undreds of systems for the drying and purification of liquids and gases rely on the
Unlike other adsorbents, zeolite molecular sieves have precisely uniform pore sizes and molecular dimensions. This translates into a sieve-like selectivity where molecules of varying size and polarity may be readily adsorbed, slowly adsorbed or completely excluded. This selectivity, combined with a high capacity over a wide range of operating conditions, gives each zeolite molecular sieve a high level of adsorption efficacy.
high adsorption efficiency of zeolite molecular sieves. These unique adsorbents are a result of synthetically produced crystalline metal aluminosilicates that have been activated for adsorption by removing their water of hydration. Since little or no change in structure occurs during this dehydration, highly porous adsorbents are formed that have a strong affinity for water and specific molecules.
Used successfully in hundreds of commercial systems for drying and purifying liquids and gases, zeolite molecular sieves are the most universally applicable adsorbents in the process industries.
Table of Contents
Purification and dehydration in one operation Dehydration without adsorbing valuable product or altering the composition High product recovery Numerous purification and dehydration cycles are possible due to the reversible adsorption process High cyclic capacity with sufficient thermal or pressure swing purging
Specific, uniform pore size is the key to adsorbent efficiency and selectivity
Based on size and charge distribution in a molecule, zeolite molecular sieves can adsorb individual molecules readily, slowly or not at all.
Page 2 What are zeolite molecular sieves? Page 4 Zeolite research and synthetic production Page 6 Crystal structure and molecular sieve types Page 8 Adsorption based on molecular size, polarity and degree of unsaturation Page 12 Zeolite molecular sieves and adsorption efficiency Page 13 Zeolite molecular sieves and co-adsorption Page 15 Regeneration cycles Page 17 Applications Page 18 Put UOPs experience and technology to work for you
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MOLSIVTM Adsorbents
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Ion Exchange Tank Sodium Silicate Sodium Aluminate Steam Makeup Tank Crystal Slurry Crystallization Tank
molecular dimensions were synthesized and patented. The synthetic zeolites sieve-like selectivity offered the consistent performance necessary for commercial use. By 1953, more than 30 pure zeolite species had been prepared. Their crystal structures and adsorption properties had been characterized, and researchers had learned how to regenerate them for repeated use in commercial applications.
Extensive QC testing insures superior product quality and consistency
Clay Binder
Naturally occurring crystalline zeolites, a subset of molecular sieves, were first noted two centuries ago. Their ability to release water when heated and readsorb upon cooling was known at that time, but their capacity to selectively adsorb molecules other than water was not recorded until the 1920s. In the early 1930s, X-ray diffraction studies revealed the zeolites as crystalline materials with precisely arrayed cavities and pores within each crystal. Since zeolites found in nature have a high degree of chemical and physical variability, these products were not viable for commercial separation processes. In the early 1950s, a division of Union Carbide Corporation, that is now part of UOP, was searching for an adsorbent to separate atmospheric gases and to be used in other industrial applications. As a result of this research, structures of silicon and aluminum oxides with uniform pore sizes and precise
As a consequence of their research, zeolite molecular sieves were substituted into existing dryer and simple adsorber systems with amazing results. The use of zeolite molecular sieves improved the drying and purifying of various gas and liquid process streams with minimal changes in technology. For more advanced
uses, however, additional process engineering knowledge was required. To address this problem, Union
Wash Water
Filter
Activated Molecular Sieve Product Mixer Particle Forming Dryer Screen Kiln
Carbide formed a large, process engineering group to develop new and comprehensive adsorption technology and design guidelines. Starting with fundamental adsorbent data, the researchers studied adsorption equilibria, adsorption kinetics, deactivation phenomena, cyclic life and scale-up factors. After much research, the group discovered how to economically manufacture the zeolites in commercially useful forms without adversely affecting their adsorption properties. In November of 1954, Union Carbide announced the availability of the first limited commercial quantities. The pure zeolites were then used within the chemical, manufacturing and petroleum refining industries to solve difficult gas purification and dehydration problems. Today, by altering existing crystalline structures for improved functionality, UOP continues to manufacture many types of zeolites for a myriad of industries.
moisture pick up. Many tests are used to determine product quality from crystallization to final firing. Examples include x-ray diffraction, McBainBakr adsorption, loss on ignition, crush
strength, density and particle size. Quality control techniques including Statistical Process Control and adherence to ISO 9000 standards ensure that crystallization and other manufacturing processes achieve exact specifications.
surrounding a smaller silicon or aluminum cation. Sodium ions or other cations make up the positive charge deficit in the alumina tetrahedra, and each of the four oxygen anions is shared, in turn, with another silica or alumina tetrahedron to extend the crystal lattice in three dimensions. In all molecular sieve types, the sodium ion can be exchanged to form other functional products. The crystal structure of zeolite molecular sieves is honeycombed with relatively large cavities. Each cavity is connected through apertures or pores. The water of hydration is contained within these cavities. Before product is used, the water of hydration is removed by heating.
he basic formula for zeolite molecular sieves is M2/nO Al2O3 xSiO2 yH2O where M is a cation of n valence. The fundamental building block of the molecular sieve crystal structure is a tetrahedra with four oxygen anions
Skeletal Tetrahedron
Packed Spheres
Solid Tetrahedron
The crystallization of molecular sieve Type A from a hydrous gel as seen through the electron microscope. Photo 1 shows development of crystallization after two hours at 100 C. Photo 2 shows completely crystallized A.
Type 3A Type 3A crystals are produced when some of the sodium ions are replaced by potassium ions. Since potassium ions are larger than sodium ions, the pore size is effectively reduced to about 3.2 angstroms. Type 4A Type 4A sodium-bearing crystals have a free aperture size of 3.5 angstroms in diameter. At typical operating temperatures, molecules with an effective diameter of up to four angstroms may be passed through this aperture. 4.2 A 2.6 A
11.4 A 6.6 A
4A
Above: Two adjacent unit cells of Type 4A light circles represent oxygen ions and dark circles represent sodium cations.
the larger cavities via a distorted ring of six oxygen atoms of 2.2 angstroms free diameter.
Type 5A When some of the sodium ions in Type 4A are replaced with calcium ions,Type 5A is produced. It features the largest pore opening of the A types, with a free aperture size of 4.2 angstroms. Type X Na86 [(AlO2)86 (SiO2)106] 264H2O Note: Na+ (sodium) can be replaced by other cations. Although Type X is based on the same building blocks as Type A, the beta cages are linked tetrahedrally instead of in a cubic arrangement. The Type X crystal has a larger, elliptical-shaped internal cavity of 13 angstroms in diameter with a pore diameter of approximately 8 angstroms for the sodium form.
enough to pass into the pore system and by choosing the proper operating conditions, zeolite molecular sieves can be adapted to suit specific applications. While the external surface area of the molecular sieve crystal is available for adsorption of molecules of all sizes, the internal area is available only to those
umerous zeolite species that differ in chemical composition, crystal structure and adsorption properties are known. By selecting the appropriate adsorbent one that allows entry of those molecules small
Common Form
Powder 1/16-inch Pellets 1/8-inch Pellets 8 x 12 Beads 4 x 8 Beads Powder 1/16-inch Pellets 1/8-inch Pellets 8 x 12 Beads 4 x 8 Beads 14 x 30 Mesh Powder 1/16-inch Pellets 1/8-inch Pellets
Molecules Adsorbed**
Molecules with an effective diameter <3 angstroms including H2O and NH3
3A
4A
1800 (1,000)
Molecules with an effective diameter <4 angstroms including ethanol, H2S, CO2, SO2, C2H4, C2H6 and C3H6
5A
1800 (1,000)
Molecules with an effective diameter <5 angstroms including n-C4H9OH, n-C4H10, C3H8 to C22H46, R-12 Molecules with an effective diameter <8 angstroms including C6H6, C7H8
13X
1800 (1,000)
30 26 26 26 26
Chart depicts basic molecular sieve types only. In all applications, these basic forms are customized for specific use. *Lbs H2O/100 lbs activated adsorbent at 17.5 torr H2O at 25C. **Each type adsorbs listed molecules plus those of preceding type.
The strong adsorptive forces in zeolite molecular sieves are primarily due to the cations that are exposed within the crystal lattice. They act as sites of strong localized positive charges that electrostatically attract the negative end
S, Cl or N atoms. Carbon monoxide, for example, will be adsorbed in preference to argon. In fact, under the influence of localized, strong positive charges on the cations, polarity may be induced in the molecules. The polarized molecules are then adsorbed strongly due to the electrostatic attraction of the cations. In hydrocarbons, the more unsaturated the molecule, the more polarizable it is and the more strongly it is adsorbed. As an example, zeolite molecular sieves will effectively remove acetylene from olefins and ethylene or propylene from saturated hydrocarbons.
of polar molecules. The greater the polarity of the molecule, the more strongly it will be attracted and adsorbed. Polar molecules are generally those that are asymmetrical and contain O,
Molecules Excluded
Molecules with an effective diameter >3 angstroms (ethane)
Applications
their adsorption is characterized by a Langmuir-type isotherm (the amount of a given compound adsorbed
Preferred adsorbent for commercial dehydration of unsaturated hydrocarbon streams (cracked gas, propylene, butylene and acetylene) Dries polar liquids such as methanol and ethanol Static desiccant in household refrigeration systems Adsorbent for static dehydration in a closed gas or liquid system Used in the packaging of drugs, electronic components and perishable chemicals Water scavenger in paint and plastic systems Used commercially in drying saturated hydrocarbon streams
increases rapidly to a saturation value as its pressure or concentration increases in the external bulk phase). Any further increase in pressure at
constant temperature causes no further increase in the amount adsorbed. With zeolite molecular sieves, this equilibrium saturation
Molecules with an effective diameter >5 angstroms (iso compounds and all 4-carbon rings)
Separates normal paraffins from branched-chain and cyclic hydrocarbons through a selective adsorption process Pressure swing purification of hydrogen
value typically corresponds to a complete filling of the internal void volume with the adsorbate. When
Used commercially for general gas drying, air plant feed purification (simultaneous removal of H2O and CO2), and liquid hydrocarbon and natural gas sweetening (H2S and mercaptans removal)
adsorbed molecules are desorbed via heat or by displacement with another material, the crystals chemical state remains unchanged.
2. The relative size of molecules and molecular sieve pores 3. The strength of adsorptive forces between molecular sieves and adsorbate
to purify the fluid while the other bed is being heated, purged and cooled. When the process design requires less than six hours for the adsorption step, additional beds can be added to permit continuous processing of the feed.
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Capacity
15 wt-%
Silica Gel
4. Adsorption temperature
Activated Alumina
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Single-bed adsorption
Single-bed adsorption can be used when interrupted product flow can be tolerated. When the adsorption capacity of the bed is reached, it can be regenerated for further use either in place or at another location. Alternatively, it can be discarded if economically feasible.
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20
30
40
50
in one of three basic types of adsorption systems: Multiple-bed adsorption Single-bed adsorption Static adsorption
With zeolite molecular sieve powders, no hysteresis occurs during desorption. Adsorption and desorption are completely reversible with their respective isothermal curves coinciding completely. However, with zeolite molecular sieve pellets or beads, further adsorption may occur at pressures near the saturation vapor pressure. This can occur as a result of condensation in the pellet or bead voids external to the zeolite crystals. In addition, hysteresis may take place during
Adsorption Desorption Out Liquid Stream In
Multiple-bed adsorption
Multiple bed adsorption is ideal for most commercial, large-scale fluid purification operations. Conventional fixed-bed, heat-regenerated adsorption systems are commonly used. A typical dual-bed installation places one bed on-stream
Static adsorption
When manufactured into various physical forms, zeolite molecular sieves can be used as static desiccants in closed gas or liquid systems.
Cooler Condenser
Multiple bed adsorption for H20 and C02 removal from natural gas before methane liquification. 10
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The isobars plotted below illustrate zeolite molecular sieve performance over a spectrum of operating temperatures. The solid lines assume the use of completely regenerated adsorbents. The capacity is lowered by any residual water left on the adsorbent, a factor of particular importance in high temperature drying operations. As an example, the dotted line isobars show the effect of two percent residual water at the start of adsorption on silica gel, zeolite molecular sieves and activated alumina. In some applications, this residual water can completely consume the adsorption capacity of silica and alumina type adsorbents. For this reason, it is best to use silica and alumina type adsorbents for the bulk separation of water. They are very effective for this purpose and offer the additional benefit of extending the life of zeolite molecular sieves. After bulk separation processes have taken place, zeolite molecular sieves can then be used to achieve very low dew point levels.
due to their exceptional adsorption efficiency. The following details typical conditions where they are effectively used.
Silica Gel
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Water Adsorbed
15 wt-%
10
0 (-18)
100 (38)
200 (93)
300 (149)
400 (204)
500 (260)
Temperature F (C)
Drying power of silica gel, zeolite molecular sieves and activated alumina under various operating temperatures.
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T I
hydrocarbons, alcohols, esters, ethers, amines, amides, ketones and others. Zeolite molecular sieves are alkaline in nature with a pH range in water slurry of 9 to 11. Most types are stable in solutions within a pH range
of 5 to 12, and a few are stable in solutions having a pH as low as 3. They are stable in most organic streams, however in vapor phase processes, gases that will hydrolize to form strong acids will readily react with the adsorbents.
and separate numerous types of materials including inorganic gases, hydrocarbons, halogenated
critical, zeolite molecular sieves can be used to solve these co-adsorption difficulties.
Zeolite molecular sievesstrong attraction for water prevents co-adsorption problems in chemical process streams.
Capacity
molecular sieve selection. Since zeolite molecular sieves adsorb water more strongly than other material, the adsorbed water concentrates at the inlet end of the bed. Here, it displaces other
wt-%
10 5 0
10 5 0 0 2 4 6 8 10
impurities that have been previously adsorbed. These desorbed impurities are then re-adsorbed farther down the column. The desorbed impurities will begin to appear in the effluent stream
100 200 300 400 500 600 700 Carbon Dioxide Pressure, mm Hg
as displacement continues. This displacement can be allowed to continue until little adsorbate, other than water, is left on the bed. However, it is possible to design and operate a zeolite molecular sieve adsorption system so that impurities are retained on the adsorbent rather than re-entering the purified stream. To accomplish this, sufficient bed must be provided to contain the impurities in addition to the water. See the figure below
Capacity
wt-%
10 5 0
Adsorption
Fuel
Sulfur Dioxide 30
Capacity
wt-%
20 10 0
Ammonia
These three graphs depict the equilibrium capacity of zeolite molecular sieves for various gas impurities. Through co-adsorption, zeolite molecular sieves will remove these materials in addition to water.
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Regeneration cycles
four types. Used separately or in combination, the major adsorptiondesorption cycles are: Thermal swing Pressure swing Purge gas stripping Displacement
surface. Once the reactivation temperature is reached, the bed is flushed with a dry purge gas or reduced in pressure. It is then returned to adsorption conditions. As a result, high loadings of water and impurities on the adsorbent can be obtained, following a cooling step.
Pressure swing
Pressure swing cycles, operating at nearly isothermal conditions, use either a lower pressure or a vacuum to desorb the bed. Advantages of this technique include fast cycling with reduced adsorber dimensions and adsorbent inventory, direct production of a high purity product and the ability to use gas compression as the main source of energy.
Thermal swing
Thermal swing cycles reactivate the sieve by elevating the temperature. Typically, the operating temperature is increased to 400 - 600F (204 316C). The bed is heated either by direct heat transfer via hot fluid in contact with the bed or by use of indirect heat transfer through a
Displacement cycles
Displacement cycles use an adsorbable purge to displace the
previously adsorbed material. The stronger the adsorption of the purge media, the more completely the bed is desorbed. In this case, lesser amounts of purge can be used, but it is consequently more difficult to remove the adsorbed purge.
-160 (-107) -200 (-129) 0 100 200 300 400 500 600 700 (-18) (38) (93) (149) (204) (260) (316) (371) Bed Temperature, F (C)
This graph is used to find the minimum obtainable dew point as a function of residual loading and effluent gas temperature during adsorption. Also shown is residual loading after regeneration as a function of regeneration temperature and purge gas dew point.
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Air dryers with a desiccant-type in-line filtration system supplies clean, dry air to truck air brake systems aiding in the prevention of air line freezeups.
Zeolite molecular sieves keep dual pane windows free of moisture and vapors.
Zeolite molecular sieves are used to purify industrial gases and for the bulk separation of oxygen from air.
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The chart below provides a brief review of how and where zeolite molecular sieves are used in industry today.
Application Air dryers Role of zeolite molecular sieves Dehydration of plastic pellets before they are molded Dehydration for instrument air Dehydration of room air with molecular sieve impregnated dessicant wheels Adsorption of nitrogen from compressed air using a pressure or vacuum swing system to obtain oxygen purity up to 95% Dehydration of compressed air on brake systems of heavy- and medium-duty trucks, buses and trains Pressure swing dryers are used to reduce the dew point of air in the brake reservoir below ambient temperature to prevent freeze-up and corrosion Removal of initial trapped moisture inside the dual-pane window and the moisture that will permeate during the life of the unit to prevent fogging Removal of vapors from organic sealing materials, paint and cleaning solvents introduced during window manufacture Dehydration of moisture-sensitive formulations added to poly coatings, epoxies and urethanes to control the curing process and coatings, adhesives, sealants, elastomers, metal-rich paints and vinyl foams to eliminate unwanted water reactions Removal of radioactive nucleotides by ion exchange cesium and strontium are exchanged preferentially into the zeolite molecular sieves to greatly reduce the volume of liquid waste Dehydration of automotive A/C, transport refrigeration, home refrigerators, freezers, residential A/C, heat pumps and commercial refrigerants to prevent freeze-up and corrosion Dehydration to protect system materials from adverse chemical reactions Removal of odor or taste from personal-care products and plastics with high silica (hydrophobic) zeolite molecular sieves. Odors are adsorbed, not masked Dehydration with zeolite molecular sieves when very low humidity conditions are required. Small desiccant packets or tablets protect products such as pharmaceuticals, medical diagnostic reagent kits, vitamins, food, candy, batteries, dry fuel propellants, machine parts, film and instruments Removal of water and carbon dioxide from air before liquefaction and cryogenic separation of nitrogen, oxygen and other atmospheric gases Separation of oxygen and nitrogen with pressure swing or vacuum swing adsorption systems Dehydration before cryogenic recovery of hydrocarbon products and helium Dehydration of high acid gas content (CO2 and H2S) natural gas and natural gas condensate streams Removal of sulfur compounds from ethane, propane and butane Removal of water and CO2 before methane liquefaction Removal of water and sulfur compounds to protect gas transmission pipelines Dehydration of natural gas liquids Desulfurization of feed streams for ammonia and other chemical plants Removal of mercury, preventing damage to aluminum heat exchangers Dehydration of alkylation feed, refinery gas streams prior to cryogenic separation, naphtha and diesel oil Purification of feedstocks to protect isomerization catalysts Removal of water, HCl and H2S from reformer streams Removal of oxygenates from etherification raffinate streams and alkylation feed Removal of nitriles from etherification feed Dehydration of ethanol Dehydration and desulfurization of LPG streams Separation of normal paraffins from branched chain and cyclic compounds Purification by pressure swing adsorption for upgrading hydrocarbon streams Dehydration and purification of NGL/ethane/propane feed Dehydration of cracked gas, C2 and C3 splitter feed and hydrogen Dehydration and purification of salt-dome-stored ethylene, propylene and various other feedstocks Removal of water, carbon dioxide, methyl alchohol and other oxygenates, hydrogen sulfide and sulfur compounds, ammonia and mercury from ethylene, propylene, butylenes, amylenes and various solvents and co-monomers Removal of trace volatile organic compounds from air streams Removal of volatile organic compounds from moisture-laden process streams
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Polymer formulations
Air separation
Natural gas
Petroleum refining
Petrochemicals
OP's expertise and innovation extends from research and development to manufacturing and from application product selection to
technical support staff, and manufacturing facilities located around the globe, UOP continues to lead the industry through our commitment to our customers. Whether you are looking to dry, purify or separate, you'll find the adsorbent solution with UOP.
technical services. To meet customer needs, UOP offers the broadest portfolio of molecular sieve and activated alumina products in the world. With sales,
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