increase in the phenol and ammonia Change in coating
nanohybrid membrane removal efficiency from 51.52%– MD simulation
with PVA coating to 82.68% and 82.89%–92.42%, DFT
increase membrane respectively. Improvement in
performance, mechanical strength and anti fouling
mechanical strength behavior
and fouling resistance
RO treatment of Commercially available cellulose Change in membrane
ammonium aqueous acetate membranes are suitable for type
solution using the removal of Organic molecules and
cellulose acetate ammonium ions from aqueous Heavy metal ions
membranes. solutions (98% removal) MD simulation
Simulation model for Simulation model results match with DFT
semi batch and experimental results
unsteady state system
Sl. Tittle Work done Conclusion Knowledge gap
No
18 Characterization of membrane–foulant Adsorption of vanillin to Results from Study of other operating
interactions with novel combination the PES surface of a experimental studies parameters
of Raman spectroscopy, surface membrane using Raman shows affinity of PES Study of different
plasmon resonance and molecular spectroscopy, surface surface for Vanillin pollutant
dynamics plasmon resonance decreases with increase
simulation (SPR) and MD simulation in pH.
MD simulation shows
solubility of Vanillin
increases with increase
in pH

19 Influence of ultrasound on the adsorption Effect of ultrasound on Ultrasound can increase Study of other molecules
of single-walled carbon adsorption of phenol on the efficiency of with other parameters
nanotubes to phenol: A study by SWNT by comparing the adsoption of phenol on
molecular dynamics simulation structural param­ SWNT by weaken the
and experiment eters, interaction energy, strength of hydrogen
hydrogen bond and bond be­
density distribution of tween phenolic hydroxyl
water molecules and water molecules
Objectives
1. Recovery of phenol and ammonia from refinery wastewater using a MOF ceramic membrane.

• Phenol and ammonia are two common compounds found in refinery waste water from processes like
distillation, cracking and hydrotreating. The removal of these compounds using a ceramic membrane
modified with a metal-organic framework for better selectivity can be studied.

1. Study of membrane fouling by refinery wastewater.

• Membrane fouling occurs due to deposition of particles on the membrane. It can also occur due to
unsuitable operating conditions like pH, temperature, etc. Membrane fouling can cause a decrease in
membrane performance leading to more operational cost or even the need of replacement. A study of
membrane fouling of the ceramic membrane by refinery wastewater composition in relevant operating
conditions can be done.