Application of Membrane Technology in Petrochemical

Sector, and Treatment of PW- A Review

- By Sreya Banerjee under the guidance of Dr. Parimal Pal

Abstract
This article is a review of the various implementations of membrane
technology based separation processes, particularly in petrochemical sector
and treatment of Process water from refineries and produced water from
petroleum exploration sites. The definition of a membrane and brief
description about the need of membrane technology has been discussed
followed by details of how a it works. Functioning and scope of application of
gas membranes and liquid membranes have been discussed. The origin of
produced water during oil drilling has been described and how processes like
Reverse Osmosis, Membrane Distillation, and Ultrafiltration are used for
treatment of refinery waste streams and wastewater streams have been
reviewed.

1. Introduction
In modern times, we are witnessing an advent in the field of membrane
technology for use in various sectors. Particularly, in the petrochemical and
related industry, new membrane-based technology is becoming more relevant
and successfully taking over the existing technologies. The main reason why
the membrane technology is gaining popularity is because of its ability to take
control of how a chemical species permeates when under its influence.
Separation of substances that have mixed up is possible only by an instrument
that takes in energy which has been supplied thermally or mechanically.
Hence, it can be said that as per the principle of separation is concerned, there
is one golden rule, in essence, energy is to be expended to attain the desired
level of separation. Membrane technology based separation occurs without
any alteration of phase and has lower energy demand.

Recovering important co-products or minor products from processes can be

easily done with the help of membrane-based separation process. The process
is diverse, easy, sensitive, energy-efficient, clean, and does not involve using
harmful materials as membrane module. However, there are certain
disadvantages of membrane technology, namely, fouling of membrane due to
accumulation of undesirable components over time, short lifespan, and low
selectivity and/or flux.

The prime role of the petrochemical industry is in the separation of various

olefins from paraffins and to finally produce poly-olefins, e.g., styrene,
butadiene, acrylonitrile, etc. Membrane-based gas separation is a lucrative
measure although it is limited by the property of membrane that the
productivity or permeability is in juxtaposition to selectivity or separation
efficiency. In this light, CMS or carbon molecular sieve membranes are
promising for olefin separation from paraffin.

As there has been improvement in drilling technology and new techniques of

petroleum exploration like hydraulic fracturing have come up, amount of
water wasted during these processes has increased manifold, demanding
better treatment technology. Membrane technology offers a wide scope yet
again in this genre. Also, waste effluent from petrochemical manufacturing
units must be treated before disposal to ensure safety. Membrane Aromatic
Recovery System (MARS) is new process of recovering important aromatics.

In this article, such conventions in membrane technology shall be reviewed.

2. How does a membrane work?

A general definition of membrane is: a selective barrier between two phases,
the term ‘selective’ being inherent to a membrane or a membrane process [1].
A membrane can be very thick or very thin, can be uniform or can be non-
uniform. The transport process through membrane can be active by nature or
passive. Passive form of transport is driven by differences of concentration,
temperature, and pressure.

The feed to a membrane module is divided into two separate streams-a)

Permeate Stream and b) Retentate Stream (also referred to as the concentrate
stream). If the objective of the process is to acquire concentration, the
retentate stream is the main product. On the other hand, if the objective of the
process is purification or the like, both the aforementioned streams can lead to
the desired product, provided, amount of impurities being removed is
satisfactory.

Figure A: Working of a membrane

Figure B: Representation of Membrane based process

Membranes are usually classified as natural and artificial, symmetric and

asymmetric. The symmetric membranes are thinner whereas asymmetric
membranes have the highly selective nature of thick membrane and high
permeation rate of thinner membrane.

Table 1: Types of Membrane Process and their Driving Forces [1].

S.No. Membrane Process Phase1 Phase2 Driving Force

1 Microfiltration L L ΔP
2 Ultrafiltration L L ΔP
3 Nanofiltration L L ΔP
4 Piezodialysis L L ΔP
5 Gas Separation G G Δp
6 Vapour Permeation G G Δp
7 Pervaporation L G Δp
8 Electrodialysis L L ΔE
9 Membrane Electrolysis L L ΔE
10 Dialysis L L Δc
11 Diffusion Dialysis L L Δc
12 Membrane Contactors L L Δc
G L Δc/Δp
13 Thermo-osmosis L L ΔT/Δp
14 Membrane Distillation L L ΔT/Δp

3. Membrane Separation in Petrochemical Sector

3.1. Membranes used in Manufacturing and Processing of
Petrochemicals
Separation of paraffins and olefins is the main job in a petrochemical
manufacturing and/or processing unit. In 1998, the United States produced 52
billion pounds of ethylene and 29 billion pounds of propylene [2]. Important
olefins come in outlet streams of processes involving ethylene and motor
gasoline production. To separate these from other hydrocarbons, lots of
processes exist, conventionally, adsorption, extractive distillation, etc.
Presently, cryogenic distillation has a monopoly in this particular field.
However the cryogenic operation is tedious and consumes a lot of energy.
Hence, membrane technology has been considered a very attractive
alternative to achieve this kind of separation.

Many polymeric membranes have been used to accomplish gas separation and
a list of the same is given list. The polymeric membranes are often clubbed
with nano-materials to form polymer-inorganic-nano composite materials [3]
that offer greater mechanical strength to the membrane. Kong and co-
researchers [4] used polyimide/TiO2 nano-particle composite membranes to
separate gases. Low content of the nano composite did not have much effect
on the permeability of the membrane. However, on increasing the nano
composite content by about 20 weight percentage, the permeability improved
without taking a toll on the selectivity of the membrane.

Liquid membranes can also be used to achieve separation. The principle of

separation with the help of liquid membrane lies in exploiting diffusivity and
solubility differences. The membrane may often have carrier, (mobile or
chemically bound with less mobility) that can form complexes with the solute
and improve flux. Transition metal ions infested as carriers in liquid
membranes are used for olefin separation. This is because it is well known that
often transition metal ions react in a reversible manner with alkene is any
solution state. Suitable transition metals that serve the purpose are Mn, Fe,
Co, Pt, Ir, Cu, Mo, Tc, Ru, Rh, Pd, Ag [3].

Figure C: Facilitated Transport Mechanism for Liquid membrane separation

process where A=olefin, B=carrier, C=paraffin [5]
Pervaporation offers solution in separation liquids with boiling points that do
not vary much or those liquids which are difficult to separate by distillation.
Composite membranes of hydrophobic nature are used to sustain
pervaporation to separate VOCs that are dissolved in water. This is widely used
to make separation happen between organics and water.

A very lucrative use of reverse osmosis in the field of petrochemical sector is

separating mixtures of various organics. The scope of this particular technology
maybe improved further to make separation of various paraffins and aromatics
possible in gasoline pool [6].

CMS or Carbon Molecular Sieve membranes both with and without Iron have
been put to test for improved separations methods of paraffins and mixed
olefins. Yu-Han Chu and co-researchers [7] have come up with results after
putting both types of membranes to test. It is noticed that a large amount of
diffusion selectivity occurs on incorporating Fe in the membrane.

Figure D: Fe complex present in porous iron containing CMS membranes [7]

3.2. Membranes used in treatment of produced water, coproduced

water and from petroleum exploration and petrochemical
industries

During petroleum exploration, deep drilling is done to reach the oil wells.
During this process, lot water is produced from earth surface and this referred
to as product water and/or sometimes co-produced water and/or sometimes
flowback water.
Figure E: Source of Produced Water and Process Water during petroleum
exploration and refining.

There are many kinds of impurities in process water from the oil refineries.
Also the produced water needs to be purified in many cases.

Figure F: BTEX present in process water [8].

The Ultrafiltration membrane process can be efficient technology in treating

PW with low salinity and less toxicity. Nanofiltration and Reverse Osmosis are
highly efficient in removal of inorganics from PW [8]. Nano-filtration and RO
differ only in terms of selectivity of the ions. For NF membranes, they are more
selective towards divalent ions. For RO membranes, they are more selective
towards monovalent ions. Most NF and RO membranes are made on support
of asymmetric UF membranes. NF membranes can be used but for specific oil
and gas operations. It must be ensured that the PW is independent of
corroding substances. UF is more used for pre-treating purposes. Membrane
Distillation is also adopted for treatment of saline water. Ceramic
microfiltration membranes are useful in this purpose.

4. Critical Discussion based on Results from various sources

As already stated earlier, membrane technology can prove to be useful if
implemented in large-scale more frequently in the petrochemical sector. The
status of how membrane technology is ruling contemporarily is given:

Table 2: Status of Membrane in the currently [9].

Category Process Status

Developed industrial MF,UF,RO, Electrodialysis Well-established unit
Membrane Separation operations. No major
Technologies breakthroughs seem imminent.
Developing industrial Gas Separation, Pervaopration A number of plants have been
Membrane Separation installed. Market size and
Technologies applications are expanding.
To-be-developed industrial Carrier Facilitated Transport Major problems are yet to be
Membrane Separation Membranes, Piezodialysis solved before large-scale
Technology implementation.

Many gas membranes are already in use for separation of olefins from their
mixture with paraffins. It can be said aptly, that on further research in the field
of how membrane technology can be put to use in the petrochemical sector,
processes can be optimised to build better results.

In case of CMS membranes to separate olefins from paraffins, it is obtained as

results by group of researchers from the USA that sorption selectivity for the
membranes shall improve noticeably if metals are put in carefully by controlled
conditions of pyrolysis [7]. Langmuir void-filling sorption is considered in this
case. The pyrolysis conditions for this case are low temperature and fast rate
of the ramp.
As for the treatment of wastewater from petrochemical plants and also for
treatment of produced water, RO is still considered the most suitable. The
schematic of how process water is treated is as follows:

Figure G: Scheme of membrane Treatment for PW [8]

5. Summary
In this review, it has been discussed how membrane technology can be used as
an efficient separation in fields of petrochemical processing and petroleum
exploration, oil drilling and treatment of wastewater from petrochemical
processing plants. Main concern of any petrochemical plant is production of
poly-olefins and that requires separation of paraffinic content and olefins from
the raw petroleum feed. This can be achieved efficiently with the help of
membrane technology, instances of which have been reviewed. As for the oil
drilling and exploration sector, the treatment of produced or flowback water is
greatly done with the help of RO alongside ultrafiltration and microfiltration.
However, the scope of membrane technology in this field is yet to be well-
defined with proper research.

6. Abbreviations
L- Liquid G-Gas ΔP- Pressure Difference

Δp- Partial Pressure Difference ΔE- Electric Potential Difference

Δc- Concentration Difference ΔT- Temperature Difference

UF- Ultrafiltration RO- Reverse Osmosis NF- Nano-filtration

MF- Microfiltration

7. References
[1] J. Mulder, Basic Principles of Membrane Technology, Springer Science and
Business Media, (2012)

[2] Facts and figures, Chem. Eng. News, 77, (1999)

[3] Maryam Takht Ravanchi, Tahereh Kaghazchi, Ali Kargari, Application of

Membrane Separation Processes in Petrochemical Industry: A Review,
Desalination 235 (2009), Elsevier

[4] Y. Kong, H. Du, J. Yang, D. Shi, Y. Wang, Y. Zhang and W. Xin, Study on
polyimide/TiO2 nanocomposite membranes for gas separation, Desalination,
146 (2002)

[5] W.S. Ho and D.C. Dalrymple, Facilitated transport of olefins in Ag-containing

polymer membranes, J. Membr. Sci., 91 (1994)

[6] M.B. Rao and S. Sirkar, Nanoporous carbon membranes for separation of
gas mixtures by selective surface flow, J. Membr. Sci., 85 (1993)

[7] Yu-Han Chu, David Yancey, Liren Xu, Marcos Martinez, Mark Brayden,
William Koros, Iron-containing Carbon Molecular Sieve membranes for
advanced olefin/paraffin separations, J. Membr.Sci., 548 (2018)

[8] Selvaraj Munirasu, Mohammad Abu Hajia, Fawzi Banat, Use of Membrane
technology for oil field and refinery produced water treatment- A review,
Process Safety and Environmental Protection, 100 (2016)

[9] R.W. Baker, Membrane Technology and Applications, John Wiley, 2nd ed.
(2004)

[10] S.P. Nunes and K.-V. Peinemann, eds., Membrane Technology in the
Chemical Industry, Wiley, 2001.