Reflux in a gas dehydration plant

Gas dehydration by adsorbent processes may lead to the damaging

regeneration reflux phenomenon during adsorbent regeneration

SAJAD MIRIAN and HOSSEIN ANISI Nitel Pars Co (Fateh Group)

XIANG YU Hengye Chemical Co
SEPEHR SADIGHI Research Institute of Petroleum Industry

D
ehydration of natural gas adsorbent is repeatedly used in used are reduced. Therefore, the
entails the removal of cycles by carrying out these total cycle time is usually
water that is associated two steps. When a regeneration designed such that at the end of
with natural gases in vapour step is carried out through the adsorption a short time is
form. The natural gas industry reduction of the total pressure, available for appropriate regen-
has recognised that dehydra- the process is called pressure eration of the adsorbent. Hence,
tion is necessary to ensure swing adsorption (PSA). the inlet section of the adsorp-
smooth operation of gas trans- Temperature swing adsorption tion bed is faced immediately
mission lines. This (TSA) is another technique with a high temperature from
pretreatment prevents the used for regenerating a bed of the start of the regeneration
formation of gas hydrates and adsorbent that is loaded with without any heating ramp.
reduces corrosion. The three the targeted impurity gas. This Heating up the adsorber with-
major methods of dehydration technology began commercially out using a heating ramp causes
are direct cooling, adsorption in the 1960s and continues a strong temperature difference
and absorption. Adsorption- today for drying continuous air in the bed. So, at the bottom,
based processes for separation and natural gas as well as the molecular sieve is very hot
of multi-component gaseous other purification applications and desorbs the adsorbed water
mixtures are becoming increas- such as carbon dioxide strip- while the top layers are still at
ingly popular. The new ping from air. TSA exploits the adsorption (low) temperature.
generation of synthetic and capacity of certain adsorbent Therefore, water desorbed in
more selective adsorbents materials, such as activated the bottom layer condenses in
developed in recent years has alumina, silica gel and zeolites, the top layer. This phenomenon
enabled adsorption-based tech- to adsorb gases at moderate is called refluxing or retro-con-
nology to compete successfully temperatures (40C, 100F) and densation. A schematic diagram
with traditional gas separation later release them when the of an adsorber with regenera-
techniques. temperature rises above 120C tion refluxing is shown in Figure
Any adsorption-based sepa- (250F). 1. To prevent this catastrophic
ration process requires two Natural gas treating units phenomenon, a good molecular
essential steps: adsorption using molecular sieves and TSA sieve formulation (binder and
during which one or more technology are usually opti- zeolite) or improvement in the
components are preferentially mised by manipulating both the regeneration condition is inevi-
adsorbed/separated; and adsorption and the regeneration tably required.
regeneration during which time. By reducing the adsorp- In this article, modelling of
these components are removed tion time, both the vessel size the regeneration reflux
from the adsorbent bed. The and the amount of adsorbent phenomenon during regenera-

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 tion is performed and the tion mode for removing the
effects of it on the adsorption residual water. At once, that
process are reviewed. bed which has completed the
Recommendations to prevent regeneration step is replaced.
this phenomenon in a commer- During the regeneration
cial scale dehydration unit (as process, a regenerative gas
a case study) are presented. Solid caked layer stream is passed through a
of adsorbent and
salt fused together heater where it is heated to
Process description approximately 270C. This hot
The purpose of a natural gas Effective gas passes upwards through
bed diameter
dehydration package is to the offline saturated dryer
reduce the water content of the Original heating the molecular sieves.
natural gas to avoid freezing bed diameter As the sieves are heated up,
and hydrate formation in the adsorbed water begins to
pipeline. In order to utilise desorb and is carried away by
natural gas for urban consump- the hot gas. The operating
tion, the water dew point conditions of the target adsorp-
should be reduced to below tion and regeneration processes
-10C, accomplished by using a and specifications of their feeds
molecular sieve adsorption unit Figure 1 Schematic of a bed faced are shown in Table 1 and Table
which adsorbs water from the with regeneration reflux 2, respectively.
inlet gas.
To perform such a process, are in adsorption and one in Mathematical modelling
water saturated natural gas regeneration. The feed stream of regeneration
from the upstream unit is sent is split into three identical A computational fluid dynamic
to the molecular sieve dehydra- streams, each of which passes modelling technique was used
tion plant where the gas stream downward through one of the to model the momentum, heat
passes through a separator to beds that are in adsorption content and mass transfer of
retain any free water carry- mode (see Figure 2). fluid through porous media,
over from the upstream Dry gas streams leaving the and also to investigate the
facilities. It is then routed to adsorption beds are joined and refluxing phenomenon in the
the molecular sieve dryers. A passed through a filter to retain regeneration process studied.
dehydration package consists any solid particles coming from To solve these set of equations,
of four dryers loaded with a the dryers. Finally, dry and commercial software (Comsol
special type of molecular sieve filtered gas is sent to the Multiphysics Ver. 4.2) was
4A; at any time three dryers municipal gas station via a
transmission pipeline. Feed and regeneration gas
Each adsorption cycle takes compositions
Adsorption Regeneration
mode mode
eight hours. After that, the
dryer is switched to regenera- Components Adsorption Regeneration
Methane, wt% 72.95 73.1
Ethane, wt% 8.13 8.14
Adsorption and regeneration Propane, wt% 4.1 4.11
operating conditions i-Butane, wt% 1.22 1.22
n-Butane, wt% 1.56 1.56
i-Pentane, wt% 0.00 0.00
n-Pentane, wt% 0.140 0.141
Specifications Value
n-Hexane, wt% 1.73 1.73
Adsorption temperature, C 47
n-Heptane, wt% 0.1897 0.19
Adsorption pressure, kPa 9101
n-Octane, wt% 0.1622 0.1625
Adsorption mass flow, kg/h 2.409e+05
n-Nonane, wt% 0.0337 0.0338
Regeneration temperature, C 270
CO2, wt% 3.79 3.8
Regeneration pressure, kPa 7929
Nitrogen, wt% 4.57 4.58
Regeneration mass flow, kg/h 4.751e+04
H2O, wt% 0.1573 0.000
Figure 2 Schematic diagram of the
dehydration unit studied Table 1 Table 2

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employed that utilises the finite
element method to discretise
6500
partial differential equations to Temperature, K
6000 543.15
ordinary differential equations
5500
and finally solve them. The 5000
following assumptions are 4500 500
considered during the mathe- 4000
Regeneration reflux
zone
matical procedure: 3500 450
To reduce computation time, 3000
2D axisymmetric mode is 2500
assumed 2000 400

The gaseous phase is an ideal 1500

Desorption
gas 1000 zone 350
Entrance and exit effects are 500 Starts at 120C-140C

negligible 0 320.14
There is no slip condition 4000 3000 2000 1000 0 1000 2000
near the dryer wall.
Figure 3 Temperature distribution during the regeneration process
Governing equations
Mathematical modelling of the the dynamic viscosity of the Results and discussions
target regeneration process is fluid; (m2) is the permeability Figure 3 shows the temperature
obtained by coupling a set of tensor of the porous medium; distribution of the adsorption
general equations (including F (kg/m4) is Forchheimer bed at an early stage in the
continuity, momentum, energy drag option; F (kg/m2s2) is the regeneration process. As is
and mass balances), and influence of gravity and other apparent in this figure, a high
particular equations such as volume forces; (Cp)eq is the regeneration gas temperature
physical properties, adsorption equivalent volumetric heat (without enough ramp-up)
and desorption isotherms and capacity at constant pressure; T leads to a large temperature
equation of state as follows: (K) is the bed temperature; Cp gradient along the bed, and
is the fluid heat capacity at creates reflux at the early
Continuity equation: constant pressure; keq is the stages of the regeneration
equivalent thermal conductiv- cycle.
+ ( u ) = Qbr
t ity (a scalar or a tensor if the At these operating conditions,
Momentum equation: thermal conductivity is aniso- due to the high pressure of the
regeneration gas, high moisture
u u 2
( + (u ) ) = [ PI + (u + (u)T ) ( u) I ] ( + f u + Qbr )u + F concentration and a large
p t p p 3 p kbr
temperature gradient are inevi-
Energy equation: tropic); Q is the heat source (or table. For the design case, the
T sink); c is the concentration of licensor charged a molecular
( C p ) eq + C p u T = (keq T ) + Q
t the species (mol/m3); D is the sieve with enough strength
diffusion coefficient (m2/s), against reflux which could work
Mass equation: and R is the reaction rate more than four years without
ci expression for the species any malfunction. But for the
+ .( Di ci ) + u ci = Ri
t (mol/m3s). Furthermore, the next loading, a regular molecu-
major particular equations are lar sieve, manufactured by
In these equations, (kg/m3) the Langmuir adsorption another company, could not
is the density of the fluid; t (s) isotherm and ideal gas law. withstand those conditions. It
is the time; u (m/s) is the The proposed equations in 2D was observed that, only three
velocity vector; Qbr (kg/m3s) is axisymmetric mode have been months from the start of run,
the mass source or mass sink; solved using the required the loaded molecular sieve was
p is the porosity of bed; P (Pa) initial and boundary ruined due to the reflux
is the pressure; (kg/ms) is conditions. phenomenon. It also increased

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 phenomenon with the follow-
Recommendations and consequences to prevent reflux phenomena
ing malfunctions:
High pressure regeneration
Recommendation Consequence gas
1 Decreasing the regeneration gas pressure Needs compressor
Higher operating cost High moisture concentrations
2 Regeneration gas temperature ramp-up Hot oil system modification (if applicable) Large temperature gradients
Higher regeneration cycle time High degree of solubility of
Adsorption cycle time limitation
3 Layer of activated alumina at the top of the bed This approach may minimise the rolling boil binder materials in water
but cannot fix the problem. Based on Figure 3, Choosing an inappropriate
the reflux happens through the bed because of
a high temperature gradient, so it can only flow direction in adsorption
reduce the reflux. We can consider it and regeneration.
a modification.
4 Change the heating gas flow direction from the This is costly. Co-current regeneration
top to the bottom of the bed requires more gas for stripping the Recommendations and
bed completely. consequences
The downward flow pushes heavy liquid
contaminants, and possibly increases fouling The recommendations proposed
rate. in Table 3 can decrease the
5 Try to reduce the heat loss through the top of This can only reduce temperature gradient
the bed by adding extra insulation and even between the top and bottom of the vessel.
reflux phenomena which are
installing a steam tracer reviewed in brief for the target
6 Reverse all flows Bed fluidisation (lifting) gas dehydration unit.
7 Using a special molecular sieve The bed can possibly operate without any
problem. According to recommenda-
tion 7 in Table 3, a special
Table 3 molecular sieve 4A (with high
resistance against reflux
the pressure drop of the dryers. remaining pellets or beads phenomena), manufactured by
Therefore, it can be concluded together to form a solid mass. Shanghai Hengye Chemical
that the molecular sieve, espe- This solid mass, formed in an Co., was loaded into the target
cially the binder and additives, annulus shape with a centre dryers about one year ago. To
should be made of appropriate opening of less than one foot, date, the dehydration unit has
raw materials to be capable of did not allow gas to pass shown a good performance
resisting the reflux phenomenon through, and consequently and no malfunction has been
and preventing operational reduced the effective diameter observed.
malfunctions. of the bed (see Figure 1).
As Figure 3 shows, for our Therefore, boiling water Acknowledgment
case study liquid water moved destroyed the molecular sieve We would like to express our great
downward until it encountered such that the severity of the appreciation to Mr F Noorbakhsh and
Mr M A Fatemi for their valuable and
the heating zone. At this point, operating conditions should be
constructive suggestions during the
boiling water created a reflux greatly reduced to extend the
planning and development of this
which ground the molecular replacement period of the research work. We would also like to
sieve into a powder. Since adsorbent. The regeneration thank Nitel Pars Company, a subsidiary of
certain components of the reflux showed some undesira- Fateh Group, for technical assistance and
binder were somewhat soluble ble effects on the adsorption financial support.
in boiling water, the molecular process which can be summa-
sieve subsequently became a rised as follows: Further reading
wet cake (mud) which was then Molecular sieve particle 1 Agarwal A, Advanced Strategies
baked by the rising hot gas. break-up for Optimal Design and Operation of
These soluble components Increasing pressure drop Pressure Swing Adsorption Processes,
Ph.D. Thesis, Carnegie Mellon University,
could ion exchange with the Gas channelling
2010.
zeolite and/or combine with Premature water breakthrough
2 Serbezov A, Sotirchos S V, Particle-bed
anions in water to form solid which all lead to poor adsorber model for multi-component adsorption-
salts (Na2CO3, CaCO3, MgCO3, performance. based separations: application to pressure
NaNO3, and so on). These solid As a consequence, these swing adsorption, Chemical Engineering
salts could then paste the effects increased the reflux Science, 54, 1999, 5647-5666.

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3 Dabrowski A, Adsorption from theory Modeling of Transport Phenomena in Sepehr Sadighi is Assistant Professor
to practice, Advances in Colloid and Porous Media, Kluwer Academic Publisher, with the Catalysis Research Division of
Interface Science, 93, 2001, 135-224. 1990. Research Institute of Petroleum Industry
4 Meyer P B Chr, Hydrothermal (RIPI), Tehran, Iran. He holds a PhD in
damaging of molecular sieve and how Sajad Mirian is a Project Manager in the chemical engineering.
to prevent it, paper presented at the Gas Adsorbents Department of Nitel Pars Co., Email: Sadighis @ripi.ir
Processors Association Europe, Feb 2003, Tehran, Iran. He holds a MSc in chemical
Paris. engineering.
5 T W J Crittenden B, Adsorption Email: ms002@nitelpars.com.
Technology & Design, Heinemann Hossein Anisi is an Adsorbent Expert
Publication, 1998. in the Adsorbents Department of Nitel
6 Nield D, Bejan A, Convection in Porous Pars Co. He holds a BSc in chemical Links
Media, 3rd ed., Springer, 2006. engineering.
7 Le Bars M, Worster M G, Interfacial Email: ms003@nitelpars.com More articles from the following
conditions between a pure fluid and a categories:
porous medium: implications for binary Xiang Yu is an Application Engineer of Corrosion/Fouling Control
alloy solidification, J. of Fluid Mechanics, Hengye Chemical Co., Shanghai, China. Gas Processing/Treatment
550, 2006, 149-173. He holds a BSc in chemical engineering. Mass Transfer & Separation
8 Bear J, Bachmat Y, Introduction to Email: hyms@foxmail.com

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