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AceChemPack
Molecular Sieve

Molecular sieves are crystalline metal alumina silicates having a three
dimensional interconnecting network of silica and alumina tetrahedra.
Natural water of hydration is removed from this network by heating to
produce uniform cavities which selectively adsorb molecules of a
specific size.
A 4
to 8-mesh sieve is normally used in gas phase applications, while the 8
to 12-mesh type is common in liquid phase applications. The powder forms
of the 3A, 4A, 5A and 13X sieves are suitable for specialized
applications.
Long known for their drying capacity (even to 90°C), molecular sieves
have recently demonstrated utility in synthetic organic procedures,
frequently allowing isolation of desired products from condensation
reactions that are governed by generally unfavorable equilibria. These
synthetic zeolites have been shown to remove water, alcohols (including
methanol and ethanol), and HCl from such systems as ketimine and enamine
syntheses, ester condensations, and the conversion of unsaturated
aldehydes to polyenals.
|
Type |
3A
molecular sieve |
|
Composition |
0.6 K2O:
0.40 Na2O
: 1 Al2O3
: 2.0 ± 0.1SiO2
: x H2O |
|
Description |
The 3A form is made by
substituting potassium cations for the inherent sodium ions of
the 4A structure, reducing the effective pore size to ~3Å,
excluding diameter >3Å, e.g., ethane. |
|
Major
Applications |
Commercial dehydration of unsaturated hydrocarbon
streams, including cracked gas, propylene, butadiene, acetylene;
drying polar liquids such as methanol and ethanol. Adsorption of
molecules such as NH3
and H2O
from a N2/H2
flow. Considered a general-purpose drying agent in polar and
nonpolar media.3
Angstrom, is obtained when part of the sodium ions of the 4
Angstrom sieve are replaced by potassium ions.
Will adsorb, in sequence of adsorption rate, helium, neon,
nitrogen and water. |
|
|
Type |
4A
molecular sieve |
|
Composition |
1 Na2O:
1 Al2O3:
2.0 ± 0.1 SiO2
: x H2O |
|
Description |
This sodium form
represents the type A family of molecular sieves. Effective pore
opening is 4Å, thus excluding molecules of effective diameter
>4Å, e.g., propane. |
|
Major
Applications |
Preferred for static dehydration in closed liquid
or gas systems, e.g., in packaging of drugs, electric components
and perishable chemicals; water scavenging in printing and
plastics systems and drying saturated hydrocarbon
streams.Adsorbed species include SO2,
CO2,
H2S,
C2H4,
C2H6,
and C3H6.
Generally considered a universal drying agent in polar and
nonpolar media.4
Angstrom, is obtained through synthesis of type A zeolite in
sodic form. Will adsorb, in sequence of adsorption rate, argon,
krypton, xenon, ammonia, carbon monoxide, C2H4, C2H2, CH3OH,
C2H5OH, CH3CN2, CS2,
CH3CL, CH3Br, and carbon dioxide. |
|
|
Type |
5A
molecular sieve |
|
Composition |
0.80 CaO : 0.20 Na2O
: 1 Al2O3:
2.0 ± 0.1 SiO2:
x H2O |
|
Description |
Divalent calcium ions in
place of sodium cations give apertures of ~5Å which exclude
molecules of effective diameter >5Å, e.g., all 4-carbon rings,
and iso-compounds. |
|
Major
Applications |
Separation of normal paraffins frombranched-chain
and cyclic hydrocarbons; removal of H2S,
CO2
and mercaptans from natural gas. Molecules adsorbed include nC4H10,
nC4H9OH,
C3H8
to C22H46,
and dichlorodifluoro-methane.5
Angstrom, is obtained through synthesis of type A zeolite in
sodic form. Will adsorb, in sequence of adsorption rate, C3-C14,
C2H5CL, C2H5Br, CH3L,
C2H5NH2, CH2CL2CH2Br2,
CHF2CL, CHF3, CF4, (CH3)NH2,
B2H6CF2CL2, CHFCL2,
and CF3CL. |
|
|
Type |
13X
molecular sieve |
|
Composition |
1 Na2O:
1 Al2O3
: 2.8 ± 0.2 SiO2
: xH2O |
|
Description |
The sodium form represents the basicstructure of
the type X family, with an effective pore opening in the 910¼
range. Will not adsorb(C4F9)3N,
for example. |
|
Major
Applications |
Commercial gas drying, air plantfeed purification
(simultaneous H2O
and CO2
removal) and liquid hydrocarbon/natural gas sweetening (H2S
and mercaptan removal).13
Angstrom, is obtained through synthesis of type X zeolite. Will
adsorb, in sequence of adsorption rate, SF6, CHCL3,
CHBr3, CHI3, N-C3F8,
CCL4, N-C4F10, N-C7H16,
CBr4, C6H6, B5H10,
(CH3)3N, C(CH4)4, (C2H5)3N,
C(CH3)C3CL, C(CH3)3Br,
and C(CH3)3CH. |
A. Regeneration (activation)
Regeneration in typical cyclic systems constitutes removal of the
adsorbate from the molecular sieve bed by heating and purging with a
carrier gas. Sufficient heat must be applied to raise the temperature of
the adsorbate, the adsorbent and the vessel to vaporize the liquid and
offset the heat of wetting the molecular-sieve surface. The bed
temperature is critical in regeneration. Bed temperatures in the
175-260° range are usually employed for type 3A. This lower range
minimizes polymerization of olefins on the molecular sieve surfaces when
such materials are present in the gas. Slow heat up is recommended since
most olefinic materials will be removed at minimum temperatures; 4A, 5A
and 13X sieves require temperatures in the 200-315 °C range.
After regeneration, a cooling period is necessary to reduce the
molecular sieve temperature to within 15° of the temperature of the
stream to be processed. This is most conveniently done by using the same
gas stream as for heating, but with no heat input. For optimum
regeneration, gas flow should be countercurrent to adsorption during the
heat up cycle, and concurrent (relative to the process stream) during
cooling. Alternatively, small quantities of molecular sieves may be
dried in the absence of a purge gas by oven heating followed by slow
cooling in a closed system, such as a desiccator.
Some common molecules and their critical
diameters.
|
Molecule |
Critical
diam. (Å) |
Molecule |
Critical diam.(Å) |
|
Helium |
2.0 |
Propylene |
5.0 |
|
Hydrogen |
2.4 |
Ethyl mercaptan |
5.1 |
|
Acetylene |
2.4 |
1-Butene |
5.1 |
|
Oxygen |
2.8 |
trans-2-Butene |
5.1 |
|
Carbon monoxide |
2.8 |
1,3-Butadiene |
5.2 |
|
Carbon dioxide |
2.8 |
Chlorodi fluoromethane
|
5.3 |
|
Nitrogen |
3.0 |
Thiophene |
5.3 |
|
Water |
3.2 |
Isobutane to
isodocosane |
5.6 |
|
Ammonia |
3.6 |
Cyclohexane |
6.1 |
|
Hydrogen sulfide |
3.6 |
Benzene |
6.7 |
|
Argon |
3.8 |
Toluene |
6.7 |
|
Methane |
4.0 |
p-Xylene |
6.7 |
|
Ethylene |
4.2 |
Carbon tetrachloride |
6.9 |
|
Ethylene oxide |
4.2 |
Chloroform |
6.9 |
|
Ethane |
4.4 |
Neopentane |
6.9 |
|
Methanol |
4.4 |
m-Xylene |
7.1 |
|
Methyl mercaptan |
4.5 |
o-Xylene |
7.4 |
|
Propane |
4.9 |
Triethylamine |
8.4 |
|
n-Butane to
n-docosane |
4.9 |
Details:
3A Molecular Sieve
4A Molecular Sieve
5A Molecular Sieve
13X Molecular Sieve
IG-3A Desiccant
13X ACS
desiccant
Refrigerant desiccant 5A
Small Oxy-en rich
Desiccant
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