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Molecular sieve

From Wikipedia, the free encyclopedia

A sealed canister, commonly filled with silica gel and other molecular sieves used as desiccant in drug
containers to keep contents dry.

Vials of mesoporous silica

A molecular sieve is a material with pores (very small holes) of uniform size. These pore
diameters are similar in size to small molecules, and thus large molecules cannot enter or be
absorbed, while smaller molecules can. As a mixture of molecules migrate through the stationary
bed of porous, semi-solid substance referred to as a sieve (or matrix), the components of highest
molecular weight (which are unable to pass into the molecular pores) leave the bed first, followed
by successively smaller molecules. Some molecular sieves are used in chromatography, a
separation technique that sorts molecules based on their size. Other molecular sieves are used
as desiccants (some examples include activated charcoal and silica gel).[1]
The diameter of a molecular sieve is measured in ångströms (Å) or nanometres (nm). According
to IUPAC notation,microporous materials have pore diameters of less than 2 nm (20 Å)
and macroporous materials have pore diameters of greater than 50 nm (500 Å);
the mesoporous category thus lies in the middle with pore diameters between 2 and 50 nm (20–
500 Å).[2]

Contents
[hide]

 1Materials
o 1.1Microporous material (<2 nm)
o 1.2Mesoporous material (2–50 nm)
o 1.3Macroporous material (>50 nm)
 2Applications
o 2.1FDA approval
 3Regeneration
 4Adsorption capabilities
 53Å
 64Å
o 6.1Polyester agent additives
o 6.2Harmful waste treatment
o 6.3Other purposes
 75Å
 8See also
 9References
 10External links

Materials[edit]
Molecular sieves can be microporous, mesoporous, or macroporous material.
Microporous material (<2 nm)[edit]

 Zeolites (aluminosilicate minerals, not to be confused with aluminium silicate)


 Zeolite LTA: 3–4 Å[3]
 Porous glass: 10 Å (1 nm), and up
 Active carbon: 0–20 Å (0–2 nm), and up
 Clays
 Montmorillonite intermixes
 Halloysite (endellite): Two common forms are found, when hydrated the clay exhibits
a 1 nm spacing of the layers and when dehydrated (meta-halloysite) the spacing is
0.7 nm. Halloysite naturally occurs as small cylinders which average 30 nm in
diameter with lengths between 0.5 and 10 micrometres.[4]
Mesoporous material (2–50 nm)[edit]

 Silicon dioxide (used to make silica gel): 24 Å (2.4 nm)[5]


Macroporous material (>50 nm)[edit]

 Mesoporous silica, 200–1000 Å (20–100 nm)[6]

Applications[edit]
Molecular sieves are often utilized in the petroleum industry, especially for drying gas streams.
For example, in the liquid natural gas (LNG) industry, the water content of the gas needs to be
reduced to less than 1 ppmv to prevent blockages caused by ice.
In the laboratory, molecular sieves are used to dry solvent. "Sieves" have proven to be superior to
traditional drying techniques, which often employ aggressive desiccants.[7]
Under the term zeolites, molecular sieves are used for a wide range of catalytic applications.
They catalyze isomerisation, alkylation, and epoxidation, and are used in large scale industrial
processes, including hydrocracking and fluid catalytic cracking.[8]
They are also used in the filtration of air supplies for breathing apparatus, for example those used
by scuba divers and firefighters. In such applications, air is supplied by an air compressor and is
passed through a cartridge filter which, depending on the application, is filled with molecular sieve
and/or activated carbon, finally being used to charge breathing air tanks.[9] Such filtration can
remove particulates and compressor exhaust products from the breathing air supply.
FDA approval[edit]
The U.S. FDA has as of April 1, 2012 approved sodium aluminosilicate for direct contact with
consumable items under 21 CFR 182.2727.[10] Prior to this approval Europe had used molecular
sieves with pharmaceuticals and independent testing suggested that molecular sieves meet all
government requirements but the industry had been unwilling to fund the expensive testing
required for government approval.[11]

Regeneration[edit]
Methods for regeneration of molecular sieves include pressure change (as in oxygen
concentrators), heating and purging with a carrier gas (as when used in ethanoldehydration), or
heating under high vacuum. Regeneration temperatures range from 175 °C to 315 °C depending
on molecular sieve type.[12] In contrast, silica gel can be regenerated by heating it in a regular
oven to 120 °C (250 °F) for two hours. However, some types of silica gel will "pop" when exposed
to enough water. This is caused by breakage of the silica spheres when contacting the water.[13]

Adsorption capabilities[edit]

Attrition
Pore Bulk Adsorbed or
Model diameter density water abrasion, Usage[14]
(Ångström) (g/ml) (% w/w) W (%
w/w)

Desiccation of petroleum cracking gas and


0.60–
3Å 3 19–20 0.3–0.6 alkenes, selective adsorption of H2O
0.68
in insulated glass (IG) and polyurethane

Adsorption of water in sodium


aluminosilicate which is FDA approved
(see below) used as molecular sieve in
medical containers to keep contents dry and
as food additive having E-number E-554
(anti-caking agent); Preferred for static
dehydration in closed liquid or gas systems,
e.g., in packaging of drugs, electric
0.60–
4Å 4 20–21 0.3–0.6 components and perishable chemicals; water
0.65
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;[12] separation of natural
gas and alkenes, adsorption of water in non-
nitrogen sensitivepolyurethane

Degreasing and pour point depression


0.45–
5Å-DW 5 21–22 0.3–0.6 of aviation kerosene and diesel, and alkenes
0.50
separation

5Å Specially designed for medical or healthy


5 0.4–0.8 ≥23
small oxygen generator[citation needed]
oxygen-
enriched

Desiccation and purification of


air; dehydration and desulphurization of
0.60–
5Å 5 20–21 0.3–0.5 natural gas and liquid petroleum
0.65
gas; oxygenand hydrogen production by
pressure swing adsorption process

High-efficient sorption, be used in


0.50– desiccation, decarburization, desulphurization
10X 8 23–24 0.3–0.6
0.60 of gas and liquids and separation ofaromatic
hydrocarbon

0.55– Desiccation, desulphurization and


13X 10 23–24 0.3–0.5
0.65 purification of petroleum gas and natural gas

Decarburization and desiccation in the air


0.55–
13X-AS 10 23–24 0.3–0.5 separation industry, separation of nitrogen
0.65
from oxygen in oxygen concentrators

0.50– Sweetening (removal of thiols) of aviation


Cu-13X 10 23–24 0.3–0.5
0.60 fuel and corresponding liquid hydrocarbons

3Å[edit]
 Approximate chemical formula: 2/3K2O•1/3Na2O•Al2O3• 2 SiO2 • 9/2 H2O
 Silica-alumina ratio: SiO2/ Al2O3≈2
3Å molecular sieves do not adsorb molecules whose diameters are larger than 3 Å. The
characteristics of these molecular sieves include fast adsorption speed, frequent regeneration
ability, good crushing resistance and pollution resistance. These features can improve both the
efficiency and lifetime of the sieve. 3Å molecular sieves are the necessary desiccant in petroleum
and chemical industries for refining oil, polymerization, and chemical gas-liquid depth drying.
3Å molecular sieves are used to dry a range of materials, such as ethanol,
air, refrigerants, natural gas and unsaturated hydrocarbons. The latter include cracking
gas, acetylene,ethylene, propylene and butadiene.
3Å molecular sieve is utilized to remove water from ethanol, which can later be used directly as a
bio-fuel or indirectly to produce various products such as chemicals, foods, pharmaceuticals, and
more. Since normal distillation cannot remove all the water (an undesirable byproduct from
ethanol production) from ethanol process streams due to the formation of an azeotrope at around
95 percent concentration, molecular sieve beads are used to separate ethanol and water on a
molecular level by adsorbing the water into the beads and allowing the ethanol to pass freely.
Once the beads are full of water, temperature or pressure can be manipulated, allowing the water
to be released from the molecular sieve beads.[15]
3Å molecular sieves are stored at room temperature, with a relative humidity not more than 90%.
They are sealed under reduced pressure, being kept away from water, acids and alkalis.
4Å[edit]
 Chemical formula: Na2O•Al2O3•2SiO2•9/2H2O
 Silica-alumina ratio: SiO2/ Al2O3≈2
4Å molecular sieves are widely used to dry laboratory solvents.[16] They can absorb water and
other molecules with a critical diameter less than 4 Å such as NH3, H2S, SO2, CO2, C2H5OH, C2H6,
and C2H4. It is widely used in the drying, refining and purification of liquids and gases (such as the
preparation of argon).

Bottle of 4Å molecular sieves.

Polyester agent additives[edit]


These molecular sieves are used to assist detergents as they can produce demineralized water
through calcium ion exchange, remove and prevent the deposition of dirt. They are widely used to
replace phosphorus. The 4Å molecular sieve plays a major role to replace sodium
tripolyphosphate as detergent auxiliary in order to mitigate the environmental impact of the
detergent. It also can be used as a soap forming agent and in toothpaste.
Harmful waste treatment[edit]
4Å molecular sieves can purify sewage of cationic species such as ammonium ions, Pb2+, Cu2+,
Zn2+ and Cd2+. Due to the high selectivity for NH4+they have been successfully applied in the field
to combat eutrophication and other effects in waterways due to excessive ammonium ions. 4Å
molecular sieves have also been used to remove heavy metal ions present in water due to
industrial activities.
Other purposes[edit]

1. The metallurgical industry - separating agent, separation, extraction of brine


potassium, rubidium, cesium, etc.
2. Petrochemical industry, catalyst, desiccant, adsorbent
3. Agriculture - soil conditioner;
4. Medicine - load silver zeolite antibacterial agent.

5Å[edit]
 Chemical formula: 0.7CaO•0.30Na2O•Al2O3•2.0SiO2 •4.5H2O
 Silica-alumina ratio: SiO2/ Al2O3≈2
5Å molecular sieves are often utilized in the petroleum industry, especially for the purification of
gas streams and in the chemistry laboratory for separating compounds and drying reaction
starting materials. They contain tiny pores of a precise and uniform size, and are mainly used as
an adsorbent for gases and liquids.
5Å molecular sieves are used to dry natural gas, along with
performing desulfurization and decarbonation of the gas. They can also be used to separate
mixtures of oxygen, nitrogen and hydrogen, and oil-wax n-hydrocarbons from branched and
polycyclic hydrocarbons.
5Å molecular sieves are stored at room temperature, with a relative humidity less than 90% in
cardboard barrels or carton packaging. The molecular sieves should not be directly exposed to
the air and water, acids and alkalis should be avoided.

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