Topic: Nanofiltration

Engr. Mohsin Ali

Membrane Separation
Membrane

Feed

Permeate

Particle or Solute
Molecule

Solvent

Pressure-driven
Operations
-Microfiltration (MF) -Ultrafiltration (UF)
-Nanofiltration (NF) -Reverse Osmosis (RO)

Pressure-driven Membrane
Processes

Pressure-driven Membrane Processes

NF:
Sometimes referred to as low-pressure RO or membrane
softening process
Lies between RO and UF in terms of selectivity of the
membrane
Designed to remove multivalent ions but can remove sodium
and chloride fairly well
Looser NF membranes are more like UF and tighter NF
membranes more closely resemble RO
Recently has been employed for organic control
Typical operating pressure: 5-14 bar (70-210 psi)

Morphology
Symmetric

Cylindrical Porous

Porous

Homogeneous

(resistance to mass transfer is determined by total membrane thickness)

Asymmetric Single Material
top layer
Porous

Porous with Top Layer

Asymmetric Composite
dense skin layer (0.1 to 0.5 m)
porous membrane (50 to 150 m)

(resistance to mass transfer determined by skin layer thickness)

Transport Mechanisms and

Performance Parameters
Separation and
Transport
mechanisms:
Molecular Sieving
Solution Diffusion
Charge effect of
membrane

Performance Parameters:

Membrane Materials
Polymeric membranes:
Polysulfone
Polyethersulfone
Polyphenylsulfone
Polyvinylidene Fluoride (PVDF)
Polypropylene (PP)
Polyethylene (PE)
Cellulose and Cellulose
acetates (CA)
Polyamide (PA)
Polyacrylonitrile (PAN)
Polytetrafluoroethylene (PTFE)
Polycarbonate (PC)
Polymethylmethacrylate
(PMMA)

Ceramic membranes:

Aalumina
Titania
Zirconia
ATZ mix

chemical, mechanical and thermal

stability
ability of steam sterilization and back
flushing
high abrasion resistance
high fluxes
durable
bacteria resistance
possibility of regeneration
dry storage after cleaning

Membrane Properties
Pure water permeability (PWP)
Pore size
Molecular Weight Cut-Off (MWCO)
Hydrophobicity/hydrophilicity
Surface/pore charge
Surface roughness
Chemical stability / chlorine tolerance

Types of
Membrane
Ino

For
aqueous
system

For nonaqueous
system

Organic Solvent
Resistant
Nanofiltration

Separation

Nanofiltratio
n

rga
ni
Me c
mb
ne ra M
s
ix
Ma ed
Me trix
Po mb
nly
mera
es
r

i
Me c
mb
ne ra
s

Permea
nce

Problem Statement
In industrial processes, Organic solvents are usually
wasted after the usage which do not cause only fatal
effects for environment but also it is waste of money
as these organic solvents are usually expensive.
The efficient recovery and re-use of these organic
solvents can provide a pathway to reduce pollution
and cost of processing.

Introduction

Organic
Solvents

Chemical
Industrie
s

Vandezande, P., L.E. Gevers, and I.F. Vankelecom, Solvent resistant

nanofiltration: separating on a molecular level. Chemical Society

Material recovery
from Dyeing Industry
Solvents and active
pharmaceutical
compounds recovery
Separation of
homogeneous
catalysts from
organic solvents
Separation of free
fatty acids from
vegetable oil
Separation of light
hydrocarbons
solvents from lube
oil

Mixed Matrix Membranes (MMM)

Zeolites

Fillers

Inorganic Filler

Polymer Matrix

Goh, P.S., et al., Recent advances of inorganic fillers in mixed matrix

membrane for gas separation. Separation and Purification Technology,
2011. 81(3): p. 243-264.

Mesoporous
silica
Activated
carbons
Carbon
nanotubes
Layered silicates
TiO2
Iron oxides
Metal Organic
frameworks
(MOFs)

Metal-Organic Framework (MOFs)

Better affinity
for the polymer
chains (because
of organic
linkers)

What is a MOF?

Crystalline material having

coordination bonds between
transition-metal cations and
organic linkers.

Porous:
molecular
sieving
effect

Why
MOFs?

Adsorbent

Easy to adjust : Size,

shape,
chemical
functionalities
of
pores

Zeolitic Imidazolate Framework (ZIF)

Characteristics of both MOFs
and zeolites.
Consist of MImM (MetalImidazolate-Metal).
Structures
similar
to
conventional aluminosilicate
zeolites.

Why ?

ZIF-8

145

ZIF
Zeolite

Abundant active surface sites

Large surface area along with high
chemical and thermal stability.
Separation of organic chemicals and
catalysts.

Research Objective and Our

Approach
Research Objective:
This research focuses on the synthesis of Zeolitic Imidazolate Framework (ZIF) based
Mixed Matrix Membranes for effective Organic Solvent Resistant Nanofiltration.

Our
Approach:
Synthesis of ZIF-8
Synthesis of Polyimide
Supports
Synthesis of Composite
Mixed Matrix Membranes
(PDMS+ZIF-8)

PDMS
Dense top layer

Porous support of Polyimide

ZIF-8

Synthesis of ZIF-8

Zn(NO3)2.6H2O + 2methylimidazole+
methanol

Stirring
(24 h)

Centrifugi
ng

Drying 120
C for 24 h

Polyimide Support Preparation

Polyimide
+ NMP+
THF

Stirrin
g

Asymmetric PI
Membrane

PI
solutio
n

Phase
Inversion
(water as
nonsolvent)

Polyimid
e
membra
ne

Synthesis of Mixed Matrix SRNF

Membranes

PDMS + nHexane+
Toluene

PDMS
Solution

PDMS
Solution
+ ZIF-8

60

Stirring
and
Sonicati
on

Coating
of
polyimid
e
membra
ne
Mixed
Matrix
SRNF
Membra
ne

Cont..

15 wt % ZIF-8

20 wt % ZIF-8

XRD Results:

This work

Reported

3
2

6
2

6
4 5

11

7 8

9
10

11
4

10
Zahmakiran, M., Iridium nanoparticles
stabilized by metal organic frameworks
(IrNPs@ ZIF-8): synthesis, structural properties
and catalytic performance. Dalton

SEM and XPS Results:

Survey
2 Scans, 54.4 s, 400m, CAE 200.0, 1.00 eV
4.00E+05

Zn2p3

Counts / s

3.00E+05

2.00E+05
O1s

N1s C1s

1.00E+05

0.00E+00
1200

1000

800

600

Binding Energy (eV)

Particle size range= 50-80 nm

400

200

FTIR Results:
Prominent peaks
in the range of
550-1550 cm-1
justify the
presence of C-C,
C-CH3, C-N
C=C, C=N come
into range of
1600-1800 cm-1
Some stretches
near 3600 cm-1

BET Results:
Material

Surface Area= 1,258.17

m/g
Pore Volume=0.608578
cm/g
Pore Size= 19.7723
(width)

Solvent

Surface

Pore

Referenc

used

Area

Volume

(m/g)

(cm3/g)

ZIF-8

Methanol

1258

0.60

This work

ZIF-8

Water

620

0.25

[1]

ZIF-8

Methanol

962

0.36

[2]

ZIF-8

Water

1079

0.31

[3]

[1] Cravillon, J., et al., Rapid room-temperature synthesis and characterization of nanocrystals of a prototypical zeolitic
imidazolate framework. Chemistry of Materials, 2009. 21(8): p. 1410-1412.
[2] Gross, A.F., E. Sherman, and J.J. Vajo, Aqueous room temperature synthesis of cobalt and zinc sodalite zeolitic
imidizolate frameworks. Dalton transactions, 2012. 41(18): p. 5458-5460.
[3] Pan, Y., et al., Rapid synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in an aqueous system.

Testing Setup:
Stainless steel
dead-end filtration
cell (Sterlitech,
USA) with 0.00146
m2 active
membrane area
Feed pressure =
10 bar
Nitrogen as carrier
gas
Feed solution of
Congo red dye

Performance Tests and Results

Discussion

Retention Study
Congo Red Dye:

Congo red dye was used as

solute to study the retention
parameter
Molecular mass= 696.66
g/mol
max at 500 nm in uv-vis
spectrophotometry

Isopropyl alcohol:
Isopropyl alcohol was
used as solvent
Molecular mass= 60.1
g/mol
Molecular size= 16.05

Boiling point= 82.6C

Cont..
22% increase in retention was observed
ZIF-8
wt % loading in PDMS

Retention %

56

57

10

68

15

75

20

87

Permeance Study
24 % increase in permeance was observed
ZIF-8 loading in PDMS

Permeance
(10 bar)

wt %

l/h m2 bar

3.15

3.65

10

3.75

15

4.05

20

4.16

Swelling Study
Toluene and IPA were used for swelling tests
Physically crosslinking of filler with the polymeric chains of PDMS decreased
the degree of swelling.
0.4 0.35
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
Swelling in IPA (ml/g)

0.34
0.28

0.32

0.3

ZIF-8 in (wt%) filled in PDMS

Swelling in Toulene (ml/g)

0.9
0.88
0.86
0.84
0.82
0.8
0.78
0.76
0.74
0.72
0.7

0.81
0.77

0.89

0.86

0.77

ZIF-8 in (wt%) filled in PDMS

Conclusions

MMMs are promising solution

for
the
separation
and
recovery of organic solvents.

The incorporation of filler not

only increased the separation
and
permeance
but
also
decreased the swelling of
membrane.

22% increase in retention was

observed by the addition of
filler

24% increase in permeance

was observed