Sulfur Removal

P ro d u c t B u lle tin
Liability
Although these instructions have been prepared by experienced technicians and have been based
on the best available inform ation derived from laboratory, pilot plant and com m ercial experience w ith
this catalyst, these technicians do not have intim ate know ledge of the custom er’s plant and
operation. Therefore, Süd-C hem ie G roup, in issuing these instructions, cannot assum e liability for
upsets and dam age to either the custom er’s plant or personnel. The custom er is urged to review
these instructions carefully and to satisfy him self that their application w ill not be hazardous to
his specific operation. Further, Süd-C hem ie G roup’s Technical Service representatives are present
at plant start-ups in an advisory capacity only and cannot be charged w ith know ledge and
responsibility for hazardous conditions that m ight result from the application of the instructions.
Sulfur Removal Product Bulletin
Introduction 4
Applications 4
Product Features 5
•G -72D 5
•G -72E 5
•G -72H 5
Design Parameters 6
•D esulfurization of H ydrocarbon Feed to Steam R eform er 6
•D esulfurization of Syngas 6
•D esulfurization of R aw N atural G as 7
•D esulfurization of C O
2
7
•D esulfurization of W et G ases 7
Adsorption Capacity 7
Mechanism and Sulfur Profile 9
Poisons 9
Trouble Shooting 10
Technical Service 11
Guarantees 11
Introduction
Zinc O xide adsorbents for sulfur rem oval from
hydrocarbon process feeds are the accepted
m ethod in industry for pretreatm ent of feed
gas to steam reform ing units. The efficiency
and capacity of the current range of Zinc
O xides allow s sulfur to be rem oved from the
process feed on a continuous basis and
to the levels necessary to protect the dow n-
stream nickel reform ing catalysts.
B esides the principal application of Zinc
O xide for sulfur rem oval in the hydrocarbon
steam reform ing plants, Zinc O xide has a
w ider range of applications in sulfur rem oval.
Zinc O xides have been developed to a state
w here they are now in effective use at
tem peratures as low as am bient and can
therefore be directly used in the desulfuriza-
tion of raw w ell head natural gas and in the
clean up of a w hole range of feedstream s
such as C O
2
, acetylene, ethylene, propylene,
air etc.
The S üd C hem ie G roup Zinc O xide ad-
sorbents are designated G -72 and are m anu-
factured in extruded form . The Süd-C hem ie
G roup have been supplying Zinc O xide
adsorbents to industry since the 1950´s. This
operating experience m akes SÜ D -C H EM IE
uniquely qualified to provide the best
products available to industry for this desulfu-
rization application as is confirm ed by the w ell
proven operation of G -72 catalysts in
hundreds of installations w orldw ide.
Applications
Purification of feed to
steam reform ing units
The hydrocarbon feed can be in the form of
•N atural gas
•LPG
•O ff gases
•N aphtha.
The nickelcatalysts in the reform ing section
are highly sensitive to sulfurpoisoning and the
sulfur content of the feed to the reform er
m ust not exceed 0.1 ppm v.
The G -72 Zinc O xides alone w ill adsorb
directly to the required level of purity sulfur in
the form of
•H
2
S
•C O S
•M ethylm ercaptan
•Ethylm ercaptan
•Propylm ercaptan.
W hen the sulfur is in the form of m ercaptans
higher than propylm ercaptan, disulfides or
thiophenes, the Zinc O xide is norm ally
preceded by a hydrogenation stage using a
C oM o catalyst (C 49 catalyst).
Purification of synthesis gas
The sulfur in synthesis gases is due to up-
stream processes alw ays in the form of H
2
S.
The copper catalysts in the LT C O conversion
reactor and the m ethanol synthesis reactor
are very sensitive to sulfur poisoning and the
sulfur content of the synthesis gas m ust be
reduced to undetectable levels in order to
m aintain satisfactory service life for these
copper catalysts.
Purification of raw natural gas
N orm ally the sulfur com pounds are in the
form of H
2
S and R SH and therefore can be
adsorbed directly by the G -72 Zinc O xide.
In this application the G -72 Zinc O xide is
w orking at tem peratures as low as am bient
and retains excellent adsorbent capacity.
As the product purity is not of m ajor concern,
rather high space velocity can be applied.
4
Purification of C O
2
G -72 Zinc O xides are also used to adsorb
H
2
S and C O S from C O
2
stream s in a w ide
range of operating tem perature and pressure.
The purified C O
2
can be fed to a steam
reform er, e.g. in m ethanol or C O plants, or is
used –after further clean-up –in the food
industry.
M iscellaneous
The G -72 series of Zinc O xides is w ell proven
in the purification of olefins, like ethylene and
propylene.
Further inform ation about this w ide field of
application is available upon request.
G -72 Zinc O xide is even used to rem ove
sulfur com pounds from air under am bient
conditions. This is to protect, for instance
exhibits in m useum s.
Product Features
S üd-C hem ie G roup m anufactures three
grades of G -72 Zinc O xide:
•G -72D - for applications at high space
velocity
•G -72E - for high sulfur containing feed
stocks
•G -72H - for purification of raw natural gas
The physical and chem ical properties of a
Zinc O xide relate to perform ance as m ea-
sured not only by sulfur adsorption efficiency
but also by physical integrity under operating
conditions. These properties in the G -72 Zinc
O xides are characterized as
•large surface area
•high crush strength
•low attrition loss
•good w ater resistance
These outstanding properties of the G -72
Zinc O xides are achieved through the unique
m anufacturing techniques w hich incorporate
a binder w ithin the zinc oxide. This m axi-
m izes sulfur pick-up, w hich is generally
higher w ith G -72 catalysts com pared to ZnO
adsorbants w ith 100 % ZnO . The optim um
properties of a zinc oxide can be tailored to
a particular application. For exam ple, for
feeds w ith low sulfur content, the criterion of
decision on the type of Zinc O xide to install
m ay be good physical strength rather than
adsorption capacity, as the Zinc O xide w ill be
in service for a long tim e and m ay never be
fully sulfur saturated.
All three Zinc O xides com prise 90% ZnO and
10% of a binder. The basic difference of
G -72D , G -72E and G -72H is the bulk density,
the internal surface area and porosity,
respectively. All G -72 types show excellent
side crush strength.
G-72D G-72E G-72H
ZnO [w t% ] 90 90 90
B inder [w t% ] 10 10 10
Shape extrusions extrusions extrusions
Size [m m ] 4.5 4.5 4.5
B ulk density [kg/l] 1.1 1.3 1.6
Surface area [m
2
/g] 50 30 10
Side crush strength [N ] 100 100 100
5
R -SH (R =C
1
-C
3
) 10 315
R -S-R (R =C
1
-C
3
) 10 400
C O S 10 270
S com pound M ax. concentration M in. operating
in H C feed [ppm v] tem perature [°C ]
Design Parameters
Purification of feed to a steam reform er
The sulfursensitive steam reform ing catalysts
require thorough desulfurization of the
hydrocarbon feedstock. This is norm ally
done by a tw o step system , com prising the
hydrogenation of organic sulfur com pounds
by C obalt-M olybdenum (C oM o) or N ickel-
M olybdenum (N iM o)catalysts follow ed by the
adsorption of the form ed H
2
S by Zinc O xide.
The standard catalysts for this w ide spread
application are G -72D and G -72E.
G -72D is used at high space velocities and/or
low sulfur concentrations. The extrem ely high
porosity and surface area m ake all of the ZnO
available for the adsorption reaction.
D ue to the higher bulk density G -72E can
pick up m ore sulfur expressed in kg S per m
3
catalyst. This higher pick up, how ever, can
only be achieved at space velocities
low er than approx. 3.000 N m
3
/m
3
/h.
The norm al operating range for the desulfu-
rization of hydrocarbons is:
•Tem perature: 300 –400°C
•Pressure: up to 60 bar
•Space Velocity: 500 –4.000 N m
3
/m
3
/h
Sulfur can be in the form of H
2
S, C O S, short
chain m ercaptans and short chain thioethers.
P lease note that there are lim itations for
the m axim um concentrations of organic S
com pounds and also for the m inim um
required tem perature to achieve the desired
gas purity.
W hen operating w ithin the follow ing lim its,
G -72D and G -72E guarantee trouble free
operation:
In the presence of higher concentrations of
the a.m . com pounds or w ith thiophens in the
feed w e strongly recom m end to use a
C oM o or N iM o hydrogenation step upstream
zinc oxide.
W hen the G -72 catalysts are used as re-
com m ended, H
2
S and other sulfur com -
pounds are rem oved to a concentration less
than 0.1 ppm v total sulfur.
Purification of synthesis gases
To protect the sulfur sensitive copper zinc
catalyst in the low tem perature C O conversi-
on reactor or the m ethanol synthesis reactor
it is possible to install a guard bed or a guard
reactor of G -72D upstream the copper zinc
catalyst.
Typical operating conditions are:
•Tem perature: 150 –250°C
•Pressure: up to 80 bar
•Space velocity: up to 10.000 N m
3
/m
3
/h
6
Purification of w et gases
At atm ospheric pressure above 100°C steam
has no adverse effect on the physical
strength of G -72 zinc oxide catalysts.
C ontact w ith high pressure steam , how -
ever, can w eaken the catalyst unless the
tem perature is m ore than 20°C above the
condensation tem perature. The catalyst can
be dam aged if capillary condensation occurs.
Sulfur rem oval in the presence of steam is
generally carried out at tem peratures below
300°C . Above this tem perature efficiency can
be lim ited because the equilibrium of the
reaction
ZnS + H
2
O ZnO + H
2
S
is reached.
At a steam /gas ratio of 0.2 m ole/m ole the
sulfur adsorption capacity w ill be approx.
80% com pared to the one of the dry gas.
Adsorption Capacity
The adsorption capacity of the three G -72
zinc oxide catalysts w ill vary w ith actual
process conditions w ith respect to:
•Tem perature
•Pressure
•Space velocity
•Inlet sulfur content
•Steam content
•R eactor design system
Figure 1 can be used as guideline for the
influence of reaction tem perature on the
sulfur pick up capacity of G -72D and G -72E.
The system w ith tw o reactors in series
interchangeable results in a m uch higher
overall sulfur pick up capacity and is there-
fore the preferred reactor system .
As it can be seen from figure 1 the optim um
sulfur pick up can be achieved at tem peratu-
res of 350 –380°C . Tem peratures higher than
380°C w ill not increase the pick up capacity
but tem peratures above 400°C w ill lead to
cracking of the hydrocarbon feed over the
catalyst.


Purification of raw natural gas
N atural gas w ith sulfur concentrations of
approx. 20 –30 ppm total sulfur can be
purified directly at the w ell or platform at
am bient tem perature.
As the sulfur pick up capacity of zinc oxide
catalysts are lim ited at low tem peratures a
zinc oxide w ith high bulk density has to be
chosen to achieve sufficient long catalyst
life tim e. As norm ally the operating pressure
is very high the porosity is not of concern.
G -72H is the catalyst of choice and adsorbs
up to 520 kg sulfur per m
3
catalyst.
The norm al operating conditions are:
•Tem perature: am bient
•Pressure: up to 80 bar
•Space velocity: up to 6.000 N m
3
/m
3
/h
U nder these conditions H
2
S and short chain
m ercaptans are picked up to result in a
productpurity in the range of 1 –5 ppm v H
2
S
depending on the operating conditions.
Purification of C O
2
The rem oval of H
2
S and other sulfur com -
ponents (m ainly C O S) from C O
2
w ith ZnO
m ust not be perform ed in the tem perature
range of 170°C to 280°C . At these tem pe-
ratures zinc oxide is partly converted to zinc
carbonate according to
ZnO + C O
2
ZnC O
3
A t tem peratures above 280°C ZnC O
3
de-
com poses and ZnO is stable in C O
2
stream s.
A s norm ally C O S is present in C O
2
w e
recom m end to run the desulfurization of C O
2
at tem peratures of m in. 300°C .
D epending on the desired life tim e and
pick-up capacity per m
3
catalyst both G -72D
and G -72E are used in the desulfurization
of C O
2
.


7
The dependence of the sulfur pick up from
the space velocity is show n in figure 2.
This graph is valid for operating pressure
higher than approx. 25 bar g. A t low er
pressure som ehow low er space velocities
have to be applied to achieve the sam e
perform ance.
Figure 2:
Sulfur pick up as a function
of space velocity
3 5
3 0
2 5
2 0
1 5
1 0
5
0
1 0 0 0 2 0 0 0 3 0 0 0 4 0 0 0 5 0 0 0
C onditions: p = 25 –50 bar g,
SV = 2.000 N m
3
/m
3
/h per bed
Feed: N atural gas
C onditions: p = 25 –50 bar g,
T = 380 –400°C
Feed: N atural gas
Figure 1:
Sulfur pick up as a function
of reaction temperature
8
3 5
3 0
2 5
2 0
1 5
1 0
5
0
1 0 0 2 0 0 3 0 0 4 0 0
S
u
l
f
u
r

P
i
c
k

U
p

[
w
t
%
]
S
u
l
f
u
r

P
i
c
k

U
p

[
w
t
%
]
Te m p e ra tu re [ C ]
S p a c e Ve lo c ity   N m
3
/m
3
/h
3
)
Mechanism and Sulfur Profile
The perform ance of zinc oxide depends on
m ore than just the percentage of ZnO or the
tons of ZnO per cubic m eter of catalyst
because not all of the ZnO is im m ediately
available for gas contact.
As sulfur (H
2
S) containing gas passes over
the catalyst particles the surface layer of ZnO
reacts, w ith the rate lim ited only by gas
diffusion. The ZnO inside the pellet reacts
m ore slow ly by solid diffusion until all of the
ZnO has reacted.
This m eans that a zinc oxide bed can be
view ed as having four zones (see figure 3):
Saturated Zone:
all ZnO is converted to ZnS
Solid D iffusion Zone:
sulfur m igrates to the center of the pellet
G as D iffusion Zone:
w here m ost of the reaction occurs
Fresh C atalyst Zone:
w here the catalyst is basically new
Figure 3 show s the sulfur adsorbed in the
bed (solid line) and the sulfur level in the gas
(dashed line). W ith tim e on stream this profile
m oves dow n the bed until the bottom of the
G as D iffusion Zone reaches the bottom of the
catalyst bed. Sulfur then begins to leak from
the bed and gradually increases as the profile
continues to m ove dow n the bed.
Poisons
G -72 catalysts are resistant against m ost of
the know n poisons for catalysts. C arryover
of dust, carbon and/or other solid m aterials
w ill physically block the pores of G -72
catalysts and therefore reduce the adsorption
capacity. It also m ay contribute to an in-
creased pressure drop.
H C l has to be avoided at any tim e as the
presence of H C l leads to the form ation of
ZnC l
2
according to
ZnO + 2H C l ZnC l
2
+ H
2
O
ZnC l
2
is volatile at operating tem peratures
and can be therefore transported to dow n-
stream equipm ent and m ay contribute to
corrosion.
It is therefore m andatory to install in the
presence of chlorine com ponents a chlorine
guard upstream the ZnO catalyst.
Figure 3:
Sulfur Profile
over G-72 D
Catalyst Bed


9
G a s D iffu sio n
F re sh C a ta lyst
S a tu ra te d
S o lid D iffu sio n
A d so rb e d S u lfu r
S u lfu r in G a s
ǟ
G
a
s

F
l
o
w
Symptoms Cause Corrective Action
H igh Pressure D rop C arbon D eposition by cracking of olefins C heck C oM o system , Increase H
2
recycle
D ust, solid particles on catalyst R em ove and/or replace top layer of
catalyst (approx. 10 % of bed is sufficient)
C atalyst breakage C hange-out catalyst and investigate
reason for catalyst breakage
Sulfur break-through Insufficient pick-up zone rem aining Single bed: Stop plant and replace catalyst
2 beds: Put 2
nd
bed in first position and
replace used catalyst in form er 1
st
bed
Tem perature too low Increase tem perature (m ax. 400 °C )
Feed rate too high R educe feed rate
C hannelling R eplace catalyst; C atalyst from low er bed
m ay be reused after screening
C hloride break-through N o C hloride Trap Install C hloride Trap
10
Trouble Shooting
Zinc O xide system s w ill norm ally operate
trouble free, the only necessary control being
to m aintain a close observation for sulfur
breakthrough (or increase from a previous
steady level) exit the bed.
Installed Zinc O xide volum es are opti-
m ally designed to approach full adsorption
capacity corresponding to scheduled plant
shut dow n cycles. H ow ever, this optim isation
obviously depends on the sulfur content
in the feed rem aining at the projected
design level, w hich is not alw ays the case in
practise.
The only practical problem that m ay arise
w ith a Zinc O xide bed –particularly if the Zinc
O xide is not preceded by a C oM o system
and is therefore the first vessel in the plant
stream –is a pressure drop increase caused
by filtering out any dust or solid particles in
the feed. This dust can also reduce the
adsorption capacity of the Zinc O xide by
blocking the pores and additionally lead to
channelling of the feed stream w ith con-
sequent poor desulfurization perform ance.
Practical recom m endation to overcom e any
possible, but rare, problem s w ith Zinc O xide
are listed below :
R eview of reactor system design
Selection of proper catalyst
Technical review s of start-up/shut-dow n procedures
Technical assistance for loading, catalyst start-up and shut-dow n
R outine perform ance evaluations
Troubleshooting
C atalyst life projections
O n-site training sem inars for engineering and operations personnel
C hem ical and physical analyses of spent catalyst
Supply of proprietary com puter program s for catalyst perform ance evaluation
Technical Service
S Ü D -C H EM IE G R O U P firm ly believes that
even an outstanding catalyst m ay not provide
the best perform ance w ithout the appro-
priate level of assistance during the phases of
selection, installation, start-up and operation.
W ithin our Technical Service G roup,w e have
a w ide range of personnel w ith specific
expertise in the areas of catalyst characte-
rization, research, catalyst installation,
start-up, plant operation, and perform ance
evaluations.
This depth of know ledge allow s us to provide
the follow ing services:
SÜ D -C H EM IE G roup also has an extensive
list of state of the art analytical and com puter
system s to further add to our list of resour-
ces.
Guarantees
Süd-C hem ie G roup grants to the user perfor-
m ance guarantees covering the perform ance
of its ZnO for desulfurization applications.
B efore granting such perform ance guarantees,
the design conditions and/or anticipated
operating conditions m ust be evaluated and
recom m endations or confirm ations given on
the basis of S üd-C hem ie G roup’s design
system .
11
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