Synthesis of Mixed Matrix Membranes for Energy and

Environmental Applications

By

Amin Khan

FA14-MSHEM-013

MS thesis

In

Chemical Engineering

COMSATS Institute of Information Technology Lahore

Pakistan
Spring 2016

I
 COMSATS Institute of Information Technology

Synthesis of Mixed Matrix Membranes for Energy and

Environmental Applications

A Thesis Presented to

COMSATS Institute of Information Technology, Islamabad

In partial fulfillment

Of the requirement for the degree of

MS (Chemical Engineering)

By

Amin Khan
FA14-MSCHEM-013

Spring 2016

II
 Synthesis of Mixed Matrix Membranes for Energy and
Environmental Applications

A Post Graduate Thesis submitted to the name of Chemical Engineering department as

partial fulfillment of the requirement for the award of Degree of M.S (Chemical
Engineering)

Name Registration number

Amin Khan FA14-MSCHEM-013

Supervisor
Dr. Asim Laeeq Khan
Assistant professor Department of Chemical Engineering
Lahore Campus
COMSATS institute of Information Technology
Lahore campus
Spring 2016

III
 Final Approval
This thesis titled Synthesis of Mixed Matrix Membranes for Energy and
Environmental Applications

Synthesis of Mixed Matrix Membranes for Energy and

Environmental Applications
By

Amin Khan

FA14-MSCHEM-013
Has been approved

For the COMSATS Institute of Information Technology, Lahore Pakistan

External Examiner: __________________________________________

Dr…………

………

Supervisor:

Dr. Asim Laeeq Khan

(Chemical Engineering)

HoD:

Dr. Asad Ullah Khan

HoD (Chemical Engineering)

IV
 Declaration
I Amin Khan having registration number FA14-MSCHEM-013 hereby declare that I have
produced the work presented in this thesis, during the scheduled period of study. I also declare that
I have not taken any material from any source except referred to wherever due that amount of
plagiarism is within acceptable range. If a violation of HEC rules on research has occurred in this
thesis, I shall be liable to punishable action under the plagiarism rules of the HEC.

Date: Signature of student:

Date of thesis submission

Amin Khan

FA14-MSCHEM-013

V
 Certificate
It is certified that Amin Khan having registration number FA14-MSCHEM-013 has carried out all
the work related to this thesis under my supervision at the department of Chemical Engineering
COMSATS Institute of Information Technology Lahore and work fulfills the requirement for the
award of MS degree.

Date:

Date of Thesis Submission

Supervisor:

Dr. Asim Laeeq Khan

(Assistant Professor)

Head of Department:

Dr. Asad Ullah Khan

(Professor)

VI
 Dedication

To my good luck charm; my mother and father, my kind supervisor Dr. Asim Laeeq
Khan and my students.

VII
 Acknowledgements
Thanks are due first to Almighty Allah for giving me the will and patience to complete this work.

I wish to express my sincere gratitude and appreciation to my supervisor Dr. Asim Laeeq Khan
for his guidance, care and suggestions which were very helpful for the preparation and completion
of this work. I am also thankful to my other teachers Dr. Asad Ullah Khan, Dr. Shahid Nazir, Dr.
Mazhar Amjad Gilani, Dr. Fahad Rehman, Dr. Murid Hussain, Dr. Maria Mustafa, Dr. Um-e-
Salma, Mr. Tariq Mehmood Raza and Mr. Amjad Riaz for their guidance, advices and motivation.
I wish to thank all my colleagues of the Chemical Engineering Department for their kind assistance
and encouragement.

I am also indebted to COMSATS Institute of Information Technology (CIIT) for my Master Study.
Librarians at CIIT also deserve special thanks for their assistance in supplying the relevant
literatures.

I acknowledge the favor of interdisciplinary Research Centre in Biomedical materials (IRCBM)

COMSATS Institute of Information Technology Lahore, especially head of IRCBM (Dr. Aqif
Anwar Chaudhary).

I wish to express my very special thanks to my friends Mr. Mohsin ali and Miss Naila Riaz who
helped me throughout my thesis work. I really want to express my special thanks to Mr. Kashif-
ur-rehman who was always there for me whenever I needed his help. My other close friends should
also be recognized for their support especially Mr. Khurram Tahir, Miss Ayesha Ilyas, Miss Saba
Khan, Mr. Raees, Mr. Zaman Tahir and Mr. Shahzad, who always cheered me up. My sincere
appreciation also extends to all my students for their best wishes, unfortunately, it is not possible
to list all of them in this limited space. I also acknowledge Mr. Muhammad Nasir and Mr.
Muhammad Akmal who helped me in fixing of apparatus.

Finally, there is no single word or expression which can adequately express my gratitude to my
family for their encouragement and support throughout my study.

Amin khan
FA14- MSCHEM -013

VIII
ABSTRACT:

The production of renewable fuels have received great attention due to the problematic effects of
non-renewable fuels on environment. Ethanol purification is very essential for obtaining fuel grade
ethanol but the conventional processes to convert bio mass to bio fuel is very high energy intensive
and costly process. Concentration of ethanol during fermentation process generally ranges up to
1-15% depending upon the source of bio mass. The water contents should be reduced to 1-3 wt%
for obtaining fuel grade ethanol. Distillation is commonly adopted technique for the separation of
ethanol from fermentation broths. However, this technique is very high energy intensive hence
opening the doors of some other techniques such as gas stripping, adsorption etc.

Another technique which is used to separate water/alcohol mixture is via hydrophobic

pervaporation. Pervaporation is a membrane based separation process in which feed is entered in
the form of liquid and vapors are obtained as permeate. Polymeric membrane and inorganic
membranes are not widely accepted due to tradeoff relationship between flux and selectivity. This
thesis mainly focused on the synthesis of Zeolitic Imidazole Framework (ZIF) based Mixed Matrix
Membrane (MMM) to increase the separation performance of ethanol/water mixture.
Polydimethylsiloxane (PDMS) is an elastomer which is widely used for hydrophobic
pervaporation due to its high selectivity, chemical stability and high hydrophobic nature. During
the course of this thesis, ZIF-67; a hydrophobic filler was selected and synthesized due to its high
chemical and thermal stability and high hydrophobic nature. ZIF-67/PDMS membranes were
synthesized using polyimide (PI) as a support. Different characterization techniques were adopted
to confirm the purity and performance of fillers and membranes. Membranes were tested on home
based pervaporation unit to check the performance parameters of pervaporation.

IX
Table of Contents
CHAPTER 1 ................................................................................................................................................. 1
Introduction and Literature Review .............................................................................................................. 1
Problem statement..................................................................................................................................... 1
1.1 Background ......................................................................................................................................... 1
1.2 Purification Techniques ...................................................................................................................... 2
1.2.1 Distillation.................................................................................................................................... 3
1.2.2 Adsorption.................................................................................................................................... 3
1.2.3 Ozonation ..................................................................................................................................... 3
1.2.4 Gas stripping ................................................................................................................................ 4
1.3 Membrane Technology ....................................................................................................................... 4
1.4 Pervaporation (PV) ............................................................................................................................. 6
1.4.1 Brief History of Pervaporation ..................................................................................................... 8
1.5 Fundamentals of pervaporation........................................................................................................... 9
1.5.1 Solution Diffusion Mechanism .................................................................................................. 10
1.5.2 Performance parameters ............................................................................................................. 12
1.6 Influence Parameters ......................................................................................................................... 13
1.6.1 Feed Composition ...................................................................................................................... 13
1.6.2 Downstream Pressure................................................................................................................. 13
1.6.3 Temperature ............................................................................................................................... 14
1.7 Pervaporation membrane materials ................................................................................................... 14
1.7.1 Polymeric membrane ................................................................................................................. 15
1.7.2 Inorganic membranes ................................................................................................................. 17
1.7.3 Mixed Matrix Membranes ......................................................................................................... 17
1.8 Metal organic Frame works .............................................................................................................. 18
1.8.1 ZIF-67 ........................................................................................................................................ 20
1.9 Common Fabrication Methods for Pervaporation Membranes ......................................................... 20
1.9.1 Solution Casting ......................................................................................................................... 21
1.9.2 Hollow Fiber Spinning ............................................................................................................... 21
1.9.3 Solution Coating ........................................................................................................................ 21
1.9.4 Interfacial Polymerization .......................................................................................................... 22

X
 1.10 Scope of thesis ................................................................................................................................ 22
CHAPTER 2 ............................................................................................................................................... 23
2.1 Introduction ....................................................................................................................................... 23
2.2 Materials ........................................................................................................................................... 24
2.3 ZIF-67 Synthesis ............................................................................................................................... 24
2.4 Membrane Synthesis ......................................................................................................................... 25
2.5 Characterization techniques .............................................................................................................. 27
2.5.1 XRD ........................................................................................................................................... 27
2.5.2 SEM ........................................................................................................................................... 27
2.5.3 BET ............................................................................................................................................ 27
2.5.4 FTIR ........................................................................................................................................... 28
2.5.5 TGA ........................................................................................................................................... 28
2.6 Pervaporation experiments................................................................................................................ 28
2.7 Results and Discussions .................................................................................................................... 30
2.7.1 Filler Selection ........................................................................................................................... 30
2.7.2 Characterization of as-prepared ZIF-67 particles ...................................................................... 30
2.7.3 Swelling Studies......................................................................................................................... 35
2.7.3 Effect of ZIF-67 Loading on PDMS/ZIF-67 Mixed Matrix Membranes (MMMs) ................... 37
2.7.4 Effect of feed temperature on PDMS/ZIF-67 Mixed Matrix Membranes (MMMs) ................. 38
Chapter 3 ..................................................................................................................................................... 40
3.1 Conclusions and future work ............................................................................................................ 40
3.2 Future works ..................................................................................................................................... 40
References ................................................................................................................................................... 41

XI
List of Figures:

Figure 1: Membrane based separation process for liquid mixture

Figure 2: Pervaporation process

Figure 3: Solution-Diffusion Model

Figure 4: Application areas of Pervaporation

Figure 5: Membrane morphology including separating layer and support

Figure 6: Mixed Matrix Membranes

Figure 7: Tetrahedral unit of ZIF-67

Figure 8: ZIF-67 Powder
Figure 9: a) 5 wt% b) 10 wt% c) 15% d) 20%
Figure 10: Homemade Pervaporation Set-up
Figure 11: XRD spectrum of ZIF-67 particles
Figure 12: XRD pattern of ZIF-67 particles in two different solvents (Water; above, Methanol;
below)

Figure 13: SEM Image of synthesized ZIF-67 (Methanol) nano particles at SEM HV and SEM
Magnification of 15 KV and 25.0kx respectively.

Figure 14: SEM Image of synthesized ZIF-67 (Water) nano particles at SEM HV and SEM
Magnification of 15 KV and 10.0k x respectively.

Figure 15: Nitrogen adsorption isotherm of synthesized ZIF-67

Figure 16: FTIR spectrum of ZIF-67 particles

Figure 17: TGA curves for ZIF-67
Figure 18: Membrane swelling with different filler loadings
Figure 19: Membrane swelling with different filler loadings
Figure 20: Effect of ZIF-67 particles on total flux at 40 0C, Feed= 90% water,10% ethanol

XII
Figure 21: Effect of ZIF-67 particles on selectivity at 40 0C, Feed= 90% water,10% ethanol
Figure 22: Effect of temperature increase on total flux
Figure 23 Effect of temperature change on selectivity

XIII
List of tables:

Table 1: Comparison of different membrane processes

Table 2: Surface are and pore volume of the prepared and some reported ZIF-67 materials.

XIV
List of Abbreviations:

Mixed matrix membranes (MMMs)

Polydimethylsiloxane (PDMS)

Poly [1-(trimethylsilyl)-1-propyne] (PTMSP)

Volatile organic compounds (VOCs)

Polyacrylonitrile (PAN)

Poly (tetrafluoroethylene) (PTFE)

Polysulfone (PSF)

Carbon nanotube (CNT)

Titanium oxide (TiO2)

Multiwalled carbon nanotubes (MWCNTs)

Porous organic cages (POCs)

Graphene oxide (GO)

Polyhedral oligomeric silsesquioxane (POSS)

Secondary building units (SBUs)

ZIFs (Zeolitic Imidazole Framworks)

Sodalite (SOD)

X-ray diffraction (XRD)

Scanning Electron Microscopy (SEM)

Brunauer–Emmett–Teller (BET)

Fourier transform infrared spectroscopy (FTIR)

Thermogravimetric analysis (TGA)

XV
 CHAPTER 1

Introduction and Literature Review

Problem statement
Renewable fuels have been considered as one of the major alternatives of current energy scarcity
problem due to the effects of fossil fuel on the climate. Among the widely used commercial
biofuels, bioethanol, obtained from the processing of biomass, is one of the most promising fuel.
However, the process of obtaining bioethanol from biomass is highly energy intensive. The major
limitation of this process is the high energy costs associated with the purification and enrichment
of ethanol. Among the various available techniques for the separation/purification of bioethanol,
hydrophobic pervaporation membrane based process is a viable alternative to supplement
distillation and removing volatile organic compounds. The methodology for making mixed matrix
membrane with Metal organic frameworks (MOFs) based fillers will make the separation process
less energy intensive and cost effective.

1.1 Background
Growing population has increased the demand of energy. Due to the drastic impacts of global
warming and concerns on energy shortage, it is extremely important to investigate and develop
both energy-saving and environment friendly procedures for chemical industries. As Global
warming and energy scarcity is amplifying day by day, it is very essential to develop and apply
some processes which can exhibit a green environment and can be energy saving for chemical
process industries. Separation processes are the main part in the assembling wheel of the chemical
process industries. They are utilized for such essential chores such as removal of contaminants
from crude materials, recovery and refinement of essential products and elimination of
contaminants from gushing water and air streams[1].

Mass separating agent is the heart of separating process. In distillation, it is heat; in extraction, the
solvent; in adsorption, the adsorbent; and in the membrane separation processes, the membrane

1
material. Separation in chemical industries usually utilizes 60-80% of the process cost. Recently,
membrane based separation is getting very much importance due to its extensive applications and
low energy requirements. This separation technique can be used to obtain pure water, less harmful
industrial waste, recapture hydrogen and pure solutions from different chemical and
pharmaceutical industries[2].

Membrane processes are physical processes which take place at ambient temperature so the
components under observation are not exposed to any thermal stress or chemical modification.
This is very significant in many chemical and biological applications where mixtures of sensitive
materials have to be parted. Membrane processes are less energy intensive and simpler than any
other continuous mode process. Down- or up scaling is simple and process costs depend hardly on
the plant size[3].

The conventional unit operations containing distillation, gas stripping and molecular sieve
adsorption are generally applied to separate and purify alcohols from alcohol/water mixtures.
However, these processes require very high energy. In addition, it is very expensive to have a
complete dewatering of alcohol through single-step conventional distillation process because of
the formation of azeotropic mixtures between alcohols and water.

To eliminate this issue, researchers have marked a very promising and energy saving step named
as pervaporation. It is an economic and environment friendly separation process and has been
considered as one of potential possibility to supplement the conventional separation processes in
dehydration of alcohols because of the simplicity in the process control and process outline, lower
energy necessities and flexibility in the process integration[3, 4]. For example, the energy request
for purification of isopropanol (IPA) from aqueous solutions may be dropped down by 87% if we
compare pervaporation with azeotropic distillation [5, 6].

1.2 Purification Techniques

There are several purification techniques which can be used for the purification of ethanol. Mostly
used techniques are following

 Distillation
 Adsorption

2
  Ozonation
 Gas stripping
 Membrane Technology (Pervaporation)

1.2.1 Distillation
Ethanol is mainly purified with the help of distillation which is the most leading and industrially
familiar purification technique. Feed is separated on the basis of difference of volatilities. In
distillation, by heating a mixture, low boiling point component of a mixture concentrated in the
vapor phase. These vapors can be obtained in liquid phase by condensing them back. Distillation
is considered as one of the best efficient separation technique but contains several operating
problems. One is the separation of aqueous/organic mixtures. In ethanol purification, a distillation
tower is designed to separate alcohol/water mixture efficiently. At top, ethanol is obtained; and at
bottom, water is obtained. It is expected that impurities even after distillation can sustain in ethanol.
Second problem is its high cost as distillation contains a repetition of vaporization and
condensation which is very costly[7].

1.2.2 Adsorption
Adsorption is a separation technique in which a large surface region of adsorbent is being utilized.
By depending upon physical and chemical properties, different compounds are simply adsorbed
on the adsorbent. Particles having high diameters are generally more adsorbed because they cannot
be diffused easily while the compounds with same polarity are more capable to be adsorbed. Pore
distribution and non-polar surface is favorable for ethanol purification as ethanol is polar which
can sustain different sized particles as impurities. From water treatment, activated carbon and
activated alumina are the most expectable adsorbents[8].

1.2.3 Ozonation
Ozone molecule consists of 3 oxygen atoms that can be decomposed into various kinds of
compounds. Chemical and physical properties of compounds such as increase in biodegradability,
volatility, and reduced toxicity change due to the decomposition of compounds. Oxidation of
ethanol can undergo with oxidation but it is not favorable on atmospheric conditions. Impurities
can be removed via ozonation without any significant damage to ethanol but still it can cause many
problems such as ozonolysis by-products and non-oxidizable compounds. Ozone cannot oxidize

3
all the compounds so it is expected that some compounds will remain even after ozonation. Being
an oxidation process, Ozonation cannot physically remove the compounds but could generate new
compounds such as by-products due to ozonation. Thus post-ozonation treatment is required for
their removal[9].

1.2.4 Gas stripping

Gas stripping is another purification technique in which the separation takes place on the basis of
volatility difference.

Henry’s law is used for the calculation

Pvap
H= (i)
Csat

Where H = Henry’s constant (moles/L atm).

Pvap = partial pressure of a pure compound (atm), and

Csat = the saturation concentration of the pure compound in the liquid phase (moles/ or mg/L)

This law is best described on the basis of vapor/liquid phases as henry’s law constant depends on
these phases. Compounds having low boiling points are usually stripped more straightforwardly
and easily. Acetaldehyde in ethanol which is an impurity can be stripped more easily due to this.
[10].

1.3 Membrane Technology

Membrane technology is considered as an essential part in industries as it offers several advantages
over other separation techniques including, less energy intensive, high selectivity and low cost.
Therefore, they are considered to be green technologies. There are different membrane processes
such as nano filtration, gas separation and pervaporation etc. [11-15]. Table 1 shows the complete
description of all the processes[16, 17].

4
Table 3: Comparison of different membrane processes

Process Membrane Principle Diving Force Feed phase Applications

type

Microfiltratio Finely micro Separation of Pressure Liquid or Gas Solids

n porous organic and gradient removal in
polymeric pharmaceutic
0.1-10 µm 35-350kPa
compounds al and
with micro electronics
pore ranges of industries
0.1-0.1-10µm

Ultrafiltration Finely micro Separation of Pressure Liquid Colloidal

porous water and gradient removal from
solutes waste water
1-100nm 140-700kPa
and food
process
industries

Reverse Dense Passage of Pressure Liquid Water

osmosis solvents gradient purification
through a
700-7000kPa
dense
membrane
that is
permeable to
solvents but
no solutes

Electro Electrically Electric Voltage Liquid Heavy metals

dialysis charged films potential is gradient recovery and
applied to DI water from
1-2 V

5
 transfer the conductive
ions spacers

Gas Dense Pressure Pressure Vapor or gas Separation of

separation gradient is gradient nitrogen from
applied to see air mixture,
700-7000kPa
the separation carbon
of gaseous dioxide
mixture removal from
natural gas
etc.

Pervaporation Dense Components Vapor Liquid Dehydration

are absorbed, pressure of solvents,
diffused and separation of
7-70kPa
desorbed azeotropic
through mixtures
vacuum

1.4 Pervaporation (PV)

Pervaporation is actually a blend of the terms permeation and vaporization in which the separation
occurs between gas and liquid phases. The process was first developed by Kober ,and is a relatively
new membrane separation process and possibly applicable to numerous cases There are three
current uses of pervaporation; water removal from organics, organic removal from aqueous media,
and the separation of organic mixtures[18, 19].

Pervaporation is promising when separating the azeotropes or mixtures having close volatility
difference. Alcohol dehydration of mixtures is now considered as a new frontier of industrial
pervaporation process plants. Currently, dehydration of solvents, in particular ethanol and
isopropanol, is the only process mounted on a large scale. Dehydration of fermentation product
directly, or following primary distillation, has become the classic example of membrane
pervaporation. In mid-1970s, Gesellschaft fur Trenntechnik (GFT), Co., Germany,
6
commercialized an economical pervaporation process for dehydrating ethanol and producing high
purities that resembled azeotropic distillation. Pervaporation is useful in process industries to
separate different azeotropes, close-boiling and heat sensitive liquid mixtures A membrane is a
gateway comprising of different materials which allow some materials to pass while others are
held back. Pervaporation is very demanding these days in chemical industries due to its several
advantages. Figure 1 demonstrates a simple membrane based separation process for aqueous
organic mixture[1, 20].

Figure 1: Membrane based separation process for liquid mixture [17]

A significant driving force is required to carry components through the membrane in

pervaporation; it does not usually depend on particular vapor/liquid equilibrium. Aqueous/organic
stream is obtained at the permeate side. Azeotropic distillation is very costly and difficult so
pervaporation is preferred to overcome on these issues[1].

Pervaporation (PV) is the best alternative to azeotropic distillation as it avoids cross contamination
of using the entertainers in azeotropic distillation[21]. Therefore, itis a highly promising
technology for the dehydration of aqueous organic mixture. In the past decade, researchers are
exploring new good performance membranes for the purpose of alcohol dehydration. An ideal
pervaporation membrane should have excellent permeability and selectivity, superior stability and
durability, high mechanical and economic viability. Inorganic membranes have high mechanical

7
stability and good performance but they are often rejected due to their fragility and high cost [3-
6].

Polymeric membranes are cheap and easy to synthesize as compared to inorganic membranes but
they are limited because of the trade-off between permeability and selectivity. Therefore, mixed
matrix membranes containing inorganic fillers embedded in a polymeric matrix may enhance the
combined characteristics of both organic and inorganic membranes in energy and environment
related separations[17]. While fabricating mixed matrix membranes (MMMs), the compatibility
of organic and inorganic phase is very important. To one side from the compatibility, the removal
of interface defects are also the key aspects of developing MMMs for pervaporation processes[6].

1.4.1 Brief History of Pervaporation

Pervaporation is a novel separation technique which is usually used to separate azeotropic
mixtures. It is a very efficient and cost effective technique for the dehydration of alcohols or
solvent mixtures. It is best applicable in different conditions such as the separation of organic-
organic mixtures or removal of different organics from aqueous solutions. Pervaporation provides
an efficient way of removal of bio-solvents without affecting the production rate of fermentation
broth [22].

Figure 2: Pervaporation process

8
As shown in fig 2, feed which is to be separated enters from the one side of membrane and
permeate is collected at the other side under the effect of vacuum. The chemical potential gradient
is the driving force in this type of separation.

The driving force can be generated by applying either vacuum pump or an inert purge (Nitrogen
or steam) on the permeate side in such a way the permeate vapor pressure is always lower than the
partial pressure of the liquid feed. Principally, vapor permeation or vapor phase pervaporation is
quite similar to pervaporation. In vapor permeation, feed which enters is in the form of vapors
rather than a liquid. Membrane requirements of vapor permeation and pervaporation are same so
the membranes currently being working in pervaporation can be used in vapor permeation
alternatively[23].

Although the origins of pervaporation can be traced to 1917, in this field was done only in the past
decade. Binning and CO-workers were the pioneers of doing first research effort in pervaporation.
Due to their work, pervaporation gained importance in separation applications. Although this work
was pursued for a number of years and several patents were published, the process was not
commercialized[23, 24].

In 1970s, the energy crises reconsider the keen interest in separation and purification technologies,
which are highly energy efficient. Because of its ability to separate aqueous azeotrope mixtures,
Pervaporation was primarily introduced in Europe. New and novel membrane materials were being
introduced till 1980s for similar separation technologies like reverse osmosis and gas separation,
which also enhanced the potential for pervaporation to be an economically technique. In the mid-
1980s numerous membrane applications were introduced which were based on new symmetric
polymer membranes from producing thermally and chemical stable as well as economic geometry
of membranes[23].

1.5 Fundamentals of pervaporation

Keeping in view the separtion properties of all techniques, pervaporation is much more complex
in comparison with the gas and liquid separations. The main reason of its complexity is the
presence of two phases in it i.e. vapor and liquid, that is why both mass and heat tranfer are
involved. Phase change undergoes from the feed to permeate. Chemical potential gradient
(fugacity gradient) acts as the driving force for mass transport, which can be developed by the use

9
of vacum pump or an inert gas on the permeate side which reduces the pressure on permeate side
less than the feed partial pressure[5].

The final separation performance of a mixture can be determined by 1) interactions in the feed
mixture and their physicochemical properties 2) the affinities of membrane material and permeate
and 3) the physical structure of the membrane. Regarding the transport mechanism in
pervaporation, there are a number of different suggestions but the most important mechanism
considered is solution diffusion model[17, 25].

1.5.1 Solution Diffusion Mechanism

In non-porous membranes, the most commonly decribed transport mechansim is solution-diffusion
model and consists of the following three steps[25]:

1) Selective sorption of the permeate from the liquid feed to the feed/membrane interface,

2) diffusion of the permeate in the membrane caused by the concentration gradient and

3) the desorption of the permeate to the vapor phase on the downstream side of the membrane.

Figure 3: Solution-Diffusion Model

Mass transport of a fluid through a non-porous, dense membrane is decsribed by this model as

Permeability (P)= Solubility (S) * Diffusivity (D)(ii)

10
Membrane material and the feed under process is governed by the solubility of the specified
component of feed in membrane. whereas diffusivity depends upon the physical and chemical
aspects like shape and size of penetrant molecules as well as interactions between the membrane
material and feed component.[26-28].

According to this mechanism, diffusion of the feed component through membrane is considered
as the rate limiting step. As a result, the solution-diffusion model assumes uniform pressure within
a membrane and the fugacity gradient is considered only as concentration gradient.

Fick’s first law is generally used to explain the diffusion process. Ji (g/cm2.s) i.e. Flux of a
component is described by the following equation [29]

(iii)

where dµi/dx is the chemical potential gradient or fugacity gradient of component I, whereas the
term Li is a proportionality coefficient which relates the flux with chemical potential driving force.
Chemical potential gradient can be the gradient in temperature, pressure, concentration or electric
potential. Considering the driving force to be the gradient in pressure and concentration, the
chemical potential gradient can be written as follows, which can be used for polymeric membranes
as well[28]:

(iv)

Where ci is the mole fraction (mol/mol) of component i, γi is the activity coefficient (mol/mol)
relating activity with mole fraction, p is the partial pressure, and vi is the molar volume of
component i. This model does not apply for inorganic membranes as the permeate is adsorbed
rather to diffuse and hence adsorption-diffusion model can be employed[30, 31].

To consider the dragging and concentration effects, much more complicated adsorption-diffusion
model based on Maxwell–Stefan theory is required. For inorganic membranes where surface
adsorption takes place, this model can describe the transport mechanism as it occurs by moving
from one adsorption position to the other one[32, 33].

11
1.5.2 Performance parameters
Pervaporation selection process is liable on its ability to separate different components from each
other. To determine the separation performance of Pervaporation, two parameters are usually used
i.e. selectivity/permeability and separation/flux factor. Flux (J) and separation factor (β) are
employed to judge the separation performance of Pervaporation process. These factors are defined
by the following equations:

𝑄
J = 𝐴𝑡 (v)

𝑦𝑖/𝑦𝑗
𝛽𝑖/𝑗 = (vi)
𝑥𝑖/𝑥
𝑗

In equation (iii) and (iv), Q is the total mass transferred over time t, A is the membrane area. x i
and yi are the mole fractions of one component in the feed and permeate, respectively, and x j and
yj are the mole fractions of the other component in the feed and permeate, respectively. After a
certain time interval, the permeate collected on downstream divided by the area of membrane is
considered as flux and is defined as the amount of permeate collected per unit time per unit area
of membrane(kg/m2-hr or kgmol/m2-hr) while separation factor is termed as the ratio of
concentrations of two components[34].

Due to the tradeoff relationship observed between separation and flux, pervaporation membrane
performance can be evaluated by the introduction of pervaporation separation index (PSI), which
can be defined as a product of separation factor and permeation flux[35]:

PSI=Jt 𝛽 (vii)

Where Jt is the total permeation flux, and 𝛽 is the separation factor. However, according to this
equation, if 𝛽 is equal to 1 and membrane possess high flux rates, the value of PSI can be large.
That’s why, the definition of PSI was later altered as a product of(𝛽 − 1) and Jt. Ideal separation
performance of membranes can be governed by this parameter with specified operating conditions
since the selectivity and flux normally show opposite behavior and it is difficult to achieve both
high selectivity and flux. However, due to the effect of specified operating conditions, there are
some restrictions to the parameter and the membrane performances comparison under different
operation conditions in the same separation system is still not possible[34].

12
1.6 Influence Parameters
The process factors that influence pervaporation flux and selectivity are:

(i) Composition (Feed),

(ii) Pressure (Downstream)
(iii) Temperature

These parameters are very important as to understand the effect of these factors on the separation
of different mixtures.

1.6.1 Feed Composition

Selectivity and flux in pervaporation are two major parameters to characterize the membranes, and
these are dependent of feed composition. Feed composition controls the liquid sorption and also
pays its vital role in membrane swelling. In two component feed mixture, Membrane swelling and
flux of a membrane is control by that component which has higher interaction with membrane
material, therefore if the concentration of that component increases, it will surely increase the flux
as well as swell the membrane. Diffusivity is a phenomenon in membrane separation which is
drastically depends on the membrane swelling but it decreases the selectivity. The whole process
can be concluded as the increase in the concentration of more interacting component in a mixture
with membrane material, not only increases in the flux but will gradually decreases the
selectivity[36-41].

1.6.2 Downstream Pressure

Permeation always needs a driving force and in pervaporation it is permeate pressure or vacuum.
To provide enough driving force is a challenge in pervaporation and it directly affects the cost of
operation due to the maintaining of vacuum. Downstream pressure not only determines the
concentration of components but also affects the membrane selectivity. In pervaporation, usually
dense membranes are used and in that case flux is always directly proportional to the concentration
and diffusivity [42-46].

13
1.6.3 Temperature
Temperature is another parameter which determines the rate of flux and selectivity of membrane
in pervaporation. The increase in temperature causes increase in flux but selectivity of membranes
usually decreases with this change. However the dependence of selectivity on temperature cannot
be easily defined because the chemistry of polymer-solvent interaction with respect to change in
temperature is very complex [47-50].

1.7 Pervaporation membrane materials

Membrane technology is attractive due to its extensive industrial applications. Different types of
membranes are used for separation purposes. Membrane can be of dense, micro porous symmetric
polymeric structure, which enables a high selectivity and flux with high PSI (Pervaporation
separation index). They have an asymmetric or composite structure which containing a thin micro
porous top layer and a porous support layer.

The material may be same or different. The first layer provides an effective separation maintaining
a high flux. The second layer provides the mechanical strength. Single plate, tube, hollow-fiber
or honeycomb structure can be used for this purpose. The sub layer should have an open structure
to avoid capillary condensation and vapor transport minimization. If the pores in the sub layer are
very large then it will be very difficult to apply a thin selective layer directly upon the support[4].

A multilayer membrane is often preferred to avoid all these problems. The support layer is usually
like an ultrafiltration membrane (made of e.g., polyacrylonitrile, polyetherimide, polysulfone,
polyethersulfone, or polyvinylidene fluoride, with pores in the range of 20–50 nm), cast on a
porous support layer consisting of a woven or nonwoven fabric. The top thin separating layer
containing thickness of 0.5-5mm is coated on this structure[51]. Fig. 5 represents a brief sketch of
pervaporation applications.

14
 Figure 4: Application areas of Pervaporation

The different materials used for the synthesis of pervaporation membranes are listed and
described below:

1. Polymeric Membranes
2. Inorganic Membranes
3. Mixed Matrix Membranes

1.7.1 Polymeric membrane

Polymeric materials are often used for pervaporation membranes due to their advantageous
properties such as high process ability and good separation performance. Basically, polymeric
membrane consists of three types which include glassy polymers, rubbery polymer or elastomeric
membranes, and ionic polymer membranes. Inherently, glassy polymers are preferred for solvent
dehydration due to its water selective nature whereas rubbery polymers are suitable for the
selective removal of organic compounds from water. For dehydration membranes, the polymer
materials should contain a proper balance of hydrophilicity and hydrophobicity[4].

Polydimethylsiloxane (PDMS) is the widely used polymeric material for the pervaporation of
organic-aqueous mixtures [52, 53]. It shows very good thermal, chemical and mechanical stability

15
along with great hydrophobic properties. Meanwhile, it is also very cheap and easily crafted
material [54-56].

Poly[1-(trimethylsilyl)-1-propyne] (PTMSP) is another very attractive hydrophobic material for

PV. It is a substituted polyacetylene that joins together a bulky trimethylsilyl side groups with rigid
backbone chain. These bulky groups minimize the rotational mobility and restrict the ability of the
polymer chains to closely pack together. PTMSP has great demand in the synthesis of vapor
separation membranes. It is a hydrophobic glassy polymer (Tg >300 ◦C) with an extremely high
free volume fraction (up to 25%) [57-60]. Non-porous, unsupported PTMSP membranes have also
been used for the separation of aqueous/ organic mixtures [4, 17, 29]. However, these membranes
show low permeate fluxes in PV [61-63].

The polyimide family has increased its demand for pervaporation based separation from the past
two decades. They are basically high temperature polymers with superior chemical and mechanical
properties along with good film forming properties. They are also very important in separating bio
fuels and liquid/liquid mixtures. Therefore they are considered to be one of the best materials for
polymeric membranes. They can be used for the concentration and recovery of alcohols from
biomass as energy sources, removal of volatile organic compounds (VOCs) from waste effluents,
and separation of aliphatic and aromatic isomers as feedstock for the chemical industry [64-67].
They exhibit very high efficiency in terms of selectivity in alcohol dehydration at broad range of
water concentrations. Their selectivity is high due to their low free volume/low mobility and the
small size of water relative to alcohol. Due to the low free volume and low solubility of water,
they show low permeation flux [68-70].

Figure 5: Membrane morphology including separating layer and support

16
Chitosan has also been reported as a polymeric material due to their better results [71-74]. By
using chitson as a material, high performance of membranes can be obtained (Flux and separation
factor) [75, 76]. There are numerous materials to make polymeric membranes, commonly used
polymers are poly (vinyl alcohol) (PVA) [77-79], chitosan [80], polyamide (PA) [81], polyimide
(PI) [82], polyacrylonitrile (PAN) [83], poly(tetrafluoroethylene) (PTFE) [84], polyethersulfone
and polysulfone (PSf) [85].

1.7.2 Inorganic membranes

These kinds of membranes are made up of inorganic materials such as zeolites, alumina and silica
etc. These materials are recognized by their good properties like thermal and chemical stability,
solvent resistivity and independence from swelling [80, 86]. There are wide applications of these
inorganic membranes because of their good permeability and selectivity. In pervaporation,
selectivity and permeability are the key targets, so inorganic membranes can play a vital role in
this application [87, 88].

Silica is one of the common material which generally give high flux but it is not sustainable in
hydrophobic environment [89]. Membranes having zeolites are so far best because of their tunable
chemical and mechanical properties [56]. Numerous zeolites are reported in literature for
pervaporation application, commonly used in studies are ZSM-5 [90], zeolite A [91], mordenite
[92], zeolite Y [93]. The commonly used fillers for MMMs which are used for pervaporation
studies are zeolites[90, 91], iron particles[85], titanium oxide (TiO2) [94], clay [95], carbon
nanotube (CNT) [96-98] and silica particles[99]. The main challenge for MMMs is the voids or
poor interaction between the polymer and fillers used in the matrix, this limitation is addressed by
using meso-porous inorganic filler and the materials used for this purpose are dual pore SBA-15
[100] and silica MCM-41 [101].

1.7.3 Mixed Matrix Membranes

It is a new class of materials for pervaporation and playing vital role in current membrane based
separation technology. Mixed matrix membranes (MMMs) comprise of inorganic filler particles
embedded in polymer matrix thereby combining the high process ability of polymers with high
permeability/selectivity of the fillers. Due to good mechanical and chemical stability these
membranes achieve high selectivity and permeability [102].

17
 Figure 6: Mixed Matrix Membranes

Kulprathipanja et al. in 1988 was the one who patented the Mixed Matrix Membranes to explore
the combine effects of polymeric and inorganic membranes[103]. Different inorganic fillers like
zeolites [104-110], multi walled carbon nanotubes (MWCNTs) [111, 112], silica [113] and
graphene oxide (GO) [114], porous organic cages (POCs) [115] and covalent organic frameworks
[116] and many others have been adopted and embedded in polymer matrix to enhance the
performance. The incorporation of inorganic fillers in polymer matrix is very difficult due to the
agglomeration of these particles which in turn creates defects in the membrane. Due to this
agglomeration, decrease in the selectivity can occur.[117, 118]. Different approaches can be used
to improve the inorganic filler dispersion in the polymer matrix. Recently, numerous works have
been focused on following approaches: (1) Modification of inorganic particles with agents which
can couple (coupling agents) to covalently bond the two phases [119-123]; (2) By Coating the
inorganic fillers with a thin polymeric layer [123]; (3) Employ hybrid particles such as polyhedral
oligomeric silsesquioxane (POSS)[124-126] or metal organic frameworks (MOFs) [127-130],
which contain both organic and inorganic components for better compatibility with the polymeric
matrix; and (4) Develop a new process for MMM fabrication [130, 131].

1.8 Metal organic Frame works

Currently, the most known advanced porous materials are hybrid metal–organic frameworks
(MOFs).There are different properties of MOFs which make them more attractive and feasible
such as new structures, high surface area, enhanced catalytically properties, high adsorption rate
and variety of pore sizes[132, 133]. Numerous types of MOFs are synthesized by different
synthesis techniques and properties of these materials are advanced by incorporating different
functionalities with the concept of secondary building units (SBUs). MOFs are basically consist
of two parts, one is the organic part which act as binding linker and the second part is inorganic
18
material (metal clusters). Different morphology of MOFs can be synthesized by just changing the
arrangement of SBUs[134, 135].

MOFs have been regarded as a new hybrid framework including Zeolitic architecture. ZIFs are
gaining great attention due to its tunable properties. ZIFs (Zeolitic Imidazole Framworks) are the
sub class of MOFs containing an organic and inorganic part. It consists of M–Im–M (where M
stands for Zn, Co cation and Im stands for the imidazolate linker) formed by a self-assembly
approach. The structures of ZIFs are quite similar to conventional alumino silicate zeolites, where
typically Zn2+ ions play the role of silicon and the imidazolate anions form bridges that mimic the
role of oxygen in zeolites, with the metal–imidazole–metal (namely M–Im–M) angle of 1450[136,
137]
. Due to this, ZIFs used to form zeolite like topologies with structure to those which can be
observed in zeolities. However, in ZIFs; structures which cannot be attained in zeolities can be
formed in ZIFs. ZIFs usually show all the properties such as ultrahigh surface areas, unimodal
micropores, high crystallinities, abundant functionalities and exceptional thermal and chemical
stabilities as it has the combine properties and advantages of MOFs and zeolites. These superior
properties make ZIFs available for many applications such as separation, sensing and
catalysis[138].

Zeolitic-Imidazolate-frameworks (ZIFs) can be used for the improvement of separation factor of

water/ethanol mixture. ZIF-7 incorporated in a chitosan polymer matrix having 5wt% MOF
loading has reported 19 times higher separation factor as compared to the neat polymer [139]. For
the dehydration of isopropanol, ZIF-90/polyimide P84 MMMs have also been synthesized with
different MOFs loadings[126]. This MOF loading is responsible for increasing the flux but
separation factor does not change much up to 20wt% filler. ZIF-71 was embedded in a polymer
matrix of polyether-block-amide which results in the improved separation factor and flux for ZIF
loading less than 20wt%. Different reports show that ZIF-71 filled PDMS membrane can enhance
the separation factor of aqueous/organic mixtures [81]. ZIF-8 showed improved results for the
compounds like iso-butanol and furfural [82]. The same results have obtained for water/n-butanol
mixtures using ZIF-8/PDMS membranes[140]. Polybenzimidazole (PBI) [129] and polyimide
Matrimids5218 [141] as polymeric matrix have also been influenced by ZIF-8 for increasing the
performance parameters. ZIF-8@siliceous meso cellular foams have been used to prepare MMMs
for water/ethanol PV [142].

19
1.8.1 ZIF-67
ZIF-67,a subset of Metal organic frameworks (MOFs) is crystalline porous material, shows many
desirable properties like good crystallinity , high surface area, chemical and thermal
stability[143].ZIF-67 (Co(Hmim)2) has same structure like ZIF-8, and is synthesized by bridging
2-methylimidazolate anions and cobalt cations resulting in a sodalite (SOD) topology. It is iso-
structural (frame structure and organic ligands) to ZIF-8 but has different metal atoms i.e. Co[143].

It has received attention due to its different applications as adsorbent, catalyst and in membranes.
It has been used as a catalyst in the formation of ethyl methyl carbonate[144], in the adsorption of
oxygen[145], as a sensor for formaldehyde detection[146], and in membranes for
CO2Capture[147]. ZIF-8 as a filler showed promising results in pervaporation application[129]
and has same frame work of ZIF-67.

Figure 7: Tetrahedral unit of ZIF-67

Therefore in this present work, ZIF-67 has been synthesized and incorporated in polymer matrix
to make high performance MMM for hydrophobic pervaporation application. It is expected that
the incorporation of hydrophobic ZIF-67 will increase the overall performance of membrane for
pervaporation application.

1.9 Common Fabrication Methods for Pervaporation Membranes

Pervaporation membranes which are commonly adopted are either asymmetric or dense. Dense
structure of membrane are usually synthesized at lab scale and are hampered at industrial scale

20
whereas asymmentric membranes can provide enhanced performance due to thin selective layer
supported by a relatively thick microporous substrate[148]. Following are some common methods:

 Solution Casting
 Hollow fiber spinning
 Solution coating
 Interfacial Polymerization

1.9.1 Solution Casting

The most common method for the fabrication of flat sheet membranes is solution casting. The
sample containing polymer and fillers are dissolved in solvent first and spread onto a flat surface.
The solvent is evaporated leaving behind a flat dense film. In case of MMM, membranes are
prepared by the incorporation of fillers into polymer matrix followed by stirring. After strirring,
sonication is used to prevent agglomeration of fillers. Subsequently, MMMs are formed by the
similar procedures as discussed before[148] .

1.9.2 Hollow Fiber Spinning

This process is used for the preparation of hollow fiber membranes. These membranes are more
acceptable if compared with flat sheet assembly. Different advantages like high packing density
etc. can be obtained by using this process. This process offers the reduction of cost and the
customization of different materials and structure for preparing different layers [149, 150]

1.9.3 Solution Coating

This process is usually applied to synthesize composite membranes. A thin selective layer is coated
on support which can be flat sheet or hollow fiber. Porosity of substrate is very important so that
the separation could mainly controlled by the coated selective layer [151, 152]. The substrate
surface and pore size distribution should be defect free to exclude intrusion of the coating solution.
To minimize the intrusion, pre-wetting technique can be adopted with low boiling point solvent
before the coating process. Pre-wetting of solvent is removed with the help of drying process. After
drying, the coated membrane is obtained. Flat sheet configuration is usually adopted in
pervaporation. Hollow fiber membranes are difficult to obtain due to the small fiber diameters.
Separation can be hindered due to the uneven coated fibers [153, 154].

21
1.9.4 Interfacial Polymerization
Interfacial polymerization is a well-known process usually adopted for reverse osmosis and Nano
filtration process for preparing thin composite membranes. This technique has also been applied
for pervaporation membranes. This process is widely used since 1960s. [155-157]. In this process,
the thin layer on the substrate top greatly affects the membrane flux [158].

1.10 Scope of thesis

The aim of this present work is to synthesize ZIF-67 based Mixed Matrix Membranes (MMM) for
the separation of ethanol-water mixtures.

In chapter 2, the synthesis of ZIF based MMM has been studied to improve the performance of
pervaporation membranes. Firstly, ZIF-67 was synthesized for the incorporation in polymer
matrix. Mixed Matrix Membranes were synthesized by using polyimide as a support and
Polydimethylsiloxane (PDMS) as a dense top separating layer. Furthermore, different
characterization techniques were adopted to confirm the purity of the samples. Different loadings
of ZIF-67 have been incorporated in membranes to enhance the performance parameters.

In chapter 3, conclusion of the work is discussed which is followed by the recommendations for
future work to explore the potential of mixed matrix membranes (MMMs) in pervaporation.

22
 CHAPTER 2
SYNTHESIS OF ZIF-67 FILLED PDMS MEMBRANES FOR BIO
ETHANOL RECOVEY
2.1 Introduction
The increase in the concentration of greenhouse gases due to the excessive use of fossil fuel has
led to the research for searching out ways to secure and sustain our energy resources. Cellulose
promises an alternative method to harness fuel due to its natural abundance, low cost and not a
human food source making it more resourceful [159]. On the same trend line bio-alcohol are more
likely to be a promising alterative to gasoline because as it offers favorable characteristics such as
high energy and low vapor pressures.[160].

Numerous purification processes such as distillation, gas stripping, adsorption and membrane
based separation processes can be employed to distill bio-alcohols. Adsorption and distillation are
prominent processes being employed for this purpose but extra cost and difficult maintenance are
some major drawbacks. On the other hand membrane based separation processes share less cost
and results in a more efficient process. The separation processes share about 60%–80% cost for
the entire bio-fuel processing [2]This account for the low concentration of the bio-fuels existing
in the fermentation broth causing difficulty in recovery of bio-fuel for further use increasing the
processing cost. And this is mainly attributed to the dilute concentration approximately 1–5 wt%
bio-alcohols in the fermentation broth, which increases the processing cost.[3].

For the past few decades, pervaporation has emerged as a promising technique for purifying bio-
alcohols and holds the potential to save up to 50% energy in contrast with the distillation processes
available[3]. To achieve such critical performance high performance membrane is essential
possessing more chemical and thermal stability to numerous feeds and different compositions.
Another issue is the hydrophilicity of membranes made of materials such as alginate, chitosan and
PVA rejecting water [161, 162].

The porous particle fillers dispersion in polymeric matrix comprising of Mixed matrix membranes
(MMMs) possess favorable features of polymers and particle fillers and holds a promising future
for PV separation material synthesis. Silicalite [131, 140], zeolite [106], silica [163], and
carbonaceous particles [164] are commonly used inorganic particles in alcohols separations. But

23
the incompatibility of inorganic and polymeric phase resulting in membrane defects constrains its
performance. As a consequence MMMs selectivity results in little or no improvement as compared
to the original polymer membranes [165]. Higher selectivity results in lower permeability are
another challenge that reduces its efficiency[166][128, 167].

Recent studies have showed that zeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, are
capable of superior thermal and chemical resistance resulting in enhanced stability and can be used
for variety of applications at higher temperature and adverse conditions [168]. Incorporation of a
super hydrophobic material such as ZIF-67 in PDMS is expected to improve alcohol separation
producing more yields. It shares another advantage that ZIF-67 particles can be synthesized at
nominal temperature resulting in an economical, time saving and convenient way in contrast to the
available hydrothermal synthesis methods available for preparation of zeolites. Most of ZIFs are
synthesized at high temperature and autogenous pressure making the process more complex and
energy consuming in contrast to ZIF-67 synthesis.[143].

In the presented word, an attempt has been made to incorporate the super hydrophobic ZIF-67
particles as fillers in MMMs to investigate the improvement in the separation process along with
the resultant flux. Ethanol recovery from aqueous/organic mixture has been chosen as the
application to test the flux and selectivity of the ZIF-67/PDMS mixed matrix membranes for
pervaporation process.

2.2 Materials
P84 Polyimide powder was purchased from HP polymer (Austria). Toluene and Methanol (CH4O)
were purchased from VWR international (UK). 4-methyl-2-pentanone (MIBK) and isopropanol
(IPA) were purchased from BDH laboratory supplies (England) and Sigma-Aldrich
respectively.N-Methylpyrrolidinone (NMP) and Tetrahydrofuran (THF) were purchased from
Merck Schuchardt OHG (Germany). PDMS monomer and crosslinker (RTV 615 A and B) were
acquired from Techsil (UK). 2-Methylimidazole (99.0%) and Cobalt nitrate hexahydrate [Co
(NO3)2.6H2O were obtained from Acros Organics and Fischer Chemicals respectively.

2.3 ZIF-67 Synthesis

Considering that ZIF-67 crystals can be synthesized at nominal temperature, room temperature
was chosen and the crystals were prepared in accordance with the previously reported literature

24
[143]. Initially the synthesis was carried out by adding 0.35 g of Cobalt nitrate hexahydrate Co
(NO3)2.6H2O in 11.3 g of methanol (CH4O). Afterwards 0.66 g of 2-methylimidazole (C4H6N2)
was dissolved in 11.3 g methanol. After homogeneous mixing the two prepared solutions were
mixed and continuously stirred for 2 h at room temperature. The solution turned in to a purple
precipitate which was isolated from the solution by centrifugation at 3500 rpm for 20 min. After
treatment the resultant solution is rinsed with methanol three times and dried overnight at 85
o
C[143].

Figure 8: ZIF-67 Powder

2.4 Membrane Synthesis

The phase inversion technique was used to prepare a porous support layer from a polymer dope
solution. By using anon-woven polypropylene support (Novatex-2471) ,a thin layer of controlled
thickness of PI solution (15 wt.% PI, 2 wt.% H2O, 62.25 wt.% NMP and 20.75 wt.% THF) was
deposited using an automatic film applicator .The ensemble was immersed for 10 min using a
water coagulation bath at room temperature after a 30 s evaporation step. The film formed by this
process was post-treated by a sequential solvent exchange. This was done by immersing the
support in IPA (3 h) and then in a mixture of MIBK, toluene and oil in a 40:40:20 (v/v)

25
compositions for 3 days supports were dried at 65 ◦C for 1 h. The support was dried and the excess
of oil and solvents was wiped off with a tissue paper.

The top selective layer of PDMS was coated on the support using dip-coating technique. A15 wt.
% PDMS solution in hexane comprising of RTV 615 A and 615 B in a ratio 10:1 was formulated
and stirred for 2 h at 60 ◦C. The ratio of 80:20 of Toluene and Hexane was used as solvents and
the coating solutions were loaded with different filler (5 wt. %, 10 wt. %, 15 wt. % and 20 wt. %).
To ensure a good dispersion of the particles fillers were added in a PDMS solution, which was
then stirred and sonicated simultaneously for 15 min each (3 times). Air bubbles that could induce
the formation of defects are removed during the membrane synthesis by keeping membrane in an
ultrasonic bath for 20 min[169].

Coating was done using PDMS solution on PI support. The angle of support plate was kept at
600.This step was repeated three times letting evaporate the hexane for 5 min in between. Cross
linking was completed in an oven at 110 ◦C for24 h. Selected membrane pictures are as follows:

Figure 9: a) 5 wt% b) 10 wt% c) 15% d) 20%

26
2.5 Characterization techniques
Different characterization techniques have been used to determine and confirm different
parameters of the sample. The details of the characterization techniques are as follow:

2.5.1 XRD
X-ray diffraction (XRD) technique is used to check the crystallinity of the sample. It’s an
important technique as the results of XRD play a key role in determining the performance of
the synthesized particles. Characteristics properties such as electronic band structure tagged
with catalyst surface characteristics are greatly influenced by the crystalline structure of the
mater. The results showed the purity of the sample as the peaks were well matched to the
reported literature. Crystalline phases and lattice parameters can be identified with XRD
which shows its significance. XRD of ZIF-67 was done with X’Pert PAN Analytical.

2.5.2 SEM
Scanning Electron Microscopy uses a beam of electrons to generate different signals. In SEM,
the sample is placed against high energy electron beam. This beam strikes the sample material
and various signals are generated as a result of that impact. The signals that obtained from
SEM give different information such as external morphology, composition, orientation and
crystallization of the sample. Different electrons such as secondary electrons and back
scattered electrons give different information. These beams are collected by a detector at the
end. The detector analyzes the obtained information and gives the image of the sample
surface. All the SEM images of fillers were taken with TESCAN Vega LMU – Variable
pressure Scanning Electron Microscope.

2.5.3 BET
Brunauer–Emmett–Teller (BET) is used to explain the physical adsorption of gas molecules on
solid surface. The analysis usually tells about the pore size and surface area of given sample
(Filler). These two parameters are important as they explain the adsorption rate of filler in MMM.
The adsorption rate will be higher for higher surface area and vice versa. Pore volume also plays
a vital role in membrane based separation. This technique helps for the selection of proper filler
which can give better results when incorporated in polymer matrix.The BET working principle is
based on physisorption phenomena. The prepared sample was exposed to nitrogen gas and the

27
catalyst surface area was calculated by analyzing the N2 volumetric adsorption on ZIF-67 surface.
BET results of ZIF-67 was taken by Tristar II 3020 whose temperature range was ambient to 4250
Celsius.

2.5.4 FTIR
Fourier transform infrared spectroscopy (FTIR) is a technique which is used to determine the
functional groups of the given sample. In FTIR, an infrared spectrum of absorption or emission of
a solid, liquid or gas is obtained. The goal of FTIR is that how efficiently a sample absorbs light
at any wavelength. As every functional group absorbs light at a specific wavelength so it becomes
very easy to compare the data with literature to identify the functional groups. ZIF-67 carries
different functional groups which were identified with the help of FTIR. The results of prepared
ZIF-67 sample was evaluated by Thermo-Nicolet 6700 P FTIR Spectrometer (USA).

2.5.5 TGA
Thermogravimetric analysis (TGA) is a technique which is used for the thermal analysis of the
given sample. In this technique, changes in different properties of materials (physical or chemical)
are observed by as a function of temperature. This technique is viable to gain different information
such as vaporization, sublimation, adsorption and absorption etc. Thermal degradation of material
is very necessary to measure as often membranes have to bear harsh conditions so it is important
to check the degradation point of fillers used in MMMs. TGA was carried out to verify the thermal
stability of ZIF-67.TGA study of ZIF-67 filler was carried out by SDT Q600 TGA /DSC, TA
Instrument.

2.6 Pervaporation experiments

The separation performance of the synthesized membranes were tested using a homemade
pervaporation unit. The selected feed solution of 90/10 wt % water/ethanol was kept in continuous
contact with the membrane. The membranes were tested on the selected temperature range of 40-
70 0C. The overall setup is divided into two parts, first one is known as feed section and other one
is called permeate section. Membrane module was installed between feed and permeate sections.
Membrane module (CF042D) operates on cross flow pattern. The effective membrane area
was0.0019 m2. Before running the whole unit, the membranes were kept in contact with feed
solution for 5 h to reach the steady state. After then, the feed was pumped with a continuous

28
volumetric flow rate of 1L/min at atmospheric pressure. Peristaltic pump was used for pumping
the feed to membrane module and retentate was sent back to the feed tank for recycling purpose.
Feed solution was heated by a heating mental to check the variability of selectivity and flux of
membranes at different temperature values. High vacuum conditions were provided during
experimentation and an oil sealed vacuum pump was used to create a vacuum of 75 torr for this
purpose. Steel Cold traps containing ice as a cooling media were used to collect the vapors
(permeate) and finally the flux and separation factor were calculated by using the equations (iii)
and (iv). All the samples were collected after every 3h. Schematic diagram of this experiment is
shown in figure 4 for better understanding.

Figure 10: Homemade Pervaporation Set-up

Flux is defined as a total mass flow of the permeating molecules i.e ethanol and water per unit time
per unit area
𝑄
J = 𝐴𝑡 (v)

The separation factor was calculated using equation (vi)

𝑦𝑖/𝑦𝑗
𝛽𝑖/𝑗 = 𝑥𝑖/𝑥
(vi)
𝑗

29
Yi(Water) and Yj(Ethanol)are the weight fractions in permeate side where as Xi(Water) and
Xj(Ethanol) are the weight fractions in feed side.

2.7 Results and Discussions

2.7.1 Filler Selection

ZIF-67 particles were selected due to their superior stability and high surface area. In addition, the
hydrophobicity of synthesized ZIF-67 particles would preferentially resist water to penetrate and
would allow ethanol to diffuse through their pores.

The ZIF-67 filler was also chosen due to their smaller aperture size (0.34 nm) which would help
ethanol molecule to diffuse. Though the kinetic diameter of water molecule (0.27 nm) is lesser
than the ethanol molecule (0.43nm) but the super hydrophobic nature of ZIF-67 particles would
resist water molecules to pass through. The average particle size of ZIF-67 particle is 4.82 nm.

Following table shows the Surface area and pore volume of ZIF-67 in different solvents:

Table 4: Surface are and pore volume of the prepared and some reported ZIF-67 materials.

Sample Solvent Surface Area Pore Volume Ref

(m²/g) (cm3/g)

ZIF-67 Water 316 0.17 [170]

ZIF-67 Water 601 0.25 [171]

ZIF-67 TEA 636 0.26 [172]

ZIF-67 Methanol 1244.74 0.665 This work

2.7.2 Characterization of as-prepared ZIF-67 particles

The crystal structure of the as-synthesized particles was confirmed by X-ray Diffraction (XRD)
analysis as shown in fig. 11.The particles were synthesized in two different solvents to check the
interaction of the polymer and metal ions with solvents in designated time. The different diffraction
peaks showed that the synthesized particles were consistent to the reported peaks of ZIF-67[143],
30
which validated that the prepared particles were successfully synthesized and well developed .The
XRD pattern is given below:

Figure 13: XRD spectrum of ZIF-67 particles

Figure 14: XRD pattern of ZIF-67 particles in two different solvents (Water; above, Methanol;
below)

31
The SEM images confirmed that the prepared particles of ZIF-67 are of nano scale with the particle
size, ranging from 100-200 nm for methanol as a solvent and for water it is 220-350 nm. Different
images are shown as below:

Figure 13: SEM Image of synthesized ZIF-67 (Methanol) nano particles at SEM HV and SEM
Magnification of 15 KV and 25.0kx respectively.

Figure 14: SEM Image of synthesized ZIF-67 (Water) nano particles at SEM HV and SEM
Magnification of 15 KV and 10.0k x respectively.

32
As synthesized ZIF-67 particles were also analyzed using Nitrogen sorption to confirm the
surface area and pore volume etc. Results revealed that the BET surface area and pore volume
came out to be 1244.74m2/g and 0.665cm3/g respectively. This high surface are and pore
volume would promote high adsorption rate in polymer matrix. Fig 15. Shows the
N2adsorption isotherm of ZIF-67 particles.

19.4
19.2
Quantity Adsorbed (mmol/g)

19
18.8
18.6
18.4
18.2
18
17.8
17.6
17.4
17.2
0 0.2 0.4 0.6

Figure 15: Nitrogen adsorption isotherm of synthesized ZIF-67

An FTIR spectrum was obtained to determine the surface chemistry of ZIF-67 particles. The IR
spectrum of ZIF-67 particles is show in fig 16. Different functional groups were present in ZIF-67
particles. These functional groups were mainly attributed by ligand i.e. 2-MIM and obtained peaks
were well indexed to the previously reported work [171]. The peaks from the range 600-1500 cm-
1
were due the stretching and bending of the imidazole group.

FTIR spectrum of ZIF-67 is given below:

33
 Figure 16: FTIR spectrum of ZIF-67 particles

TG analysis was done to check the thermal stability of ZIF-67 particles. The TGA curve showed
weight loss up to 3.5% at 100-200 °C. This weight loss could be due to the escape of different
guest molecules such as methanol or ligand (2-MIM). After 200 °C, the major weight loss in the
particles occurred up to 500 °C. This weight loss was mainly due to the decomposition of the
ligand. This report showed that the prepared particles were thermally stable and could be used for
thermally harsh applications. Moreover, TGA results also justified the absence of any solvent in
the sample. Methanol was used as a solvent to synthesize theZIF-67 particles having the boiling
point of about 64.7 °C, so if there would have been solvent in it then the curve must had sharp
decrease at that temperature. The material was pure and stable and the TGA curve was well
matched when compared with the reported literature [173].

34
 120

100
Weight loss (%)

80

60

40

20

0
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)

Figure 17: TGA curves for ZIF-67

2.7.3 Swelling Studies

Pervaporation follows the solution-diffusion mechanism and it follows a three step process i.e.
sorption-diffusion-desorption. The separation is based upon the selective sorption and diffusion of
the material. Degree of swelling was done to investigate the effect of incorporation of ZIF-67
particles in PDMS membrane. The properties of unfilled PMDS membranes were changed after
the incorporation of fillers. As expected, the neat PDMS showed the highest swelling for longer
chain alcohols such as methanol and ethanol (fig. 17 & 18). The Hildebrand solubility parameter
for methanol and ethanol is 29.6 Mpa0.5 and 26.5 Mpa0.5 respectively, which is much closer to the
solubility parameter of PDMS i.e. 15.5 Mpa0.5 resulting in a strong affinity to the PDMS matrix.
By filling the PDMS matrix with ZIF-67, the free volume of the PDMS matrix was decreased
resulting in the decrease of membrane swelling. The fillers occupied the vacant spaces in the
polymer matrix due to the better physical interactions between ZIF-67 and PDMS matrix.

35
 0.9
0.8 0.85
0.7
Ethanol Swelling (ml/g)
0.72
0.6 0.69 0.68
0.62
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20
ZIF-67 (wt%) in PDMS

Figure 18: Membrane swelling with different filler loadings

0.8
0.68
0.7
0.62
0.56
Methanol swelling (ml/g)

0.6
0.53
0.49
0.5

0.4

0.3

0.2

0.1

0
0 5 10 15 20
ZIF-67 (wt%) in PDMS

Figure 19: Membrane swelling with different filler loadings

36
2.7.3 Effect of ZIF-67 Loading on PDMS/ZIF-67 Mixed Matrix Membranes (MMMs)
Effect of ZIF-67 loading on the performance of membranes is presented in Fig 20 and Fig 21.
Increasing the fillers loading in polymer matrix significantly increased the total flux and
selectivity. The addition of fillers in the polymer matrix imparts porosity in the matrix leading to
enhancement in the total flux through the membrane. The flux of the membranes was increased by
66.1 % and the selectivity was increase by 48.73%.

Total flux Vs ZIF Loading at 40 0C

3

2.5
Total Flux(kg\m2.hr)

1.5

0.5

0
0 5 10 15 20 25
ZIF-67 loading (wt%)

Figure 20: Effect of ZIF-67 particles on total flux at 40 0C, Feed= 90% water,10% ethanol

37
 Selectivity Vs Zif loading at 40 0C
18

16

14

12
Selectivity

10

0
0 5 10 15 20 25
ZIF-67 loading (wt%)

Figure 21: Effect of ZIF-67 particles on selectivity at 40 0C, Feed= 90% water,10% ethanol

2.7.4 Effect of feed temperature on PDMS/ZIF-67 Mixed Matrix Membranes

(MMMs)
The effect of feed temperature on the total flux and selectivity was also investigated (Fig. 22 and
Fig 23). The effect of temperature was studied from 40°C to 70°C .The results showed that by
increasing the temperature, the total permeation flux (water & ethanol) increased while the
selectivity decreased. Similar behavior was observed at all loadings of fillers. The permeation flux
of water was greater than the ethanol due to the fact that the kinetic diameter of water (0.27nm) is
less than the ethanol (0.43nm) therefore the water would easily diffuse through the aperture size
(0.34nm) of filler by increasing temperature. The degree of membrane swelling increases by
increasing the temperature which results in the increase of motion of polymer chains. According
to free volume theory, thermal movement of polymer chains are directly related with the free
volume [174]. As the temperature was increased, the free volume and activity of permeating
molecules was also increased due to the increase in frequency and amplitude of chains. This
resulted in the increase of total flux and consequently the selectivity was decreased. The results

38
revealed that on increasing the feed temperature, the total flux was improved by 66 % for 20 wt%
membrane.

3.5

3
Total Flux(kg\m2.hr)

2.5

1.5

0.5

0
40 50 60 70

Temperature (oC)
0% 5% 10% 15% 20%

Figure 22: Effect of temperature increase on total flux

14
13
12
SELECTIVITY

11
10
9
8
7
6
40 50 60 70

Temperature (oC)
0% 5% 10% 15% 20%

Figure 23 Effect of temperature change on selectivity

39
 Chapter 3

3.1 Conclusions and future work

PDMS/ZIF-67 mixed matrix membranes (MMM) were synthesized for hydrophobic pervaporation
of ethanol/water mixture. As synthesized ZIF-67 particles were incorporated in polymer matrix
with different loadings i.e. 5 wt% to 20 wt%. The following conclusions are obtained from the
work:

 ZIF-67 particles were synthesized having high surface area (1,244.7446 m²/g) and pore
volume (0.665776 cm³/g) which attributed to the higher separation when incorporated in
polymer matrix.
 The incorporation of ZIF-67 particles in PDMS membrane has enhanced the flux and
separation factor simultaneously.
 The enhancement in total flux were observed on increasing the temperature from 40 0C to
70 0C as high temperature favors the diffusion permeating molecules.
 The PDMS/ZIF-67 blend decreased the swelling rate as compared to the neat PDMS.

In summary, the incorporation of fillers (ZIF-67) in PDMS matrix has increased the separation
performance of pervaporation membrane. The best results were obtained at 40 0C with 20 wt%
ZIF loading. The total flux and selectivity was enhanced by 66% and 48.73% respectively.

3.2 Future works

There are several extensions possible to increase the separation performance of mixed matrix
membranes. Crosslinking of different polymers can be adopted to enhance the separation. It has
been recommended to use different types of hydrophobic ZIFS to check the results. The interaction
of polymer/filler blend can be improved by the modification or crosslinking of fillers and
polymers. It is highly recommended to check the organic/organic separations with ZIF-67/PDMS
membranes.

40
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