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SECTION 22

Sulfur Recovery
Sulfur is present in natural gas principally as hydrogen sul- combustion section reacts with unburned H2S to form elemen-
fide (H2S) and, in other fossil fuels, as sulfur-containing com- tal sulfur. The principal reactions taking place (neglecting those
pounds which are converted to hydrogen sulfide during process- of the hydrocarbons and other combustibles) can then be writ-
ing. The H2S, together with some or all of any carbon dioxide ten as follows:
(CO2) present, is removed from the natural gas or refinery gas
by means of one of the gas treating processes described in Sec- Thermal or Combustion Reaction Section
tion 21. The resulting H2S-containing acid gas stream is incin- H2S + 112 O2 SO2 + H2O Eq 22-2
erated, or fed to a sulfur recovery unit. This section is concerned
H @ 0 C 517 900 kJ
with recovery of sulfur by means of the modified Claus and
Claus tail gas clean-up processes. Redox processes are touched Combustion and Catalytic Reaction Sections
upon. For a discussion and description of other sulfur recovery 3
processes, see Maddox1. 2 H2S + SO2 Sx + 2 H2O
x Eq 22-3
H @ 0C 126 360 kJ
THE CLAUS PROCESS
Overall Reaction
The Claus process as used today is a modification of a pro- 3
cess first used in 1883 in which H2S was reacted over a catalyst 3 H2S + 112 O2 Sx + 3 H2O
x Eq 22-4
with air (oxygen) to form elemental sulfur and water.
H @ 0C 644 260 kJ
H2S + 12 O2 S + H2O Eq 22-1
This is a simplified interpretation of the reactions actually
Control of this highly exothermic reaction was difficult and taking place in a Claus unit. The reaction equilibrium is compli-
sulfur recovery efficiencies were low. In order to overcome these cated by the existence of various species of gaseous sulfur (S2,
process deficiencies, a modification of the Claus process was de- S3, S4, S5, S6, S7, and S8) whose equilibrium concentrations in
veloped and introduced in 1936 in which the overall reaction relation to each other are not precisely known for the entire
was separated into (1) a highly exothermic thermal or combus- range of process conditions. Furthermore, side reactions involv-
tion reaction section in which most of the overall heat of reac- ing hydrocarbons, H2S, and CO2 present in the acid gas feed can
tion (from burning one-third of the H2S and essentially 100% of result in the formation of carbonyl sulfide (COS), carbon disul-
any hydrocarbons and other combustibles in the feed) is re- fide (CS2), carbon monoxide (CO), and hydrogen (H2). Gamson
leased and removed, and (2) a moderately exothermic catalytic and Elkins2 cover the basic theory involved in the Claus pro-
reaction section in which sulfur dioxide (SO2) formed in the cess; however, they ignore the many potential side reactions
and also the existence of S3, S4, S5, and S7.

FIG. 22-1
Nomenclature

(PH2O)2 (PSx)3/x
Kp =
(PH2S)2 (PSO2) 3
1
H = heat content or enthalpy, kJ/kg or kJ/kg-mole = [Mols H2O]2 [Mols Sx]3/x x

Kp = equilibrium constant [Mols H2S]2 [Mols SO2] Total Mols


For the low pressure, vapor phase Claus reaction P = partial pressure, kPa
3 = total pressure, kPa
2 H2S + SO2 2 H2O + Sx
x

DEFINITIONS OF WORDS AND Residence time: the period of time in which a process stream
will be contained within a certain volume or piece of equip-
PHRASES USED IN SULFUR RECOVERY ment, seconds.
Acid gas: feed stream to sulfur recovery plant consisting of Tail gas cleanup unit: a process unit designed to take tail gas
H2S, CO2, H2O, and usually less than 2 mol % hydrocarbons. from a Claus sulfur recovery plant and remove additional
Claus process: a process in which 13 of the H2S in the acid gas sulfur with the goal of meeting environmental sulfur emis-
feed is burned to SO2 which is then reacted with the remain- sion standards.
ing H2S to produce sulfur. This is also referred to as the
modified Claus process.

22-1
For the usual Claus plant feed gas composition (water-satu- 980C plus and in the catalytic converters by lower oper-
rated with 3080 mol % H2S, 0.51.5 mol % hydrocarbons, the ating temperatures of less than 371C.
remainder CO2), the modified Claus process arrangement re-
sults in thermal section (burner) temperatures of about 980 to To attain an overall sulfur recovery level above about 70%,
1370C. The principal molecular species in this temperature the thermal, or combustion, section of the plant is followed by
range is S2 (Fig.22-21) and conditions appear favorable for the one or more catalytic reaction stages. Sulfur is condensed and
formation of elemental sulfur by direct oxidation of H2S (Equa- separated from the process gases after the combustion section
tion 22-5) rather than by the Claus reaction (Equation22-6). and after each catalytic reaction stage in order to improve equi-
librium conversion. Although Fig.22-2 indicates that the Claus
2 H2S + O2 2 H2O + S2 Eq 22-5 reaction is favored by lower temperatures, the process gases
must be reheated prior to being fed to the catalytic reaction
H @ 0C = 313 900 kJ stage in order to maintain acceptable reaction rates and to en-
3 sure that the process gases remain above the sulfur dewpoint as
2 H2S + SO2 2 H2O + S2
2 Eq 22-6 additional sulfur is formed. Fig.22-3 is the flow sheet of an ex-
H @ 0C = +47 060 kJ ample three-stage Claus sulfur recovery plant; Fig. 22-4 shows
the mechanical arrangement of an example small, package-
However, both laboratory and plant measurements indicate type, two-stage Claus plant.
the more highly exothermic oxidation of H2S to SO2 (Equa-
tion22-2) predominates and the composition of the equilibrium Gases leaving the final sulfur condensation and separation
mixture therefore is determined by the slightly endothermic stage may require further processing. These requirements are
Claus reaction (Equation22-6). established by local, state, or national regulatory agencies.
These requirements can be affected by the size of the sulfur re-
Fig.22-2 is a representation of theoretical equilibrium con- covery plant, the H2S content of the plant feed gas, and the geo-
version as a function of temperature for graphical location of the plant.
 n acid gas from a wellhead-type treater, with about
A
3.5mol % hydrocarbons (Curve1) CLAUS PROCESS CONSIDERATIONS
An acid gas from a refinery treater, with about 7mol % The Claus sulfur recovery process includes the following
hydrocarbons and 1mol % mercaptans (Curve2) process operations:

 ure H2S (Curve3)


P C
 ombustion burn hydrocarbons and other combusti-
bles and 1/3 of the H2S in the feed.
These curves indicate:
W
 aste Heat Recovery cool combustion products. Be-
S
 ulfur recovery would be expected to be lower for a feed cause most Claus plants produce 10354140 kPa (ga)
gas from a refinery than for a wellhead treater because of steam at 185254C, the temperature of the cooled pro-
higher hydrocarbon content cess gas stream is usually about 315370C.
 he calculated equilibrium conversion for both acid gas
T S
 ulfur Condensing cool outlet streams from waste
feeds follows closely the idealized curve for pure H2S heat recovery unit and from catalytic converters. Low
pressure steam at at 345480 kPa (ga) is often produced
 onversion of H2S to elemental sulfur is favored in the
C
and the temperature of the cooled gas stream is usually
reaction furnace by higher operating temperatures of

FIG. 22-2
Theoretical Equilibrium Percent Conversion of Hydrogen Sulfide to Sulfur3

22-2
FIG. 22-3
Example Three-Stage Sulfur Plant
(Straight-Through Operating with Acid Gas-Fueled Inline Burners for Reheating)

FIG. 22-4
Example Package-Type Sulfur Plant

22-3
about 177C or 127149C for the last condenser generat- Numerous side reactions can also take place during the
ing 100 kPa (ga) steam or preheating boiler feed water. combustion operation, resulting in such products as hydrogen
(H2), carbon monoxide (CO), carbonyl sulfide (COS), and carbon
R
 eheating Reheat process stream, after sulfur conden- disulfide (CS2). Thermal decomposition of H2S appears to be the
sation and separation, to a temperature high enough to most likely source of hydrogen since the concentration of H2 in
remain sufficiently above the sulfur dewpoint, and gener- the product gas is roughly proportional to the concentration of
ally, for the first converter, high enough to promote hy- H2S in the feed gas. Formation of CO, COS, and CS2 is related
drolysis of COS and CS2 to H2S and CO2. to the amounts of CO2 and/or hydrocarbons present in the feed
COS + H2O CO2 + H2S Eq 22-7 gas. Plant tests indicate concentrations of H2 and CO in the
product gas to be approximately at equilibrium at reaction fur-
CS2 + 2H2O CO2 +2 H2S Eq 22-8 nace temperatures; Fig.22-7 indicates potential COS and CS2
Catalytic Conversion Promote reaction of H2S and SO2 formation in the Claus furnace.
to form elemental sulfur (Equation22-3) Heavy hydrocarbons, ammonia, and cyanides are difficult to
burn completely in a reducing atmosphere. Heavy hydrocar-
Process Variations bons may burn partially and form carbon which can cause deac-
Several variations of the basic Claus process have been de- tivation of the Claus catalyst and the production of off-color
veloped to handle a wide range of feed gas compositions. Some sulfur. Ammonia and cyanides can burn to form nitric oxide
of these are shown in Fig.22-5. Straight-through operation re- (NO) which catalyzes the oxidation of sulfur dioxide (SO2) to
sults in the highest overall sulfur recovery efficiency and is cho- sulfur trioxide (SO3). SO3 causes sulfation of the catalyst and
sen whenever feasible. can also cause severe corrosion in cooler parts of the unit. Un-
burned ammonia may form ammonium salts which can plug
Fig.22-6 can be used as a guide in Claus process selection. the catalytic converters, sulfur condensers, liquid sulfur drain
legs, etc. Feed streams containing ammonia and cyanides are
Combustion Operation sometimes handled in a special two-combustion stage burner or
Most Claus plants operate in the straight-through mode. in a separate burner to ensure satisfactory combustion.
The combustion is carried out in a reducing atmosphere with Flame stability can be a problem with low H2S content feeds
only enough air (1)to oxidize one-third of the H2S to SO2, (2)to (a flame temperature of about 980C appears to be the mini-
burn hydrocarbons and mercaptans, and (3)for many refinery mum for stable operation). The split flow, sulfur recycle, or di-
Claus units, to oxidize ammonia and cyanides. Air is supplied rect oxidation process variations often are utilized to handle
by a blower and the combustion is carried out at 20100 kPa these H2S-lean feeds; but in these process schemes, any hydro-
(ga), depending on the number of converters and whether a tail carbons, ammonia, cyanides, etc. in all or part of the feed gas
gas unit is installed downstream of the Claus plant. are fed unburned to the first catalytic converter. This can result

FIG. 22-5
Claus Process Variations

22-4
FIG. 22-6 FIG. 22-7
Claus Plant Configurations Potential COS and CS2 Formation in Claus Furnaces19

Feed composition, mol% COS, CS 2


Feed H2S
Claus Variation Suggested formation, %
Concentration, Mol% Hydrocarbon
Water CO2 H2S of sulfur in
(as C3H8) feeda,b
55 100 Straight-through
0 6 4 90 0.5
30 55 Straight-through or straight-through with
0 6 14 80 1.5
acid gas and/or air preheat
0 6 24 70 2.5
15 30 Split-flow or straight-through with feed 0 6 34 60 3.5
and/or air preheat 0 6 44 50 4.5
10 15 Split-flow with acid gas and/or air preheat 0 6 54 40 5.5
0 6 64 30 6.5
5 10 Split-flow with fuel added or with acid gas
0 6 74 20 7.5
and air preheat, or direct oxidation or
2 6 4 88 2.0
sulfur recycle
2 6 14 78 3.0
<5 Sulfur recycle or variations of direct 2 6 24 68 4.5
oxidation or other sulfur recovery 2 6 34 58 6.0
processes. 2 6 44 48 7.0
2 6 54 38 9.0
2 6 64 28 11.0
in the cracking of heavy hydrocarbons to form carbon or carbo-
2 6 74 18 14.0
naceous deposits and the formation of ammonium salts, result-
4 6 4 86 3.5
ing in deactivation of the catalyst and/or plugging of equipment.
4 6 14 76 5.0
A method of avoiding these problems while still improving
4 6 24 66 6.0
flame stability is to preheat the combustion air and/or acid gas,
and to operate straight-through. An example of such an ar- 4 6 34 56 8.0
rangement is shown in Fig.22-8. Steam-, hot oil-, or hot gas- 4 6 44 46 10.0
heated exchangers and direct fired heaters have been used. The 4 6 54 36 12.0
air and acid gas are usually heated to about 230260C. Some- 4 6 64 26 14.0
times split flow is combined with acid-gas preheat. Other methods 4 6 74 16 18.0
of improving flame stability are to use a high intensity burner, a
Maximum. Actual production varies with operating temperature
add fuel gas to the feed gas, or to use oxygen or oxygen-enriched and pressure, residence time, burner mixing and burner
air for combustion. efficiency.
b
Units feeding <30% H2S may operate other than straight
Acid gas enrichment, using an absorber / regenerator pair is
through, causing reduced COS and CS2 production proportional
an alternative that concentrates the H2S fed to the thermal re-
to amount fed to main burner.
actor to stabilize the flame, increase thermal oxidation temper-
ature and reduce the size of the Claus equipment. The major
drawbacks are the increases in capital costs (may be balanced
Operation with significant amounts of ammonia present sim-
by reductions in the thermal reactor and Claus reaction train),
ilar issues. If the ammonia is concentrated in one stream with
operational complexity and the operational requirement for re-
less than 100 ppmw ammonia in the clean stream, a two stage
generation energy. A challenge with absorption systems is the
thermal reactor design can be used where the ammonia stream
absorption H2S selectivity, which allows mercaptans, COS and
is fed only to the first stage with some of the clean stream, and
CS2 to pass through the absorber. These can be routed to the
the balance of the clean stream is feed to the second stage of the
incinerator if the sulfur recovery target allows or can be routed
thermal reactor. The first stage will require a minimum of
to a COS hydrolysis reactor or upstream of the hydrogenation
1230C oxidation temperature to destroy the ammonia.
reactor, possibly through an in-line burner, to convert these sul-
fur species to H2S at some cost in hydrogen. Fig. 22-32 gives the theoretical flame temperature for a
straight-through operation and for a split-flow operation with
Operation with significant amounts of BTEX in the feed is a
two-thirds of the acid gas bypassing the combustion section. For
significant hurdle because destruction of aromatics requires op-
each operation there are isotherms, which represent the tem-
eration of the thermal reactor in excess of 1200C. Air and acid
perature of the acid gas feeding the combustion section. The
gas feed preheat, fuel enrichment of the acid gas stream and
isotherms for temperatures above 40C represent acid-gas pre-
oxygen-enrichment of the air mentioned previously can be used
heat. For the split-flow operation, the part of the acid gas that
to increase the thermal reactor temperature. Acid gas enrich-
bypasses the combustion section is not preheated. This figure
ment, an extra cycle of absorption/regeneration discussed above,
can also be used for combinations of straight through and split
can also be used to increase the acid gas H2S concentration and
flow. In this case, the split flow (i.e., the amount of acid-gas
hence thermal reactor temperature. Activated carbon bed re-
bypass) should be minimized, which will maximize the overall
generative absorption has also been used to remove aromatics
sulfur recovery and minimize the problems associated with
from the acid gas feed. Xylene has roughly 13 times the deacti-
acid-gas bypass that are mentioned in the foregoing paragraph.
vation effect on alumina as that of toluene, which has roughly
For acid-gas temperatures different than the isotherm values,
70 times the deactivation effect of benzene per reference 37.
and for acid-gas bypasses less than two thirds, corresponding
Activated carbon has the strongest affinity for the heavier aro-
flame temperatures can be estimated by linear extrapolation/
matics.
interpolation of the curves.

22-5
Waste Heat Recovery Operation on the cooling medium available. A large temperature difference
between process gases and cooling medium should be avoided,
Most Claus plants cool the process gases leaving the com- however, because of the possible formation of sulfur fog; this is
bustion section by generating steam in a fire-tube waste heat especially important for the final sulfur condenser.
boiler. Steam pressures usually range between 1035 and 4140
kPa (ga). The waste heat boiler outlet temperature is therefore Reheating Operation
normally above the sulfur dewpoint of the process gases; how-
ever, some sulfur may condense, especially during partial loads, The temperature of the process gas at the inlet of the cata-
and provision should be made to drain this sulfur from the pro- lytic converters should be such that the effluent gas tempera-
cess stream (or the piping should be arranged so the sulfur will ture is:
drain through downstream equipment). H
 igher (by 1417C) than the expected outlet sulfur dew-
Other methods of cooling the hot combustion gases include point
the use of glycol-water mixtures, amine solutions, circulating  s low as possible to maximize H2S conversion but high
A
cooling water (no boiling), and oil baths. The utilization of one enough to obtain a satisfactory Claus reaction rate
of these alternate cooling fluids can be especially advantageous
at locations where good quality boiler feed water is not avail-  igh enough for hydrolysis of COS and CS2 (for the first
H
able, or where steam generation is not desired. catalytic converter only)
Some small Claus units use a closed steam system. Steam is Fig.22-9 shows the methods of reheat commonly used.
generated at 140210 kPa (ga), condensed with air in an elevat-
ed condenser, and the steam condensate returned by gravity to T
 he hot gas bypass method takes a slip-stream of hot pro-
the boiler as feed water. cess gases from the waste heat recovery unit, usually at
480-650C, and mixes this stream with the sulfur con-
Sulfur Condenser Operation denser outlet gases upstream of the catalytic converter.

Sulfur is condensed ahead of the first catalytic converter (ex-  he direct fired method of reheating uses inline burners
T
cept in the case of split-flow operation) and following each cata- burning either fuel gas or acid gas, with the combustion
lytic converter in order to promote the Claus reaction. These products being mixed with the sulfur condenser outlet
condensers (other than the one following the last catalytic con- gases.
verter) are typically designed for outlet temperatures of 166 T
 he indirect reheat methods use direct fired heaters or
182C which results in a condensed liquid sulfur of reasonably heat exchangers to heat the sulfur condenser outlet gas-
low viscosity and a metal skin temperature (on the process gas es; high pressure steam, hot oil, and hot process gases
side) above the sulfurous/sulfuric acid dewpoint. The final sulfur have been used. Electrical reheating has also been used.
condenser outlet temperature can be as low as 127C, depending

FIG. 22-8
Sulfur Recovery Process with Acid Gas and Air Preheat

22-6
FIG. 22-9
Alternate Methods of Reheating3

Hot gas bypass reheating is normally the lowest cost alter- ally not possible and COS and CS2 hydrolysis may be more dif-
native, is relatively simple to control, and results in low pres- ficult. However, indirect reheating usually results in the highest
sure drop. Its disadvantage is lower overall sulfur recovery, overall sulfur recovery, and deactivation of the catalyst (because
particularly at reduced throughput. The hot gas bypass method of sulfation, carbon deposits, etc.) is less likely to occur.
is sometimes used for the first two catalytic converters and an
indirect method of reheat used for the third converter.
Catalyst Converter Operation
Direct fired reheating uses an inline burner which usually
The Claus reaction is exothermic at converter temperatures,
burns a portion of the Claus plant feed gas but which some-
and the reaction equilibrium is favored by lower temperatures.
times burns fuel gas. This reheating method can be designed to
However, carbonyl sulfide (COS) and carbon disulfide (CS2) hy-
heat the process gases to any desired temperature level. Pres-
drolyze more completely at higher temperatures as shown by
sure drop is also relatively low. Potential disadvantages of in-
Fig.22-10. The first catalytic converter is therefore frequently
line burners are the possible formation of SO3, if acid gas is
operated at temperatures high enough to promote the hydroly-
burned (sulfates deactivate the catalyst) and of soot, if fuel gas
sis of COS and CS2; the second and third catalytic converters
is burned (soot can plug and also deactivate the catalyst). A
are operated at temperatures only high enough to obtain ac-
well-mixed, high-intensity burner capable of operating substoi-
ceptable reaction rates and to avoid liquid sulfur deposition and
chiometrically without producing soot should be utilized for
associated catalyst deactivation. A three converter Claus unit
burning fuel gas. Burner requirements are less stringent for
will utilize inlet temperatures in the following range: (1)first
burning acid gas; the H2S:SO2 ratio in the inline burner outlet
converter, 232249C; (2)second converter, 199221C; (3)third
gases is usually maintained at about 1:2 to 1:3. Precautions
converter, 188210C.
must be taken, however, to avoid oxygen breakthrough from the
inline burners. Oxygen in as low a concentration as 30ppmv A temperature rise occurs across each catalytic converter
can rapidly sulfate the catalyst. because both the Claus and COS/CS2 hydrolysis reactions are
exothermic. The temperature rise will generally be 44100C
Indirect reheating, which involves a heat exchanger ahead
for the first converter, 1433C for the second converter, and
of each catalytic converter, is the most expensive alternative and
38C for the third converter. Because of heat losses, measured
results in the highest pressure drop. In addition, converter inlet
temperatures for the third converter will often show a small
temperatures are limited by the temperature of the heating me-
temperature drop.
dium. For example, the use of 4140 kPa steam at 254C as the
heat source would limit the converter inlet temperature to a The foregoing is based on using the regular Claus catalyst in
maximum of about 243C. Thus, catalyst rejuvenation is usu- all of the converters. Regular catalyst is made of activated alu-

22-7
FIG. 22-10 Reaction furnaces are designed for a residence time of at
least 0.5 seconds; plant tests indicate this is adequate to reach
Hydrolysis of COS and CS2 with Activated
equilibrium. Feed gases richer in H2S generally require less
Alumina Catalyst in Sulfur Converter
residence time than leaner feeds. The thermal reactor should
COS + H2O = H2S + CO2
be purged with 5 volumes of nitrogen (over a span of 15 min-
CS2 + H2O= 2 H2S + CO2
utes to ensure displacement of the volume) before start-up.
The refractory in the external reaction furnace serves to re-
sist the high flame temperatures and to protect the steel shell.
Refractories capable of withstanding high temperatures nor-
mally have a high alumina content, e.g., 8590% alumina. How-
ever, these refractories have relatively poor insulating proper-
ties and will not provide adequate protection for the steel shell.
Therefore, an insulating refractory layer is normally placed
against the steel shell, and a layer of high alumina refractory
covers the insulating refractory. Occasionally, three different
refractories have been used in reaction furnaces. (See Section8
for additional information regarding refractories.)
Refractory selection and design is important because the
steel shell can be overheated (above 343C) resulting in direct
sulfide (H2S) attack, or can be cooled below the dewpoint of SO2
and SO3, resulting in acid condensation and rapid corrosion.
External insulation or shrouding for personal protection is of-
ten installed to allow metal temperatures above about 204C,
which is generally safely above the acid dewpoint.
Interior refractory checker walls and matrix block are some-
times installed in external-type reaction furnaces to improve
mixing, stabilize the flame and to serve as a heat buffer. This is
of greater importance if ammonia or cyanides or high concen-
trations of hydrocarbons are present in the feed gas. Alterna-
tively, choke rings can be used to promote mixing.

mina (Al2O3). The primary function of activated alumina is to Reaction furnace burner types available are tangential and
increase the rate of the Claus reaction (Equation 22-3) and en- axial burners. Tangential burners tend to be low intensity, re-
sure full equilibrium conversion to sulfur. It also helps hydrolyze quiring significant thermal reactor volume to complete mixing
the carbon sulfides, COS and CS2, to H2S and CO2 in the first of combustion products. Axial burners are often offered as a
converter (Equation 22-7 and Equation 22-8); but it achieves rea- high intensity design maximizing mixing, allow full effective-
sonable hydrolysis only at high temperatures of 300 to 340C ness of the residence time in the thermal reactor and aid flame
(Fig. 22-10), which reduces the equilibrium conversion to sulfur stability.
in the Claus reaction (Fig. 22-2). A catalyst made of activated
titania (i.e., titanium dioxide TiO2) can achieve greater than 90% Waste Heat Recovery Operation
hydrolysis of the carbon sulfides at temperatures of 300340C, For most internal reaction furnace-type waste heat recovery
and reasonable hydrolysis at lower temperatures where Claus units, the acid gas burner is installed inside a single, large,
conversion is enhanced. Up to 50% of the sulfur in the plant tail first-pass firetube (radiant section) and the process gas then
gas can be in the form of carbon sulfides, and therefore titania in flows through one or more additional tube passes (convection
the first converter can be a way to achieve higher sulfur recov- section). The first pass firetube is cooled externally and there-
ery. However, titania is very expensive, and can be 1015 times fore does not require refractory protection; however, pass plates
the cost of activated alumina. Sometimes a combination such as and other uncooled metal surfaces exposed to the process gases
50-50% activated alumina and titania is used. When this is done, at temperatures above about 343C should be protected with
the titania should be placed in the bottom of the bed to protect it refractory. Tube sizes for the convection section passes range
from contamination. from 25150 mm with a tube mass velocity of 1024 kg/(s m2).
To ensure a reasonable tube life, the inlet end of each tube
MECHANICAL CONSIDERATIONS is protected by inserting a ceramic ferrule that extends about
Combustion Operation 75150 mm beyond the inside of, and about 75 mm outside of
the tube sheet. This prevents the hot gases from directly con-
Combustion is carried out in the reaction furnace which may tacting the tube at the critical junction of tube and tubesheet.
be either external (separate from waste heat recovery facility) These ceramic ferrules should also be wrapped with a thin layer
or internal (combined with waste heat recovery facility). At the of insulation (310 mm thick). The inlet tube sheet should be
normal operating temperature of 9801370C, external furnac- protected by a refractory overlay, usually about 75 mm thick.
es require a refractory lining to protect the steel shell, but with
internal furnaces, the steel fire tunnel (i.e. firetube) is sur- A recent development has been the advent of two piece fer-
rounded by the cooling medium, and refractory is not required. rules. These ferrules have hex heads designed to protect the
For small Claus units, an internal furnace is less expensive. For tube sheet as well as the tube inlets. The tube sheet is covered
units larger than about 30 t/d, an external furnace is usually with an insulating board perforated for the tubes and then hex
more economical. head ferrules are inserted. The hex heads are sized to the tube

22-8
pitch to provide hexagonal tiling of the plane, therefore also tubes. Waste heat boilers utilizing flexible, thin tubesheets
protecting the tube sheet. These hex heads allow for thermal have extremely good service histories.
expansion, unlike the monolithic refractory overlay used with
plain ferrules, and hence are less susceptible to thermally medi- Sulfur Condenser Operation
ated cracking.
Sulfur condensers may be single pass or multi-pass units.
Waste heat recovery units are usually designed to meet Both natural circulation- and kettle-type condensers are used;
pressure containment requirements according to SectionI of horizontal units are recommended. Condensers are designed
the ASME Code rather than to TEMA standards. A two-pass with a minimum tube diameter of 25 mm. Normally 12BWG
tube welding procedure is normally used. Conventional practice steel tubes are used, installed with a 1319 mm ligament be-
is to apply the first-pass weld before tube rolling (or after a light tween tubes.
rolling), which allows venting to eliminate gas traps. The first-
For Claus units smaller than about 100 long ton per day, the
pass weld is usually pressure tested to locate all weld pinholes
sulfur condensers are frequently installed in a single horizontal
for repairing prior to subsequent tube rolling and final welding.
shell with internal full cross sectional baffles separating the
After final welding, the completed tube attachment is lightly
condenser services.
rolled. During the final hydrotest, the tube weld surfaces should
be inspected using a dye-penetrant test. Sulfur condensers operate at much lower heat fluxes than
waste heat boilers and usually operate at lower shell side pres-
Tube rupture in the waste heat boiler is an important
sures. Both of these factors significantly reduce the mechanical
relief case if combined with tail gas diverter valves. This
design requirements for tubesheets and tube attachments. Sul-
case can potentially be mitigated by blow through to the sul-
fur condensers are designed to meet either ASME SectionI or
fur pit of the sulfur seal legs if these legs are designed for
SectionVIII Codes. Tubes are typically rolled, seal welded, and
this contingency.
re-rolled.
Tube sizes range between 50 and 150 mm. Tube spacing is
The design mass velocity for the sulfur condenser tubes var-
based on a minimum ligament (distance between outer edge of
ies from 15 to 39 kg/(s m2) with a typical minimum mass veloc-
each tube) dimension of 1925 mm. The design mass velocity in
ity at design conditions of 24 kg/(s m2). The design mass veloc-
these tubes ranges between 5 kg/(s m2) and 39 kg/(s m2). For
ity should be sufficiently high to prevent sulfur fogging from
most installations, the tube mass velocity will be 10 to 24 kg/
occurring during turndown conditions.21 If sulfur fogging does
(s m2). Allowable tube side pressure drop often determines tube
occur, the liquid sulfur will not adequately separate from the
velocity.
process gas in the separator downstream of the condenser. The
Both kettle-type and natural circulation-type waste heat tube velocity is also limited by the allowable tube side pressure
boilers are used as horizontal units to ensure total submergence drop, which is usually about 24 kPa.
of the tubes.
Sulfur condensers are subject to plugging with solid sulfur.
The advantages of the natural circulation-type unit which In the design of the plant piping system, the condensers should
has a separate elevated steam disengaging drum, include: be the low points in the system and should also slope toward the
sulfur drain end. This allows any liquid sulfur present upstream
I mproved steam quality because of surface blowdown ca- of the condenser, as well as that formed in the condenser, to
pability and more sophisticated steam/water separation drain into the liquid-vapor separator chamber and out through
devices. the sulfur drain.
M
 ore water holdup above the hot process tubes which To allow access to the tubes for cleaning and inspection, sul-
provides additional time to react to emergency conditions fur condensers should have inspection ports and manways at
and lessens the chance of tube failure from overheating. both ends. Additional access to the tubes should be provided by
B
 etter steam/water circulation at the critical tube/ using bolted cover (end) plates.
tubesheet junction. Vapor-liquid separator chambers are installed downstream
The advantages of the kettle-type boilers include: of the sulfur condensers to separate the liquid sulfur from the
process gases and to allow the liquid sulfur to drain from the
Lower installed cost system. These separator chambers can be integral parts of the
condenser or separate vessels and may be provided with wire-
Ability to handle a much wider range of load conditions
mesh type mist eliminators or impingement plates to reduce
Both kettle-and natural circulation-type waste heat boilers liquid sulfur entrainment. A superficial gas velocity of 69 m/s
should be considered severe-service applications. Some early is commonly used as a basis for sizing the separator chambers.
boilers were designed to TEMA standards and the resulting
Sulfur condensers are usually designed to generate low
thick tubesheets combined with the high heat flux resulted in
pressure steam of about 140700 kPa (ga) on the shell side. The
failures at the tube-tubesheet juncture.
final sulfur condenser is often used to heat boiler feed water,
The tubesheet design is based upon the thermal, mechanical but care must be taken not to over cool the stream and solidify
stresses at the tube-tubesheet attachment. Tubesheets are usu- sulfur. Sometimes 100kPa (ga) steam is generated, condensed
ally thin (1938 mm) resulting in acceptable temperature pro- and returned in a closed circuit.
files at the tube weld, the ligaments between tubes, and the
portion of tubesheet not cooled by water. The deflection of these Reheating Operation
thin tubesheets during operation reduces the stress transmit-
ted to the tube-tubesheet attachment. Natural circulation-type Hot Gas Bypass MethodPiping and valves are usually
units have tube patterns arranged to accommodate the bending of stainless steel (although sometimes refractory-lined piping is
stress at the patterns outer boundaries, while kettle-type units used) in order to handle the hot corrosive process gas ranging
have stayrods to stiffen the portions of the tubesheet without from 480 to 650C. An additional valve is sometimes installed

22-9
in the process stream downstream of the hot gas bypass extrac- especially in smaller units, are of stainless steel. Vapor process
tion point in order to improve turndown capability. piping must also have proper allowance for thermal expansion.
Either convoluted expansion joints or expansion loops are
Direct (Inline Burner) MethodInline burners are used. Convoluted joints should be constructed of series 300
usually designed to raise the temperature of the process gas at stainless steel, and insulated to prevent either water and/or
least 28C above the normal operating inlet temperature of the sulfur condensation. The expansion joints should be installed in
catalytic converter. This extra heat release capacity is useful vertical pipe runs so, if condensation does occur, the liquid can
during a heat soak or catalyst rejuvenation operation. Usu- drain freely. If liquid sulfur does not drain, it could solidify,
ally, a portion of the acid gas is burned in the inline burner; causing the convolutes to be inoperable. Undrained water re-
however, other fuels, such as natural gas, can be used. The sults in corrosion because of the acids formed.
burner is installed in a refractory lined combustion chamber
and the hot combustion gases are mixed with the process gas to Carbon steel process piping is normally adequate. Because a
reach the reactor inlet temperature. The retention time in the Claus plant operates below 103 kPa (ga) pressure, schedule40
mixing chamber is usually between 0.1 and 0.3 seconds. pipe is normally used for small lines. For 350 mm or larger
lines, standard weight pipe is adequate. For process lines over
Indirect (Heating Exchanger) MethodHeat exchang- 750 mm in diameter, the piping thickness can be the same as
ers used for reheating are normally constructed to the same the catalyst bed vessel walls.
mechanical requirements as sulfur condensers. These exchang-
ers should slope toward the inlet end so any liquid sulfur pres- Valves should be steel and fully jacketed. Smaller valves
ent can drain back into the liquid-vapor separator located usually have integral jackets; large valves may have fabricated
downstream of the upstream sulfur condenser. jackets. Valves in liquid sulfur service should be full-opening
gate or plug type to permit rodding out. Liquid sulfur normally
Catalyst Converter Operation drains by gravity from the condensers into a sulfur collection
pit or storage vessel with a liquid sulfur seal on each drain line
Catalytic converters are usually designed for a flow at oper-
to prevent gases from escaping to atmosphere. Sulfur drain
ating conditions of 2040Sm3/h of process gas per m3 of catalyst
lines often include both horizontal and vertical sections of pip-
bed. Because of pressure drop considerations, this usually re-
ing. Because of potential plugging of these lines, facilities should
sults in a bed depth of 9151525 mm. The catalyst is activated
be installed to clean-out (usually by rodding) these lines to pre-
alumina (Al2O3) or promoted activated alumina which is in-
vent a plugged sulfur drain from causing premature unit shut-
stalled on top of a 75150 mm thick layer of more dense support
down. As shown in Fig.22-11, these rodding-out facilities usu-
material. Catalyst bulk density is about 720850 kg/m3; the
ally include both horizontal and vertical crosses at each change
support medium, which usually has a bulk density of 13601600
in piping direction. The crosses are often equipped with exter-
kg/m3, reduces migration of catalyst and/or catalyst fines from
nal valves. Valves are also often placed in the horizontal sec-
the reactor bed to the sulfur condenser downstream. These cat-
tions of the sulfur drain lines to allow easy cleaning of these
alyst fines can plug the sulfur drain legs and condenser tubes.
segments, either mechanically or with steam, while the unit
The catalyst and support material are installed on top of stain-
continues to operate.
less steel wire screens which are tied to carbon steel grating. A
minimum of 75 mm of the support material may be placed on Each sulfur liquid/vapor separator should have a separate
top of the catalyst bed to serve as a gas flow distributor. drain line and sulfur seal to facilitate detection of plugging.
Each sulfur seal should be equipped with a sight port (oriented
For Claus units smaller than about 100t/d, the catalyst
away from sidewalks, etc.) so the sulfur draining into the stor-
beds are frequently installed in a single horizontal vessel, with
age pit can be observed. When the flow of liquid sulfur stops,
internal partition plates. For larger units, individual catalyst
remedial action can be taken to eliminate the restriction or plug
bed vessels are used. Vertical (stacked) beds are sometimes
so as not to cause additional damage to the plant.
used but this is usually not economical for units smaller than
about 800t/d. Internal refractory lining of these vessels is not Steam-jacketing is the preferred method of heating liquid
necessary unless it is planned to regenerate the catalyst in sulfur lines but ControTrace external formed tube jacketing
place; in this case the grating floor design must also be adequate is an economical alternative to traditional double pipe jack-
for the expected elevated temperatures. If internal refractory is eting. Internal (gut) steam lines are sometimes used, especially
not used, a minimum of 75 mm external insulation is recom- for longer lines. Skin Effect Current Tracing (SECT) which uti-
mended. If a refractory lining is installed, the outside insula- lizes the skin effect phenomenon exhibited when an alternating
tion thickness can be reduced to 2550 mm. Most converters current passes through a steel pipe has also been used to heat
have internal refractory from the bottom to about 150mm long pipelines. For short lines, steam tracing may be satisfac-
above the top of the catalyst bed, which protects against high- tory. Steam is the most common heating medium, but hot oil
temperature upsets. and hot water (under pressure) can also be used. Pressurized
hot water has an advantage over hot oil in the higher heat ca-
Nozzles in the bottom of the catalyst bed vessels should be
pacity of water over organic hot oils. This advantage has been
installed flush with the vessel interior.
utilized in very long molten sulfur lines. Disadvantages of hot
Piping water are the higher vapor pressure and the need for corrosion
inhibition. The liquid sulfur lines should be designed to main-
The piping systems in Claus plants which require special tain the sulfur at a minimum temperature of 138C which cor-
attention are liquid sulfur lines and vapor process lines. Since responds to a steam pressure of at least 345 kPa (ga). High
sulfur freezes at about 118C, liquid sulfur lines must be ade- pressure steam above about 690 kPa (ga) or superheated steam
quately heated and insulated. Process lines are also insulated should normally not be used because of the possibility of heat-
to prevent sulfur from condensing and/or desubliming to the ing the sulfur into the highly viscous region. (Fig. 22-16).
solid form and to keep the metal temperature above the dew-
points of sulfurous/sulfuric acids. Process lines operating at Since the liquid sulfur is used as a seal to prevent process
temperatures above 343C are often lined with refractory or, vapors from being vented to the atmosphere, the net liquid

22-10
column head must be large enough to withstand the maximum to the required temperature. Normally the incinerator is sized
expected operating pressure. For most plants this maximum for at least 0.5 second residence time, and sometimes for as
operating pressure is the same as the air blower maximum dis- much as 1.5 seconds residence time. Generally, the longer the
charge pressure. The density of liquid sulfur is about 1800 kg/ residence time, the lower the incinerator temperature needed to
m3, so for a 69 kPa seal, the required net sulfur seal depth is meet the environmental requirements. This is illustrated by
3.9 m. Minimum safety factors would require at least a 4.0 m Fig.22-12 which shows the relationship between residence time
seal depth, and often an extra 150300 mm is added to the cal- and temperature for a typical installation to meet a maximum
culated depth to allow for upsets, lower sulfur density, etc. H2S requirement of 10ppmv.
The incinerator and stack can sometimes be combined into a
CLAUS UNIT TAIL GAS HANDLING single vessel. The incinerator is the enlarged base, and the
The tail gas from a Claus unit contains N2, CO2, H2O, CO, smaller diameter stack is mounted on top of the incinerator.
H2, unreacted H2S and SO2, COS, CS2, sulfur vapor, and en- The burner is normally mounted horizontally in the side of the
trained liquid sulfur. Because of equilibrium limitations and incinerator. The tail gas is sometimes fed through the burner,
other sulfur losses, overall sulfur recovery efficiency in a Claus but it can also be fed into the incinerator adjacent to the burner.
unit usually does not exceed 9697%. Venting of this tail gas Both the incinerator and stack are refractory lined to pro-
stream without further processing is seldom permitted; the tect the steel from the high temperatures. This refractory is not
minimum requirement is normally incineration, the principal as elaborate as that used for the reaction furnace at the front of
purposes of which are to reduce H2S concentrations to a low the Claus unit, because of lower operating temperatures. The
level (which value will depend on the local regulations) and to incinerator is normally designed for a maximum operating tem-
provide the thermal lift for dispersion of SO2 upon release to perature of 1095C. Refractories rated as low as 1205C have
atmosphere through a stack. Depending upon the size of the been used in incinerator-stack installations; one layer of refrac-
Claus unit, the H2S content of the feed gas, and the geographi- tory is generally sufficient. The refractory is usually an insulat-
cal location, a tail gas cleanup process may be required in order ing castable rated for service conditions of 1205C or above, ex-
to reduce emissions to the atmosphere. cept where flame impingement is anticipated. A high alumina
castable (above 60% alumina) is used in the area of flame im-
Incineration pingement.
Incineration of the H2S (as well as the other forms of sulfur) For vertical incinerators installed at the base of the stack,
in the Claus plant tail gas to SO2 can be done thermally or cata- protection for the incinerator steel floor is important. The best
lytically. Thermal oxidation normally is carried out at tempera- method to protect the floor is to allow for ambient (cooling) air
tures between 480C and 815C in the presence of excess oxy- circulation below the floor even though the floor is refractory
gen. Most thermal incinerators are natural draft operating at lined. If there is no cooling below the floor, or if the space is too
sub-atmospheric pressure with air flow controlled with damp- restricted (too close to grade), the floor refractory usually will
eners; the excess oxygen level varies between 20% and 100%. A not provide adequate protection.
typical concentration of oxygen in the stack effluent is 2.0%.
Although the Claus unit tail gas contains some combustibles The steel components (floor, walls, stack shell) should be
for example, H2S, COS, CO, CS2, H2, and elemental sulfur (in kept below 343371C and above 149C to remain above the
the case of split-flow plants, some hydrocarbons) these acid gas-dewpoint. This requires careful design of both the in-
combustibles are at too low a concentration to support combus- side refractory lining and outside insulation. Normally the re-
tion because they generally amount to less than 3% of the total fractory thickness to protect the incinerator shell (either verti-
tail gas stream. The entire tail gas stream must therefore be cal or horizontal type) will be between 50 and 100 mm, with an
incinerated at a high enough temperature for oxidation of sul- average of about 75 mm. The incinerator floor on the vertical
fur and sulfur compounds to SO2.
Incinerator fuel consumption can be reduced significantly
FIG. 22-11
by utilizing catalytic incineration. This involves heating the tail
gas stream to about 316427C with fuel gas and then passing Typical Relationship of Sulfur Seal and Drain
the heated gas along with a controlled amount of air through a
catalyst bed. Catalytic incinerators are normally forced draft,
operating at a positive pressure in order to maintain closer con-
trol of excess air. Catalytic incineration is a proprietary process
which should be considered where fuel costs for conventional
(thermal) incineration are high.
Another method of improving overall fuel economy involves
recovering heat from the incinerator outlet gases. Saturated
steam at pressures ranging between 345 and 4140 kPa (ga)
has been produced, and saturated steam has been superheated,
using waste heat from the incinerator outlet gases. The effect of
lower emission temperature upon dispersion of the outlet
stream, and therefore upon the required stack height, must be
considered in evaluating this alternative. Incinerators with
waste heat recovery are normally forced draft operating at a
positive pressure.
Fuel required for thermal incineration is determined by the
amount of heat needed to heat the Claus tail gas, air, and fuel

22-11
FIG. 22-12
Typical Relationship Between Incinerator Residence Time and Required Temperature

style units normally has refractory thicknesses ranging be- tem be monitored on a periodic basis. In some areas, stack emis-
tween 100 and 150 mm. sions must be monitored and recorded continuously.
The incinerator and stack should also be insulated on the Periodically monitored stacks should be equipped with plat-
outside to prevent low shell temperatures. This insulation can forms, sample nozzles, and utilities located at an appropriate
be in the form of an air gap (usually 75100 mm) with either elevation. These design details are specified in current state or
stainless steel or aluminum sheathing, or can be a thin (25 mm Environmental Protection Agency regulations. This equipment
thick) layer of blanket type insulation covered with either an supports, typically by an outside vendor, a periodic measure-
aluminum or a stainless steel overlay. Care should be taken not ment of the stack flow rate and stack gas composition, which
to over-insulate because overheating of the steel shell can then can be used to determine a reasonably accurate emission rate.
result. Atmospheric emissions usually are expressed in total kg/h of
sulfur dioxide, or expressed as SO2 concentration in ppmv re-
Another method of handling potential corrosion of the out- ported on a water and oxygen free basis. The detailed stack
side shell of the stack is to make the most critical section of the sampling procedures are covered in EPA or state and/or local
stack (say the top 4.6 m) of unlined and uninsulated stainless regulations and procedures.
steel.
Where continuous monitoring is required, stack gas analyz-
Stacks can be designed as free-standing, guyed, or derrick- ers (which measure the amount of SO2 in the stack gas) are in-
supported structures. Selection of the type of stack support is stalled on the stack. These instruments are often coupled with
dictated by the required stack height diameter and by windload a flow measuring instrument so there is a continuous record of
and/or seismic criteria for the particular installation site. A both the flow and SO2 content of the stack gas. This allows the
guyed stack is often the most economical design; however, this total daily emission level to be determined.
requires plot space for guy anchors and cables. A free standing
steel stack is a common design for heights not exceeding 76 m. Tail Gas Clean-up Processes
Stacks taller than about 107 m are usually derrick-supported
steel stacks or are free-standing, reinforced concrete stacks. Fig.22-13 is a summary of some of the available Claus tail gas
Typical design stack velocities are between 12m/s and 30m/s cleanup (TGCU) processes, not all of which are proven commer-
with allowable pressure drop generally determining the design cially. Many of these processes fit roughly into four categories:
stack velocity.
P
 rocesses based on converting all the sulfur in the Claus
Most governmental air control bodies (federal, state, and/or unit tail gas to H2S, then recovering sulfur from this H2S.
local) require that the emissions from the incinerator-stack sys-

22-12
P
 rocesses that directly oxidize the tail-gas H2S to sul-
FIG. 22-13
hur.
Claus Tail Gas Clean Up Processes
P
 rocesses based primarily on the continuation of the
Claus reaction to produce additional sulfur under more
favorable equilibrium conditions than normally found in Claus Tail Gas Cleanup Processes
the Claus units, either through operation at tempera-
tures below the sulfur dewpoint or in the liquid phase at Reduce to H2S, Absorb and Recycle to Claus
a temperature above the melting point of sulfur. SCOT (Shell Global Solutions)
ARCO (BP/Black & Veatch)
Processes based on liquid redox chemistry. Hydrogenation/MDEA (Worley Parsons/UPO/Dow)
 rocesses based on converting all the sulfur components
P Hydrogenation/Flexsorb (ExxonMobil)
in the tail gas to SO2 and recovering the SO2 for further HCR (Siirtec Nigi)
processing. D
 irect Oxidation to Sulfur
Superclaus (Jacobs Comprimo)
Final selection of a tail gas treating process should consider
the applicable pollution regulations, initial investment, long C
 laus Reaction Continuation on Solid Bed
term (continuing) operating costs, and the operating advantag- (sub-dewpoint)
es and disadvantages of each process. Since many of these tail CBA (BP/Black & Veatch)
gas treating processes are proprietary, the process developer or Clinsulf Sub-dewpoint (Linde AG)
a contractor authorized to design and install these systems MCRC (Jacobs Comprimo)
should be consulted for more definitive information. Sulfreen (Lurgi/Prosernat)
Sultimate (Prosernat)
H2S Recovery Processes
C laus Reaction Continuation in Liquid Phase Catalyst
In these processes, essentially all forms of sulfur in the
(sub-dewpoint)
Claus tail gas are converted to H2S by hydrogenation and hyroly-
Clauspol (Prosernat)
sis. The Beavon-Stretford process then recovers elemental sul-
fur directly from the H2S in this tail gas stream in a Stretford Oxidize to SO2, Absorb and Recycle to Claus
unit. The SCOT, ARCO, Hydrogenation MDEA, Hydrogenation Cansolv (Shell Global Solutions)
FLEXSORB, and HCR processes remove the H2S using an L
 iquid Redox
amine solution that is selective for H2S over CO2. The H2S and LO-CAT (Merichem)
any coabsorbed CO2 from the reenerated solution are recycled to Sulfint (Prosernat)
the front end of the Claus unit. Sulferox (Shell/Dow)
BSR-Stretford can reduce the H2S content in the absorber CrystaSulf (Crystatech)
off gas to 10 ppmv. Generally the amine-based processes (i.e., Paques (Shell/NATCO)
SCOT et al.), using generic amines such as MDEA without ad- R
 educe to H2S and React/Oxidize to Sulfur
ditives, are limited to about 100150 ppmv. However, using pro- Hydrogenation/Selectox (Worley/Parsons)
prietary amines (such as Ineos GAS/SPEC TG-10, Exxons FLEX-
SORB SE, or Dows UCARSOL HS 102), these processes can also
achieve 10 ppmv H2S. All of these processes result in overall sul- stream is usually monitored for drops in pH, indicating poor
fur recovery in excess of 99.9%. BSR-MDEA was developed by operation of the upstream hydrogenation reactor slipping SO2.
Parsons and Unocal (Unocals version sold to UOP) SCOT was
H2S is then selectively absorbed using MDEA or a hindered
developed by Shell in the 70s and first demonstrated in 1973.
amine (FLEXSORB SETM for example) for recycle to the ther-
Currently the SCOT process has more than 1000 licensees.
mal oxidizer. CO2 is slipped to prevent recycling this component
A recent innovation has been the use of a low temperature and thereby limiting the Claus throughput.
hydrogenation catalyst, enabling the hydrogenation reactor to
Finally the treated vent gas is either incinerated or vented
be preheated by high pressure steam rather than using an in-
if local environmental regulations allow.
line burner with its attendant soot mediated catalyst deactiva-
tion. This improves the heat integration within the Claus unit Direct Oxidation Processes
and hydrogenation catalyst life.
MODOP (Mobil Oil Direct Oxidation Processes)27 and SU-
The SCOT (illustrated in Fig. 22-14) and similar processes PERCLAUS 99 and 99.528 are Claus TGCU processes that in-
hydrogenate sulfur species, selectively absorb the resultant H2S clude air oxidation of tail gas H2S to sulfur using special cata-
and combust the residual gas. The absorbed H2S is usually lysts. In MODOP, all forms of sulfur in the Claus tail gas are
routed to the thermal reactor. converted to H2S in a sulfur-reduction (i.e., hydrogenation/hy-
The tailgas is preheated, and if necessary hydrogen added drolysis) unit. Cooling of the reduction-unit effluent includes
before being sent to the TGTU hydrogenation reactor. Low tem- direct contact with recirculating water which reduces the water
perature hydrogenation catalysts have been developed that re- vapor in the effluent to about 5-9%. The effluent combines with
quire preheating with only high pressure steam (generated in air, and enters a MODOP reactor where the H2S is oxidized to
the thermal reactor waste heat boiler and incinerator waste sulfur with the aid of titanium-dioxide catalyst. The prior re-
heat boiler) at around 4100 kPa(ga) (41 barg). This is the con- moval of water vapor in the reduction unit increases the conver-
figuration shown in Fig. 22-14. sion to sulfur. MODOP can achieve 99.5% overall recovery by
using three Claus stages followed by sulfur reduction and one
The hydrogenated stream is then cooled by quenching with MODOP stage, or by using two Claus stages followed by sulfur
water in a quench tower. Ammonium hydroxide or caustic is reduction and two MODOP stages.
added to neutralize absorbed acids. The quench recirculation

22-13
In the SUPERCLAUS process Claus tail gas is reheated and  eparation and recovery of solid sulfur. Depending on the
S
mixed with Claus-blower air, and is processed in a SUPER- regeneration process, this may precede or succeed the
CLAUS reactor employing a proprietary catalyst achieving up next step.
to 99% recovery depending upon the quality of the acid gas and
whether there are two or three Claus converters. Addition of a  egeneration of the spent redox reagent (i.e. Fe++L) by
R
sulfur-reduction unit, upstream of the SUPERCLAUS reactor reacting it with oxygen dissolved in the solution:
can result in an overall sulfur recovery of 99.5%. 1
/2O2 + 2H+ + 2Fe++L H2O + 2Fe+++L
Continuation Processes The iron is said to be oxidized.
The dry-bed subdewpoint processes include CBA (Cold Bed Thus the reagent is reduced as it converts H2S to sulfur and
Adsorption) of the United States, Clinsulf of Germany, MCRC is oxidized as it is regenerated with oxygen/air, and hence the
(Maximum Claus Recovery Conversion) of Canada, and Sulfreen term redox.
of France. Generally, the licensors of these processes report sul-
Redox processes can remove and convert to sulfur up to
fur recoveries of 9999.5%. The processes have not been widely
99.9% of the H2S in sour natural gas and acid gas. Their turn-
used in the U.S. because the attainable sulfur recovery level will
down capabilities are very good, and they can be designed for
seldom meet local air quality requirements. Incineration of the
large variations in H2S concentrations. However, the sulfur
residue gas is still required and the stack gases from tail gas
color is a brown/tan yellow rather than the bright yellow pro-
treaters of this type generally contain 12002000ppmv SO2.
duced in Claus plants. The redox solutions are corrosive, and
The Prosernat process Clauspol continues the Claus reaction much of the equipment must be alloy or coated. Also, chemical
also at sub-dewpoint, but in the presence of a catalyst containing consumption can be high, and disposal of spent chemicals can
liquid solvent, which is fed counter-currently with the incoming be a problem. The solution must usually be analyzed daily with
Claus tail gas in a packed tower. The process operates above the addition of chemicals.
melting point of sulfur so the product sulfur is recovered as a
Nevertheless, redox can be considered for various combina-
liquid. Any liquid and vapor sulfur present in the Claus tail gas
tions of the following:
is also recovered. Prosernat reports sulfur recoveries to 99.8%.
N atural gas or acid gas containing less than 20 t/d of sul-
A typical subdewpoint sulfur plant will resemble a conven-
fur.
tional Claus plant in the process flow through the waste heat
boiler, the first catalytic converter, the first condenser, and the Sour natural gas for which CO2 does not have to be re-
first reheat unit. At this point in the process flow, the subdew- moved.
point plant differs significantly from the conventional Claus Acid gas with very low concentrations of H2S.
plant and the different subdewpoint processes (CBA, Clinsulf,
MCRC, Sulfreen, and Sultimate) differ in the downstream pro- Established redox processes include the following:
cess sequencing. Generally one converter in the subdewpoint  tretford licensed by British Gas, uses a vanadiam redox
S
plants is operating below the dewpoint temperature of sulfur. reagent.
Other converters may be operating in a cooling or in a regen-
eration mode. Bed switching is a common feature of these LO-CAT licensed by Merichem, SulFerox licensed by
plants so the subdewpoint bed is regenerated periodically. The Shell/Dow, and Sulfint licensed by Prosernat. All employ
subdewpoint catalytic converter temperature means a signifi- iron redox reagents.
cantly higher equilibrium constant for the Claus reaction, thus  rystaSulf licensed by Crystatech uses a proprietary metal-
C
resulting in less unreacted H2S and SO2 in the tail gas. Like the lic redox agent
Prosernat process, close control of the H2S:SO2 ratio is essential
for effective subdewpoint operation; and any COS and CS2 pres- P
 aques licensed by Shell/NATCO uses a caustic solution
ent in process gas pass through to the plant tail gas incinera- (uses no iron) regenerated by thiobacteria.
tor. See Section 21 Hydrocarbon Treating for a more detailed
Although the principles of the dry-bed subdewpoint process- discussion of these processes broken into subsections titled
es are similar, each process claims to have unique and desirable Liquid Redox Processes, Liquid Phase Claus Reaction Pro-
features. The licensors of these processes should be consulted cesses, and Biological Processes.
for details.
SO2 Recovery Processes
Liquid Redox
The SO2 recovery processes involve incineration of the Claus
Liquid redox sulfur recovery processes all share the follow- tail gas as the first step. This converts essentially all the forms
ing major operations: of sulfur to SO2.
R
 emoval of the acid gas, H2S, from a gas stream by ab-  ANSOLV uses an SO2 selective amine solution that can
C
sorption into an alkaline solution to form the ions S and recycle SO2 from tail gas to the Claus reactor from after
2H+; oxidation of the tail gas.
 onversion (i.e. oxidation) of the S to elemental sulfur
C F
 or small Claus units, a solution of NaOH may be used
(S) by the action of a redox reagent (i.e. catalyst) such as to scrub SO2 from the incinerator outlet stream; the re-
iron attached to a legend (also called chelant)(i.e. Fe+++L) ulting sulfite solution after further oxidation to sulfate
which keeps the iron in solution: with air (or another oxidizing agent such as hydrogen
peroxide) can be disposed of underground or at an ap-
S + 2H+ + 2Fe+++L S + 2H+ + 2Fe++L
roved disposal facility.
The reagent is said to be spent and the iron reduced.

22-14
Acid Gas Enrichment in Claus Plants reactant, oxygen. This reduces the amount of inert nitrogen and
therefore the process gas, and increases the acid-gas processing
Acid gas enrichment refers to enrichment of the hydrogen capacity. It also reduces the tail gas rate and therefore the in-
sulfide feed to a Claus furnace reaction. The objective is to in- cinerator fuel-gas requirements. If the concentration of H2S in
crease the Claus thermal reactor temperature and stabilize the the acid gas is high, however, the design temperatures of an
burner flame. A solvent selective for H2S is contacted with the existing reaction furnace and waste-heat boiler can limit the
feed gas and the enriched regeneration off-gas becomes the degree of oxygen enrichment, and this has to be designed for. As
acid gas feed to the Claus thermal reactor. There are econo- well, any part of the plant that must handle an increased sulfur
mies that can be achieved with acid gas enrichment in combi- rate must be checked for adequacy. Reference 29 presents a
nation with SCOT style tail gas treating units. The acid gas comprehensive checklist for this purpose.
enrichment and the tail gas treatment unit can use a common
solvent and solvent regenerator. Also amine from the tail gas Oxygen enrichment is achieved by injecting oxygen into the
treatment contactor can potentially be used as a semi-lean regular air stream or into a burner of special design. The oxy-
solvent in the acid gas enrichment contactor. gen can be from pressurized-gas storage, an air-separation
plant, a pressure-swing adsorption (PSA) process, or liquid
See Section 21 Hydrocarbon Treating for a more detailed storage with a vaporizer. Following is a list of commercial oxy-
discussion of Acid Gas Enrichment. gen-enrichment processes and their licensors. The unique fea-
ture of each of these processes is the method of limiting the
Oxygen Enrichment in Claus Plants furnace operating temperature. The licensors should be con-
Oxygen enrichment refers to enrichment of the oxygen in a tacted for details.
Claus furnace reaction. The objective is to increase the sulfur C
 OPE (Claus Oxygen-based Process Expansion) by Air
processing capacity of an existing Claus train (or trains), and Products/Goar Allison
thereby avoid having to build an additional train or increase
the thermal reactor temperature of a low H2S concentration OxyClause by Lurgi
acid gas. The concept is to use oxygen-enriched air to a Claus
reaction furnace instead of atmospheric air as the carrier of the  URE/DCP (Double Combustion Process) by Worley Par-
S
sons/BOC

FIG. 22-14
SCOT Style Tail Gas Treating Unit

22-15
FIG. 22-15 of the rings and the interatomic distances are different. Amor-
4, 36
phous sulfur is prepared by rapidly chilling liquid sulfur which
Heat Capacity of Solid Sulfur at Constant Pressure has been heated to near its boiling point. Amorphous sulfur,
which slowly changes to the rhombic crystalline form at ambi-
ent temperatures, is also referred to as rubber sulfur and its
presence is not desired. The approximate density of each solid
sulfur form is as follows:
Rhombic 2066 kg/m3
Monoclinic 1954 kg/m3
Amorphous 1922 kg/m3
The heat capacity of solid sulfur is shown in Fig.22-15.
The melting points of solid sulfur range from 113C for
rhombic sulfur to 120C for amorphous sulfur. Pure crystals of
monoclinic sulfur melt at 115C. When melted, sulfur becomes
a brownish-yellow, transparent liquid (lambda sulfur), whose
molecular structure is also octatomic. As liquid sulfur is heated
to about 160C, the structure of the liquid undergoes an abrupt
change; its color becomes a dark reddish brown and its viscosity
increases significantly. Long chain polymers, ( sulfur), exist in
equilibrium with octatomic sulfur molecules. Fig.22-16 shows
how the viscosity of pure liquid sulfur changes with tempera-
ture and Fig.22-17 shows how dissolved H2S affects the viscos-
ity of liquid sulfur. As the temperature is increased above
160C, the color of liquid sulfur darkens and turns to a brown-
ish-black above 250C and remains dark up to the boiling point
of 444C. Fig.22-18 and Fig.22-19 show how the density and
heat capacity, respectively, of liquid sulfur change with tem-
perature. Fig. 22-20 shows the thermal conductivity of liquid
sulfur.
Several sulfur molecules are present in the vapor phase, but
the principal sulfur species are S2, S6, and S8. Fig.22-21 shows
the distribution of sulfur species as a function of temperature.
In sulfur plant vapors, the distribution of sulfur species is simi-
lar but not identical to that shown in Fig.22-21 because of the
presence of components other than sulfur. The S1 equivalent
vapor pressure and latent heat curves are convenient to use in
process calculations although they may not be rigorous when
components other than sulfur are present. The viscosity of sul-
fur vapors is shown in Fig.22-24; the heat capacity of sulfur
vapors is shown in Fig.22-25.

SULFUR STORAGE AND HANDLING


Sulfur can be stored and handled as a liquid (at about 138C)
Emerging Processes or as a solid (at ambient temperature). A Claus sulfur recovery
plant will usually be provided with a rundown tank or pit (which
The following processes are in the development stage by
may be either of steel or of acid-resistant concrete) sized for 1-5
surveying GPA and Laurence Reid papers. For details, please
days production. If the sulfur is handled as a liquid, it can be
refer to the references given.
pumped from the rundown tank either directly to tank truck or
P
 ROClaus (Parsons) A Claus tail gas treatment pro- railroad tank car or to intermediate liquid sulfur storage. If the
cess employs selective reduction followed by selective oxi- sulfur is handled as a solid, it is pumped to storage block (where
dation to achieve up to 99.5% overall sulfur recovery.30 the sulfur is allowed to cool and solidify) or to sulfur-forming
facilities such as a pastillator, flaker, a prilling tower, etc.
K
 VS-MECS SULFOX Produces sulfuric acid from waste
gases using wet catalytic oxidation.30 Serious environmental and/or safety problems can occur in
the handling of liquid sulfur produced in Claus units. As shown
in Fig.22-26, the total solubility of H2S in liquid sulfur increas-
PROPERTIES OF SULFUR es with temperature because of the formation of hydrogen poly-
Sulfur is a solid at ambient temperatures; it exists in two sulfides (H2Sx). Sulfur is produced in Claus units at tempera-
octatomic crystalline forms (rhombic and monoclinic) and an tures of 138154C but in storage, or during transportation, the
amorphous form. Up to about 96C, rhombic crystals are the temperature of the sulfur may drop as low as 127C. Under
stable form; above this temperature and up to its melting point, these conditions, H2S is emitted and accumulates in the vapor
monoclinic sulfur is the stable variety. Both crystalline forms space above the liquid sulfur.
consist basically of eight-membered rings, but the arrangement

22-16
FIG. 22-16
Viscosity of Liquid Sulfur12, 36

22-17
FIG. 22-17 FIG. 22-18
Effects of Hydrogen Sulfide on the Viscosity Density of Liquid Sulfur26, 36
of Molten Sulfur12, 18

Concentrations of H2S exceeding its lower explosive or flam-


mability limit of 3.5mol % (in air) have been measured in the
pressures at condenser outlets.34 This is particularly true for
vapor space of railroad tank cars. Emission of H2S from liquid
the thermal condenser (i.e., 200300%), and to a lesser extent
sulfur during solid sulfur forming operations can also present
for the first converter condenser. It is believed35 that this is
serious operating and/or environmental problems.
caused by a combination of two factors. One is sulfur condensa-
H2S concentrations in the vapor space of the sulfur pit will tion in the waste-heat boiler at temperatures higher than the
be typically maintained at less than 25% of the lower explosive condenser-outlet temperature, which increases the formation of
limit by an air sweep. This sour sweep gas, motivated by a H2Sx and therefore the amount of dissolved H2S. This is feasible
steam eductor can be routed to the incinerator, or more typi- because temperatures inside the flow-boundary layers of the
cally, to the thermal reactor for a reduction in stack SO2 emis- waste-heat boiler tubes can be below the sulfur dewpoint tem-
sions. perature. The second factor is a combination of chemical equi-
librium, reaction kinetics, and transport phenomena in the con-
The H2S/H2Sx content of Claus sulfur is dependent on the denser tubes, which results in residual H2S and H2Sx higher
partial pressure of H2S in the process stream and the operating than predicted at the condenser outlet. Thus it is not feasible to
temperature. Typical measured concentrations (as H2S) in predict the amount of residual H2S and H2Sx in the sulfur product.
ppmw are as follows:
Degasification facilities handling Claus sulfur are normally
Reference Ref. 17 Ref. 34 designed on the basis of an average value of 250 to 300ppmw
From thermal condenser 500700 280630 total H2S.

From first conv. condenser 180280 90220 Tests using railroad tank cars with liquid sulfur containing
7ppmw, 15ppmw, and 100ppmw of total H2S indicated that
From second conv. condenser 70110 1080 15ppmw H2S is the upper limit for safe handling of liquid sul-
fur and, therefore, degasification facilities should be designed
From tail-gas coalescer 510 NA
for a maximum of 10ppmw H2S.17, 24 Commercial degasification
These H2S concentrations are well above values that would processes are available from BP, Elf Aquitaine, Exxon Mobil,
be predicted from laboratory chemical-equilibrium and solubil- Enersul, Shell, and Goar Allison and Associates.
ity data applied to corresponding temperatures and H2S partial

22-18
FIG. 22-19
Heat Capacity of Liquid Sulfur5, 36

FIG. 22-20
Thermal Conductivity of Liquid Sulfur36

22-19
FIG. 22-21
Distribution of Sulfur Vapor Species39

1.00

S2
S8
0.8
Mole Fraction of Species

0.6

0.4

S6

0.2 S7
S5
S3
S4
0
100 200 300 400 500 600 700 800 900 1,000 1,100 1,200

Temperature, C

CLAUS PLANT STARTUP AND and/or boiling-out are commenced and either the pilot burners
or the main gas burners are lit.
SHUTDOWNPROCEDURES
Heating the catalytic converters and all other equipment to
Initial Startup near normal operating temperatures by burning fuel gas is nec-
For the initial startup, three important procedures must be essary to prevent condensation of liquid sulfur on the catalyst
followed before putting a Claus sulfur recovery plant in service. beds when acid gas is fed to the unit. The pilot burners are lit
These are: first and after about 30minutes, the main burners are used to
gradually raise the temperatures of the refractory and all the
C
 uring of all refractory (in combustion chamber, piping, equipment. Each catalytic converter should be heated until the
inline burners, incinerator, stack, etc.) outlet temperature is about 204C. Usually the Claus plant is
ready for startup when the catalytic converters are hot. Acid
 leaning of the waste heat boiler and other steam-pro-
C gas is then fed to the plant while continuing to burn fuel gas.
ducing equipment When combustion of the acid gas is assured, the fuel gas rate is
 eating of the catalyst beds and all other equipment to
H gradually reduced to zero. The air rate is then adjusted to give
proper operating temperatures optimum sulfur recovery.

Curing of the refractory, which involves carefully controlled Subsequent Startups


heating, is necessary because, if wet refractory is heated too
quickly, the contained water will vaporize too rapidly, damag- Claus plant startups after the plant has been in operation
ing the refractory. The manufacturer of the refractory (or re- are either hot startups or cold startups. A hot startup is when
fractories) should be consulted regarding suitable curing proce- the catalyst bed temperatures have not dropped below about
dures. 204C and other temperatures in the unit have not dropped be-
low about 149C; a cold startup is when the unit temperatures
Cleaning of the waste heat boiler and other steam-produc- have dropped below these values.
ing equipment is necessary to remove oil and grease. The equip-
ment can be boiled out with water plus boil-out chemicals (such A hot startup does not require that the plant be heated with
as sodium hydroxide and sodium carbonate) or it can be cleaned fuel gas. The fuel gas pilots are lit and acid gas is fed to the
chemically. If a chemical cleaning procedure is chosen, any plant. When stable acid gas combustion has been established,
steam produced during the refractory curing can be fed to the the pilots are turned off and the air rate adjusted for optimum
plant steam headers; if a boil-out procedure is followed, any sulfur recovery. Excess air should not be used.
steam produced should be vented to atmosphere. Under either A cold startup requires that the plant be heated with fuel
procedure, the steam-producing equipment should be filled gas as in the initial startup procedure with two exceptions. The
with water to prevent tube damage before refractory curing

22-20
FIG. 22-22
Vapor Pressure of Sulfur9, 20, 36

22-21
FIG. 22-23
Heat of Vaporization of Sulfur9

FIG. 22-24
Viscosity of Sulfur Vapor12, 36

22-22
FIG. 22-25
Heat Capacity of Equilibrium Sulfur Vapors7, 10, 16, 36

refractory need not be cured (unless refractory repairs have the catalyst beds. Fuel gas is then added to the burner and as
been made) nor the steam-producing equipment boiled out. Sec- soon as the fuel gas flame is established, the acid gas is gradu-
ond, excess air should normally not be used during the heating ally shut off. The air rate is then adjusted to provide (as close as
procedure, unless the unit has been completely purged of all possible) the stoichiometric requirement for combustion of the
sulfur and sulfur compounds as part of a planned shutdown. fuel gas. Insufficient air, which can result in carbon formation
and fouling of the unit, should be avoided; excess air is more
Shutdowns acceptable but because sulfur fires within the unit are possible
even with a small amount of excess air, temperatures should be
The procedures to be followed during a planned shutdown of
closely monitored and the combustion products should be ana-
a Claus sulfur recovery unit are an important part of plant op-
lyzed regularly. Control of the combustion temperature (to pre-
erations.
vent damaging the refractory) is obtained by injecting an inert
If the plant is being shutdown for only a few hours (for ex- gas (usually steam, although nitrogen and carbon dioxide can
ample, for reasons unrelated to the sulfur plant operation) the be used). This purging of the plant by combustion of fuel gas
procedure may only involve: should be continued at least until sulfur stops draining from the
unit. If it is planned to enter the unit for maintenance or other
R
 aising the catalyst bed temperatures by 1722C, in or- work, the fuel gas is then shut off, but the flow of air is contin-
der to provide added assurance that sulfur condensation ued until the unit is sufficiently cooled and thoroughly purged
will not occur during the shutdown period of hazardous materials. If entry to the unit is not scheduled,
Shutting off the air and acid gas both air and fuel gas are shut off, and the unit is blocked in.

 locking in (isolating) the plant to prevent the entrance


B Emergency shutdowns can cause serious problems if proper
of air precautions are not taken. If the plant cannot be placed in op-
eration soon after an emergency shutdown, an inert gas should
If a longer shutdown period is planned, the air rate is re- be fed to purge the plant. Otherwise, sulfur in the unit may so-
duced (after the catalyst bed temperatures have been raised) to lidify and damage the plant, or require replacement of the cata-
give an H2S/SO2 ratio at the front end of 2.5/1 to 3/1 and the lyst beds, and manual cleaning of the waste heat boiler and
plant is operated in this manner for several hours to rejuvenate sulfur condenser tubes.

22-23
FIG. 22-26
H2S and H2Sx to Total H2S Solubility (at 1 bar H2S vapor pressure)

22-24
FIG. 22-27
Equilibrium Constant for Claus Reaction

(a) 100

Kp

S2

10
1000 1050 1100 1150 1200 1250 1300
Temperature, C

(b) 1000000

100000

10000
Kp

S6

1000 S8

100

10
200 250 300 350 400
Temperature, C

22-25
FIG. 22-28
Enthalpies of Paraffin Hydrocarbons, Combustion Products and Sulfur Compounds40
(Based on datum of 0.0 kJ/kg-mole @ 0C)

Enthalpies of Paraffin Hydrocarbons, C1-C6 kJ/kg-mole Enthalpies of Combustion Gases, kJ/kg-mole


C C1* C2 C3 nC4 iC4 nC5 nC6 C N2* O2* Air H2* CO* CO2* H2O*
15 519.2 756.3 1052 1414 1379 1720 2042 15 437.6 452.4 436.2 439.5 437.9 548.7 512.5
25 868.8 1275 1778 2388 2331 2905 3450 25 729.5 756 727.2 732.3 730.1 921 855.7
50 1758 2626 3680 4934 4833 6004 7132 50 1460 1521 1455 1464 1461 1873 1719
100 3617 5565 7862 10510 10350 12800 15220 100 2923 3074 2915 2924 2927 3861 3461
150 5614 8826 12540 16730 16550 20400 24260 150 4390 4648 4383 4381 4398 5941 5221
200 7770 12400 17700 23570 23390 28760 34220 200 5863 6237 5861 5838 5878 8100 6994
250 10090 16290 23310 30990 30820 37870 45050 250 7344 7838 7351 7293 7369 10330 8779
300 12590 20460 29340 38940 38820 47650 56690 300 8836 9449 8857 8748 8873 12620 10580
350 15240 24910 35770 47390 47320 58070 69060 350 10340 11070 10380 10200 10390 14970 12390
400 18040 29620 42550 56310 56280 69080 82120 400 11860 12700 11920 11660 11930 17370 14220
450 20990 34560 49670 65650 65680 80630 95800 450 13390 14330 13470 13120 13480 19830 16070
500 24060 39740 57100 75380 75480 92680 110100 500 14940 15970 15050 14570 15050 22330 17950
550 27250 45120 64830 85490 85640 105200 124800 550 16510 17630 16640 16040 16640 24880 19850
600 30560 50710 72830 95940 96160 118100 140100 600 18090 19290 18240 17500 18250 27480 21780
650 33980 56490 81090 106700 107000 131500 155900 650 19690 20960 19870 18980 19870 30110 23750
700 37500 62450 89590 117800 118100 145200 172000 700 21300 22650 21500 20450 21510 32780 25740
800 44820 74840 107200 140800 141200 173600 205500 800 24580 26050 24820 23430 24830 38220 29840
900 52510 87820 125700 164800 165300 203300 240300 900 27910 29500 28190 26450 28210 43780 34090
1000 60530 101300 144800 189600 190200 233900 276300 1000 31290 33000 31600 29510 31630 49440 38470
1100 68850 115200 164500 215100 215800 265500 313400 1100 34710 36540 35050 32620 35100 55180 43000
1200 77470 129600 184700 241300 242100 298000 351400 1200 38170 40140 38540 35780 38600 60990 47650
1300 86350 144200 205400 268100 268900 331200 390300 1300 41660 43780 42050 38990 42130 66860 52420
1400 95470 159200 226500 295400 296200 365100 430100 1400 45180 47470 45590 42250 45690 72790 57300
1500 104800 174400 247900 323100 323900 399700 470600 1500 48730 51190 49160 45560 49270 78760 62280
1600 114400 189900 269700 351100 352000 434900 511900 1600 52310 54950 52740 48920 52870 84770 67360
1700 124100 205500 291700 379500 380500 470800 553900 1700 55900 58750 56350 52320 56490 90810 72520

Enthalpies of Sulfur Compounds kJ/kg-mole


C S2 SO2* SO3* H2S* CS2 COS S3 S4 S5 S6 S7 S8
15 482.4 590.1 756.7 504.6 669.3 609.3 722.8 967.1 1294 1666 1971 2306
25 806.5 990.2 1272 841.5 1122 1022 1210 1623 2168 2792 3302 3864
50 1625 2013 2596 1686 2273 2076 2447 3295 4391 5653 6688 7819
100 3293 4146 5376 3392 4654 4269 4986 6763 8976 11540 13650 15950
150 4997 6377 8303 5129 7123 6557 7595 10360 13720 17580 20820 24290
200 6730 8687 11350 6911 9668 8927 10260 14060 18590 23750 28120 32810
250 8486 11060 14510 8745 12280 11370 12960 17830 23570 30000 35530 41460
300 10260 13480 17770 10640 14940 13870 15690 21660 28660 36310 43020 50240
350 12050 15950 21120 12590 17660 16420 18450 25540 33840 42680 50570 59130
400 13850 18450 24550 14600 20420 19030 21230 29460 39100 49090 58180 68140
450 15670 21000 28060 16670 23210 21680 24030 33410 44430 55530 65820 77260
500 17490 23570 31640 18790 26040 24360 26840 37380 49820 62010 73490 86480
550 19330 26190 35280 20970 28900 27090 29660 41370 55250 68510 81190 95820
600 21170 28830 38990 23190 31780 29840 32500 45390 60720 75040 88910 105300
650 23020 31500 42740 25460 34690 32630 35340 49410 66220 81580 96650 114800
700 24880 34210 46540 27760 37610 35440 38180 53450 71740 88160 104400 124400
800 28630 39700 54270 32480 43520 41140 43890 61570 82810 101400 120000 143800
900 32410 45290 62140 37340 49480 46920 49620 69710 93890 114700 135600 163400
1000 36220 50960 70130 42320 55490 52760 55360 77880 105000 128000 151200 183100
1100 40060 56720 78220 47420 61540 58670 61120 86070 116000 141500 166800 202800
1200 43930 62540 86390 52620 67620 64620 66880 94280 127000 155100 182500 222500
1300 47840 68430 94630 57920 73730 70610 72650 102500 137900 168800 198200 242100
1400 51770 74370 102900 63320 79860 76640 78430 110700 148800 182600 213900 261600
1500 55730 80350 111300 68810 86010 82700 84210 119000 159700 196500 229600 281100
1600 59720 86380 119700 74380 92190 88790 89990 127200 170500 210400 245300 300400
1700 63730 92440 128100 80030 98380 94910 95780 135500 181300 224300 261000 319700

*NIST, all others see Reference 40.

22-26
CLAUS PROCESS CALCULATION Material Balance (Combustion/Reaction Section)

Process calculations for a Claus sulfur recovery unit are Feed Gas Air
complicated by the existence of various species of gaseous sulfur kmols/h kmols/h

(S2, S3, S4, S5, S6, S7, and S8) whose equilibrium concentrations H2S 132.06
in relation to each other are often not precisely known, and by
the number of side reactions involving other feed gas compo- CO2 70.05
nents such as CO2, hydrocarbons, ammonia, etc., which take H2O 13.50 9.94
place simultaneously. These calculations are usually carried SO2
out by computer with equilibrium conditions and compositions. N2 264.36
A data base which is often utilized for these Claus plant calcula- O2 70.31
tions is the JANAF (Joint Army Navy Air Force) tables.8
S2
Reasonably accurate process calculations can be carried out S6
manually, however, if side reactions are ignored. The following S8
example illustrates a simplified method of calculating the sig-
nificant process parameters for a 100t/d (feed) Claus plant. Hydrocarbons (as C1) 2.14

Example 22-1 217.75 344.61
Feed Gas @ 43.3C & 143 kPa (abs) Ambient Conditions Combustion Reaction
Products Products
mol % kmols/hr Dry Bulb kmols/h kmols/h

H2S 60.65 132.06 Temperature 37.8C H2S 88.04 88.04 x
CO2 32.17 70.05 Wet Bulb CO2 72.19 72.19
H2O 6.20 13.50 Temperature 23.9C H2O 71.73 71.73 + x
Hydrocarbons Air Blower Discharge SO2 44.02 44.02 12 x
(as C1) 0.98 2.14 Temperature 82.2C
N2 264.36 264.36
100.00 217.75 S2 3
4 x
Step 1 Combustion/Reaction Section S6
Calculate air required to burn 13 of the H2S in the feed and S8
for total combustion of hydrocarbons Hydrocarbons (as C1)

H2S + 112 O2 H2O + SO2 From Equation 22-2 540.34 540.34 + 14 x
H @ 0C = 517 900 kJ
ssume P through the burner and furnace is 11 kPa. Then P =
A
CH4 + 2O2 CO2 + 2 H2O Eq 22-9 131.6 kPa (abs) = 1.3 atm (abs).
H @ 0C = 802 800 kJ
At equilibrium,
Find oxygen required:
3 1
[H2O]2 [S2] 2
3
H2S SO2 (13) (32) (132.06) = 66.03 kmols/h O2 2

[H2S]2 [SO2] total mols


K
p=
Hydrocarbons (as C1) 2 (2.14) = 4.28 kmols/h O2

[71.73 + x]2 [34 x] 2
3
Total = 70.31 kmols/h O2 [1.3] 1
2
[88.04 x ] [44.02 2 x] [540.34 + 4 x]
=
Assume x = kmols of H2S reacting 2 1 1

2 H2S + SO2 2 H2O + 32 S2 from Equation 22-6 Equilibrium


x, kmols/h Kp Temperature
x 12 x x 3
4 x (assumed) (calculated) (from Fig.22-27)

H @ 0C = +47 060 kJ 61.35 28.14 1164C
As an alternative to reading Fig. 22-27 the following ap-

proximation can be used:
Equilibrium Temperature (C) = 592.5 + 1215 ln (Kp)
374.8 ln (Kp)2 + 50.47 ln (Kp)3
Determine flame temperature by heat balance for each value of
x using the thermodynamic data in Fig.22-28. For example, at
x = 61.35 kmols/h.

22-27
FIG. 22-29 FIG. 22-30
Heat of Dissociation of Sulfur Vapor Species7, 10, 16 Molar Heat of Condensation of S6 and S8

450
430
Heat of Dissociation, MJ/kgmol

430
410

Heat of Condensation, kJ/kg


390 380

370
350 330
330
310 280
290
270
230
250
100 300 500 700 900
Temperature, C 180
S6 100 150 200 250 300 350 400

S8 Temperature, C
S6
S8

As an alternative to interpolating Fig. 22-28 for molar enthal-


pies in kJ/kgmol, the following nequations can be used in the
Please note that the calculations following were rounded for
range of 0C to 400C.
printing but were carried in full precision in actual calculation.
H2S = 20.1 + 32.5 T + 0.00968 T2 Feed Gas

CO2 = 26.7 + 37.7 T + 0.0147 T2 H @ 43.3C


H2O = 4.55 + 34.4 T + 0.00292 T2 kmols/h kJ/kmol kJ/h

CH4 = 29.2 + 32.5 T + 0.0312 T2 H2S 132.06 1445 190 893
CO2 70.05 1633 114 411
O2 = 10.9 + 30.7 T + 0.00279 T2
H2O 13.50 1490 20 121
N2 = 4.45 + 29 T + 0.00164 T2 Hydrocarbons (as C1) 2.14 1495 3 199

SO2 = 37.1 + 40.9 T + 0.0136 T2 217.75 328 623
S2 = 13.4 + 32.7 T + 0.00496 T2 Combustion Air
H @ 82.2C
S6 = 86 + 115 T + 0.0202 T2
kmols/h kJ/kmol kJ/h
S8 = 92.3 + 158 T + 0.0317 T2
O2 70.31 2531 177 989
Slig (as S1) = 66.42 T 0.05758 T2
N2 264.36 2399 634 287
where T = temperature (C). H2O 9.94 2843 28 258

Likewise for the temperature range 900C to 1400C. 344.61 840 534
H2S = 2871 + 40 T + 0.00521 T2 Reaction Products

CO2 = 4241 + 50.3 T + 0.00335 T 2 H @ 1164C


H2O = 111 + 32.2 T + 0.00621 T2 kmols/h kJ/kmol kJ/h

SO2 = 2994 + 50.7 T + 0.00324 T2 H2S 26.69 50 740 1 354 116
CO2 72.19 58 838 4 247 494
N2 = 922 + 30.4 T + 0.00181 T2
H2O 133.09 45 998 6 122 007
S2 = 493 + 35.1 T + 0.00156 T2
SO2 13.35 60 401 805 981
N2 264.36 36 910 9 757 624
S2 46.01 42 471 1 954 264

555.69 24 241 485

22-28
Heat in, kJ/h: Total heat duty
Feed Gas = 328 623 17 133 573 + 1 668 817 + 2 935 558 = 20 706 133 kJ/h
Combustion Air = 840 534 Note: Partial pressure of sulfur vapor
H2S Combustion (42.02 kmols/h) (517 900) = 22 797 958
S2 + S6 + S8
HC Combustion (2.14 kmols/h) (802 800) = 1 717 982 = (Total Pressure)
Total Mols
Claus Reaction (61.36/2 kmols/h) (47 060) = 1 443 623
0.07 + 5.86 + 7.09
= (131.7) = 3.28 kPa
24 241 485 522.69
The flame temperature is approximately 1164C.
From Fig.22-22, the vapor pressure of sulfur at 371C is ap-
Step 2 Waste Heat Boiler Duty proximately 30.4 kPa, so no sulfur is condensed.

Assume that 1723 kPa (ga) steam is generated in the waste


Step 3 1st Sulfur Condenser
heat boiler and therefore that the temperature of the cooled Assume a pressure drop through the condenser of 3.44 kPa,
combustion products is 371C. From Fig.22-21 (ignoring S7), with the process stream further cooled to 177C. From Fig. 22-
the distribution of sulfur vapor species at 371C is approxi- 22, the vapor pressure of sulfur at 177C is 0.111 kPa so the
mately 0.5mol % S2, 45mol % S6, and 54.5mol % S8. The cooled stream is below the sulfur dewpoint. From Fig. 22-21, the distri-
combustion product composition and waste heat boiler heat bution of sulfur species is 14.5mol % S6 and 85.5 mol % S8. If no
balance are therefore as follows: condensation took place, there would be 1.74 kmols/h of S6 and
Reaction Products H @ 1164C 10.26 kmols/h of S8. [Note: (6)(1.73) + (8)(10.20) = (2)(46.01)]

kmols/h kJ/kmol kJ/h Uncondensed sulfur
0.111
128.15 0.111
H2S 26.69
50 740 1 354 116 =
[522.69 (1.73 + 10.20)]
CO2 72.19
58 838 4 247 494
= 0.443 kmols/h
H2O 133.09
45 998 6 122 007
S6: 0.145 (0.443) = 0.0642 kmols/h uncondensed
SO2 13.35
60 401 805 981
1.73 0.0642 = 1.67 kmols/h condensed
N2 264.36
36 910 9 759 624 S8: 0.853 (0.443) = 0.3779 kmols/h uncondensed
S2 46.01
42 471 1 954 264 10.20 0.3779 = 9.82 kmols/h condensed
S6 Condenser Outlet Conditions
S8 H @ 177

555.69 24 241 485 kmols/h kJ/kmol kJ/h

Cooled Reaction Products H @ 371C
H2S 26.69 6076 162 150
kmols/h kJ/kmol kJ/h CO2 72.19 7107 513 035
H2O 133.09 6176 821 943
H2S 26.69
13 410 357 879 SO2 13.34 7628 101 790
CO2 72.19
15 983 1 153 836 N2 264.36 5189 1 371 719
H2O 133.09
13 160 1 751 465 S2 (vapor)
SO2 13.34
17 009 226 961 S6 (vapor) 1.73 20 902 36 160
N2 264.36
10 989 2 905 100 S8 (vapor) 10.20 28 867 294 442
S2 0.07
12 801 833
S6 5.86
45 359 265 695 521.60 3 301 239
S8 7.09
62 889 446 143
H: 7 107 912 3 301 239 = 3 806 673 kJ/h
522.69 7 107 912
Fig.22-30 H:
H: 24 241 485 7 107 912 = 17 133 573 kJ/h
S6 (vapor) Sliq (1.67) (418.2 6 32.04) = 134 227 kJ/h
From Fig.22-29
Fig.22-30 H:
S2 (vapor) S6 (vapor) (5.86) (284 900) = 1 668 817 kJ/h
S8 (vapor) Sliq (9.82) (287.2 8 32.04) = 722 900 kJ/h
From Fig.22-29
Fig.22-29 H:
S2 (vapor) S8 (vapor) (7.09) (413 800) = 2 935 558 kJ/h
S2 (vapor) S6 (vapor) (0.00227) (284 900) = 650 kJ/h

22-29
Fig.22-29 H: Feed Gas @ 246C Outlet Conditions

S2 (vapor) S8 (vapor) (0.014 065) (413 800) = 5820 kJ/h kmols/h kmols/h

Total Duty H2S 26.69 26.69 y
3 806 673 + 134 227 + 722 900 + 650 + 5820 CO2 72.19 72.19
H2O, 133.09 133.09 + y
= 4 670 270 kJ/h
SO2 13.34 13.34 y/2
Step 4 1st Reheater N2 264.36 264.36
One of the principal purposes of reheating is to maintain the S6 0.12
process gas above the sulfur dewpoint throughout the catalyst S8 0.34 0.43 +(316)y
bed. To estimate the dewpoint temperature at the bed outlet,
assume that 20% of the H2S in the feed will be converted to 510.13 510.13 0.3125y
sulfur in the first catalyst bed. Total sulfur (as S1) at the bed
outlet will then be at equilibrium
3 1
[H2O]2 [S8] 8
3
 .0644 (6) + 0.3787 (8) + 0.2 (132.06) = 29.83kmols/h vapor
0 8

[H2S]2 [SO2] total mols


as S1 assuming a pressure drop for the reheater and catalyst K
p=

bed of 6.89 kPa,
[133.09 + y]2 [0.43 + 316 y] 8
3
[1.2] 58
[26.69 y]2 [13.34 y/2] [510.13 0.3125y]
Sulfur vapor pressure (as S1) then is: =

29.84
(121.3) = 7.06 kPa (abs)
512.4 converging moles converted to balance enthalpy in and out:
From Fig.22-22, the vapor pressure of sulfur at 229.4C is
y, mols/h Kp Equilibrium Temperature
about 7.1 kPa. The preheater outlet temperature is therefore
(assumed) (calculated) (from Fig.22-27)
set 16.7C higher or 246C.
H @ 246C H @ 177C 17.47 4 134 305C
As an alternative to reading Fig. 22-27 the following ap-
kmols/h kJ/kmol kJ/h kJ/h proximation can be used:

H2S 26.69 8 601 229 837 162 150 Equilibrium Temperatuire (C) = 637.0 54.75 ln (Kp) +
2.069 ln (Kp)2 0.03324 ln (Kp)3
CO2 72.19 10 137 731 796 513 035
H2O 133.09 8 635 1 149 194 821 943 For the assumed value of y, calculate the total outlet stream
the (using the data in Fig.22-28 or the approximations provid-
SO2 13.34 10 847 144 744 101 790 ed earlier) and the overall converter heat balance. For example,
N2 264.36 7 238 1 913 357 1 371 719 for y = 17.47 kmols/h
S6 0.12 29 426 3 531 2 508 H @ 305C
S8 0.34 40 694 13 836 9 815 Outlet Stream
kmols/h kJ/kmol kJ/h
510.13 4 185 996 2 982 960
H2S 9.22 10 847 99 987
Reheater Heat Duty = 4 185 996 2 982 960
CO2 72.19 12 856 928 100
= 1 203 036 kJ/h
H2O 150.56 10 772 1 621 905
Note: At 246C, the molecular distribution of sulfur vapor SO2 4.61 13 721 63 237
species (Fig.22-21) is 0.255 S6 and 0.745 S8. N2 264.36 9 013 2 382 676
Step 5 1st Catalytic Converter S6 0.12 36 915 4 430
S8 3.71 51 112 189 397
In the temperature range of 204C371C prevailing in the
catalytic reactors, the Claus reaction equilibrium involving for- 504.76 5 289 733
mation of S2, S6, and S8 should all be used in equilibrium calcu- Heat Balance
lations. However, a good approximation is obtained (usually
within 1% total overall conversion) if only the reaction to form Heat In (from Step4) = 4 185 996 kJ/h
S8 is considered. Claus Reaction (17.47/2) (126 360) = 1 103 732 kJ/h
Assume y mols of H2S react. Total Heat Out = 5 289 733 kJ/h

2 H2S + SO2 2 H2O + 38 S8 NOTE: At 305C, the molecular distribution of sulfur spe-
cies (Fig.22-21) is 0.35 S6 and 0.65 S8 but we were examining
y 1
2 y y 3
16 y only S8 formation here. The heat in plus heat of reaction equals
H @ 0C = 126 360 kJ the heat out, validating the convergence.

22-30
Step 6 2nd Sulfur Condenser Fuel

Repeat procedure of Step 3. H @ 37.8C

kmols/h kJ/kmol kJ/h
Step 7 2nd Reheater
CH4 10.67 1302 13 892
Repeat procedure of Step 4.
CO2
Step 8 2nd Catalyst Converter O2
N2
Repeat procedure of Step 5.
H2O
These calculation steps are continued for the number of
catalytic converter stages being utilized. For this example, a 10.67 13 892
three-stage plant is assumed and the total calculated conver- Air
sion efficiency is about 98%. Total recovery efficiency, after al-
lowing for sulfur vapor losses and about 12% for liquid sulfur H @ 37.8C
entrainment, is about 97% and the tail gas composition is ap-
proximately as follows: kmols/h kJ/kmol kJ/h

H @ 148.9F CH4

kmols/h kJ/kmol kJ/h CO2

H2S 1.76 5 074 8 930 O2 37.12 1154 42 815
CO2 72.19 5 913 426 841 N2 139.55 1103 153 925
H2O 158.01 5 182 818 863 H2O 5.25
1300 6 821
SO2 0.88 6 354 5 592
N2 264.36 4 359 1 152 322 181.91 203 561
S6 (vapor) 0.009 17 485 157
S8 (vapor) 0.010 24 137 241 Products

Sliq (as S1) 0.635 8 613 5 469 H @ 538F

497.85 2 418 416 kmols/h kJ/kmol kJ/h

This is the feed to the incinerator. Assuming 50% excess air H2S
(based upon combustibles) and an outlet temperature of 538C, CO2 82.86 24 511 2 030 895
the fuel gas requirement and stack gas volume can be iterated H2O 184.59 19 348 3 571 453
for energy balance:
SO2 1.65 25 904 42 715
Step1. Calculate oxygen required for combustibles in feed gas N2 403.91 16 081 6 495 365
H2S + 32 O2 H2O + SO2 from Equation 22-2 S (as S1)
H @ 0C = 517 900 kJ O2 12.37 17 313 214 198

S1 + O2 SO2 Eq 22-10 685.38 12 354 625
H @ 0C = 317 800 kJ
Heat Balance
H2S: 1.5 (1.76) = 2.640 kmols/h O2
Heat Out 12 354 625 kJ/h
S1: 1.0 (1.488) = 1.488 kmols/h O2

4.128 kmols/h O2 Heat In
+ 50% = 6.192 kmols/h O2 Feed @ 148.9C 2 418 416 kJ/h
CH4: 2.0 (10.67) = 21.34 kmols/h O2 Air @ 37.8C 203 561 kJ/h
+ 50% = 32.01 kmols/h O2 Fuel @ 37.8C 13 892 kJ/h
H2S Combustion 176 (517 900) = 911 504 kJ/h
Step 2. Calculate net heat release for fuel (assumed to be meth- S1 Combustion 0.635 (317 800) = 201 803 kJ/h
ane) at 50% excess air, using 10.67kmols/h as the base rate. S6 Combustion 0.01 (1 880 900) = 16 928 kJ/h
S8 Combustion 0.01 (2 473 900) = 24 739 kJ/h
CH4 + 2.O2 CO2 + 2 H2O
CH4 Combustion 10.67 (802 800) = 8 563 783 kJ/h

H @ 0C = 802 800 kJ
12 354 625 kJ/h
The heat in plus heat of reaction equals the heat out, vali-
dating the convergence.

22-31
SULFUR PRODUCT SPECIFICATIONS INSTRUMENTATION
A sulfur product meeting the following specifications will Since the quantity of acid gas being handled by the sulfur
normally satisfy the requirements of the major consumers of recovery unit is determined by upstream sweetening facilities,
sulfur such as manufacturers of sulfuric acid, chemicals, fertil- the sulfur plant feed gas rate is normally not controlled. How-
izers, etc.: ever, during startup or in an emergency, part or all of the feed
gas can be directed to flare.
Purity 99.5%99.9% by weight (dry basis)
For the main burner, the volume of feed gas is measured
Acidity (as H2SO4) Less than 0.01% by weight and the amount of air is controlled in ratio with the amount of
Moisture Less than 1.0% by weight acid gas. Both feed-forward25, in which the measured feed gas
flow rate and assumed composition are used, and feed-back, in
Ash Less than 0.05% by weight which the measured ratio of H2S:SO2 in the plant tail gas is
Carbonaceous Matter Less than 0.025% by weight used, can be utilized to adjust the air/feed gas ratio for maxi-
mum sulfur recovery. A combination feed-forward/feed-back
Arsenic, Tellurium, control system, in which the feed gas flow rate is used to control
Selenium Commercially Free* a main air valve and to set an approximate air/feed gas ratio
and the ratio of H2S:SO2 in the tail gas is used to control a trim
Color (see Note below) Bright yellow at ambient temperature air valve, is often utilized.
* Contents of less than 0.25ppmw of arsenic and 2.0ppmw of For inline burners, the process stream temperature is nor-
selenium and tellurium are usually considered as commercial- mally used to adjust the combustion air rate and the amount of
ly free. fuel (either acid gas or fuel gas) is controlled in ratio with the
NOTE: The color of sulfur is an important property because amount of air. Because these burners normally operate with a
it gives an immediate indication of product purity. The sulfur is near substoichiometric air, this control system will result in a
a bright yellow if the impurity content is less than about 0.02% more rapid response to changes in process requirements.
by weight. Small amounts of carbon (soot) change the bright Although conventional orifice meters can be used for acid
yellow color to dull yellow or green; dark sulfur in which the gas and air measurement, the venturi meter is often more suit-
yellow color has a shade of gray or brown usually contains able. Thermocouples are used for most temperature measure-
0.1%0.5% by weight of carbon. For sulfuric acid manufactur- ments and a DCS data historian plots can be useful to opera-
ers, however, sulfur color is usually less important than ash tions by indicating trends. Tail gas analyzers (for H2S and SO2)
and heavy metal contents. are usually of the ultraviolet type although chromatographic
analyzers have been utilized successfully. Except at the front of
the plant and on air, acid gas or fuel gas systems, pressure
gauges are not normally installed. Sample connections should
be as short as possible; sample valves should be plug valves.
Sample connections and valves should be fully steam-jacketed.
FIG. 22-31 Measurement of reaction furnace temperature is sometimes
Plot Showing That a Slight Change in Air to Acid Gas used as an indication of satisfactory air/acid gas control. Both
Ratio at the Head End of the Plant Will Make a thermocouples (ceramic thermocouples are gaining ground
Significant Change in the Tail Gas Ratio, H2S:SO2 because of improvements in service life) and infra-red type
instruments have been utilized; however, the response time for
infra-red instruments can be poor.
Conventional infra-red instruments often can be utilized as
flame monitoring devices for both the main burner and the in-
line burners; combination infra-red/ultraviolet (flicker-type)
instruments have also been used successfully.

OPERATIONAL ASPECTS
Overall Claus plant conversion efficiency is maximized by
maintaining the stoichiometric H2S:SO2 ratio of 2:1 in the pro-
cess gas to the catalytic converters. The most suitable point for
this determination is at the outlet of the last sulfur condenser
because a slight change in the air:acid gas ratio at the front of
the plant will result in a significant change in the H2S:SO2 ratio
in the tail gas and in the theoretical overall sulfur recovery
(Fig.22-31). An H2S:SO2 ratio in the tail gas of between 1:1 and
3:1 can be considered normal although the desired goal should
be a 2:1 ratio.
Operation of a higher terminal H2S:SO2 ratio has benefits for
a SCOT type unit in the reduction of hydrogen consumption in
the SCOT reactor and improved hydrogenation operating mar-
gin, reducing the incidences of SO2 breakthrough from SCOT
reactor to the quench tower which would lead to low quench wa-

22-32
ter pH and accelerated corrosion. The operation at higher H2S to CLAUS PLANT MAINTENANCE
SO2 ratios has to be balanced against the higher load on the tail
gas amine unit and H2S recycle to the thermal reactor. Maintenance and repair of Claus plant equipment requires
special precautions because of the physical properties of sulfur
A simple method of determining the H2S:SO2 ratio is by the and the potential hazards and/or toxicity of many plant process
use of stain tubes. This determination should be done at least streams. Equipment handling liquid sulfur should be drained
once every 8 hours during startup, plant test runs, and when- completely and other equipment should be purged of all hazard-
ever significant changes in plant operating variables are ob- ous materials (see shutdown portion of this section). A satisfac-
served. Other analytical procedures involving wet chemistry, tory welding procedure can involve sandblasting and/or grind-
chromatography, or UV photometry are also suitable for adjust- ing to a bare metal surface, extensive preheating, and the use of
ing plant operations. Type309 stainless steel rod.
Because of the effect of temperature upon the Claus reaction
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22-34