1.1.1.

Beds Design Fundamentals

Each vendor has criteria for designing beds for their material, but some rules of thumb
are that the bed should be sized for a superficial flow velocity of about 50 ft/min and a
residence time of 10 seconds. Generally, the fixed beds are designed by considering the
following aspects:
1. Knowing the gas composition, operating pressures, operating temperatures, and
the applied processes to define suitable adsorbent characteristics, and define
location of the bed to avoid any process interference, avoid any process
incompatibility, and ensure optimum operating conditions. [115]
2. Packing with a sufficient quantity of adsorbents to provide the required removal
efficiency, typically reaching undetectable level as much as below 0.01 µg/Nm 3
during a specified lifetime interval for changing out the spent material. The
amount are estimated based on the sorbent characterized capacity against the fluid
properties; maximum and minimum flow rate (velocity/contact time), and
maximum mercury concentration (load). [176-178]
3. Pressure drop is affected by many parameters including; fluid velocity, fluid
distribution, solid suspension in fluid, particles size, particles crush strength &
possibility of dust generation, particles packing & distribution, bed porosity, bed
dimensions, fluid density, and fluid viscosity. By considering all the fixed and
optimum input parameters, the pressure drop determines the diameter of the bed.
4. Ensuring good distribution of the fluid through the adsorbent bed, which is
determined by the bed dimensions.
5. Flow direction either downward or upward, is generally specified according to
design velocities.
6. Support structure of the bed including; the wire meshes, and inert (ceramic) balls
to prevent fluidization, and particles escape.
Evaluation of experimental breakthrough curves enables defining bed capacity, range of
mass transfer zone, adsorbent usage rate, and volume of fluid treated by mass balance,
and integrating the area under the curve, which is proportional to the capacity according
to the following equations. [109, 171-174]
Co Q tb Ct
Breakthrough capacity Qb = m ∫0 (1- C ) dt (2.36)
o
Co Q ts Ct
Saturation capacity Qs = m
∫0 (1- Co) dt (2.37)
Where tb and ts are breakthrough and saturation times respectively, m mass of adsorbent,
Co inlet concentration, and Q flaw rate. [109]
According to the above evaluation and known bed height L, the mass transfer zone where
adsorption occurs and propagates through the bed in which:
 bed saturation varies from 100% saturated to fresh free adsorbents,
 fluid concentration changes from inlet concentration to approaching zero or the
designed specification,
this MTZ is approximated by [109, 171-174]
MTZ = L Qb / Qs (2.38)
and length of unused bed (LUB) or called virgin zone to be approximated by
LUB = L ( 1 - Qb/Qs) (2.39)

1.1.2. Mercury Removal Unit Operation

Operation commences by introducing the natural gas into fresh sorbate-free bed where
the selective mass transfer occurs between mercury molecules and the surface of solid
sorbents.
Accordingly, the first layers of the bed uptake mercury from the gas in the beginning till
holding the maximum amount of mercury that can be trapped i.e. maximum sorption
capacity, and thus being saturated and can't uptake anymore.
The subsequent layers are still active and accommodate the uptake of upcoming mercury
molecules, and the position of those active layers is moving with time in the direction of
flow till reaching the bottom layers, which when saturated, the mercury will start passing
out of the bed, which is called breakthrough, and the unit has to be shutdown, unloaded
from the spent material, and reloaded with new fresh charge of adsorbents. [171-174]
From the above scenario, three distinct zones in the bed are commonly defined as the
following: [171-174]

1- The saturated zone that does not uptake mercury,

2- The mass transfer zone (MTZ) where adsorption occurs and propagates through
the bed in which bed saturation varies from 100% saturated to fresh free
adsorbents, and fluid concentration changes from inlet concentration to desired
effluent concentration,
3- Virgin zone, which is unused guard layer and free of mercury.

The below simple sketches explain the three zones.

Figure Error! No text of specified style in document.-10 Concentration Fronts through
Columns and Zones Classification

Generally, the removal efficiency is normally affected by certain factors that can be
summarized as below. [115]
1- Gas flow rate (velocity)
 The higher the flow rate, the more rapid bed saturation, and hence the earlier
breakthrough occurs.
 Higher flow rate than the design leads to general shorter lifetime, and shorter
contact time, which adversely influences uptake rate, in addition to higher
pressure-drop.
  Lower flow rate leads to longer contact time, which improves adsorption rate,
but less turbulence may decrease external film mass transfer coefficient and
increase undesirable axial dispersion effects.
2- Gas mercury concentration
 The higher the concentration, the more rapid bed saturation, MTZ propagates
more rapidly, and hence the earlier breakthrough occurs with shorter lifetime.
 Higher concentration than the design leads to breakthrough and general
shorter lifetime.
3- Sorbent characteristics
 Sorbent composition, porosity, pore size, surface area, pore volume,
tortuosity, surface pH, synthesis procedure, particle size, and crush strength
are all characteristics influence adsorption and pressure drop.
4- Gas composition
 Adsorption is influenced by gas composition such in cases of co-adsorption
potential for other species, existing poisoning impurities that may block pores
(fouling), capillary condensation potential by water or heavy hydrocarbons,
and liquid carryover potential.
5- Operating pressure
 Pressure has effect on physical adsorption, which is usually promoted by
higher pressure.
6- Operating temperature
 Operating temperature affects both physical and chemical adsorption
according to thermodynamic features of the adsorption process whether
exothermic that will be promoted by lower temperature or endothermic
promoted by higher temperature.
7- Bed length
 The higher the bed height, the higher the capacity, the longer the lifetime, the
later the breakthrough, but the higher the pressure-drop.
8- Contact time
 Longer residence time normally increases the chance of mercury uptake and
achieves higher removal and it is function of flow rate and bed dimensions.
9- Bed porosity/density and particles distribution
 The lower bed porosity negatively affects pressure drop, although it indicates
much dense bed and higher removal capacity, while the much high porosity
gives chance to channeling and axial dispersion effects in addition to lower
capacity.
In more details and classification, the most recent advancement in mercury removal
technology can be summarized through the following options of available technologies
[4,10-16].
1- Non-regenerative bed of sulfur-impregnated activated carbon is an efficient
technology to capture mercury in the stable form of Mercuric Sulfide but with
limitations. The sorbents must have high surface area and porosity. The sulfur
impregnation process also must be careful to avoid the blockage of pores and
affecting adsorption efficiency negatively in addition to keeping the sulfur tightly
deposited within the carrier to avoid the risk of sulfur stripping by the process
stream, particularly at high temperature, resulting in performance deficiency and
process contamination with sulfur. This technology is not suitable for wet gas
near dew point conditions, liquid hydrocarbons, and liquid carryover problems
because the sulfur solubility in hydrocarbons, particularly in aromatics, leads to
sulfur leaching with these applications and conditions resulting in performance
deficiency and process contamination with sulfur [4,10-13].
2- One more tolerant technology is the use of metal sulfide or mixed sulfides
chemically bonded to a solid carrier such as activated carbon or alumina to
capture mercury in the stable form of Mercuric Sulfide. Copper and zinc are the
prevalent chosen metals and other proprietary metals. Metal oxides are also used
alternatively with H2S applications that transform the oxides into sulfides and
accordingly remove the mercury. This non-regenerative advanced technology
withstands and tolerates liquid carryover, and it is used with liquids applications.
The sorbent structure is well designed to avoid capillary condensation with gases
near dew point conditions. These adsorbents are more expensive than activated
carbons, but they can be treated and recycled through smelters after being a spent
material, and the problem of sulfur leaching is eliminated [4,10-15].
3- Halide-impregnated activated carbon is a technology used with liquid
hydrocarbons, but it is sensitive to liquid water that will cause dissolution and loss
of the halide active agent and will add corrosion problems. Some proprietary
ingredients are claimed to have water tolerance. Potassium iodide impregnated
carbon is a water sensitive type that must be placed downstream a dehydration
unit [10,12,16].
4- Ion-exchange-resins applications are mainly used with naphtha feeds to
petrochemical plants [12].
5- Regenerative bed of silver-coated molecular sieves is a technology that is usually
combined with existing dyers beds for dual function of dehydration and mercury
removal by amalgamation with the silver surface. The bed is regenerated to strip
the mercury and the water and recover them in liquid phase. The advantages of
this technology are the direct saving of the additional cost of mercury removal
beds and the decrease of pressure drop and recompression cost in applications
because just layers of existing dryers are replaced with these mercury adsorbents
without affecting dehydration performance. This technology is suitable for gas
and liquid phases [4,10-12].
6- A technology of mercury removal plant is applied with crude oil, where it consists
of different equipment that remove mercury from the crude oil in successive
stages by using separation, filtration, and reaction with sulfur agents [9].
7- The most recent technology is the innovation of ionic liquids supported within a
solid carrier to remove all different forms of mercury. They are characterized by
low vapor pressure, high thermal stability, non-volatility in room temperature,
non-flammability, controllable miscibility with a range of fluids and gasses,
modifiable solubility, and extraction capabilities. Ionic liquids can oxidize
elemental and organic mercury to inorganic mercury (II) species, and remove all
mercury species. The solid supported ionic liquids can be loaded in existing
adsorber beds without plant modification [10].