Professional Documents
Culture Documents
year 2011-2012
A
review
of
Alumina:
Most
abundant
and
productive
material
of
the
mother
nature.
TABLE
OF
CONTENT
1.
INTRODUCTION
...........................................................................................................................
3
2.
ALUMINA
AS
A
MATERIAL
.......................................................................................................
4
2.1.
NOMENCLATURE
.....................................................................................................................
4
2.2.
STRUCTURE
AND
MINERALOGICAL
PROPERTIES
........................................................
8
2.2.1.
STRUCTURE
OF
ALUMINA
PHASES
.....................................................................................................
8
2.2.2.
PSEUDOMORPHOSIS
..............................................................................................................................
9
2.2.3.
SURFACE
AREA
OF
ALUMINA
.............................................................................................................
12
2.2.4.
POROSITY
..............................................................................................................................................
13
2.2.5.
SORPTIVE
CAPACITY
...........................................................................................................................
15
2.3.
MECHANICAL
PROPERTIES
OF
ALUMINA
.....................................................................
16 2.4.
THERMAL
PROPERTIES
OF
ALUMINA
............................................................................
20 2.5.
CHEMICAL
PROPERTIES
OF
ALUMINA
...........................................................................
22 2.5.1.
WET
CHEMICAL
REACTIONS
OF
SINTERED
ALUMINA
..................................................................
22
2.5.2
REACTION
OF
CHEMICAL
ELEMENTS
WITH
ALUMINA
...................................................................
23
1.8.
COLLOIDAL
PROPERTIES
OF
ALUMINA
.........................................................................
24 3.
ALUMINA
MEMBRANES
..........................................................................................................
26 3.1.
INTRODUCTION
.....................................................................................................................
26 3.1
PREPERATION
OF
ALUMINA
MEMBRANES
....................................................................
29 3.2.1.
MACROPOROUS
ALUMINA
MEMBRANE
PREPARATION
................................................................
29
3.2.2.MESOPOROUS
ALUMINA
MEMBRANES
.............................................................................................
31
3.2.3
MICROPOROUS
ALUMINA
MEMBRANES
...........................................................................................
35
4.DESIGN
OF
THE
MEMBRANE
MODULES
.............................................................................
38 4.1
DIFFERENT
TYPES
OF
MODULES
......................................................................................
38 4.1.1
ALUMINA
MEMBRANE
MODULES
.......................................................................................................
39
4.1.2.
COMMERCIALIZED
MODULES
OF
MEMBRANE
ALUMINA
...............................................................
42
4.2.
SEPARATION
CHARACTERISTICS
FOR
ALUMINA
MEMBRANES
.............................
45 5.
APPLICATIONS
...........................................................................................................................
49 5.1.
CERAMIC
MEMBRANES
........................................................................................................
49 5.2.
ALUMINA
MEMBRANES
APPLICATIONS
........................................................................
52 5.2.1.
LIQUID
PHASE
SEPARATION
APPLICATIONS
...............................................................................
52
5.2.2.
GAS
PHASE
SEPARATION
.................................................................................................................
63
6.SUMMARY
AND
CONCLUSIONS
..............................................................................................
74 APPENDIX
A
:
MEMBRANE
MATERIAL
SHEET
.....................................................................
75 APPENDIX
B:
CHEMICAL
INTEREST
OF
ALUMINA
..............................................................
77 REFERANCES
...................................................................................................................................
85
1. INTRODUCTION Ceramists are not close agreement as to the substances included in the term of ceramics, nor do they seem to have devised as simple, consistent definition of the term that is entirely satisfactory. Kingerly defined it as the art and science of making and using solid articles which have as their essential component, and are composed in large of inorganic nonmetallic materials. L. Mitchell defined ceramics as all high-temperature chemistry and physics of nonmetallic materials, and the techniques of forming products at high temperatures. The first definition allows inclusion of materials having melting points below room temperature, as, for example ice; while the second does not exclude certain organic substances that may been produced at high temperatures, such as carbon disulfide. Although materials of all kinds, including organic substances, are involved in the preparation of ceramics, it is believed that these definitions are too broad to cover the ceramic applications of alumina. The investigation of alumina as a ceramic material was undertaken to provide information under the following specifications: a review dealing with alumina both from a theoretical and a practical point of view, and including information on the nomenclature, properties of alumina, alumina as a membrane material and finally industrial alumina membrane applications. The following information has been gathered: A general review tried to be gathered to understand deeply about alumina material and also alumina membranes. occurrence in nature crystal or mineralogical characteristics mechanical, thermal, chemical and colloidal properties. alumina membranes fabrication, modules and industrial applications.
2. ALUMINA AS A MATERIAL
2.1. NOMENCLATURE De Morveau suggested the word alumine in 1786 as the proper name for the basic earth of alum. This was Anglicized to Alumina in England while Germany tornerde is still used, meaning clay earth. The term alumina is presently used rather indefinitely in ceramic literature to denote; 1. aluminous material of all types taken collectively 2. the anhydrous and hydrous aluminum oxides taken indiscriminately 3. the calcined or substantially water free alimunium oxides without distinguishing the phases present 4. corundum or alpha alumina, specifically. It is often used interchangeably with the molecular formula Al2O3. The true meaning is sometimes hard to determine from the context. More than 25 alumina solid phases is defined in recent years. But it is doubtful if all of them really exist or not. These phases includes, amorphous hydrous and anhydrous oxides, crystalline hydroxides and oxides, and aluminas containing small amounts of oxides of alkalies or alkaline earths, designated as beta aluminas. The phases found in the nature, and few of artificial types, have common or mineralogical names. Most of them also are defined by greek letter formulas. Corundum, emery, sapphire, and ruby are more or less pure forms found in the nature and known for antiquity as abrasives and gem stones. All consist of the the phase designated alpha alumina (! Al2O3). Figure 1 shows the dehydration sequence of alumina hydrates in air. Diaspore Another native mineral, described by Hay in 1801, was named diaspore by him, from the Greek for scatter because it flew apart upon heating. 4
Gibbsite Vaquelin in 1802 gave its formula as Al2O3 3H2O. Dewey named a well- crystallized mineral gibbsite for G. Gibbs an American mineralogist. It corresponded with the formula Al(OH)3 or Al2O3 3H2O. It is the principal phase of the trihydrate bauxites. Bauxites Berthier examined a mineral from Les Baux in southern France, containing about %52 Al2O3 and 20% bound water, from which it was supposed that the mineral was Al2O3 2H2O. The mineral was named bauxite by St. Clair Deville. Bohemite After X- Ray diffraction became generally used for analysis of chemical components a new pattern of bauxite is discovered. This bauxite has %15 bound
water
Al2O3
H2O.
This
component
named
bohemite
for
both
natural
and
artificial
products.
These
phases
are
the
izomers
of
diaspore.
In
USA,
the
word
bauxite
has
come
to
mean
any
highly
aluminous
ore
composed
mainly
of
one
or
more
of
phases,
gibbsite,
boehimite
and
diaspore.
In
reality
no
phase
corresponding
to
Al2O3
2H2O
has
been
found.
In
1925,
Haber
devised
a
system
of
nomenclarature
for
trivalent
alumina
phases
the
known.
The
alpha
series
included
diaspore
and
corundum
(alpha
alumina);
the
gamma
series
included
hydrargillite
(gibbsite),
bauxite
(bohemite),
and
gamma
alumina.
The
classification
was
obviously
based
on
the
end
product
of
calcination,
but
this
is
somewhat
arbitrary
because
gamma
alumina
also
transforms
to
alpha
alumina.
Bayerite
A
new
phase
is
identified
by
Bhm
in
aluminum
hydroxide
precipitates
that
had
aged
moist
for
several
months
at
room
temperature.
The
water
content
was
about
that
of
gibbsite,
but
the
X-Ray
pattern
was
different,
indicating
an
isomer
of
gibbsite.
This
phase
called
Bayerite
by
Fricke
in
1928
on
the
erroneous
supposition
that
it
was
normal
product
of
the
Bayern
process.
L.
Milligan
had
already
shown
in
1922
that
the
Bayer
product
is
predominantly
gibbsite.
Bayerite
was
claimed
to
have
been
found
in
nature
by
Gedeon,
and
more
recently
(1963)
by
Gross
and
Heller.
The
failure
of
Haber
classification
system
to
distinguish
between
bayerite
and
gibbsite
prompted
the
devising
of
the
Alcoa
system
of
nomenclature
(Frary).
In
this
system,
the
choice
of
Greek
letters
was
initially
based
on
the
relative
abundance
of
phase
in
nature.
Gibbsite
was
called
alpha
alumina
trihydrate;
bohemite,
alpha
alumina
monohydrate;
bayerite
beta
alumina
trihydrate;
and
diaspore,
beta
alumina
monohydrate.
Gamma
alumina
and
beta
alumina
had
the
same
significance
as
in
the
Haber
system.
Table
1:
Nomenclature
of
Crystalline
Aluminas
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
5)
Mineralogical
Name
Phase
of
Form
Name
Symposi um
(1)
Alcoa
(2)
! !"! !! 3!! !
! !"! !! 3!! !
! !"! !! !! !
! !"! !! !! !
Chi
Eta
Gamma
Kappa
Ioata
(17)
Alpha
Haber
(3)
! !"(!")!
! !"(!")!
! !"(!")!
! !"(!")!
Aluminas
Corundum,
Sapphire
Zeta
Alumina
Chi
Eta
Gamma
Kappa
Alpha
Gamma
Alpha
Chi
+
Gamma
Gamma
Delta
Kappa
+
Theta
Alpha
Rho
Chi
+
Gamma
Eta
Gamma
Kappa
+
Delta
Alpha
2
Xi ,
Xi
(13)
1
French (5)
Other
Hydroxides Gibbsite (6) Al(OH)3 Hydrargillite Bayerite (7) Nordstrandite (1) Randomite (8) Bayerite II (8) Bauxite (9) Bohemite (10) Diaspore Tohdite (11) Al(OH)3 Al(OH)3
AlO Al2O M2O 11 Al2O3 (14) M2O 6 Al2O3 (15) MO 6 Al2O3 Li2O 5 Al2O3 (10)de Lapparent (11)Yamaguchi (12)Steinheil (13)Cowley (14)Rankin and Merven (15)Scholder (16)Barlett (17)P.A. Foster
(1)
Ginsberg,
Huttig,
Strunk-Lichtenberg
(2)
Edwards,
Frary,
Stumpf,
et
al.
(3)
Haber,
Weiser,
and
Milligan
(4)
Rooksby,
Day,
and
Hill
(5)
Thibon,
Tertian,
and
Papee
(6)
Dewey
(7)Fricke
(8)Teter,
Gring,
and
Keith
(9)Bhm
Standardization of the nomenclature for aluminas is very desirable particularly to avoid the confusion in the hydrous phases. Gingsberg reported the conclusions of a symposium held in 1957, in which an attempt was made to devise a universal standard nomenclature. Some features of the proposed system are improvements, for example the substitution of hydroxide instead of hydrate, namely, aluminum trihydroxide for alumina trihydrate; aluminum oxide hydroxide for alumina trihydrate; aluminum oxide hydroxide for alumina monohydrate. Also, it was agree to use the Alcoa nomenclature for the transition aluminas, but to designate some of them as forms rather than phases, to imply the present uncertainty about them. The confusion in naming the hydroxide phases has not been resolved, however.
2.2. STRUCTURE AND MINERALOGICAL PROPERTIES The remarkable range of properties of the hydrous and non hydrous crystalline properties of alumina has been interesting for researchers, and its structure has been induced much scientific curiosity. Examples of these structural peculiarities are the factors determining the phenomena of transition phases, and the exceptional strength and hardness of corundum. Besides the ideal crystal structures, which are a rarity in actual ceramic systems, defect crystal structure and microstructure are significant. Gross structure beyond the crystal lattice beyond the crystal lattice is also of ceramic interest. 2.2.1. Structure of Alumina Phases Crystal structure is the main factor controls the properties of aluminas. In general, the phases of most significance in alumina are those produced by pseudomorphic dehydration. The crystal structures of alumina phases are shown in Table 2. Mineralogical properties of the various phases are shown in Table 3.
2.2.2. Pseudomorphosis Achenbach (1931), Damerell (1932), and Teritan (1950) have shown that the dehydration of gibbsite crystals is pseudomorphic, that is, external shape of the crystals is retained and there is an orientation relationship of the crystal axes of the new phases to those of the original. The crystals lose transparency and smoothness upon heating, and fine-grained fibers develop parallel to the hexagonal surface. Void space resulting from the loss of water from the gibbsite and increasing density of the transition phases is distributed in microporosity of very high surface area in the porous skeleton (Weitbrecht and Fricke). Pseudomorphosis is of considerable importance because of its effect on surface area of the intermediate phase structures, and on crystal size and size distribution of the fully calcined aluminas for ceramic forming processes. With the basis of alumina structure, all the transition aluminas have oxygen ions in approximately cubic close packing. The differences in their patterns represent changes in intensities of reflections resulting from differences in distribution of the aluminum ions. The initial cationic disorder of the low-temperature phases depends upon the source of the alumina. The transitions become more ordered with increasing heat treatment.
Table 2: Crystal Structure of the Aluminas (WALTER , Alumina as a Ceramic Material, 1970, page 30)
Phase
Formula
Crystal
System
Mole- Space
cules
Group
!
!!
! !!
Angle
Ref.
Hydrated Aluminas Gibbsite ! !"! !! 3!! ! ! !"! !! Bayerite 3!! ! Nordstrandite !"! !! 3!! ! Bohemite ! !"! !! !! ! Diaspore ! !"! !! !! ! Transition Aluminas Chi Eta Gamma Delta Iota Theta Kappa Corundum ! !"! !! Al2O !"# !"! !! Beta Aluminas (21) !"! ! 11!"! !! !! ! 11!"! !! !"# 11!"! !! !"# 6!"! !! !"# 6!"! !! !"# 6!"# Zeta Alumina !"! ! 11!"! !!
Monoclinic Monoclinic Monoclinic Orthorhombic Orthorhombic Cubic Cubic (Spinel) Tetragonal Tetragonal Orthorhombic Monoclinic Orthorhombic
4 2 8 2 2 10 10 32 4 4 32 2 1 1 1 2 2 2 2
!" !! !" !! ! !! ! !!
7.95 7.9 7.95 7.95 7.79 7.967 7.967 23.47 7.73 7.78 2.92 5.63 2.95 11.86 8.49 12.73 13.96 4.758 4.98 7.915 5.58 5.58 5.56 5.54 5.56 5.58 12.991 22.45 22.67 22.55 21.83 21.95 22.67
! !! ! !! ! !! ! !! ! !! ! !! ! !!
7.9
(1) Megav (2) Swanson, Coo Isaacs, & Evans (3) Unmack (4) Lippens (5) Swanson & Fuyat (6) Saalfeld (7) Brindey & Nakahira (8) Verwey
(9) Stumpf (10) Teritan & Papee (11) Rooymans (12) Reichertz & Yost (13) Kohn (14) Beevers & Brouhult (15) Laderqvist (16) Bragg (17) Adelskld
(18) Kordes (19) Braun (20) Hoch & Johnson (21) Scholder & Mansmann (22) Filonenko, Larov, Andreeva & Prevszer
10
Table
3
:
Mineralogical
Properties
of
the
Alumina
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
31)
Phase
!
Hydrated
Aluminas
Gibbsite
1.568
Bayerite
1.583*
Bohemite
1.649
Diaspore
1.702
!
Transition
Aluminas
Chi
Eta
Gamma
Delta
Iota
Theta
Kappa
Corundum
Al2O
AlO
!
Al2O3
Beta
Aluminas
Sodium
Beta
1.7604
1.635
- 1.650
1.642
Index
of
Refraction
nd
Cleav- erge
Mohs Hard
Dens. Measured g/ml 2.42 2.53 3.01 3.44 3.0 ! 2.5-3.6 3.2 ! 3.2 ! 3.71 ! 3.56 3.3 3.96-3.98 3.84
Ref.
Potassium Beta 1.640 1.668 Magnesium Beta 1.629 1.665-1.680 Calcium Beta 1.752 1.759 1.754 1.763 Barium Beta 1.694 1.702 Lithium Zeta 1.735 *Average ! Estimate (1) Dana (8) Rankin & Mervin (2) Roth (9) Kordes (3) Montoro (10) Toropov (4) Ervin (11) Filonenko (5) Bonshtedt (12) Wisnyi Kupletskkaya (13) Filonenko, Larov, (6) Thibon Andreeva & Pevzner (7) Foster, P. A. (14) Fricke & Severin
(15) Coble (16) Bragg, Gottfried, West (17) Kato & Yamauchi (18) Beevers & Brohult (19) Stumpf (20) Gingsberg (21) Biltz & Lemke
11
2.2.3.
Surface
Area
of
Alumina
Alumina
is
widely
used
as
a
catalyst
or
catalyst
support
in
many
heterogeneous
catalytic
processes
owing
to
its
high
surface
area,
superior
chemical
activity
and
low
cost.
In
order
to
prepare
the
thermal-stable
alumina
with
high
surface
area
and
large
pore
volume,
two
ways
have
been
adopted.
One
is
that
some
additives
including
silica,
phosphoric
oxide,
barium
oxide,
cerium
oxide
and
lanthanum
oxide
have
been
added
to
alumina.
But
the
presence
of
these
additives
will
modify
the
original
properties.
The
other
way
is
using
some
new
methods
and
techniques,
such
as
sol-gel
method
and
supercritical
drying
techniques.
Table
4
lists
the
specific
surface
areas,
pore
volumes,
and
pore
diameters
measured
for
samples
of
Al2O3.
The
results
show
that
the
alumina
samples
prepared
using
-cyclodextrin
template
had
the
higher
surface
areas
(124-484
m2/g),
larger
pore
volumes
(0.7-1.27
mL/g)
and
more
thermal
stability
than
samples
prepared
without
using
-cyclodextrin.
The
sample
A-773
exhibits
the
highest
SBET
(484
m2/g)
among
the
alumina
samples
calcined
at
different
temperatures.
When
the
temperature
exceeds
773
OK,
the
SBET
decreases
rapidly,
but
the
pore
volume
changes
a
little.
After
calcination
at
1273
OK,
the
A-1273
maintains
surface
area
of
124.2
m2/g
and
pore
volume
of
0.70
mL/g.
However,
B-773
and
B-1273
have
the
surface
areas
of
348
and
98.3
m2/g,
respectively.
The
pore
volume
of
B-1273
is
only
0.54
mL/g.
Table
4:
Specific surface areas, pore volumes, and pore diameters measured for samples of Al2O3
Sample
A-773
A-923
A-1073
A-1273
B-773
B-923
B-1073
B-1273
SBET
(m /g)
484.34
285.27
220.86
124.22
348.01
228.28
201.2
98.3
2
Pore Volume (mL/g) 0.98 1.27 0.87 0.7 1.08 1.14 0.74 0.54
Pore Diameter (A) 60.85 24.41 20.49 72.23 24.54 28.15 24.67 72.16
Harris and Sing study on gels formed by hydrolysis of aluminum isopropoxide. 1100 m2/g of surface area is detected. Storage of these unstable gels in the
12
presence of water vapor caused loos in surface area to about 500 m2/g. The adsorption isotherms of nitrogen, determined at -196 OC on the outgassed products were of the reversible S-type, characteristic of physical adsorption on nonporous solids. Gels that have been dehydrated at room temperature approximately to the formula Al2 . 3H2O showed no X-ray evidence of crystalline structure. 2.2.4. Porosity Porosity, and special case, permeability significantly affect the properties of alumina ceramics, and in a wide range of magnitude. Porosity is generated in sintered alumina structures for various reasons, some of which are to improve permeability to gases and liquids for porous diaphragms and diffuser plates, to increase the thermal insulation of refractories, and to improve the fuel combustion in radiant heaters. Volatile or combustible burn-outs (sawdust, naphthalene) have been used to generate pores. Gas generators include: hydrogen peroxide and aluminum powder with acids or alkalies. Calcining mixtures of ground and unground Bayer alumina at high temperatures can develop gross porosity beyond 50% by volume. Uniformly distributed porosity is attained by bisque firing fine-ground alumina in the undersintered range 1000 to 1400 OC. Barrett, Joyner and Hallenda applied adsorption - desorption on sintered alumina to have further information about pore shape and pore distribution. In literature five general types of hysteresis loops are defined, from which fifteen capillary shapes could be deduced. The adsorption isotherms of the activated forms of alumina fit the three main types, A, B and E, all of which have steep desorption curves. Type A has a steep sorption branch, type B a gradual sorption branch, with a broad hysteresis range, and type E a gradual sorption branch with a narrow hysteresis range. The pore shapes are mainly open and closed tubular capillaries, ink bottle shapes, and slit shapes. In figure 2 the pore size distribution curves were derived from the N2 physisorption isotherms according to the B-J-H method, Figure 2 a and b show, respectively, the pore size 13
distributions
for
the
commercial
Al2O3;
and
the
ceramic
foams
obtained
from
the
same
aluminas.
Figure
2:
a)
N2
physisorption
isotherm
of
commercial
-alumina;
(b)
Pore
size
distribution
of
commercial
-alumina;
(c)
N2
physisorption
isotherm
of
commercial
-alumina
ceramic
foam;
(d)
Pore
size
distribution
of
commercial
?-alumina
ceramic
foam.
Hayes, Budworth, and Roberts; investigated the permeability of sintered aluminum tubes (total porosity 4 to 9 %, purity 99.3 to 99.8% Al2O3). These tubes at first were impermeable to oxygen, nitrogen and argon at temperatures below 1500 OC. At 1500 to 1750 OC, the specimens showed appreciable permeation to oxygen, presumably by a surface diffusion process. The diffusion coefficient was about 100 !"2/sec. very slight or no permeation was found for nitrogen, and none for argon. After continued exposure for 100 hours at 1700 OC, permeation by normal channel-flow developed suddenly and swamped the earlier phenomena. The permeation of nitrogen through hot-pressed sintered alumina (4 to 14% total porosity) was predominantly by Knudsen flow.
14
2.2.5. Sorptive Capacity The strong desiccating action of activated alumina has been known at least since 1879. The properties that make the activated aluminas particularly suitable for desiccant use are: the ability to develop high surface area during formation of dehydration; a high degree of chemical inertness; resistance to softening, swelling, and disintegration when immersed in water or other liquids; high resistance to shock and abrasion; and the ability to return to the original highly adsorptive from by a suitable thermal regenerative treatment. Alumina is also use for special type of adsorption called chromatography, in which the identification and separation of adsorbed ions are usually based on a visual, spatial order of adsorption. Typical properties of desiccant, commercial alumina samples are shown in Table 5. A partial list of gasses and liquids that can be dried by activated alumina (Alcoa brochure, June 1, 1967) includes the following. Gasses Acetylene, air, ammonia, argon, carbon dioxide, chlorine, cracked gas, ethane, ethylene, freon, furnace gas, helium, hydrogen, hydrogen chloride, hydrogen sulfide, methane, natural gas, nitrogen, oxygen, propane, propylene, and sulfur dioxide. Liquids Benzene, butadiene, butane, butene, butyl acetate, carbon tetrachloride, chloro benzene, cyclohexane, ethyl acetate, freon, gasoline, heptane, n hexane, jet fuel, kerosene, lubricating oils, naphtha, nitrobenzene, pentane, pipe-line products, propane, propylene, styrene, toluene, transformer oils, vegetable oils and xylene.
15
Table
5:
Typical
Properties
of
Desiccant,
Chromatographic
And
Catalytic
Aluminas
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
39)
Typical
properties
Al2O3
%
Na2O
%
Fe2O3
%
SiO2
%
Loss
on
ignition
(1100
OC)
%
SO3
%
CaO
%
Nickel
Formate
%
Form
Surface
area
m /g
Bulk
density,
loose
kg
/m
Bulk
density,
packed,
kg/m
Spesific
Gravity
Static
sorption
at
60%
RH
Crushing
Strenght
Pore
volume
ml/gm
pH
Sieve
Analysis
On
80
mesh
%
Through
270
mesh
%
3 3 2
F-1 92.00 0.90 0.08 0.09 6.50 Granular 210.00 832.9620 881.0175 3.30 14-16 55.00
H-151 90.00 1.60 0.13 2.20 6.00 Ball 390.00 816.9435 848.9805 3.1-3.3 22 - 25 75.00
F-20 92.00 0.90 0.08 0.09 6.20 Granular 210.00 929.0730 3.30 9.00 2 max 5 max
T-71 99.5 + 0.01 0.06 0.04 0.00 0.09 0.06 Granular 0.50 1217.4060 0.15-0.20
Ball
180-280
1089.2580 1361.5725
2.3. MECHANICAL PROPERTIES OF ALUMINA Alumina has remarkable mechanical properties in comparison with conventional porcelains and other single oxide ceramics. None of the likely refractory single oxide contenders approaches pure sintered alumina in bending and tensile strength, and is exceed only by stabilized ZrO2 in compressive strength. Many if the advantageous strength characteristics are retained to lesser extent by the high and low alumina porcelains. The interest in mechanical properties stems from several applications such as possible substitution of alumina ceramics for refractory metal parts in air-bone equipment, or fabrication forms in which high mechanical strength, membrane, hardness or thermal shock resistance is important.
16
The
mechanical
tests
of
particular
significance
include:
flexural,
compressive,
tensile
torsional,
and
impact
strengths;
modulus
of
elasticity
and
rigidity;
Poissons
ratio
and
bulk
modulus;
fatigue,
creep,
internal
friction,
thermal
shock
resistance,
and
flaw
detection;
and
hardness.
Structural
applications
of
aluminum
oxide
in
the
high
temperature
field
require
knowledge
of
the
effect
of
temperature
on
mechanical
properties.
Data
on
mechanical
properties
of
alumina
is
collected
in
Table
6
and
7.
The
data
in
the
table
include
information
taken
from
ceramic
literature
as
well
as
average
values
for
commercial
production,
taken
from
the
standards
of
alumina
ceramic
manufacturers
association
and
the
literature
of
several
studies.
Table
6
is
belonging
to
typical
properties
and
specifications
of
commercial
grades
of
3
kinds
of
alumina.
Hydrated
aluminas,
prepared
in
a
modern
Bayer
plant,
is
indicated
the
specimen
of
C.
And
specimen
A
belongs
to
calcined
aluminas,
which
specimen
T
indicates
tabular
alumina.
Data
on
the
mechanical
properties
of
alumina
is
collected
in
Table
7.
The
data
in
the
table
include
information
taken
from
the
ceramic
literature,
as
well
as
average
values
for
commercial
production,
taken
from
the
standarts
of
the
Alumina
Ceramic
Manufacturers
Association.
Table
6:
Typical
Properties
and
Spesifications
of
Hydrated
Aluminas-Series
C-30
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
21)
Typical
Properties
Al2O3
%
SiO2
%
Fe2O3
%
Na2O
%
Moisture
(110
C)
%
Specific
Gravity
Sieve
Analysis
on
100
mesh
%
on
200
mesh
%
on
325
mesh
%
through
270
mesh
%
O
A 98.9 0.02 0.03 0.45 1.0 3.6-3.8 4-15 50-75 88-98 2-12
17
Table
7:
Mechanical
Properties
of
Alpha
Alumina
Oxide
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
45)
Sapphire
Bending
Strength
(Modulus
of
Rupture)
O
Temp
C
Flame-fused,
O
oriented
0 between
optic
axis
a and
bar
axis
Flame-fused,
oriented
45
between
optic
axis
and
a
,b bar
axis
Flame-fused,
oriented
45 between
optic
axis
and
a
,b bar
axis
S25OC=142500
e
-11.83PG-0.60+3.33P
O
O
Sapphire
MPa 680 180 300 480 313 567 333 220 567
(1)
(18)
S1200OC=73000e
Polycrystalline
Alumina
(99.9%
Al2O3
98%
theoretical
density,
hot
pressed)
(2)
-11.33PG-0.60+3.33P
Crystal Size (microns) 1 2 10 15 O Temperature C O 25 C 447 320 O 400 C 347 247 O 1000 C 327 247 O 1350 C 247 107 Commercial Grades of Polycrystalline Alumina Nominal % Al2O3 %99.9 (5) %99 (3) %94 (3) O 25 C 413 347 307 O 980 C 153 113 Compressive Strength (MPa) Sapphire Polycrystalline O Temperature C 100 % Al2O3 (7) 99% Al2O3 (3) 94 % Al2O3 (3) O 25 C 295 3733 2000 2000 O 25 C 3300 2840 O 400 C 1420 O 800 C 1233 O 1000 C 853 O 1200 C 473 O 1400 C 237 O 1600 C 47 Mohs Scale Hardness on the 9
18
Table 7 continued Single Crystal Orientation 45 O to optic axis (9) 473 350 350 587 Tensile Strength MPa Filaments Uncoated (10) 467 Coated (10) (e) Polycrystalline 94 % Al2O3 (3) 85 % Al2O3 (3)
173
117
1400
251
243
227
225
209
63
57
123
28
Modulus
of
Elasticity
(E)
X
108
MPa
6 -3.95P
E
(polycrystalline)=59.49
X
10
e
,
where
P
=
fractional
pore
volume
(8)
Single
Crystal
(12)
Polycrystalline
Ruby
O Temperature
C
Sapphire
(0.75%Cr (11)
94
%
Al2O3
(3)
85
%
Al2O3
(3)
2O3)
O 25
C
35.07
36.07
39.53
26.80
21.27
O 500
C
32.07
33.00
38.18
O
1000
C
29.00
30.07
36.59
O
1200
C
27.93
29.00
35.77
ompliances
Elastic
constants
Elastic
C
(
X10
MPa)
48.03
48.16
14.27
15.82
10.72
-2.27
Modulus
of
Ridity(G)
X
10
MPa
8 8
( X10 MPa) 2.35 2.17 6.94 -0.72 -0.36 0.49 Polycrsytallined Alumina Cold-Pressed 94 % Al2O3 (3) Zero Porosity Density 3.62 (3) (14) 15.93 11.33 (13)
O Temperature
C
25
C
O
Sapphire
(13)
15.53
(Reuss)
16.05
(Vogit)
Hot-Pressed
Zero
Porosity
(14)
15.51
a Loading rate 94.7 MPa/minute; b minimum creep at 45O; c zero porosity; d less than 5% porosity; e rupture
time less than one minute. (1) Wacthman &Maxwell (1959) (2) Springs Mitchell & Vasilos (1964) (3) Coors Prorcelain Data Sheet 0.001, August 1964 (4) Diamonite Products Manufacturing Company (1963) (5) Frenchtown Porcelain Co., Bull. 5462 (7) Ryshewitch (1941) (9) Wachtman & Maxwell (1954) (8) Knudsen
(10) Berezhkova &Rozhanskii (11) Crandall, Chung, & Gray (1961) (12) Wachtman &Lam (1959) (13) Wahtman, Tefft, Lam & Stinchfield (1960) (14) Lang (1960) (15) Ryshewitch (1951) (16) Spriggs & Brisette (17) Kingery & Pappis (18) Passmore, Spriggs & Vasilos (1965)
19
2.4.
THERMAL
PROPERTIES
OF
ALUMINA
Chemical
and
thermal
stability,
relatively
good
strength,
thermal
and
electrical
insulation
characteristics
combined
with
availability
in
abundance
have
made
alumina
attractive
for
engineering
applications.
Thermal
properties
of
alumina
are
listed
below
on
the
Table
8.
Table
8:
Thermal
properties
of
alumina.
(WALTER
,
Alumina
as
a
Ceramic
Material,
1970,
page
64)
Melting
Point
Boiling
Point
Vapor
Pressure
!Al2O3
!Al2O3
T K
2309
2325
2370
2393
2399
2459
2478
2487
2545
2565
2605
Heat
of
Formation
at
298.16
O K
(kcal/mole)
-612.8
-609.4
-304.2
-417.8
-400.4
-138
-248
0.03550922 ! 4.0884 10
23.15
8.43
12.16
48.967
59.75
(9)
(16)
(15)
(8)
(9)
(9)
O
2051.0
9.7
3530
(3800
200
K)
Atm
8.7
X
10
1.03
X
10
1.66
X
10
1.68
X
10
2.15
X
10
3.78
X
10
5.81
X
10
9.1
X
10
2
X
10
1.29
X
10
1.91
X
10
O Entrophy
at
298.16
K
(kcal/mole)
33.51
-6 -6 -6 -6 -6 -6 -6 -6 -6 -6 -6 O
(1) (2)
! Al2O3 3H2O ! Al2O3 3H2O Amorphous ! Al2O3 H2O ! Al2O3 H2O ! Al2O3 AlO Al2O
0.035549846 ! 3.9085 10!! ! ! 11.2306 !"!!" ! + 17.23778
(b)
0.03031602 ! + 8.3979 10!! ! ! 2.81406 ! 10! / ! 12.87764
(c)
Specific
Heat
(cal/g
K)
! Al2O3
3H2O
0.2694
+
6.43
X
10!!
t
(d)
0.2855
at
25
0.348264
8.019
X
10 T
47.8423/T
(d,e)
-6
20
400
500
600
700
800
1318
1510
1660
! Al2O3
Temperature
Range
O
(9)
(10) (11)
Thermal
Expansion,
Linear
(X
10
/ C)
Single
Crystal
(12)
Orientation
0
1.95
4.39
6.26
7.31
7.96
8.65
8.84
8.98
9.08
9.18
O
Polycrystalline
O
C-axis
90
1.65
3.75
5.51
6.52
7.15
7.8
7.96
8.12
8.2
8.3
O
(12) 1.89 4.1 6.03 6.93 7.5 8.08 8.25 8.39 8.49 8.58
-273.16 to 0 -73 to 0 0 to 127 327 527 927 1127 1327 1527 1727
Thermal Conductivity (cal/sec cm C) O O cal/sec cm C Temperature C -263 -253 -233 -223 25 100 300 500 700 900 1100 1300 1500 1700 1900 3 9 14 12 0.086 0.069 0.038 0.025 0.018 0.015 0.014 0.014 0.013 0.014 0.015
(13)
21
(a)
Range
400
K
to
1200
K;
(b)
Range
678
K
to
1330
K;
(c)
Range
1290
K
1673
K;
(d)
T= Kelvin;
(e)
Range
of
equation
400
to
1200 K.
(1)
Schneider,
Nat.
Bur.
Stds.
Private
communication,
Nov
,
1968
(2)
Brewer
&
Searcy
(3)
Rossini,
Wagman,
et.
Al.
N.
B.
S.
Circ.
500,
1952
(4)
Russel
et.
Al.
(1955)
(5)
Barany
&
Kelley
(6)
Kerr,
Johnson,
&
Hallett
(7)
Mah
(8)
Roth,
Wirths,
&
Berendt
(1942)
(9)Furukawa
et.
Al.
(10)
Shomate
&Naylor
(11)
Sheindlin(1964)
(12)
Wachtman,
Scuderi,
&
Cleek
(13)Coors
Porcelain
Co.
(AD
995)
(14)
Panyushkin
&Maltsev
(15)
Banashek,
Sokolov,
Rubinchik
&
Fomin
(16)
Sokolov,
Banashek,
&
Rubinc
O
2.5.
CHEMICAL
PROPERTIES
OF
ALUMINA
Chemical
reactions
of
alumina
of
general
ceramic
interest
include
the
resistance
to
attack
of
sintered
alumina
by
various
reagents,
particularly
at
high
temperatures.
High
temperature
chemistry
includes
those
chemical
phenomena,
which
occur
above
1000
OC.
Such
temperatures
are
attained
by
combustion,
by
electrical
heating,
or
by
chemical
explosions
and
nuclear
reactions
(Margrave,
1962).
Some
example
studies
are
listed
below
due
to
understand
further
chemical
behavior
of
alumina.
2.5.1.
Wet
Chemical
Reactions
of
Sintered
Alumina
In
aqueous
solution,
aluminum
oxide
exhibits
an
amphoteric
behavior.
It
can
be
expressed
by
the
following
equilibra:
! !! !! + 3 !!! !"(!")! !"!! + !! !!
Impermeable alumina has been marked resistance to wet chemical corrosion. As a rule the lower phases of alumina and the hydrous aluminas show increasing chemical reactivity as they decrease in density. Early experiments on the resistance of sintered alumina to attract were intended to demonstrate its suitability as a container, crucibles, etc., for thermal reactions (Winzer, 1932). Concentrated H2SO4, HCl, HNO3, H3PO4, and 20% NaOH dissolved no more than 0.02% of a 30 X 35 mm crucible within six hours, as indicated by loss in weight of the crucible. This is not necessarily indicative of chemical inertness, as for example; phosphoric acid readily reacts even with coarsely crystalline tabular alumina to form slowly soluble phosphate bonds at temperatures below the
22
boiling point of the acid. Dawihl and Klingler (1967) state that sintered alumina containing 3% silicates is far more resistant to corrosion by HCl, HNO3, and H2SO4 in concentrations from 10 to 95% acid and up to 100 OC than titanium, cast silicon and Cr Ni steels. Finely divided alumina is rapidly dissolved by HF, hot concentrated H2SO4, mixtures of these acids, ammonium fluoride, molten alkali bisulfates or pyrosulfates, and by concentrated HCl, especially when under pressure. All these reagents have been used to dissolve alumina in analytical procedures. Sintered alumina dissolves in concentrated H2SO4 faster than some high alumina porcelains containing clay binders (85% Al2O3). Karpacheva and Rozen found that the densest sintered alumina reacts with heavy water, H218O, the following reaction rates, as percent reaction, within 80 minutes, were observed. Temp C Rate (% 80 min) 200 20 400 30 600 50 900 97
Hot water solutions of the free alkali hydroxides and carbonates cause perceptible reaction, the rate being correspondingly faster and higher temperatures and under pressure. 2.5.2 Reaction of Chemical Elements with Alumina Some reactions of interest between the chemical elements and alumina are shown in the Table 9. Reaction of molten alumina with some refractory metals and allots are included. These are presented in alphabetical order, in general, for convenience of reference. Detailed information is given with references in Appendix A related to element interactions with alumina. For references see Appendix A. 23
Table 9: Interest Between The Chemical Elements And Alumina Aggressively attraction Attraction Molten Lithium Potassium Carbon Florine Copper BaO SRO Bishmut Cerium Chromium Iron Manganse Molybdenum Nickel Niobium Palladium Platinum Tantalum Titanium Zirconium Tungusten Sodium Antimony Arsenic Beryllium Chlorine Cobalt Gallium Lead Mercury Nitrogen Phosphorus Silver Sulfur Selenium Tellurium Tin Uranium
No Attraction
Limited attraction
1.8. COLLOIDAL PROPERTIES OF ALUMINA Surface of pure alumina is defined alkaline. By electrophoretic methods Fricke and Keefer (1949) determined the isoelectric point of zero point charge (zpc) of gamma alumina to be at 9.0 pH, that of amorphous Al(OH)3 at pH 9.4, that gibbsite at pH 9.20, and that of bohemite at pH 9.40 to 9.45. The potential determining ions were considered to be H+ and OH-, which enter into electrochemical reaction at the surface in the case of aluminum oxide. The essential part of the surface reaction schematically is as follows:
H H
H 3O+
OH $
24
Table
10
:
isoelectric
point
of
hydrated
alumina
(OConor
1956)
Aging
Conditions
Precipitation
Excess
Alkali
Equivalent
Alkali
Deficent
Alkali
Fresh
Preparation
Rapid
Aging
by
Heating
Suspension
Aged
4
Months
5.08
6.63
7.29
6.79
7.28
7.43
5.78
7.06
7.32
Zeta potential of natural corundum reported positive in water 17-20 OC, but it changes to negative on heating to 1000 OC. (OConor 1956) The interaction between the liquid and the surface can be estimated by contact angle (q) measurements. The details of the interactions between the surface and the solvents were explored by analysis of the effect the properties of the liquid on varying the equilibrium contact angle with water (!!" ) with the different anodic alumina surfaces. These values were determined from the intersection of the fits for advancing and receding angles versus contact angle hysteresis with ordinate at ! q=0, one finds the equilibrium angle !!" . For different samples results vary between 62.6 - 73.3. Results obtained Wihelmy Method. (Redon et. al., 2005)
25
3. ALUMINA MEMBRANES 3.1. INTRODUCTION In recent years there has been a growing interest in utilizing inorganic membranes to address a variety of separation problems in many industries Various inorganic membranes made from metals, inorganic polymers and ceramics have been proposed for liquid and gas separation applications. Membrane technologies play an increasingly important role in pollution prevention, resource recovery and waste treatment activities. Due in large part to cost considerations, polymeric membranes dominate these applications, however, the use of polymeric membranes in separations involving aggressive materials such as many organic solvents, acids, bases and oxidants is often limited by the tolerance of the polymeric material to extreme conditions. The interest in utilizing such membranes in separations has increased since the advent of consistent-quality, commercially available ceramic membranes with narrow pore size distributions. Ceramic membranes are noted for their excellent mechanical strength and tolerance to solvents, as well as pH, oxidation, and temperature extremes. For example, they can be used at significantly higher temperatures, have better structural stability without the problems of swelling or compaction, generally can withstand more harsh chemical environments, are not subjected to microbiological attack, and can be backflushed, steam sterilized or autoclaved. An ideal ceramic membrane must be highly selective, permeable and durable. For aqueous applications, or aqueous/organic separations it is desirable for the ceramic to be hydrophilic to maximize flow and minimize fouling. The membrane selectivity is primarily dependent upon the pore size distribution; the narrower the pores size distribution, the more selective the membrane. Mechanical integrity is, enhanced in such applications by slip-casting a relatively thin selective membrane onto a thicker, more permeable support yielding an asymmetric membrane.
26
The former forms of dense (or nonporous) membranes of palladium or its alloys, silver and zirconia have shown to be permeable only to certain gases (e.g., hydrogen and oxygen). These materials are used in sensors, electrodes and coatings. Their industrial use as a separation tool, however, is limited primarily by low permeability compared to microporous metal or ceramic membranes. Currently, microporous stainless steel, silver and ceramic membranes such as alumina, zirconia and glass are available commercially. In Table 11 the selected commercial alumina membranes are listed. Data collected from web based information. Among the ceramic membranes, alumina is gaining acceptance for liquid phase separations. Like zirconia membranes, alumina membranes for liquid phase separations came to commercial fruition from uranium isotope enrichment work. (Hsieh, Bhave, and Fleming, 1988)
Table 11 : Selected commercial Alumina Membranes Manufacturer Trade Name Application Membrane Material ! !"!! ! Al2O3 Support Material ! Al2O3 Membrane pore diameter 40-100 ! 0.2-5 m 0.2-1 m 0.2-5 m Membrane support configuration Tube and multichannel element
Alcoa / SCT
Membralox
UF
MF
! Al2O3
Norton
Ceraflo
MF
! Al2O3
! Al2O3
NGK
MF
Al2O3
Al2O3
Alcan/Anotec
Anopore
UF
Al2O3
Al2O3
MF
Al2O3
Al2O3
Alumina membranes are constantly growing area. In the Figure 3, it can be seen that, the publication numbers are highly increasing parallel with the membrane research especially during recent years. This data is collected from sciencedirect.com.
27
In the first figure publications on alumina membranes is evaluated. Second figure evaluates the trend It can be concluded that; Second figure evaluates the trends of alumina membranes trend It can be concluded that; trends of alumina membranes are rising correlated with general trends with of membrane publications during years. of membrane publications during years.
membranes. Alumina The main reasons why alumina is still trending research topic can be explained membranes are promising by following reasons. During the last several decades, many investigations have and developing area in been focused on porous anodic alumina (PAA) due to its benefits of tunable membrane society. nanopore diameter and long-range ordered feature of the porous nanochannels in macroscopic domain. The pore diameter of the PAA nanochannel can precisely be controlled from a few nanometers to several hundreds of nanometers by applying regarding electrolyte, voltage (or current), and reaction temperature during the electrochemical anodization reaction of aluminum substrate. Moreover, reaction time provides a tunability in the thickness of the porous nanochannels from a hundred of nanometers to a hundred of micrometers. Such easy control ability of the pore diameter and the thickness makes the PAA one of the interesting materials, which are frequently being applied in nanoscience. So
28
far, the studies to utilize the PAA have been performed in a wide range of research fields such as nanomaterial design, molecular sieving, photonic and optical device, and catalysis.
3.1
PREPERATION
OF
ALUMINA
MEMBRANES
3.2.1.
Macroporous
Alumina
Membrane
Preparation
Porous
ceramic
membranes
with
pore
size
ranging
from
0.1
to
50
mm
and
porosity
above
about
40%
are
used
for
filtration
(e.g.,
hot
gas
filtration),
diffusion
(e.g.,
waste
water
treatment),
dispersion
rolls,
inkpads
for
fingerprinting
and
numerous
other
applications.
In
particular,
filtration
is
important
for
the
petrochemical,
mining
and
chemical
industries.
The
anodizing
of
pure
aluminum
in
various
acidic
electrolytes
has
attracted
considerable
attention
in
recent
years
since
it
opens
up
the
possibility
of
preparing
films
with
well-controlled,
uniform
pores
from
tens
to
several
hundreds
of
nanometers
in
diameter.
The
basic
cell
structure
containing
cylindrical
pores
has
long
been
known
and
methods
for
preparing
regular
pore
arrangements
in
a
hexagonal
pattern
with
interpore
distances
of
between
50
nm
and
500
nm
have
been
reported.
The
preparation
of
regular
pore
arrays
typically
involves
electrolytic
polishing
and
multiple
anodising
steps
or
even
mechanical
pre-texturing.
As-prepared
porous
anodic
alumina
(PAA)
membranes
are
amorphous
to
X-ray
diffraction
(XRD).
Their
chemical
composition
is
not
stoichiometric
Al2O3
but
incorporates
a
considerable
quantity
of
anion
impurities
and
hydroxyl
groups
incorporated
from
the
electrolyte
into
the
alumina
structure
or
bound
to
the
alumina
surface.
(Kirchner,
et.
al)
PAA has proved to be useful for fabricating many materials, especially as a template for the synthesis of metallic or semiconductor nanometer -scaled wires and particles. After chemical functionalizing, PAA membranes can be utilized for catalytic or optical purposes. Further, the porous film itself may be employed for filtration, gas separation or as a photonic crystal. Because it is a ceramic oxide,
29
PAA has considerable potential in high-temperature applications, although severe problems can occur when certain types of PAA membranes are heated. Macroporous alumina membranes also can be made from particles or discontinuous fibers by the use of a binder or by sintering. The sintering of ceramic particles is perhaps the simplest approach to forming a porous ceramic filter, however, the sintering of bulk ceramics is a very energy expensive process due to the high temperatures required. The pore size is controlled by the starting particle size, sintering time and temperature. This method is generally used to produce alumina microfiltration filters, which contain larger pores and supports for ultrafiltration membranes, which contain smaller pores. (Avci et. al. ) Binders are most commonly in the form of fine particle dispersions (colloid). The silica colloid is an example. After application by wet forming (as in paper making), drying and appropriate heat treatment is needed. The binder technology is central to the technology of membrane fabrication. A binder is necessary to hold the ceramic particles or fibers together to form a membrane. It must be used in a sufficient quantity in order for the membrane to have acceptable mechanical strength. However, it must not block the pores in the membrane, as is the case if it is used excessively. Thus, an effective binder should be able to bind the particles or fibers together and result in a mechanically strong membrane, even when it is used in a very small proportion. In addition, the binder must be able to withstand high temperatures, as encountered in hot gas filtration. Silica and vitreous glass are widely used binders in the refractory and ceramic industry. It is often used in the form of an aqueous dispersion. The silica colloid is particularly attractive due to the high temperature resistance of silica compared to vitreous glass and the good binder dispersion enabled by the small particle size of the silica in the colloid. The average size of the silica particles in the colloid can range from under 10 nm to over 80 nm. The silica binder is easy to use, but it tends to fill the open or continuous porosity of the filter membrane.
30
Phosphate has been utilized as a binder in the refractory industry for many years. Pirogov et al. used a phosphoric acid (H3PO4) binder in a mullite-corundum body in their study to determine the optimum content of graphite and SiC additives. Birchall et al. studied the mechanical properties of an unsintered SiC compact bonded by aluminum phosphate (AlPO4) glass. Toy and Whittemore evaluated the reactivities of several calcined aluminas with phosphoric acid and demonstrated that a glassy AlPO4 phase and aluminum metaphosphate (Al(PO3)3) are effective bonding phases. 3.2.2.Mesoporous Alumina Membranes Of the present technologies, solgel is the best method for making ceramic ultrafiltration membranes. However, the pore size is generally limited to the sizes of the ceramic precursor particles prior to sintering. For solgels, the particle size distribution is difficult to control, and they must be used immediately after preparation to avoid aggregation or precipitation. (Johns et. al) Commercially available membranes are currently ! -Al2O3 membranes are currently thermally stabilized at 650 OC, with a mean pore size equal to 5 nm. Such membranes can be used for Nanofiltration of aqueous solutions containing inorganic salts or amino acids. They can also be used for gas permeation applications. However these membranes present a rather low chemical stability in aqueous media at very high pH values. More over, their structural evolution has to be taken into account for high temperature applications. (Ayral) Sol-gel process can be applied generally; Solution must be prepared An example of Boehmite ( ! -AlOOH) sol from an inorganic precursor was prepared as in shown figure 4. Pretreatment alumina supports (synthesized or provided). Heating, or solution applications. Membrane solution contacts with support. Penetration of the solution into the voids of the support occurs by capillary action. The support was then shaken to remove any excess solution, and dried at room temperature.
31
The coated support was heated up to 600-1000 OC step by step and held remained in temperature range for stabilization. Multiple coatings were obtained by treating a previously coated filter.
It
was
reported
the
unsupported
membrane
was
obtained
by
dying
the
sol
layer:
!"#$% ! !"##$ !"#
!"#$%& !"#$%& !"#$%&
!!"#! !!"#$%!"&
the
sol
layer
was
formed
by
dipping
the
layer
was
dried
at
room
temperature,
the
drying
step
removes
excess
water,
cracks
formed
easily
during
drying
step.
Fig.4.
Preparation
procedure
of
boehmite
sol
In order to obtain the Al2O3 membrane without crack, a method, rapid gelation processing for preparation of gel layer can be used. The sols of ! !"##$ are atomized firstly then sprayed onto a substrate. The gel layer was obtained from sols directly. No crack was observed. 32
Figure
5
is
the
schematic
diagram
of
the
rapid
gelation
processing.
The
sols
are
atomizing
by
a
high-velocity
gas,
and
sprayed
into
the
substrate
(glass
or
ceramics
plate
coated
with
cellulose
acetate
film.
After
drying,
the
resulting
gel
is
placed
in
acetone
to
dissolve
the
cellulose
acetate
and
to
obtain
the
unsupported
gel
film).
The
0.1-
200
m
of
thickness
of
the
membrane
can
be
obtained
without
cracking
at
conventional
drying
rate.
When
the
thickness
of
membrane
is
higher
than
200
~ m,
cracking
can
be
prevented
at
controlled
drying
rate.
The
transparent
boehmite
gel
membranes
obtained
by
rapid
gelation
were
fired
at
a
temperature
(>350C)
to
form
! -alumina
membrane.
Figure
5:
Schematic
drawing
of
the
rapid
gelation
processing,
1
-
nozzle,
2
-
atomizing
sol
and
3
- substrate.
Mesoporous -alumina membranes are formed by dip-coating a porous substrate in a Boehmite (-AlOOH) precursor sol, will be treated by heat and sintering steps. The quality and properties of the membrane depend on the dispersion rheology and quality of the Boehmite sol and the dip-coating process as such. A high quality Boehmite sol is prepared by hydrolysis and condensation of an aluminum alkoxide: ATSB ([C4H9O]3Al), followed by one or more purification
33
steps.
Five
steps
in
total
are
necessary
for
a
single
layer
mesoporous
-alumina
membrane
preparation:
1.
Boehmite
sol
preparation
2.
Boehmite
sol
purification
3.
Dip-coating
sol
preparation
4.
Dip-coating
procedure
5.
Heat
treatment/sintering
In
the
Figure
6
an
example
of
dip
coating
process
is
shown.
Figure
6:
Filter
ring
assembly
for
mesh
filtering:
top
filter
ring
(left),
bottom
filter
ring
(middle)
and
assembly
diagram
with
nylon
mesh
(right).
The
thickness
of
the
top
filter
clamp
ring
can
be
increased
to
increase
the
filtration
volume.
Currently
it
can
hold
~10
ml.
In laboratory scale experiments to the synthesis of mesoporous alumina membranes using slip-casting technique has been tried. Catalytic membranes with precise active layer width and location were prepared by sequential slip casting of Pt/Al and alumina sols. Different distributions of catalyst within the membrane can be easily obtained by varying the thickness of the slip-cast layers as well as their arrangement. The layer widths are controlled by the slip-casting parameters, including slip-casting time, alumina content and particle size. The catalyst loading and dispersion of the active layer can be controlled precisely. The effects of sintering temperature (600-1200C) on the membrane's pore
34
structure, morphology, phase structure, surface area and gas permeability are observed. ( Yeung et. al; 1996) 3.2.3 Microporous Alumina Membranes In the slipcasting method, a porous support is usually made first by conventional ceramic processing techniques to provide rigid structure with relatively large pore size for slip deposition. Since particle size directly related with pore size, the slip used, as the membrane precursor needs to contain well-dispersed particles of uniform size. Depending on the desired pore size of the membrane, the membrane precursor particles may be prepared by precipitation, classification, sol-gel method, etc. In the sol-gel techniques, ultrafine particles of a few nm in diameter can be prepared by polycondensation or redox reactions of aluminum salts or hydrolysis and condensation of aluminum alkoxides. After treatment with a peptizing agent such as an acid and optionally with a viscosity modifier, the slip is deposited on the porous support by the dipping or slipcasting procedure. This procedure for filtration based on capillary pressure drop created by the contact of the slip with the support. (Leenaars, Burggraaf 1985) This pressure drop forces the dispersion medium (e.g water to flow into the dry pores of the support while the slip particles are retained and concentrated at the surface forming a thin membrane. The membrane precursor is then dried and calcined to provide the required pore size for specific applications and the needed bonding between the membrane and the support. These steps must be done with a great sensibility to avoid cracks, which can occur due to shrinkage upon drying and/or calcining. (Hsieh, Bhave, and Fleming, 1988) The slipcasting method is commonly used for making commercial alumina membranes. Method can be replied to organize intermediate layers between thin, permeable, selective membrane and the thick, porous support, which provides the needed mechanical strength. T Thus, alumina membranes, like many other porous inorganic membranes, are composite in nature. The cross-
35
section
of
a
multi-layered
alumina
membrane
composite
can
be
exemplified
by
the
scanning
electron
micrograph
of
Figure
7.
In
general,
the
selective
membrane
layer
has
a
thickness
of
2-10
!m.
This
thickness
is
a
trade-off
between
high
flux
and
mechanical
stability.
The
intermediate
layers
are
generally
10-20, !m
thick.
The
bulk
support
constitutes
the
majority
of
the
pore
volume
and
thickness.
If
the
membrane
precursor
particles
are
so
fine
that
they
penetrate
the
relatively
large
pores
in
the
support,
the
permeability
of
the
membrane/sup
port
composite
will
decrease
due
to
partial
or
complete
blockage
of
the
pores
in
the
support.
To
prevent
fine
particles
from
penetrating
into
the
support,
one
or
more
intermediate
layers
of
graded
particle
size
are
used.
Figure
7:
Cross-sectional
scanning
electron
micrograph
of
a
three-layered
alumina
membrane/support
composite
(pore
diameter
of
0.2,
0.8
and
10
m,
respectively,
in
each
layer)
The
ability
to
consistently
produce
high
quality
alumina
membranes
on
a
commercial
scale
has
been
the
key
to
wider
acceptance
of
ceramic
membranes
as
a
separation
tool.
The
surface
morphology
of
a
high
quality
alumina
membrane,
shown
in
Figure
8,
displays
uniform
particle
size.
36
Figure 8: Top-view scanning electron micrograph of an alumina membrane (pore diameter of 0.2 !m)
Typically, membranes and supports have a porosity of 30-60% by volume. This range provides a good compromise between permeability and strength. Membrane science has a leading role in innovative processes and is considered one of the main strategic axes of research activities in all developed countries. Advanced technology programs in the USA or Japan involve them, and with an annual growth rate of 10 to 20 %, and a total world market above 10 billion Euros around 2010, membranes are likely to become more and more important in the future. Besides flat membranes as motivated by literature, anisotropic membranes consist of an extremely thin surface layer supported on a much thicker, porous substructure. The surface layer and its substructure may be formed in a single operation or separately. Multi layer membranes and their production will be motivated in next chapter.
37
4.DESIGN OF THE MEMBRANE MODULES The separation science and technology using all the kinds of different membranes is highly influenced by the membrane module configuration as far as the efficiency of a membrane process depends on the design of its module. The cost reduction of membrane module has led to the commercialization of membrane process some decades before depends on the sort of application and the different materials used. In practice, the commercial available membrane modules are assembled in units consisting usually of several membranes, sometimes from many thousands of them.
4.1 DIFFERENT TYPES OF MODULES Currently, four main types of membranes modules are in the market: (a) planar, (b) spiral, (c) tubular (d) hollow fibers modules and (e) honeycomb. The modules are closely related to the geometry of the membranes and therefore of the materials. Each commercial module is consisted of a number of membranes, placed in different ways. The structure of membrane can be (a) symmetric, (b) anisotropic and (c) composite and according to the sort of use, also two main categories can be distinguished: (a) vibrating membrane and (b) submersible membranes. Besides, in terms of geometry, two types of different geometry can exist: (a) planar and (b) tubular [Remigy, 2007]. From these basic configurations, many other secondary modes can also occur such as vibrating hollow fiber modules and many others. In Table 12, main parameters of membrane modules are gathered. The Table 1 is presented in Filtration Membranaire published by CNRS in 2007 and it is only representative for actual membrane technology trends. All the information concerning membrane technology needs frequent updating because membrane engineering is a state-of-the-art research and market field.
38
Table
12
Comparison
of
performances
for
different
modules
and
membranes
[Remigy,
2007]
Different
perfomance
of
membranes
modules
Geometry
Cost
of
inventissement
(U$$/m2,
2000)
Energy
cost
Hydraulic
diameter
Comptability
Membranes
replacement
Pretreatment
Moyen
1
to
5
100
to
400
Membrane
by
membrane
Moyen
Medium
0,8
to
1,2
300
to
1000
Entire
module
Medium
Important
12
to
20
10
to
300
Tube
by
tube
Low
Low
0,1
to
1
1000
to
15000
Entire
module
Medium
(entire
filtration
internal/exte rnal)
Medium
to
low
(external/int ernal)
Cleaning
Material
Good
All
the
materials
Difficult
to
medium
Polymers
All
the
materials
Polymer
Excellent
Medium
Planar
50
to
200
Spiral
5
to
100
Tubular
50
to
200
Hollow
fibers
5
to
20
4.1.1 Alumina membrane modules Alumina membranes characterized as inorganic, ceramic membranes are usually fabricated in tubular or less often planar module, composite or anisotropic, in some cases immerged, monolith, disk mode. On the other side, vibrant or immerged modules in hollow fibers and planar or spiral geometry are commonly polymer (organic) membranes modes. The most recent trend appeared in alumina membrane market is honeycomb module which combines some of the most important advantages of previous modes.
39
Planar
module:
In
general,
membranes
of
planar
module
are
less
met
in
current
market
trends
and
represent
either
older
membrane
systems
either
pilot
or
patent
scale
applications.
They
are
based
on
conventional
filter
press
design
and
membrane
feed
spacers
and
product
spacers
are
layered
together
between
two
end
plates.
The
most
common
uses
of
plate
and
frame
modules
concerns
electrochemical
applications
as
ion
exchange,
electrodialysis,
pervaporation
systems,
electrosensors
and
membrane
electrode
assembly.
These
applications
concern
all
the
different
kinds
of
membranes
as
metal
or
polymer
membranes.
Figure
9
a
planar
aluminium
module
is
given
as
a
patent
for
an
improved
proton
exchange
membrane.
The
membrane
could
be
used
in
membrane
module
unit
as
electrochemical
cells
having
internal
passages
parallel
to
the
membrane
surface.
The
passages
in
the
membrane
extend
from
one
edge
to
another
and
allow
fluid
flow
through
the
membrane
and
give
access
directly
to
the
membrane.
The
invention,
awarded
by
NASA
in
1997,
is
related
to
applications
in
as
electrode
assemblies
for
fuel
cells,
electrolyzes,
electrochemical
hydrogen
and
oxygen
pumps,
and
related
devices
[Gonzalez-Martin
et
al.,
1997].
Figure
9
Membrane
electrode
assembly
containing
internal
passages
[Gonzalez-Martin
et
al.,
1997]
Tubular module: Alumina membranes most of the times have tubular mode which is composed of a number of tubular membranes with an internal relatively
40
small
diameter.
They
may
be
unique
tubes
assembled
in
a
module
using
joints
or
monolithic
composed
of
several
tubes
(Figure
10
and
11).
The
selective
part
is
located
inside
the
tube
or
tubes.
Feed
is
made
at
one
end
of
the
module
and
the
fluid
flows
inside
the
tubes
or,
the
retentate
springs
at
the
other
end.
The
permeate
pass
through
the
body
of
the
tube
or
out
of
the
monolith
to
the
external
part.
Figure
10
Schematic
side-view
of
membrane
module
consisting
of
multi-channel
elements
Figure
11
Cross-section
of
a
monolithic
multi-channel
membrane
element
[Hsieh
et
al.,
1998]
In general, the main advantages and disadvantages of tubular noticed in the literature are because of ceramic material properties, the most common substance for which they are made of. (a) Advantages:
41
No pre-treatment, accepts slurries in large particles (about one-tenth the diameter of the tube) Easy to clean, use of mechanical cleaning Very low compactness of the order of 10 to 300 m2/m3 Relatively high investment Energy costs can be significant, due to a high rate of circulation Fragility in the case of ceramic membranes
(b) Disadvantages:
As
an
example
for
diameter
difference,
in
laboratory
scale
of
Stoitsas
et
al.
(2005)
research
work,
alumina
and
silica
membrane
specimens
for
gas
separation
are
of
tubular
geometry
with
a
length
340103m,
an
internal
diameter
of
8103m
and
an
external
diameter
of
14103m
when
the
membrane
surface
per
specimen
is
8.5103m2.
In
this
case,
the
ceramic
membrane
is
an
asymmetric
4- layer
system.
The
first
layer
operates
as
a
support,
the
third
as
a
microltration
layer
(pore
sizes
of
100
or
200nm
depending
on
the
ring
temperature)
and
the
fourth
as
an
ultraltration
layer
with
a
pore
size
of
35nm.
The
second
layer
(pore
size
of
500nm)
serves
to
bridge
the
gap
between
the
macroporous
support
and
the
microltration
layer.
Honeycomb:
Honeycomb
pore
size
membrane
is
part
of
the
new
generation
membranes
for
microfiltration
and
ultrafiltration
applications.
It
is
available
for
ceramic
membranes
either
of
alumina
or
carbon
supports.
The
term
honeycomb
concerns
the
microstructure
of
porous
in
porous
layer
and
because
of
this
geometry,
the
membrane
is
suitable
for
special
applications.
4.1.2.
Commercialized
modules
of
membrane
alumina
Tubular
mode
The
figure
below
(Figure
12)
is
from
Veolia
Water
Solutions
&
Technologies
(VWS)
manual
for
new
ceramic
membrane
modules.
42
The
industry
utilizing
the
CeraMem
technology
provides
a
variety
of
inorganic
microfiltration
(MF)
and
ultrafiltration
(UF)
membranes.
In
CeraMem
technology,
typical
multi-channel
ceramic
membrane
has
multiple
parallel
passageways
that
run
from
a
feed
inlet
end
face
to
an
opposing
outlet
end
face.
The
surfaces
of
the
passageways
are
coated
with
permselective
membrane.
A
feed
stream
is
introduced
under
pressure
at
the
inlet
end
face,
flows
through
the
passageways
over
the
membrane,
and
is
withdrawn
at
the
downstream
end
face
as
retentate.
Permeate
flux
passes
through
the
membrane
flows
into
the
porous
monolith
material.
Under
an
applied
pressure,
the
combined
permeate
from
all
the
passageways
flows
through
the
porous
monolith
support
to
the
periphery
of
the
monolith
and
is
removed
at
the
monolith
exterior
surface
[veoliawaterst.com/ceramem].
Honeycomb
module
The
Anopore
inorganic
membrane
(Anodisc)
in
honeycomb
module
is
a
novel
material
with
precise,
no
deformable
honeycomb
pore
structure
(Figure
13)
with
no
lateral
crossovers
between
individual
pores
that
filters
at
precisely
the
stated
cut-off,
allowing
no
larger
sized
particles
to
pass
through
the
membrane.
43
Figure 13 AnoporeTM alumina membrane with honeycomb pore size distribution [whatman.com]
The AnoporeTM inorganic membrane is composed of a high purity alumina matrix that is manufactured electrochemically [whatman.com]. This kind of membrane shows a high thermal permeability and selectivity and it can be applied for a wide range of special applications as pharmaceutical or laboratory ultrafiltration process. Generally, commercial alumina membranes have an asymmetric structure with membrane deposition on the inside surface of a tube (or channel). The diameter of module depends on the kind of application. Large scale units can be used eg. in wastewater treatment plants and small scale units can be used eg. in gas separation. A typical industrial installation will have several of these modules arranged in series and/or parallel configuration [Sondhi et al., 2007].
44
4.2. SEPARATION CHARACTERISTICS FOR ALUMINA MEMBRANES For future looking through membrane uses it is important to summarize the most crucial separation characteristics as crossflow mode, flux or rejection properties. Crossflow Crossflow filtration is a pressure-driven separation process in which a stream flows parallel to the filter surface. For microfiltration applications such a parallel flow creates shear forces and/or turbulence to sweep away particulates and prevent blinding of the filter surface. The feed flows past the inside surface of the tube (or channel) and the permeate (filtrate) flows through the porous support to the shell side of the module. This is generally true for all crossflow membrane modules such as tubular, hollow fiber, spiral wound, or plate and frame modules. Inorganic membranes used in commercial large-volume applications are, however, available only in single tubes or multi-channel elements as described earlier. Such membrane-based separation devices have to satisfy certain performance cri-membranes used in commercial large-volume applications are, however, available only in single tubes or multi-channel elements as described earlier. Such membrane-based separation devices have to satisfy certain performance criteria to justify a cost-effective process as flux or filtration rate, long term flux stability and separation or rejection properties of the membrane. Flux This is one of the most important performance criteria for cost effective membrane technology, particularly for large-scale separations. In membrane separation processes the (permeate) flux may be influenced by such factors as crossflow velocity, transmembrane pressure differential, temperature and feed characteristics.
45
Crossflow
velocity
This
is
the
average
rate
at
which
the
process
fluid
flows
parallel
to
and
across
the
membrane
surface.
Due
to
continuous
removal
of
filtrate
(permeate)
through
the
membrane,
the
crossflow
velocity
is
somewhat
higher
at
the
inlet
than
at
the
outlet
of
the
membrane
element.
For
many
particulate
filtration
applications
(e
.g.,
MF)
it
is
generally
recommended
to
be
in
the
velocity
range
of
1-5
m/sec
depending
on
process
stream
properties
such
as
viscosity,
particulate
loading,
etc
.,
and
on
constraints
imposed
by
pressure
drop
limitation
In
MF
with
an
alumina
membrane,
for
instance,
a
crossflow
velocity
in
the
range
3-5
m/sec
is
recommended.
An
increase
in
crossflow
velocity
generally
results
in
an
increase
in
flux,
since
at
higher
shear
rates
the
removal
of
particulates
at
the
membrane
surface
is
more
effective.
A
higher
crossflow
velocity,
however,
results
in
a
substantially
higher
tube
side
pressure
drop
which
may
pose
a
problem
to
the
membrane
material.
For
most
polymeric
hollow
fibers,
the
allowable
transmembrane
pressure
difference
is
limited
to
about
30
psig,
since
the
typical
fiber
burst
pressure
is
only
about
50-60
psig.
In
contrast,
alumina
membranes
do
not
suffer
from
this
limitation
and
usually
have
a
pressure
rating
of
250
psig
or
higher.
In
Figure
14,
a
simplified
circuit
of
crossflow
membrane
is
designed,
with
feed
and
retentate
and
pressure
application
points
illustrated.
Figure
14:
Simplified
schematic
of
crossflow
membrane
filtration
[Hsieh
et
al.,
1998]
46
Feed It has been found that the flux behavior for pure water (e.g., filtered tap or deionized water) through a single tube is similar to that through a multi-channel alumina membrane element (such as Membralox). However, for scale-up studies, alumina membranes with tube bundles or multi- channel monolithic elements should be used over single tubes to obtain hydrodynamic and fluid management data. Flux stability Critical factor determining process and economic viability of separation applications with membranes is also flux stability. In MF and OF applications, flux decay can be a serious problem. Flux decay is usually a direct result of an increase in the hydraulic resistance of the membrane due to fouling, eg. excessive accumulation of debris/particulates at the membrane surface or in the pores. The phenomenon of membrane fouling is only partially understood. In general, fouling is more severe with symmetric membranes. The majority of alumina membranes have an asymmetric pore structure with a pore size variation across the entire thickness of membrane/support composite. Such asymmetric membranes are thus expected to be less susceptible to internal pore fouling. Many liquid streams contain extraneous matter in the form of small particles, macromolecules, etc. During the filtration operation, these substances are often concentrated near the membrane surface and can precipitate or agglomerate on the surface as well as in the pores. Flux decay was observed in the filtration of tap water with a single-tube alumina membrane when the backflushing technique for cleaning was not employed. This may be due to membrane fouling by trace quantities of particulate and colloidal matter, since prefiltered water showed a higher flux in comparison to unfiltered tap water. A stable flux for extended operation can be obtained if flux decay due to fouling can be controlled.
47
Rejection characteristics One of the important parameters determining membrane rejection characteristics is the mean pore diameter of MF and OF membranes having narrow pore size distributions. In general, the smaller the pore diameter (i.e., the tighter the membrane), the higher will be the rejection coefficient to particulates/ solutes of greater nominal size. However, as pore size decreases, permeability to liquid also decreases rapidly.
48
5. APPLICATIONS 5.1. CERAMIC MEMBRANES There are a variety of industrially important liquid or gas phase systems where the general membrane technology has been successfully applied for separation purposes. Such membrane processes as MF, UF, and reverse osmosis (RO) using polymeric membranes have been in commercial practice for over two decades. However, in recent years ceramic membranes are also being considered for crossflow MF and OF applications and also gas separation application [Laitinen, 2004]. Ceramic membranes are usually composed by metal oxides as aluminum, titanium or zirconium oxide as they are or mixed. They are formed from different layers of particular length and the support is consisted of porous - alumina in tubes unit. The active layer is consisted from alumina (Al2O3, or ), from zirconium (ZrO2) or titanium oxide (TiO2). The main advantages or ceramic membranes can be listed as: sufficient resistance at high temperature ( to 300 C) chemical resistance pH range from 0 to 14 compatibility of organic solvents and ionizing radiation support of sterilization
Organic membranes are hardly resistant to solvents eg. polymeric membranes including PTFE used in wastewater treatment process and on the other side inorganic membranes are more readily used for such kind of application [Remigy et al., 2007]. In applications of industrial wastewater treatment as solvent recycling from polluted solution, conventional reclamation technologies, such as distillation and standard filtration, suffer significant limitations in terms of technical viability, cost, and user friendliness when ceramic membrane technology performs important advantages, as listed in Table 13 [Ciora et al., 2003].
49
Table 13 Advantages of ceramic membrane technology for the recovery of spent high flash solvents [Ciora et al., 2003] M&P Ceramic Membrane Technology Advantage 1. Excellent solvent resistance 2. Excellent recoverd product quality 3. Low temperature operation 4. Good product recovery ratios 5. No additional waste disposal problem 6. Low tech 7. Implemented on small scale Technology is easily implemented. No special training required. Minimal maintenance etc. Most high flash solvent waste is highly segmented with numerous small-scale generators of waste solvent Waste volume necessary for disposal is <10% of original volume >90% solvent recovery can be aschieved No thermal degradation of solvent Finished product quality similar to virgin material Comments Can be used to treat entire range of high flash solvents
At the same moment, considerable disadvantages often limit ceramic membranes in pilot or small scale applications and render polymeric membranes as the most widely applied membranes. Ceramic membranes are related to high cost of preparation, fragility and high cost of installation and as also limited variety of modules (only tubular and more rarely planar). In addition, some ceramic active layers are sensitive to basic attacks when they are deemed to be generally very resistant to alkaline pH [Remigy et al., 2007]. Inorganic membranes can be classified according to the principal component they consist of apart from other layers or additives to carbon, metal and composite membranes [Remigy et al., 2007]. Analytically, the most important applications of these categories are gathered below: 50
Carbon
If the membranes are absolutely consisted of carbon they are used for gas separation. For the filtration field, carbon membranes comprise a carbon porous layer on which a metal oxide layer is deposited (zirconium or alumina). A wide variety of metals can be used for the manufacture of filtration membranes. Two metals, however, stand out: steel (including stainless steel) and aluminum. The stainless steel membranes are composed of sintered particles while those of aluminum are formed of a film of anodized aluminum. The metal membranes are exclusively microfiltration membranes or high UF with a pore size of not less than 20 nm. In Table 13, the most important advantages and drawbacks are revised for the different kinds of materials. Note that the comparisons in terms of thermal and chemical resistance ignore the other materials in the manufacture of modules (seals, adhesives). Combination of different materials Metals
51
5.2. ALUMINA MEMBRANES APPLICATIONS In the recent years of membrane technology development, alumina ceramic or composite membranes are of great interest for a wide range of applications and new structures compositions. They offer a largely independent control of pore size, pore topology, pore orientation, molecular functionalization and pore wall composition. A developing research field focuses on nanosize of porous alumina membranes creating a potential for molecular separators, materials for the inclusion of conducting or semiconducting nanostructures. The use of porous ceramic membranes often offers a solution for aggressive environments as corrosive solutions or high temperature process [Levanen et al., 2004]. The following sections will give more information on applications or possible application areas of alumina ceramic membranes divided in two main categories: 1. Liquid phase separation 2. Gas phase separation Remarkable is that in the analysis of applications below, alumina is one the components of membranes. In many cases composite membranes are studied with many different layers and at least one alumina coat. 5.2.1. Liquid phase separation applications Most of the commercial liquid phase applications for ceramic membranes are either for microfiltration or ultrafiltration. The first large-scale commercial success of ceramic membranes has been in the food and beverage industries. However, significant applications are found also in other areas, such as biotechnology, pharmaceutical, petrochemical, and other process industries as well as in environmental control. In recent years also ceramic nanofiltration membranes have been developed. Microfiltration is mostly applied in cases
52
where liquid streams contain particulates, and ultrafiltration is used when smaller molecules are removed. Some of the important liquid phase applications where alumina membranes are employed are: treatment of industrial and municipal water, sterilization of liquids in the pharmaceutical industry, clarification and sterilization of beverages, e .g. wine, beer and fruit juices, cell harvesting and sterilization, cheese-making by ultrafiltration and wastewater treatment. A number of studies on crossflow filtration can be found in the recent literature [Laitinen et al., 2004]. Although many of them deal specifically with polymeric membranes, the principles of crossflow filtration, in general, can also be applied to membranes made of inorganic materials such as alumina. In all these application areas the ceramic membranes have to compete with the polymeric membranes which are becoming more and more stable and which have an advantage of much lower prices. The use of ceramic membranes can only be justified in cases, where they give much better performance, or in cases, where there are no suitable polymeric membranes available [Hsieh et al., 1998]. In the following part, the applications of alumina membranes in gas phase separation process are gathered in Table 14. i. Food processing Generally, the major advantages of ceramic membranes in the area of food and beverages are their resistance to alkaline cleaning solutions, their stability in steam sterilization, better capability to withstand higher operating pressures, and a consistent pore size. In crossflow microfiltration applications, the major advantage of the ceramic membranes has been the possibility to use uniform transmembrane pressure, which for example in dairy industry has enabled high fluxes and low fouling. The market share of inorganic membranes in the food and dairy industry was about 10% at 1990s and tomorrow this percentage is 53
Table
14
Liquid
phase
separation
process
of
alumina
membranes
and
composite
alumina
membranes
Porous
alumina
membrane
appications
Liquid
phase
separation
applications
Food
processing
Clarification
of
natural
fruit
juices
Filtration
of
sugar
cane
juice
Alcoholic
beverages
Environmental
applications
fruit
juice
industry
(orange,
apple,
grape
etc.)
sugar
concenration
breweries,
wineries
Petrochemical industry wastewater treatment petrochemical industry, oil recovery Pulp and paper industry wastwater treatment Municipal wastewater treatment Activated sludge treatment Nuclear industry wastewater treatment Fluoride removal Arsenic removal from water resources Arsenic and fluoride removal Chromium and arsenic removal Biotechnology and Pharmaceutical applications Fermentation broths Fungal cells separation Penicillin recovery Lysozyme ultrafiltration recovery of valuable antibiotics diafiltrationm polysaccharide production recovery of a water-soluble water reuse in production line municipal wastewater treatment plants, water reuse depollution of wastewater sludge, compost municipal wastewater, chemical industry wastewater depollution of water sources and groundwater depollution of water sources and groundwater metal industry wastewater, valuable metals recovery
supposed to be doubled [Bhave et al., 1991]. The main applications can be roughly divided into (a) concentration of soluble molecules and suspended solids and (b) clarification by removing suspended solids. As already mentioned, the main usage of inorganic membranes is in the dairy industry, in which the key to success has been the invention of transmembrane pressure mode. Some studies have also been made concerning the usage of inorganic membranes for the concentration of other vegetable and animal proteins as well as for the processing of starch and sugar. 54
(a) Clarification of natural fruit juices Clarification or fruit juice such as apple, cranberry and grape is one of the most successful and widely practiced industrial applications of ceramic membranes. Ceramic membrane filtration provides a particularly attractive alternative, replacing such conventional treatments as gelatin addition, holding/decanting, diatomaceous earth, cake filtration, and polishing, with a single unit operation. Membranes produce superior clarity juice and deliver higher yields compared with conventional clarification processes. (b) Filtration of sugar cane juice In the filtration of sugar cane juice, ceramic membranes as carbon/carbon or alumina/alumina [Jiratananon et al., 1997] can be used in several different stages in the raw and refined sugar production. One interesting opportunity is in the microfiltration/ultrafiltration of clarified juice (714 Brix) and/or pre-evaporated juice (20-25 Brix) as a pretreatment prior to ion exchange or chromatographic separations. Pretreated and filtered juice is softened, evaporated and purified using ion exchange and chromatographic processes leading to a better quality refined sugar. Typical operating conditions include feed temperatures of 90100oC, a high crossflow velocity (47 m/s) and transmembrane pressures up to 5bar. The need to purchase, use and dispose of filter aids is eliminated. In some applications, the cost of equipment necessary to dewater filter-aid sludge may be comparable to the cost of the membrane system. [Sondhi et al., 2005]
(c) Alcoholic beverages In the area of alcoholic beverages, alumina membranes are used for the clarification and sterilization of the final products. Composite multilayer ceramic membranes membranes applications exist for the filtration of wine and beer [Gillot et al., 1986] as well as for sake and vinegar [Hagasewa et al., 1991]. By membrane filtration the amount of waste generated and chemicals used during the production can be considerably decreased. The use of membrane filtration instead of a conventional process is advantageous also since membrane filtration produces a sterile product and further sterilization is not necessary. For Membralox membranes these applications have existed since 1988 [Gillot et al., 1990]. In breweries as well as in wineries membrane filtration can be used to 55
replace
clarification,
stabilization
and
sterilization
steps.
The
alumina
membrane
Membralox
is
for
example
used
to
further
concentrate
tank
bottoms
or
centrifuge
concentrates
[Gillot
et
al.,
1990].
ii. Environmental
applications
The
increasing
concern
for
the
environment
and
tighter
legislation
on
emissions
are
increasing
widely
the
applications
of
ceramic
membranes.
In
many
chemical
process
applications
there
is
a
growing
need
to
treat
not
only
the
waste
streams,
to
meet
the
increasingly
stringent
environmental
regulations,
but
also
to
recover
and
reuse
the
chemicals.
The
nature
of
these
process
streams
can
vary
and
in
some
cases
the
process
may
require
aggressive
operating
and/or
cleaning
conditions.
Examples
of
such
applications
include
the
filtration
of
chemical
solvents,
dye
and
pigment
wastewater
from
dye
processing
and
colouring
plants,
and
highly
variable
wastewater
containing
detergents,
polymers
and
organic
solvents
[Sondhi
et
al.,
2007].
Environmental
applications
can
be
roughly
divided
into
wastewaters
from
various
sources,
as
well
as
oily
wastes
and
sludges.
In
the
following
part
the
process
industry
wastewaters
from
the
chemical,
textile,
and
pulp
and
paper
industry
are
discussed
as
well
as
wastewaters
from
the
nuclear
industry
and
sludge
from
municipal
wastewater
dehydration.
(a) Petrochemical
industry
wastewater
The
wastewater
applications
in
the
petrochemical
industry
include
the
treatment
of
acidic
and
alkaline
process
wastewaters
from
a
vinyl
chloride
monomer
manufacturing
facility.
Lahier
and
Goodboy
(1993)
have
shown
that
the
high
content
of
heavy
metals
from
acidic
wastewater
can
be
removed
by
using
two-stage
membrane
filtration
with
alumina
microporous
membranes.
As
a
pretreatment
the
pH
of
the
wastewater
was
adjusted
from
0.7
to
12.
In
the
first
filtration
stage,
the
precipitated
metal
hydroxides
were
separated
from
the
water
and
in
the
second
filtration
stage
the
filtered
metals
were
concentrated
to
17-20
w.w%.
The
water
recoveries
from
the
filtrations
were
80%
and
99.5%.
In
Lahier
and
Goodboy
research
work,
alumina
microfiltration
membranes
were
evaluated
for
treatment
of
3
aqueous
streams
containing
heavy
metals,
oils,
and
solids
at
petrochemical
manufacturing
facilities.
They
have
also
shown
that
an
alkaline
waste
stream
containing
dichloroethane,
water,
and
calcium/iron
hydroxides
can
be
treated
with
ceramic
membranes.
56
(b) Pulp and paper industry In pulp and paper industry the main interest in studying the possible applications of ceramic membranes has been in bleach plant effluent treatments. The wastewater sources in paper industry comes from disk filtration, flotation and close loop water circulation as well as the clarification of coating colour basin. In Laitinen et al. (1998) as well as in many 90s references [Petterson et al., 1988; Gaddis et al., 1995], alumina membranes are used for wastewater ultrafiltration for suspended solids (SS), COD, color and colloidal material removal. Laitinen tried flat sheet - and -alumina membranes and modified -alumina membranes and concluded in quite low COD removal is achieved (under 22%), iron and odor from color wastewater treated sufficiently and SS and colloids was almost totally remover. Fouling of membrane seems to be the most considerable problem for large scale application of the method. Great advantage of wastewater treatment of pulp industry without using chemical compounds is recycling feasibility, In some cases [Laitinen et al., 2001] existing results have showed that ultrafiltration permeate was satisfactory for continuous recycling and the pulp produced with recycling had better strength properties than when recycling was not used. Hence, toxic discharges were reduced, waste management became more effective, and the need for maintenance was reduced. (c) Municipal wastewater Ultrafiltration/microfiltration is suitable for tertiary treatment of municipal wastewater after standard treatment steps. The final product can be reused as the level of pollutants and microorganisms falls short of environmental legislation limits. In Vera et al. (1997) a study on the filtration of the secondary clarified suspension is studied using alumina microfiltration membranes of 0.14m pore size. The membrane system proved to serve as a total barrier for suspended solids, total coliform, fecal coliform and fecal streptococci. This fact together with the reductions of turbidity, COD and phosphorus removal from secondary treatment made the microfiltered water perfectly adapted to irrigation. A critical flux of 100 l/(mh) was achieved at 1bar pressure and 3 m/s crossflow velocity. Other possible application studied is ceramic membrane microfiltration of hotel wastewater in order to reuse it in secondary purposes, such as toilet flushing [Laitinen, 2004]. Nevertheless, Because of the high cost of membrane installation and performance, the wide scale application seems to be not yet necessary in this kind of municipal wastewater and activated sludge treatment.
57
(d) Activated sludge Xing et al. (2001) has studied the use of a bioreactor combined with -alumina and zirconia ceramic ultrafiltration membranes for the reclamation of urban wastewater. According to results, the treated water could be reused directly for municipal purposes, such as toilet flushing and car washing, and after softening treatment for industrial purposes such as cooling supply and process water. Removal of ammoniac nitrogen and suspended solids was product of membrane separation however COD removal efficiency was attributed more than 90% by bioreactor and no by ceramic membranes. (e) Nuclear industry In the nuclear industry, composite alumina ceramic membranes have been studied for the treatment of radioactive waste streams. AEA Technology in England has done excessive pilot plant studies with ceramic membranes and the results have shown that, for a low-level radioactive general site waste, good alpha and beta/gamma removal can be achieved. [Laitinen,2004]. Cadmium adsorption from silica-alumina membrane is simulated by Pacheso et al. (2006) from nuclear and chemical wastewater treatment. Sol-gel structured nanoparticles of silica and alumina are used for multilayer composite alumina membranes fabrication.
(f) Fluoride removal Nanofiltration (NF) is an attractive technique for reducing fluoride anions (F-) concentrations to acceptable levels in drinking water, however commercial membranes show minimal chloride of fluoride selectivity. In laboratory scale, multilayer organic membranes (polystyrene sulfonate) with porous alumina supports exhibited Cl, F and Br high selectivity, three times more than the commercial available membranes [Pagana et al., 2007]. Moreover, chloride/fluoride selectivity is essentially constant over Cl-/F- feed ratios from 1 to 60, so these separations will be viable over a range of conditions [Seong et.al, 2007].
58
(g) Arsenic removal from water resources Alumina ceramic membranes can be used for As(V) from water resources as contaminated water. For such kind of application, -Al2O3/-Al2O3 can be used. The concentration of arsenic ions decreased from 1ppm, which was originally to power in 5ppb. Therefore, the concentration of ions As (V) in output was lower than the maximum permissible limit set for drinking water [Pagana et al., 2009].In Laitinens doctorate thesis, published in 2004 from Finland Technical University, from all the membrane separation process studied applied in a wide range of wastewaters, alumina membranes assumed to be suitable for arsenic removal from bore well water if flocculation was used as a pretreatment as well as for the treatment of the stone cutting wastewater. The fluxes achieved in short-term experiments for the bore well water were promising and the optimization of operation conditions should be considered [Laitinen, 2004]. (h) Arsenic and fluoride removal In a similar recent study, Wu et al. (2011) highly ordered mesoporous aluminas and calcium-doped aluminas were synthesized. Their uoride adsorption characteristics, including adsorption isotherms, adsorption kinetics, the effect of pH and co-existing anions were investigated. These materials exhibited strong afnity to uoride ions and extremely high deuoridation capacities. The highest deuoridation capacity value reached 450 mg/g. These materials also showed superb arsenic removal ability: 1 g of mesoporous alumina was able to treat 200 kg of arsenic contaminated water with a pH value of 7, reducing the concentration of arsenate from 100 ppb to 1 ppb.
59
(i) Chromium
and
arsenic
removal
In
laboratory
scale,
separation
processes
have
been
developed
for
ion
Cr
(III)
removal
from
water
using
-alumina
membranes
[Pagana
et
al.,
2000;
Sklari
et
al.,
2005].
In
Pagana
et
al.
(2000)
is
described
how
two
pilotic
system
have
been
developed
with
concentration
of
chromium
ions.
In
the
conclusion
of
this
study,
the
concentration
of
ions
Cr
(III)
in
output
is
assumed
to
be
significantly
lower
than
the
maximum
permissible
limit
set
for
drinking
water
(greek
standars).
By
the
same
research
group,
a
combined
process
of
removing
ions
As
(V)
and
Cr(III)
from
simulated
wastewater
using
nanostructruded
alumina
membranes
provided
also
sufficient
results.
The
concentrations
of
arsenic
and
chromium
ions
decreased
from
1ppm
and
0.5ppm,
which
was
originally
to
power
in
5ppb
and
3ppb,
respectively.
Therefore,
the
concentrations
of
ions
As
(V)
and
Cr
(III)
in
output
was
lower
than
the
maximum
permissible
limits
set
for
drinking
water.
In
the
figure
below
(Figure
15)
the
pilot
system
is
illustrated
[Pagana
et
al.,
2008].
Figure
15
Flow
diagram
of
the
Cr
(III)
removal
process
[Pagana
et
al.,
2008]
In this work, asymmetric multilayer porous ceramic membranes are developed. Composite -Al2O3 membranes made by solgel method are prepared for chromium and aersinc ions removal from water solutions. As(V) removal is achieve d by a two stage adsorption ultraltration processes in series. Moreover, Cr(III ) removal is achieve d by an adsorptionult raltrat ion parallel
60
process
(Figure
15)
using
membrane
ultrafiltration
in
a
pilot
system
(see
characteristics
inTable
15
).
Table
15:
Basic
characteristics
of
membrane
ultrafiltration
process
applied
in
Pagana
et
al.,
2007
pilot
system
for
chromium
removal
(Pagana
et
al.,
2007)
Chromium
removal:
basic
characteristics
of
the
membrane
ultrafiltration
process
Feed
volume
Final
permeate
volume
Average
permeate
flux
Pressure
difference
Membrane
surface
A
(A=2rl)
100%
100%
60ml
min-1
3.105
Nm-2
0.05m2
In general, the adsorption-ultraltration ion process using ceramic membranes may oer a low cost eective alternative arsenic and chromium purication technology basically in terms of membrane stability, applied pressure and product ux with the additional advantage of being suitable for small local and decentralized units for point-of-use. However, further experiments should be carried out in order to provide more accurate an d widely accepted conclusions [Pagana et al., 2007]. iii. Biotechnology and Pharmaceutical applications
In general framework, in biotechnology and pharmaceutical applications, the biocompatibility of the membranes is important [Shackleton et al., 1987]. In such kind of applications, the main interest has been on the filtration of fermentation broths. In biotechnology, ceramic membranes have been used for primary extraction, purification, and concentration of biomass, antibiotics, vitamins, amino acids, organic acids, enzymes, biopolymers, and biopesticides [Cueille et al., 1990]. There are also applications in the treatment of vaccines, recombinant proteins, cell cultures, and monoclonal antibodies as well as in continuous fermentation. The alumina membranes have several features that indicate the practical benefit in analytical and diagnostic separations. They are transparent, allowing to view the retained materials from either side of the membrane.
61
The capillary pore structure allows no lateral diffusion of liquids along the membrane. Nanoporous alumina membranes are usually prepared electrochemically in sulfuric or phosphoric acid bath. After preparation they are used for microfiltration of biological media, such as human red blood cells and bovine serum albumin [Laitinen, 2004]. (a) Fermentation broths Alumina membranes are used for fermentation broth clarification at numerous installations worldwide, successfully competing with other technologies such as polymeric membranes, vacuum filtration and centrifugation. These systems are often used for the recovery of valuable antibiotics from dilute solutions. Typical operating conditions include feed temperatures of 3060C, high crossflow velocity (58 m/s) and trans-membrane pressures up to 6bar [Laitinen, 2004]. (b) Fungal cells separation Haarstrick et al. [1990] have studied microfiltration using alumina microporous membrane in the separation of fungal cells and the purification of the produced polysaccharide. They concluded that crossflow microfiltration could be an alternative to conventional separation including purification processes and suggested that a diafiltration mode should be used in order to avoid the problems arising from the high viscosity of the broths. (c) Penicillin recovery An alumina microfiltration membrane has been used in laboratory scale [Adikane et al., 2001] to optimize penicillin G recovery from fermentation broth. Reduction over 40% has been achieved in processing time by optimizing the crossflow velocity. Moreover, it is showed that the operating fluxes could be regenerated and a 98% recovery of penicillin G could be obtained over 12 cycles.
62
(d) Lysozyme ultrafiltration Group of Baudry et al. (2001) has studied the use of modified ceramic membranes by alumina and zirconium oxide used for lysozyme and lactoferrin ultrafiltration. It is concluded that as other studies had prouved, adsorbed protein on the membrane surface was able to highlight UF mechanism. The enhanced selectivity was observed when the protein to be retained had additional interactions with the membrane surface. Conrad et al. (1998) studied microfiltration for the recovery of a water-soluble, chiral compound of therapeutic interest from a bioconversion broth of whole cells and soybean oil. It is assumed that that it was possible to use microfiltration to harvest an aqueous product stream from the oil-water bioconversion broth. 5.2.2. Gas phase separation The use of membranes in gas separations has grown at a very rapid pace in recent times. One particularly interesting application of gas separation with membranes is the removal of dilute heavy organics from light gas streams such as the removal of solvents from the exhaust of different process industries [Javaid et al., 2005]. Gas mixtures can be separated by either dense or porous membranes. Microporous inorganic membranes have often been modied using in many cases different types of alumina and studied as possible materials for achieving solubility based separation. The dense ceramic membranes are mostly impermeable to all other gases, giving extremely high selectivity towards oxygen or hydrogen. Oxygen permeation through a dense ceramic membrane is due to a large number of oxygen vacancies that are generated by doping and the electron holes produced by the defect reaction exist in the solid electrolyte. Under a gradient of oxygen partial pressure imposed on the membrane at a high temperature, the oxide ions are transported along with holes from the high partial pressure side to the low partial pressure side. Similarly, when hydrogen is exposed to a mixed proton conducting membrane, it may be transferred through the membrane under a hydrogen partial pressure gradient. Again, apart from the membrane bulk diffusion, the
63
surface
reactions
are
also
important
and
need
to
be
taken
into
consideration
for
the
hydrogen
permeation.
In
microporous
ceramic
membranes,
the
gas
permeation
behaviour
may
be
dominated
by
Knudsen
diffusion,
surface
diffusion,
multilayer
diffusion,
capillary
condensation
or
molecular
sieving
(i.e.
congurational
diffusion)
and
is
strongly
dependent
on
the
pore
size
and
pore
size
distribution
of
the
membrane,
operating
temperature
and
pressure,
and
the
nature
of
the
membrane
and
the
permeating
molecules
[Laitinen,
2004].
Gas
separation
using
porous
ceramic
membranes
is
one
of
the
important
research
topics
[Wiley,
2007].
Recently,
most
of
the
development
membrane
separation
activities
have
been
focused
on
gas
separations,
particularly
as
ionic
conductors
for
oxygen
transport
and
as
molecular
sieve
membranes
for
hydrogen
separations.
Their
use
in
environmental
applications
has
been
very
limited
due
to
cost
considerations,
although
they
offer
several
unique
advantages
in
this
area,
such
as
chemical
and
thermal
stability
and
rugged
structural
stability
[Sondhi
et
al.,
2007].
Table
16
:
Gas
separation
by
porous
alumina
membranes
[Kaldis
et
al.,
2004]
Pore
diameter
()
~100
~100
~100
1020
200-400
~10
~10
~10
~10
~30
~30
~30
100-200
100-200
Operating
temperature
(oC)
25-75
25-75
25-75
800
10
31-77
65-70
78-84
82-88
65-70
78-89
82-88
196-197
196-197
Applied
pressure
differenece
(kPa)
3.03
-
16.2
3.03
-
16.2
3.03
-
16.2
343
152-252
4.04-39.4
23.2-106
23.2-106
He/N2
He/C2H6
He/Kr
H2/H2S
H2/H2S
H2O/air
H2O/CH3OH
H2O/C2H5OH
H2O/(CH3)2CHOH
H2O/CH3OH
H2O/C2H5OH
H2O/(CH3)2CHOH
H2/He
H2/CO
Gas
mixture
64
100-200 100-200 100-200 100-200 100-200 100-200 100-200 100-200 100-200 100-200 300-400
He/N2
H2/CO2
H2/CO
He/N2
H2/CO2
H2/C2H6
H2/C3H8
H2/He
He/N2
H2/CO2
235U/238U
Sustainable
membranes
in
high
temperatures
are
strongly
needed
for
energy
production
application
as
biomass
burning
(organic
waste
gasification,
coal
gasification
etc.).
Ceramic
membranes
are
appropriate
for
such
kind
of
applications
because
of
their
high
thermal
stability
and
corrosion
resistance.
In
installations
as
coal
gasification
plants,
gas
separation
is
needed
for
emission
treatment
after
combustion
or
other
processes.
Usually,
carbon
dioxide
is
the
substance
which
must
be
isolated
in
order
to
fit
environmental
requirements.
Membrane
technology
is
one
of
the
promising
tools
in
these
applications
and
many
research
works
has
been
realized
in
recent
years.
In
the
following
part,
the
applications
of
alumina
membranes
in
gas
phase
separation
process
are
gathered
in
Table
17.
Table
17
:
Gas
phase
separation
process
of
alumina
membranes
and
composite
alumina
membranes
Porous
alumina
membrane
appications
Gas
phase
separation
applications
Carbon
dioxide
capture
CO2/N2
separation
H2/CO2
separation
Hydrocarbons
separation
Acetone
recovery
Propane
separation
Catalytic
reactors
VOCs
oxidation
Methane
to
ethane
reaction
Industrial/Scientific
applications
Nox
control,
gas
phase
streams
from
energy
plants
gazification,
combustion
emissions
paint,
ink,
oil
industry
natural
gas
processing,
petroleum
refining
air
pollution,
VOCs
recovery
gas
treatment
65
There
is
growing
consensus
among
the
scientific
community
that
the
rising
atmospheric
levels
of
CO2
as
a
result
of
human
activities
(e.g.,
fossil
fuel
burning,
cement
production).
Membrane
processes
appear
to
be
an
attractive
option
to
carry
out
gas
separations
in
terms
of
their
lower
environmental
impact
and
energy
costs
compared
to
more
conventional
separation
technologies
(e.g.,
distillation,
absorption,
adsorption,
crystallisation).
On
the
guidance
of
a
recent
study
recently
published
by
Lito
et
al.
(2011),
different
adsorption
models
have
been
screened
to
account
for
CO2
and
N2
adsorption
in
MFI-alumina
samples
[C.- H.
Nicolas
et
al.,
2011].
(a) CO2/N2
separation
In
Sang
H.
Hyun
et
al.,
(1995)
top
layers
of
-Al2O3
composite
membranes
have
been
modified
for
improving
the
separation
factor
of
CO2
to
N2.
The
separation
factor
through
the
TiO2
supported
-Al2O3membrane
was
found
to
be
fairly
enhanced
by
silane
coupling,
but
in
case
of
the
-Al2O3
supported
membrane
was
not.
The
CO2/N2
separation
factor
through
the
modified
-Al2O3
/
TiO2
composite
membrane
is
1.7
at
90C.
The
separation
factor
is
proportional
to
the
CO2
concentration
in
the
gas
mixture,
and
the
modified
membrane
is
stable
up
to
100C.
The
main
mechanism
of
the
CO2
transport
through
the
modified
-Al2O3
layer
is
known
to
be
a
surface
diffusion.
(b) H2/CO2
separation
Coal
gasification
is
called
any
process
of
converting
coal
into
gas
for
many
different
uses
as
illuminating,
heating
etc.
In
the
figure
above
(
Figure ) an integrated gasification combined cycle is shown (IGCC). In IGCC (a) air separation and gasification, (b) gas cleaning, (c) gas conditioning and (d) gas separation are combined for total air treatment after coal gasification are aligned (Figure 16). Using conventional technology, it is possible to build the IGCC plant
66
above,
technologies
such
as
cryogenics,
solvent
extraction,
adsorbents
in
pressure
or
temperature
swing
adsorption,
and
low
temperature
polymeric
membranes.
Due
to
compliance
with
sorption
mechanisms,
these
technologies
operate
best
at
low
temperatures
(<50oC).
The
problem
here
is
that
gas
separation
follows
downstream
from
gas
conditioning.
The
gasification
of
coal
predominantly
produces
syngas
(CO
and
H2)
with
some
remaining
hydrocarbons,
CO2
and
water.
Hence,
the
syngas
requires
further
processing.
Figure
16:
A
conventional
air
treatment
process
with
carbon
capture
[Diniz
et
al.,
2007]
The syngas requires further processing through the WGS reaction (see equation below), in order to maximise H2 production. CO + H2O CO2 + H2 H =-41. 2 kJ.mol-1 The WGS reaction is exothermic and the conversion is limited by thermodynamic equilibrium as the conversion to H2 and CO2 decreases with increasing temperature. The reaction is therefore carried out in two stages, in high (350- 400oC) and low temperature (250-300oC) shift reactors with interstage cooling. In addition, further cooling to <50oC is required to reduce the temperature to the temperature acceptable by conventional gas separation technologies. Cooling large stream of hot gases is capital intensive, and incurs a loss of power production; furthermore, these processes are likely to deliver CO2 at reduced pressures, which will have to be re-compressed to >100atm for transportation and storage. Hence, conventional processes will attract large energy penalties. In order to reduce efficiency losses, an alternative is to separate gases at higher temperatures. In this case, inorganic membranes derived from ceramics, silica, 67
metal
and
by
further
doping
or
alloying
showed
preferential
H2
selectivity
over
CO2
at
high
temperatures
(>200oC)
[see
e.g.
recent
work
of
Joe
Da
Costa
in
Australia].
These
technologies
can
also
operate
in
membrane
reactor
arrangements
for
the
water
gas
shift
reaction,
which
allow
for
shifting
the
reactions
to
higher
conversions
due
to
the
extraction
of
hydrogen
from
the
reaction
chamber.
The
advantage
here
is
two:
1.
CO2
is
kept
at
high
pressure
thus
reducing
requirements
for
CO2
compression
downstream.
2.
As
H2
is
selectivity
taken,
the
syngas
stream
is
reduced
by
up
30-35%
depending
on
the
recovery
rate.
Although
CO2
will
have
to
be
cooled
down
prior
to
compression,
the
volumes
are
reduced
thus
requiring
a
lower
cooling
duty.
Therefore,
inorganic
membranes
and
their
incorporation
in
MRs
are
foreseen
to
be
the
technology
of
choice
for
advanced
IGCC
plants
as
depicted
in
Figure
17.
Figure
17:
An
Advanced
scheme
for
IGCC
with
carbon
capture
[Diniz
et
al.,
2007]
The scheme shown above (Figure 18) for gas separation and conditioning is being developed in Australia by the University of Queensland as the research provider under the R&D program directed by the Centre for Low Emission Technology (www.clet.net). The use of a higher temperature membrane allows further simplification of the gas cooling, conditioning and separation step, but this scheme requires a high temperature membrane tolerant to the syngas.
68
Figure
18:
Schematic
of
a
multi
tube
membrane
module
for
H2
and
CO2
separation
[Diriz
et
al.,
2007]
In Diriz et al. (2007) for high temperature gas separation membrane, commercial D-alumina tubes coated with a top -alumina layer, dip-coated with cobalt and selective silica layer. The best membrane performance delivered H2 purity in excess of 98% at 300o C. The positive energy of activation for H2 permeation coupled with the negative energy of activation for CO2 permeation of metal doped silica membranes provide a favourable fundamental property for engineering design of gas separation at higher temperatures (up to 500o C) such as those required in a coal gasification process. The process integration provided by Diriz et al. is potentially beneficial for the next generation of high temperature processing unit operations in low emissions coal gasification. 69
ii.
Hydrocarbons
separation
(a) Acetone recovery Huang et al. (1997) modied alumina membranes for recovery of acetone from nitrogen by reducing the pore size to enhance multilayer diffusion and capillary condensation transport mechanisms [Huang et al. 1997]. Depending on the temperature and the feed composition, the separation factor varied from being less than 10 to as high as 200 is dominant. The modied membranes showed higher acetone permeability and higher separation factors as compared to polymeric membranes. However, the performance was strongly inuenced by temperature and feed composition. (b) Propane separation Hydrocarbons as propane or butane are usually by-products of natural gas processing and petroleum refining and they are commonly used as a fuel for engines, heating appliances etc. In Randon et al. (1995) alumina membrane are modied and gas permeation experiments were conducted using nitrogen and propane. The modied membrane exhibited signicantly high propane permeance. The modication had made the membrane hydrophobic and improved the membranes solubility-based separation characteristics. Other attempt for alumina membrane modification using different alkyl trichlorosilanes showed a signicant increase in propane/nitrogen selectivity accompanied, by a loss in permeance, after modication. In comparison to PDMS, one of the best-known polymers for solubility-based separations, the hybrid membranes exhibited equal or greater propane/nitrogen selectivity although at lower propane permeance [Javaid et al., 2005]. McCarley and Way (2001), in a similar study, modied 5nm alumina membranes with C18 trichlorosilane. They conducted both single gas and mixed gas permeation experiments at xed transmembrane pressures. The treated membrane showed a signicant increase in ideal selectivity for heavier gases (n-butane) over lighter gases (nitrogen and methane).
70
iii.
Catalytic reactors
The application of porous ceramic membranes as catalytic reactors starts in the 1980s. The driving force for this change was the possibility of integrating reaction and separation, which had already been achieved in the field of biochemical reaction engineering using polymeric membranes. These, however, were not applicable at the temperatures used in most of the processes of interest in the chemical process industry [Lafarga et al., 1998]. Since the materials used in the manufacture of ceramic membranes are also commonly used as conventional catalyst supports (as alumina), there has been a strong interest in the development of membrane reactors by researchers with previous experience on heterogeneous catalysis, who adapted many of the preparation and characterization techniques used in this field. The most important and valuable fact is that membrane itself is the catalyst [Coronas et al., 1999] and it can be used for a wide range of applications. Catalytic membranes are used to improve contact efficiency with the objective of attaining higher conversions by decreasing mass transfer resistances. Membrane reactor with catalytic surface aims to improve the contact in gasliquidsolid systems by providing a well-defined contact region: the liquid-filled pores of the catalytic zone of the membrane in close proximity to the gas interphase. This does not require a permselective membrane and avoids the problem of catalyst recovery that appears in slurry reactors.
Poorly permselective inert porous membranes such as mesoporous alumina, mesoporous glass etc. can reveal attractive for a number of dehydrogenation reactions. Inltrated MFI/alumina composite membranes have been used as O2 distributors but also as barriers for dehydrogenation reactions in MRs [Julbe et al., 2001]. (a) VOCs removal Volatile Organic Compounds (VOCs) are among the most common air pollutants emitted from chemical, petrochemical, and allied industries. VOCs are one of the main sources of photochemical reaction in the atmosphere leading to various environmental hazards and on the other hand, these VOCs have good commercial value. Hence, growing environmental awareness has put up stringent regulations to control the VOCs emissions. In such circumstances, it becomes mandatory for 71
each
VOCs
emitting
industry
or
facility
to
opt
for
proper
VOCs
control
measures.
There
are
many
techniques
available
to
control
VOCs
emission
(destruction
based
and
recovery
based)
with
many
advantages
and
limitations
[Khan
et
al.,
2000].
One
of
these
methods
for
removal
and
no
so
often
for
VOCs
recovery
is
gas
separation
with
ceramic
membranes
-
zeolithe
and
alumina
membranes
in
most
of
the
cases.
By
the
University
of
Zaragoza
in
Spain
team
and
other
research
groups
this
concept
has
already
been
demonstrated
eg.
using
hydrogenation
reactions
over
Pt/Al2O3
catalysts
in
membrane
module.
In
Figure
19,
it
is
illustrated
a
flow-through
membrane
in
which
the
permeation
of
a
premixed
feed
stream
takes
place.
This
was
the
approach
employed
in
works
by
Saracco
et
al.
(1999),
who
used
catalytically
modified
fly
ash
filters
for
alcohol
dehydration
and
for
the
reduction
of
nitrogen
oxides
with
NH3.
Pina
et
al.
(1999)
used
Pt/Al2O3
and
perovskite-containing
membranes
operating
in
the
Knudsen
regime
for
the
purification
(by
catalytic
combustion)
of
air
streams
containing
volatile
organic
compounds
(VOCs)
in
low
concentrations.
According
to
this
study,
since
in
the
Knudsen
diffusion
regime
the
probability
of
collisions
between
the
molecules
and
the
wall
of
the
pores
is
maximised,
this
type
of
membrane
would
be
expected
to
give
high
contact
efficiency
in
the
reaction
of
diluted
streams,
such
as
those
commonly
encountered
in
VOC
removal.
The
results
of
Pina
et
al.
(1999)
showed
that
the
membrane
could
perform
very
efficiently
in
the
combustion
of
VOCs
at
low
temperatures,
although
at
the
expense
of
a
significant
pressure
drop.
Figure
19:
Applications
of
membrane
reactors
[Coronas
et
al.,
1999]
72
The industrial application of this type of reactor surely requires optimization of the membrane structure aimed to reducing the pressure drop. Otherwise, its use would be restricted to applications involving reaction simultaneous with gas filtration, where the pressure drop is already present. (b) Methane to ethane reaction In Lafarga D. and Santamaria J. projects published in international literature [Lafarga et al., 1994; Sebastian et al., 2009] a new reactor concept has been developed and tested for the conversion of methane into ethane, ethylene and higher hydrocarbons via oxidative coupling. The basic idea consists of providing a low oxygen concentration in the reactor in order to increase hydrocarbon selectivity. To this end, oxygen is supplied to the reacting mixture by permeation through a porous wall as a modified alumina membrane, which is capable to withstand the temperatures and pressures involved, and at the same time give adquate values of oxygen flux [Lafarga et al., 1994]. Concluding, despite the plethora of studies appeared in the open and patent literature focusing on the development of ceramic materials for gas mixture separations [Koutsonikolas et al., 2010] no many industrial processes have been commercialized. Although alumina membrane is the most used in large scale, polymer membranes are still dominating in commercial field of separation process. The lack of selectivity combined with their high unit cost most often ascribed to the support, as well as their lack of hydrothermal stability in some cases, act as key economical and technological barriers for the industrial implementation.
73
6.SUMMARY AND CONCLUSIONS The term alumina includes large number of chemical compounds: amorphous, crystalline trihydroxides, monohydroxides, transition aluminas and stable anhydrous alumina. Alumina takes attention with good thermal, mechanical and chemical stabilitiy, as a material for industrial applications. With wider applications of membrane, alumina is trending topic. Alumina pore size distributions can be controlled easily modifications on operation conditions from a hundred of nanometers to a hundred of micrometers. Besides traditional pathways like sintering and anodic oxidation, alternative methods - sol-gel methods, dip coating, rapid gelation- are introducing with alumina membrane synthesis. The optimum range that will provide a good compromise between permeability and strength is being improved also with additives. According to literature overview, alumina membranes are applied especially in the areas where the advantages of ceramic membranes can be exploited. In biotechnology and pharmaceutical industry their resistance to microbial attack and biological degradation is really very important and their good thermal and chemical stability are often the factors that have made them beneficial in wastewater treatment and gas separation applications. However, they suffer from poor steam stability, fouling and cracking and because of this alumina is often mixed with additives such as metals or oxides to improve such kind of drawbacks [Laitinen, 2004]. Modifications can also be used to increase selectivity by surface adsorption or molecular sieving effects and a wide range of research field in ceramic membrane is oriented to this direction.
74
1. INTRINSIC PROPERTIES Nature 1. 1. General physicochemical properties Bulk density at RT kg/m3 1. 2. Mechanical properties Tensile Strength (MPa) Bending Strenght Mpa Modulus of Elasticity (E) X 108 MPa Compressive Strenght Mpa Modulus of Ridity(G) X 108 MPa Hardness on the mohs scale 1. 3. Thermal properties Melting point OC Boiling Point OC 1. 4. Surface properties Zero point of charge Water contact angle SBET (m2/g) Pore Diameter (A) Pore Volume (mL/g) 1. 5. Chemical properties Operating pH range Compatibility with solvent 1 Compatibility with solvent 2 a polycrystalline alumina 94% b polycrystalline alumina 85% c polycristalline alumina 99.9% d polycristalline alumina 85.5%
High
Low
1217.406
800.925
2051.0 9.7 3530 200 f 9.45 9 g 73.3 62.6 484.34 98.3 72.23 20.49 1.27 0.54
phosphoric acid - HF well HCl- HNO3 weak e polycristalline alumina 100% f gamma alumina g bohemite
75
2. CHARACTERISTICS OF COMMERCIAL MEMBRANES BASED ON THIS MATERIAL Membrane name Memrbalox Membrane manufacturer Pall Membrane shape capillary tube, multichannel, monolithic Membrane structure symmetric Support nature ultrapure -alumina, zirconia, titania Membrane type porous Average pore size 5m Molecular weight cut-off 1-5kg/mol Water permeance at RT 300 l/(mh bar) Membrane name Anopore Membrane manufacturer Myriad Membrane shape disc Membrane structure symmetric Support nature polypropylene Membrane type porous Average pore size 0.02-0.1m Molecular weight cut-off 0,1m Water permeance at RT 1 m/m Membrane name Cram inside Membrane manufacturer TAMI Membrane shape Disc Membrane structure Porous, plate, tubular, multichannel Support nature Alumina/titania/zirconia Membrane type dense, porous Average pore size 0,14-1,40m Molecular weight cut-off 1-300kg/mol Water permeance at RT 800 -1200 l/(mh bar)
76
APPENDIX B: Chemical Interest Of Alumina Alkali Metals Ryshkewitch (1960) stated that molten lithium attracts alumina aggressively, potassium to lesser degree, and sodium the least. Reed claimed that the corrosion resistance of sintered alumina to both liquid and vaporized sodium is good at 900 OC. A commercial sintered alumina article disintegrated within 168 hours at 940 OC, however. A synthetic sapphire cylinder (1/4 in. diameter by 1 in. length lost about 1% in weight in 168 hours ay 900 OC but remained clear. Kelman, Wilkinson, and Yaggee found that sodium potassium did not attract below 500 OC, but caused corrosion at 600 OC. Kolosova et al. found a weight loss of only 0.01 to 0.06% in 35 hours at 400 OC for sintered alumina immersed in molten alkali (79%K, 21%Na). The behavior of vaporized alkali metals on oxides and other dielectric materials has been of interest for thermoelectric converters. Wagner and Coriell (1959) tested Al2O3, BN, ZrO2, MgO, HfO2, ThO2, CaO, and NbC to exposure to cesium vapor at temperatures as high as 1475 OC. Only fused alumina remained unaffected by the test. It was concluded that cesium probably reacts with impurities in the contacting material, but the effect can ben observed only when the surface areas available for reaction are relatively large, as is the case with sintered specimens. Higgings attributed pitting of single crystals by cesium vapor at 600 OC to silicon. And barium impurities; neutron irradiation increased the attack. C. E. Addams (1959) observed that rubidium effectively condensed at high temperatures only on oxides with which it could form stable complex compounds. Cowan and Stoddard (1964) stated that glasses could not be used in thermionic converter seals because of alkali metal (cesium) corrosion. Alkaline Earth Metals
77
Jaeger and Krasemann (1952) observed no reaction of calcium, barium, or strontium to their boiling points (about 1150 OC). This is likely, since BaO and SRO can be reduced to the metals (thermite reaction) by metallic aluminum at 1100 OC in a vacuum (Gvelisiani and Pazukhin). Magnesium also shows no attract to its boiling point (1100 OC). Aluminum Aluminum reacts with alumina at 1100 OC to form Al2O, and at 1600 OC to form AlO (Hoch and Johnston). Antimony, Arsenic Jaeger and Krasemann claimed no attract of sintered alumina. Beryllium Beryllium (melting point 1500 OC) shows no attract of sintered alumina. A slight darkening of the Alumina, caused by formation an interfacial layer of chrysoberyl, BeO Al2O3 (melting point 1870 OC), and Be 3Al2O3 (melting point 1910 OC) are identified compounds (Lang, Fillmore, and Maxwell, 1952; Galakhov, 1957). Bishmut The corrosion resistance is good to 1400 OC (Reed). The reaction product is Bi2O32Al2O3 (Levin and Roth, 1964). Carbon Carbon reduces alumina to normal carbide Al4C3 (Prescott and Hinckle) at above 1700 OC (Jaeger and Kresemann), initiating at as low as 1310 OC (Komarek et al.),
78
but requiring about 2400 OC for complete conversion (Kohlmeyer and Lundquist). Two oxicarbides also exist at about 2030 OC, Al4O4C (Foster, Long and Hunter; Cox and Pidgeon). The presence of Fe2O3, SiO2, TiO2, and V2O5 as impurities in sintered alumina might induce deterioration at lower temperatures (Stroup), as low as 1380 OC (Kroll and Schlechten). The reduction to metallic aluminum occurs at about 2000 OC (Miller, Foster, and Baker). Graphite does not wet molten alumina, but severely pitted in contact with it in water-free, inert atmosphere or vacuum (Barlett and Hall). Cerium Ceric oxide, CeO, forms no compounds with alumina (Wartenberg and Eckhardt). Cerous oxide, Ce2O3, forms Ce2O3 11 Al2O3 and Ce2O3 Al2O3, both of which decompose in air to form Al2O3 and CeO2 at temperatures above 800 OC (Leonov and Keler). Chlorine Chlorine does not attack, except in the presence of carbon (Singer and Thurnauer). Chromium Chromium wets alumina at 1650 OC in a reducing atmosphere (Blackburn, Shelvin and Lowers). Cobalt Cobalt neither wets nor reacts with sintered alumina to above its melting point (1480 OC) in a reducing atmosphere (Sieverts and Moritz; Tumanov et. al.). Copper
79
Copper reacts with the transition aluminas at 800 OC in air to form CuAl2O4, which is stable to 1000 OC. It then converts to CuAlO2, which is stable in air to about 1260 OC (Hahn and de Lorent, 1955; Misra and Chaklader, 1963). Fluorine Winzer claimed attack of sintered alumina at 1700 OC by dry fluorine. Gallium Sintered alumina is inert to gallium to 1000 OC (Kelman et al.). Wartenberg and Reusch (1932) found solid solutions above 810 OC with Ga2O3. Hydrogen Jaeger and Krasemann observed no reduction of alpha alumina in hydrogen up to the melting point, only a surface darkening L. J. Trostel, Jr. (1965) noted that hydrogen attacks alumina refractories below 1600 OC, however in the presence of water vapor. Iron Iron can be melted in sintered alumina under reducing conditions, but wets about 1600 OC (Blckburn et. al.). The spinel FeO Al2O3, dissolves to about 6% alumina at 1750 OC (McIntosh, Rait, and Hay; Fischer and Hoffman). Muan and Gee (1956), and Muan (1958) found limited solubility for Fe2O3 in corundum. Richards and White; Atlas and Sumida; and Turnoc and Lindsley investigated the spinel reactions; Fe2O3 Al2O3 has a structure similar to kappa alumina, and requires above 1320 OC prepare. Lead
80
No
reaction
occurs
with
alumina
at
the
melting
point
of
lead
(327
OC).
In
lead- bismuth
eutectic
alloy
(44.5%
Pb),
Gangler
found
0.000
mils/year
loss
at
1090
OC.
Lead
aluminate
is
unstable
above
970
OC
(Geller
and
Bunting).
Manganese
does
not
attack
sintered
alumina
to
above
the
melting
point
(1260
OC)
in
a
reducing
atmosphere.
Although
it
is
more
active
than
iron,
cobalt
or
nickel it can be distilled in sintered alumina to give a spectroscopicially pure product (Sieverts and Moritz). Mercury Kelmann et al., and Hahn, Frank, et. al. found no reaction with alumina at 300 OC. Molybdenum Alumina is not reduced by molybdenum even above the melting point of alumina. Discoloration may occur at 2100 OC in a dry, inert atmosphere (He). Nickel No attack occurs in dry inert atmosphere Nickel can be melted in sintered alumina in hydrogen atmosphere (Economos and Kingery). Wetting occurs at 1800 OC. Niobium
81
Mass spectrometric and thermogravimetric analysis at 1800 to 2200 OC indicates the principal reaction is !!! !! + 3 !" 2 !" ! + 3!"# ! . Secondary reactions under neutral conditions are: !!! !! + !" !!! ! ! + !"!! ! !!! !! + 2 !" + 1 2 !! !!! ! ! + !"!! + !"# (!) (Grosmann, 1966). Nitrogen Nitrogen does not attack (Jaeger and Krasemann). Palladium, Platinum Both metals can be handled in the molten conditions in sintered alumina. (Jaeger and Krasemann) Phosphorus No attack was observed in moderate temperatures (Jaeger). Silver No compounds can be prepared with silver and alumina (Hahn, Frank et. al.). Sulfur, Selenium, Tellurium These elements do not attack alumina. Tantalum Tantalum reacts only slightly with molten alumina in water free inert atmosphere, H2, N2, CO, or in vacuum (Bartlett and Hall). Alloy 90 Ta-10W shows 82
slight reaction. Tantalum carbide and 4 TaC ZrC react only slightly (Bartlett and Hall). Tin No reaction occurred in molten tin at 1000 OC. Titanium, Zirconium No reaction occurred in an inert atmosphere below 1800 OC, at which temperature black discoloration of the grains and corrosion occurred (Economs and Kingery). Titanium nitride wets molten alumina with negligible corrosion in water free inert atmosphere (Barlett and Hall). Titanium + Aluminum-Hardened Nickel-Base Alloy Decker, Rowe and Freeman found that trance amounts of zirconium or boron picked up from zirconia or magnesia crucibled reduced cracking of the hardened nickel-base alloys during hot-working and increased their rupture strength and ductility. It was desirable to compensate for this effect when making heats in sintered alumina crucibles. Tungusten Jager and Kresemann observed no reaction between tungusten and alumina. Wallace et. al. (1961) investigated the reactions in a Knudsen cell-oven operable at 2500 OC in conjunction with a Nier-type mass spectrometer. Jacodine (1961) observed a growth of nodules or hillocks of alumina in the investigation of heater-cathode breakdown of alumina-coated heaters operated at 1200 OC and 180 volts dc. Tungusten wets molten alumina with negligible corrosion in water- free inert atmosphere (Barlett and Hall).
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Uranium Jaeger and Krasemann found no reaction between uranium and sintered alumina to 1200 OC. Dykstra (1960) found no solid solution between Al2O3 and uranium oxide. Vanadium Burdese obtained reaction between V2O5 and gamma alumina at 500 OC to form Al2O3 V2O5. Zirconium Boride (ZrB2) and Zirconium Carbide (ZrC) Molten alumina wets and reacts moderately in water free, inert atmosphere (Barlett and Hall).
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REFERENCES Walter H. Gitzen; Alumina as a ceramic material; The American Ceramic Society Ohio; 1970 Ayral Andre; Colloidal Alumina: Definitions, Properties, Hydrosol Making and Application for Ceramic Memranes ; CNRS-ENSCM- UM2; France Bhatnagar A., Kumar E., Sillanp M., Nitrate removal from water by nano- alumina: Characterization and sorption studies, Chemical Engineering Journal, Volume 163 (2010) 317-323 Diniz da Costa J., Reed G., Thambimuthu K., High Temperature Gas Separation Membranes in Coal Gasification, Energy Procedia. 1 (2009) 295-302 Diniz da Costa J.C., Reed G.P., Thambimuthu K., High Temperature Gas Separation Membranes in Coal Gasification, Energy Procedia, Volume 1, Issue 1 (2009) 295- 302 Favre E., Carbon dioxide recovery from post-combustion processes : Can gas permeation membranes compete with absorption, Journal of Membrane Science 294 (2007) 5059 Favre, E., Carbon dioxide recovery from post-combustion processes: can gas permeation membranes compete with absorption, Journal of Membrane Science 294 (2007) 5059 Feng X., Pan C., Ivory J., Ghosh D., Integrated membrane/adsorption process for gas separation, Chemical Engineering Science, Vol. 53 (1998) 168 198 Franz J., Scherer V., An evaluation of CO2 and H2 selective polymeric membranes for CO2 separation in IGCC processes, Journal of Membrane Science (2010) 173- 183 Franz J., Scherer V., Impact of ceramic membranes for CO2 separation on IGCC power plant performance, Energy Procedia 4 (2011) 645652 Gu Y., Hacarlioglu P., Oyama S.T., Hydrothermally stable silicaalumina composite, membranes for hydrogen separation, Journal of Membrane Science 310 (2008) 2837 Hofmann Ph., Panopoulos K.D., Fryda L.E., Schweigerc A., Ouweltjes J.P, Karl J., Integrating biomass gasication with solid oxide fuel cells: Effect of real product gas tars, uctuations and particulates on Ni-GDC anode, International journal of hydrogen energy 33 (2008) 2834 2844 Hsieh H., Bhave R., Fleming H., Microporous alumina membranes, Journal of 85
Membrane Science, 39 (1988) 221-241 Hyun S., Jo S., Kang B., Surface modification of y-alumina membranes by silane coupling for CO2 separation, Journal of Membrane Science 120 (1996) 197-206 Hyun S., Jo S., Kang B., Surface modification of -alumina membranes by silane coupling for CO2 separation, Journal of Membrane Science, Volume 120, Issue 2 (1996) 197-206 Huang P., Xu N., Shi J., Lin Y.S., Recovery of volatile organic solvent compounds from air by ceramic membranes, Ind. Chemical Engineering, Res. 36 (1997) 3815 Idrees M., Yan L., Hamdani S., Synthesis and characterization of ceramic (alumina) membrane sheet, Proceedings of The Eleventh Symposium of Malaysia Chemical Engineers (1995) Javaid A., Ford D.M., Solubility-based gas separation with oligomer- modied inorganic membranes: Part II. Mixed gas permeation of 5 nm alumina membranes modied with octadecyltrichlorosilane, Journal of Membrane Science (2003) 157-163 Javaid A., Hughey M.P., Varutbangkul V., Ford D.M., Solubility-based gas separation with oligomer-modied inorganic membranes, Journal of Membrane Science (2001) 141-155 Javaid A., Membranes for solubility-based gas separation applications Review, Chemical Engineering Journal (2005) 219226 Jiraratananon R., Uttapap D., Tangamornsuksun C., Self-forming dynamic membrane for ultrafiltration of pineapple juice, Journal of Membrane Science 129 (1997) 135-143 Jones C., Fidalgo M., Wiesner M., Barron A., Alumina ultraltration membranes derived from carboxylatealumoxane nanoparticles, Journal of Membrane Science 193 (2001) 175184 Julbe A., Farrusseng D., Guizard C., Porous ceramic membranes for catalytic reactors- overview and new ideas, Journal of Membrane Science 181 (2001) 3-20 Kaldis S., Energy and capital cost analysis of CO2 capture in coal IGCC processes via gas separation membranes, Fuel Processing Technology (2004) 337-346 Koros W.J., Evolving Beyond the Thermal Age of Separation Processes: Membranes Can Lead the Way, www.interscience.wiley.com (2011) Koros W.J., Fleming G.K., Membrane-based gas separation, Journal of Membrane Science (1993) 83-89 Koutsonikolas D.E., Kaldis S.P., Sklari S.D., Pantoleontos G., Zaspalis V.T, Sakellaropoulos G.P., Preparation of highly selective silica membranes on defect- free c-Al2O3 membranes using a low temperature CVI technique, Microporous and Mesoporous Materials 132 (2010) 276281 86
Krishnan G., Simulation of a Process to Capture CO2 From IGCC Syngas Using a High Temperature PBI, Membrane, Energy Procedia (2009) 4079-4088 Kuzniatsova T., Mottern M.L., Shqau K., Yu D., Verweij H., Micro-structural optimization of supported alumina membranes, Journal of Membrane Science 316 (2008) 8088 Lafarga D., Santamaria J., Menndez M., Methane oxidative coupling using porous ceramic membrane reactorsI. reactor development, Chemical Engineering Science, Volume 49, Issue 12 (1994) 2005-2013 Laitinen N., Development of a ceramic membrane filtration equipment and its applicability for different wastewaters, Lappeenranta University of Technology (2002) Laitinen N., Kulovaarab M., Levnenc E., Luonsib A., Teilleriab N., Nystrma M., Ultrafiltration of stone cutting mine wastewater with ceramic membranes a case study, Desalination 149 (2002) 121125 Laltmen N., Luonsi A. , Levanen E., Mantyla T., Modified and unmodified alumina membranes in ultrafiltration of board mill wastewater fractions, Desalination 115 (1998) 63-70 Li W., Cao C.-Y., Wu L.-Y., Ge M.-Fa., Superb uoride and arsenic removal performance of highly ordered mesoporous alumina, Journal of Hazardous Materials 198 (2011) 143 150 Li W., Cao C.-Y., Wu L.-Y., Ge M.-F., Song W.-G., Superb fluoride and arsenic removal performance of highly ordered mesoporous aluminas, Journal of Hazardous Materials, Volume 198 (2011) 143-150 Metz B., Davidson, O., Coninck H., Loos M., Meyer, L., Stockage du dioxide de carbone, Rapport spcial du GIEC (IPCC) rsum lintention des dcideurs et rsum technique, International Panel on Climate Change (2005) Nicolas C.-H., Sublet J., Schuurman Y., Role of adsorption and diffusion pathwa ys on the CO 2/N 2 separation performance of nanocomposite (B)-MF I-alumina membranes, Chemical Engineering Science 66 (2011) 6057 6068 Pacheco S., Tapia J., Medina M., Rodriguez R., Cadmium ions adsorption in simulated wastewater using structured aluminasilica nanoparticles, Journal of Non-Crystalline Solids 352 (2006) 54755481 Pagana A.E., Sklari S.D., Kikkinides E.S., Zaspalis V.T., Microporous ceramic membrane technology for the removal of arsenic and chromium ions from contaminated water, Microporous and mesoporous materials V.110 (2008) 150- 156 Pruneanu S., Mihailescu G., Neamtu S., Olenic L., Biro L. P., Applications of nanoporous alumina membranes, IEEE (2001) 59-62
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Rabiller-Baudry M., Chaufer B., Lucas D., Michel F., Ultrafiltration of mixed protein solutions of lysozyme and lactoferrin: role of modified inorganic membranes and ionic strength on the selectivity, Journal of Membrane Science, Volume 184 (2001) 137 -145 Ciora R., Liu P., Ceramic Membranes for Environmental Related Applications, Media and Process Technology Inc. Fluid/Particle Separation Journal, Vol. 15 (2003) 45-51 Sandeep K. Dalvie and Ruth E Baltus, Transport studies with porous alumina membranes, Journal of Membrane Scrence (1992) 241-254 Sandeep K.D., Ruth B., Transport studies with porous alumina membranes, Journal of Membrane Science, 71 (1992) 241-255 Sen M., Manna A., Parimal P., Removal of arsenic from contaminated groundwater by membrane-integrated hybrid treatment system, Journal of Membrane Science, Volume 354, Issues 12 (2010) 108-113 Xomeritakis, G., Tsai, C.Y., Jiang, Y.B., Brinker, C.J., Tubular ceramic- supported solgel silica-based membranes for ue gas carbon dioxide capture and sequestration, Journal of membrane Science 341 (2009) 3036 A.F .M . Leenaars and A .J . Burggraaf, The formation of supported membranes, J . Colloid Interface Sci, 105 (1985) 27. K. Vasanthakumar, S. C. Vanithakumari, and U. Kamachi Mudali Fabrication of Nanoporous Alumina Membranes by Single Step Anodization and Their Microscopic Characterization Corrosion Science and Technology Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, India H.P . Hsieh*, R.R. Bhave And H .L. Fleming; Microporous Alumina Membranes Aluminum Company Of America, Alcoa Laboratories, Alcoa Center, PA 15069 (U.S.A .), 1988 R.W. Baker, Membrane Separation systems: Recent Developments and Future Directions, Noyes Data Corp., Park Ridge, NJ, 1991. Inorganic Membranes: Markets, Technologies, Players, Business Communications Co. Inc., Norwalk, CT, Marketing Study GB-112N 1997 Membrane Sicence And Technology Series,3; Inorganic Membranes For Separation And Reaction; H. P. HSIEH, Elseiver, 1996 A. Kirchner , K.J.D. MacKenzie, I.W.M. Brown, T. Kemmitt, M.E. Bowden MacDiarmid; Structural characterization of heat-treated anodic alumina membranes prepared using a simplified fabrication process Institute for Advanced Materials and Nanotechnology
88
G.G. Avci, A. Misirli, V. Gunay, Processing and characterization of microfiltration supports prepared from alumina powders, Ceram. Int. 22 (1996) 2326. Christopher D. Jones a, Maria Fidalgo b, Mark R. Wiesner b, Andrew R. Barron ; Alumina ultrafiltration membranes derived from carboxylatealumoxane nanoparticles XiaoRong Huang*, GenLiang Meng, ZhongTao Huang, JianMing Geng ; Preparation of unsupported alumina membrane by sol-gel techniques Jiansheng Li, Xiaoyang Wang, Lianjun Wang , Yanxia Hao, Youla Huang, Ye Zhang, Xiuyun Sun, Xiaodong Liu Nanjing; Preparation of alumina membrane from aluminium chloride University of Science and Technology, School of Chemical Engineering, Weon-Sik Chae, Sung-Jae Im, Jin-Kyu Lee, and Yong-Rok Kim; Novel Fabrication of Nanoporous Alumina Membrane Microtubes: 2-Dimensional Nanoporous Arrays on Every Facets of Microtubes; December 15, 2004 K.L. Yeung, J.M. Sebastian, A. Varma; Mesoporous alumina membranes: Synthesis, characterization, thermal stability and nonuniform distribution of catalyst; USA 1996 Rocio Redon, A. Vazques-Olmos, M.E Mata Zamora, A. Ordonez- Medrano,; Contact Angle Studies on Anodic Porous Alumina; Mexico 2005
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