Professional Documents
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Sulfur Recovery
Sulfur is present in natural gas principally as hydrogen sul- Thermal or Combustion Reaction Section
fide (H2S) and, in other fossil fuels, as sulfur-containing com-
pounds which are converted to hydrogen sulfide during H2S + 112 O2 SO2 + H2O Eq 22-2
processing. The H2S, together with some or all of any carbon H @ 25C 518 900 kJ
dioxide (CO2) present, is removed from the natural gas or re-
finery gas by means of one of the gas treating processes de- Combustion and Catalytic Reaction Sections
scribed in Section 21. The resulting H2S-containing acid gas 3
stream is flared, incinerated, or fed to a sulfur recovery unit. 2 H2S + SO2 S + 2 H2O Eq 22-3
This section is concerned with recovery of sulfur by means of x x
the modified Claus and Claus tail gas clean-up processes. Re- H @ 25C 96 100 kJ
dox processes are touched upon. For a discussion and descrip- Overall Reaction
tion of other sulfur recovery processes, see Maddox1.
3
3 H2S + 112 O2 S + 3 H2O Eq 22-4
x x
THE CLAUS PROCESS
H @ 25C 615 000 kJ
The Claus process as used today is a modification of a proc- This is a simplified interpretation of the reactions actually
ess first used in 1883 in which H2S was reacted over a catalyst taking place in a Claus unit. The reaction equilibrium is com-
with air (oxygen) to form elemental sulfur and water. plicated by the existence of various species of gaseous sulfur
H2S + 12 O2 S + H2O Eq 22-1 (S2, S3, S4, S5, S6, S7, and S8) whose equilibrium concentrations
in relation to each other are not precisely known for the entire
Control of this highly exothermic reaction was difficult and range of process conditions. Furthermore, side reactions in-
sulfur recovery efficiencies were low. In order to overcome volving hydrocarbons, H2S, and CO2 present in the acid gas
these process deficiencies, a modification of the Claus process feed can result in the formation of carbonyl sulfide (COS),
was developed and introduced in 1936 in which the overall carbon disulfide (CS2), carbon monoxide (CO), and hydrogen
reaction was separated into (1) a highly exothermic thermal (H2). Gamson and Elkins2 cover the basic theory involved in
or combustion reaction section in which most of the overall the Claus process; however, they ignore the many potential
heat of reaction (from burning one-third of the H2S and essen- side reactions and also the existence of S3, S4, S5, and S7.
tially 100% of any hydrocarbons and other combustibles in the
feed) is released and removed, and (2) a moderately exother- For the usual Claus plant feed gas composition (water-satu-
mic catalytic reaction section in which sulfur dioxide (SO2) rated with 30-80 mol % H2S, 0.5-1.5 mol % hydrocarbons, the
formed in the combustion section reacts with unburned H2S remainder CO2), the modified Claus process arrangement re-
to form elemental sulfur. The principal reactions taking place sults in thermal section (burner) temperatures of about 980 to
(neglecting those of the hydrocarbons and other combustibles) 1370C. The principal molecular species in this temperature
can then be written as follows: range is S2 (Fig. 22-19) and conditions appear favorable for the
FIG. 22-1
Nomenclature
H = heat content or enthalpy, kJ/kg or kJ/kg-mole Acid Gas: feed stream to sulfur recovery plant consisting of
Kp = equilibrium constant H2S, CO2, H2O, and usually less than 2 mol % hydrocar-
For the low pressure, vapor phase Claus reaction bons.
3 Claus Process: a process in which 13 of the H2S in the acid
2 H2S + SO2 2 H2O + Sx gas feed is burned to SO2 which is then reacted with the
x
(PH2O)2 (PSx)3/x remaining H2S to produce sulfur. This is also referred to as
Kp = the modified Claus process.
(PH2S)2 (PSO2) Residence Time: the period of time in which a process
3
1 stream will be contained within a certain volume or piece
2
[Mols H2O] [Mols Sx]
3/x
x
= of equipment, seconds.
[Mols H2S]2 [Mols SO2] Total Mols
Tail Gas Cleanup Unit: a process unit designed to take
tail gas from a Claus sulfur recovery plant and remove
P = partial pressure, kPa additional sulfur with the goal of meeting environmental
= total pressure, kPa sulfur emission standards.
22-1
formation of elemental sulfur by direct oxidation of H2S (Eq To attain an overall sulfur recovery level above about 70%,
22-5) rather than by the Claus reaction (Eq 22-6). the thermal, or combustion, section of the plant is followed by
2 H2S + O2 2 H2O + S2 Eq 22-5 one or more catalytic reaction stages. Sulfur is condensed and
separated from the process gases after the combustion section
H @ 25C = 314 500 kJ and after each catalytic reaction stage in order to improve
equilibrium conversion. Although Fig. 22-2 indicates that the
3 Claus reaction is favored by lower temperatures, the process
2 H2S + SO2 2 H2O + S Eq 22-6
2 2 gases must be reheated prior to being fed to the catalytic re-
action stage in order to maintain acceptable reaction rates and
H @ 25C = +47 500 kJ to ensure that the process gases remain above the sulfur dew-
However, both laboratory and plant measurements indicate point as additional sulfur is formed. Fig. 22-3 is the flow sheet
the more highly exothermic oxidation of H2S to SO2 (Eq 22-2) of an example three-stage Claus sulfur recovery plant; Fig.
predominates and the composition of the equilibrium mixture 22-4 shows the mechanical arrangement of an example small,
therefore is determined by the slightly endothermic Claus re- package-type, two-stage Claus plant.
action (Eq 22-6). Gases leaving the final sulfur condensation and separation
Fig. 22-2 is a representation of theoretical equilibrium con- stage may require further processing. These requirements are
version as a function of temperature for established by local, state, or national regulatory agencies.
These requirements can be affected by the size of the sulfur
An acid gas from a wellhead-type treater, with about
recovery plant, the H2S content of the plant feed gas, and the
3.5 mol % hydrocarbons (Curve 1)
geographical location of the plant.
An acid gas from a refinery treater, with about 7 mol %
hydrocarbons and 1 mol % mercaptans (Curve 2)
Pure H2S (Curve 3) CLAUS PROCESS CONSIDERATIONS
These curves indicate: The Claus sulfur recovery process includes the following
Sulfur recovery would be expected to be lower for a feed process operations:
gas from a refinery than for a wellhead treater because Combustion burn hydrocarbons and other combusti-
of higher hydrocarbon content bles and 1/3 of the H2S in the feed.
The calculated equilibrium conversion for both acid gas Waste Heat Recovery cool combustion products. Be-
feeds follows closely the idealized curve for pure H2S cause most Claus plants produce 1030-3450 kPa (ga)
Conversion of H2S to elemental sulfur is favored in the steam at 185-243C, the temperature of the cooled proc-
reaction furnace by higher operating temperatures of ess gas stream is usually about 315-370C.
980C plus and in the catalytic converters by lower oper- Sulfur Condensing cool outlet streams from waste
ating temperatures of less than 371C. heat recovery unit and from catalytic converters. Low
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
FIG. 22-5
Claus Process Variations
pressure steam at at 345-480 kPa (ga) is often produced Numerous side reactions can also take place during the com-
and the temperature of the cooled gas stream is usually bustion operation, resulting in such products as hydrogen
about 177C or 127-149C for the last condenser. (H2), carbon monoxide (CO), carbonyl sulfide (COS), and carb-
Reheating Reheat process stream, after sulfur conden- on disulfide (CS2). Thermal decomposition of H2S appears to
sation and separation, to a temperature high enough to be the most likely source of hydrogen since the concentration
remain sufficiently above the sulfur dewpoint, and gen- of H2 in the product gas is roughly proportional to the concen-
erally, for the first converter, high enough to promote hy- tration of H2S in the feed gas. Formation of CO, COS, and CS2
drolysis of COS and CS2 to H2S and CO2. is related to the amounts of CO2 and/or hydrocarbons present
COS + H2O CO2 + H2S Eq 22-7 in the feed gas. Plant tests indicate concentrations of H2 and
CS2 + 2 H2O CO2 + 2 H2S Eq 22-8 FIG. 22-6
Catalytic Conversion Promote reaction of H2S and SO2 Claus Plant Configurations
to form elemental sulfur (Eq 22-3)
Process Variations Feed H2S Claus Variation
Concentration, Mol% Suggested
Several variations of the basic Claus process have been de-
veloped to handle a wide range of feed gas compositions. Some 55 - 100 Straight-through
of these are shown in Fig. 22-5. Straight-through operation 30 - 55 Straight-through or straight-
results in the highest overall sulfur recovery efficiency and is through with acid gas and/or air
chosen whenever feasible. preheat
Fig. 22-6 can be used as a guide in Claus process selection. 15 - 30 Split-flow or straight-through
with feed and/or air preheat
Combustion Operation 10 - 15 Split-flow with acid gas and/or air
Most Claus plants operate in the "straight-through" mode. The preheat
combustion is carried out in a reducing atmosphere with only enough 5 - 10 Split-flow with fuel added or with
air (1) to oxidize one-third of the H2S to SO2, (2) to burn hydrocarbons acid gas and air preheat, or direct
and mercaptans, and (3) for many refinery Claus units, to oxidize oxidation or sulfur recycle
ammonia and cyanides. Air is supplied by a blower and the combus- <5 Sulfur recycle or variations of
tion is carried out at 20-100 kPa (ga), depending on the number of direct oxidation or other sulfur
converters and whether a tail gas unit is installed downstream of the recovery processes.
Claus plant.
22-4
CO in the product gas to be approximately at equilibrium at catalytic converter. This can result in the cracking of heavy
reaction furnace temperatures; Fig. 22-7 indicates potential COS hydrocarbons to form carbon or carbonaceous deposits and the
and CS2 formation in the Claus furnace. formation of ammonium salts, resulting in deactivation of the
catalyst and/or plugging of equipment. A method of avoiding
Heavy hydrocarbons, ammonia, and cyanides are difficult to burn
these problems while still improving flame stability is to pre-
completely in a reducing atmosphere. Heavy hydrocarbons may
heat the combustion air and/or acid gas, and to operate
burn partially and form carbon which can cause deactivation of the
"straight-through". An example of such an arrangement is
Claus catalyst and the production of off-color sulfur. Ammonia and
shown in Fig. 22-8. Steam-, hot oil-, or hot gas-heated ex-
cyanides can burn to form nitric oxide (NO) which catalyzes the
changers and direct fired heaters have been used. The air and acid
oxidation of sulfur dioxide (SO2) to sulfur trioxide (SO3); SO3 causes
gas are usually heated to about 230-260C. Other methods of im-
sulfation of the catalyst and can also cause severe corrosion in cooler
proving flame stability are to use a high intensity burner, add fuel
parts of the unit. Unburned ammonia may form ammonium salts
gas to the feed gas, or to use oxygen or oxygen-enriched air for com-
which can plug the catalytic converters, sulfur condensers, liquid
bustion.
sulfur drain legs, etc. Feed streams containing ammonia and cya-
nides are sometimes handled in a special two-combustion stage Waste Heat Recovery Operation
burner or in a separate burner to ensure satisfactory combustion.
Flame stability can be a problem with low H2S content feeds (a Most Claus plants cool the process gases leaving the com-
flame temperature of about 980C appears to be the minimum for bustion section by generating steam in a fire-tube waste heat
stable operation). The split flow, sulfur recycle, or direct oxidation boiler. Steam pressures usually range between 1035 and 3450 kPa
process variations often are utilized to handle these H2S-lean feeds; (ga). The waste heat boiler outlet temperature is therefore nor-
but in these process schemes, any hydrocarbons, ammonia, cya- mally above the sulfur dewpoint of the process gases; however,
nides, etc. in all or part of the feed gas are fed unburned to the first some sulfur may condense, especially during partial loads, and
provision should be made to drain this sulfur from the process
FIG. 22-7 stream (or the piping should be arranged so the sulfur will drain
through downstream equipment).
Potential COS and CS2 Formation in Claus Furnaces19
Other methods of cooling the hot combustion gases include the
Feed composition, mol% COS, CS2 use of glycol-water mixtures, amine solutions, circulating cooling
formation, % of water (no boiling), and oil baths. The utilization of one of these
Hydrocarbon
(as C3H8)
Water CO2 H2 S sulfur in feeda,b alternate cooling fluids can be especially advantageous at loca-
tions where good quality boiler feed water is not available, or
0 6 4 90 0.5 where steam generation is not desired.
0 6 14 80 1.5
0 6 24 70 2.5 Some small Claus units use a closed steam system. Steam is
0 6 34 60 3.5 generated at 140-210 kPa (ga), condensed with air in an elevated
condenser, and the steam condensate returned by gravity to the
0 6 44 50 4.5
boiler as feed water.
0 6 54 40 5.5
0 6 64 30 6.5 Sulfur Condenser Operation
0 6 74 20 7.5
2 6 4 88 2.0 Sulfur is condensed ahead of the first catalytic converter
(except in the case of split-flow operation) and following each
2 6 14 78 3.0
catalytic converter in order to promote the Claus reaction.
2 6 24 68 4.5 These condensers (other than the one following the last cata-
2 6 34 58 6.0 lytic converter) are typically designed for outlet temperatures
2 6 44 48 7.0 of 166-182C which results in a condensed liquid sulfur of rea-
2 6 54 38 9.0 sonably low viscosity and a metal skin temperature (on the
2 6 64 28 11.0 process gas side) above the sulfurous/sulfuric acid dewpoint.
The final sulfur condenser outlet temperature can be as low
2 6 74 18 14.0
as 127C, depending on the cooling medium available. A large
4 6 4 86 3.5 temperature difference between process gases and cooling me-
4 6 14 76 5.0 dium should be avoided, however, because of the possible for-
4 6 24 66 6.0 mation of sulfur fog; this is especially important for the final
4 6 34 56 8.0 sulfur condenser.
4 6 44 46 10.0
4 6 54 36 12.0
Reheating Operation
4 6 64 26 14.0 The temperature of the process gas at the inlet of the cata-
4 6 74 16 18.0 lytic converters should be such that the effluent gas tempera-
a ture is
Maximum. Actual production varies with operating
temperature and pressure, residence time, burner mixing About 14-17C higher than the expected outlet sulfur
and burner efficiency. dewpoint
b
Units feeding <30% H2S may operate other than "straight As low as possible to maximize H2S conversion but high
through," causing reduced COS and CS2 production enough to obtain a satisfactory Claus reaction rate
proportional to amount fed to main burner.
High enough for hydrolysis of COS and CS2 (for the first
catalytic converter only)
22-5
FIG. 22-8
Sulfur Recovery Process with Acid Gas and Air Preheat
Fig. 22-9 shows the methods of reheat commonly used. stoichiometrically without producing soot should be utilized
for burning fuel gas. Burner requirements are less stringent
The hot gas bypass method takes a slip-stream of hot
for burning acid gas; the H2S:SO2 ratio in the inline burner
process gases from the waste heat recovery unit, usually
outlet gases is usually maintained at about 1:2 to 1:3. Precau-
at 480-650C, and mixes this stream with the sulfur con-
tions must be taken, however, to avoid oxygen breakthrough
denser outlet gases upstream of the catalytic converter.
from the inline burners. Oxygen in as low a concentration as
The direct fired method of reheating uses inline burners 30 ppmv can rapidly sulfate the catalyst.
burning either fuel gas or acid gas, with the combustion
products being mixed with the sulfur condenser outlet Indirect reheating, which involves a heat exchanger ahead
gases. of each catalytic converter, is the most expensive alternative
and results in the highest pressure drop. In addition, con-
The indirect reheat methods use direct fired heaters or verter inlet temperatures are limited by the temperature of
heat exchangers to heat the sulfur condenser outlet the heating medium. For example, the use of 4140 kPa steam
gases; high pressure steam, hot oil, and hot process gases at 254C as the heat source would limit the converter inlet
have been used. Electrical reheating has also been used. temperature to a maximum of about 243C. Thus, catalyst re-
Hot gas bypass reheating is normally the lowest cost alter- juvenation is usually not possible and COS and CS2 hydrolysis
native, is relatively simple to control, and results in low pres- may be more difficult. However, indirect reheating usually re-
sure drop. Its disadvantage is lower overall sulfur recovery, sults in the highest overall sulfur recovery, and deactivation
particularly at reduced throughput. The hot gas bypass of the catalyst (because of sulfation, carbon deposits, etc.) is
method is sometimes used for the first two catalytic converters less likely to occur.
and an indirect method of reheat used for the third converter.
Catalyst Converter Operation
Direct fired reheating uses an inline burner which usually
burns a portion of the Claus plant feed gas but which some- The Claus reaction is exothermic at converter temperatures,
times burns fuel gas. This reheating method can be designed and the reaction equilibrium is favored by lower tempera-
to heat the process gases to any desired temperature level. tures. However, carbonyl sulfide (COS) and carbon disulfide
Pressure drop is also relatively low. Potential disadvantages (CS2) hydrolyze more completely at higher temperatures as
of inline burners are the possible formation of SO3, if acid gas shown by Fig. 22-10. The first catalytic converter is therefore
is burned (sulfates deactivate the catalyst) and of soot, if fuel frequently operated at temperatures high enough to promote
gas is burned (soot can plug and also deactivate the catalyst). the hydrolysis of COS and CS2; the second and third catalytic
A well-mixed, high-intensity burner capable of operating sub- converters are operated at temperatures only high enough to
22-6
FIG. 22-9
Alternate Methods of Reheating3
obtain acceptable reaction rates and to avoid liquid sulfur pensive. For units larger than about 30 t/d, an external fur-
deposition. A three converter Claus unit will utilize inlet tem- nace is usually more economical.
peratures in the following range: (1) first converter, 232-
249C; (2) second converter, 199-221C; (3) third converter, Reaction furnaces are designed for a residence time of at
188-210C. least 0.5 seconds; plant tests indicate this is adequate to reach
equilibrium. Feed gases richer in H2S generally require less
A temperature rise occurs across each catalytic converter residence time than leaner feeds.
because both the Claus and COS/CS2 hydrolysis reactions are
exothermic. The temperature rise will generally be 44-100C The refractory in the external reaction furnace serves to re-
for the first converter, 14-33C for the second converter, and sist the high flame temperatures and to protect the steel shell.
3-8C for the third converter. Because of heat losses, measured Refractories capable of withstanding high temperatures nor-
temperatures for the third converter will often show a small mally have a high alumina content, e.g., 85-90% alumina.
temperature drop. However, these refractories have relatively poor insulating
properties and will not provide adequate protection for the
steel shell. Therefore, an insulating refractory layer is nor-
mally placed against the steel shell, and a layer of high alu-
MECHANICAL CONSIDERATIONS mina refractory covers the insulating refractory. Occasionally,
three different refractories have been used in reaction fur-
Combustion Operation naces. (See Section 8 for additional information regarding re-
fractories.)
Combustion is carried out in the reaction furnace which may
be either external (separate from waste heat recovery facility) Refractory selection and design is important because the
or internal (combined with waste heat recovery facility). At the steel shell can be overheated (above 343C) resulting in direct
normal operating temperature of 980-1370C, external fur- sulfide (H2S) attack, or can be cooled below the dewpoint of
naces require a refractory lining to protect the steel shell, but SO2 and SO3, resulting in acid condensation and rapid corro-
with internal furnaces, the steel fire tunnel (i.e. firetube) is sion. External insulation or shrouding for personal protection
surrounded by the cooling medium, and refractory is not re- is often installed to allow metal temperatures above about
quired. For small Claus units, an internal furnace is less ex- 204C, which is generally safely above the acid dewpoint.
22-7
FIG. 22-10 Waste heat recovery units are usually designed to meet pres-
sure containment requirements according to Section I of the
Hydrolysis of COS and CS2 in Sulfur Converter ASME Code rather than to TEMA standards. A two-pass tube
COS + H2O = H2S + CO2 welding procedure is normally used. Conventional practice is
CS2 + 2 H2O = 2 H2S + CO2 to apply the first-pass weld before tube rolling (or after a light
rolling), which allows venting to eliminate gas traps. The first-
pass weld is usually pressure tested to locate all weld pinholes
for repairing prior to subsequent tube rolling and final weld-
ing. After final welding, the completed tube attachment is
lightly rolled. During the final hydrotest, the tube weld sur-
faces should be inspected with a dye-penetrant test.
Tube sizes range between 50 and 150 mm. Tube spacing is
based on a minimum ligament (distance between outer edge
of each tube) dimension of 19-25 mm. The design mass
velocity in these tubes ranges between 5 kg/(s m2) and 39
kg/(s m2). For most installations, the tube mass velocity will
be 10 to 24 kg/(s m2). Allowable tube side pressure drop often
determines tube velocity.
Both kettle-type and natural circulation-type waste heat
boilers are used as horizontal units to ensure total submer-
gence of the tubes.
The advantages of the natural circulation-type unit which
has a separate elevated steam disengaging drum, include:
Improved steam quality because of surface blowdown ca-
pability and more sophisticated steam/water separation
devices.
More water holdup above the hot process tubes which
provides additional time to react to emergency conditions
and lessens the chance of tube failure from overheating.
Better steam/water circulation at the critical tube/tu-
besheet junction.
Interior refractory checker walls are sometimes installed in The advantages of the kettle-type boilers include:
external-type reaction furnaces to improve mixing and to Lower installed cost
serve as a heat buffer. This is of greater importance if ammonia Ability to handle a much wider range of load conditions
or cyanides or high concentrations of hydrocarbons are present Both kettle-and natural circulation-type waste heat boilers
in the feed gas. should be considered as severe-service applications. Some
early boilers were designed to TEMA standards and the re-
Waste Heat Recovery Operation sulting thick tubesheets together with the high heat flux re-
sulted in failures at the tube-tubesheet juncture.
For most internal reaction furnace-type waste heat recovery
units, the acid gas burner is installed inside a single, large, The tubesheet design is based upon the thermal, mechanical
first-pass firetube (radiant section) and the process gas then stresses at the tube-tubesheet attachment. Tubesheets are
flows through one or more additional tube passes (convection usually thin (19-38 mm) resulting in acceptable temperature
section). The first pass firetube is cooled externally and there- profiles at the tube weld, the ligaments between tubes, and
fore does not require refractory protection; however, pass the portion of tubesheet not cooled by water. The deflection of
plates and other uncooled metal surfaces exposed to the proc- these thin tubesheets during operation reduces the stress
ess gases at temperatures above about 343C should be pro- transmitted to the tube-tubesheet attachment. Natural circu-
tected with refractory. Tube sizes for the convection section lation-type units have tube patterns arranged to accommodate
passes range from 25-150 mm with a tube mass velocity of the bending stress at the patterns outer boundaries, while
kettle-type units have stayrods to stiffen the portions of the
10-24 kg/(s m2).
tubesheet without tubes. Waste heat boilers utilizing flexible,
thin tubesheets have extremely good service histories.
External reaction furnace-type waste heat recovery units
are usually single pass exchangers with small tubes (50-75 Sulfur Condenser Operation
mm). The inlet ends of these tubes are exposed to the hot com-
Sulfur condensers may be single pass or multi-pass units.
bustion gases (and possibly to the flame). To ensure a reason-
Both natural circulation- and kettle-type condensers are used;
able tube life, the inlet end of each tube is protected by
horizontal units are recommended. Condensers are designed
inserting a ceramic ferrule that extends about 75-150 mm be-
with a minimum tube diameter of 25 mm. Normally 12 BWG
yond the inside of, and about 75 mm outside of the tube sheet.
steel tubes are used, installed with a 13-19 mm ligament be-
This prevents the hot gases from directly contacting the tube
tween tubes.
at the critical junction of tube and tubesheet. These ceramic
ferrules should also be wrapped with a thin layer of insulation Sulfur condensers operate at much lower heat fluxes than
(3-10 mm thick). The inlet tube sheet should be protected by waste heat boilers and usually operate at lower shell side pres-
a refractory overlay, usually about 75 mm thick. sures. Both of these factors significantly reduce the mechani-
22-8
cal design requirements for tubesheets and tube attachments. sulfur present can drain back into the liquid-vapor separator
Sulfur condensers are designed to meet either ASME Section I located downstream of the upstream sulfur condenser.
or Section VIII Codes. Tubes are typically rolled, seal welded,
and re-rolled. Catalyst Converter Operation
The design mass velocity for the sulfur condenser tubes var- Catalytic converters are usually designed for a flow at operat-
ies from 15 to 39 kg/(s m2) with a typical minimum mass ve- ing conditions of 20-40 Sm3/h of process gas per m3 of catalyst
locity at design conditions of 24 kg/(s m2). The design mass bed. Because of pressure drop considerations, this usually results
velocity should be sufficiently high to prevent sulfur fogging in a bed depth of 915-1525 mm. The catalyst is activated alumina
from occurring during turndown conditions.21 If sulfur fog- (Al2O3) or promoted activated alumina which is installed on top
ging does occur, the liquid sulfur will not adequately separate of a 75-150 mm thick layer of more dense support material. Cata-
from the process gas in the separator downstream of the con- lyst density is about 720-850 kg/m3; the support medium, which
denser. The tube velocity is also limited by the allowable tube usually has a density of 1360-1600 kg/m3, reduces migration of
side pressure drop, which is usually about 2-4 kPa. catalyst and/or catalyst fines from the reactor bed to the sulfur
condenser downstream. These catalyst fines can plug the sulfur
Sulfur condensers are subject to plugging with solid sulfur. drain legs and condenser tubes. The catalyst and support mate-
In the design of the plant piping system, the condensers should rial are installed on top of stainless steel wire screens which are
be the low points in the system and should also slope toward tied to carbon steel grating. A minimum of 75 mm of the support
the outlet end. This allows any liquid sulfur present upstream material may be placed on top of the catalyst bed to serve as a
of the condenser, as well as that formed in the condenser, to gas flow distributor.
drain into the liquid-vapor separator chamber and out
For Claus units smaller than about 100 t/d, the catalyst beds
through the sulfur drain. are frequently installed in a single horizontal vessel, with in-
To allow access to the tubes for cleaning and inspection, sul- ternal partition plates. For larger units, individual catalyst
fur condensers should have inspection ports and manways at bed vessels are used. Vertical (stacked) beds are sometimes
both ends. Additional access to the tubes should be provided used but this is usually not economical for units smaller than
by using bolted cover (end) plates. about 800 t/d. Internal refractory lining of these vessels is not
necessary unless it is planned to regenerate the catalyst in
Vapor-liquid separator chambers are installed downstream place; in this case the grating floor design must also be ade-
of the sulfur condensers to separate the liquid sulfur from the quate for the expected elevated temperatures. If internal re-
process gases and to allow the liquid sulfur to drain from the fractory is not used, a minimum of 75 mm external insulation
system. These separator chambers can be integral parts of the is recommended. If a refractory lining is installed, the outside
condenser or separate vessels and may be provided with wire- insulation thickness can be reduced to 25-50 mm. Most con-
mesh type mist eliminators or impingement plates to reduce verters have internal refractory from the bottom to about
liquid sulfur entrainment. A superficial gas velocity of 6-9 m/s 150 mm above the top of the catalyst bed, which protects
is commonly used as a basis for sizing the separator chambers. against high-temperature upsets.
Sulfur condensers are usually designed to generate low Nozzles in the bottom of the catalyst bed vessels should be
pressure steam of about 140-700 kPa (ga) on the shell side. installed flush with the vessel interior.
The final sulfur condenser is often used to heat boiler feed
water, but care must be taken not to over cool the stream and Piping
solidify sulfur. Sometimes 100 kPa (ga) steam is generated, The piping systems in Claus plants which require special
condensed and returned in a closed circuit. attention are liquid sulfur lines and vapor process lines. Since
sulfur freezes at about 118C, liquid sulfur lines must be ade-
Reheating Operation quately heated and insulated. Process lines are also insulated
to prevent sulfur from condensing and/or desubliming to the
Hot Gas Bypass Method Piping and valves are usu- solid form and to keep the metal temperature above the dew-
ally of stainless steel (although sometimes refractory-lined
points of sulfurous/sulfuric acids. Process lines operating at
piping is used) in order to handle the hot corrosive process gas
temperatures above 343C are often lined with refractory or,
ranging from 480 to 650C. An additional valve is sometimes especially in smaller units, are of stainless steel. Vapor process
installed in the process stream downstream of the hot gas by-
piping must also have proper allowance for thermal expan-
pass extraction point in order to improve turndown capability.
sion. Either convoluted expansion joints or expansion "loops"
Direct (Inline Burner) Method Inline burners are are used. Convoluted joints should be constructed of series 300
usually designed to raise the temperature of the process gas stainless steel, and insulated to prevent either water and/or
at least 28C above the normal operating inlet temperature of sulfur condensation. The expansion joints should be installed
the catalytic converter. This extra heat release capacity is use- in vertical pipe runs so, if condensation does occur, the liquid
ful during a "heat soak" or catalyst rejuvenation operation. can drain freely. If liquid sulfur does not drain, it could solidify,
Usually, 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 Carbon steel process piping is normally adequate. Because
and the hot combustion gases are mixed with the process gas a Claus plant operates below 103 kPa (ga) pressure, sched-
to reach the reactor inlet temperature. The retention time in ule 40 pipe is normally used for small lines. For 350 mm or
the mixing chamber is usually between 0.1 and 0.3 seconds. larger lines, standard weight pipe is adequate. For process
lines over 750 mm in diameter, the piping thickness can be the
Indirect (Heating Exchanger) Method Heat ex- same as the catalyst bed vessel walls.
changers used for reheating are normally constructed to the
same mechanical requirements as sulfur condensers. These Valves should be steel and fully jacketed. Smaller valves
exchangers should slope toward the inlet end so any liquid usually have integral jackets; large valves may have fabri-
22-9
cated jackets. Valves in liquid sulfur service should be full- expected operating pressure. For most plants this maximum
opening gate or plug type to permit rodding out. Liquid sulfur operating pressure is the same as the air blower maximum
normally drains by gravity from the condensers into a sulfur discharge pressure. The density of liquid sulfur is about 1800
collection pit or storage vessel with a liquid sulfur seal on each kg/m3, so for a 69 kPa seal, the required "net" sulfur seal depth
drain line to prevent gases from escaping to atmosphere. Sul- is 3.9 m. Minimum safety factors would require at least a 4.0 m
fur drain lines often include both horizontal and vertical sec- seal depth, and often an extra 150-300 mm is added to the
tions of piping. Because of potential plugging of these lines, calculated depth to allow for upsets, lower sulfur density, etc.
facilities should be installed to clean-out (usually by rodding)
these lines to prevent a plugged sulfur drain from causing pre-
mature unit shutdown. As shown in Fig. 22-11, these "rodding- CLAUS UNIT TAIL GAS HANDLING
out" facilities usually include both horizontal and vertical
crosses at each change in piping direction. The crosses are The tail gas from a Claus unit contains N2, CO2, H2O, CO,
often equipped with external valves. Valves are also often H2, unreacted H2S and SO2, COS, CS2, sulfur vapor, and en-
placed in the horizontal sections of the sulfur drain lines to trained liquid sulfur. Because of equilibrium limitations and
other sulfur losses, overall sulfur recovery efficiency in a Claus
FIG. 22-11 unit usually does not exceed 96-97%. Venting of this tail gas
stream without further processing is seldom permitted; the
Typical Relationship of Sulfur Seal and Drain minimum requirement is normally incineration, the principal
purposes of which are to reduce H2S concentrations to a low
level (which value will depend on the local regulations) and to
provide the thermal lift for dispersion of SO2 upon release to
atmosphere through a stack. Depending upon the size of the
Claus unit, the H2S content of the feed gas, and the geographi-
cal location, a tail gas cleanup process may be required in order
to reduce emissions to the atmosphere.
Incineration
Incineration of the H2S (as well as the other forms of sulfur)
in the Claus plant tail gas to SO2 can be done thermally or
catalytically. Thermal oxidation normally is carried out at
temperatures between 480C and 815C in the presence of ex-
cess oxygen. Most thermal incinerators are natural draft op-
erating at sub-atmospheric pressure with air flow controlled
with dampeners; the excess oxygen level varies between 20%
and 100%. Although the Claus unit tail gas contains some
combustibles for example, H2S, COS, CO, CS2, H2, and ele-
mental sulfur (in the case of "split-flow" plants, some hydro-
carbons) these combustibles are at too low a concentration
to burn since they generally amount to less than 3% of the total
allow easy cleaning of these segments, either mechanically or tail gas stream. The entire tail gas stream must therefore be
with steam, while the unit continues to operate. incinerated at a high enough temperature for oxidation of sul-
fur and sulfur compounds to SO2.
Each sulfur liquid/vapor separator should have a separate
drain line and sulfur seal to facilitate detection of plugging. Incinerator fuel consumption can be reduced significantly
Each sulfur seal should be equipped with a sight port (oriented by utilizing catalytic incineration. This involves heating the
away from sidewalks, etc.) so the sulfur draining into the stor- tail gas stream to about 316-427C with fuel gas and then
age pit can be observed. When the flow of liquid sulfur stops, passing the heated gas along with a controlled amount of air
remedial action can be taken to eliminate the restriction or through a catalyst bed. Catalytic incinerators are normally
plug so as not to cause additional damage to the plant. forced draft, operating at a positive pressure in order to main-
tain closer control of excess air. Catalytic incineration is a pro-
Steam-jacketing is the preferred method of heating liquid prietary process which should be considered where fuel costs
sulfur lines. Internal (gut) steam lines are sometimes used, for conventional (thermal) incineration are high.
especially for longer lines. Skin Effect Current Tracing (SECT)
which utilizes the skin effect phenomenon exhibited when an Another method of improving overall fuel economy involves
alternating current passes through a steel pipe has also been recovering heat from the incinerator outlet gases. Saturated
used to heat long pipelines. For short lines, steam tracing may steam at pressures ranging between 345 and 3100 kPa (ga)
be satisfactory. Steam is the most common heating medium, has been produced, and saturated steam has been super-
but hot oil can also be used. The liquid sulfur lines should be heated, using waste heat from the incinerator outlet gases.
designed to maintain the sulfur at a minimum temperature of The effect of lower emission temperature upon dispersion of
138C which corresponds to a steam pressure of at least 345 the outlet stream, and therefore upon the required stack
kPa (ga). High pressure steam above about 690 kPa (ga) or height, must be considered in evaluating this alternative. In-
superheated steam should normally not be used because of the cinerators with waste heat recovery are normally forced draft
possibility of heating the sulfur into the highly viscous region. operating at a positive pressure.
(Fig. 22-15) Fuel required for thermal incineration is determined by the
Since the liquid sulfur is used as a seal to prevent process amount of heat needed to heat the Claus tail gas, air, and fuel
vapors from being vented to the atmosphere, the "net" liquid to the required temperature. Normally the incinerator is sized
column head must be large enough to withstand the maximum for at least 0.5 second residence time, and sometimes for as
22-10
much as 1.5 seconds residence time. Generally, the longer the lined. If there is no cooling below the floor, or if the space is
residence time, the lower the incinerator temperature needed too restricted (too close to grade), the floor refractory usually
to meet the environmental requirements. This is illustrated will not provide adequate protection.
by Fig. 22-12 which shows the relationship between residence
time and temperature for a typical installation to meet a maxi- The steel components (floor, walls, stack shell) should be
mum H2S requirement of 10 ppmv. kept below 343-371C and above 149C. This requires careful
design of both the inside refractory lining and outside insula-
The incinerator and stack can sometimes be combined into tion. Normally the refractory thickness to protect the incin-
a single vessel. The incinerator is the enlarged base, and the erator shell (either vertical or horizontal type) will be between
smaller diameter stack is mounted on top of the incinerator. 50 and 100 mm, with an average of about 75 mm. The incin-
The burner is normally mounted horizontally in the side of the erator floor on the vertical style units normally has refractory
incinerator. The tail gas is sometimes fed through the burner, thicknesses ranging between 100 and 150 mm.
but it can also be fed into the incinerator adjacent to the burner.
The incinerator and stack should be insulated on the outside
Both the incinerator and stack are refractory lined to protect to prevent low shell temperatures. This insulation can be in
the steel from the high temperatures. This refractory is not as the form of an air gap (usually 75-100 mm) with either a stain-
elaborate as that used for the reaction furnace at the front of less steel or aluminum sheathing, or can be a thin (25 mm
the Claus unit, because of lower operating temperatures. The thick) layer of blanket type insulation covered with either an
incinerator is normally designed for a maximum operating aluminum or a stainless steel overlay. Care should be taken
temperature of 1095C. Refractories rated as low as 1205C not to over-insulate because overheating of the steel shell can
have been used in incinerator-stack installations; one layer of then result.
refractory is generally sufficient. The refractory is usually an
insulating castable rated for service conditions of 1205C or Another method of handling potential corrosion of the out-
above, except where flame impingement is anticipated. A high side shell of the stack is to make the most critical section of
alumina castable (above 60% alumina) is used in the area of the stack (say the top 4.6 m) of unlined and uninsulated stain-
flame impingement. less steel.
For vertical incinerators installed at the base of the stack, Stacks can be designed as free-standing, guyed, or derrick-
protection for the incinerator steel floor is important. The best supported structures. Selection of the type of stack is dictated
method to protect the floor is to allow for ambient (cooling) air by the required stack height diameter and by windload and/or
circulation below the floor even though the floor is refractory seismic criteria for the particular installation site. A guyed
FIG. 22-12
Typical Relationship Between Incinerator Residence Time and Required Temperature
22-11
stack is often the most economical design; however, this re- above the melting point of sulfur so the product sulfur is re-
quires plot space for guy anchors and cables. A free standing covered as a liquid. Any liquid and vapor sulfur present in the
steel stack is a common design for heights not exceeding 76 m. Claus tail gas is also recovered. IFP reports sulfur recoveries
Stacks taller than about 107 m are usually derrick-supported to 99.8%.
steel stacks or are free-standing, reinforced concrete stacks.
Typical design stack velocities are between 12 m/s and 30 m/s A typical subdewpoint sulfur plant will resemble a conven-
with allowable pressure drop generally determining the de- tional Claus plant in the process flow through the waste heat
sign stack velocity. boiler, the first catalytic converter, the first condenser, and the
first reheat unit. At this point in the process flow, the subdew-
Most governmental air control bodies (federal, state, and/or point plant differs significantly from the conventional Claus
local) require that the emissions from the incinerator-stack plant and even different types of subdewpoint plants (CBA,
system be monitored on a periodic basis. In some areas, stack Clinsulf, MCRC, and Sulfreen) differ in the downstream proc-
emissions must be monitored and recorded continuously. The ess sequencing. Generally one converter in the subdewpoint
stack should therefore be equipped with platforms, sample plants is operating below the dewpoint temperature of sulfur.
nozzles, and utilities located at an appropriate elevation. Other converters may be operating in a cooling or in a regen-
These design details are specified in current state or Environ- eration mode. Bed switching is a common feature of these
mental Protection Agency regulations. This equipment per- plants so the subdewpoint bed is regenerated periodically. The
mits a periodic measurement of the stack flow rate and stack subdewpoint catalytic converter temperature means a signifi-
gas composition, which can be used to determine a reasonably cantly higher equilibrium constant for the Claus reaction,
accurate emission rate. Atmospheric emissions usually are ex- thus resulting in less unreacted H2S and SO2 in the tail gas.
pressed in total kg/h of sulfur dioxide, or expressed as SO2 Like the IFP process, close control of the H2S:SO2 ratio is es-
concentration in ppmv reported on a water and oxygen free sential for effective subdewpoint operation; and any COS and
basis. The detailed stack sampling procedures are covered in CS2 present in process gas pass through to the plant tail gas
EPA or state and/or local regulations and procedures. incinerator.
Where continuous monitoring is required, stack gas analyz- Although the principles of the dry-bed subdewpoint proc-
ers (which measure the amount of SO2 in the stack gas) are esses are similar, each process claims to have unique and de-
installed on the stack. These instruments are often coupled sirable features. The licensors of these processes should be
with a flow measuring instrument so there is a continuous consulted for details.
record of both the flow and SO2 content of the stack gas. This
allows the total daily emission level to be determined. SO2 Recovery Processes
Tail Gas Clean-up Processes The SO2 recovery processes involve incineration of the Claus
Fig. 22-13 is a summary of some of the available Claus tail tail gas as the first step. This converts essentially all the forms
gas cleanup (TGCU) processes, not all of which are proven of sulfur to SO2.
commercially. All of these processes fit roughly into four cate- The Wellman-Lord Process involves using a basic solu-
gories: tion to absorb the SO2 which is generally recovered from
Processes based primarily on the continuation of the the solution as essentially pure SO2. This SO2 is available
Claus reaction to produce additional sulfur under more as a liquid or a vapor.
favorable equilibrium conditions than normally found in For small Claus units, a solution of NaOH may be used
the Claus units, either through operation at tempera- to scrub SO2 from the incinerator outlet stream; the re-
tures below the sulfur dewpoint or in the liquid phase at sulting sulfite solution after further oxidation to sulfate
a temperature above the melting point of sulfur. with air (or another oxidizing agent such as hydrogen
Processes based on converting all the sulfur components peroxide) can be disposed of underground or at an ap-
in the tail gas to SO2 and recovering the SO2 for further proved disposal facility.
processing.
Processes based on converting all the sulfur in the Claus
H2S Recovery Processes
unit tail gas to H2S, then recovering sulfur from this H2S. In these processes, essentially all forms of sulfur in the
Processes that directly oxidize the tail-gas H2S to sul- Claus tail gas are converted to H2S by hydrogenation and hy-
phur. drolysis. The Beavon-Stretford process then recovers elemen-
tal sulfur directly from the H2S in this tail gas stream in a
Continuation Processes Stretford unit. The ARCO (Atlantic Richfield), BSR (Beavon
The dry-bed subdewpoint processes include CBA (Cold Bed Sulfur Removal)-MDEA, Exxon, Resulf and SCOT processes
Adsorption) of the United States, Clinsulf of Germany, MCRC remove the H2S using an amine solution that is selective for
(Maximum Claus Recovery Concept) of Canada, and Sulfreen H2S over CO2. The H2S and any coabsorbed CO2 from the re-
of France. Generally, the licensors of these processes report generated solution are recycled to the front end of the Claus
sulfur recoveries of 99-99.5%. The processes have not been unit.
widely used in the U.S. because the attainable sulfur recovery
BSR-Stretford can reduce the H2S content in the absorber
level will seldom meet local air quality requirements. Incin- off gas to 10 ppmv. Generally the amine-based processes (i.e.
eration of the residue gas is still required and the stack gases SCOT et al.), using generic amines such as MDEA without
from tail gas treaters of this type generally contain 1200- additives, are limited to about 100-150 ppmv. However, using
2000 ppmv SO2. proprietary amines (such as Dows GAS/SPEC, Exxons FLEX-
The IFP process Clauspol II continues the Claus reaction SORB SE, Shells SCOT-LSS or Union Carbides UCARSOL
also at sub-dewpoint, but in the presence of a catalyst contain- HS 102), these processes can also achieve 10 ppmv H2S. All of
ing liquid solvent, which is fed counter-currently with the in- these processes result in overall sulfur recovery in excess of
coming Claus tail gas in a packed tower. The process operates 99.9%. BSR-MDEA was developed by Parsons and Unocal
22-12
FIG. 22-13 tion-unit effluent, with the associated water-vapor removal, is
unnecessary because water does not impede SUPERCLAUS
Claus Tail Gas Clean Up Processes
catalysis.
Claus Tail Gas Cleanup Processes Final selection of a tail gas treating process should con-
sider the applicable pollution regulations, initial invest-
ment, long term (continuing) operating costs, and the
Extend Claus Reaction on Solid Bed (sub-dew- operating advantages and disadvantages of each process.
point) Since these tail gas treating processes are proprietary, the
CBA (Amoco/Pritchard/Ortloff) process developer or a contractor authorized to design and
Clinsulf SDP (Linde AG) install these systems should be consulted for more defini-
MCRC (Delta Hudson) tive information.
Sulfreen (Lurgi Bamag / SNEA(P))
Extend Claus Reaction in Liquid Phase Cata- Liquid Redox
lyst (sub-dewpoint) Liquid redox sulfur recovery processes all share the follow-
Clauspol 300 (IFP) ing major operations:
Direct Oxidation to Sulfur Removal of the acid gas, H2S, from a gas stream by ab-
Superclaus 99 (Stork Comprimo) sorption into an alkaline solution to form the ions S
Oxidize to SO2, Absorb and Recycle to Claus and 2H+;
Chiyoda Thoroughbred (CT121) Conversion (i.e. oxidation) of the S to elemental sulfur
Elsorb (Elkem Technology) (S) by the action of a redox reagent (i.e. catalyst) such
Wellman-Lord (Lurgi Bamag) as iron attached to a legend (also called chelant)(i.e.
Fe+++L) which keeps the iron in solution:
Reduce to H2S, Absorb and Recycle to Claus
ARCO (ARCO/Pritchard) S + 2H+ + 2Fe+++L S + 2H+ + 2Fe++L
BSR/MDEA (Parsons/UPO)
The reagent is said to be "spent" and the iron "reduced."
Clintox (Linde AG)
Exxon Separation and recovery of solid sulfur. Depending on the
HCR (Nuovo IGI) regeneration process, this may precede or succeed the
Resulf (TPA) next step.
SCOT (Shell) Regeneration of the spent redox reagent (i.e. Fe++L) by
Reduce to H2S and React/Oxidize to Sulfur reacting it with oxygen dissolved in the solution:
BSR/Selectox (Parsons/UOP) 1/2O2 + 2H+ + 2Fe++L H2O + 2Fe+++L
MODOP (Mobil Oil)
Superclaus 99.5 (Stork Comprimo) The iron is said to be "oxidized."
Thus the reagent is reduced as it converts H2S to sulfur and
(Unocals version sold to UOP), SCOT by Shell, and Resulf by is oxidized as it is regenerated with oxygen/air, and hence the
TPA. term "redox."
Direct Oxidation Processes Redox processes can remove and convert to sulfur up to
27 99.9% of the H2S in sour natural gas and acid gas. Their turn-
MODOP (Mobil Oil Direct Oxidation Processes) and SU-
down capabilities are very good, and they can be designed for
PERCLAUS 99 and 99.528 are Claus TGCU processes that in- large variations in H2S concentrations. However, the sulfur
clude air oxidation of tail gas H2S to sulfur using special color is a brown/tan yellow rather than the bright yellow pro-
catalysts. In MODOP, all forms of sulfur in the Claus tail gas
duced in Claus plants. The redox solutions are corrosive, and
are converted to H2S in a sulfur-reduction (i.e., hydrogena- much of the equipment must be alloy or coated. Also, chemical
tion/hydrolysis) unit. Cooling of the reduction-unit effluent in- consumption can be high, and disposal of spent chemicals can
cludes direct contact with recirculating water which reduces be a problem. The solution must usually be analyzed daily
the water vapor in the effluent to about 5-9%. The effluent with addition of chemicals.
combines with air, and enters a MODOP reactor where the
H2S is oxidized to sulfur with the aid of titanium-dioxide cata- Nevertheless, redox can be considered for various combina-
lyst. The prior removal of water vapor in the reduction unit tions of the following:
increases the conversion to sulfur. MODOP can achieve 99.5%
overall recovery by using three Claus stages followed by sulfur Natural gas or acid gas containing less than 20 t/d of
reduction and one MODOP stage, or by using two Claus stages sulfur.
followed by sulfur reduction and two MODOP stages. Sour natural gas for which CO2 does not have to be re-
moved.
SUPERCLAUS 99 does not include a sulfur-reduction unit.
Claus tail gas is reheated and mixed with Claus-blower air, Acid gas with very low concentrations of H2S.
and is processed in a SUPERCLAUS reactor employing a pro- Established redox processes include the following:
prietary catalyst. SUPERCLAUS 99 achieves up to 99% recov-
ery depending upon the quality of the acid gas and whether Stretford licensed by British Gas, uses a vanadiam redox
there are two or three Claus converters. SUPERCLAUS 99.5 reagent.
does include a sulfur-reduction unit, and can achieve an over- ARI-LO-CAT II licensed by Wheelabrator Clean Air Sys-
all sulfur recovery of 99.5%. Its description is similar to the tems, SulFerox licensed by Dow, and Sulfint licensed by
MODOP description; however, direct-contact cooling of reduc- IFP. All employ iron redox reagents.
22-13
PROPERTIES OF SULFUR FIG. 22-14
Heat Capacity of Solid Sulfur at Constant Pressure4
Sulfur is a solid at ambient temperatures; it exists in two
octatomic crystalline forms (rhombic and monoclinic) and an
amorphous form. Up to about 96C, rhombic crystals are the
stable form; above this temperature and up to its melting
point, monoclinic sulfur is the stable variety. Both crystalline
forms consist basically of eight-membered rings, but the ar-
rangement of the rings and the interatomic distances are dif-
ferent. Amorphous sulfur is prepared by rapidly chilling liquid
sulfur which has been heated to near its boiling point. Amor-
phous sulfur, which slowly changes to the rhombic crystalline
form at ambient temperatures, is also referred to as "rubber"
sulfur and its presence is not desired. The approximate den-
sity of each solid sulfur form is as follows:
Rhombic 2066 kg/m3
Monoclinic 1954 kg/m3
Amorphous 1922 kg/m3
22-14
FIG. 22-15
Viscosity of Liquid Sulfur12
22-15
FIG. 22-16 Degasification facilities handling Claus sulfur are normally
Effects of Hydrogen Sulfide on the Viscosity designed on the basis of an average value of 250 to 300 ppmw
total H2S.
of Molten Sulfur12, 18
Tests using railroad tank cars with liquid sulfur containing
7 ppmw, 15 ppmw, and 100 ppmw of total H2S indicated that
15 ppmw H2S is the upper limit for safe handling of liquid
sulfur and, therefore, degasification facilities should be de-
signed for a maximum of 10 ppmw H2S.17, 24 Commercial de-
gasification processes are available from Amoco, Elf
Aquitaine, Exxon, Procor, and Shell.
22-16
FIG. 22-18
Heat Capacity of Liquid Sulfur5
below about 149C; a cold startup is when the unit tempera- Shutting off the air and acid gas
tures have dropped below these values.
Blocking in (isolating) the plant to prevent the entrance
A hot startup does not require that the plant be heated with of air.
fuel gas. The fuel gas pilots are lit and acid gas is fed to the
plant. When stable acid gas combustion has been established, If a longer shutdown period is planned, the air rate is re-
the pilots are turned off and the air rate adjusted for optimum duced (after the catalyst bed temperatures have been raised)
sulfur recovery. Excess air should not be used. to give an H2S/SO2 ratio at the front end of 2.5/1 to 3/1 and the
plant is operated in this manner for several hours to rejuve-
A cold startup requires that the plant be heated with fuel nate the catalyst beds. Fuel gas is then added to the burner
gas as in the initial startup procedure with two exceptions. and as soon as the fuel gas flame is established, the acid gas
The refractory need not be cured (unless refractory repairs is gradually shut off. The air rate is then adjusted to provide
have been made) nor the steam-producing equipment boiled (as close as possible) the stoichiometric requirement for com-
out. Second, excess air should normally not be used during the bustion of the fuel gas. Insufficient air, which can result in
heating procedure, unless the unit has been completely purged carbon formation and fouling of the unit, should be avoided;
of all sulfur and sulfur compounds as part of a planned shut- excess air is more acceptable but because sulfur fires within
down. the unit are possible even with a small amount of excess air,
Shutdowns temperatures should be closely monitored and the combustion
products should be analyzed regularly. Control of the combus-
The procedures to be followed during a planned shutdown tion temperature (to prevent damaging the refractory) is ob-
of a Claus sulfur recovery unit are an important part of plant tained by injecting an inert gas (usually steam, although
operations. nitrogen and carbon dioxide can be used). This purging of the
plant by combustion of fuel gas should be continued at least
If the plant is being shutdown for only a few hours (for ex- until sulfur stops draining from the unit. If it is planned to
ample, for reasons unrelated to the sulfur plant operation) the enter the unit for maintenance or other work, the fuel gas is
procedure may only involve then shut off, but the flow of air is continued until the unit is
Raising the catalyst bed temperatures by 17-22C, in or- sufficiently cooled and thoroughly purged of hazardous mate-
der to provide added assurance that sulfur condensation rials; if entry to the unit is not scheduled, both air and fuel gas
will not occur during the shutdown period are shut off, and the unit is blocked in.
22-17
FIG. 22-19
Distribution of Sulfur Vapor Species2
Emergency shutdowns can cause serious problems if proper A data base which is often utilized for these Claus plant cal-
precautions are not taken. If the plant cannot be placed in culations is the JANAF (Joint Army Navy Air Force) tables.8
operation soon after an emergency shutdown, an inert gas
should be fed to purge the plant. Otherwise, sulfur in the unit Reasonably accurate process calculations can be carried out
may solidify and damage the plant, or require replacement of manually, however, if side reactions are ignored. The following
the catalyst beds, and manual cleaning of the waste heat boiler example illustrates a simplified method of calculating the sig-
and sulfur condenser tubes. nificant process parameters for a 100 t/d (feed) Claus plant.
22-18
FIG. 22-20
Vapor Pressure of Sulfur9, 20
22-19
FIG. 22-21
Heat of Vaporization of Sulfur9
FIG. 22-22
Viscosity of Sulfur Vapor12
22-20
FIG. 22-23
Heat Capacity of Equilibrium Sulfur Vapors7, 10, 16
Total = 70.31 kmols / h O2 Assume P through the burner and furnace is 11 kPa. Then P
Assume x = kmols of H2S reacting = 131.6 kPa (abs).
22-21
FIG. 22-24
H2S and H2Sx to Total H2S Solubility
(at 1 bar H2S vapor pressure)
22-22
Feed Gas % S2, 45 mol % S6, and 54.5 mol % S8. The cooled combustion
H @ 43.3C product composition and waste heat boiler heat balance are
kmols/h kJ/kmol kJ/h therefore as follows:
H 2S 132.06 1474 194 656
Reaction Products
CO2 70.05 1606 112 500 H @ 1166C
H 2O 13.50 1456 19 656 kmols/h kJ/kmol kJ/h
Hydrocarbons (as C1) 2.14 1549 3 315
217.75 330 127 H2S 26.33 49 713 1 308 943
CO2 72.19 59 123 4 268 089
Combustion Air H2O 133.44 46 039 6 143 444
H @ 82.2C
SO2 13.17 59 500 783 615
kmols/h kJ/kmol kJ/h
N2 264.36 37 008 9 783 435
O2 70.31 2425.9 170 565
S2 46.28 42 103 1 948 516
N2 264.36 2396.6 633 565
H2O 9.94 2770.5 27 539 S6
344.61 831 669 S8
555.77 24 235 042
Reaction Products
H @ 1149C Cooled Reaction Products
kmols/h kJ/kmol kJ/h H @ 371C
H 2S 29.06 48 876 1 420 336 kmols/h kJ/kmol kJ/h
CO2 72.19 58 154 4 198 137 H2S 26.33 13 477 354 849
H 2O 130.71 45 272 5 917 503
CO2 72.19 15 939 1 150 636
SO2 14.53 58 572 851 051
H2O 133.44 12 956 1 728 849
N2 264.36 36 436 9 632 221
S2 44.24 41 482 1 835 164 SO2 13.17 16 697 219 899
555.09 23 854 412 N2 264.36 10 959 2 897 121
S2 0.0635 12 784 812
Reaction Products S6 5.889 32 565 191 775
H @ 1204C
S8 7.137 42 384 302 495
kJ/kmol kJ/h
522.58 6 846 436
H 2S 51 666 1 501 414
CO2 61 386 4 431 455 H: 24 235 042 6 846 436 = 17 388 600 kJ/h
H 2O 47 830 6 251 859
SO2 61 665 895 992 From Fig. 22-28
N2 38 343 10 136 355
S2 (vapor) S6 (vapor) (5.889) (279 026) = 1 643 186 kJ/h
S2 43 551 1 926 713
25 143 788 From Fig. 22-28
Heat in, kJ/h: S2 (vapor) S8 (vapor) (7.137) (414 624) = 2 959 171 kJ/h
Feed Gas = 330 127 Total heat duty
Combustion Air = 831 669
H2S Combustion (44.02 kmols/h) (518 822) = 22 838 527 17 388 606 + 1 643 186 + 2 959 171 = 21 990 963 kJ/h
HC Combustion (2.14 kmols/h) (802 587) = 1 717 535
Note: Partial pressure of sulfur vapor
Claus Reaction (58.98/2 kmols/h) (47 387) = 1 397 413
24 320 445 S2 + S6 + S8
= (Total Pressure)
Total Mols
By interpolation, flame temperature is approximately 1168C.
0.0635 + 5.889 + 7.137
Similarly for x = 61.25 kmols/h, the calculated flame tem- = (131.7) = 3.34 kPa
perature is 1166C, and for x = 63.52 kmols/h, 1164C. Plotting 522.58
the assumed values of x versus calculated equilibrium tem-
From Fig. 22-20, the vapor pressure of sulfur at 371C is ap-
perature and flame temperatures (Fig. 22-27) gives a value of
proximately 30.4 kPa, so no sulfur is condensed.
x = 61.7 kmols/h (equivalent to 70.1% conversion) and a tem-
perature of 1166C which meet both thermodynamic equilib- Step 3 1st Sulfur Condenser
rium and heat balance conditions.
Assume a pressure drop through the condenser of 3.44 kPa,
Step 2 Waste Heat Boiler Duty with the process stream further cooled to 177C. From Fig. 22-20,
the vapor pressure of sulfur at 177C is 0.111 kPa so the stream
Assume that 1723 kPa (ga) steam is generated in the waste is below the sulfur dewpoint. From Fig. 22-19, the distribution of
heat boiler and therefore that the temperature of the cooled sulfur species is 14.5 mol % S6 and 85.5 mol % S8. If no conden-
combustion products is 371C. From Fig. 22-19, the distribu- sation took place, there would be 1.74 kmols/h of S6 and 10.26
tion of sulfur vapor species at 371C is approximately 0.5 mol kmols/h of S8. [Note: (6)(1.74) + (8)(10.26) @ (2)(46.28)]
22-23
FIG. 22-25
Equilibrium Constant for Claus Reaction
22-24
FIG. 22-26
Enthalpies of Paraffin Hydrocarbons, Combustion Products and Sulfur Compounds11
(Based on datum of 0.0 kJ/kg-mole @ C)
Enthalpies of Combustion Gases kJ/kg-mole Note: Values are based upon datum of 0.0 kJ/kg-mole @ 0C
C N2 O2 Air H2 CO CO2 H2O
16 453 456 453 446 453 565 521
Uncondensed sulfur
25 726 733 727 719 729 912 839
38 1101 1109 1100 1088 1101 1391 1268 0.111
= [522.58 (1.74 + 10.26)]
93 2721 2756 2721 2698 2724 3552 3147
128.15 0.111
149 4345 4426 4350 4329 4354 5836 5050
204 5978 6127 5992 5955 5996 8227 6980
260 7622 7860 7650 7578 7657 10716 8936 = 0.444 kmols / h
316 9283 9623 9327 9164 9334 13291 10932
371 10962 11416 11025 10823 11035 15945 12960 S6: 0.145 (0.444) = 0.0644 kmols/h uncondensed
427 12660 13235 12744 12444 12756 18668 15026
482 14379 15082 14484 14091 14500 21455 17129 1.74 0.0644 = 1.676 kmols/h condensed
538 16117 16952 16245 15749 16266 24300 19269
593 17878 18841 18027 17373 18054 27196 21450 S8: 0.853 (0.444) = 0.3787 kmols/h uncondensed
649 18962 20750 19827 19029 19864 30145 23669
704 21462 22674 21650 20683 21692 33122 25928 10.26 0.3787 = 9.88 kmols/h condensed
760 23281 24614 23488 22376 23539 36146 28214
816 25118 26568 25342 24079 25402 39216 30564
871 26982 28540 27221 25753 27282 42310 32936
927 28842 30517 29098 27444 29168 45427 35332
982 30726 32494 31006 29122 31075 48590 37774
1038 32611 34495 32913 30820 33006 51754 40240
Condenser Outlet Conditions
1093 34518 36518 34820 32564 34937 54963 42752 H @ 177C
1149 36448 38519 36751 34378 36867 58173 45287 kmols/h kJ/kmol kJ/h
1204 38356 40542 38705 36216 38821 61406 47846
H2S 26.33 6154 162 035
1260 40333 42589 40658 38053 40775 64663 50451
1316 42287 44636 42612 39868 42752 67942 53056
CO2 72.19 7029 507 424
1371 44241 46683 44589 41728 44729 71222 55708 H2O 133.44 6013 802 375
1649 54149 57034 54368 50893 54708 87807 69268 SO2 13.17 7452 98 143
1927 64198 67570 64686 60523 64802 104717 83317 N2 264.36 5160 1 364 098
2204 74316 78293 74874 70431 74990 121882 97739
2482 84527 89179 85178 80387 85271 139141 112439
S2 (vapor)
2760 94808 95575 90737 95599 156540 127395 100251 S6 (vapor) 1.74 15 129 26 324
3038 105158 106042 101134 105973 174031 142514 111439 S8 (vapor) 10.26 19 680 201 917
3316 115532 122766 116579 111671 116393 191662 157796 521.49 3 162 316
3593 125953 134210 127186 122417 126837 209387 173147
22-25
FIG. 22-27 0.0644 (6) + 0.3787 (8) + 0.2 (132.06) = 29.83 kmols/h vapor
as S1 assuming a pressure drop for the reheater and cata-
Calculation of Reaction Furnace Temperature
lyst bed of 6.89 kPa,
Sulfur vapor pressure (as S1) then is:
29.84
(121.3) = 7.06 kPa (abs)
512.4
From Fig. 22-20, the vapor pressure of sulfur at 229.4C is
about 7.1 kPa. The preheater outlet temperature is therefore
set 16.7C higher or 246C.
H @ 246C H @ 177C
kmols/h kJ/kmol kJ/h kJ/h
H 2S 26.33 8 694.7 228 931 162 035
CO2 72.19 10 090 728 397 507 424
H 2O 133.44 8 444.7 1 126 861 802 375
SO2 13.17 10 647.9 140 233 98 143
N2 264.36 7 208.9 1 905 745 1 364 098
S6 0.12 21 259.5 2 551 960
S8 0.34 27 660.8 9 405 7 501
509.95 4 142 123 2 942 536
22-26
FIG. 22-28
Heat of Dissociation of Sulfur Vapor Species
22-27
FIG. 22-29
Molar Heat of Condensation of S6 and S8
allowing for sulfur vapor losses and about 12% for liquid sulfur H @ 25C = 518 757 kJ
entrainment, is about 97% and the tail gas composition is ap-
proximately as follows: S1 + O2 SO2 Eq 22-10
H @ 148.9C
kmols/h H @ 25C = 595 489 kJ
kJ/kmol kJ/h
H2S 1.76 5 153 9 069 H2S: 1.5 (1.76) = 2.640 kmols/h O2
CO2 72.19 5 834 421 156 S1: 1.0 (1.488) = 1.488 kmols/h O2
H2O 158.01 5 048 797 634 4.128 kmols/h O2
SO2 0.88 6 201 5 457
+ 50% = 6.192 kmols/h O2
N2 264.36 4 344 1 148 380
S6 (vapor) 0.009 12 696 114 Feed Air
S8 (vapor) 0.010 16 514 165 H @ 37.8C
Sliq (as S1) 0.635 8 871 5 633 kmols/h kmols/h kJ/kmol kJ/h
497.85 2 376 342 H2S 1.76
CO2 72.19
This is the feed to the incinerator. Assuming 50% excess air
H2O 158.01 0.876 1 267.9 1 111
(based upon combustibles) and an outlet temperature of
SO2 0.88
538C, the fuel gas requirement and stack gas volume can be
calculated as follows: N2 264.36 23.28 1 100.5 25 620
S (as S1) 1.488
Step 1. Calculate oxygen required for combustibles in feed gas O2 6.19 1 108.4 6 861
H2S + 32 O2 H2O + SO2 from Eq 22-2 498.69 30.35 33 592
22-28
FIG. 22-30 Fuel
Calculation of Converter Outlet Temperature H @ 37.8C
kmols/h kJ/kmol kJ/h
CH4 10.0 1340 13 400
CO2
O2
N2
H 2O
10.0 13 400
Air
H @ 37.8C
kmols/h kJ/kmol kJ/h
CH4
CO2
O2 30.0 1108.4 33 252
N2 112.81 1100.5 124 147
H 2O 4.24 1267.9 5 376
147.05 162 775
Combustion Products
H @ 538C
kmols/h kJ/kmol kJ/h
CH4
CO2 10 24 292 242 920
O2 10 16 946 169 460
N2 112.81 16 111 1 817 482
H2O 24.24 19 262 466 911
157.05 2 696 773
22-29
Total Heat Release sult in a more rapid response to changes in process require-
Fuel = 9.83 (802 596) = 7 889 579 kJ/h ments.
H2S (From Step 1) 913 240 kJ/h Although conventional orifice meters can be used for acid
gas and air measurement, the venturi meter is often more suit-
S (From Step 1) 886 211 kJ/h able. Thermocouples are used for most temperature measure-
9 688 970 kJ/h ments and a multipoint strip chart temperature recorder can
be useful to operations by indicating trends. Tail gas analyzers
(for H2S and SO2) are usually of the ultraviolet type although
SULFUR PRODUCT SPECIFICATIONS chromatographic analyzers have been utilized successfully.
Except at the front of the plant and on air, acid gas or fuel gas
A sulfur product meeting the following specifications will systems, pressure gauges are not normally installed. Sample
normally satisfy the requirements of the major consumers of connections should be as short as possible; sample valves
sulfur such as manufacturers of sulfuric acid, chemicals, fer- should be plug valves. Sample connections and valves should
tilizers, etc.: be fully steam-jacketed.
Purity 99.5%-99.9% by weight (dry basis) Measurement of reaction furnace temperature is sometimes
used as an indication of satisfactory air/acid gas control. Both
Acidity (as H2SO4) Less than 0.01% by weight thermocouples and infra-red type instruments have been util-
Moisture Less than 1.0% by weight ized; however, thermocouple life is short (6-9 months reported)
and the response time for infra-red instruments can be poor.
Ash Less than 0.05% by weight
Carbonaceous Matter Less than 0.025% by weight Conventional infra-red instruments often can be utilized as
flame monitoring devices for both the main burner and the
Arsenic, Tellurium, inline burners; combination infra-red/ultraviolet (flicker-type)
Selenium Commercially Free* instruments have also been used successfully.
Color (see Note below) Bright yellow at ambient
temperature
OPERATIONAL ASPECTS
*Contents of less than 0.25 ppmw of arsenic and 2.0 ppmw of Overall Claus plant conversion efficiency is maximized by
selenium and tellurium are usually considered as "commer- maintaining the stoichiometric H2S:SO2 ratio of 2:1 in the
cially free." process gas to the catalytic converters. The most suitable point
NOTE: The color of sulfur is an important property because for this determination is at the outlet of the last sulfur con-
it gives an immediate indication of product purity. The sulfur denser because a slight change in the air:acid gas ratio at the
is a bright yellow if the impurity content is less than about front of the plant will result in a significant change in the
0.02% by weight. Small amounts of carbon (soot) change the H2S:SO2 ratio in the tail gas and in the theoretical overall
bright yellow color to dull yellow or green; "dark" sulfur in sulfur recovery (Fig. 22-31). An H2S:SO2 ratio in the tail gas
which the yellow color has a shade of gray or brown usually of between 1:1 and 3:1 can be considered normal although the
contains 0.1%-0.5% by weight of carbon. For sulfuric acid desired goal should be a 2:1 ratio.
manufacturers, however, sulfur color is usually less important A simple method of determining the H2S:SO2 ratio is by the
than ash and heavy metal contents. use of stain tubes. This determination should be done at least
once every 8 hours during startup, plant test runs, and when-
ever significant changes in plant operating variables are ob-
INSTRUMENTATION served. Other analytical procedures involving wet chemistry,
chromatography, or UV photometry are also suitable for ad-
Since the quantity of acid gas being handled by the sulfur justing plant operations.
recovery unit is determined by upstream sweetening facilities,
the sulfur plant feed gas rate is normally not controlled. How- Because of the effect of temperature upon the Claus reaction
ever, during startup or in an emergency, part or all of the feed equilibrium, control of temperatures at various points in the
gas can be directed to flare. process sequence is important. Unexpected changes in oper-
ating temperatures usually denote changes in conversion ef-
For the main burner, the volume of feed gas is measured and ficiency. For example, a decrease in the temperature rise
the amount of air is controlled in ratio with the amount of acid across a catalytic converter bed is an indication of declining
gas. Both feed-forward25, in which the measured feed gas flow catalyst activity which may be caused by adsorption of elemen-
rate and assumed composition are used, and feed-back, in tal sulfur on the active surface area of the catalyst. Operating
which the measured ratio of H2S:SO2 in the plant tail gas is the catalyst bed at a temperature 28-56C higher than normal
used, can be utilized to adjust the air/feed gas ratio for maxi- for 24-48 hours will remove this sulfur from the catalyst and
mum sulfur recovery. A combination feed-forward/feed-back can restore its activity.
control system, in which the feed gas flow rate is used to con-
trol 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 CLAUS PLANT MAINTENANCE
a trim air valve, is often utilized.
Maintenance and repair of Claus plant equipment requires
For inline burners, the process stream temperature is nor- special precautions because of the physical properties of sulfur
mally used to adjust the combustion air rate and the amount and the potential hazards and/or toxicity of many plant proc-
of fuel (either acid gas or fuel gas) is controlled in ratio with ess streams. Equipment handling liquid sulfur should be
the amount of air. Because these burners normally operate drained completely and other equipment should be purged of
with a near substoichiometric air, this control system will re- all hazardous materials (see shutdown portion of this section).
22-30
FIG. 22-31
13. Lagas, J. A., Stop Emissions from Liquid Sulfur, Hydrocarbon
Plot Showing That a Slight Change in Air to Acid Gas Processing, Vol. 61, 85-89 (October 1982)
Ratio at the Head End of the Plant Will Make a Significant 14. Goar, B. G., Sulfur Forming and Degassing Processes, 1984 Gas
Change in the Tail Gas Ratio, H2S:SO2 Conditioning Conference, University of Oklahoma
15. Goar, B. G., and Sames, J. A., Tail Gas Clean Up Processes A
Review, 1983 Gas Conditioning Conference, University of Okla-
homa
16. West, J. R., Ind. Eng. Chem., Vol. 42, 713-718 (April 1950)
17. King, F. W., Oil & Gas J., Vol. 72, 164-165 (June 3, 1974)
18. Rubero, P. A., J. Chem. Eng. Data, Vol. 9, 481-484 (1964)
19. Parnell, D. C., Hydrocarbon Processing, Vol. 64, 114-118 (Sept.
1985)
20. Ford, G. P., and LaMer, V. K., J. Phys. Chem., Vol. 72, 1959-1964
(1950)
21. Johnston, H. E., Kelley, M. D., and McKinley, D. L., Ind. Eng.
Chem., Vol. 42, No. 11, 2298-2302 (1950)
22. Wiewiorowski, T. K. and Touro, F. J., J. Phys. Chem., Vol. 70,
No. 1, 234-238 (1966)
23. Ando, M. and Kawahara, H., Hydrocarbon Processing, Vol. 55,
90-92 (December 1976)
24. Solinhac, J., Fr Patent No. 1435788 (1964)
25. Dougherty, J. F. and Morgan, D. J., Oil & Gas J., Vol. 78, 68-70
(May 26, 1980)
26. Kellas, A. M., J. Chem. Soc., Vol. 113, 903-922 (1918)
27. Kettner, R., Liermann, N., New Claus Tail-Gas Process Proved
A satisfactory welding procedure can involve sandblasting in German Operations, Oil & Gas Journal, Jan. 11, 1988, p 63-
and/or grinding to a bare metal surface, extensive preheating, 66.
and the use of Type 309 stainless steel rod. 28. Berben, P.H., Borsboom, J., Lagas, J.A., SUPERCLAUS, the An-
swer to Claus Plant Limitations, 38th Canadian Chemical En-
gineering Conference, Oct. 2-5, 1988.
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