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THE CLAUS REVISITED

By
J. B. Hyne
HyJay R&D, Ltd.
and
University of Calgary
Calgary, Alberta, Canada

and

B. Gene Goar
GOAR, ALLISON & ASSOCIATES, INC.
P.O. Box 131390
Tyler, Texas 75713
THE CLAUS REVISITED
by
J. B. Hyne, HyJay R&D, Ltd.
and
University of Calgary
B. Gene Goar; Goar, Allison & Associates,
Inc.

ABSTRACT
The basic Claus process, now 112 years: old, has undergone
many modifications and almost endless process unit additions,
in attempts to improve its overall sulfur recovery efficiency.
This paper is meant to provoke new thinking and discussion
about "revisiting" the fundamental concepts of the process and
pursuing genuinely new and novel ideas for improved recoveries
in the range of 99+% to meet ever more stringent emission
regulations. Some major units to be "revisited" are: (1) the
Front End Furnace, (2) the Waste Heat Boiler, and (3) the
Catalytic Stages. Can industry achieve these process
improvements by consolidation rather than more additions?
INTRODUCTION
This contribution to the 1996 Laurance Reid Gas
Conditioning Conference (LRGCC) is scheduled for presentation
just before the traditional LRGCC "Roundtable" session when
participation "from the floor" is the essence of the
afternoon. It is therefore hoped that the presentation will be
as much provocative as it is informative. We are "revisiting"
the fundamental principles of a process that has served the
industry well, both in its early manifestations and as it has
been modified and added to over the last half century or more.
These additions have been driven by the need to achieve ever
higher sulfur recovery efficiencies, not so much to produce
more sulfur, but to reduce the amount of it that eventually
becomes a toxic emission to the environment. The industry has
achieved remarkable success in this endeavor. Overall recovery
rates in the 70% range in the 1950's have been increased to
remarkably high 90% values in the 1990's. But still the demand
for squeezing out the last tenths of a percent continue, and
the competition between processes is now one of getting from
99% to 99.9% or better in the most economical manner possible.
Anything is possible if you throw enough money at the problem.
But recovering additional sulfur at a cost in excess of
$2,000/ton, when the commodity sells at less than $50-100/ton,
is not viewed by business as being "economical". The
environmental price of doing business may indeed be a valid
charge against the bottom line, but minimizing that charge is
always warmly received by the shareholders!

How can revisiting the Claus system, as we are about to do,


contribute to this process? We suggest that such a revisit may
provoke some new thinking, or uncover some unexpressed ideas
that might lead to the identification of some fundamental
feature of the current Claus process that alone, or TOGETHER
WITH OTHER SYNERGISTIC CHANGES, could lead to a significant,
yet cost effective method of climbing through the final 1% of
sulfur recovery efficiency to reach closer to 100%. Most of
the improvements to the Claus process over the years have been
more "add-on" than "systemic" in nature. More catalytic
stages, added tail gas clean-up units, inline reheaters,
coalescers and demisters, and the like. Recently some more
fundamental changes have appeared on the scene, and these will
be reviewed in our "revisit". But are these changes being
integrated in a way that maximizes the benefit in the overall
system? By INTEGRATING can we really OPTIMIZE?

Much has happened in recent years in many peripheral


fields that is important to improving Claus technology.
Membranes, high temperature materials, instrumentation for
process monitoring, catalyst design and manufacture, knowledge
of combustion and flame dynamics, are but a few of these
fields. Have we taken full advantage of them? Has the industry
claimed its share of NASA investment spin-off?

Our starting point must, of course, be what we presently


understand. Thus, in general terms, we will look at the
various units of the Claus sulfur recovery system in sequence,
but try to emphasis the links between them. What you change in
one unit may prompt changes in another, either out of
necessity or to optimize the benefit.

The challenges are not new and the questions we will pose
may not be new either. But perhaps by assembling them in what
is hoped is an integrated format of "Revisiting the Claus" as
a whole, we may stimulate the discussion and suggestions for a
"systemic" reworking of the Claus, not just one more retrofit.
By the word "systemic", we mean the complete Claus system
working together as a whole. To use a human medical analogy,
we are concerned about "systemic" effects on the whole body,
and not just the effects on the brain, the heart, the lungs,
the liver, etc. The healthy body is one in which all parts
function together for the benefit of the whole.

PREPARING THE CLAUS FEED(s)

High efficiency recovery of sulfur from a feed gas


stream(s) containing hydrogen sulfide is very dependent upon
the composition of that feed stream(s). In the early days of
Claus sulfur recovery, the front end furnace (FEF) was widely
regarded as the plant "incinerator", where you "burned-up"
your upstream mistakes. Any undesirable sidestream or off-gas
was sent to the furnace with little thought as to its effect
on the overall Claus. Sour water stripper off-gases,
head-space gases from tankage, and other such side streams
were and still are sent to the front end furnace for
"destruction". This might have been acceptable when 80%
overall sulfur recovery was acceptable; but, when 99.5+% is
the recovery target, the precise composition and quantity of
these sidestream feeds can be crucial in determining the
recovery efficiency.

Hydrocarbon carry-over into the Claus feed stream is well


known to be a critical factor. The main source of this
contaminant is, of course, the upstream gas sweetening unit.
There is convincing evidence (Ref. 1) that hydrocarbon
carry-over in excess of 0.5 Mol% can lead to very undesirable
carbon (Carsul) deposition on the downstream catalyst beds
with consequent loss of activity. Aromatics (BTX) are even
more undesirable (Ref. 2), presumably because of their greater
tendency to polymerize rather than degrade to small gaseous
species. Yet many Claus plants continue to operate with feed
hydrocarbon content over 1.5 Mol%, either from carry-over from
the sweetening process or intentionally added in a sidestream
being sent for "destruction" in the Claus furnace.

These hydrocarbons can also be the major source of COS


and CS2 in the furnace effluent being fed to the catalytic
stages. In the temperature regimes of many front end reaction
furnaces, the hydrocarbons can react with the sulfur rich
environment to produce COS and CS2. Using methane as a simple
hydrocarbon example:

CH4 + SO2 + .5 O2 ------> COS + 2 H2O


CH4 + 2 S2 -------------> CS2 + 2 H2S

Here we see a good example of systemic synergism. Because the


feed is contaminated with reactive hydrocarbons that can yield
COS and CS2 in the front end furnace, it is necessary to
operate the first catalytic converter at an elevated
temperature to achieve hydrolysis of these species and remove
them from the system before they reach the tail gas
incinerator and become SO2 emissions.

COS + H2O Temp. > CO2 + H2S


Catalyst

CS2 + 2 H2O Temp.> CO2 + 2 H2S


Catalyst

This elevated temperature catalytic hydrolysis results in


diminished Claus catalytic conversion because of the
exothermic nature of this stage, as seen in Fig. 1. Thus a
greater conversion load is placed on the subsequent Claus
catalytic steps. Since all of these are equilibrium processes,
the cascade effect of loss of Claus conversion in the first
bed is reflected all the way down the system. The end result
may only be 0.1% in the tail gas. This may have been of no
consequence when we were satisfied with 96% recovery and 4%
loss went out as SO 2 emissions. But now we are down to the
last 1% emission, and are now at precisely the stage of trying
to find ways of getting such tiny amounts of sulfur out of the
tail gas. Even if the plant in question is equipped with a
reductive tail gas clean-up (TGCU) system, such as SCOT (Ref.
3), removing as little as 0.1% of the sulfur from the tail gas
could represent a 10% reduction in the load on the tail gas
clean-up unit.

The synergism within the overall Claus unit is clearly


seen in the above example. The days of achieving a "great leap
forward" in sulfur recovery by a single add-on modification
are gone. The final step to sulfur-free plant emissions will
only be accomplished by "optimal integration" of all of the
component units of the system.
The acid gas feed stream should flow through a liberally
sized Acid Gas Knockout Drum to prevent entry of entrained
liquids (water and/or amine) into the burner and FEF. If the
SRU handles Sour Water Stripper off-gas, it should pass
through its own knockout drum also.

The need to reduce water content of the acid gas feed


streams may not be apparent. If the amine acid gas stream
enters the SRU saturated with water vapor at 140F, instead of
the more usual 120F temperature, it will carry 70% more H2O
vapor into the plant. If Sour Water Stripper off-gas enters
saturated at 200F, instead of 180F, it will carry 54% more
H2O vapor into the plant. Of course, H2O decreases the
conversion of H2S to sulfur because it is a product of the
Claus reaction. The message is "try to minimize the amount of
H2O present in the feed streams to the SRU as much as
practical".

The Sour Water Stripper off-gas, containing H2S/NH3/H2O,


can be a major offender to recovery efficiency and smooth
operations in a SRU. Alternate methods of disposing of this
troublesome stream should be sought and developed. Chevron
developed their "WWT" process for splitting the SWS off-gas
into an NH 3 product stream and a "H2S-rich/NH3-free" acid gas
stream (Ref. 4). But, it has met with resistance from industry
due to (1) high capital cost, (2) operating difficulties, and
(3) a contaminated anhydrous NH3 product that has been
difficult to market. New technology is still needed.

What potential solutions are there to such up-stream


challenges? The most obvious may be the tightening of the
operating parameters of the gas sweetening system. The degree
to which the acid gas from the sweetening unit can be rendered
hydrocarbon-free depends to some extent on the composition of
the sour gas feed to the gas processing plant. That in turn
may dictate the selection of the type of sweetening solvent
(alkanolamines, Sulfinol, Hot Pot, etc.) The ability of the
sweetening process to reduce the hydrocarbon carry-over into
the acid gas stream, however, is
critical to the question of how much COS, CS2 and Carsul
appears downstream. Operators tend to err on the side of
letting some hydrocarbon spill into the sulfur plant, rather
than letting sulfur (H2S) escape into the sales gas stream. It
is a fine line to walk, but one that is well worth the effort
in terms of minimizing costs of achieving near 100% recovery.

The design of the upstream gas sweetening system(s)


should be reviewed to evaluate several factors that can have
an effect on the carry-over of hydrocarbons to the SRU, such
as:
Adequate residence time in the Rich Solution Flash Tank
& provision of proper skimming facilities,
Proper cleanliness and good condition of the
sweetening solution with regard to solids
(mainly iron sulfide), degradation products
(heat stable salts & organic acids), and
dissolved hydrocarbons. Both particulate
filters (bag or sock type) and charcoal filters
are essential,
Possible need for a "Filter-Sap" type inlet
separator ahead of all amine contactors,
Review of operating conditions to be sure that
hydrocarbons are not being condensed from the
gas stream by the sweetening solution itself.

Further improvement in sweetening solvent chemistry and


plant design may yield a reduction in hydrocarbon carry-over.
But carry-over (mists) of the solvents themselves can
contribute to COS, CS2 and Carsul formation, since most of the
solvents have significant organic character. Modern membrane
technology may be approaching the point where permoselectivity
may be great enough to allow passage of the "desirables" in
the acid gas feed into the SRU and rejection of the
hydrocarbons to other disposal.

Perhaps the most probable improvement will again come


from synergism within the overall sulfur plant.
Oxygen-enrichment of the "air" stream fed to the front end
furnace, which is discussed in detail later, will result in
significantly higher temperatures in this thermal reactor.
These temperatures, especially over 14001500C (2S52-2732F),
will virtually assure destruction of any CS2 and COS in the
furnace (Ref. 5). However, raising furnace temperatures to
this level introduces some additional systemic challenges, as
we will see later. Once again the need to address the totality
of the Claus sulfur recovery system is brought into focus.
A common and often substantial component of Claus acid gas
feed is carbon dioxide. It is a natural companion of hydrogen
sulfide that has been generated by thermal sulfate reduction
in geological formations (Ref. 6). It is less likely to be a
significant component in hydrogen sulfide containing refinery
process gas streams. But, it does appear in a lot of refinery
gas streams also. CO2 is widely regarded in the gas processing
industry as a diluent (or inert) in the process gas stream,
much as nitrogen is viewed (to be discussed later).
Nonetheless, at elevated temperatures, such as will be
encountered in oxygen-enriched Claus operations, carbon
dioxide can enter into a variety of reactions with other
components present in or generated during the furnace
reactions. Some of these are outlined below in general terms.

CO2 + H2S <-------> COS + H2O

CO2 + S2 + 1/2 O2 -----> COS + SO2

CO2 + C ---------> 2 CO

2CO2 + HS <---------> 2CO + H2 + SO2

CO2 ------------------> CO + 1/2 O2

As seen, these reactions can introduce into the effluent gas


stream from the front end furnace reaction products that could
have both a positive and a negative influence on downstream
processes. The COS is undesirable and must be hydrolyzed; and,
the hydrogen could be useful in a reductive tail gas clean-up
unit, if it survives into lower temperature regimes. Again, we
see the synergism between the various steps in the overall
Claus coming into play.

Perhaps the most important aspect of higher carbon


dioxide concentrations in the feed gas is the fact that every
mole of CO2 that passes through the sulfur recovery process
displaces a mole of hydrogen sulfide that might other wise be
accommodated, i.e., it increases hydraulic loading and
backs-out H2S. If its concentration becomes too high, then it
can affect the stability of the flame in the furnace and the
combustion temperatures that can be reached. Burning CO2-rich,
lean acid gas has been a problem in many sulfur recovery
systems, and various techniques have been devised (Ref. 7,8)
to try and overcome this problem.

Selective absorption of hydrogen sulfide from the sour gas


feed to the sweetening system, using sterically-hindered
alkanolamines which prefer hydrogen sulfide over carbon
dioxide, has met with considerable favor in recent years, not
withstanding cost factors. MDEA has been the popular choice of
amines for many selective-H2S removal sweetening systems. With
formulated MDEAbased solvents, (containing special additives),
rejection of 80-90% of the CO2 present in a gas stream is
possible, in some applications. The U.O.P. "Ucarsol" solvents
and DOW "GasSpec" solvents are examples. Exxon offers their
Flexsorb-SE solvents, also.

What remains to be fully explored is the use of permo-


selective membranes and advanced pressure swing adsorption
(APSA) technologies to selectively reject carbon dioxide in
favor of hydrogen sulfide. Such separations are inherently
feasible and are becoming less costly and more reliable as
their application in other areas of technology are proven.
Installing such a system ahead of a front end reaction
furnace, however, is still not an accepted practice despite
the fact that in acid gas streams with CO2 concentrations above
15 Mol%, the economic benefits in terms of enhanced throughput
could be attractive. But, our gas processing industry has a
lot of inertia and is quite resistant to change. Besides, who
wants to be the guinea pig? Industry should be anxious to try
new ideas and new concepts. We all know they are not. Will
this change in the future?
THE FRONT END REACTION FURNACE

A Quick Look at the Past

The front end furnace (FEF) or thermal reactor of a Claus


sulfur recovery unit (SRU) has long been regarded as a
relatively unsophisticated component in an otherwise well
developed sequence of chemical engineering processes that make
up the typical sulfur plant. Despite the fact that more than
50-60% conversion of the hydrogen sulfide in the acid gas feed
to the SRU occurs in the FEF, even in the most rudimentary
units, relatively little "research and development" (R & D)
was directed at this component of the overall system until
relatively recently. Upstream gas sweetening systems have been
exhaustively researched. Downstream catalytic converter units
have been the target of improved catalyst research, improved
reactor design, and more tightly controlled operating
conditions. Tail gas treating unit "add-one" have all been
greatly upgraded in the recent push toward 100% recovery of
sulfur values. But the lowly FEF has been seen by many as
something akin to a "disposal" furnace, where up-stream
mistakes can be burned-up and useful steam generated from the
thermal energy released.
TRW's S-100 Process - a sulfur recovery system with a
front end furnace that operated on H2S and pure O2 at near
3000C (5432F), and looked like a space-age rocket engine -
was likely another spin-off of all the space-age R @ D that
has gone into this field of human endeavor. A key feature of
the S-100 process was, of course, the precise engineering
design of its BURNER system. The feed gases were precisely and
accurately fed into the combustion
chamber in a very special way. This was a far cry from earlier
(primitive) FEF burner designs, where a single acid gas feed
pipe protruded into the combustion chamber surrounded by a
shroud of oxidant air that might or might not mix thoroughly
with the acid gas during its short residence time in the
fire-box.

Efforts have been made by burner manufacturers to improve


the mixing characteristics in the FEF by introducing multiport
burners or by tangential injection to increase turbulent flow
and residence time (Ref. 9). The "checkered wall" found some
favor as a device for improving "air/acid gas" mixing in the
furnace and heat reflection back into the front of the FEF.
These efforts are now being overshadowed by a new generation
of burner developments. A much more sophisticated
understanding of the fluid dynamics of the combustion
processes (Ref. 1O) involved are leading to significant
further improvements in FEF performance. There is much to be
gained in conversion efficiency, reduced maintenance and
operational lifetime by fine tuning your front end furnace and
its burner. More sophisticated swirl-vane type acid gas
burners can improve mixing efficiency dramatically. The use of
a good burner and its proper operation is considered to be of
paramount importance to the performance of the FEF and the
whole SRU. The "burner/FEF" is considered the "heart & lungs"
of the Claus process.

Optimizing the Combustion Process

While the general chemical nature of the acid gas oxidation


process that goes on in the FEF is well recognized, the
details of the formation, concentrations, reaction kinetics
and relative lifetimes of the FREE RADICAL species (Fig. 2)
that are the essence of flame chemistry is far less well
understood. It is these very fast free radical reactions,
rather than the more commonly cited molecular species
interconversions, that really determine the flame structure
and internal flame dynamics in an FEF. Many of these free
radical reactions are completed in milliseconds at the 1,000C+
(1800F+) temperatures of an FEF; but, they can still be the
key factor in determining the shape and the temperature
profile of FEF flames. It is these parameters that will in
turn decide whether furnace refractory limits will be exceeded
in oxygen-enriched Claus technology. Despite the importance of
this kinetic information, much of the data that are already
available have been obtained at much lower temperatures than
those that are characteristic of the FEF. A quick look at the
extrapolations in Fig. 3 will demonstrate that the known lack
of linear dependence of rate on temperature (due to the
temperature dependence of enthalpy, dH/dt) makes predicting
high-temperature kinetic rates from low temperature data a
very tricky and dicey business. Much more high-temperature,
kinetic-rate data measurements are needed if we are to have
any
hope of REALLY designing FEF's that operate in an
optimal and well controlled manner.

Due to the endothermic effect of thermal


cracking of compounds such as H2S, NH 3, CO 2 & H 2O in
the flame at O2-enriched higher FEF temperatures, it
is our belief that actual temperatures "seen" by the
refractory are much lower than normally calculated
by available computer simulators. At FEF temperature
levels above 1400-1500C (2552-2732F), we believe
the difference in "actual" versus calculated flame
temperatures can be as much as 150-250C
(302-482F), or more. There are too many unknowns in
the flame reactions at elevated temperatures to be
able to predict the "real" temperatures very
accurately from theoretical calculations. We feel
that "reality factors" must be applied to the
calculated values. But, how is this done? Very
carefully! From field data.

Notwithstanding the lack of detail on sour gas


flame kinetics at elevated temperatures, it has been
accepted that thorough mixing of the acid gas (fuel)
and the oxidant (air) in the proper proportions is a
necessary prerequisite to optimization. Carefully
aligned fuel and oxidant entry ports now improve
mixing. Turbulent and laminar flow configurations
are both offered (Ref. 11) in various new burner
designs, especially when high temperatures
associated with oxygen-enrichment have to be
accommodated. Each has its advantages and
disadvantages. Can thermal cracking of hydrogen
sulfide, a strongly endothermic reaction, be
encouraged within the flame in order to absorb some
of the enhanced exothermicity of the oxygen enriched
H2S combustion?

Can this cracking reaction be optimized to control


furnace temperature, (system synergism again), and
can this hydrogen be preserved for later use in
reductive tail gas treatment? Can this heat
absorption be accomplished in a separate "ceramic
tube cracker" located within the fire-box, but
yielding a separate product stream that contains
high concentrations of recoverable hydrogen (Ref.
12), possibly for feed back into refinery HDS units?
Yes, we think these goals are well within reach. We
just need the R&D effort and the industry
commitment.
Measurements - Knowing What is Going On

We think it fair to say that of all the units in a


Claus sulfur recovery system, the operator knows least
about what is going on inside the Front End Furnace.
In 90% or more of existing FEF's, the only direct
observation of the FEF process is visually through a
sight glass that may or may not be plugged! And yet
this is the unit in the entire process train that is
recovering by far the largest amount of sulfur, and
where the "stage" is being set for downstream
operations.

We have noted above the importance of knowing how


the feed gases are mixing and burning in the FEF. The
simple fact of the matter is that very few FEF
operators have any meaningful information on the
conditions within-their furnace. We suggest that with
the coming of more sophisticated FEF designs, and
especially higher temperatures within the flame zones,
it has become almost mandatory that the operator have
access to a continuous record of the flame temperature
profile within the fire-box. Without it is equivalent
to flying without radar. You may have a general idea
of where you are going, but not much of a chance if
anything unexpected gets in the way.

Measuring and Monitoring Temperature Profiles

Ceramic sheathed thermocouples have long been used


to probe the combustion zones in the FEF. Their
performance, however, has been "spotty" due in part to
their limited mechanical strength and relatively
fragile nature, and due to the limited extent to which
they can penetrate beyond the inner surface of the
furnace refractory and into the actual flame zone.
This latter capability is essential if a full flame
temperature profile is to be obtained across the
furnace. This is the only way that a true picture of
the flame homogeneity (or lack of it) can be obtained.
Also with time, the H2 present in the furnace at the
elevated temperatures causes the "fused bead" of the
thermocouple metals to separate, and ultimate failure
of the device occurs. It is usually just a matter of
time.

Improvements in ceramic material properties and


thermocouple metallurgy will undoubtedly make it
possible to probe deeper into the flame zones of
FEF's; but, current interest seems to be turning more
toward "non-invasive" type temperature probes such as
Infrared (JR) Thermometry (optical pyrometers).
Current devices of this type (Ref. 13) have the great
advantage of being located outside of the furnace and
looking into the flame zone using a selective band
width within the IR spectral range. This means longer
life and easier servicing. But the pyrometer device is
still an integrative one that looks at the total
emissivity and radiant energy of the flame zone,
rather than being able to read a temperature at a
given point within the furnace zone. New developments
will undoubtedly add not only these capabilities, but
hopefully also a "scanning" function whereby one IR
thermometer assembly can scan within the flame zone
and produce a temperature profile scan along and
across the fire-box volume. This would be a wonderful
additional monitoring capability.

A serious challenge with such pyrometers is one of


proper care and maintenance. In many instances, the
viewport serving the pyrometer becomes partially or
fully plugged with sulfur and/or debris, due to
insufficient N2 purge. The operators many times are
quick to condemn the IR device as unreliable or "no
good". This puzzles us greatly. If you are a person
that wears glasses, can you see through your lens if
they are covered with mud? Maybe this is another
manifestation of the low regard in which the FEF is
held.

Recent advances in lower temperature THERMOGRAPHY


suggest that routine scanning of the outside skin of
an FEF may well be capable of development as a tool
for monitoring changes in temperature within the
combustion zone. Modern thermographic systems can
detect, quite reproducibly, changes in skin
temperature of as little as 0.1C; and, this
calibration can be related back to correspondingly
larger changes at the heat source within the FEF
itself. The day may not be far off when the control
room has a continuous color screen view of the glowing
"innards" of the FEF, with superimposed digital
temperature values wherever and whenever desired,
along with a complete temperature profile of its outer
skin from front to back.

Monitoring Molecular Species in the FEF

In a paper such as this, it is appropriate to gaze


into the crystal ball and try to see what may be in
the future. We suggest that the time is not far off
when feed-back of tail gas analysis data as a means of
controlling the front-end air/gas ratio will be
history. The analytical data will come straight from
the furnace itself. A virtually instantaneous analysis
of whether the furnace feed and combustion behavior is
doing all the things it is designed to do may be
available, viz.; provide the proper ratio of H2S to SO2
for the catalytic stages; destroy all the COS, CS2 and
NH 3 compounds; incinerate all carried over
hydrocarbons, mercaptans, solvents and other potential
Carsul formers to carbon dioxide and catalytically
treatable sulfur compounds. It can be done. Modern
science seems to be having a love affair with
acronyms, and the names of the new "non-invasive"
spectroscopic techniques that, in modified form, may
accomplish these species analyses in the furnace
flames are perfect examples:

LFI .......Laser Induced Fluorescence (Ref. 14)


MPI .......Multiphoton Ionization Spectroscopy(Ref.
15)
REMPI .....Resonance Enhanced MPI(Ref. 16)
ZEKE .... Zero Kinetic Energy
(photoelectron spectroscopy)(Ref. 17)
CARS ... Coherent Anti-Stokes Raman Scattering
(Ref. 18)

The common availability of high powered, tunable


and narrow wavelength band lasers is at the root of
the development of many of these techniques for taking
the fingerprint of the high energy species that
populate the FEF flame and measuring their
concentration to very low levels. Indeed we may get
more information than we bargained for, but surely
this is the route to accomplishing the ultimate in
recovery efficiency .... knowing quite precisely what
is going on in the "heart and lungs" of the most
important Claus reactor unit, the FEF. Are such
analytical devices now available? Yes, for laboratory
work, such as measuring the important high temperature
kinetic data talked about above. But not yet for use
in the field. Time scales for a "lab to field" model
are ever shrinking. Stay tuned. It may be sooner than
you think. No doubt, cost will be a factor in the
early days, but costs of electronic devices trend
downward with time.

Oxygen Enrichment

FEF performance and its monitoring has probably


been pushed more by the introduction of
oxygen-enrichment of "air" feed than by any other
single factor. The potential for significant increases
in throughput of acid gas made possible by reducing
and possibly even excluding aerobic nitrogen, and
replacing it with oxygen offers attractive economic
alternatives to new plant construction for gas
processors and refiners alike. The latter are faced
with ever increasing demands for deeper
desulfurisation and for stand-by capacity (redundancy)
in the event of failure of other sulfur recovery
trains in the overall operation. Indeed much of the
new burner design is equally strongly driven by these
same demands.

Oxygen-enrichment, however, means higher


temperatures, and higher oxygen-enrichment approaching
a pure oxygen feed means even higher temperatures. FEF
flame temperatures in the 1600-1650C (2900-3000F)
range are not "unthinkable", as oxygen levels in the
"air"-stream feed move beyond 40-70 Mol% O2. As the
"fellow traveler", nitrogen (and carbon dioxide)
species are reduced in the burner feeds, the
concentration of the reactive species increases
proportionately and the potential for much more
intense thermal runaways is increased, not
withstanding the tempering effect of increased water
vapor concentration in the process gas. Are these high
combustion flame temperatures necessarily the
temperatures that will be reached on the inside
surfaces of the furnace refractory? Will the tubesheet
see these temperatures and be able to survive? What
happens to the thermal load on the waste heat boiler?
What are the dangers of incomplete combustion and
breakthrough of oxygen into the downstream catalytic
sections, with consequent catalyst sulfation and
damage? What will be the consequence and utility of a
higher residual hydrogen content in the feed to the
catalytic stages? Again we see the consequences
throughout the whole system of making one change at
one point in the system.

The availability of the means to measure and


monitor internal temperature profiles is again
emphasized as a critical element in providing the
"comfort zone" that the operator requires to avoid
possible runaway temperature excursions in the coming
days of higher and higher oxygen-enrichment.

Also, the use of higher limit and more forgiving


refractory materials must be explored. Can affordable
refractories be found to withstand (practically) FEF
temperatures of 1900-2000C (3452-3632F)? We believe
they can and will be found!

Ammonia Destruction

This refinery SWS acid gas treatment problem is


one that could benefit enormously from better
monitoring and fine tuning of FEF operation. (The SRU
could benefit even more if the SWS acid gas was never
put into the SRU. But for now, it is normally done).
Both burner design and oxygen-enrichment (higher
temperatures) hold promise of yielding significant
reduction in ammonia handling problems and/or NOx
emissions. But, the desirable elemental nitrogen form
of the end product of the destruction of ammonia is
mid-way along the oxidation scale from ammonia to
NO x's; and, stopping oxidation efficiently at the N2
stage requires careful control of the reaction
conditions in the furnace, especially when oxygen is
plentiful. Here's another good reason for fine tuning
your FEF.

Two-zone Claus furnaces have been developed (Ref. 19)


that provide the opportunity to destroy ammonia in the
hotter front zone. If the overall temperature in the
furnace is much higher, such compartmentalisation of
the FEF may no longer be necessary or practical to
achieve this important refinery task. Also, it is
difficult to control the proper split of clean acid
gas between the front and rear zones. If too little
acid gas goes to the front zone, SO3 formation can
occur and cause severe downstream problems -
corrosion, catalyst deactivation and salts formation.

A much different (and simpler) approach was


patented and developed by Comprimo (Ref. 20), which
uses a special burner and other FEF design features to
destruct ammonia very effectively at levels of up to
28 Mol% NH3 in the combined acid gas feed. This system
feeds all of the acid gases (including SWS off-gas) to
the burner located on the front of the FEF, i.e., no
front/side split scheme is required.

Alternate methods of handling the NH3-rich SWS


acid gas should be developed. Can this offensive acid
gas stream be kept out of the FEF and handled in an
environmentally acceptable manner? We think it can. As
mentioned earlier, one method developed by Chevron,
called WWT, has not met with much acceptance in
industry. Another known concept is in the "embryo"
stage. What route can you imagine to dispose of this
troublesome stream? Think about it!

THE TUBESHEET AND WASTE HEAT BOILER

The tubesheet between the FEF and the Waste Heat


Boiler (WHB) is arguably one of the most severe
services and most likely failure points in the
high-temperature end of the sulfur plant. Although
traditionally faced with refractory to protect the
underlying steel of the WHB tubesheet from
high-temperature corrosive (sulfiding) attack by the
furnace gases, failures in refractory by erosion and
cracking are fairly common. Also, the ceramic ferrules
used in the tube inlets can and do fail. Better
ferrules need to be developed, both from material and
shape standpoints. Much has been accomplished in
recent times (Ref. 21) to improve the situation; but,
it is critically important that this area of potential
problems be thoroughly examined in any
oxygen-enrichment scenario. If the FEF experiences a
higher-temperature flame generated by
oxygen-enrichment, and the burner design is such that
the flame impinges in a selective way on parts of the
tubesheet, say as a result of laminar flow within the
fire box, the frequency of tube/tubesheet failures
could well increase. It is, therefore, once again
imperative that the operator have some means of
monitoring the conditions at the face of the
tubesheet, most conveniently by temperature probe/
profile. It is not unrealistic to imagine locating
surface-type thermocouples, with computer read-outs,
welded to the front-face of the tubesheet (under the
refractory) to monitor its temperature.

Modern ceramic materials are quite capable of handling


temperatures well in excess of 1600C (2912F), even in
the presence of such aggressive species as H2S, S 2, S,
SO2, SO3, SO, and the many other radical and molecular
species that may well persist in the flame as far as
the tubesheet at such high operating temperatures. The
challenge will come in trying to mate these ceramics,
with their traditionally low thermal conductivity, to
the high thermal conductivity metals that are needed
for heat exchange in the Waste Heat Boiler itself. It
may be recalled that this was also a problem in early
re-entry vehicles used in the Space Program when heat
shield tiles had a nasty habit of parting company with
the underlying metal they were designed to protect.
That challenge was met, and the problem was solved! So
can the problem of placing refractory on tubesheets be
solved! Let's pursue it.

The gases entering the Waste Heat Boiler tubes in


a Claus sulfur recovery system that have been stripped
of much of their diluent nitrogen and/or carbon
dioxide will be hotter, no question about it. They
will also contain species such as S2 that are
subsequently converted (shifted) at lower temperatures
to S 8, and by reaction with hydrogen to hydrogen
sulfide, with the release of much heat.

4 S 2 <------> S8 + heat
diatomic sulfur cycloocta sulfur

S2 + 2 H2 - 2 H2S + heat

Derivative (side) reactions that may have normally


occurred at lower temperatures in the furnace may now
occur within the Waste Heat Boiler tubes. The duty of
the WHB may well now be significantly different as a
result of upstream changes in the operating system.
Again we see the synergy effect.
This may call for significant reconsideration of
both the metallurgy and the mechanical design of the
WHB. Is the traditional "shell and tube" fire-tube
boiler design still appropriate for this kind of
service? Can we install a catalytic "hydrogen sulfide
thermal cracker" in the WHB zone? Yes we can. Can we
use a radically different type of WHB? Yes, we think
you can.

Other WHB designs that could be considered are:


Recirculation-gas type fire-tube boilers,
with a recycle blower (fan)
Water-tube, vertical WHB's,
Firetube type boilers with a side injection
of a "quench-freeze" stream just
upstream of the front tube-sheet, and
Possibly other types, yet to be developed.
The lowly Waste Heat Boiler may not be
recognizable when it becomes part of a new kind of
"thermal reactor" step in the Claus sulfur recovery
train.

While it may be a "biased" viewpoint, it is


nonetheless arguable that, until recently, the Front
End Reaction Furnace and its associated Waste Heat
Boiler in a sulfur plant have been the most ignored
and neglected units in the system as far as
sophistication is concerned. And yet they are the
very "heart and lungs" of the Claus sulfur recovery
plant. What happens in the high-temperature flame of
the FEF, determines (almost without exception) what
will be fed to the catalytic converters, the
condensers, the coalescers, the tail gas clean-up
unit, and finally the incinerator and the atmosphere.
A few percent improvement in conversion in the FEF
could well translate into the needed few tenths of a
percent improved recovery at the tail end of the
plant, in the continuing struggle to reach ever
closer to the elusive 100% sulfur recovery.

Getting the best out of your FEF and WHB


requires the kind of sophistication that is now being
offered in improved burner design, oxygen-enrichment,
operating parameter control and, most importantly,
accurately measuring and monitoring what is happening
within the FEF and the WHB. The medical profession
took a long time to finally go in and "fix" the heart
of the human. Let us hope that we can learn from this
piece of medical history that the FEF is the heart of
the sulfur plant, and it is in need of some TLC. But,
we are only likely to try to improve and "fix" it,
once we truly appreciate its crucial role in the
total SRU.

CATALYTIC CONVERTERS

A Quick Revisit of Basics

Early in the development of the Claus sulfur


recovery process it was recognized that the redox
reaction between hydrogen sulfide and the sulfur

dioxide produced from it in the combustion furnace


was an overall exothermic equilibrium reaction.
Thus, in order to maximize the conversion to
elemental sulfur, S8, thermodynamics indicates that
lower temperatures are preferred (sub-dewpoint) and
interstage product sulfur removal and dehydration
(H 2O removal) are also helpful in achieving higher
overall conversion efficiencies.

This basic understanding of the Claus reaction


mechanism led to the first "modification" of Claus's
sulfur recovery process by I.G. Farbenindustrie in
1940; namely, the separation of the combustion and the
redox reaction steps. Reducing the temperature to
favor the redox conversion, however, reduces reaction
rate and hence the need for rate enhancing catalysts
to reduce residence time and enhance throughput.

Much research and development has been undertaken


to further optimize the catalytic redox reaction.
While this exothermic equilibrium reaction remains a
key process in the overall Claus sulfur recovery
system, the key to recovery efficiency lies in the
extent to which the equilibrium can be displaced to
the product side. When that equilibrium conversion has
been maximized, any further sulfur recovery must
depend upon non-equilibrium controlled tail gas
clean-up processes. Have we reached the limit of
equilibrium controlled recovery? Or can we squeeze a
few more tenths of a percent out of the system to
reach the ever more elusive 99.999% "environmentally
friendly" target without resorting to energy
intensive, cost expensive, non-equilibrium tail gas
clean-up processes?

In the rest of this section, we look at some of


the areas in the catalytic Claus units where some
further improvement is being or might be sought; and,
the synergistic effects that these actions could have
on other units in the overall system.

Working at Sub-dewpoint

Low temperature, sub-dewpoint operation has been


extensively applied to the Claus process, both in the
main catalytic converters (e.g. MCRC, CBA) and tail
gas clean-up units (e.g. Sulfreen). The challenge in
these applications has been to overcome the inevitable
effects of sulfur deposition on the catalyst and
optimize the resulting regeneration system that is
required. Cycling of reactors between sulfur recovery
service and regeneration modes means expensive
replication of catalyst beds and the hardware
associated with them, such as troublesome switching
valves and complex piping. Catalysts that are not
negatively affected by repeated sulfur deposition
within their fine pore structure have been developed.
Thirty years ago we were content to talk about simple
catalyst porosity, and attempted to maximize that
property and hence the available surface area per unit
weight (like 250-320 m 2/gm.) Then there was
subdivision into micro - and macroporosity and
specification of the roles that each played. Now we
have micro-, meso -, and macroporosities, each with
their own pore size distribution ranges and each
associated with ever more specific catalytic functions
(Ref. 22). Now we "dope" the tried and true alumina
with special polyvalent metal species to meet specific
oxidation requirements. The catalyst business has
indeed become much more sophisticated with time.

One of these specific functions is the ease with


which liquid sulfur (sub-dewpoint)can enter and leave
the pores; and EQUALLY IMPORTANT, how easily hydrogen
sulfide and sulfur dioxide can diffuse through the
absorbed sulfur to reach the catalytic sites that are
"wetted" by that sulfur? Wiewiorowsky and Tuoro (Ref.
23) and Kerr and Jagodinsky (Ref. 24) showed years ago
that the Claus reaction between hydrogen sulfide and
sulfur dioxide proceeded very efficiently in liquid
sulfur medium with either homogeneous or heterogeneous
catalysts. To date, however, the presence of liquid
sulfur on or in the catalyst structure has been
generally viewed as "undesirable".

If one pauses to consider what has to occur when


two molecules of H2S react with one molecule of SO2 to
produce one molecule of Ss at catalytic reactor
temperatures, it is clear that there is more to this
than first meets the eye. If this is a single step
reaction, a very large number of molecules must
organize themselves on the catalytic sites, and
sit-down in proper sequence and order on the catalyst
surface to produce a whole number of molecules of
product, viz.
16 H 2S + 8 SO2 <----------------> 16 H2O + 3 S8

This is clearly entropy forbidden by the 2nd law of


thermodynamics, and suggests immediately that the
Claus conversion of one sulfur atom contained in
hydrogen sulfide and one sulfur atom contained in
sulfur dioxide to the eight-atom containing
cyclooctasulfur must proceed via a number of steps.
This stepwise mechanism allows the sequential building
of a sulfur chain to take place until it is long
enough to "calve-off" an S8 sulfur molecule. The
growing intermediate chain is almost certainly a
polysulfide, likely hydrogen polysulfide; and, what
better reaction medium to grow a polysulfide than
liquid sulfur? Thus, we suggest that having liquid
sulfur on the catalyst surface may, under certain
circumstances, be an advantage to the Claus redox
reaction rather than a hindrance.

What are these circumstances? Like so many things in


nature when a little is good, more is not always
better. So it may be with liquid sulfur on the Claus
catalyst. Once the initial hydrogen sulfide and sulfur
dioxide in the sulfur in contact with the catalyst
surface has reacted, it is important that the product
water escape readily, AND that more hydrogen sulfide
and sulfur dioxide diffuse from the gas phase through
the liquid sulfur onto the reaction sites on the
catalyst surface. Thus, too thick a layer (or film) of
sulfur in the catalyst pores will slow diffusion of
the reactants to the reaction sites, and not enough
sulfur will deny the reactants the medium that is most
suitable for the formation of the essential
polysulfide intermediates. The challenge is to design
a catalyst system that maintains these essential
criteria. At least, we now seem to have a handle on
what the criteria may be. It may be "ideal" to leave
the sub-dewpoint catalyst wetted with a layer of
liquid sulfur of just the "right" thickness, and no
more or no less. But, how can this layer thickness be
controlled? There may be ways to accomplish this. Time
will tell.

Removing the Water Product

Even the most elementary thermodynamic treatment


of Claus chemistry shows that removing the produced
water as it is formed assists in improving the
equilibrium conversion of hydrogen sulfide to sulfur.
Yet, little has been successfully accomplished in
introducing this rather obvious step into the
traditional Claus process.

There appear to be two major stumbling blocks to


interstage dehydration. One is thermodynamic. First,
cooling the reacting gas stream to condense out water
and then reheating to continue the catalytic reaction
in the next stage is a very inefficient process as far
as energy conservation is concerned. Large temperature
cycles in any reaction sequence are seldom efficient.
The second stumbling block is the separation of the
sulfur product that will inevitably contaminate the
water. A variety of attempts have been made to
optimize this separation using pressure filters,
centrifugation and added chemicals. None appear to
have as yet been refined to the point where they can
be readily and economically incorporated into the
Claus stream.

Amoco (Standard Oil Co.) was issued a U.S. Patent


(No.4,526,590) on July 2, 1985, that describes a
process they had devised to cool the condenser
effluent down to the water dewpoint, and just "take
the consequences" of condensing/solidifying sulfur in
full stride. As far as we know, this process was never
commercialized. Even if this process could have been
demonstrated commercially, it would probably have been
wrought with many other problems, in addition to the
obvious one of solid sulfur plugging. When H2O vapor is
condensed from a process gas stream containing H2S,
SO 2, S, O2 COS, CS2, etc., an aqueous stream is produced
that contains all sorts of sulfur compounds. These
"Wackenroeder" products include polythionic acids and
very sticky, amorphus sulfur. This aqueous stream
tends to attack and corrode away everything it comes
in contact with -carbon steel, stainless steel,
refractory, concrete, etc. Is trying to condense
water, at essentially one atmosphere of pressure, out
of such SRU process gases still "mission impossible"?

Air Products was issued a U.S. Patent (No.


4,684,514) on August 4, 1987, teaching the method of
recovering sulfur from an H2S-bearing stream, wherein
the process is operated under high pressure (say
50-150 psig or greater), and water is condensed
concurrently with liquid sulfur. The high-pressure
operation permits water condensation at temperatures
of 138-185C (280-365F), i.e., well above the sulfur
freezing point of 119C (246F). This was a clever
idea, but as far as we know, it has never been reduced
to commercial practice. Air Products may have overcome
the problem of plugging equipment with solid sulfur,
but our guess is that old "Mr. Wackenroeder" will
still-haunt-any such commercial unit.

The recent development that may hold promise for


interstage dehydration is the work in the
high-temperature membrane field. Hydrophilic membranes
capable of preferentially passing water at elevated
temperature relative to other components of the gas
stream may hold promise for at least partial
dehydration of the Claus gas stream. Even if this
could be accomplished, however, there remains the
challenge of treatment and disposal of this separated
water, which will undoubtedly contain sulfur in
various forms. Indeed it is a form of sour water; and,
the Claus process itself has tended to be the
treatment "process of choice" for such waste streams
originating from other sources, i.e., sour water
stripper offgases.

It should also be remembered that it is the water


present in the Claus reaction stream that is used in
the first catalytic reactor for hydrolysis of COS and
CS 2. As has been noted, however, higher front end
reaction furnace temperature operation accompanying
oxygen-enrichment, may remove these carbon-sulfur
species and obviate the need for the "anti-Claus"
hydrolysis conditions in the first reactor.

Removing the Passenger Gases

The most common "passenger" gas in the Claus


process is, of course, the nitrogen that enters the
system through the front end furnace as air demand.
Carbon dioxide in natural gas is also in this category
of "excess baggage". Both occupy valuable process
equipment volume and heat exchanger capacity, and
their removal has an immediate benefit in terms of
throughput capacity and better conversion in a given
Claus system, as we have discussed earlier.

Oxygen-enrichment reduces the amount of passenger


nitrogen; and, carbon dioxide rejection in upstream
H2S-selective sweetening units will reduce the
concentration of this passenger gas in the system.
Perhaps not so readily recognized is the similar
effect of direct sulfur dioxide generation through
burning sulfur in oxygen, as in the "NOTICE" process
(Ref. 25). Thus the sulfur dioxide needed to react
catalytically with the sour gas hydrogen sulfide is
generated independently, and the front end furnace air
feed is markedly reduced. Where the high temperature
incineration role of the front end furnace is not
essential, the possibility exists for elimination of
the FEF. The potential problems with the NoTICE
process are: (1) high capital cost of the
SO 2-generation step, (2) the perceived safety hazards
of the SO2-generation step, and (3) the need to still
combust some H2S in the FEF with oxygen.

Whatever the mechanism for removing the passenger


gases, there is an important system consequence of
this action. These passenger gases act as "thermal
diluents" providing an important vehicle for
conducting away the heat generated in the exothermic
reactions that occur within the catalytic reactors.
When they are removed, the concentration of the
reactants in the catalyst beds increases and the
potential for generating hot spots or even thermal
runaways increases with consequent thermal sintering
damage to the pore structure of the catalyst. This
effect is tempered somewhat by the higher water vapor
(H 2O) content present. Most catalytic materials
currently in use in the Claus system are not good
thermal conductors. Will it therefore be necessary to
develop catalysts that have improved thermal
conductivity and that can carry away reaction heat
from the catalytic surface with greater efficiency?
This will certainly be important if the sub-dewpoint
operation benefits discussed earlier are to be
optimized. Careful thermal control is also a feature
of some of the tail gas clean-up add-on processes such
as SUPERCLAUS (Ref. 26,27), and increased reactant
concentration in the absence of the passenger gases
may also have significant consequences in this part of
the system.

Catalytic Reactor Design

In any heterogeneous catalytic gas phase reaction,


such as occurs in the present Claus reactor, gas/solid
surface contact is critical to efficiency. This may be
modified if operation under sub-dewpoint conditions
with a film of liquid sulfur in place on the catalyst
surface becomes more common; but, then gas diffusion
"in and out" of the surface liquid sulfur film will
become critical.

Do current catalytic reactor designs really


optimize this contact phenomenon? By and large, we
pack a horizontal vessel with porous catalyst
granules, install a gas dispersion system at the
reactant inlet and hope for the best as far as
optimizing gas/catalyst contact is concerned. Not
infrequently, channeling occurs through the catalyst
bed and reactant gases pass preferentially through the
channels. Catalyst charges can shift due to flowing
gas effects, resulting in significant variation in bed
thickness (dunes of catalyst), through which the gases
must pass. Can catalyst bed geometry be improved? Yes,
we feel this is quite do-able. Can continuous
regeneration of the type used in many FCCU systems be
incorporated? This would be very difficult, we feel.

However, Linde A.G. (German Linde) has developed


their "isothermal Claus reactor" system,-called
"Clinsulf" (Ref. 28,29). It has been commercialized in
Western Europe, mostly in Germany. The catalyst beds
contain coiled heat exchangers, installed directly in
the catalyst beds, to absorb the exothermic heat as it
is generated by the Claus reaction. Cost and
mechanical complexity may be challenges.

Comprimo, Shell, and others have used the


"toaster" design for very large Claus and SCOT "Co-Mo"
catalyst beds. The catalyst is held in relatively thin
vertical layers (like slices of toast) by special
support screens; and, the process gases pass through
the catalyst beds in a horizontal manner. This type of
reactor design exhibits very low pressure drop, and
should lend itself well to large SRU Trains.

Radial-flow reactors have been used for years in


other process industries (Petro-chemical plants, for
example), but are not normally applied to Claus units.
Why not? They appear to have good utility for such
service. Is this an area deserving further
exploration?

Stacked (pancake-type) reactors have been used in


some large SRU's in Canada (1750 LTPD trains).
Catalyst loading can be difficult in such vessels;
and, process piping "to and from" the various
compartments (beds) is awkward. Large, bellows-type
expansion joints in such piping can be a real
maintenance headache. But, the catalyst beds seem to
function well; and, the des-ign saves a lot of plot
space (real estate). These designs have not been too
popular in industry. But, they deserve
reconsideration.

A new reactor design should accomplish several


desirable features, such as: (1) low pressure drop (2)
good flow distribution, (3) uniform bed depth, with no
possibility for "dunning", (4) ease of loading and
unloading catalyst, (5) ease of sampling catalyst
"on-stream", (6) friendly to temperature & sample
monitoring, (7) friendly to piping to and from other
equipment, and (8) inexpensive to fabricate and
install. Can such a reactor design be achieved? We
think it can, if we really put our minds to it.

Perhaps, the most discouraging feature of


catalyst-bed operation is the relatively limited
monitoring that is done within the bed itself. One
might forgive the absence of instrumentation in the
very aggressive atmosphere of the FEF, but placing
thermocouples and sample probes at key locations
within the catalyst beds is not a great technical
challenge. More recently this has become more
commonplace; but, many Claus operators of older SRU's
still have precious little information on what is
really happening inside their catalytic reactors. Much
could be done to fine tune and observe catalyst
reactor operation and efficiency by having both more
sample analyses and temperature data available. Like
information from the FEF, such data would make delayed
tail-gas analysis feed-back to the front end ratio
controller obsolete. Why not read the mail before it
is sent, rather than reading yesterday's mail
tomorrow?

Other Consequences of Upstream Changes

The upstream change with the greatest likely


consequence on catalytic reactor operation will be
oxygen-enrichment and higher FEF temperature
operation. It may no longer be necessary to run the
first catalytic converter under COS and CS2 hydrolysis
conditions, with consequent loss in Claus efficiency.
Sensitivity of catalyst to Carsul and other polymer
deposition may be less critical if higher FEF
temperatures convert these impurities to carbon
dioxide. But, potential hazards from possible high
temperatures or "oxygen breakthrough" will have to be
monitored more carefully. Risks of thermal degradation
and sulfation of catalysts during upset conditions
will have to be factored into design parameters; and,
if the reactants are more concentrated due to
rejection of the passenger gases, these undesirable
consequences may happen much more rapidly. All of this
should be carefully considered in future designs.
SULFUR CONDENSERS

The key elements of a sulfur condenser are to


cool-down the process gas stream from the WHB or a
catalytic converter to the "sulfur dewpoint" of the
stream, and condense out as much liquid sulfur as
practical, and properly separate that condensed sulfur
from the main gas stream (Ref. 30,31). If the gas is
cooled too much (close to 119C (246F), the sulfur
freezing point), solid sulfur plugging can occur. If
the gas is cooled not enough, then either (1) very
little liquid sulfur is removed from the gas,
and/or (2) the sulfur that is condensed is very hot
(say 200-260C) (392-500F), and the sulfur is so
viscous that it will hardly flow from the condenser
outlet channel, through the seal pot, to the pit. So,
there is a practical, optimum temperature for each
condenser, depending upon: (1) the sulfur "load" in
the gas, (2) the reheater duty required to reheat the
effluent gases, (3) the position in the SRU train
(first, last or other), and (4) the desired approach
to the sulfur freezing point (last condenser typically
cools gas to 130-132C (266-270F).

Another key consideration is how the condensed


sulfur is removed from the gas stream. If you have
ever-witnessed a blowing rain storm, you know that all
of the liquid (rain) doesn't necessarily go straight
down and all of the gas (wind) doesn't magically go
sideways. The same principles apply-in the outlet
channel of a sulfur condenser. Reduction is gas
velocities, impingement baffles and demister pads
should all be used to good advantage. We feel that
every condenser should have a properly designed, and
adequately heated, demister pad in its outlet channel.
In addition, the last (final) condenser should be
followed by a properly designed coalescer vessel
(discussed later).

The last point to be discussed here, is the need


to remove the liquid sulfur from the outlet channel at
the same rate at which it is condensed. If you don't
do this, you eventually end up with a "constipated"
condenser; and, it gets real mean, just like the human
body when it experiences this condition. The condenser
outlet channel should have a sulfur boot or tangential
liquid sulfur outlet nozzle, which has its own
steam-jacketed, full-bore plug valve located as close
to the outlet nozzle as possible. The steam-jacketed
sulfur rundown line should be close-coupled to a
properly designed, steam-jacketed "seal pot" of
sufficient depth to keep from "blowing" the seal even
during upset operations. The outlet from the seal pot
should empty into a steam-jacketed "look box", with a
hinged lid and a snout for leading the sulfur to its
center for better observation and less cooling of the
liquid sulfur. All of these items should be
inter-connected with easily roddable, steam-jacketed,
liberally-sized sulfur rundown lines.

The condenser tubes should slope from inlet to outlet


end at least 1/8"/Foot. For plants with very high
turn-sown requirements, we prefer a slope of
1/4"/Foot. The mass velocities of the total "gas +
liquid" stream flowing through the tubes should be
designed to fall between 2-6 lbs/sec-Ft 2. Below 1-1.5
lbs/sec-F2 mass velocity, you will experience sulfur
fogging, for sure. (Very bad for overall operation and
recovery efficiency). Above 6.5-7 lbs/sec-Ft2, you may
experience frothing and re-entrainment of condensed
sulfur in the tubes. (Bad for excessive loading of the
demister pad and gas/liquid separation).

Now that we understand all of the "good design rules"


of sulfur condensers, what can we do to improve their
operation and ability to do their job? Here's some
things to consider:

Never, never use vertical sulfur condensers,


Where possible and practical, locate condensing
passes in separate shells (try to avoid
multi-pass condensers in one shell) - this is for
ease of maintenance,
Always slope condenser tubes,
Always use demister pads in outlet channels,
Design intermediate condensers to cool the gas and
condense the sulfur at the optimum temperature,
Design the last condenser to cool the gas to
130-132C
(266-270F),
Provide properly designed liquid sulfur outlet
nozzles from the outlet channel,
Provide liberally-sized, steam-jacketed sulfur
rundown lines, with quality plug (block) valves,
that flow into well-designed, proper-depth seal
pots, that have proper and friendly look boxes,
Shy away from using sulfur condensers as BFW
preheaters (corrosion and mechanical problems),
Select tube size and tube count to comply with the
rules on mass velocities,
Properly insulate the inlet and outlet channels and
their cover plates (dollar plates), on all
condensers - this is to reduce corrosion of these
areas.

Where do the opportunities lie for significant


improvements in sulfur condenser design? We feel some
worthy goals would be: (1) improve the gas/liquid
separation by superior devices in the outlet channels,
such as special vanes, better demister pads, better
heating facilities for demister pads, etc.; (2) devise
a clever (and practical) way to vary the mass flow
velocities through condenser tubes at low turn-down
rates, (such as "on-stream" baffle closure to blank
tubes in the inlet channel, to keep velocities up
above 23 lb/sec-Ft2 during extreme turn-downs, and
then between 3-5.5 during normal operations - tricky,
but needed), and (3) find a way to promote the Claus
reaction further in the liquid sulfur phase flowing
inside the condenser tubes before the gas/liquid
separation occurs in the outlet channel (this could
involve hydrogen polysulfide chemistry).
There are at least two phenomena that can cause the liquid
sulfur produced from a condenser to contain high
levels of hydrogen polysulfides (H2SX): (1) at higher
sulfur temperatures, say 200220c (392-428F), the
liquid sulfur will contain more H2SX, and (2) during
high O2-enrichment operation, the partial pressure (pp)
of H 2S in the gas stream is increased, due to
elimination of the diluent gas (N2); and, the higher pp
of H 2S causes more H2SX in the liquid sulfur. Be aware
of these points and design around them. Run condensers
at about 190C (374F) maximum outlet temperature; and,
provide for the extra H2S X in "O2-enriched" operation
produced sulfur in the design of your liquid sulfur
product degassing system.

A very interesting recent development is


Comprimo's "Deep Cooler" sulfur condenser (Ref. 32)
that you heard about yesterday. This special condenser
operates at 100-110C (212-230F), which is about 14C
(25F) below the sulfur solidification point of 119C
(246F), and yet does not plug with solid sulfur. If
the Deep Cooler is placed in tandem behind the last
sulfur condenser in the train, it can increase the
overall sulfur recovery by about 0.3%, which is a
significant step toward the 99.5%+ recovery goal we
are seeking today.

REHEATERS

The preferred type of reheaters in Claus SRU's is


the indirect-heat type, such as: (1) steam reheaters,
(2) hot-oil reheaters, (3) electric reheaters (small
SRU's), (4) gas-fired indirect reheaters (next to last
choice, because of low energy efficiency), and (5)
gas/gas heat exchangers (last choice, due to turn-down
problems and high capital cost). The opportunity to
improve indirect reheaters from a process stand point
is not too great. If high-pressure steam (500-600
psig) is available, it is the preferred heat-medium
above all others.

Also, both acid-gas fired and fuel-gas fired


direct reheaters are used by some contractors in some
designs. The main opportunity to improve the design
and operation of these direct reheaters is to use good
quality, swirl-vane, high-turn-down, high-efficiency
type burners. Also, good-quality, very accurate
metering and flow controls of fuel (or acid gas) and
air to these burners in absolutely essential.

The inlet temperature to a catalytic converter (the


reheater outlet temperature) should be set such that
the lower bed (gas) temperature (in the lowest row of
bed thermocouples) is about 1015C (18-27F) higher
than the actual sulfur dewpoint of the process gas at
this point. (This rule is not true for the 1st
catalytic converter, where COS/CS2 hydrolysis is a
goal.) This "sounds" real good, but the question is
how do you determine the sulfur dewpoint from an
operator's viewpoint? The only way you can do this
today is by calculation of the "sulfur dewpoint"
temperature by a computer simulator, such as SULSIM.
So, these dewpoint values are determined by the design
engineer; and, all of the catalyst bed inlet
temperatures are set in the design phase to honor the
above rules. The problem is that plant feeds and
process conditions change with time; and, the "real"
sulfur dewpoints are somewhat different than those
predicted in the original design. But, the operator
doesn't have a computer, loaded with SULSIM, at his
command. So, what does he do? Being a good operator,
he runs on the "safe" side, and sets the inlet
temperatures higher than actually required to have
some safety margin above the outlet sulfur dewpoints,
and stay out of trouble. (He plays rectus protectus!)
Of course, the higher than necessary bed outlet
temperatures depress the Claus reaction efficiency.

What is badly needed by the industry is a "Sulfur


Dewpoint Analyzer" (SDA). If this device were
available, the operator could read the outlet dewpoint
and set the catalytic bed inlet temperature
accordingly to hold the proper *T margin - or, this
could be done automatically in this day of DCS
computer controls. Our guess is that the first vendor
to come out with a reliable "SDA" will sell a bunch of
them to industry, unless they cost an "arm & a leg".
The "SDA" is truly a needed new piece of SRU
instrumentation that would help us tune our Claus unit
better for increased recovery. Who knows, someone may
be working on one now.

TAIL GAS COALESCERS

Even if the last sulfur condenser has a demister


pad in its outlet channel, we feel that a final tail
gas "coalescer" vessel is justified and should be
recommended. The type normally used is a vertical
vessel (heat-traced or steam-jacketed externally) with
a horizontal demister pad located near the top. The
demister pad should consist of two layers (say each
4-6" thick) of York Style 326, S.S. (304 or 316) mesh
(or equal), sandwiched around (above and below) a 304
S.S. or 316 S.S. serpentine steam coil, made of 1-1
1/2" size pipe, with 180 return bends, and as many
coil passes as practically possible in the vessel. The
mesh pads must actually touch the steam coil, and not
just sit on a support grid that in turn touches the
steam coil. The pads should be sandwiched around and
wired (with 304 or 316 SS wire) to the steam coil. A
minimum size 2" x 3" steam-jacketed sulfur rundown
line should exit the bottom head of the vessel, and
the vessel should sit on legs (for rodding purposes),
and not a vessel skirt.

An alternate type of tail gas coalescer is a


centrifugal type. Peerless, PECO (cyclo-tube) and
Porta-Test all make acceptable types. A horizontal
centrifugal type is preferred, mounted in-line in a
horizontal pipe run of the tail gas line. The whole
coalescer shell should be completely steam-jacketed or
heavily steam- heat traced with "Contro-trace" and
Thermon cement, or equal. The centrifugal coalescer
must have its own steam-jacketed run-down line and
seal pot. Since liquid sulfur has a specific gravity
of about 1.8 (referred to water at 1.0), it is easily
"slung" from the gas stream by centrifugal motion and
force.

The ultimate type of tail gas coalescer is the


"aerosol mist" removal type built by Pall,
Monsanto-Brink or Koch (Flexifiber). These type
filter/coalescer devices are not normally installed on
SRU tail gas lines. But, if you have a sulfur-mist
(aerosol size) carry-over problem, the vendors say
they are ready to tackle the problem with you, and do
a special design for a SRU tail gas application.

The absolute "ultimate" tail gas coalescer system


would have a vertical vessel (with horizontal mesh
pad), followed by a centrifugal separator, followed by
an "aerosol mist" removal type. You may never see such
a three-element installation; but, the opportunity is
there for someone to come up with a "Super Coalescer"
device that incorporates the features of all three in
one vessel, and yet is not prohibitive in cost. This
is a very worthy goal for some young, aspiring
scientist or engineer.

What is to be gained by removing essentially all


of the liquid sulfur mist from the final condenser
effluent gas? We feel that a well designed demister
pad in the final condenser outlet channel still lets
liquid sulfur entrainment through the pad amounting to
about 2 lbs sulfur/ 100 mols of sulfur-free gas. This
can result in a recovery loss of 0.2-0.3%, if it is
not recovered. While this amount of entrained sulfur
may sound very small, and may not have been too
significant for recovery levels of 95-96%, it can
represent a third (1/3) to half (1/2) of the final
0.5-1.0% of unrecovered sulfur present in the
untreated SRU tail gas, when going for 99-99.5%
recovery before tail gas clean-up in a TGCU. As a
matter of fact, improving demister and coalescer
efficiencies may prove to be one of the most cost
effective "TGCU processes".

TAIL GAS CLEAN-UP (TGCU)

In the ideal, fully optimized Claus sulfur recovery


plant there would be no requirement for a TGCU unit.
Indeed, with full oxygen-enrichment and 100%
conversion, there would be nothing but steam, carbon
dioxide and a little nitrogen going up the stack. But
as society demands ever more containment of industrial
effluents (while continuing to do relatively little
about their own personal waste and effluent!), it is
unlikely that the equilibrium Claus can ever be pushed
far enough to meet the virtual 100% recovery goal.
Indeed it is remarkable that we have been able to
reach 99% plus recovery with equilibrium reaction
chemistry.

The systemic improvements that have been discussed


in this revisit of the Claus may well enable a
99.5-99.7% recovery goal to be reached. It may be
argued that if the regulatory requirement is 99.9%,
and this can only be reached by non-equilibrium type
tail gas clean-up, such as the hydrogen reductive
processes, why bother with further improvements in the
equilibrium sections of the Claus? Why not simply take
care of everything in Tail Gas treating? We feel this
is a defeatist attitude, and should not be adopted by
industry. Why add-on a trailer, if the car can be
tuned better or expanded with a top-carrier and carry
the load itself?

The answer lies in relative costs and loading on


the tail gas treatment system. If the challenge is to
remove the last 0.5% of sulfur from the SRU effluent
stream, and improvements upstream can squeeze out just
0.1% more of that 0.5%, this amounts to a 20%
reduction in the load on the more expensive
non-equilibrium tail gas clean-up final step.

Also, if the Claus can be pushed to recovery


levels of 99.599.7%, then what "wisdom" is there in
spending twice the capital cost of the SRU (SCOT cost
= SRU cost) to achieve 99.95%? The answer is "there is
no wisdom in unreasonable laws". The federal and state
regulatory agencies should be challenged to defend
their laws, and to demonstrate the wisdom of such a
recovery level of 99.95%. When it costs $2000 - 8000
per ton of incremental SO2 abated, with sulfur selling
at less then $50-100/ton, something appears to be
badly wrong with the logic for such "wisdom".
And furthermore, if the regulatory agencies are to
require Claus SRU's to achieve 99.95% recovery, then
all other potential SO2 emitters should have to live by
the same law. This should include: (1) utility power
plants, (2) chemical plants, (3) ore smelters, and (4)
even volcanoes! Yes, Mother Nature continues to be a
major polluter according to some regulatory agency
rulings. But, Mother Nature marches on unimpeded.

Nonetheless, it is likely that non-equilibrium tail


gas cleanup systems will continue to find favor (or be
decreed) in plants located in urban areas where the
effluent load of certain toxic species on the
biosphere is already high and further loading is
unacceptable. In more remote locations, however, it
may well be more justifiable to limit the expenditure
of further "greenhouse gas producing" energy sources,
such as carbon dioxide, in favor of slightly higher
tonnages of sulfur dioxide, which, in moderation, is
biologically assimilatable by the environment.

INCINERATION

Typical Claus SRU thermal incinerators operate at


600-650C (1112-1202F), with 25% excess air (or more),
and typically use a 150-200' tall, hot,
refractory-lined stack. Here is a real opportunity to
save considerable fuel gas and operating cost by using
catalytic incinerators for SRU tail gas. The operating
(fuel) cost for a catalytic unit can be half (1/2)
that of a thermal unit. Also, much less CO2 is
generated and dumped to the atmosphere. However, the
catalytic incinerator capital cost is usually more;
and, they are much less "forgiving" than thermal
incinerators. Catalytic units have gained much wider
acceptance in Europe than in North America. There are
a few catalytic incinerators operating in the U.S. and
Canada. If the tail gas comes from a SCOT TGCU, rather
than a 3-Stage Claus SRU, there is much less risk for
thermal runaways in the catalytic units. Both types
should be evaluated for future SRU's. Future energy
savings could be important to our industry and our
society.

CONCLUDING REMARKS

The purpose here has been to revisit the Claus


sulfur recovery process for the purpose of identifying
those areas where modern technology, materials and
control systems may permit yet further improvement in
recovery efficiency. Considering that the old Claus
process has been around some 112 years, we are not
likely to find some revolutionary single further
improvement in the Claus process that will be the
panacea to the gas processor's problems of meeting the
environmental laws and challenge. More likely, by
viewing the system as a whole and considering it as an
integrated system full of synergism, we will find that
a few more tenths of a percent recovery can be found
in several places by careful attention to the systemic
interlinkages.

The gas conditioner is being tempted by completely


new replacements for the Claus process for recovery of
sulfur from hydrogen sulfide that involve solution
redox chemistry, electrolysis, thermal and plasma
cracking (Ref. 33,34), among others. Some of these
processes may find application in specialized areas;
but, the Claus process will continue, for the
foreseeable future, to handle the bulk of the sulfur
recovery load, provided that it can continue to
benefit from creative and systemic thinking on the
part of those who design and operate it.

Claus has been a real "work horse" for the gas


processing industry for well over seventy-five years.
Claus is still very much alive and not likely to be
replaced anytime soon. So, why not resolve ourselves
to the fact that Claus will be with us for a long time
to come? Let's look for improvements in many small
ways, which, when added together and compounded, will
yield a much larger recovery improvement overall. We
believe that the industry we have been part of for
over forty years can, must and will "rise to the
occasion".
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