Synthesis & Characterization of Silylated MCM-41/Polysulfone Mixed Matrix

Membrane for CO2/CH4 Separation

by

Yoong Kai Bin

18491

Extended proposal submitted in partial fulfilment of

the requirements for the
Bachelor of Engineering (Hons)
(Chemical Engineering)

September 2016

Universiti Teknologi PETRONAS,

32610, Bandar Seri Iskandar,
Perak Darul Ridzuan

Open

ABSTRACT

Mixed matrix membrane has been developed rapidly in the gas separation
technology. However, the incompatibility between polymer matrix and inorganic
filler has been a major concern in mixed matrix membrane. MCM-41 is chosen for
this study as its mesoporous structure is suitable for gas separation applications.
MCM-41 was synthesized via templating method and then modified by surface
silylation with trimethylchlorosilane to enhance its hydrophobicity for good
dispersion and adhesion in mixed matrix membrane. Polysulfone (PSf) is
incorporated with silylated MCM-41 to form mixed matrix membranes. The
silylation is expected to increase hydrophobicity of the MCM-41 and thus, the
resulting mix matrix membrane is expected to has better permeability and selectivity.

CHAPTER 1
INTRODUCTION

1.1

Background of Study
Natural gas is an important element of the energy supply around the globe

and the annual natural gas consumption is expected to increase from 120 trillion
cubic feet in year 2012 to 203 trillion cubic feet in year 2040 according the
International Energy Outlook 2016 (IEO2016). Natural gas is primarily comprised of
methane (CH4), along with a small amount of lights alkanes and impurities.
However, Malaysia crude natural gas contains high amount of carbon dioxide (CO 2)
content as impurity. The composition of the natural gas from offshore of Terengganu,
Malaysia is shown in Table 1.1(Bakar & Ali, 2010). Since CO 2 reduces the energy
content of the natural gas and causes corrosion in pipeline, it is essential to remove
CO2 via gas separation process.
Table 1.1

Chemical composition of crude natural gas provided by Bergading

Platform offshore of Terengganu, Malaysia (Bakar & Ali, 2010)
Gases
CH4
C2H6
C3H8
CO2
H2S

Composition (%)
40-50
5-10
1-5
20-30
0-1

Several gas separation technologies have been developed including

absorption, adsorption, cryogenic distillation and membrane separation (Shimekit &
Mukhtar, 2012). The most promising technology in gas separation is membrane
separation due to its high efficiency, low energy consumption, excellent intrinsic
transport properties, high process ability and relatively low operating cost
(Rezakazemi, Amooghin, Montazer-Rahmati, Ismail, & Matsuura, 2014).
1.2

Problem Statement
The polymeric membranes possess some limitations despite of the cost

savings and high efficiency. The polymeric membranes normally face an upper
bound limitation because of the trade-off relationship between selectivities and
permeabilities (Robeson, 1991). Inorganic membranes such as carbon molecular
sieves membranes and zeolite membranes were subsequently discovered. Their
separation performances were beyond Robesons upper bound but these materials are
expensive to fabricate.
This leads to the emergence of mixed matrix membranes in gas separation
technology. This approach combines the excellent gas separation performance of
inorganic materials and the economical process ability of the polymeric materials
(Moore, Mahajan, Vu, & Koros, 2004). However, voids exist between inorganic
fillers and polymers due to weak contact of inorganic particles around the polymer
matrix and poor dispersion of the inorganic particles.
In this study, Polysulfone is chosen as the polymer and MCM-41, a
mesoporous material with a hierarchical structure from a family of silicate and
alumosilicate solids is incorporated into the polymer matrix to form mixed matrix
membrane. To overcome the incompatibility between MCM-41 and polysulfone,
modification of MCM-41 by surface silylation with Trimethylchlorosilane was
studied.

1.3

Objectives
1. To modify MCM-41 by surface silylation with trimethylchlorosilane.
2. To synthesize and characterize silylated MCM-41/Polysulfone Mixed
Matrix Membranes (MMMs).
3. To perform gas permeation test for pure carbon dioxide and methane
gases.

1.4

Relevancy and Feasibility

Mixed matrix membranes are known as a very effective method in gas

separation processes including the removal of carbon dioxide in natural gas. Hence,
identification of new polymeric and inorganic materials for MMM is gaining strong
interest in ongoing research projects. This study is relevant to the field since it
focuses on the modification of inorganic filler for fabrication of MMM.
The proposed study is compulsory to be completed within 28 weeks. A
detailed plan and Gantt chart is shown in chapter 3 and the research project is
feasible within the time frame. All the chemicals and equipment required for
fabrication of MMMs and analytical equipment required for characterization and gas
separation performance test are available in the university.

CHAPTER 2
LITERATURE REVIEW

2.1

Membrane Technology
Membrane technology is a process which involves the application of

membrane as thin barrier between miscible fluids to separate a mixture. The driving
forces for membrane process are pressure drop and concentration difference. The
permeability and selectivity are generally the two key factors in determining the
performance of a membrane. Permeability is defined as the ability of the permeates
to pass through a membrane whereas selectivity is the ratio of permeability of the
more permeable component to that of the less permeable (Goh, Ismail, Sanip, Ng, &
Aziz, 2011).
Membrane technology is preferred over the other gas separation operations
like absorption process and cryogenic distillation because of the attractive features
including the ability to separate chemical species without a phase change, low
thermal energy consumption and simplicity in operation (Rufford et al., 2012).

2.2

Mixed Matrix Membranes (MMMs)

The emergence of MMMs in membrane technology has been vital due to the

limitations of both polymeric and inorganic materials. This approach combines the
excellent gas separation performance of inorganic materials and the economical
process ability of the polymeric materials (Moore et al., 2004).
In the preparation of MMM, inorganic materials are dispersed into polymer
matrix. Figure 2.2 indicates the MMM where the dispersion of inorganic materials is
embedded in the polymer matrix. In order to improve gas separation performance of
MMM, inorganic materials act to create favored permeation pathways for selective
permeability as well as posing a barrier for undesired permeation (Jadav & Singh,
2009).

Figure 2.2:

Schematic diagram of MMM (Aroon, Ismail, Matsuura, & MontazerRahmati, 2010)

Since the inorganic materials have specific structure, surface chemistry and
high mechanical strength, they can undoubtedly improve the properties of MMMs
compared with the conventional polymeric membranes (Aroon et al., 2010). Besides
of excellent gas separation performance, MMMs possess higher thermal stability
(Bakhtiari, Mosleh, Khosravi, & Mohammadi, 2012). Table 2.2 compares the
different properties between polymeric membrane, inorganic membrane and MMM.

Table 2.2:

Comparison of the properties for membranes (Ismail, Goh, Sanip, &

Aziz, 2009)

Properties

Polymeric
membrane
Low
Moderate

Inorganic
membrane
High
High

Moderate
High

Mechanical
Strength

Good

Poor

Excellent

Solvent
compatibility

Limited

Wide range

Limited

Swelling

Frequently
occur
Moderate

Free of swelling

Free of swelling

Moderate

Exceeds Robeson
upper boundary

Handling

Handling

Handling

Cost
Chemical and
thermal stability

Separation
performance
Handling

MMM

2.3

Mesoporous Silica MCM-41

In year 1992, researchers at ExxonMobil Corporation discovered a family of

silicate/aluminosilicate mesoporous molecular sieves with remarkably large uniform
pore structures known as M41S (Sayari, 1996). The members of M41S include
MCM-41 in hexagonal form, MCM-48 in cubic form and MCM-50 in lamellar form
as shown in figure 2.2. Among these three members, MCM-41 has been
experimented widely because the other members are either hard to obtain or
thermally unstable (Vartuli et al., 1994).

The different structures of the M41S family (ALOthman,

Figure 2.2:

2012)
MCM-41 has exclusively high surface areas and narrow pores with diameter
ranges from 15 to 100 . Pore size can be tailored during synthesis by the nature of
the surfactant compound, variation of the reactant stoichiometry, the auxiliary
chemicals,

the

synthetization.

reaction

conditions,

or

functionalization

techniques

after

(ALOthman, 2012). The pore sizes of MCM-41 are defined as

mesopores by IUPAC. Since the pores of MCM-41 are significantly larger than those
micropores which exist in crystalline materials, it is involved in application of gas
separation, catalysis, adsorption and advanced composite materials (Chen et al.,
2009).

2.4

Silylation of MCM-41

Silylation is a mechanism where a silyl group is introduced into a molecule.

This process usually occurs in substitution for active hydrogen. Since the active
hydrogen is replaced by a silyl group, the polarity of the compound is reduced due to
the reduction of hydrogen bonding(Orata, 2012).
The silylation reaction is driven by leaving group which is able to stabilize a
negative charge in the transitional state. In the intermediate step of reaction
mechanism, a bimolecular transition state is produced (Khnel et al., 2007). This
indicates that the leaving group must has a low basicity. For instance, when
trimethylchlorosilane is used as reagent in this mechanism, the leaving group is the
chlorine atom.

Figure 2.4:

Reaction mechanism of silylation (Orata, 2012)

Trimethylchlorosilane (TMCS) is a common silylating reagent for silica

surface and it has been applied to mesoporous molecular sieves (Kisler, Stevens, & O
Connor, 2001). MCM-41 belongs to mesoporous family and therefore, TMCS has
been used to provide a hydrophobic layer on the surface of MCM-41 to improve its
stability (O'Connor, 2002).

CHAPTER 3
METHOLOGY

3.1.

Flow Chart of Project Activities

Figure 3.1:

Flow Chart of Project Activities

3.2

Gantt-Chart of FYPI

10

Week
Tasks

Status

1 2 3

Selection and Confirmation of

Compl

Project Topic
Preliminary

eted
Compl

4 5 6 7

8 9 1 1 1 1 1
0 1 2 3 4

Background

X X X X

Research
Literature Review

eted
Compl

Selection of Polymer

eted
Compl

Selection of Inorganic Filler

eted
Compl

Selection of functionalization

eted
Compl

for MCM-41
Development of Methodology

eted
Compl

X X

Submission

X X

X X X X X
X
X

of

Extended

eted
Ongoi

Proposal Draft
Submission
of

Extended

ng
Ongoi

Proposal
Development of Experimental

ng
Ongoi

X X

Proposal
Proposal Defense Presentation

ng
Pendin
g
Pendin
g
Pendin
g
Pendin
g

Synthetization of MCM-41
Functionalization of MCM-41
Submission of Interim Report
Draft
Submission of Interim Report

X
X
X
X

Pendin
g

CHAPTER 4
CONCLUSION & RECOMMENDATION

11

The major challenge of the mix matrix membrane is the incompatibility of the
organic materials and polymer matrix. The low hydrophobicity between the two
compounds will cause particle agglomeration during the fabrication of MMM.
Silylated MCM-41 is expected to increase the hydrophobicity and this could avoid
agglomeration among particles in MMM. Therefore, the resulting MMM is expected
to has better permeability without sacrificing the selectivity. The major
recommendation of future study is on the amount of loading of silylated MCM-41
into MMMs during the fabrication.

12

REFERENCES
ALOthman, Z. A. (2012). A review: fundamental aspects of silicate
mesoporous materials. Materials, 5(12), 2874-2902.
Aroon, M. A., Ismail, A. F., Matsuura, T., & Montazer-Rahmati, M. M. (2010).
Performance studies of mixed matrix membranes for gas
separation: a review. Separation and purification Technology, 75(3),
229-242.
Bakar, W. A. W. A., & Ali, R. (2010). Natural Gas: INTECH Open Access
Publisher.
Bakhtiari, O., Mosleh, S., Khosravi, T., & Mohammadi, T. (2012).
Preparation, characterization and gas permeation of polyimide
mixed matrix membranes. Journal of Membrane Science &
Technology, 2011.
Chen, J., Xia, N., Zhou, T., Tan, S., Jiang, F., & Yuan, D. (2009). Mesoporous
carbon spheres: Synthesis, characterization and supercapacitance.
Int. J. Electrochem. Sci, 4, 1063-1073.
Goh, P. S., Ismail, A. F., Sanip, S. M., Ng, B. C., & Aziz, M. (2011). Recent
advances of inorganic fillers in mixed matrix membrane for gas
separation. Separation and purification Technology, 81(3), 243-264.
Ismail, A. F., Goh, P. S., Sanip, S. M., & Aziz, M. (2009). Transport and
separation properties of carbon nanotube-mixed matrix membrane.
Separation
and
purification
Technology,
70(1),
12-26.
doi:http://dx.doi.org/10.1016/j.seppur.2009.09.002
Jadav, G. L., & Singh, P. S. (2009). Synthesis of novel silica-polyamide
nanocomposite membrane with enhanced properties. Journal of
membrane science, 328(1), 257-267.
Kisler, J., Stevens, G., & O Connor, A. (2001). Adsorption of proteins on
mesoporous molecular sieves. Materials Physics and Mechanics, 4,
89-93.
Khnel, E., Laffan, D. D., LloydJones, G. C., Martnez del Campo, T.,
Shepperson, I. R., & Slaughter, J. L. (2007). Mechanism of methyl
esterification of carboxylic acids by trimethylsilyldiazomethane.
Angewandte Chemie International Edition, 46(37), 7075-7078.
Moore, T. T., Mahajan, R., Vu, D. Q., & Koros, W. J. (2004). Hybrid
membrane materials comprising organic polymers with rigid
dispersed phases. AIChE journal, 50(2), 311-321.
O'Connor, A. J. (2002). Jing Yang, Antje Daehler." Michelle L. Gee, Geoffrey
W. Stevens" and. Nanoporous Materials III, 141, 221.
Orata, F. (2012). Derivatization reactions and reagents for gas
chromatography analysis: INTECH Open Access Publisher Rijeka.
Rezakazemi, M., Amooghin, A. E., Montazer-Rahmati, M. M., Ismail, A. F., &
Matsuura, T. (2014). State-of-the-art membrane based CO 2
separation using mixed matrix membranes (MMMs): an overview
on current status and future directions. Progress in Polymer
Science, 39(5), 817-861.
Robeson, L. M. (1991). Correlation of separation factor versus
permeability for polymeric membranes. Journal of membrane
science,
62(2),
165-185.
doi:http://dx.doi.org/10.1016/03767388(91)80060-J
Rufford, T. E., Smart, S., Watson, G. C. Y., Graham, B. F., Boxall, J., Diniz da
Costa, J. C., & May, E. F. (2012). The removal of CO2 and N2 from
13

natural gas: A review of conventional and emerging process

technologies. Journal of Petroleum Science and Engineering, 9495,
123-154. doi:http://dx.doi.org/10.1016/j.petrol.2012.06.016
Sayari, A. (1996). Catalysis by crystalline mesoporous molecular sieves.
Chemistry of Materials, 8(8), 1840-1852.
Shimekit, B., & Mukhtar, H. (2012). Natural gas purification technologiesmajor advances for CO2 separation and future directions: INTECH
Open Access Publisher Croatia, Europe.
Vartuli, J., Schmitt, K., Kresge, C., Roth, W., Leonowicz, M., McCullen,
S., . . . Schlenker, J. (1994). Effect of surfactant/silica molar ratios
on the formation of mesoporous molecular sieves: inorganic
mimicry of surfactant liquid-crystal phases and mechanistic
implications. Chemistry of Materials, 6(12), 2317-2326.

14