MOLECULAR SIEVE

PROCESS ADSORBENT

DYNOCEL 643
Typical Properties

Physical Pore Diameter 3Å

Shape Spherical or Extrudate
Crush Strength 16 Lb ( 4 x 8 Mesh)
10 Lb (8 x 12 Mesh)

Water Adsorption Capacity* ≥ 20.5 lbs water/100 lbs

*at 25oC and 17.5 mm Hg
Heat of Adsorption 1800 BTU/Lb H2O
Specific Heat 0.23 BTU/Lb °F
Moisture Content 1.5% in Maximum Weight

3 3
Bulk Density – 4 x 8 mesh 43 lbs/ft (688 kgs/m )
3 3
8 x 12 mesh 45 lbs/ft (720 kgs/m )

Size – nominal 4 x 8 mesh, 1/8”, 3.0 mm

(other sizes available on request) 8 x 12 mesh, 1/16”, 1.5 mm

Availability Packaging 1 MT Supersacks

150 Kg Steel drums available

Application Dynocel 643 is used to dehydrate vapor phase and liquid phase olefinic
hydrocarbons. Dynocel 643 does not require a preload step.

www.porocel.com | ph: 1-501-888-8690 | fax: 1-501-888-9169

10300 Arch Street Pike, Little Rock, Arkansas 72206 Nov 2014
 Page 1/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

1 Identification
Product identifier Molecular Sieve
Trade name: Dynocel 643
Porocel Product Grouping Code: 039
Application of the substance / the mixture
Adsorbent
Anti-moisture agent
Intermediate
Preparation of catalysts
Drier/ Catalyst
Water treatment
Details of the supplier of the safety data sheet
Porocel Industries, LLC
10300 Arch Street Pike
Little Rock, AR 72206 (USA)
Email: [email protected]
Information department: Health, Safety, & Environmental Department
Emergency telephone number:
For 24 hour emergency assistance, call CHEMTREC in the USA at (800)424-9300; internationally, call collect
at (703)527-3887.

2 Hazard(s) identification
Classification of the substance or mixture
The product is not classified, according to the Globally Harmonized System (GHS).
Label elements
GHS label elements Not applicable.
Hazard pictograms Not applicable.
Signal word Not applicable.
Hazard statements Not applicable.
Classification system:
NFPA ratings (scale 0 - 4)
Health = 0
0 Fire = 0
0 0 Reactivity = 0

HMIS-ratings (scale 0 - 4)
HEALTH 0 Health = 0
FIRE 0 Fire = 0
REACTIVITY 0 Reactivity = 0
(Contd. on page 2)
US

47.1.2
 Page 2/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 1)
Other hazards
Results of PBT and vPvB assessment
PBT: Not applicable.
vPvB: Not applicable.

3 Composition/information on ingredients
Chemical characterization: Mixtures
Dangerous components: Not applicable.
Non-dangerous components:
1318-02-1 zeolite ≤100%
Additional information: Compositions are represented as ranges to account for batch variability.

4 First-aid measures
Description of first aid measures
General information: No special measures required.
After inhalation: Supply fresh air; consult doctor in case of complaints.
After skin contact: Generally the product does not irritate the skin.
After eye contact: Rinse opened eye for several minutes under running water.
After swallowing: If symptoms persist consult doctor.
Information for doctor:
Most important symptoms and effects, both acute and delayed
No further relevant information available.
Indication of any immediate medical attention and special treatment needed
No further relevant information available.

5 Fire-fighting measures
Extinguishing media
Suitable extinguishing agents: Use fire fighting measures that suit the environment.
Special hazards arising from the substance or mixture No further relevant information available.
Advice for firefighters
Protective equipment: No special measures required.

6 Accidental release measures

Personal precautions, protective equipment and emergency procedures Not required.
Environmental precautions: Do not allow to enter sewers/ surface or ground water.
Methods and material for containment and cleaning up: Pick up mechanically.
Reference to other sections
See Section 7 for information on safe handling.
See Section 8 for information on personal protection equipment.
See Section 13 for disposal information.
(Contd. on page 3)
US

47.1.2
 Page 3/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 2)
Protective Action Criteria for Chemicals
PAC-1:
None of the ingredients are listed.
PAC-2:
None of the ingredients are listed.
PAC-3:
None of the ingredients are listed.

7 Handling and storage

Handling:
Precautions for safe handling No special measures required.
Information about protection against explosions and fires: No special measures required.
Conditions for safe storage, including any incompatibilities
Storage:
Requirements to be met by storerooms and receptacles: No special requirements.
Information about storage in one common storage facility: Not required.
Further information about storage conditions: None.
Specific end use(s) No further relevant information available.

8 Exposure controls/personal protection

Additional information about design of technical systems: No further data; see item 7.
Control parameters
Components with limit values that require monitoring at the workplace:
The product does not contain any relevant quantities of materials with critical values that have to be monitored
at the workplace.
Additional information: The lists that were valid during the creation were used as basis.
Exposure controls
Personal protective equipment:
General protective and hygienic measures:
The usual precautionary measures for handling chemicals should be followed.
Breathing equipment: Not required.
Protection of hands:
The glove material has to be impermeable and resistant to the product/ the substance/ the preparation.
Due to missing tests no recommendation to the glove material can be given for the product/ the preparation/
the chemical mixture.
Selection of the glove material on consideration of the penetration times, rates of diffusion and the degradation
Material of gloves
The selection of the suitable gloves does not only depend on the material, but also on further marks of quality
and varies from manufacturer to manufacturer. As the product is a preparation of several substances, the
resistance of the glove material can not be calculated in advance and has therefore to be checked prior to the
application.
(Contd. on page 4)
US

47.1.2
 Page 4/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 3)
Penetration time of glove material
The exact break through time has to be found out by the manufacturer of the protective gloves and has to be
observed.
Eye protection: Not required.

9 Physical and chemical properties

Information on basic physical and chemical properties
General Information
Appearance:
Form: Solid
Color: Light beige
Odor: Odorless
Odor threshold: Not determined.
pH-value: Not applicable.
Change in condition
Melting point/Melting range: Undetermined.
Boiling point/Boiling range: Undetermined.
Flash point: Not applicable.
Flammability (solid, gaseous): Not determined.
Decomposition temperature: Not determined.
Auto igniting: Product is not selfigniting.
Danger of explosion: Product does not present an explosion hazard.
Explosion limits:
Lower: Not determined.
Upper: Not determined.
Vapor pressure: Not applicable.
Density: Not determined.
Relative density Not determined.
Vapor density Not applicable.
Evaporation rate Not applicable.
Solubility in / Miscibility with
Water: Insoluble.
Partition coefficient (n-octanol/water): Not determined.
Viscosity:
Dynamic: Not applicable.
Kinematic: Not applicable.
Solvent content:
VOC content: 0.00 %
Solids content: 100.0 %
(Contd. on page 5)
US

47.1.2
 Page 5/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 4)

Other information No further relevant information available.

10 Stability and reactivity

Reactivity No further relevant information available.
Chemical stability
Thermal decomposition / conditions to be avoided:
No decomposition if used according to specifications.
Possibility of hazardous reactions No dangerous reactions known.
Conditions to avoid
Avoid immediate contact with high concentrations of chemicals having a high heat of adsorption such as olefins,
strong acids, etc. Once wetted, the product can heat up to the boiling point of water, simply flood with water to
cool the product.
Incompatible materials: No further relevant information available.
Hazardous decomposition products: No dangerous decomposition products known.

11 Toxicological information
Information on toxicological effects
Acute toxicity:
Primary irritant effect:
on the skin: No irritant effect.
on the eye: No irritating effect.
Sensitization: No sensitizing effects known.
Additional toxicological information:
The product is not subject to classification according to internally approved calculation methods for
preparations:
When used and handled according to specifications, the product does not have any harmful effects according
to our experience and the information provided to us.
Carcinogenic categories
IARC (International Agency for Research on Cancer)
1318-02-1 zeolite 3
NTP (National Toxicology Program)
None of the ingredients are listed.
OSHA-Ca (Occupational Safety & Health Administration)
None of the ingredients are listed.

12 Ecological information
Toxicity
Aquatic toxicity: No further relevant information available.
Persistence and degradability No further relevant information available.
Behavior in environmental systems:
Bioaccumulative potential No further relevant information available.
Mobility in soil No further relevant information available.
(Contd. on page 6)
US

47.1.2
 Page 6/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 5)
Additional ecological information:
General notes:
Water hazard class 1 (Self-assessment): slightly hazardous for water
Do not allow undiluted product or large quantities of it to reach ground water, water course or sewage system.
Results of PBT and vPvB assessment
PBT: Not applicable.
vPvB: Not applicable.
Other adverse effects No further relevant information available.

13 Disposal considerations
Waste treatment methods
Recommendation: Smaller quantities can be disposed of with household waste.
Uncleaned packagings:
Recommendation: Disposal must be made according to official regulations.

14 Transport information
UN-Number
DOT, ADR, ADN, IMDG, IATA Not applicable.
UN proper shipping name
DOT, ADR, ADN, IMDG, IATA Not applicable.
Transport hazard class(es)
DOT, ADR, ADN, IMDG, IATA
Class Not applicable.
Packing group
DOT, ADR, IMDG, IATA Not applicable.
Environmental hazards:
Marine pollutant: No
Transport in bulk according to Annex II of
MARPOL73/78 and the IBC Code Not applicable.
UN "Model Regulation": Not applicable.

15 Regulatory information
Safety, health and environmental regulations/legislation specific for the substance or mixture
Sara
Section 355 (extremely hazardous substances):
None of the ingredients are listed.
Section 313 (Specific toxic chemical listings):
None of the ingredients is listed.
(Contd. on page 7)
US

47.1.2
 Page 7/7
Safety Data Sheet
acc. to OSHA HCS
Printing date 09/27/2018 Reviewed on 08/13/2018

Trade name: Dynocel 643

(Contd. of page 6)
TSCA (Toxic Substances Control Act):
Zeolites are considered a mixture according to TSCA reporting requirements. All of the ingredients of this
mixture are either listed on the TSCA inventory, or are exempted from listing.
Proposition 65
Chemicals known to cause cancer:
None of the ingredients are listed.
Chemicals known to cause reproductive toxicity for females:
None of the ingredients are listed.
Chemicals known to cause reproductive toxicity for males:
None of the ingredients are listed.
Chemicals known to cause developmental toxicity:
None of the ingredients are listed.

Carcinogenic categories
EPA (Environmental Protection Agency)
None of the ingredients are listed.
TLV (Threshold Limit Value established by ACGIH)
None of the ingredients are listed.
NIOSH-Ca (National Institute for Occupational Safety and Health)
None of the ingredients are listed.
GHS label elements Not applicable.
Hazard pictograms Not applicable.
Signal word Not applicable.
Hazard statements Not applicable.
Chemical safety assessment: A Chemical Safety Assessment has not been carried out.

16 Other information
This information is based on our present knowledge. However, this shall not constitute a guarantee for any
specific product features and shall not establish a legally valid contractual relationship.
Abbreviations and acronyms:
ADR: Accord européen sur le transport des marchandises dangereuses par Route (European Agreement concerning the International
Carriage of Dangerous Goods by Road)
IMDG: International Maritime Code for Dangerous Goods
DOT: US Department of Transportation
IATA: International Air Transport Association
ACGIH: American Conference of Governmental Industrial Hygienists
EINECS: European Inventory of Existing Commercial Chemical Substances
ELINCS: European List of Notified Chemical Substances
CAS: Chemical Abstracts Service (division of the American Chemical Society)
NFPA: National Fire Protection Association (USA)
HMIS: Hazardous Materials Identification System (USA)
VOC: Volatile Organic Compounds (USA, EU)
PBT: Persistent, Bioaccumulative and Toxic
vPvB: very Persistent and very Bioaccumulative
NIOSH: National Institute for Occupational Safety
OSHA: Occupational Safety & Health
TLV: Threshold Limit Value
PEL: Permissible Exposure Limit
REL: Recommended Exposure Limit
US

47.1.2
 10300 Arch Street Pike, Little Rock, Arkansas 72206
ph: 501-888-8690 fax: 501-888-9169

Application Bulletin #1A:

Adsorption and Catalysis – The Basics

August 2010
 Application Bulletin #1A:
Adsorption and Catalysis – The Basics

The following is intended to serve as an introduction to adsorption and catalysis by way of term definition
(GLOSSARY OF TERMS) and by offering an overview of the different classes of adsorbents and
catalysts and their utility (ADSORBENT OVERVIEW).

GLOSSARY OF TERMS

Abrasion Number: The abrasion number of an adsorbent medium defines the resistance of the particles
to degradation upon handling. It is determined by horizontal sample agitation under specified test
conditions. Typically reported as the percentage of weight retained by the sample after a given time.

Absorption: The taking up of a liquid or gas by capillary, osmotic, or solvent action. The dissolution of
a gas or liquid in a liquid phase.

Acid Site: On a solid surface, a local atomic configuration that is acidic in behavior. The density and
acid strengths of such sites are important in chemisorption and numerous catalytic reactions.

Acid, Acidic: A proton (H+) donor or electron-pair acceptor in neutralization reactions; opposite of
bases. Examples: binary compounds of hydrogen with most nonmetallic elements and most simple
oxides and/or hydroxy compounds of nonmetals or metalloids.

Acid-washed: Adsorbent which has been contacted with an acid, often for the purpose of modifying
surface pH or removal of unwanted components from the solid.

Activated Carbon: A crude form of graphite, with a random or amorphous structure, which is highly
porous over a broad range of pore sizes, from visible cracks and crevices to cracks and crevices of
molecular dimensions.

Activation: A process of developing optimum chemical or surface reactivity in a solid material, usually
by appropriate heating.

Activated Alumina: Any of several synthetic high-surface-area transition-alumina products made by

proprietary activation processes; available in various convenient forms and modifications. Chi/rho/eta-
alumina.

Adsorbate: That which is adsorbed on the adsorbent.

Adsorbent: Any solid having the ability to concentrate significant quantities of other substances on its
surface. Examples: activated carbon, activated alumina.

Adsorber: A vessel designed to hold adsorbent media.

2
Adsorption: The taking up of a liquid or gas or of a dissolved substance, to a few molecular layers in
thickness, on a solid surface, and held there by molecular forces. Often subdivided into Chemisorption
and Physisorption.

Adsorption Front: The adsorbent loading gradient that exists in the active, or critical, bed depth of an
adsorber. It corresponds to the gradual transition from "fresh" (or "virgin") to "spent" (or "exhausted")
adsorbent media. Also reffered to as the Mass Transfer Zone.

Adsorption Isotherms: The profile of adsorbent loading capacity at a given temperature as a function of
adsorbate concentration (partial pressure, relative humidity, etc...).

Alpha-Alumina: The highest-temperature, hardest, most chemically stable and inert crystalline form of
alumina, Al2O3. Found in nature as "corundum," or made synthetically by intense heating of alumina
hydrates or other aluminas, usually to temperatures from 900°C (1650°F) to even above the melting point
(2050°C, 3720°F).

Alumina: Aluminum oxide, Al2O3, in any of its many forms. As a general term, includes the lower-
temperature transition alumina forms (containing perceptible hydroxide as well as oxide anions) and may
even include alumina hydrates and a few related compounds such as dawsonite.

Alumina Trihydrate: The true hydroxide of aluminum, Al(OH)3, also written Al2O3.3H2O, in any of
several crystalline forms. Occurs in nature as a constituent of bauxite. Also made synthetically by the
Bayer Process. Synonymous with gibbsite.

Aluminate: The negative ion (anion) or radical of aluminum, usually written Al02,,made by dissolving
alumina hydrate in aqueous base or caustic (sodium aluminate). Similarly, the anion contained in
numerous other compounds, e.g., spinel, clays, and other minerals.

Aluminum Hydroxlde: Properly, aluminum trihydroxide or alumina trihydrate; loosely, a general term
for any of the alumina hydrates.

Amorphous: Lacking a detectable crystallinity; liquid-like (i.e., disordered) in its structure, though solid
in appearance.

Amphoteric: Under different circumstances, capable of acting either as an acid or a base in

neutralization reactions.

Angstrom: A unit of length: one-tenth nanometer (1A = 0.1 nm = 10-10m). About equal to the diameter
of a single atom of hydrogen.

Anion: A negatively-charged atom or radical (chemically-bonded cluster of atoms). Attracted to the

anode in electrochemical systems, hence the name.

Attrition: The act of wearing or chipping away of a formed, granular, or particulate solid by rubbing and
impact, usually between pieces of like material.

3
Attrition Loss: The weight-% of fines produced when a sample of solid material is subjected to attrition
in a standardized test. The mode and severity of attrition (by air jet, shaking, etc...) and the size definition
of "fines" are ordinarily mated to anticipated use conditions.

Backwash: An operating procedure used to remove suspended solids from an adsorber bed. Liquid is
typically pumped into the bottom of the adsorber, flows upward through the bed, and exits through a
backwash outlet. The upward flow expands the bed and removes the suspended solids, fines, and
entrained air. The percent bed expansion and time required for backwashing is a function of the
backwash rate and temperature.

Base, Basic: A proton (H+) acceptor or electron-pair donor in neutralization reactions; opposite of acids.
Examples: the oxides or hydroxides of Li, Na, K, Mg, Ca, Ba, and other strongly metallic elements;
other compounds of like or similar behavior.

Basic Site: On a solid surface, a local atomic configuration that is basic in behavior. The density and
strengths of such sites are important in chemisorption and some catalytic reactions.

Bauxite: A mineral or ore containing one or more alumina hydrates in conjunction with other oxidic
compounds of aluminum, silicon, iron, etc... The principal source of synthetic aluminas, aluminum, and
other derivatives via the Bayer Process.

Bayer Hydrate: Gibbsite, a particular crystalline form of alumina trihydrate, Al (OH)3, the primary
product of the Bayer Process.

Bayer Process: The near-universal commercial process for producing aluminas (and hence aluminum)
from bauxite. Consists of digestion in hot caustic to yield a solution of sodium aluminate; separation of
undissolved solid wastes ("red mud"); and precipitation of gibbsite, Al (OH)3, from the liquor by seeding
and cooling, followed by filtration and washing.

Bed Depth: The amount of adsorbent, expressed in length units, which is parallel to the flow of the
stream and through which the stream must pass.

Bed Support: A layer of material, such as tabular alumina spheres, placed on the bottom screen of a
tower and underlying a stationary bed of somewhat finer formed adsorbent or catalyst media.

BET (Brunauer-Emmett-Teller): An instrumental method for determining surface area of a solid

sample measuring monomolecular nitrogen gas adsorption at the temperature of liquid nitrogen (-210°C, -
346°F). Some other sorbates are also used.

Boehmite: The most common crystalline form of alumina monohydrate. A constituent of bauxite; also,
an important synthetic: the major component of commercial gel-derived alumina, also called substrate
alumina.

Bound: Chemically combined, including chemisorbed; sometimes also physically bound, as in

physisorption.

Bulk Density: Computed from the bulk volume of an unconsolidated solid. The overall volume (volume
of container) occupied, including the inter-particle packing space.

Bulk Volume: The volume of container occupied by a quantity of unconsolidated solid material in the
form of particles, grains, agglomerates, nodules, pellets, etc... Must be given other descriptors, as "loose,"
"packed," and the manner of packing.

4
Catalyst: A chemically active agent which functions to increase the rate of some chemical reaction
without itself being appreciably consumed or altered. Often such agents are solids (heterogeneous
catalysts), distributed as very thin layers over the immense surface area of a suitable porous solid
substrate.
Cation: A positively-charged atom or radical (chemically-bonded cluster of atoms). Attracted to the
cathode in electrochemical systems, hence the name.

Caustlc: Usually, caustic soda or sodium hydroxide (NaOH), and most often applied to aqueous
solutions thereof. Also refers to the chemically basic or alkaline quality of this material.

Chemisorption: The taking up of a liquid or gas or of a dissolved substance wherein a new chemical
compound or bond is formed between the sorbent surface atoms and those of the sorbate.

Classifier: A device used to segregate or separate otherwise like solid particles into two or more groups
according to some characteristic such as size, or by magnetic or electrostatic particles.

Claus Catalyst: An active alumina or modified alumina catalyst, available in spherical form in various
sizings, used to promote the Claus reactfon. By extension, similar catalysts for the destruction of
carbonyl sulfide (COS) and/or carbon disulfide (CS2), often accompanying H2S in refinery gas streams.

Claus Reaction: The reaction of H2S with SO2 to form elemental sulfur; employed on a large scale to
destroy byproduct hydrogen sulfide in natural gas plants and petroleum refineries. Applicable as well as
to the processing of other fossil fuels (shale oil, coal, etc.). A catalytic reaction.

Combined Water: That fraction or percentage composed of H2O that is chemically combined as part of
one or more compounds present (hydrate).

Compaction: The act of forcing particulate or granular material together (consolidation) under pressure
or impact to yield a relatively dense mass or formed object. Usually followed by drying, curing, or firing
in refractory, ceramic, and powder-metallurgical manufacture.

Conversion: The change of one material or substance into another (chemical), or of one crystalline form
or phase into another (physical); or of one product into another by virtue of one or a combination of the
above.

Counter Current: Refers to process flows in opposing directions (ex: upflow to downflow).

Crush Strength: The linear compressive force or load required to crush (fracture) a brittle material in
the form of grain, spheroids, etc..., in a prescribed test procedure either on individual entities or in bulk.

Crystal: That form or particle or piece of a substance in which its atoms are distributed in one specific
orderly geometrical array, called lattice, essentially throughout. Crystals exhibit characteristic optical and
other properties and growth or cleavage planes, in characteristic orientations.

Crystalline: That form of a substance which is comprised predominantly of (one or more) crystals, as
opposed to glassy or amorphous solids and liquid.

Dehydration: Removal of water.

Desiccant: A material used to dry another or to dry the atmosphere, by virtue of its ability to adsorb
water (activated alumina, zeolite, silica gel, etc...).

5
Desorption: The opposite of adsorption. A phenomenon where an adsorbed molecule leaves the surface
of the adsorbent. The reversal of any of the processes of sorption: the removal or re-evaporation of a
sorbed substance.

Dew Point: The temperature at which air or other gas containing a given concentration of water vapor is
or would become saturated, i.e., in equilibrium with liquid water. Also used for condensibles other than
water.

Diffusion: The relatively slow movement of one or more kinds of atoms, molecules, or ions through a
host material, in consequence of concentration or temperature gradients.

Dryer (Drier): A device for drying a material or product by evaporation or adsorption of water.

Extrudate: The product of extrusion; any cylindrical, prismatic, or pellet shaped material so made. A
useful form of a solid catalyst or catalyst substrate.

Extrusion: The process of forcing a plastic material or mixture through the opening(s) of a die at
relatively high pressure. The material may thus be compacted (as in ceramic forming), and emerges in
elongate cylindrical or ribbon (or wire, etc.) form having the cross-section of the die opening. Ordinarily
followed by drying, curing, activating, or firing.

Fines: A loose term used for a fraction of a particulate or granular solid: the finer sizings of a
distribution; or, finer than some specified diameter or size; or finer than desired or specified for a given
product; etc... Criteria must be understood in the particular usage, though "passing through 325-mesh
screen" is common.

Fluid (Fluidized) Bed: A bed of particulate or granular solid that is lifted and diluted by an upflow of
gas or liquid so that the mixture is fluid and turbulent.

Free: Uncombined chemically, e.g., a free element is that uncombined elemental substance. Also, e.g.,
"free moisture" or free water is water present in a material by absorption or occlusion as opposed to water
of hydration or otherwise chemically combined.

Free Water: That fraction or percentage composed of H2O that is present as "moisture," "dampness," or
"wetness"; i.e. absorbed and occluded.

Gamma-Alumina: A particular crystalline transition alumina, derived thermally from boehmite and
hence a major component of lightly calcined gel alumina.

Gel: A colloidal state comprised of interdispersed solid and liquid, in which the solid particles or
ligaments are themselves interconnected or interlaced in three dimensions.

Gibbsite: A particular crystalline form of alumina trihydrate; occurs in bauxite but is most notable as the
primary product of the Bayer Process, hence the synthetic raw material from which aluminum and most
aluminas of commerce are in turn derived.

Hardness: Resistance of a solid material to indenting and abrasion; a measure of the cohesive forces
between its atoms.

Hardness Number: A quantitaive measure of material (adsorbent or catalyst) degradation due to

physical contact with a test medium.

6
Heat of Adsorption: The heat given off when molecules are adsorbed.

Heterogeneous: Of a body of material or matter, comprised of more than one phase (solid, liquid, and
gas) separated by boundaries; similarly of a solid, comprised of more than one chemical, crystalline,
and/or glassy species, separated by boundaries.

Homogeneous: Of a body of material or matter, alike through throughout; hence, comprised of only one
chemical composition and phase, without internal boundaries.

Humidity: Quantitative measurement of the water-vapor content of air or other gas.

Hydrate: A crystal or chemical substance containing chemically combined water in fixed proportions
relative to its other constituents.

Hydration: The act or process of taking up water chemically, as opposed to adsorption or absorption.
Forming a hydrate.

Hydrolysis: A chemical reaction in which water is the agent used to convert a chemical species into two
new chemical species.

Hygroscopic: The ability or tendency to take up moisture, usually from the air, but from other moist
materials as well.

Immiscible: Of two phases, the inability to dissolve in one another to form a single solution; mutually
insoluble. May occur in a limited range of ratios of the two, or at any ratio.

Iodine Number: Refers to the milligrams of iodine adsorbed by one gram of carbon at a filtrate
concentration of 0.02N iodine.

Ion Exchange: A chemical process involving intimate contact of a solid and a liquid (e.g. aqueous
solution), whereby ions on the surface of the former are exchanged for other ions contained in the latter.
Used for water softening and other selective chemical processes.

lon: A charged particle of atomic or molecular dimensions that contains one, two, three, etc..., electrons
above or below the neutral complement (anion, cation). May be mobile, as in aqueous solutions or melts,
or identifiable within chemical compounds.

Loss of Ignition (LOI): The fractional or percentage weight loss of a material on heating in air from an
initial defined state (usually, dried) to a specified temperature such as 1000°C (1832°F), and holding there
for a specified period such as 1 hour. Fixed procedures are usually designed such that LOI represents the
loss of combined H2O, CO2, certain other volatile inorganics, and combustible organic matter.

Macropore Volume: The volume fraction of a porous solid comprised of all connected pores or
openings larger than a designated equivalent size, determined arbitrarily. In some alumina products, this
limit is set at a diameter of 350 Angstroms; in others, at 750 A.

Mass Transfer Zone: The adsorption gradient that exists in the adsorber bed, corresponding to the
gradual transition of the adsorbent from "fresh" (or "virgin") to "spent" (or "exhausted"). Also referred
to as the MTZ. In a fluid process moving through a porous solid bed (desiccant or absorber) that part of
the bed at any instant in which the reaction is in progress. Upstream of this zone the bed is saturated,
while downstream of it the active agent in the fluid has been exhausted.

7
Mechanical Properties: Those characteristics of a material that relate force, load or stress to
deformation, flow, and/or fracture: elastic modulus, brittleness, ductility, malleability, yield stress,
"toughness," creep, viscosity, various expressions of "strength," etc...

Medium, Media: A quantity of material contained in some volume or location, generally for the purpose
of reacting or performing some other useful operation.

Mercury Porosity: The volume fraction of connected pores, voids, and channels in a material as
determined using mercury intrusion at high pressures.

Mesh, Mesh Size: The opening(s) or size of opening(s) in a designated sieve or screen, corresponding to
the approximate diameter of particles below which they will pass through and above which they will be
retained on the screen. "Mesh Sizes" are given as number of wires per inch of standard screen
construction, e.g. Tyler, U.S. or B.S.; these are translated by tables into equivalent particle diameters in
inches, millimeters (mm), or microns (um or u).

Micropore Volume: The volume fraction of a porous solid comprised of all connected pores or openings
smaller than a designated equivalent size, determined arbitrarily. In some alumina products, this limit is
set at a diameter of 120 Angstroms.

Miscible: Of two phases, the ability of each to dissolve in the other. May occur in a limited range of
ratios of the two, or in any ratio.

Molasses Number: The ratio of the optical densities of the filtrate of a molasses solution treated with a
standard activated carbon and the activated carbon in question.

Molecular Sieve: One of a family of zeolite minerals or other (often, synthetic) crystalline materials
characterized by connected voids in the crystal lattice that are of molecular dimensions; hence having
size-selective adsorptive, catalytic, and other surface properties.

Neutralization: In chemistry, the reaction of an acid and a base to form a salt. Originally HY + XOH =
H2O + XY; now much broader, including many nonaqueous systems and analogous reactions.

Nominal: Approximate or typical or represented by (a dimension, composition, etc.), as opposed to

actual or accurate.

Oxidation: A type of chemical reaction characterized by the removal of electrons from, hence a positive
change in valence of, some contained atom. Often caused by oxygen of the air.

Oxidize: To form an oxide from the elements, or otherwise in general to cause oxidation.

Particle Size: The size or size range (usually, equivalent diameter) of a given or typical particle,
expressed either as nanometers, micrometers, millimeters, etc., or as mesh or sieve size.

Particle Size Distribution: The population of particles of a loose or suspended material for each size
increment between the minimum and maximum size present; expressed either by increment or
cumulatively, usually by weight fraction or wt.-%. Especially important to the bulk density, and to the
density achievable by compaction.

8
pH: An instrumental measure of acidity or alkalinity of water and aqueous solutions: the negative
logarithm of the concentration of free hydrogen ion, H+. At room temperature, pH = 7 is neutral; values
below 7 are increasingly acidic; values above 7 are increasingly alkaline or basic.

Phase: Any homogeneous volume of gas, liquid (including glass), or specific crystalline solid, including
its constant or fixed chemical identity. In a multiphase system, the total of each one of these present,
regardless of its own subdivision or distribution in the system, is one phase.

Physical Properties: Those characteristics of any substance, material or mixture which describe its non-
chemical interactions with gravity (e.g. weight, density), heat, radiation (e.g. color, transmission,
refraction), magnetism, electricity or electric fields, changes of state (e.g. melting, boiling), etc...; and
often by inclusion, the mechanical properties. Thus all properties except chemical and nuclear
properties.

Physisorption: A subtype of adsorption in which the bonding of sorbate to the surface is weak
("physical") and the sorbate is not chemically altered and, thus, easily reversed.

Pore: A small opening, void, interstice, or channel within a consolidated solid mass or agglomerate;
usually larger than atomic or molecular dimensions.

Pore Size: The characteristic or equivalent dimensions or range of same (e.g., diameter) of a pore or
family of pores in a material; usually measured indirectly by differential liquid (e.g., Hg) intrustion or
cryogenic gas adsorption-desorption; or, microscopically on a section.

Pore Size Distribution: The specific pore volume of all measurable pores in each of a set of equivalent
diameter increments from the smallest to the largest present in a material; expressed either by increment
or cumulatively. Most commonly measured by mercury intrusion at successively higher pressures.

Pore Volume: The volume of the internal void spaces in a granule, smaller than 0.1 mm and large
enough to allow access to helium. Measured as the difference in the volumetric displacement by granular
activated carbon in mercury and in helium at standard conditions.

Pore Volume Fraction: The porosity of a solid, otherwise sub-classified, when expressed as cm3/cm3 or
correspondingly in per cent by volume.

Pore Volume, Specific: The porosity of a solid, otherwise sub-classified, when expressed as cm3/g or
similarly.

Porosity: Has meaning only for a consolidated form of solid, whether that be a particle, agglomerate,
grain, formed object such as a nodule, pellet, or larger monolithic mass or object. Any such single unit
has a nominal volume, sometimes also called the envelope volume. Given that characteristic volume for
reference, the porosity is the volume (hence, volume fraction) of pores contained in the solid within it.
Since pores can be described in various specific ways, there is an equal number of corresponding
expressions of porosity: Macroporosity; Microporosity; Size Increment; Connected or Open Porosity,
also called Apparent Porosity; Closed or Blind Porosity; Total Porosity, the sum of Connected plus
Closed Porosity.

Porosity may also be expressed as determined by a given instrument or technique, as e.g.: Mercury
Porosity, with approximates Connected Porosity; Water Absorption, which also approximates Connected
Porosity.

9
To eliminate the problem of determining nominal volume and also for engineering convenience, porosity
with any of the above modifiers is often determined and expressed in cubic centimeters per gram (cc/g or
cm3/g) instead of volume fraction. Porosity should not be confused with the interstitial volume or
packing space between particles of an unconsolidated solid.

Quartz: One of several crystalline forms of silica, SiO2; others include cristobalite and tridymite. All
occur as minerals, also synthetic. Fused silica, one of the most refractory of all industrial and optical
glasses, is none of these and should not be misnamed as "quartz."

Reactivation: The removal of adsorbates from spent adsorbent media which will allow the adsorbent to
be reused.

Reactivity: The susceptibility of a material to chemical change or action often by virtue of its state of
subdivision, surface area, metastable form, composition, etc... The opposite of inertness.

Reduce, Reduction: To cause or conduct a chemical reaction characterized by addition of electrons to,
hence a negative change in valence of, some contained atom. The opposite and complement of oxidation.

Regeneration: A process, conducted periodically or cyclically, of restoring an active agent such as a

desiccant, scavenger, or catalyst substantially to its initial condition after it has been reversibly altered by
performance of its function or by contamination or "poisoning."

Relative Humidity: The water-vapor content per unit volume of air or other gas, divided by the
saturation level at the same temperature and pressure, i.e., by the content that would be in equilibrium
with liquid water.

Sieve: A standard wire mesh or screen, especially when used in graded sets to determine the mesh size or
particle size distribution of particulate and granular solids.

Sieve Analysis: The particle size distribution of a particulate or granular solid or sample thereof, when
determined by passage through the retention on a graded set of sieves.

Silica: Silicon dioxide, SiO2, in any of its crystalline or glassy forms.

Silica Gel: A precipitated colloidal mass or gel of indefinitely hydrated silica; also, the dried or activated
product of same. Useful as desiccant, scavenger, and catalyst substrate.

Soda: Sodium carbonate (Na2CO3) or bicarbonate (NaHCO3) or hydroxide (caustic soda, NaOH); or
any contained or combined form of sodium in a material, including as impurity expressed as the
equivalent Na2O.

Solution: A homogeneous or single-phase, variable-composition mixture of one substance (solute) in

another (solvent), in which the former is dispersed as separated molecules, ions, or atoms. The solvent or
the solution may be solid, liquid, or gas.

Sorbate: In any process of sorption, the species in the fluid medium which enters preferentially into the
solid and adheres to its surfaces.

Sorption: In general, the taking up of some substance (sorbate) into or on the surface of another
(sorbent), without specification of the type of process.

10
Substrate: A body, board, or layer of material, on which some other active or useful material(s) or
component(s) may be deposited or laid as for example in electronic circuitry laid on an alumina ceramic
board. In catalysis, the formed, porous, high-surface-area carrier on which the catalytic agent is widely
and thinly distributed for reasons of performance and economy.

Surface: Of solids, the external boundary; or, alternatively, the total of external and all internal surfaces
bounding pores, voids, channels, crevices, cracks, etc...

Surface Activity, Acidity, Basicity: The extent and degree of adsorptivity or reactivity (acidity, basicity,
etc...) of a given area of accessible solid surface, resulting from chemical modification and crystalline or
other imperfections thereon.

Surface Area: The area, per unit weight of a granular or powdered or formed porous solid, of all
external plus internal surfaces that are accessible to a penetrating gas or liquid.

Tabular: From "table": Plate-like or platelet in crystal morphology or habit.

Tabular Alumina: High fired, dense alpha-alumina, whose relatively large crystals or grains are
predominantly of tabular or platelet morphology.

Transition: A physical change from one crystalline form to another or a change of state (solid, liquid,
gas), in any direction.

Transition Aluminas: A family of metastable crystalline aluminas containing minor but detectable OH-
as well as O- ions. Produced more or less sequentially by gradual heating of the different alumina
trihydrates and monohydrates; also, in some cases, synthesized by other processes. Examples are active
alumina, substrate alumina, and the light-burned calcines.

Vapor: Same as gas; a condensable gas.

Viscosity: A measure of the resistance of a fluid (liquid or gas) or semi-fluid material to motion in shear.
Determined by specified instrumental methods.

Void: Any empty (or gas-filled) space in a solid material. For a bed, the percent by volume of the
interstices to total bed volume. A void in a liquid is called a bubble.

Voids: The percent by volume of the interstices to total bed volume.

Volatile: A relative term expressing the tendency to form vapor, e.g., at room temperature or in some
other temperature domain.

Volatilize: To vaporize, convert to the vapor or gas state, including to boil; applied also to a component,
including as a result of decomposition or other chemical change. To sublime (pass from solid to gas
without intervening liquid).

Water Adsorption: The amount of liquid water adsorbed by a consolidated (though porous) solid under
a fixed test procedure; commonly expressed as weight-% of the dry material. Can be converted
arithmetically to cm3/gram or to volume-% as a measure of porosity.

11
ADSORBENT OVERVIEW

Adsorption refers to the concentration of a fluid component (gas or liquid phase) onto the surfaces of a
solid. This can be a purely physical interaction between the adsorbent and adsorbate species (physical
adsorption or physisorption), or can involve a chemical reaction (chemical adsorption or chemisorption).

Adsorbents whose reactivity is based on physisorption can be divided into two basic categories. The first
are oxygen-containing compounds such as silica gel, activated alumina, and zeolitic molecular sieves.
These agents are hydrophilic in nature and will show a preference towards the adsorption of polar
compounds. The second group contains carbon as the major component. This includes activated carbon,
activated coke, and carbon molecular sieves. These adsorbents are hydrophobic in nature and are
therefore primarily used to remove organics from gases and aqueous streams.

Silica Gels and Alumino-Silicates

Silica gels are composed entirely of silicon dioxide (SiO2) while alumino-silicates are silica gels that
contain anywhere from 0.1-3.0% alumina (Al2O3). Industrial applications are primarily limited to the
dehydration of gases and organic liquids, support materials in fixed bed processes and inert
binder/support material in catalyst formulation. They are the most chemically inert of all adsorbent
materials and provide the greatest capacities for water adsorption at high relative humidity levels.
Although their adsorption capacities are high, binding energies of the adsorbate are sufficiently low to
allow simple thermal or reduced pressure regeneration.

Silica-based adsorbents are indispensable in processes involving highly corrosive environments such as
acid drying. Their superior dimensional stability and physical strength allow the design and operation of
economical deep fixed adsorption beds. Other adsorbents such as aluminas and molecular sieves cannot
service these applications.

These adsorbents are finding utility in the refining and petrochemical industries beyond traditional
dehydration. Silica gel can be effective at removing aromatics from dry paraffinic streams. The recovery
of polar organics from non-polar solvents is also a growing application.

Activated Aluminas

Aluminas are materials composed of aluminum oxide (Al2O3). Activated aluminas generally refer to a
class of aluminum oxides that are very hydrophilic in nature and possess high degrees of bulk porosity.
As a result, they exhibit high adsorption capacities for water and other polar substances. As with silica
gels, once saturated they are easily regenerated by thermal desorption of the adsorbed species.
Traditionally, their value as adsorbents paralleled that of silica and alumino-silicates with their primary
utility being bulk desiccation agents in the dehydration of gases and organic solvents. Adsorbate binding
energies on alumina are somewhat greater than that of silica, making activated aluminas more attractive
when low to moderate water levels are specified in process effluent. Shown below is the adsorption
profile of water on activated alumina:

12
 Adsorption Profile of Water on Activated Alumina

Second H H H H
Physisorbed
Water Layer
O O

First H H H H
Physisorbed
Water Layer
O O
Chemisorbed H H H H
Hydrate O O O O

Aluminum Al Al Al Al
Oxide
Base Structure O O O

Over the last ten years many alumina products have been developed based upon various chemical and
thermal treatments designed to control surface chemistry. This has resulted in a range of adsorbents that
display significant selectivity toward the removal of impurities such as H2S, COS, CO2, organic
oxygenates, and HCl.

Activated aluminas have also found utility in the removal of fluoride ions, arsenic and trace metals from
water, and reduction of HF and organic fluorides in hydrocarbon streams.

Due to their inherent strength and attrition-resistance, aluminas are also important support materials for
fixed bed processes. A wide range of choices are currently available. Dense, highly inert aluminas resist
water pick-up during handling, and are beneficial to processes in which water entrainment, silica content
and catalytic activity is detrimental. By contrast, active bed support aluminas can be used to increase
effective capacity in many adsorber units such as dryers, defluorinators, and chloride guards. They can
also provide additional catalytic activity in alumina-based catalytic processes such as Claus.

Molecular Sieves

Zeolitic molecular sieves are a group of natural or synthetic aluminum silicates that form a regular crystal
lattice. This lattice resembles an assemblage of cages interconnected by a network of tunnels, or
channels, and varies in structure depending upon the type of zeolite. The alumina units of the channels
and cages are negatively charged and thus require cations to balance the system. Zeolites generally
behave excellently as physical adsorbents, holding onto molecules via Van der Waals type attractions. In
addition, they possess a natural affinity for polar species and are ideally suited to separate component
mixtures based on dipole interactions.

Another important feature of zeolites is that the cations in the lattice structure are exchangeable. It is
therefore possible to control the size of the tunnel diameters via ion-exchange. For example, a Type A
Zeolite in the K+-form has a channel diameter of 0.29nm, while the same Zeolite in the Ca2+-form has a
channel diameter of 0.44nm. The significance of this is that zeolites can also be used to separate chemical

13
species based upon their critical molecular diameter (size selectivity) and be "tailor-made", within limits,
for specific applications. Size selectivity in the hydrophobic carbon-based molecular sieves can also be
controlled, but to a lesser extent.

Due to their relatively high adsorbate binding energies and short mass transfer zones, molecular sieves are
ideally suited for dehydration applications where very low product water concentrations (ppb) are
desired. In this aspect they are superior to their silica and alumina counterparts, whose comparatively
long mass transfer zones result in low concentration breakthrough early in the adsorption cycle.
However, molecular sieves tend to display poorer chemical resistance (especially to acids), are more
prone to coking, and require more energy for their effective regeneration.

In general, silicas and aluminas are used when initial adsorbate concentrations are high (>1% by volume)
and complete removal is not required. Molecular sieves are best utilized with initially low adsorbate
concentrations (<0.5%) and complete removal is mandated. Composite fixed bed adsorber designs are
often used that combine an initial adsorbent zone of alumina or silica with a polishing molecular sieve
zone following. This approach serves to maximize adsorption capacity and product purity while
minimizing the energy requirements of regeneration. In addition, versatility in function can be
manipulated by incorporating specialized adsorbents into the design. For example, an adsorbent bed
containing a desiccant alumina, followed by a base-promoted alumina and a Zeolite Type 4A would
provide a high capacity for complete dehydration as well as hydrogen sulfide removal.

High silica-content molecular sieves, also known as silicates, were developed for the removal of volatile
organics and other pollutants from gases. Characterized by their hydrophobicity, silicates have low
adsorption capacity for water and are ideally suited for the selective removal of organics such as alcohols,
aldehydes, nitriles, benzene, etc..., in humidified streams. Their pore size also results in the exclusion of
larger molecules, resulting in the selective removal of light organics from heavier liquid hydrocarbons.

In addition to being an integral part in emerging design strategies of fixed bed adsorbers, molecular sieves
are also finding new uses in industry. As with aluminas and silicas, zeolites are being used in the
selective removal of a wide range of aromatics and polar organics from less polar process streams. They
are also being used in certain ion-exchange applications.

Activated Carbons

Activated carbons are manufactured from a wide variety of organic carbon sources such as wood, peat,
lignite, coal, etc... They are universally characterized by very high porosity and their strong hydrophobic
nature. In addition to the base carbon structure, activated products also contain small amounts of
hydrogen and oxygen which are chemically bonded in the form of various functional groups such as
carbonyl, carboxyl, phenol and others. In addition, activated carbon source materials also have mineral
components that become concentrated during manufacture. These differences in composition, which are
reflected in the carbon's chemical characteristics, results in an endless array of products having a wide
variety of applications.

The traditional use of activated carbons as adsorbents has been in the removal of organic impurities from
potable and wastewater. Their large adsorptive capacities and strong affinity for hydrocarbons make
them ideally suited for industries involved in water purification.

The purification of gas streams is another important historical use for these materials, with the primary
application being organic vapor removal. One example in this category is the recovery of hydrocarbons
from storage tank vents. Solvent recovery, trace metal removal, precious metal recovery and
concentration, and desulfurization are other significant industrial applications.

14
One application with special pertinence to oil refining involves the treating of amine and glycol absorber
solutions. Amine solutions used in the recovery of acid gases and glycol systems used for dehydration
are sensitive to the build-up of contaminants. These contaminants cause foaming that decreases
efficiency. A ctivated carbon beds are used to purify these solutions, resulting in improved performance.

Activated carbons are also experiencing increased utility as catalyst supports. They presently serve this
function in several palladium-catalyzed hydrogenation processes and the Merox process in oil refining for
converting mercaptans to disulfides.

The future potential for carbon-based products in processing is significant. The availability of a growing
range of specialty products based on impregnation of chemically active species on carbon substrates for
specific applications demonstrates this potential. Some examples:

Chemical Impregnant Application

Copper Sulfur removal

Copper and Chromium Salts Toxic gas removal
Iodine Hydrogen sulfide and mercury removal
Zinc Salts Ammonia removal
Sulfur Mercury removal
Manganese Dioxide Hydrogen sulfide and formaldehyde removal
Iron Salts Divalent sulfur compound removal
Potassium Hydroxide General acid gas (H2S, SO2, NOX, Cl2) removal
Silver Immobilized biocide for bacterial growth inhibition
and removal

Ion-Exchange Resins

Ion-exchange resins are another class of adsorbents that are rapidly finding new applications in a wide
range of industries. These resins are organic polymeric materials that can function as adsorbents (both
chemical and physical) and catalysts, and are available in an expanding variety of both cation- and anion-
exchange forms. Cation-exchange resins are typically obtained and used in either the acid (H+) or sodium
(Na+) form and can be divided into two classes according to their active functional groups:

1) Strongly acidic resins that are based on polystyrene with sulfonic acid groups and can be
considered analogous to sulfuric acid:

Rx-SO3H ~ H2SO4

2) Weakly acidic resins that are based on polyacrylic acid matrices having carboxylic acid groups
and can be considered analogous to acetic acid:

RxCO2H ~ CH3CO2H

15
Similarly, anion-exchange resins can also be either polystyrene- or polyacrylic-based. The functionality
in these cases consists of a variety of alkyl ammonium groups which are usually obtained in either the
hydroxide (OH-) or chloride (Cl-) forms. Anion-exchange resins are also divided into two basic classes:

1) Strongly basic resins whose functionalities are quarternary ammonium groups and can be
considered analogous to sodium hydroxide:

Rx-NR3OH ~ NaOH

2) Weakly basic resins whose functionalities are amine groups and can be considered analogous to
ammonium hydroxide:

Rx-NH3OH ~ NH4OH

The acidic protons or positive ions on cation-exchange resins can be readily exchanged with other ions of
the same charge, while the basic or negative ions on anion-exchange resins will also readily exchange
with ions of like charge. This exchange behavior is central to several important aspects of their utility:

Conversion - A major application of ion-exchange systems is liquid processing involving the

replacement of one ionic species for another. The primary aim is to exchange a deleterious ion in a
solution with an innocuous one. A notable example is water softening. A cation-exchange resin in
the sodium form is used to adsorb scale-forming ions such as calcium, magnesium and other divalent
ions and replace them with sodium. Once used to capacity, the adsorption bed is back-washed with
sodium chloride to regenerate the Na+-exchanged form of the resin.

Purification and Deionization - Ion-exchange resin systems can be designed to achieve essentially
complete removal or demineralization of aqueous streams. This typically involves the utilization of a
composite resin bed containing both the hydrogen form of a cation resin and the hydroxide form of an
anion resin. The resins can be either staged in separate zones or intimately mixed. The cation resin
adsorbs all positively charged species, replacing them with hydrogen ion in solution. The anion resin
adsorbs all negatively charged species and replaces them with hydroxide. The end result is total ion
removal and replacement with H+ and OH- (H2O).

Concentration - Solutions containing low-level or trace amounts of valuable ionic constituents can
be processed using ion-exchange resins. The targeted ionic species are concentrated on the resin via
the exchange mechanism. Recovery of the valued material in a much more concentrated form is
accomplished during regeneration. Efficient ion-exchange systems have been designed for the
reclamation of copper, chromium, uranium, gold and many other metals. The concentration approach
is also useful as a means of pollution reduction.

Fractionation - This is a variance on the concentration principle. Different resins display varying
degrees of affinity for different ionic species. A correctly designed ion-exchange system can be used
for the selective removal of one or more ions from a mixture. This strategy again has proven utility in
the concentration and recovery of valuable metals or the ion-specific removal of a deleterious species.

The base structures of both cation- and anion-exchange resins can be varied by adjusting the degree of
cross-linking in the polymeric backbone. Minimizing cross-linking in the base structure yields materials
known as "gels". Gels possess swelling characteristics that are advantageous in certain aqueous
applications. High degrees of structural cross-linking result in "macrorecticular" resins. These materials
are highly porous and possess a much higher degree of mechanical integrity. They are well-suited for
gaseous and non-aqueous applications as well as a variety of aqueous-based processes.

16
There are currently literally dozens of anion and cation exchange resins having a wide variety of
properties being marketed for very diverse ion-exchange applications. This availability provides great
latitude in application-specific design.

Rising waste disposal costs and the growing economic incentives of metal recovery have given rise to
another class of adsorbents closely related to ion-exchange materials known as Chelation Resins. Based
upon the same polymeric structures as traditional ion-exchange resins, Chelation Resins contain
functionalities specially designed for metal ion adsorption via chelation as opposed to ion displacement.
Resins are currently available for the selective removal of mercury and precious metals from aqueous
solutions, the selective removal of heavy metals, decalcification and the selective removal of toxic
metals. Other resins containing the same chelation functionalities but having a silicon oxide-based
backbone are also available. These materials are particularly valuable in non-aqueous service.

Several classes of resins exist that are used strictly as physical adsorbents. While closely related in
structure to standard ion-exchange resins, these may or may not have ion-exchange groups. Their
macroporous structure and chemical properties give them unique adsorptive properties. The primary
applications for these materials include the removal of organics and weakly ionic species from gases and
aqueous streams, and the decolorization of liquids.

Ion-exchange resins can also be used to significant advantage as reagents and catalysts in processes as a
source of Bronsted acids and bases and non-volatile amines. These applications are reviewed in the
following section.

Chemisorbents and Catalysis

Although catalytic systems exist for a great number of processes, the purpose of this review is to cover
only those that have utility in the purification of gas and liquid streams, i.e. the removal of low level or
trace amounts of contaminants.

The discipline of catalysis as it applies to gas and liquid purification can be divided into two categories:
1) chemisorption - an extension of standard adsorption with the main difference being that the adsorbed
species is chemically converted in the process as opposed to just being bound, and 2) conversion - in
which the catalyst assists in a chemical transformation but results in no permanent adsorption of reactants.

Examples of catalysts available for gas purification as chemisorbents include:

• Supported zinc oxides and mixtures of copper and zinc oxides for the removal of H2S, COS,
mercaptans (RSH) and arsine (AsH3) from hydrocarcarbon gases. In this case, the species are
chemisorbed and converted to copper and zinc sulfides and arsenides with the liberation of carbon
dioxide or water.

• Iron oxide-based adsorbents for the removal of H2S and light mercaptans from hydrocarbons.

• Supported reduced nickel and copper for the adsorption of a wide range of sulfur species from liquid
hydrocarbons via metal sub-sulfide formation.

• Sodium, calcium and magnesium oxides to remove chloride ion from hydrocarbons.

17
All the above examples involve irreversible chemisorption in which the catalyst is consumed in the
process. Other agents are used in a truly catalytic mode involving conversion with no permanent
adsorption of the targeted species. The following are examples of some general catalytic processes that
can be used in gas and liquid purification:

• Hydrodesulfurization of hydrocarbons to convert organic sulfur compounds to hydrogen sulfide.

• Selective hydrogenation for applications such as the reduction of levels of acetylenes in olefins.

• Nitrogen oxides (NOX) conversion.

• Merox-type processes for the conversion of mercaptans to disulfides.

• Methanation for hydrogen, CO and CO2 reduction via conversion to methane.

• Hydrolysis of carbonyl sulfide to hydrogen sulfide and carbon dioxide.

As previously mentioned, ion-exchange resins have demonstrated significant utility as catalysts in which
acid or base is the catalytic agent. Organic reactions such as condensations, hydrolyses, substitutions and
insertions can in many cases be catalyzed by the addition of acidic or basic reagents. Fixed acid or base
carriers provide several advantages over their homogeneous counterparts:

• Resins are easily separated from the reaction mixture via simple filtration.

• Resins can be utilized in fixed bed configurations, allowing continuous flow operation.

• Corrosion problems are greatly reduced.

• Reactions producing unwanted by-products can be more easily controlled.

• A variety of costly processing steps such as neutralization, precipitation, distillation and extraction
can be eliminated.

• Ion-exchange catalysts can easily be recovered, regenerated and reused.

Conventional gel-type resins are typically used in aqueous systems in processes such as olefin hydration
and ester formation and hydrolysis. Non-aqueous applications use macrorecticular resins. Although they
fall under the category of bulk conversion as opposed to purification processes, the production of MTBE
(methyl tertiary-butyl ether) and TAME (tertiary-Amyl methyl ether), important gasoline blending
components, are good examples of non-aqueous resin-catalyzed reactions.

Another important aspect of catalytic properties of resins is their utility in converting difficult to remove
contaminants into more easily trapped by-products. An example is the removal of organic oxygenates of
medium polarity from hydrocarbon streams. Strongly acidic or basic resins can be used to hydrolyze
esters to their acid and alcohol by-products. Subsequent adsorption of these highly polar oxygenates
yields significantly enhanced effective ester removal capacity over that obtainable without hydrolysis.

18
 10300 Arch Street Pike, Little Rock, Arkansas 72206
ph: 501-888-8690 fax: 501-888-9169

Application Bulletin #2:

Regenerative and Non-Regenerative Fixed Bed
Adsorber Configurations

August 2010
 Application Bulletin #2:
Regenerative and Non-Regenerative Fixed Bed
Adsorber Configurations

OVERVIEW - FIXED BED ADSORBER CONFIGURATIONS

Fixed bed adsorption systems can be designed as regenerative or non-regenerative and configured in a
variety of ways, depending upon situational economics and operating options and flexibility. Porocel
offers a complete line of both regenerative and non-regenerative adsorbents which are application-
specific. The following is a review of these options with advantages, disadvantages, and selection
guidelines offered.

NON-REGENERATIVE SYSTEMS

Single Bed with By-Pass: The simplest configuration of a non-regenerative adsorption system involves
operation of a single bed. When the adsorbent is spent, the bed is by-passed, purged, un-loaded, and re-
charged with fresh material. The re-charged bed is then brought back on-line. Please contact Porocel if
you would like more information regarding this design mode.

Single Bed with By-Pass configuration should be considered when:

• Adsorbent material has a relatively long projected life (>1 year).

• Adsorbent material has good mass transfer characteristics (no low-level adsorbate breakthrough is
suffered early in adsorbent life).

• Downstream process can withstand short periods of exposure to adsorbate.

2
The process flow diagram shown below illustrates typical piping and valve layout for a Single Bed with
By-Pass configuration.

Single Bed with By-Pass

OPEN
FEED
CLOSED

VENT

ADSORPTION
BY-PASS BED

PURGE

EFFLUENT

Parallel Beds with Swing Operation: This configuration uses two beds connected in parallel to each
other. While one bed is in service, the other sits in stand-by. Once the first bed is spent, operation swings
to the second. The first is then purged, un-loaded, re-charged and placed in stand-by. Please contact
Porocel if you would like more information regarding this design mode.

Parallel Beds with Swing Operation configuration should be considered when:

• Adsorbent material has moderate projected life (~<6 months).

• Adsorbent material has good mass transfer characteristics (no low-level adsorbate breakthrough is
suffered early in adsorbent life).

• Downstream process cannot withstand short periods of exposure to adsorbate.

3
The process flow diagram shown below illustrates typical piping and valve layout for a Parallel Bed
configuration:

Parallel Beds with Swing Operation

OPEN
PURGE
CLOSED
FEED

BED BED
#1 #2

EFFLUENT

VENT

Series Beds with Lead/Lag Configuration: This configuration uses two beds connected in series with
both being on-line. The first, or lead bed, is monitored for unacceptable adsorbate breakthrough, at which
time it is taken off-line and re-charged. The second, or lag, bed stays on-line and becomes lead. The first
bed, once re-charged, is brought back on-line in the lag position. Please contact Porocel if you would
like more information regarding this design mode.

Series Beds with Lead/Lag configuration should be considered when:

• Adsorbent material has moderate projected life (>6 months).

• Adsorbent material has poor mass transfer characteristics (low-level adsorbate breakthrough is
suffered early in adsorbent life).

• Downstream process cannot withstand any period of exposure to adsorbate.

4
The process flow diagram shown below illustrates typical piping and valve layout for Lead / Lag
configuration:

Series Beds with Lead/Lag Configuration

FEED

OPEN

CLOSED

LEAD LAG
BED BED

EFFLUENT

5
REGENERATIVE SYSTEMS (THERMAL SWING)

Regenerative adsorption systems will commonly use two beds, with one operating in the adsorption mode
while the second is being regenerated. Porocel’s Dynocel 628, for the regenerable removal of CO2 or
H2S from process streams, would be an example of a product designed for this mode of operation.
Thermally regenerative systems use heat to desorb the concentrated adsorbate species from the adsorbent
media once the adsorbent bed is used to capacity. Different sources for the regen stream may be used. A
typical thermally regenerative adsorption system will follow the sequence of cycles described below:

• Adsorption Cycle - The adsorption bed is actively adsorbing the targeted components from the
process stream. Flow direction through the bed may be dictated by several process variables, but is
usually determined by the fixed bed pressure drop profile.

• Drain Cycle (Liquid Service Only) - The adsorption bed is drained of liquid phase material to assist
in facilitating subsequent regeneration cycles. The drain cycle is downflow to take advantage of
gravity and may be assisted by regeneration gas pressure.

• Heat Cycle - Adsorbed material is removed, or desorbed, from the adsorbent bed by introduction of a
heated gaseous stream. The regen stream may be a slipstream of the process stream or some alternate
stream. Heat Cycle flow runs counter-current to adsorption flow to maximize regeneration efficiency.

• Cool Cycle - The adsorption bed is cooled by the unheated regeneration stream, bringing the bed
down to Adsorption Cycle temperatures. Cool Cycle flow runs co-current to adsorption flow to avoid
"back-loading" the bed with adsorbate or other contaminants.

• Fill Cycle - The adsorption bed is slowly filled with process stream material to complete cooling,
purge the bed of regen material, and generally ready it for being brought back on-line. Fill Cycle
flow runs co-current to adsorption flow to avoid "back-loading" the bed with adsorbate.

• Standby - The newly regenerated adsorption bed stands idle, filled with process fluid, waiting to be
brought on-line.

• Parallel Adsorption (Pressure Equalization) Cycle - The newly regenerated adsorption bed is
slowly brought on-line in parallel with the bed in the Adsorption Cycle. The two are run in parallel
for several minutes to allow pressure equalization before the used bed is taken off-line for
regeneration.

Closed Loop Regeneration - Feed Recycled to Feed: This configuration uses a slipstream of the
adsorption unit feed to regenerate the adsorbent bed. The regen stream is heated to desorb material off
the bed, then cooled to condense and knock-out the bulk of the desorbed material before being tied back
into the main process feed downstream of the take-off point (typically around a control valve to take
advantage of the pressure drop driving force). The return tie-in is upstream of the active bed, allowing the
regen stream material to be processed through the bed operating in the Adsorption Cycle.

Advantages of the closed loop configuration include no loss of process throughput, and process protection
from external contamination.

Disadvantages include regeneration with unpurified feed and resultant adsorbate residual on the adsorbent
(i.e. effective loss in adsorbent capacity), and possible contaminant concentration in the process feed if
adequate adsorbate knock-out and removal from the regen stream is not possible.

The process flow diagram shown below illustrates typical piping and valve layout for a Closed Loop
Regeneration system. Please contact Porocel if you would like more information regarding this
design mode.
6
 Closed Loop Regeneration
(Feed Recycled to Feed - Configuration #1)

PROCESS EFFLUENT

REGENERATING
COOLER HEATER
ADSORBING

KNOCK-OUT

DRAIN

FEED
PROCESS FEED
DRUM

7
 Closed Loop Regeneration
(Feed Recycled to Feed - Configuration #2)

PROCESS EFFLUENT

REGENERATING
COOLER
ADSORBING

HEATER

KNOCK-OUT

DRAIN

PROCESS FEED
FEED
DRUM

8
Closed Loop Regeneration - Product Recycled to Feed: This configuration is similar to the other
Closed Loop methods, with the difference being the use of a slipstream of the purified product as the
regen stream material.

Advantages include process protection from external contamination, optimum regeneration efficiency,
and maximum adsorbent recovery due to minimum adsorbate residual being left on the adsorbent media.

Disadvantages include a required increase in unit throughput to balance regeneration requirements, and
possible contaminant concentration in the process feed if adequate adsorbate knock-out and removal from
the regen stream is not possible.

The process flow diagram shown below illustrates typical piping and valve layout for a Closed Loop
Regeneration utilizing product recycled to feed. Please contact Porocel if you would like more
information regarding this design mode.

9
 Closed Loop Regeneration
(Product Recycled to Feed)

PROCESS EFFLUENT

REGENERATING
COOLER HEATER
ADSORBING

KNOCK-OUT

DRAIN

FEED
DRUM PROCESS FEED

Open Loop Regeneration - Alternate Purge Stream: This configuration utilizes an alternate purge
stream, separate from the process, to effect regeneration. Common alternate stream sources are ambient
air, plant nitrogen, or fuel gas. Please contact Porocel if you would like more information regarding
this design mode.

Advantages include isolation from the process, and greater flexibility in the control of regeneration
conditions (pressure, temperature, and flow rate).

Disadvantages include the possible introduction of contaminants into the process from the regen stream
source, and extra hardware and controls required for regen system operation.

10
The process flow diagram shown below illustrates typical piping and valve layout for an Open Loop
Regeneration utilizing an alternate purge stream.

Open Loop Regeneration

(Alternate Purge Stream)

PROCESS EFFLUENT

REGENERATING
COOLER HEATER
ADSORBING

KNOCK-OUT

VENT

DRAIN

ALTERNATE STREAM

FEED
DRUM PROCESS FEED

11
 10300 Arch Street Pike, Little Rock, Arkansas 72206
ph: 501-888-8690 fax: 501-888-9169

Application Bulletin #6:

Molecular Sieve

November 2014
 Application Bulletin #6:
Molecular Sieve

OVERVIEW
Molecular sieves are a group of either naturally occurring or synthetic (man-made) aluminosilicate
materials. Synthetic aluminosilicate is combined in such a way that distinct crystal structures called
sodalite cages are formed.
The sodalite cages are constructed of alternating alumina (AlO4-)
and silica (SiO4-) molecules. When sodalite cages are linked
together molecular sieve crystals are formed. Different molecular
sieve crystals are formed based on how the sodalite cages are
attached to each other. Molecular sieve crystals have a large internal
cavity with uniform pore openings.

The large cavity of the

molecular sieve crystal houses
cations. The cations typically
present in synthetic molecular
sieves are either potassium, sodium or calcium. The cations housed
in the cavity of the zeolite crystal determine the effective pore
diameter of the zeolite crystal and give the molecular sieve its
adsorptive potential.
For example, Type A zeolite containing potassium (K), also known as
Potassium A (KA), has a pore diameter of 0.29nm (2.9 Å) while Type
A containing calcium (Ca), also known as Calcuim A (CaC), has a
pore diameter of 0.49nm (4.9 Å). The significance of this
characteristic is that molecular sieve can be used to separate chemical species based upon the critical
molecular diameter of the chemical species. The table below highlights the molecules that will be
adsorbed or rejected by the various types of molecular sieve.

Molecular Sieve Molecules Adsorbed Molecules Excluded

3A – 2.9Å H2O, NH3, He CH4, CO2, C2H4, H2S
4A – 4.2Å All of the above and CO2, H2S, C2H4 C3H8, C2H5SH, C6H6
5A – 4.9Å All of the above and C3H8, C2H5SH, n-paraffins C6H6, i-paraffins
13X – 10.8Å less than 10.8Å in diameter more than 10.8Å in diameter

Besides determining the pore diameter of the crystal, the cations also provide charged adsorption sites.
The polarity of a chemical species will affect the molecular sieve capacity for that species. Water, with a
dielectric constant of 80, is one of the most polar chemicals known and is also one of the most strongly
absorbed species.
The concentration of the chemical species also influences the molecular sieve capacity for that species.
Generally, the higher the concentration the higher the molecular sieve capacity for that species but only to
a point. Once the molecular sieve’s maximum equilibrium loading capacity has been reached, its capacity
for that species will not increase even if the concentration of the species increases.

Application Bulletin #6 2
November 2014
MOLECULAR SIEVE TYPES
The most common synthetic molecular sieves used in adsorption applications fall into 2 general classes:

Molecular Sieve Type A Structure

Type A molecular sieve is cube shaped. Each of the 6 faces of the

Type A crystal contains a pore opening. The diameter of this pore
opening is determined by the cations that occupy the zeolite crystal
cavity.

Molecular Sieve Type X Structure

Type X molecular sieve is elliptical shaped. Each of the 3 faces

of the Type X crystal contains a pore opening. The diameter of
this pore opening is determined by the cations that occupy the
zeolite crystal cavity.
.

Table 2: Type A and Type X Molecular Sieves

Molecular Sieve Type Cation Crystal Type Pore Diameter

+
Type 3A (KA) Potassium (K ) A 2.9 Angstroms
+
Type 4A (NaA) Sodium (Na ) A 4.2 Angstroms
Type 5A (CaA) Calcium (Ca2+) A 4.9 Angstroms
Type 13X (NaX) Sodium (Na+) X 10.8 Angstroms

MOLECULAR SIEVE PARTICLE SHAPE AND SIZE

When first produced, synthetic molecular sieve is a powder. Some applications for molecular sieve are
able to use molecular sieve powder but most industrial molecular sieve applications, and especially those
adsorption applications in the hydrocarbon processing industry, require that the molecular sieve be a
larger sized shape. The larger shaped sizes used in adsorption applications are formed when binders are
added to the molecular sieve powder. These binders allow the formation of spherical and extrudate
molecular sieve shapes and these are the shapes commonly used in adsorption applications. Molecular
sieve users will often have a preference to use either the spherical (bead) or extruded (pellet) shape. It is
for this reason that Porocel offers molecular sieve in both shapes. Porocel feels that, in some applications,
beads or pellets might be preferred but the customer’s preference will always be considered.

Application Bulletin #6 3
November 2014
Typically molecular sieve beads and pellets are provided in either 1/16 inch diameter or 1/8 inch diameter
sizes. Depending on the application either size, or a combination of both, can be used. Typically, liquid
phase adsorption applications use 1/16 inch molecular sieve and vapor phase adsorption applications use
1/8 inch molecular sieve. 1/16 inch diameter molecular sieve demonstrates a higher adsorption pressure
drop than 1/8 inch molecular sieve but a lower regeneration gas rate may be used. 1/8 inch diameter
molecular sieve provides a lower adsorption pressure drop then 1/16 inch molecular sieve but a higher
regeneration gas rate will be required. Due to its smaller diameter, 1/16 inch molecular sieve provides
improved mass transfer versus 1/8 inch molecular sieve. Porocel will consider all of the process
parameters and provide an optimized design and molecular sieve loading configuration whether for a
grassroots or an existing adsorption system.
INFLUENCE OF ADSORBATE PROPERTIES ON MOLECULAR SIEVE ADSORPTION
As previously stated, the molecular sieve affinity for the adsorbate (the species to be adsorbed) is based
upon 3 factors; adsorbate polarity, adsorbate critical diameter and adsorbate concentration. Table 3 lists
molecules common in the hydrocarbon processing industry, their critical molecular diameters and pure
component dielectric constants.

Table 3: Critical Diameters and Dielectric Constants for various molecules

Critical
Molecular Dielectric
Adsorbate Molecule Diameter
Symbol/Formula Constant (ϵ)
(Å)
Water H2O 2.6 80
Methanol CH3OH 3.3 33.6
Ethanol C2H5OH 4.5 24.3
Ammonia NH3 3.8 16.9
Hydrogen Sulfide H2S 3.6 9.2
Ethyl Mercaptan C2H5SH 5.1 6.9
Thiophene C4H4S 5.3 2.7
1,3-Butadiene C4H6 5.2 2.6
Carbon Disulfide CS2 3.8 2.6
Benzene C6H6 5.9 2.3
Propylene C3H6 4.6 1.8
Carbon Dioxide CO2 3.8 1.6
Oxygen O2 2.8 1.5
Nitrogen N2 3.4 1.4
Hydrogen H2 2.6 1.2
Carbon Monoxide CO 3.5 -
Acetylene C2H2 3.0 -
Ethylene C2H4 4.2 -

Due to the electric fields created by the cations inside the molecular sieve cavities, significant, induced
dipoles can be caused in olefins and other molecules. The induced dipoles will cause the otherwise
nonpolar molecules, such as olefins, to behave as polar molecules and exhibit molecular polarity. A
significant heat of adsorption may be observed if such molecules are adsorbed by the molecular sieve and
this is certainly the case with olefins. In order to avoid operating problems, a molecular sieve with a pore
diameter smaller than the critical diameter of the olefin should be used in order to prevent the significant
heat release caused by the heat of adsorption of the olefin. The use of a preload step will be required to
Application Bulletin #6 4
November 2014
control the heat of adsorption of the olefin if it is necessary to use a molecular sieve to remove an
adsorbate that will also adsorb the olefin. It is the inducement of dipoles which might cause the
competitive adsorption between two molecules that might be expected to be easily separated.
Molecular sieves affinity for a particular adsorbate is also based on the concentration of the adsorbate in
the process stream. Especially for vapor phase systems, the higher the adsorbate concentration the higher
the molecular sieve capacity for that adsorbate. It is possible that a less polar adsorbate with a higher
concentration might be preferentially adsorbed versus a more polar adsorbate with a lower concentration.
Isotherms are often used to graphically represent a molecular sieve’s pure component capacity for an
adsorbate where no preferential adsorption is possible. Isotherms depict the adsorptive capacity at varying
temperatures and pure component concentrations.

Example of Pure Component Isotherm

T1

T2

T3

Decreasing Process Temperature

Capacity on Adsorbent
Adsorbate Loading

T4

T5

Increasing Adsorbate Concentration

Adsorbate Concentration In Process Fluid

(ex: partial pressure, %RH, ppm)

The above isotherm illustrates the factors mentioned below that influence molecular sieve capacity.

 Adsorbate Concentration 
higher concentration = higher partial pressure = higher adsorbent loading 
 Process Temperature
lower temperature = higher adsorbent loading
 Process Pressure (for vapor phase only)
higher pressure = higher partial pressure = higher adsorbent loading 

Application Bulletin #6 5
November 2014
Common molecular sieve applications are summarized in Table 4.

Table 4: Molecular Sieve Application Summary

Industry Application Sieve Type(s)

Petrochemical Olefin (monomer) dehydration 3A
Olefin (monomer) purification 13X
Co-monomer and solvent purification 13X
Oil Refining Dehydration of miscellaneous vapor and liquid phase streams 3A, 4A
H2S, COS, CO2 and mercaptan removal from miscellaneous
5A, 13X
vapor and liquid phase streams
Oxygenate removal 13X
Natural Gas Processing Dehydration 4A
H2S and CO2 removal 5A
Mercaptan removal 13X
LNG Plants Feed pretreatment 4A, 5A, 13X
Ethylene Plants Cracked gas dehydration 3A
Hydrogen purification 4A, 5A
Acid gas removal from feed and product streams 13X
Ethanol Production Bulk water removal at ethanol/water azeotrope 3A
Drying and purification of ethanol product 3A, 4A
Hydrogen Production General drying and purification via PSA and TSA 4A, 5A
Ammonia Production Purification of natural gas feed 4A, 5A, 13X
Drying and purification of reformer gas prior to ammonia
3A, 4A
loop
Treating of ammonia off-gas streams 4A
Air Separation Drying and CO2 removal from air to a cryogenic unit 4A, 5A, 13X
Drying and purifying high purity O2, N2, Ar, CO2 and blended
4A, 5A, 13X
gases
Separation of oxygen from air via PSA or VSA 3A
Chemical Storage Underground cavern drying and treating 4A, 13X
Storage tank drying and treating 4A, 13X
Product recovery from vent streams 5A, 13X

MOLECULAR SIEVE ADSORPTION

Molecular sieves are particularly useful to remove polar molecules from paraffinic or olefinic
hydrocarbon process streams. An operational concern with the use of larger pore molecular sieves, such
as 13X, is the requirement of a pre-load step prior to its application in an olefinic process stream.
Molecular sieve adsorbents have a very small useful adsorption capacity for acidic molecules (H2S, CO2,

Application Bulletin #6 6
November 2014
COS, etc.) in olefinic process streams so promoted activated alumina or promoted activated
alumina/molecular sieve blended adsorbents are typically used to remove these contaminants from
olefinic process streams.

Molecular sieves are typically

utilized in dual bed adsorption
systems with one adsorber bed in
the adsorption cycle and the other
adsorber bed in the regeneration
cycle. The 2 adsorber beds will
switch back and forth between the
adsorption and regeneration
cycles at some frequency
typically determined by the
duration of the adsorption cycle.

After some period of time,

usually 3 to 5 years or more, the
spent molecular sieve will be replaced with fresh molecular sieve. It is beneficial to consider the current
or future operational requirements of the adsorption unit prior to reloading so that the fresh molecular
sieve, or combination of adsorbents, can be tailored to meet the expected demand on the adsorption unit.

POROCEL PRODUCTS
Porocel offers various grades of molecular sieve and will make adsorbent and operating recommendations
based on your unique application. A general description of Porocel’s molecular sieve products is listed
below.

Dynocel 641
Shape Spherical or Extrudate
Size 1/8” or 1/16” (3.0mm or 1.5mm)
Minimum Equilibrium Water Capacity, wt% 26
Heat of Adsorption, BTU/lb H2O 1800
Used to remove water, mercaptans, oxygenates, high molecular
weight sulfur compounds and other contaminants from vapor
phase and liquid phase olefinic hydrocarbons.
Application
Dynocel 641 is used to remove water, carbon dioxide,
hydrogen sulfide, oxygenates, mercaptans, high molecular
weight sulfur compounds and other contaminants from vapor
phase and liquid phase paraffinic hydrocarbons.
Preload Step Required Yes
Dynocel 643
Shape Spherical or Extrudate
Size 1/8” or 1/16” (3.0mm or 1.5mm)
Minimum Equilibrium Water Capacity, wt% 20.5
Heat of Adsorption, BTU/lb H2O 1800
Used to dehydrate vapor phase and liquid phase olefinic
Application
hydrocarbons.
Preload Step Required No

Application Bulletin #6 7
November 2014
 Dynocel 644
Shape Spherical or Extrudate
Size 1/8” or 1/16” (3.0mm or 1.5mm)
Minimum Equilibrium Water Capacity, wt% 21.5
Heat of Adsorption, BTU/lb H2O 1800
Used to dehydrate various vapor phase and liguid phase process
Application streams such as air, natural gas, carbon dioxide, hydrogen,
oxygen, refrigerants, solvents, etc.
Preload Step Required Yes
Dynocel 645
Shape Extrudate
Size 1/8” or 1/16” (3.0mm or 1.5mm)
Minimum Equilibrium Water Capacity, wt% 21.5
Heat of Adsorption, BTU/lb H2O 1800
Dynocel 645 is used to dehydrate and desulfurize vapor phase
Application
and liquid phase hydrocarbons.
Preload Step Required Yes

Porocel offers a comprehensive range of purification adsorbents and technical services. We would
appreciate the opportunity to be of service.

For more information please contact your local Porocel representative or contact us at www.porocel.com.

Application Bulletin #6 8
November 2014
 10300 Arch Street Pike, Little Rock, Arkansas 72206
ph: 501-888-8690 fax: 501-888-9169

Application Bulletin #12:

Adsorber Loading/Startup and Shutdown/Unloading
Guidelines

June 2015
 Application Bulletin #12:
Adsorber Loading/Startup and Shutdown/Unloading
Guidelines

Porocel activated alumina is generally packaged in 2,000 LB (907 KG) supersacks, 100-400 LB (45-180
KG) steel drums or 50-100 LB (22-45 KG) bags, loaded and shipped on pallets. Porocel molecular sieve
is generally packaged in 2,205 LB (1,000 KG) supersacks, 100-400 LB (45-180 KG) steel drums loaded
and shipped on pallets. Porocel uses high-quality, robust containers and pallets. Besides the protection
provided by the container, Porocel products are typically shipped with a protective sheathing which adds
an additional safeguard to protect the products during shipping. Some Porocel activated alumina is
shipped in pneumatic trucks.

STORAGE

Porocel adsorbents should be stored using means to protect it from the atmosphere and the environment.
Most adsorbents are hydrophilic so have the affinity to adsorb moisture. Care should be taken to ensure
that the containers remain intact and unopened. Tears and punctures in the container may allow the
product to become contaminated. Additionally, any contact with liquid water should be avoided.
Keeping the containers away from direct contact with the ground is very important. The containers
should be stored on their original shipping pallet or something similar. The containers should be kept
high and dry.

It is preferable to store the containers indoors. If indoor storage is unavailable, the containers stored
outside should be covered by a tarpaulin.

Prior to use, the containers should be inspected and any debris (dust, feathers, etc.) or moisture that may
have collected on the top of the containers should be removed.

FIXED BED ADSORBER LOADING

Proper configuration and loading of fixed bed adsorbers is critical to achieving optimal performance and
service life. The following is a review of adsorber vessel loading configurations and guidelines then
followed by adsorber vessel basic loading guidelines. The information presented here is general in nature
and intended only as guidelines. Porocel technical service will be happy to review and comment on your
detailed adsorber vessel loading and unloading procedures.

Adsorber vessel loading configurations and guidelines

 For gas phase service, adsorbent media size is typically 5x8 mesh or nominal 1/8” (3mm) diameter.
For liquid phase service, adsorbent media size is typically 7x14 mesh, or nominal 1/16” (1.5mm)
diameter. Media can be granular, spherical, or cylindrical extrudate, depending upon the adsorbent
used.

 Adsorbents often require support by larger sized media to prevent support screen blinding and media
loss through screens and support grates, etc. Support media should be loaded to a minimum depth of
3” (75 mm) per layer, with layers graded such that no transition is greater or less than 1/2 the
diameter between adjacent layers in order to prevent media migration. The support media in direct

2
 contact with the fixed support grate should be at least twice the diameter of the largest screen or
support structure opening.

 For adsorber vessels without fixed support grating – the initial layer of large sized support media
used to fill the adsorber vessel bottom head should fill the bottom head to at least 6” (150mm) above
the top of the flow distributor then spread evenly and leveled before the next support layer is added.

 For adsorber vessels with fixed support grating – a wire cloth screen may be installed directly on
top of the fixed support grate to minimize media migration. Wire cloth screen specifications should
indicate a 4 mesh wire cloth screen followed by a 20 mesh wire cloth screen both constructed of
stainless steel wire.

The 4 mesh wire cloth screen may be cut such that its diameter is equal to or slightly larger than the
adsorber vessel internal diameter. Wire cloth screen specifications should indicate a 4 mesh wire cloth
screen constructed of 0.092" (2.3mm) diameter stainless steel wire. The 4 mesh wire cloth screen
should be tied to the fixed support grate using stainless steel tie wire. If the wire cloth screen has to be
constructed of multiple pieces of wire cloth the pieces of wire cloth should overlap by 6” (150mm)
then tied with stainless steel wire.

The 20 mesh wire cloth screen should be cut such that its diameter is 12” (300mm) larger than the
adsorber vessel internal diameter. Wire cloth screen specifications should indicate a 20 mesh wire
cloth screen constructed of 0.016" (0.4mm) diameter stainless steel wire. If the wire cloth screen has
to be constructed of multiple pieces of wire cloth the pieces of wire cloth should overlap by 6”
(150mm) then tied with stainless steel wire. The 6” (150mm) overlap will provide a cradle for the
support media and prevent media migration.

20 mesh wire cloth is the smallest sized wire cloth that should be installed in an adsorber vessel.
Wire cloth with openings smaller than 20 mesh may act as a particulate trap causing an
artificial yet excessively high pressure drop that could affect performance or require the
adsorbent to be replaced.

 Each support media layer should be spread evenly and level across the adsorber vessel cross section
before the next layer of support media or adsorbent is loaded. Uneven layering of the support media
or adsorbent may lead to channeling of the process flow causing poor performance of the adsorber.

 If the support media layers cannot be evenly spread and leveled across the adsorber cross section then
a minimum depth of 6” (150 mm) of support media should be loaded. The additional amount of
support media should ensure some covering of the layer immediately below.

 Whether or not top support media is installed the top of the adsorbent should be evenly spread and
leveled across the adsorber cross section.

 A wire cloth screen may be installed directly on top of the adsorbent media layer to serve as hold-
down to minimize media migration that can be caused by flow impingement. Wire cloth screen
specifications should indicate a 20 mesh wire cloth screen constructed of 0.016" (0.4mm) diameter
stainless steel wire.

 The wire cloth screen should be cut such that the diameter is 12” (300mm) larger than the adsorber
internal diameter. If the wire cloth screen has to be constructed of multiple pieces of wire cloth the
pieces of wire cloth should overlap by 6” (150mm) then tied with stainless steel wire. The 6”
(150mm) overlap will provide a cradle for the support media and prevent media migration.

 Topping support media should be placed on top of the wire cloth screen. A 6" (150 mm) layer of 1/2”
(13mm) diameter inert support media is typically sufficient.
3
 A headspace of 3 feet (900mm) is recommended between the upper distributor and top bed layer in
order to minimize flow impingement and adsorbent disruption.

Example of Adsorber Vessel Bottom Support Structure

1/16" (1.5mm) Bulk Adsorbent Media

3" (150mm) of 1/8" (3mm) Support Media

3" (150mm) of 1/4" (6mm) Support Media
3" (150mm) of 1/2" (13mm) Support Media
Fixed Support Grate with 6” (150mm) overlap
wirecloth screen
3' (900mm) Void Space

Flow Distributor

FIXED SUPPORT GRATE RECOMMENDATIONS

SS SCREEN
(20 MESH, .016" WIRE, ROUND WEAVE)

SS SCREEN
(10 MESH, .025" WIRE, ROUND WEAVE)

SS SCREEN
(4 MESH, .054" WIRE, ROUND WEAVE)

SUPPORT GRID

FIXED SUPPORT CONFIGURATIONS: SUPPORT GRID vs. NO SUPPORT GRID

Pros Support Grid Cons

Ease of unloading fixed bed media Lack of easy access to bottom head volume
Less problems with pressure drop Reduction in usable active volume
Larger solid/fluid disengagement cross-sectional area
Ease of optimizing support media layer(s)
Good fluid disengaging volume

Pros No Support Grid Cons

Ease of access to bottom head volume Increased difficulty in complete removal of fixed bed media
Allows use of more vessel volume for active media No fluid disengaging volume
Necessity of filling vessel head with support media
Bottom head volume not easily serviced "garbage" trap
Flow restriction at outlet port --> pressure drop
Smaller solid/fluid disengagement cross-sectional area

4
 Example of Adsorber Vessel Top Support Structure

Flow Distributor

3' (900mm) Headspace

6" (150mm) of 1/2" (13mm) Support Media

Wire cloth Screen with 6” (150mm) overlap

1/16" Bulk Adsorbent Media

 Typically, both the adsorber top and bottom support media can be either inert or active material,
depending upon the application. Active support, such as Porocel's Durocel 242, may provide
additional adsorber capacity in some processes. Examples of situations where active support material
may be utilized:
 Most non-regenerative adsorption applications, including Sulfur Guard Beds, HF Alkylation
Defluorinators, and Distillate Treaters.
 Regenerative adsorption applications, including Air Dryers, CO2 and H2 Dryers, LPG Dryers,
Alky Feed Dryers, Isom Feed Dryers, and Sulfur Guard Beds.
 Catalytic processes in which activated alumina is used as the primary catalyst, including Claus
Units and HF Alkylation Defluorinators.

PLEASE REFER TO POROCEL APPLICATION BULLETIN #26 Bed Support Products and
Usage Guidelines FOR ADDITIONAL DETAILS RELATING TO BED SUPPORTS.

Adsorber vessel basic loading guidelines

 It is considered best industry practice to take outages during the loading of any fixed bed process
vessel. Outages will help to ensure the proper loading of an adsorbent vessel and may even help with
troubleshooting if necessary at some later date. All outages should be made from the same reference
point such as the top flange. A handy place to record outages is on the loading diagram that has been
supplied by the adsorbent manufacturer.
 The adsorber vessel should be visually inspected to ensure that the adsorber vessel is clean and free of
any debris or dust that may have collected during construction (if a new unit) or during inspection (if
an existing unit) and especially if any repairs or modifications were made to the adsorber vessel
during the shutdown or turnaround.
 The fixed bed grate or bottom flow distributor, as appropriate, should be inspected to ensure that it is
been properly installed and that is in good repair. Supply should be checked that rope insulation is on
hand for installation with the fixed bed grate.
 If equipped, thermocouples, sample ports, etc. should be inspected to ensure that they are in good
repair.
 If applicable, the 4 mesh wire cloth screen should be installed in tied to the fixed bed grate. The 20
mesh wire cloth screen would then be installed.

5
 Bottom support media should be loaded through a lower manway or lowered in containers into the
vessel and spread evenly and leveled across the adsorber cross section before the next layer of support
media or adsorbent is loaded. If the bottom support media is being loaded into a 20 mesh screen it is
important to load the support media around the edge of the adsorber vessel first to help hold the 20
mesh screen in place before all of the initial support media layer is added. Care should be taken to
ensure that the 20 mesh wire cloth screen is held against the adsorber vessel wall by the support
media and not allowed to fold over.
 Most spherical, granular and extruded adsorbent can withstand a freefall of ~20 feet (~6 to 7 meters)
without suffering damage. However, this will vary from adsorbent to adsorbent and should be
verified by the manufacturer. Typically, the bulk of the adsorbent may loaded by controlled dumping
through a top manway or through a loading port. The use of a loading sock with the discharge end
maintained 1 to 3 feet (0.3 to 1.0 meter) above the bed, is preferred. Granular materials should be
progressively dispersed and leveled across the vessel cross section to avoid uneven distribution. Once
loaded, the top of the adsorbent bed should be spread evenly and leveled.
 A 20 mesh wire cloth screen should be laid on top of the adsorbent.
 Top support media should be loaded using the same procedures as the bottom support media. The top
support media should be spread evenly and leveled prior to vessel closure and start-up.

PNEUMATIC LOADING GUIDELINES

System configuration or operating convenience may dictate pneumatic conveyance as the method of
choice for vessel loading. While not recommended due to its inherent detrimental aspects (increased
media attrition, dust generation, etc…), pneumatic loading can be effective if specific guidelines are
adhered to. In general, loading conditions are adjusted and maintained to promote “plug flow” as
opposed to “dispersed flow” during media transport:

Plug Flow

Dispersed Flow

Dispersed flow will yield:

 Greater media attrition

 Increased dust generation

6
 Higher pressure drop
 Loss of media
 Decreased operating efficiency

Plug flow will yield:

 Less media attrition

 Decreased dust generation
 Lower pressure drop
 Less loss of media
 Increased operating efficiency

The following illustrates a typical pneumatic loading configuration:

Typical Pneumatic Loading Schematic

(8)

Blower
Intake (6)

Blower Tank

(2)
(3)
(7)
Blower (1)
Discharge Line

(8)
(5) (4)

General guidelines for pneumatic loading:

1) The Product Butterfly Valve should be set at 100% open AT ALL TIMES during material
transport and loading.

2) The ideal Product Loading Rate is ~650 to 700 pounds per minute (~295 to 320 kg/min),
depending upon product density variation. This approximates maximum product flow density for
near-plug flow conditions.

3) The Optimum Blower Rate is ~300 CFM for a 4 inch diameter hose. This corresponds to ~1000
rpm on the Power Take-Off Drive.

4) Line Pressure should be maintained at 8 to 10 psi (0.56 to 0.7 kg/cm²) for most applications
conveying 30 to 50 feet (9 to 15 meters) vertically. Just enough pressure should be used to create
a SLIGHT HOSE SURGE or jump with the Butterfly Valve fully open.

7
 5) The Line Pressure should be adjusted by venting the Blower Discharge Line.

6) Tank Pressure is typically maintained at 1 to 2 psi (~0.1 kg/cm²) above Line Pressure,
depending upon vertical height. This pressure differential can also affect hose surge and should
be adjusted accordingly.

7) Clear Plastic Hoses should be used for material transport to allow visual monitoring of the
transfer. Stainless Steel Hoses should NEVER be used. Steel hoses will aggravate material
attrition and breakage. The length of hose should be minimized and the hose should be kept
straight and free of twists and kinks.

8) All Hose Bends should be long-radius (3 foot minimum).

FIXED BED ADSORBER STARTUP

The startup procedures for a fixed bed adsorber filled with an adsorbent such as activated alumina or
molecular sieve is straightforward, in most cases requires only standard safety precautions. The
information presented here is general in nature and intended only as guidelines. Porocel technical service
will be happy to review and comment on your detailed startup procedures.

 Once the adsorber vessel is loaded in accordance with previous recommendations, all flanges and
valves should be closed or blinded, ensuring isolation from both ambient air and the process.

 If the adsorber is to be operated in air service, care need not be taken to remove entrained air
(oxygen) from the unit.

 If the service is sensitive to oxygen (ex: hydrocarbon, hydrogen), care must be taken to reduce
entrained oxygen levels down to acceptable levels. This is most readily accomplished by either of the
following two methods:

1) The adsorber vessel can be cycled through a sequence of pressurizations/depressurizations until

oxygen levels are deemed acceptable. Common gases used are the process feed, regeneration gas
or nitrogen. The first pressurization should be to ~15 psig (1 kg/cm²g), holding for ~5 minutes,
followed by venting to ~1 psig (~0.07 kg/cm²g). The second pressurization should be to ~30 psig
(2 kg/cm²g), again holding for ~5 minutes, followed by venting to 1 psig (0.07 kg/cm²g). Two
pressurization/depressurization cycles are typically adequate. Vent gas should be monitored for
oxygen with an appropriate analyzer. Acceptable levels should be in accordance with plant safety
guidelines, with maximum oxygen levels measuring well below explosion thresholds. If
necessary, additional cycles should be performed until specifications are met. Vented gas is
typically sent to the fuel gas or flare systems.

2) The adsorber vessel can be purged with nitrogen or other acceptable gas to remove entrained
oxygen. A minimum purge rate to achieve a pressure drop of 0.02 psi per foot is necessary to
avoid channeling of the purge gas. If the purge flow direction is upward a maximum purge rate
to achieve a pressure drop of 0.21 psi/ft (0.016 kg/cm2) must be avoided to prevent fluidization of
the adsorbent. Channeling of the purge gas will yield an ineffective purge and fluidization of the
adsorbent will most likely require the adsorber vessel to be reloaded. Effluent gas should be
monitored for oxygen with an appropriate analyzer. Acceptable levels should be in accordance
with plant safety guidelines, with maximum oxygen levels measuring well below explosion
thresholds. Purge should continue until specifications are met. Purge gas is typically sent to the
fuel gas or flare systems.

8
 After the adsorber vessel is adequately purged, the process stream can be introduced and brought up
to pressure. It is common for an exotherm to be realized upon initial charging of a fresh adsorber
with process feed. This is due to the heat of adsorption of various components in the process stream.
This exotherm can result in adsorber bed temperatures temporarily rising as high as ~150F (~65C),
but will quickly dissipate. If this temporary temperature elevation is a concern to downstream
operations, the process stream can be temporarily routed to the regeneration cooling system, fuel gas
or flare systems. A temporary increase in feed flowrate will also assist in dissipating the heat of
adsorption more quickly.

In olefinic service, the initial heat of adsorption exotherm is of particular concern due to the danger of
promoting exothermic reactions such as olefin polymerization or olefin hydrogenation. In these
cases, the exotherm can be mitigated by incorporation of a pre-loading step. For example, the olefinic
feed can be slowly bled in with nitrogen to maintain the adsorber vessel temperature below a certain
threshold until the adsorber bed is fully pre-loaded with olefin. Alternatively, the final stages of the
regeneration cooling step can be performed with purified effluent, thereby pre-loading the adsorber
vessel at an elevated temperature. Pre-loading during the cooling step may minimize the heat of
adsorption effects. Porocel should be consulted to determine the best alternative for a specific
application.

 If the adsorber is to be operated in thermally regenerative service, it is common to step the unit
through one regeneration cycle prior to bringing the adsorber vessel on-line although this step is not
required.

ADSORBER VESSEL SHUTDOWN

Adsorption units are shut down for 2 reasons these being either a process outage, either planned or
unplanned, with no maintenance work planned for the adsorption unit or a process outage, either planned
or unplanned, with maintenance work planned for the adsorption unit. The following is presented for the
case where maintenance work is planned for the adsorption unit. The information presented here is
general in nature and intended only as guidelines. Porocel technical service will be happy to review and
comment on your detailed adsorber vessel shutdown procedures.

Hydrocarbon freeing versus adsorbent deactivation

A clear distinction should be made between hydrocarbon freeing an adsorber vessel and adsorbent
deactivation. Described below are 3 methods commonly used to hydrocarbon free an adsorber vessel.
Cautions are provided when the method being discussed does not deactivate the adsorbent. A “spent”
adsorbent may still have the ability to adsorb water when exposed to the atmosphere. Heat will be
released if water is adsorbed from the atmosphere by the spent adsorbent heat. The heat released may be
enough to cause the spent adsorbent to smoke, or even ignite, if other necessary conditions exist. The only
way to ensure that spent adsorbent will not release heat when exposed to the atmosphere is if the spent
adsorbent has been fully deactivated.

Adsorber vessel purging guidelines

Method (i) – Gas Regeneration followed by Nitrogen Purge

Note: Method (i) is intended to free the adsorber vessel of hydrocarbons and not necessarily deactivate
the spent adsorbent. The spent adsorbent when exposed to the atmosphere, especially in high humid
conditions, may adsorb moisture from the environment causing a release of heat. The heat released may
be enough to cause the spent adsorbent to smoke, or even ignite, if other necessary conditions exist.

9
 1) Regenerate the adsorber by heating and cooling with a clean vapor that is free of reactive
materials. If the regeneration gas contains unwanted compounds use nitrogen or an alternate gas.
Test the bed outlet gas for the presence of any unwanted compounds.

2) After regeneration, isolate the adsorber and depressure to atmospheric pressure. Leave the flare
line open and install blind flanges on all inlet and outlet lines.

3) Connect the nitrogen purge source at the opposite end of the adsorber vessel away from the flare
line. Maintain a high enough nitrogen flowrate to achieve a pressure drop > 0.01 psi./ft. to ensure
sufficient flow distribution. Porocel can calculate the required nitrogen flowrate to achieve a
pressure drop > 0.01 psi./ft. upon request.

Alternately, the repetitive pressuring and depressuring of the adsorber vessel with the nitrogen
may effectively purge the adsorber vessel. Consider down flow direction while pressuring and
depressuring through the adsorber vessel to avoid lifting of the support media and adsorbent. The
repetitive pressuring and depressuring of the adsorber vessel is not always a reliable method to
purge the adsorber vessel so should only be considered as your operating experience indicates.

4) Check the purge outlet and maintain the nitrogen purge until the outlet is at an acceptable LEL for
any flammables and any other environmental concerns are negated.

5) A more difficult approach, that may be more effective, is to use nitrogen to cool the adsorber
vessel following the heat step. Cooling and purging the adsorber vessel with nitrogen will prevent
the adsorption of hydrocarbons or contaminants on the freshly regenerated adsorbent.

Method (ii) – Gas Regeneration followed by Water Flooding

1) Regenerate the adsorber vessel by heating and cooling with a clean vapor that is free of reactive
materials. If the regeneration gas contains unwanted compounds use nitrogen or an alternate gas.

2) After regeneration, isolate the adsorber vessel and depressure to atmospheric pressure. Leave the
flare line open and install blind flanges on all inlet and outlet lines.

3) Use water from a source that is safe and compatible with the internal components of the adsorber
vessel. Start filling the adsorber vessel with the water and avoid overfilling it by monitoring the
filling rate and liquid level. A calibrated differential pressure gauge can be used (if available) for
14.7 psi is equal to 34 ft. of water. Another option to check the pressure differential is to have
calibrated gauges at the top and bottom. Since the adsorbent is freshly regenerated a significant
amount of heat (1,800 BTU per pound of water) will be liberated when it is exposed to water. If
too small a flowrate of water is used to flood the adsorber vessel steam will be produced and the
adsorber vessel may heat up. Using a sufficiently high enough flowrate of water to flood the
adsorber vessel will prevent the formation of steam or the adsorber vessel from heating up as the
liquid water will act as a heat sink and control the heat of adsorption at an acceptable level.

A sufficient amount of water should be planned for water flooding. It is best to have a volume of
water available that is equal to 2 empty adsorber vessel volumes per adsorber vessel.

10
 4) After adsorber vessel is completely filled, shut off the water source and flare line, but open a vent
line to the atmosphere to break the vacuum. Drain the adsorber vessel to an approved disposal
location.

5) Pressurize the adsorber vessel with nitrogen with sufficient flow to ensure the outlet is at an
acceptable LEL for any flammables and any other environmental concerns are negated. If
flammables are above the LEL repeat the water flood method and outlet gas monitoring.

Method (iii) – Steam Purging

1) Heat the adsorber vessel with a clean vapor but do not cool the adsorber vessel bed to avoid the
condensation of steam in the adsorber vessel.

2) After the heating step, isolate the adsorber vessel and depressured to atmospheric pressure. Leave
flare line open and install blind flanges on all inlet and outlet lines. Connect the steam source to
the adsorber vessel. Open the steam and maintain a high enough steam flowrate to achieve a
pressure drop of >0.01 psi./ft. to ensure sufficient flow distribution.

3) To ensure that the steam purging is sufficient, complete a nitrogen purge to check the outlet LEL
level. Ensure that the LEL is acceptable and if not reconnect the steam and purge again.

4) Once LEL is low enough, cool the adsorber vessel with nitrogen until the outlet temperature is
<120F.

5) Down flow steam and nitrogen flow is preferred for Method (iii).

ADSORBER VESSEL UNLOADING

Unloading an adsorber vessel is typically a straightforward process. General considerations which should
be made in advance include those for HSE, containment of the spent adsorbent while on-site and disposal
of the spent adsorbent. The unloading guidelines presented below assume that the adsorber vessel has
been hydrocarbon freed. The information presented here is general in nature and intended only as
guidelines. Porocel technical service will be happy to review and comment on your detailed adsorber
vessel unloading procedures.

Adsorber vessel unloading guidelines

 A full review of the HSE considerations should be made and care taken to ensure that all personnel
have been informed of these considerations and that the appropriate PPE has been provided.

 If possible, the top of the adsorbent bed should be visually inspected prior to unloading. Photos and
outages should be taken if the top of the adsorbent bed seems disturbed, unlevel or abnormal in any
fashion. Documenting the condition of the top of the adsorbent bed prior to unloading can be useful
for troubleshooting and process optimization.

 It is most convenient to collect samples of the spent adsorbent while the adsorber vessel is being
unloaded. Please check with Porocel to confirm the suitable sample size and location from which the
spent adsorbent sample(s) should be collected. Spent samples can be useful for troubleshooting and
process optimization.

11
 Once the top of the adsorbent bed has been visually inspected the adsorber vessel can be unloaded by
standard methods (vacuum, gravity dump).

 Periodic inspection of the spent adsorbent should be made as the unloading of the adsorber vessel
proceeds to ensure that little or no heat is being released by the spent adsorbent upon its exposure to
the atmosphere.

 Periodic inspection of the spent adsorbent should be made as the unloading of the adsorber vessel
proceeds to ensure that smoke is not being released by the spent adsorbent, upon its exposure to the
atmosphere.

 The spent adsorbent has the potential to release heat hours or days after it has been unloaded from the
adsorber vessel. Periodic inspection of the spent adsorbent should be made if the spent adsorbent is
being stored in an open top container. An open top container may allow the spent adsorbent to release
heat by adsorbing water from the atmosphere or from other environmental conditions such as rain.

 The spent adsorbent should be disposed of according to local, state and federal requirements.

12
 10300 Arch Street Pike, Little Rock, Arkansas 72206
ph: 501-888-8690 fax: 501-888-9169

Application Bulletin #13:

On-Line Moisture Analysis

August 2010
 Application Bulletin #13:
On-Line Moisture Analysis

OVERVIEW - MOISTURE ANALYZERS IN PROCESS OPERATIONS

Oil refinery and chemical plant operations are often adversely affected by the presence of unacceptable
levels of moisture in various process streams. Even trace concentrations of water can aggravate a variety
of problems, including catalyst poisoning and deactivation, corrosion, and fouling. Specific examples of
refinery applications where low moisture levels are critical include:

• Alkylation Unit Feed

• Isom Unit Feed

• Reformer Hydrogen Streams

• LPG and Propylene Production

• Hydrogen Production

• Carbon Dioxide Production

Since the presence of water directly impacts unit operations and maintenance issues, it is highly desirable
to continuously monitor the moisture levels in these process streams. This is usually accomplished with
the installation of on-line analytical equipment capable of accurately measuring low levels of moisture in
gases and liquid hydrocarbons. Several analyzer types are suitable for this service. The two most
common instrument classes are reviewed here, including general descriptions, installation and operational
guidelines, maintenance issues, common operational problems, and advantages and disadvantages of each
technology. Diagrams relating to each system are included at the end of their respective sections.

MASS DIFFERENTIAL-BASED MOISTURE ANALYZERS

General Description

Analyzers based on change in mass measurements are useful devices for accurately measuring trace
moisture levels in a variety of gaseous and liquid process streams. Suitable liquid streams are essentially
limited to non-polar hydrocarbons. These analyzers cannot be used in applications containing polar
compounds such as alcohols or other species that will interfere with analyzer response to water. All
sample streams must be in the gas phase. In liquid service applications, the sample must first be
vaporized before being introduced to the analyzer system. With proper installation and maintenance,
these analyzers can provide accurate moisture measurements down to the hundreds of parts per billion
range. The primary manufacturer of mass differential-based moisture analyzers is Ametek (formerly a
DuPont subsidiary).

2
Operation Overview

Mass differential-based moisture analyzers are comprised of two distinct parts: the Sensor Unit and the
Control Station. The Sensor Unit and the Control Station are integrated through an electrical cable,
allowing the two units to be up to several thousand feet apart. This permits the Sensor Unit to be installed
in a hazardous sampling location, while the Control Station can be placed in safe area such as an analyzer
shed, control room, etc…

The Sensor Unit works on a water mass principle, with the sensor being a quartz crystal coated with a
hydrophilic membrane. Weight change of the crystal, as determined by water pick-up and release in the
membrane, is reflected in a crystal vibrational frequency shift which, in turn, is converted to a moisture
level reading by the Control Station. See Figure 1A for a functional block flow diagram.

The Analyzer can only be used to measure moisture levels in gases. For liquid applications, the sample
must first be vaporized. The gas stream is processed by the Analyzer system in one of three ways:

(1) Straight Sampling - Sample gas is routed to the Field unit sensor crystal with no pre-treating. This
provides a Sensor response corresponding to a relative moisture level in the gas.

(2) Reference Sampling- Sample gas is passed over a desiccating adsorbent prior to being routed to the
Sensor crystal. This operation provides a base-line Sensor response corresponding to a dry gas
condition.

(3) Calibration Sampling - Dried sample gas is "water-loaded" by passing through a water reservoir
under very accurately controlled temperature and flow conditions prior to being routed to the Sensor
crystal. This provides a gas of known water concentration for use in calibration of the Analyzer.

In typical operation, the Sensor crystal is alternately exposed to a Straight Sample and a Reference
Sample, relaying the raw signal data to the Control Station. The Control Station processes the data,
generating a moisture level reading by measuring the Sensor response difference between the Straight and
Reference samples. This measurement is performed once a minute. See Figure 1B for the gas flow
diagram.

The moisture reading is visually displayed at the Control Station. Analog outputs (current or voltage) are
available. The Analyzer set-up is typically configured to output parts per million by volume (ppmv).
Correct operation and signal output requires the accurate input of the pressure at which the Probe sensor
measurement is taken.

3
Figure 1A: Analyzer Functional Block Flow Diagram
Figure 1B: Analyzer Gas Flow Diagram

5
Installation Guidelines

The Sensor Unit should be installed near the sample source, with upright support available for the dryer
(the dryer must be mounted vertically for proper operation, i.e., avoidance of channeling through the
adsorbent bed). The Sensor Unit can be setup in one of two basic configurations, using either the dried
sample gas or a separate gas source as the reference gas. See Figures 1C and 1D.

In both gas and liquid service, the Sensor must be installed in a sample loop coming off the main process
stream. The tap for the sample line is cut at a 45° angle and installed through a ball valve in a horizontal
section of the process line. The sample tap should extend half way into the line (as shown in Figure 1E)
to minimize exposure to solid contaminants in the process.

In liquid service applications, pressure reduction is used to allow vaporization of the liquid sample. Heat
tracing of the line may be required if condensation of water or heavier hydrocarbons is a concern.

The Analyzer operates under a small back pressure (~ 1 kg/cm²g / 15 psig), which permits exhausting to a
pressurized vent such as a flare system.

Figure 1C: Using Dry Sample Gas as Reference

Figure 1D: Using a Separate Source of Reference Gas

Figure 1E: Typical Sample Line Installation

7
Maintenance Guidelines

• Weekly - The Analyzer calibration should be checked weekly by entering the calibration mode which
re-calibrates the Analyzer based upon sensor response to the gas conditioned for Calibration. Gas
flow rate and conditions through the calibration loop should be verified and re-set if necessary.

• Quarterly - The filter frit should be replaced and the entire system should be leak-tested. Also, the
system pressure should be checked, with proper setting at 1.0 kg/cm²g (15psig) or manufacturer’s
specification.

• Semi-annually - Refill the moisture generator with distilled or deionized water.

• Annually - Replace the dryer molecular sieve and the contaminant trap activated charcoal (if used).

Common Problems

The following are descriptions of the most common problems encountered when using mass differential-
based moisture analyzer systems. If any of these problems are encountered or suspected, the Analyzer
manufacturer should be contacted for best course of corrective action:

• All Analyzer data handling assumes a gas system pressure set at 1.0 kg/cm²g (15 psig) (or other
manufacturer-specified setting). Calculations and moisture read-outs will be off if the system
pressure deviates. Reset the back pressure if necessary.

• Accurate Calibration Gas generation depends upon a dry Reference sample stream, a full water
reservoir at 60°C (140°F), and an accurately set gas flow rate of 500 cc/min @ 25°C (77°F) and 760
mmHg (15 psig) (or other manufacturer-specified settings). If these conditions are not met, an
accurate Calibration standard will not be generated. A Calibration standard reading artificially high
will result in high Straight Sample moisture readings, while a low Calibration standard will yield low
readings. The gas flow rate should be set using a bubble-meter and adjusted accordingly if
temperature and pressure conditions vary from manufacturer’s specifications.

• If the sensor comes in direct contact with a liquid, either water or hydrocarbon, the most likely result
will be an irreversibly damaged sensor and a permanent moisture level reading of "0". Eventually,
the sensor will dry out and oscillations may resume. However, the calibration will no longer be valid.
Re-calibration will be necessary if the sensor is salvageable.

Advantages / Disadvantages

Mass differential-based moisture analyzers have the following advantages:

(1) Wide working range.

(2) True calibration check ‘built in’.

(3) Auto-zeroing is inherent in the design.

(4) Available in explosion-proof configuration.

Disadvantages include:

(1) Relatively expensive and bulky.

(2) Cannot be used in-line.

8
(3) Has a 1-minute response time.

CAPACITANCE-BASED MOISTURE ANALYZERS

General Description

Analyzers based on change in capacitance measurements are useful devices for accurately measuring
trace moisture levels in a variety of gaseous and liquid process streams. Suitable liquid streams include
non-polar hydrocarbons and polar hydrocarbons in which water has some finite solubility. These
analyzers cannot be used in applications containing alcohols or other species in which water is completely
miscible (the sensor responds to molecules of high polarity in a similar fashion as it does with water,
making differentiation between the species difficult). In liquid service, the analyzer’s sensor element can
be used to measure moisture content in the liquid stream directly, or in the gas phase by first vaporizing
the sample. With proper installation and maintenance, these analyzers can provide accurate moisture
measurements down to the hundreds of parts per billion range. Manufacturers of capacitance-based
moisture analyzers include Endress & Hauser, General Eastern, Kahn, MCM, Michell Instruments,
Molecular Controls, Ondyne, Panametrics, and Shaw Moisture Meters.

Operation Overview

Capacitance-based systems are typically comprised of two distinct parts: the Probe and the Control Unit.
The Probe can be installed in one of several acceptable configurations that affords direct exposure to the
process stream of interest. The Control Unit can be installed locally in a suitable enclosure or remotely
(up to several thousand feet away from the Probe) in an analyzer shed, control room, etc…

The Probe works on a capacitance principle. The Probe sensor is comprised of a "sandwich" of aluminum
and gold thin films separated by an insulating layer aluminum oxide. The porous aluminum oxide
adsorbs moisture according to the partial pressure of water in the process stream, resulting in a
capacitance change in the sensor. Change in capacitance controls an oscillator which, in turn, provides a
frequency output that corresponds to moisture level in the fluid being measured. This frequency output is
received and converted by the Control Unit to the user-selected moisture level reading. The Probe will
also have temperature sensing capability that is automatically utilized for temperature-compensated
moisture level calculations.

The Control Unit houses the electronics and performs the following three main functions:

(1) Receives and processes signals from one or more Probes remotely installed and hard-wired to the
Control Unit.

(2) Provides a display readout of both temperature and moisture level, as signaled by the Probe(s), in one
of a variety of units selected by the user. Pressure indication and other options are also usually
available.

(3) Outputs user-programmable signals that can be recorded or logged by the user. Several output
channels are available for assigning to Probe signals being received and processed by the Control
Unit from the Probe(s). Output selection includes standard 0-20mA, 4-20mA, or 1-5V. For example,
outputs 1 & 2 can be assigned to one probe’s moisture and temperature inputs, respectively, as a 4-
20mA signal. Outputs 3 & 4 can similarly be assigned to a second probe. Output signals are fully
spanable by the user to incorporate the desired data ranges. An RS-232 serial port is also available
for direct communication to a local computer, plant network, or other data tracking system.

For gas service, the Control Unit set-up is typically configured to output "ppmv", "dewpoint", or "%
relative humidity". Correct operation and signal output requires the accurate input of the pressure at
which the Probe sensor measurement is taken. If "ppmw" is the preferred unit of measure, the molecular
weight of the gas is also required. Any output requiring a coinciding temperature reading will obtain the

9
reading from the Probe temperature sensor for the necessary temperature compensation. Care must also
be taken in situations where measurement is being made at a pressure lower than that of the process. If
condensable components exist in the sample stream, a lower temperature resulting from pressure
reduction may result in condensate and probe fouling. If condensation is a concern, the sample line
should be appropriately heat traced.

For liquid service, the Control Unit set-up is typically configured to output "ppmw". Correct operation
and signal output requires the generation and input of a calibration curve relating water solubility to
hydrocarbon composition (see Instrument Manual for details). If process stream composition changes
significantly, a new solubility curve must be entered. Care must also be taken to prevent flashing of the
liquid sample at or before the sampling point. A two-phase situation will result in inconsistent and
erroneous results. To avoid sample flashing, measurement in liquid service should be taken at process
pressure, with pressure let-down occurring after the sample point.

Installation Guidelines

There are several acceptable methods for installation of capacitance-based moisture probes. The most
common of these are described below:

(1) In-line Mounting - This method measures the process stream directly. The probe is installed
vertically in the process line using a 1/2-inch pipe thread connection. The probe should be inserted a
minimum of one inch into the pipe without contacting the pipe walls (Figure 2A). If the pipe is too
small, the probe should be installed in an expansion or an elbow (Figures 2B and 2C).

(2) Bypass Mounting - This installation method also allows direct measurement of the process stream,
with the difference being a piping configuration that can accommodate probe by-pass (Figure 2D).
This configuration provides an advantage when it is necessary to service the probe without
interrupting process flow.

(3) Sample System Mounting (Single Probe) - This method is the most preferred because it provides
the greatest versatility for measurement conditions. The probe is mounted in a flow cell that is
connected to a line tapping the main process flow. Pressure is regulated by valves on either end of
the flow cell. Sample effluent can be tied back into the process (at some lower pressure point), sent to
a flare system, or vented to atmosphere. Figure 2E shows a typical sample system configuration, with
measurements capable of being obtained at either atmospheric or system pressure. When selecting
measurement conditions, care must be taken to avoid condensation (in gas service) and flashing (in
liquid service) at the sensor. In some cases, heat tracing the sample line may be required to avoid
condensation. Measurements in liquid applications are typically made at process pressure. In
corrosive service, a purge line can be used to dilute the sample, thereby minimizing exposure to the
corrosive agent as well as ensuring that liquid water does not condense on the probe sensor (Figure
2F).

(4) Sample System Mounting (Dual Probe) - This configuration is similar to a single probe sample
system with the difference being the inclusion of a second probe connected in parallel. One probe is
kept under a dry stream (such as nitrogen) while the other is in service. Appropriate valving enables
switching between the two probes for calibration checks as well as the removal of one probe for
servicing without losing measuring capability (Figure 2G).

10
Figures 2A - D: Probe Mounting Configurations

11
Figure 2E: Sample System Configuration
for High Pressure Applications

Figure 2F: Sample System Configuration

for Corrosive Applications

12
Figure 2G: Sample System Configuration (Dual Probe)

13
Maintenance Guidelines

The following maintenance should be performed regularly on capacitance-based Moisture analyzers:

• After Every Use - The Probe should be purged and dried with nitrogen. If the response time of the
Probe sensor begins to lag, this indicates that the sensor is contaminated. The sensor can be cleaned
with a pure hydrocarbon liquid such as toluene.

• Semi-annually - The Probe should be sent to the manufacturer for routine re-calibration.

• When Not In Use - The Probe should always be stored with the protective sheath or cover in place
and in a clean, dry environment. This prevents the sensor from becoming saturated from moisture
present in the ambient air.

Common Problems

The following are descriptions of the most common problems encountered when using capacitance-based
moisture analyzer systems. If any of these problems are encountered or suspected, the Analyzer
manufacturer should be contacted for best course of corrective action:

• Failure to adhere to the maintenance schedule as outlined above or by the manufacturer.

• Probe sensors can typically withstand pressures up to several thousand psi. For applications
exceeding the manufacturer’s specified limit, a regulator should be used in the sample line for
pressure reduction.

• Probe sensors can typically withstand temperatures up to ~70° C (158° F). For process applications
exceeding this limit, a cooling coil should be installed in the sampling loop. Caution should be used
when employing the technique, since the heavier sample fractions will tend to condense or separate
(due to solubility constraints) in the sample line, resulting in potential for probe fouling.

• High sample flow rates generally improve probe sensor performance. However, excessive flow can
damage the sensor by particle abrasion. The maximum recommended linear flow velocity for liquid
service is ~16 feet (5 meters) per second. A flow of 1 to 7 cubic feet per hour is ideal for gas service.

• The sensor should not be used in corrosive situations where the sample might attack aluminum or
gold (ex: HCl, H2S). Use under these conditions greatly reduces the life of the sensor. A sample
dilution system can sometimes be used to allow the analysis of potentially corrosive process streams.

• In gas service, condensation of heavier fractions in the process stream will result in sensor fouling.
Avoiding condensation may involve adjustment of sample line pressure, heat tracing the sample line,
or conditioning the sample upstream of the probe sensor by passage through a high-efficiency
coalescer.

• In liquid service, reduction in pressure upstream of the sample point can result in flashing of the
sample stream (especially in light hydrocarbon applications). Two-phase flow will yield inconsistent
and erroneous results. In applications where flashing is a concern, measurements should be taken at
process pressure.

• In liquid service, shifting liquid composition can significantly alter Probe sensor response and output.
The process stream must be monitored, with significant compositional changes being accounted for
by adjustments in water solubility calibration data.

14
Advantages / Disadvantages

Capacitance-based aluminum oxide sensors have the following advantages:

(1) Wide dynamic range from 0.1 ppm to 100 per cent

(2) Relatively stable, with low hysteresis and temperature coefficients

(3) Response is flow-independent

(4) Intrinsically safe

(5) High selectivity for water

(6) Wide range of temperature and pressure operability

(7) Require little or no maintenance

Disadvantages include:

(1) Slow drifts in calibration (which may accelerate at higher operating temperatures or in certain gases).

(2) Corrosive gases affect probe response (analogous silicon or tantalum oxide sensors may be viable
alternatives).

(3) Sensors need simple temperature control at high temperatures and dew points.

(4) Sensor response is not absolute and requires periodic calibration.

15