Solid Desiccant Dehydration

Several solid desiccant processes are available to dry liquid hydrocarbons. Liquid velocity
is usually 3-5 ft/minute through solid desiccant beds with a minimum travel of at least 5
feet to ensure good distribution. Direction of flow can be up-flow or down-flow in the
adsorption cycle. Special care must be taken in designing the bed supports in the liquid
dehydrator vessels to prevent desiccant loss, desiccant damage, and to ensure proper
distribution. Layers of ceramic balls are installed in decreasing size from the support
screen. The support ball sizes may vary with the type and size of solid desiccant used
but the layers of support balls should never be graduated in size more than twice the
diameter of the balls being supported. The regeneration of solid desiccant beds is very
similar to gas dehydrators with the following exceptions:
Liquid draining and filling time must be allowed.
Pressuring and de-pressuring must be done carefully to avoid bed movement.
Adequate bed cooling is required before liquid re-entry to minimize flashing.
It is important to prevent movement of the bed particles to prevent attrition that would
require premature replacement. Also, desiccant dust particles can cause downstream
plugging, equipment damage, and excessive filter maintenance. Liquid and vapor
velocities must be controlled carefully and flashing of liquids or accelerated blow-down
rates that would lift or float all or portions of the bed should be avoided. Desiccant
bed life can be extended by doing several or all of the following activities:
Prevent the desiccant particles from moving.
Keep contaminants out of the dehydrating portion of the bed by upstream
conditioning or by providing a sacrificial layer of less expensive desiccant to act as
a catcher of any compounds.
Prevent overheating the bed to reduce the formation of carbon during the
regeneration cycle.
Analyze the heating/cooling regeneration temperature cycles to minimize the time
the bed is at elevated temperatures.
This will also minimize energy requirements. A typical heating/cooling regeneration
temperature cycle plot is shown in Fig. 20-87, with a description of the stage activities.

There are typically four (4) distinct stages in a normal cycle:

Stage 1First bed-heating stage
Stage 2Desorption stage

Stage 3Second bed-heating stage

Stage 4Bed-cooling stage
For a period of time after the heat source is introduced into a desiccant bed being
dehydrated, the bed must be heated to a temperature where the water will start to be
desorbed (Stage 1).
As the water is desorbed (Stage 2), the bed temperature will usually rise only a few
degrees because the regeneration gas heat is utilized to provide the heat of vaporization
of the water being removed. The completion of the water desorption stage is
characterized by a rapid increase in bed temperature measured as the outlet
temperature. At this point the heating may be discontinued while bed heating will
continue from residual heat in the heating cycle (Stage 3). As the unheated regeneration
gas stream continues to pass through the bed, the bed will be cooled (Stage 4). At near
ambient pressures, regeneration of silica gel and alumina can be accomplished at 300F.
Molecular sieve requires 500-550F to maintain the low dew point potential, and the
higher temperatures may increase desiccant life by providing more complete removal of
adsorbed hydrocarbons. Capacity and performance data for new solid desiccants are
usually presented based on a static test. Under operating conditions (dynamic) the
performance data may be significantly different. Typically the effective capacity at
operating conditions is about one-half of the capacity at equilibrium (static) conditions
for most solid desiccants. This operating characteristic must be considered when
designing a dehydration system and can be influenced by careful design and good
control of operating parameters such as temperatures, contaminant levels, regeneration
cycles, and desiccant selection. Solid desiccant manufacturers should be consulted for
the most current product information and design criteria.
Molecular Sieve
Molecular sieve is not normally used for liquid dehydration because the required level of
water removal is usually moderate and the cost of molecular sieve is considerably more
than other types of suitable desiccants, such as activated alumina. However, in extreme
cases where the moisture content of the liquid must be kept at an unusually low
concentration, molecular sieve should be considered. Molecular sieve may be used for
removing other undesirable compounds, such as H2S, COS, mercaptans, etc., from liquid
streams. Dehydration may be a secondary benefit of using this type of treating method.
ADSORPTION PROCESSES

The two types of adsorption are physical adsorption and chemisorption. In physical
adsorption, the bonding between the adsorbed species and the solid phase is called van
der Waals forces, the attractive and repulsive forces that hold liquids and solids together
and give them their structure. In chemisorption, a much stronger chemical bonding
occurs between the surface and the adsorbed molecules. This chapter considers only
physical adsorption, and all references to adsorption mean physical adsorption. Physical
adsorption is an equilibrium process like vaporliquid equilibria and equations analogous
to Equation 6.1 apply. Thus, for a given vapor-phase concentration (partial pressure) and
temperature, an equilibrium concentration exists on the adsorbent surface that is the
maximum concentration of the condensed component (adsorbate) on the surface. Figure
6.6 shows the equilibrium conditions for water on a commercial molecular sieve. Such
curves are called isotherms. The figure is based upon a waterair mixture but is
applicable to natural gas systems. The important parameter is the partial pressure of
water; total pressure has only a minor effect on the adsorption equilibrium. Because
adsorbate concentrations are usually low, generally only a few layers of molecules will

build up on the surface. Thus, adsorption processes use solids with extremely high
surface-to-volume ratios. Commercially used synthetic zeolites (i.e, molecular sieves)
have surface-to-volume ratios in the range of 750 cm2cm3, with most of the surface for
adsorption inside of the adsorbent. In the case of molecular sieves, the adsorbent
consists of extremely fine zeolite particles held together by a binder. Therefore,
adsorbing species travel through the macropores of the binder into the micropores of the
zeolite. Adsorbents such as silica gel and alumina are formed in larger particles and
require no binder. Pore openings that lead to the inside of commercial adsorbents are of
molecular size; they normally range from approximately 4 (1 108 cm) to 100 .
Molecular sieves have an extremely narrow pore distribution, whereas silica gel and
alumina have wide distributions. However, a molecular sieve binder, which
is usually about 20% of the weight of the total adsorbent, has large pores capable of
adsorbing heavier components. Two steps are involved in adsorbing a trace gas
component. The first step is to have the component contact the surface and the second
step is to have it travel through the pathways inside the adsorbent.
Because this process is a two-step process and the second step is relatively slow, solid
adsorbents take longer to come to equilibrium with the gas phase than in absorption
processes. In addition to concentration (i.e., partial pressure for gases), two properties of
the adsorbate dictate its concentration on the absorbent surface: polarity and size.
Unless the adsorbent is nonpolar, which is not the case for those used in gas plants,
polar molecules, like water, will be more strongly adsorbed than weakly polar or nonpolar
compounds. Thus, methane is displaced by the weakly polar acid gases that are
displaced by the strongly polar water. How size affects adsorption depends upon the pore
size of the adsorbent. An adsorbate too large to fit into the pores adsorbs only on the
outer surface of adsorbent, which is a trivial amount of surface area compared with the
pore area. If the pores are sufficiently large to hold different adsorbates, the less volatile,
which usually correlates with size, adsorbates will displace the more volatile ones.
Therefore, ethane is displaced by propane. In commercial practice, adsorption is carried
out in a vertical, fixed bed of adsorbent, with the feed gas flowing down through the bed.
As noted above, the process is not instantaneous, which leads to the formation of a mass
transfer zone (MTZ) in the bed. Figure 6.7 shows the three zones in an adsorbent bed:
1. The equilibrium zone, where the adsorbate on the adsorbent is in equilibrium with the
adsorbate in the inlet gas phase and no additional adsorption occurs
2. The mass transfer zone (MTZ), the volume where mass transfer and adsorption take
place
3. The active zone, where no adsorption has yet taken place
In the mass transfer zone (MTZ), the concentration drops from the inlet value, yin, to the
outlet value, yout, in a smooth S-shaped curve. If the mass transfer rate were infinite,
the MTZ would have zero thickness. The MTZ is usually assumed to form quickly in the
adsorption bed and to have a constant length as it moves through the bed, unless
particle size or shape is changed. The value of yin is dictated by upstream processes; the
yout value is determined by the regeneration gas adsorbate content. The length of the
MTZ is usually 0.5 to 6 ft (0.2 to 1.8 m), and the gas is in the zone for 0.5 to 2 seconds
(Trent, 2004). To maximize bed capacity, the MTZ needs to be as small as possible
because the zone nominally holds only 50% of the adsorbate held by a comparable
length of adsorbent at equilibrium. Both tall, slender beds, which reduce the percentage
of the bed in the MTZ, and smaller particles make more of the bed effective. However,
smaller particle size, deeper beds, and increased gas velocity will increase pressure drop.
For a point in the MTZ, the gas phase adsorbate content increases in time from yin to
yout in an S-shaped curve that mirrors the curve shown in Figure 6.7.

In principle, beds can be run until the first sign of breakthrough. This practice maximizes
cycle time, which extends bed life because temperature cycling is a major source of bed
degeneration, and minimizes regeneration costs. However, most plants operate on a set
time cycle to ensure no adsorbate breakthrough. Trent (2004) presents data that show a
change in the LD from 0.8 to 2.7 in the bed increases the useful adsorption capacity
from 8.7 to 10.0 wt% in useful water capacity for an equal amount of gas dried.
However, the pressure drop increases from 0.4 to 4.3 psi (0.020 to 0.20 kPa). When used
as a purification process, adsorption has two major disadvantages:
It is a fixed-bed process that requires two or more adsorption beds for continuous
operation.
It has limited capacity and is usually impractical for removing large amounts of
impurity.
However, adsorption is very effective in the dehydration of natural gas because water is
much more strongly adsorbed than any of the alkanes, carbon dioxide, or hydrogen
sulfide. Generally, a higher degree of dehydration can be achieved with adsorbents than
with absorption processes. Although this discussion uses molecular sieve as the example
of an adsorbent to remove water, with the exception of regeneration temperatures, the
basic process is the same for all gas adsorption processes. Figure 6.8 shows a schematic
of a two-bed adsorber system. One bed, adsorber #1 in Figure 6.8, dries gas while the
other bed, adsorber #2, goes through a regeneration cycle. The wet feed goes through
an inlet separator that will catch any entrained liquids before the gas enters the top of
the active bed. Flow is top-down to avoid bed fluidization. The dried gas then goes
through a dust filter that will catch fines before the gas exits the unit. This filter must be
kept working properly, especially if the gas goes on to a cryogenic section with plate-fin
heat exchangers, as dust can collect in the exchangers and reduce heat transfer and
dramatically increase pressure drop.

Figure 6.8 shows a slip stream of dry gas returning to the bed that is being regenerated.
(Sales gas is sometimes used instead of a slip stream. The sales gas stream has the
advantage of being free of heavier hydrocarbons that can cause coking.) This gas is
usually about 5 to 10% of gas throughput. Regeneration involves heating the bed,
removing the water, and cooling. For the first two steps, the regeneration gas is heated
to about 600F (315C) to both heat the bed and remove adsorbed water from the
adsorbent. If COS formation is a problem, it can be mitigated by lowering regeneration
temperatures to 400 to 450F (200 to 230C) or lower, provided sufficient time for

regeneration is available, or by switching to 3A. Regeneration gas enters at the bottom

of the bed (countercurrent to flow during adsorption) to ensure that the lower part of the
bed is the driest and that any contaminants trapped in the upper section of the bed stay
out of the lower section. The high temperature required makes this step energy intensive
and in addition to furnaces, other heat sources (e.g., waste heat from gas turbines that
drive compressors) are used when possible. The hot, wet regeneration gas then goes
through a cooler and inlet separator to remove the water before being recompressed and
mixed with incoming wet feed. To complete the regeneration, unheated regeneration gas
passes through the bed to cool before it is placed in drying service. Gas flow during this
step can be concurrent or countercurrent. The Engineering Data Book (2004b)
recommends that the bed pressure not be changed more than 50 psimin (6 kPas).
Therefore, if the adsorption process operates at high pressure, regeneration should take
place at as high a pressure as possible to reduce the time needed for changing the
pressure. However, as Malino (2004) points out, higher pressures increase the amount of
water and hydrocarbons that condense at the top of the bed and fall back onto the
adsorption bed. This unavoidable refluxing is a major cause of bed aging, as it leads to
adsorbent breakdown and subsequent fines agglomeration (Richman, 2005). The caking
leads to higher pressure drop. Condensation at the bed walls can also occur, which can
cause bed channeling.