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PTQ supplement
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Predicting corrosion rates in amine and
sour water systems
C
orrosion is a ubiquitous prob-
lem in gas treating in the
petroleum and natural gas
industries, in syngas plants, in
processing unconventional gases
such as shale and coal seam gas,
and in numerous other treating
applications. The primary impuri-
ties removed in the treating process
are the acid gases carbon dioxide
and hydrogen sulphide. The corro-
sion of equipment and piping is an
inevitable consequence of removing
these very gases with amines, and
of handling sour water. There are
other corrosive impurities that
either enter in small amounts with
the gas, such as HCN and oxygen,
or that are produced in the amine
system itself, mostly heat stable
salts (HSS) derived from HCN.
Corrosion rates are affected by the
nature of the corrosive agent,
temperature, fuid velocity, the
presence of solids, and the metal-
lurgy involved.
1
To prevent
equipment failures, mitigate risk
and select optimal materials, one
must be able to predict corrosion
rates pertinent to the particular
processing conditions. This article
describes the underpinnings of a
chemistry-based predictive corro-
sion model built on both public and
much proprietary corrosion rate
data. The model includes depend-
ence on ionic solution composition
(speciation), fuid velocity, temper-
ature, HSSs, and metallurgy.
Corrosion in alkaline systems
Although the concepts presented
here apply equally to pH-neutral
and acidic systems, these systems
are not addressed because the
amount of corrosion data available
A chemistry-based predictive model predicts corrosion rates in specic
processing conditions
NATHAN A HATCHER, CLAYTON E JONES, G SIMON WEILAND and RALPH H WEILAND
Optimized Gas Treating, Inc.
for modelling is not as extensive.
The corrosive action of H
2
S is inher-
ently different from that of CO
2
in
that H
2
S can and does form a rela-
tively robust, protective iron
sulphide layer on the metal surface.
On the other hand, iron carbonate
forms a more fragile layer, so it
offers much less protection. There
are several tenets embedded in the
model:
The corrosive agents are acids
In and of itself, the amine (or
ammonia) is not corrosive
The iron sulphide flm can
protect against further corrosion
Iron carbonate also offers protec-
tion but to a lesser degree
High fuid velocities physically
increase corrosion rates
Higher temperature increases
corrosion rates
Heat stable salts chemically exac-
erbate corrosion.
Although technically incorrect,
the industry continues to bandy
about such terms as amine corro-
sion and alkaline stress corrosion
cracking to describe corrosion that,
at the root level of chemistry, is
really caused by dissolved acid
gases in various forms. For exam-
ple, nearly 60 years ago,
Polderman
2
reported that 20 wt%
MEA without acid gas was actually
less corrosive to steel than pure
water. As far as the corrosive
agents themselves are concerned,
the important parameter is the
chemical activity of the dissolved
acid gas species responsible for
corrosion. The activity (vs concen-
tration) changes with the amine
type, amine concentration, acid gas
loadings, the concentrations and
identities of HSSs, and temperature.
This may make some amine
systems appear to be more suscep-
tible to corrosion than others;
however, the essential point is that
it is the activity of the corrosive
species that is of direct importance,
not the type of amine per se.
The chemical species of interest
are: bisulphide ion (HS
), free phys-
ically dissolved H
2
S, bicarbonate
ion (HCO
3
+ OH
Fe(H
2
0)
6
+2
+
n HCOO
+ Fe(n HCOO
)
(2n)
+
(6 n)H
2
0
There are very few quantitative
measurements of the effect of HSSs
In their simplest stoichiometric
forms, the basic corrosion reactions
of dissolved H
2
S species with iron
are:
H
2
S(aq) + Fe(s) FeS(s) + H
2
(g)
2HS
-
(aq) + Fe(s) FeS(s) + H
2
(g) + S
=
(aq)
For CO
2
, the relevant reactions
are:
CO
2
(aq) + Fe(s) + H
2
O FeCO
3
(s) + H
2
(g)
2HCO
3
-
(aq) + 2Fe(s) 2FeCO
3
(s) + H
2
(g)
The oxidation reaction with
hydrogen sulphide is faster than the
reaction with bisulphide; however,
the alkalinity of the amine (and
ammonia) solutions means that the
dissolved H
2
S is predominantly in
the bisulphide form, with very little
remaining as free molecular hydro-
gen sulphide. This is also true of
dissolved carbon dioxide. The
concentrations of free H
2
S and CO
2
are pH dependent and pH is a func-
tion of amine strength, total
dissolved acid gas, temperature,
and to a lesser extent HSS concen-
trations. However, heat stable salt
species and their concentrations do
affect the speciation of the solution,
especially in lean solvents.
As discussed by Cummings et al
1
,
the sequence of physico-chemical
steps in the process of oxidising
iron consists of transporting the
acid from the bulk solution to the
metal surface, adsorption of the
acid onto the surface, reaction with
iron, and transport of reaction prod-
ucts back into the bulk solution. The
steps are similar to what occurs in
heterogeneous catalysis. The reac-
tion of H
2
S with the iron component
of various iron-based metallurgies
forms solid iron sulphide and
hydrogen gas, and as the reaction
proceeds, the surface of the iron is
changed to a mosaic of iron and
sulphide ions. The surface expands
by addition of sulphide, and the
liberation of hydrogen gas exacer-
bates the expansion. The surface
layer is somewhat porous, and it
adheres to the surface of the free
metal. The iron-H
2
S and iron-HS
reactions form reaction products in
completely different phases, as do
the reactions with carbon dioxide
and bicarbonate. Thus, because
reaction products are continually
removed from the reacting solution,
it follows from Le Chateliers princi-
ple that there is a strong
thermodynamic driving force
powering continued corrosion.
What limits the corrosion reac-
tions is primarily the amount of
bare, unreacted iron that the passi-
vating flm leaves available at the
metal surface. A secondary factor is
the concentrations of dissolved
reactant gases, H
2
S and CO
2
, which
are other parameters. Thus, H
2
S,
HS
, CO
2
and HCO
3
all react with
unprotected iron. To control the
concentration of dissolved gas in
their various forms, most practi-
tioners adopt a rich amine acid gas
loading, upper limit of <0.4 to 0.5
moles of total acid gas per mole of
molecular amine.
Passivation
In a new amine unit or in one that
has just been cleaned, during the
period immediately following intro-
duction of H
2
S, for example, the
corrosion rate climbs exponentially.
Measurements by Cummings et al.
3
using a bench-scale mini-amine
plant with relatively lean amine
indicated in some cases over 600
mpy corrosion rate during this
phase of operation. Eventually, the
corrosion rate levels off and begins
to fall as the iron sulphide layer
increasingly occludes contact
between H
2
S and iron (passivation).
Finally, once the iron sulphide layer
is established, the system settles
down to a nominal (and hopefully
low) residual corrosion rate. The
time over which the fnal steady
corrosion rate is attained is on the
order of hours or even days. During
these three phases of passivation,
the solution frst becomes nearly
black, and then it changes to dark
green, lighter green, and fnally
slightly amber. Chelated iron
(which results from complexation)
scatters light and turns otherwise
contaminant-free solution to amber.
The coloration depends on the size
of the iron sulphide particles. The
results of experiments on the time
dependence of iron passivation by
carbon dioxide are sparse. In one
gas ogrt.indd 2 06/03/2014 13:37
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gas linde.indd 1 04/03/2014 10:42
on corrosion and, although data on
certain HSSs are included in the
current model, more data over a
broader range of species and condi-
tions would be very welcome.
Model
Our mechanistic, chemistry-based
corrosion rate model was
28 Gas 2014 www.eptq.com
developed on the basis of the
sequence of steps outlined earlier,
namely, diffusion of the corrosive
agent to the surface, adsorption,
reaction with iron, and either depo-
sition or diffusion of products away
from the surface. The parameters in
the model have been regressed to a
large number of corrosion
measurements taken in well-con-
trolled bench scale fow
apparatuses and static equipment
using both H
2
S and CO
2
rich amine
systems and sour water. Although
the details of the quantitative
model are proprietary to Optimized
Gas Treating, Inc., the corrosion
rate in the model is a function of
the important factors:
Corrosion rate = f(a
H
2
S
,a
HS
_, a
CO
2
, a
HCO
3
_
, v, T)
Here: a
H
2
S
= activity of dissolved H
2
S
a
HS
_ = activity of bisulphide ion in
solution
a
CO
2
= activity of dissolved CO
2
a
HCO
3
_
= activity of bicarbonate ion in
solution
T = absolute temperature
v = superfcial fuid velocity in
pipe.
The model contains many of the
elements that comprise the tenets
discussed earlier and in a form
consistent with the various steps
occurring during corrosion, includ-
ing adsorption isotherms and the
temperature dependence of both
reaction kinetics and turbulent
diffusion. The model even includes
corrosion by water alone as a limit-
ing case in highly dilute solutions.
Data for corrosion by H
2
S were
correlated over the range of condi-
tions shown in Table 1. Although
scatter in the data is sizeable, if for
no other reason than that repeata-
ble corrosion rate measurements
are hard to make, especially by
weighing coupons, Figure 1 shows
that this model fts the measure-
ments over nearly three orders of
magnitude. Data for corrosion by
CO
2
were taken in both a static cell
and in a fow apparatus. Parameter
ranges and a parity plot comparing
the model with measurements of
corrosion in CO
2
-only amine
systems are shown in Table 2 and
Figure 2, respectively.
In correlating the model,
Arrhenius kinetics was found to ft
the data well. This is in agreement
with the proposal of Cummings et
al.
3
These authors assumed a power
law kinetics expression in terms of
molecular and ionic concentrations;
however, we found a better ft
using activities rather than concen-
100
1000
10
1 M
o
d
e
l
c
o
r
r
o
s
i
o
n
r
a
t
e
,
M
P
Y
0.1
0 1 10 100 1000
Measured corrosion rate, MPY
Rich amine
Sour water
Figure 1 Parity plot of measured vs model corrosion rates in rich amine and sour water
systems containing H
2
S only
100
1000
10
1 M
o
d
e
l
c
o
r
r
o
s
i
o
n
r
a
t
e
,
M
P
Y
0.1
0 1 10 100 1000
Measured corrosion rate, MPY
Figure 2 Parity plot of measured vs model corrosion rates in amines containing CO
2
only
gas ogrt.indd 3 12/03/2014 12:58
www.eptq.com Gas 2014 29
3 Cummings A L, Veatch F C, Keller A E,
Corrosion and corrosion control methods in
amine systems containing H
2
S, NACE Corrosion
1997 Conference, Paper No, 341.
Nathan A Hatcher joined Optimized Gas
Treating, Buda, Texas, as Vice-President,
Technology Development, in 2009. He holds a
BS in chemical engineering from the University
of Kansas and is currently a member of the
Amine Best Practices Group.
Email: nate.hatcher@ogtrt.com
Clayton E Jones joined Optimized Gas Treating,
Inc as a Software Development Engineer in
2012. He holds a BS in chemical engineering
from McNeese State University and a MS in
chemical engineering from the University of
New Mexico.
G Simon Weiland recently joined Optimized
Gas Treating as a Software Development
Engineer. He will receive a BS in chemical
engineering from the University of Oklahoma
in May 2014.
Ralph H Weiland is a co-founder of Optimized
Gas Treating with ofces in Clarita, OK,
Houston, TX and Buda, TX. He holds BASc,
MASc and PhD degrees in chemical engineering
from the University of Toronto.
Email: ralph.weiland@ogtrt.com
underpinning lends it not only to
confdent interpolation, but also to
reliable extrapolation to conditions
well outside measured ranges.
References
1 Cummings A L, Waite S W, Nelsen D K,
Corrosion and corrosion enhancers in amine
systems, Brimstone Sulfur Conference, Banff,
Alberta, April 2005.
2 Polderman L D, Dillon C P, Steel A B, Oil &
Gas J., 16 May 1955, 180.
trations. Note that neither amine
strength, nor amine type, nor
ammonia content appears explic-
itly, although these parameters
have signifcant effects on the activ-
ity of the corrosive species in
solution because speciation
depends on the amine type, its
concentration, and the temperature.
Corrosion of other metallurgies is
included in the models capabilities,
as is the corrosion of common pipe
fttings. The models mechanistic
Parameter Range
Lab velocity 025 m/s
Temperature 55120C
Sour water 130 wt% NH
4
HS equivalent
3.510 bar H
2
S partial pressure
Amines MEA (1830 mass %)
DEA (30 mass %)
MDEA (45 mass %)
0.10.8 mole H
2
S/mole amine
Calculated pH 6.09.5
Parameter ranges for corrosion by H
2
S
Table 1
Parameter Range
Lab velocity 013.5 m/s
Temperature 20160C
Amines MEA (630 mass %)
DEA (1040 mass %)
AMP (935 mass %)
MDEA (35 mass %)
0.00.4 mole CO
2
/mole amine
Calculated pH 8.411.36
Parameter ranges for corrosion by CO
2
Table 2
www.eptq.com PTQ Q1 2014 91
Ivelina Shishkova is R&D Department
Manager with Lukoil Neftohim Burgas. She
holds a MS in organic chemistry engineering
and a PhD in petroleum rening from Soa
Chemical and Technological and Metallurgical
University, and has authored more than 20
technical papers.
Email: Shishkova.Ivelina.K@neftochim.bg
Rosen Dinkov is the Quality Manager in the
Process Engineering department of Lukoil
Neftohim Burgas. His research interests include
crude oil characterisation, bio/conventional
fuels blends characterisation and modelling of
renery distillation processes. He holds a MS
in organic chemistry engineering from Burgas
University and a PhD in the technology of
fossil and synthetic fuels from the University
of Chemical Technology and Metallurgy, Soa.
Email: Dinkov.Rosen.K@neftochim.bg
Vladimir Jegorov is the Sales Development
Manager for Grace in the CIS region. Prior to
joining Grace, he was an FCC process engineer
at the Mazheikiai renery in Lithuania.
Petko Petkov is a full professor and rector
of the Burgas University Assen Zlatarov. He
teaches in the social science department in
the eld of oil rening and lubricants, and has
authored more than 180 scientic papers and
ve books.
Email: PST_Petkov@abv.bg
higher FCC C
4
yield led to higher
production of alkylate, which
resulted in the production of 2%
more premium grade gasoline.
References
1 Watanbe K, Nagai K, Aratani N, Saka Y,
Chiyoda N, Mizutani H, Techniques for octane
enhancement in FCC gasoline, 20th Annual
Saudi-Japan Symposium, Dhahran, December
2010. 17. Montgomery J A, Guide to Fluid
Catalytic Cracking, Part 1, 1993.
Ivan Chavdarov is a Chemical Engineer in
the Process Engineering department of Lukoil
Neftohim Burgas, Bulgaria. His activities are
focused on guiding the operation of the units
of the FCC complex, troubleshooting support
and optimisation of the performance of the
FCC complex.
Email: Chavdarov.Ivan.S@neftochim.bg
Dicho Stratiev is Chief Process Engineer with
Lukoil Neftohim Burgas. He holds a MS in
organic chemistry engineering, and a PhD and
a DSc in petroleum rening from the Burgas
University Assen Zlatarov. He has authored
more than 130 papers.
Email: Stratiev.Dicho@neftochim.bg
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Figure 3 Effect of changing the RVP on
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the Resolution catalyst period
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grace.indd 4 11/12/2013 12:49
gas ogrt.indd 4 11/03/2014 12:32
enersul.indd 1 10/03/2014 11:01
Zeolite based dryers in ethylene plants
S
team cracking represents more
than 95% of ethylene produc-
tion. This article focuses on
product stream drying duties in
ethylene production based on steam
cracking of paraffnic hydrocarbons.
Steam cracker feeds can be sepa-
rated into two categories:
Natural gas liquids (NGLs):
ethane, propane and butane
Heavier hydrocarbons such as
naphtha and gasoils.
North America (>5%) and the
A review of the role and nature of adsorbent dryers in the production of ethylene
by steam cracking
VASSILIOS ZAFIRAKIS and HANS HOEFER
Grace Materials Technologies
Middle East (>80%) use gaseous
feedstock to produce ethylene,
whereas in Europe (>80%), in Asia-
Pacifc (>81%) and in Latin America
(>65%) naphtha and gasoil feeds
dominate. On the world scale,
ethylene feedstocks are as follows:
Naphtha 52%
Gasoil 6%
Ethane 28%
Propane 8%
Butane 3%
Other 3%
Process sections of an ethylene
plant
In general, ethylene production has
four major sections:
1. Cracking heater section including
transfer line heat exchangers
(TLE)
2. Gasoline fractionator and quench
water tower
3. Compression section with both
acid gas removal and a main
drying unit
4. Chilling train and separation
www.eptq.com Gas 2014 31
Compression
Compression
Methanising
Deethanising
Depropanising
C
2
H
2
hydrogenation
C
3
H
4
hydrogenation
Demethanising
Acid gas
removal
Drying
PSA
Cracking
C
2
-cut
drying
C
3
-cut
drying
H
2
drying
Water
quench
Chilling
Ethylene
fractionation
Propene
fractionation
Feedstock
liquid
High
purity
hydrogen
Medium
purity
hydrogen
Methane
Ethylene
Propene
TLE and oil
quenching
Primary
fractionation
Pyrolysis
fuel oil
Debutanising
C
4
-cut
Pyrolysis
gasoline
Figure 1 Simplied process ow diagram for ethylene production by liquid cracking with a front-end demethaniser. In green boxes:
zeolite based adsorbers.
gas grace.indd 1 11/03/2014 09:30
32 Gas 2014 www.eptq.com
550-650C. The lowest temperature
refers to the start of the cracking
cycle (SOR), while the highest
temperature represents the maxi-
mum temperature, where the coil
and the TLE need to be cleaned
(EOR) and the heater has to be shut
down.
Gasoline fractionator and quench
water tower
One of the major differences
between liquid and gas crackers is
the use of a gasoline fractionator.
Liquid crackers require gasoline or
primary fractionators. This is not
necessary for crackers using ethane
or propane as feedstock (see Figure
2).
Furthermore:
For liquid feedstock downstream
of the TLEs, the required cooling to
temperatures of 200-230C cannot
be performed in standard shell and
tube heat exchangers; condensation
of a signifcant portion of liquids in
the cracked gas leads to excessive
fouling by carbon deposits.
section for cracked gas separation
into the desired products.
A variety of commercial process
routes is available. Whereas crack-
ing heaters, quench towers and
compression sections are similarly
confgured (sections 1-3 above), for
separation (section 4) three main
process routes are established. They
are characterised by the frst sepa-
ration tower and the position of the
unit for hydrogenation of C
2
acety-
lenes in the cracked gas. These
three process sequences are:
1. Demethaniser frst with tail-end
hydrogenation
2. Deethaniser frst with front end
hydrogenation
3. Depropaniser frst with front end
hydrogenation.
Cracking heater section and TLEs
The ethylene industry is served by
a limited number of licensors and
contractors with their own ethylene
process technologies. They have
designed and built most of the
worlds ethylene plants. In the
process route shown in Figures 1, 2,
3 and 4 hydrocarbon feedstock
(ethane, propane, butane, naphtha
and gasoil) is fed into a pyrolysis
heater (furnace) and preheated to
temperatures of 500-650C. Steam
enters the heater coil and the
hydrocarbon/steam mixture is
further heated to temperatures of
750-890C. Within this range, satu-
rated hydrocarbon molecules crack
to form olefns such as ethylene,
propylene and butene, and diole-
fns, as well as other hydrocarbon
molecules such as methane,
benzene, toluene, and hydrogen
and other products. After this
pyrolysis reaction the produced gas
from the heater coils is rapidly
cooled in tubular heat exchangers
(transfer line exchangers, TLE)
against boiler feed water, produc-
ing high pressure steam (HPS). In
the case of gaseous feeds, the gas
leaves the TLE at a temperature of
300-400C. For liquid feeds such as
light to heavy naphtha, tempera-
tures are 420-450C, and for gasoil
Compression
Compression
Methanising
Deethanising
Depropanising
C
2
H
2
hydrogenation
C
3
H
4
hydrogenation
Demethanising
TLE
Acid gas
removal
Drying
Drying
PSA
Cracking
C
2
-cut
drying
C
3
-cut
drying
H
2
drying
Water
quench
Chilling
Ethylene
fractionation
Propene
fractionation
Feedstock
gas
Gasoline
High
purity
hydrogen
Medium
purity
hydrogen
Methane
Ethylene
Propene
C
4
+
hydrocarbons
Figure 2 Simplied process ow diagram for ethylene production by gas cracking with a front-end demethaniser. In green boxes: zeolite
based adsorbers
gas grace.indd 2 11/03/2014 09:43
Therefore, the cracked gas is further
cooled by injection of oil (oil
quench) by means of devices called
quench fttings. Oil quenching is
performed downstream of the TLEs
after each heater, or in the
combined cracked gas line (transfer
line) from all heaters. The mixed
two-phase fow of cracked gas and
quench oil is separated in the
bottom section of the primary frac-
tionator. In this tower the cracked
gas is separated from the fuel oil,
which leaves the tower from the
bottom. The overhead is directed to
the quench water tower
For gaseous feedstock, cracked
gas from the TLEs is further cooled
to about 200C against feed or
boiler feed water (BFW) in the
so-called secondary TLE, before
entering the quench water tower
where the cracked gas is further
cooled.
In a liquids cracking plant, this
tower essentially works as a partial
condenser to the upstream oil frac-
tionators, which condense both the
www.eptq.com Gas 2014 33
steam and a signifcant part of the
gasoline components. Part of the
gasoline is used as refux for the
upstream oil fractionator. The
remaining gasoline leaves the unit
after stripping in a side tower for
stabilisation.
The cracked gas leaves the top of
the quench tower at a temperature
of 35-40C, slightly above atmos-
pheric pressure and enters the
compression section of the plant.
Compressor section, acid gas
removal and drying of cracked gas
The cracked gas is compressed in
four to fve stages to pressures of
35-37 bar. Usually, compression of
the charge gas from gaseous feed-
stock cracking takes place in
centrifugal compressors employing
four stages, while fve compressor
stages are required for compression
of cracked gas from the cracking of
liquid feedstocks such as naphtha
or gasoil. Consequently, in plants
processing gaseous feedstock a
higher compression ratio is
employed, yielding a higher
discharge temperature compared to
liquid based plants. The number of
stages depends primarily on gas
composition and the highest
temperature allowed for the
discharge of the different compres-
sion stages. Such a temperature is
typically below 100C in order to
avoid excessive equipment fouling
through polymerisation of diolefns
and other precursors in the cracked
gas. As the pressure increases at
the different compressor stages,
water and hydrocarbons are
condensed in the downstream cool-
ers and separated from the gas in
the interstage separators.
Water is returned to the quench
water tower while the hydrocar-
bons from the frst three stages are
recycled to the gasoline stripper in
the upstream hot section of the
plant. The acid gas removal system
is usually positioned after the third
or fourth compression stage.
Cracked gas leaving the acid gas
removal unit has a remaining acid
Compression
Compression
Methanising
Deethanising
Debutanising Depropanising
C
2
H
2
hydrogenation
C
3
H
4
hydrogenation
Chilling and
demethanising
TLE and oil
quenching
Acid gas
removal
Primary
fractionation
Drying
Drying
PSA
Cracking
C
2
-cut
drying
C
3
-cut
drying
H
2
drying
Water
quench
Chilling
Ethylene
fractionation
Propene
fractionation
Feedstock
liquid
Pyrolysis
fuel oil
High
purity
hydrogen
Medium
purity
hydrogen
Methane
Ethylene
Propene
C
4
-cut
Pyrolysis
gasoline
Figure 3 Simplied process ow diagram for ethylene production by liquid cracking with a front-end deethaniser. In green boxes: zeolite
based adsorbers
gas grace.indd 3 11/03/2014 09:44
34 Gas 2014 www.eptq.com
purity is withdrawn from the
lowest temperature separator; this
can be further purifed in a down-
stream system. The condensates
produced over several stages are
fed to the demethaniser (see Figure
1). In recent plants, mixed refriger-
ants are used instead of cascade
refrigeration systems.
The process diagrams in Figures 3
and 4 show simplifed process
routes for liquid cracking plants
using a separation sequence of
deethaniser frst (see Figure 3) or
depropaniser frst (see Figure 4).
2,5
The separation section
The layout of the separation section
depends on the selected separation
sequence, the feedstock and the
targeted products. The following
represents the demethaniser frst
concept (see Figure 1):
Demethaniser
Deethaniser, acetylene converter,
acetylene converter dryer
Ethylene fractionator (splitter)
ment. Therefore the condensate
always contains traces of free
water. This needs to be considered
in the design of downstream
condensate dryers. Complete
removal of water is mandatory for
the charged gas or liquid streams to
be cooled to temperatures below
15C in the downstream chilling
train and the separation section, to
avoid the plugging of lines and
equipment due to formation of
hydrates and ice. For the removal
of moisture from these streams, the
most current technology uses solid
alumino-silicates (zeolitic molecular
sieves) which will be discussed
later. Previously, dual systems
(glycol followed by alumina) were
employed.
After drying, the cracked gas is
partially condensed in several
stages of a cascade refrigeration
system (propylene, ethylene, meth-
ane), resulting in cold product
streams at temperatures of -135C
to -145C. Hydrogen of 95% mole
gas content of about 1 ppmv.
Depending on the technology
selected downstream of the acid
gas removal system, one or two
additional compression stages may
be employed. Additional C
2
- and C
3
rich condensate is produced in
these compression stages. This is
fed into the stripper, where the C
2
and lighter fractions are forced
through the tower top back to a
compression section operating at
lower pressure. The bottoms of this
tower are sent to the downstream
depropaniser. If the operating
temperature in the depropaniser is
lower than 15C, the bottom stream
has to be dried to avoid the forma-
tion of hydrates.
The cracked gas is saturated with
water before compression as well
as after each intercooler stage and
down-stream of the acid gas
removal system. The condensate is
also saturated with water, while
excess water separation depends on
the design of the separator equip-
Compression
Compression
Methanising
Deethanising Depropaniser
C
2
H
2
/ C
3
H
4
hydrogenation
C
3
H
4
hydrogenation
Chilling and
demethanising
Acid gas
removal
PSA
Cracking
C
2
-cut
drying
C
3
-cut
drying
H
2
drying
Water
quench
Ethylene
fractionation
Propene
fractionation
Feedstock
liquid
High
purity
hydrogen
Medium
purity
hydrogen
Methane
Ethylene
Propene
TLE and oil
quenching
Primary
fractionation
Pyrolysis
fuel oil
Debutanising
C
4
-cut
Pyrolysis
gasoline
Drying
Chilling
Figure 4 Simplied process ow diagram for ethylene production by liquid cracking with a front-end depropaniser. In green boxes:
zeolite based adsorbers
gas grace.indd 4 11/03/2014 09:44
www.eptq.com Gas 2014 35
provider may minimise by chemi-
cal modication of the selected
adsorbent.
Kinetics or, better, mass transfer
kinetics, is the overall term related
to intra-particle mass transfer char-
acteristics causing breakthrough
behaviour as well as lost bed mass.
Lost bed mass is that part of the
adsorber bed which is still active
even though the breakthrough has
just started. Fast kinetics provides a
sharp breakthrough curve with a
small lost bed mass, while slow
to be adsorbed (the adsorbate). In
practice, one has to distinguish
between equilibrium capacity,
given through isotherms, and the
typically lower overall dynamic
capacity, which is characterised by
specic operating conditions.
Selectivity is the ratio of the
amount of purposely adsorbed
component to that of all others in a
uid to be processed. In reality,
selectivity is never 100% for the
targeted adsorbate due to co-
adsorption, which the adsorbent
Depropaniser, methyl acetylene
and propadiene (MAPD) converter,
MAPD converter dryers
Propylene fractionator (splitter)
Debutaniser.
The purpose of the demethaniser
is the separation of methane and
other lights (CO, H
2
) from C
2
+
components which are sent to the
deethaniser. This tower separates
C
2
components (acetylene, ethylene,
ethane) from heavier hydrocarbons.
C
2
hydrocarbons leave the deetha-
niser as the overhead product,
while the C
3
and heavier compo-
nents, the bottoms, are directed to
the depropaniser. The overhead of
the deethaniser is heated and
hydrogenated in order to convert
the acetylenes into ethylene and
ethane. Because traces of water
may be present during this hydro-
genation, drying of the C
2
hydrocarbons is necessary before
they enter the ethylene fractionator,
typically operating at -10C to
-35C and 16-18 bar. The ethylene
product is the overhead of the
ethylene fractionator. The bottom
product of the ethylene fractionator
is ethane, which is recycled back to
the heaters for cracking to extinc-
tion. In the depropaniser, C
3
+
hydrocarbons are separated into
two fractions. The C
3
fraction as
overhead and the heavier C
4
frac-
tion leaving the tower as bottom
product are sent to the debutaniser.
Due to the very low C
3
+ fraction in
ethane based crackers, C
3
and C
4
separators are not present.
Zeolitic adsorbents in
ethylene plants
Any adsorbent has basically seven
features, six which qualify such
material for specic adsorption
duties, namely:
Capacity
Selectivity
Kinetics
Process compatibility
Regenerability
Mechanical stability (crush
strength, attrition)
Cost.
Adsorption capacity is the
amount of adsorbate related to
adsorbent mass, which is a function
of operating temperature and the
partial pressure of the component
SweetSulf
TM
Sprex
AdvaSulf
TM
AdvAmine
TM
COSWEET
TM
HySWEET
Leader in H
2
S Removal
Sour Gas Treating Problems Solved
Absorbs the H
2
S, Rejects the CO
2
Cost-Effective for Grassroots and Retrofits
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2
S to Less Than 10 ppm
Vast Commercial Experience (100 + units)
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exxon.indd 1 07/03/2014 09:52
www.eptq.com Gas 2014 39
molecules are positioned during the
adsorbing phase, relying on strong
physical forces called physisorp-
tion; this is fully reversible, in
contrast to chemisorption where
chemical reactions are involved.
plants, because it reduces product
losses through low co-adsorption.
The 3A zeolite has a channel
system with precisely dimensioned
openings and negatively charged
cages. In these cages, adsorbed
The cost however, which may be
generated by a production loss due
to a malfunction of the adsorption
unit, is far higher than the cost of a
changeout of the unit. Reported
cases comprise the selection of
non-process-compatible adsorbents
and/or a design which is not
adequate for the process unit.
Therefore, during design and
changeout of an adsorber unit,
consultation with experienced
adsorbent suppliers is inevitable for
ensuring reliable unit operation.
Industrially relevant adsorber
zeolites are artifcially crystallised
alkaline and alkaline earth alumi-
no-silicates, which have the general
formula (M, M)[(AlO
2
)
x
(SiO
2
)
y
]
zH
2
O. Such zeolites are crystalline
solids consisting of tetrahedral SiO
4
and A
l
O
4
building blocks, forming
microporous structures. Each
aluminum tetrahedron carries a
negative charge, which has to be
neutralised with a metal ion (M,
M) such as Na
+
, K
+
and/or Ca
2+
.
Per unit cell, the SiO
4
and A
l
O
4
tetrahedra form eight truncated
octahedra, which build one soda-
lith cage, and are stacked in a cube
resulting in an A-type zeolite.
The 3A type zeolite, the work-
horse of ethylene plant dryers, is
produced via Na
+
-> K
+
ion
exchange, starting from an 4A type
zeolite with a pore opening of
about 4 (0.4 nm), whereas the
larger K
+
ions narrow the pore
openings by about 1 (0.1 nm, see
Figure 5).
The impact of Na
+
/K
+
ion
exchange on the dimension of
A-type zeolite pore orifces, and the
subsequent change of equilibrium
adsorption capacities for various
adsorbates, is shown in Figure 6.
The adsorption of all adsorbates is
reduced when K
+
concentration
increases. Reduction of water
capacity, however, is much less
pronounced than for any other
adsorbate shown. In ethylene
drying, an A-type zeolite with a K
+
exchange of 50% already shows
effcient moisture pick-up features
and, in parallel, low adsorption
capability for ethylene. This is
important for the application of 3A
zeolite in drying ethylene rich
streams, as occurs in ethylene
Carbon dioxide at 700 torr, 25C
Ethylene at 700 torr, 25C
Ethane at 700 torr, 25C Methanol at 4.0 torr, 25C
Water at 4.5 torr, 25C
Oxygen at 700 torr, 183C
0.15
0.25
0.30
0.20
0.10
0.05
g
a
b
s
o
r
b
a
t
e
/
g
a
b
s
o
r
b
e
n
t
0
0 0.1 0.2 0.3 0.4 50. 0.6 0.7 0.8 0.9 1.0
Exchange of K,
K
+
/ (K
+
+Na
+
)
Figure 6 Impact of Na
+
/K
+
ion exchange on equilibrium adsorption capacities measured
on powders
7
Figure 7a Ball-and-stick representation of the structure Figure 7b Microporous channels
with openings of a 3A zeolite, consisting of eight sodalith cages. 3 for moisture
transportation Figure 7c Sodalith cages with diameter >0.8 nm
Figure 7d 3A zeolite pore structure comprising moisture adsorbance channels and cages
for moisture transportation and storage
a
b
c d
gas grace.indd 7 11/03/2014 09:44
40 Gas 2014 www.eptq.com
tions are 15-20 wt%. This reduces
the nominal equilibrium adsorption
capacity by approximately the same
percentage because clay based
binders have limited to no adsorp-
tion properties.
The binder is fundamentally
important to both the mechanical
stability and the catalytic activity of
the molecular sieve body. Figure 9
shows the principal dependence of
the amount of used binder on the
crush strength of the zeolite bead
and its corresponding water equi-
librium capacity. With increasing
binder concentration the crush
strength also increases but, at the
same time, the equilibrium water
adsorption capacity deteriorates.
Catalytic activity in the adsorbent
body has to be minimised.
Consequently, for ethylene plant
adsorbents reactive metal-free clay
binders have to be selected.
Beside the degree of K
+
exchange
and the type and amount of binder,
the fring conditions for beads in
the adsorbent manufacturers
calciner play an important role in
the beads performance, in terms of
mechanical stability and adsorption
properties. The two key process
parameters are calcination tempera-
ture and residence time. These
parameters also impact co-adsorp-
tion behaviour towards ethylene
and eventually to polymerisation
and coking.
In summary, the selected optimal
binder ensures a number of impor-
tant characteristics for the fnal
adsorber bead, namely:
The right meso- and macroscopic
transportation pore confguration
A mechanically stable bead with
low attrition
Minimised catalytic activity when
exposed to the reactive species of
hydrocarbon feedstock.
The uniform crystalline structure
of zeolitic molecular sieves, in
combination with a secondary
transportation pore system,
provides predictable and reliable
adsorption properties.
Typically, zeolitic adsorber beads
are commercially available in bead
sizes ranging from 1 mm to 5mm in
diameter. Depending on the adsor-
bent duty, bead size is selected by
trading adsorption kinetics with
molecules with the right dynamic
dimensions may enter the pores,
whereas larger molecules will be
rejected. Figure 8 depicts a symbolic
3A zeolite structure with water
molecules adsorbed from a wet
ethylene stream.
After crystallisation resulting in a
particle size of approximately 10,
the individual A-type zeolite crys-
tals, however, are far too small for
use in fxed bed adsorbers.
Consequently, they are mixed with
a clay binder for moulding into
macroscopic beads. Around binder
zeolite contact points the pores of
the zeolite will be at least partly
blocked. Typically binder propor-
The interconnecting channels allow
the adsorbate molecules to travel
into the cages (adsorption) or leave
them (desorption). Both channels
and cages build up the 3A zeolite
pore system shown in Figures 7a to
7d, according to the University of
Princetons ZEOMICS library.
8
The red spheres represent oxygen
atoms, the sticks are oxygen-alumi-
num and oxygen-silicon bonds. For
a better view of the Na
+
ions, the K
+
ions and the truncated octahedra
are omitted.
The 3A zeolite framework of
symmetrically orientated tetrahedra
and octahedra and its pore struc-
ture is stereo-selective; smaller
15
25
20
10
5
W
a
t
e
r
a
d
s
o
r
p
t
i
o
n
c
a
p
a
c
i
t
y
,
w
t
%
0
0 5 10 15 20 25 30
Amount of binder, wt%
Water adsorption capacity
Crush strength (arbitrary units)
Figure 9 Principal dependence of binder amount on crush strength and equilibrium water
capacity
9
Figure 8 Idealised stereo-selective moisture adsorption on a 3A zeolite
gas grace.indd 8 11/03/2014 09:44
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www.eptq.com Gas 2014 43
for adsorbate molecules is the driv-
ing force. In depressurisation mode,
the pressure inside the adsorber
vessel will be lowered by a factor >
10. At low pressures the affnity of
the zeolite pores for the adsorbate
molecules is signifcantly reduced,
resulting in adsorbate release from
the adsorber bed. When the sorbent
material has been suffciently freed
of adsorbate, the adsorber is ready
for the next cycle.
In order to allow continuous
TSA/PSA gas conditioning, two or
more adsorber beds in the gas
treatment unit are in adsorption,
regeneration or standby modes.
Dryers in ethylene plants
Complete removal of the water
contained in cracked gas is manda-
tory in order to avoid plugging of
downstream cryogenic sections due
to freezing or formation of
hydrates. Depending on the
cracked feedstock and the confgu-
ration of the ethylene plant the
following dryers may be in opera-
tion (the frst three are mandatory
for all ethylene plants):
1. The charge gas dryer or main
ethylene dryer, located after the
acid gas removal unit
2. The condensate dryer for condi-
tioning the gasoline stream from
the condensate stripper
3. The acetylene converter or
secondary dryer downstream of the
C
2
acetylene converter
4. The MAPD converter dryer
downstream of the MAPD
converter
its accepted maximum impurities
level, the adsorber has to be
regenerated.
Two regeneration methods are
used: thermo-swing adsorption/
desorption (TSA) and pressure
swing adsorption/desorption
(PSA). They rely on the fact that,
apart from the physic-chemical
nature of the adsorbate, adsorption
and desorption are pressure,
temperature and time controlled. In
TSA units, temperature is the
process variable; in PSA units pres-
sure is the variable.
In an ethylene plant, with the
exception of the Hydrogen PSA
purifer, all other adsorption units,
including the hydrogen dryer
downstream of the methanator, are
TSA types. In the TSA case, thermal
regeneration is accomplished by
passing hot product gas through
the bed, heating it up to a tempera-
ture signifcantly above the
temperature during adsorption.
The hot adsorber bed decreases its
affnity for adsorbates and releases
them into the gas fow now acting
as purge fuid. After completion,
the adsorber bed is cooled down,
regaining its adsorption capacity.
Then the unit is ready for the next
cycle. Typical regeneration gas
temperatures are 240C for 3A
molecular sieves and 250-280C for
4A molecular sieves.
In contrast, pressure swing regen-
eration takes place at the same
temperature as adsorption. In the
adsorption mode at elevated pres-
sures the affnity of zeolite pores
pressure drop and mechanical
stability. As a rough guide, the
smaller the beads the better the
kinetics, but the higher the pressure
drop the lower the single piece
crush strength, and vice versa.
Commercial adsorber beads have a
comparatively narrow bead size
range in order to have as close as
possible to mono-disperse particle
distribution characteristics targeting
adsorber bed porosities of 30% to
35%. Depending on the suppliers
philosophy, zeolitic adsorber extru-
dates or pellets with L/D ratios
from nearly 1 to 5 are in use.
Extrudates with higher L/D ratios
may lead to a lower space flling
and a lower bulk density. They
tend to have favourable mass trans-
fer properties, however, sacrifcing
adsorption capacity and jeopardis-
ing the adsorber beds mechanical
stability. The pressure drop for
beads is more favourable than for
extrudates (see Figure 10), even in
the typical gas velocity range
between 5 to 12 m/min.
Even more importantly, plant
operators occasionally report signif-
icantly increased dust formation
when loading and unloading the
adsorber vessel, as a result of extru-
date breakage and split-offs.
Adsorber zeolites have a strong
affnity for polar and polarisable
molecules, whereas the higher the
degree of polarity, the higher the
selective adsorption power. Since
water is the most polar molecule
known, it is the preferred adsorb-
ate. In a moisture-containing
hydrocarbon stream, next to water
heavier hydrocarbons will be
picked up frst.
Depending on the water/hydro-
carbon ratio, for some time the
zeolite adsorber bed will simultane-
ously pick up water and some
hydrocarbons. At the end of the
adsorption cycle, the part of the
adsorber bed next to the inlet is
enriched with adsorbed water,
whereas the middle part of the bed
contains a higher concentration of
hydrocarbons. The outlet part of
the bed carries the lightest hydro-
carbons. This effect is given by the
higher polarity of water over heav-
ier and lighter hydrocarbons.
Before the product gas has reached
12
20
18
16
14
10
8
6
4
2
P
r
e
s
s
u
r
e
d
r
o
p
,
m
b
a
r
/
m
0
0 2 4 6 8 10 12 14 16 18 20
Superficial velocity, m/min
2.5-5.0 mm beads
3.7 mm extrudates
Figure 10 Pressure drop development of beads vs extrudates
gas grace.indd 9 11/03/2014 09:44
44 Gas 2014 www.eptq.com
stage at lower operating pressure
(see Figure 3). This is often used
when the depropaniser rst with
front end hydrogenation route has
been chosen.
The compressor section of an
ethylene plant is prone to fouling,
given the nature of the cracked gas,
which may contain varying concen-
trations of hydrogen, parafns and
aromatics as well as reactive
compounds such as acetylenes,
olens and diolens. Under certain
conditions, compounds such as
butadiene, styrene, isoprene and
vinyl acetylene may form polymers.
Consequently, charged gas dryers,
which are embedded in this section,
are also impacted by this fouling
tendency. Such fouling is the result
of oligomerisation, polymerisation
and condensation reactions, given
by:
Free radical polymerisation
reactions
Diels-Alder polymerisation of
active Dienes (Cyclopentadiene,
Methyl cyclopentadiene, and so on).
The radical polymerisation reac-
tions are caused by heat alone, but
hydrocarbons into the regeneration
off-gas due to absorption and
co-adsorption outperforming the
dual system of glycol based absorb-
ers followed by alumina adsorbers
More economical to regenerate.
Two design options with differ-
ent operating pressures are used,
depending on the selected process
route, which also dene the posi-
tions of the dryers in the ethylene
plant:
1. Dryers operated at high pressure
(26-37 bar, 13-15C)
2. Dryers operated at low pressure
(12-25 bar, 12-14C).
The dryer operating temperature
is usually set at 2-3C above the
hydrate formation temperature. It
has to be kept in mind that a
temperature rise by 1C results in a
6.5% increase in water load to be
removed by the dryer. Therefore
careful temperature control is
advised.
Typically, the dryers are posi-
tioned after the last compression
stage, as in option 1 (see Figures 1
and 2). In option 2, the dryers are
positioned after the next-to-last
5. The hydrogen dryer downstream
of the methanator for upgrading
the hydrogen stream from the cold
box and or the PSA unit for hydro-
gen of high purity.
The charge gas dryers or main
cracked gas dryers
The main cracked gas dryer is posi-
tioned in the compressor section
downstream of the acid removal
unit (caustic and water wash
tower). Complete removal of water
to a level below <1 ppmv is manda-
tory. A specially developed 3A
molecular sieve is state-of-the-art
technology for operating such
dryers. It has almost completely
replaced the dual system of glycol
absorbers followed by alumina
adsorbers. The main technical and
commercial reasons for replacing
earlier drying concepts with zeolitic
molecular sieves are:
Achieving gas specications <0.1
ppmv water content
Achieving signicantly lower
green oil formation
Achieving longer on-stream time
Signicantly lower losses of
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HOERBIGER sets standards in
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Image_ad_KT_2014.indd 1 06.03.2014 15:46:22
gas grace.indd 10 11/03/2014 09:45
www.eptq.com Gas 2014 45
shows a typical aging curve and
the corresponding pressure drop
development of a naphtha based
ethylene plants charged gas dryer.
are enhanced by peroxides. Also,
the Diels-Alder condensation reac-
tion contributes to fouling due to
formation of heavy hydrocarbons
condensing on the metal surfaces
and gradually dehydrogenating.
Both polymerisation reactions are
catalysed in the presence of iron.
The temperature is a key variable
for such reactions.
10,11
Grace and others encountered the
following experiences regarding the
operation of charge gas dryers:
All gas cracking units show a
high fouling rate in the compressor
section, whereas plants based on
liquid cracking report low to
moderate fouling.
Lower pressure charge gas dryers
have to cope with a higher water
load (see Table 1) and are more
prone to fouling compared to those
plants with the dryers set up at
higher pressures (32-37 bar vs 12-22
bar) after the last compression
section. This fouling is caused by
non-condensed and non-separated
heavier fouling precursors.
Regarding the frst experience, it
is known that gas-based plants,
typically operating four compressor
stages, generate higher discharge
gas temperatures because of the
higher compression ratios per
stage. This effect is further
enhanced by higher concentration
of hydrogen and its higher isotropic
exponent k=C
p
/C
v
:
T
s
, P
S
= Suction temperature,
pressure
T
D
, P
D
= Discharge temperature,
pressure
By contrast, higher content of
aromatics in the cracked gas from
liquid based crackers helps to
dissolve and wash out polymers
generated by the heat of the
compression.
Undesired charged gas-adsorber
bed interactions sooner or later lead
to deterioration of the adsorber
bed. Consequently, adsorber bed
capacities will be reduced and the
pressure drop will increase; both
are caused by the formation of
polymerisates and coke. Figure 11
Dryer operating pressure, bar 35 15
Operating temperature, C 15 15
Water content of charge gas, mg/STDm
3
450 840
Charged gas water content as a function of operating pressure
Table 1
47% 50%
3%
>4.5 years
2.5-4.5 years
<1.5 years
18%
50%
32%
Cycle times too short
Pressure-drop issues
Vessel inspections
11%
81%
8%
Kept employed dessicant
Changed technology for
general improvement
Change of targeted contaminants
80
100
90
70
60
B
e
d
d
e
t
e
r
i
o
r
a
t
i
o
n
d
u
e
t
o
a
g
e
i
n
g
,
%
0.19
0.21
0.17
0.15
0.18
0.20
0.16
P
r
e
s
s
u
r
e
d
r
o
p
,
b
a
r
50
0 6 12 18 24 30 36 42 48 54 60
Months of operation
Pressure drop
Bed deterioration
Figure 11 Ethylene plant charged gas dryer bed aging and pressure drop increase
Figure 12a Desiccant life time in ethylene
plants
Figure 12b Reasons for changeout
Figure 12c Consequences of the changeout
a b
c
It is run at high pressure over an
operational plant period of 60
months, equalling about 650 regen-
eration cycles. After 650 cycles, the
adsorption bed capacity has been
reduced to nearly 70% and the
pressure drop over the bed has
increased from 0.15 bar to 0.21 bar.
According to an AIChE survey,
12
operators from gas (60%) and
liquid (40%) processing ethylene
plants reported the observations
shown in Figures 12a to 12c.
The design philosophy for a
gas grace.indd 11 11/03/2014 09:45
18-20 bar for the gas phase, and
16-28 bar for the liquid phase, with
temperatures typically in the range
35-50C. The best desiccant for this
drying step, like the second drying
step, is a 3A type zeolite with espe-
cially low polymerisation and
coking characteristics. Such a desic-
cant can be used for gas and liquid
phase operations. The regeneration
gas and the regeneration tempera-
ture are the same as for the above
charged gas dryer.
The condensate dryer
Depending on the technology
chosen, hydrocarbon condensates
generated at the fourth compres-
sion stage have to be separated in
the knockout drum upstream of the
charge gas dryer. These condensate
dryers operate at pressures in the
range 30-35 bar, at temperatures of
12-15C. Typically, two dryers are
required: one in service, the other
in regeneration or standby mode.
The state-of-the-art adsorbent is a
special 3A type zeolite. The hydro-
carbon condensates contain
oligomer and/or polymer precur-
sors, which are formed in the
upstream compression section.
Consequently, the selected adsor-
bent should exhibit little tendency
to coking and polymerisation.
Depending on cycle times, which
are 24-48 hours, the lifetime may
reach ve to six years. The conden-
sate is saturated with water,
depending on composition and
operating conditions. The quality of
the upstream separator must ensure
that practically no traces of free
water reach the dryers. If free water
is expected always to be present in
the condensate, a layer of macropo-
rous silica gel is installed in the bed
inlet to guard the zeolitic adsorber
bed against free water. The mois-
ture concentration in the outlet is
specied to be below 1 ppmv. This
is to avoid the formation of
hydrates in downstream piping and
equipment. The regeneration gas
and the regeneration temperature
are the same as for the dryers.
The hydrogen dryer
In addition to methane, hydrogen
off-gas from the ethylene plants
cold box contains carbon monoxide
46 Gas 2014 www.eptq.com
any freezing or gas hydrate forma-
tion in the ethylene splitter. The
secondary dryer runs in a one-
vessel mode with a service time of
20 days prior to regeneration.
Consequently, during regeneration
the secondary dryer step is
bypassed. The desiccant of choice
for the secondary dryer is a type
3A zeolite with especially low
polymerisation and coking charac-
teristics. Such desiccant should
exhibit low co-adsorption for acety-
lene and olens. Depending on the
employed technology and the
selected separation sequence of the
rst tower, the operation conditions
are: pressures of 20-30 bar and
temperatures of -30-30C. The
regeneration gas and the regenera-
tion temperature are the same as
for the charged gas dryer.
The MAPD converter dryer
The MAPD converter dryer is posi-
tioned between the methyl
acetylene and propandiene hydro-
genation unit (MAPD) and the
ethylene splitter to remove any
moisture formed during the hydra-
tion of the C
3
cut. This dryer is
needed to avoid any water content
in the nal product, which is espe-
cially important for naphtha based
crackers. Typically, two vessels are
installed, one in service, the other in
regeneration mode, for both liquid
and gas phase operations, depend-
ing on the chosen hydrogenation
technology. The moisture content of
the inlet uid is typically specied
at <100 ppmv. For gas and liquid
phases, the dryer outlet uid mois-
ture contents are specied to be
below 1 ppmv. The corresponding
operating pressures are in the range
charged gas dryer depends on the
contractor:
Main/guard bed conguration
(Lummus, Technip Stone &
Webster): the moisture analyser is
installed between beds. The guard
bed height is typically sized for six
to eight hours of additional adsorp-
tion time, allowing operators to
take action in case breakthrough
conditions occur. An additional
function of the such guard bed is to
adsorb trace contaminants such as
ammonia and methanol
The single bed (Linde) adsorbent
section below the moisture analyser
functions as a guard bed. In this
design, one support grid has been
omitted and in the same available
volume more adsorbent material
can be installed. Furthermore, this
concept allows an easier loading of
the adsorbent material. Both
options are shown in Figure 13:
Typical arrangements: two or
three vessels in total, one or two in
adsorption, one in regeneration
mode
Flow: downwards during adsorp-
tion, upwards during regeneration
Regeneration gas: methane frac-
tion from demethaniser overhead,
also utilised for all subsequent
dryers. Typical regeneration gas
inlet temperature range is 210-230C
Adsorption time typically 48-64
hours.
Typical lifetimes of low pressure
operated units are less than ve
years, while high pressure units
may achieve more than ve years
of operation.
The secondary dryer
The secondary dryer is positioned
between the acetylene converter
and the ethylene splitter. Its
purpose is to remove moisture
formed in the acetylene converter
during the selective hydrogenation
of C
2
acetylenes. This is caused by
the presence of free oxygen from
decomposed oxygenates and/or
oxygen ingress into the ethylene
unit. A typical specied moisture
load for the inlet gas is below 20
ppmv. Licensors offer designs with
a limit of 50-100 ppmv of moisture
as a safety margin. The targeted
moisture concentration of the outlet
gas is below 1 ppmv, thus avoiding
x = 0.8 to 1.0 mm
x x
Figure 13 Typical design layouts for
charged gas dryers. Left: main bed/guard
bed. Right: single bed
gas grace.indd 12 11/03/2014 09:45
www.eptq.com
are zeolitic compounds with very
promising adsorption characteris-
tics. Unfortunately, these materials
are still either diffcult to produce,
or thermomechanically or chemi-
cally not stable enough to serve as
adsorbents in ethylene plants.
The shale gas boom leading to
the erection of megacrackers is
expected to rely on established
adsorption technology. Specially
developed 3A type zeolites will
continue to play a dominant role in
this industrial application.
References
1 True W R, Oil & Gas Journal, July 2013, 90-
103.
2 Falqi F H, The Miracle Petrochemicals,
Olens Industry: An In-Depth Look at Steam
Crackers, 7-8, Universal-Publishers, Boca Raton,
Florida, USA, 2009.
3 Kniel L, et al, Ethylene Keystone to the
Petrochemical Industry, 1980, 78-107, Marcel
Dekker Inc. New York, NY.
4 Kapur S, Cracking Technology for the
Production of Ethylene, Chapter 6.1, Handbook
of Petrochemicals Production Processes,
McGraw-Hill Professional, 2004.
5 Zimmermann H, et al, Ethylene, Ullmanns
Enzylopdie der Technischen Chemie, 2007,
34-47, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim.
6 Knaebel K S, Adsorbent Selection,
Adsorption Research Inc, www.adsorption.
com/publications/AdsorbentSel1B.pdf (June
2004), 2003.
7 Breck D W, et al, J. Am. Chem. Soc., Vol. 78,
No. 23, Dec 1956, 5967.
8 http: //helios. princeton. edu/zeomics/
cgi-bin/view_structure.pl?src=iza&id=LTA&
token=e8279dfc54f813ef8f88b9baad8 bcc72
9 Rode E J, et al, Molecular sieve adsorbent
properties and their impact on cracked gas
drying, AIChE Spring National Meeting 1997,
Houston, TX.
10 De Haan S, et al, Overview of Cracked Gas
Compressor Fouling: Theories and Practices,
Presented at: 2001 Spring National Meeting,
23-26 April 2001, Houston, TX.
11 Snider S, Olen Plant cracker Gas
Compressor Fouling, PTQ Gas, 2007, 36-40.
12 OBrien B, et al, Cracked Gas Drier Survey,
Spring National Meeting, 21-25 March 2010,
San Antonio, TX.
Hans Hoefer, a materials scientist by
education, worked for almost 27 years for WR
Grace in the Adsorbents Business as Manager
for Research & Development, Technical
Customer Service and Market Development.
Vassilios Zarakis is Manager of Technical
Customer Services Adsorbents with WR
Grace, Worms Germany. He holds a Masters
in process engineering from the University of
Stuttgart, Germany.
(CO). Since this acts as an inhibitor
for palladium and silver hydro-
genation catalysts, untreated
hydrogen off-gas cannot be used
for hydrogenation (acetylene
converter, MAPD converter). For
this reason, the CO has to be
removed. There are basically two
established options (refer to process
fow diagrams):
1. A methanation reactor for low
grade hydrogen
2. PSA for high grade hydrogen
purifcation.
In the frst case, CO in the hydro-
gen rich stream is catalytically
converted to methane:
CO + 3H
2
-> CH
4
+ H
2
O
H
2
O is a poison for the hydro-
genation catalyst and has to be
removed. A TSA dryer equipped
with a 3A or a 4A type zeolite has a
typical cycle time of 24 hours. The
operating pressure is 6-30 bar at
15-30C. The regeneration tempera-
ture is 240C. The regeneration gas
is the demethaniser overhead. If the
feed is free of olefnic and acety-
lenic compounds, the lifetime may
be between fve and 10 years.
In the second case, the hydrogen
rich stream is purifed by a three-
layer PSA unit consisting of: 5A
type zeolite to remove nitrogen and
CO; activated carbon to remove
methane and CO
2
; and activated
alumina to eliminate H
2
O and NH
3
.
The adsorption pressure is 15-30
bar. The desorption pressure is
typically lowered by factors of
10-13 but is always kept slightly
above atmospheric pressure. The
operating temperature is 15-35C.
The high grade hydrogen has a
typical purity of 99.5 vol% with
concentrations of CO <10 ppmv,
CH
4
<10 ppmv, and N
2
<10 ppmv.
Outlook
The adsorption technology
discussed here has its roots in the
early 1950s. Over the years, a lot of
progress has been made in the
adsorbents performance and
economical feasibility. Although
nowadays there are about 160 differ-
ent zeolite structures, none of those
could replace the type 3 A zeolite
for ethylene drying. Certainly there
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