SECTION 22

Sulfur Recovery
Sul fur is present i n natural gas pri nci pal l y as hydrogen sul -
fide (H
2
S) and, i n other fossi l fuels, as sul fur-contai ni ng com-
pounds whi ch are converted to hydrogen sul fi de during
processing. The H
2
S, together wi th some or al l of any carbon
dioxi de (CO
2
) present, i s removed from the natural gas or re-
finery gas by means of one of the gas treati ng processes de-
scri bed i n Secti on 21. The resul ting H
2
S-contai ning aci d gas
stream i s flared, i nci nerated, or fed to a sul fur recovery unit.
Thi s secti on i s concerned wi th recovery of sulfur by means of
the modi fi ed Cl aus and Cl aus tail gas clean-up processes. Re-
dox processes are touched upon. For a di scussi on and descri p-
tion of other sul fur recovery processes, see Maddox
1
.
THE CLAUS PROCESS
The Cl aus process as used today i s a modi fi cation of a proc-
ess fi rst used i n 1883 in whi ch H
2
S was reacted over a catal yst
wi th ai r (oxygen) to form elemental sul fur and water.
H
2
S +
1

2
O
2
S + H
2
O Eq 22-1
Control of thi s hi ghl y exothermi c reacti on was di ffi cul t and
sul fur recovery effici encies were l ow. I n order to overcome
these process defi ci enci es, a modi fi cation of the Cl aus process
was devel oped and introduced in 1936 in which the overall
reacti on was separated i nto (1) a highl y exothermi c thermal
or combusti on reaction secti on i n whi ch most of the overall
heat of reacti on (from burni ng one-third of the H
2
S and essen-
tial l y 100% of any hydrocarbons and other combusti bl es i n the
feed) i s rel eased and removed, and (2) a moderatel y exother -
mi c catal yti c reacti on secti on i n whi ch sul fur di oxi de (SO
2
)
formed i n the combusti on secti on reacts wi th unburned H
2
S
to form el emental sulfur. The pri nci pal reacti ons taki ng pl ace
(negl ecting those of the hydrocarbons and other combusti bl es)
can then be written as foll ows:
Thermal or Combusti on Reacti on Section
H
2
S + 1
1

2
O
2
SO
2
+ H
2
O Eq 22-2
H @ 25C 518 900 kJ
Combusti on and Catal yti c Reacti on Secti ons
2 H
2
S + SO
2

3
x
S
x
+ 2 H
2
O Eq 22-3
H @ 25C 96 100 kJ
Overal l Reacti on
3 H
2
S + 1
1

2
O
2

3
x
S
x
+ 3 H
2
O Eq 22-4
H @ 25C 615 000 kJ
Thi s is a si mpli fied interpretati on of the reacti ons actuall y
taki ng pl ace i n a Cl aus uni t. The reaction equi l i bri um i s com-
pli cated by the exi stence of various speci es of gaseous sulfur
(S
2
, S
3
, S
4
, S
5
, S
6
, S
7
, and S
8
) whose equi l i bri um concentrations
i n rel ati on to each other are not preci sel y known for the enti re
range of process condi ti ons. Furthermore, side reactions i n-
vol ving hydrocarbons, H
2
S, and CO
2
present i n the acid gas
feed can resul t in the formati on of carbonyl sul fi de (COS),
carbon di sul fi de (CS
2
), carbon monoxi de (CO), and hydrogen
(H
2
). Gamson and Elki ns
2
cover the basic theory i nvol ved in
the Cl aus process; however, they i gnore the many potenti al
si de reactions and al so the exi stence of S
3
, S
4
, S
5
, and S
7
.
For the usual Cl aus pl ant feed gas composi ti on (water-satu-
rated wi th 30-80 mol % H
2
S, 0.5-1.5 mol % hydrocarbons, the
remai nder CO
2
), the modi fi ed Cl aus process arrangement re-
sul ts i n thermal secti on (burner) temperatures of about 980 to
1370C. The pri nci pal molecul ar speci es i n thi s temperature
range is S
2
(Fi g. 22-19) and conditi ons appear favorabl e for the
H = heat content or enthal py, kJ/kg or kJ/kg-mole
K
p
= equi li bri um constant
For the l ow pressure, vapor phase Cl aus reacti on
2 H
2
S + SO
2
2 H
2
O +
3
x
S
x
K
p
=
(P
H
2
O
)
2
(P
S
x
)
3/x
(P
H
2
S
)
2
(P
SO
2
)
=
[Mol s H
2
O]
2
[Mol s S
x
]
3/x
[Mols H
2
S]
2
[Mol s SO
2
]

Total Mols

3
x
1
P = parti al pressure, kPa
= total pressure, kPa
Acid Gas: feed stream to sul fur recovery pl ant consi sting of
H
2
S, CO
2
, H
2
O, and usual l y l ess than 2 mol % hydrocar-
bons.
Claus Process: a process i n whi ch
1

3
of the H
2
S in the aci d
gas feed is burned to SO
2
whi ch is then reacted with the
remai ni ng H
2
S to produce sul fur. Thi s is also referred to as
the modi fied Cl aus process.
Residence Time: the peri od of ti me i n whi ch a process
stream wi ll be contai ned wi thi n a certai n volume or pi ece
of equi pment, seconds.
Tail Gas Cleanup Unit: a process uni t desi gned to take
tai l gas from a Cl aus sulfur recovery pl ant and remove
addi tional sulfur wi th the goal of meeting environmental
sulfur emi ssion standards.
FIG. 22-1
Nomenclature
22-1
formati on of el emental sul fur by di rect oxi dati on of H
2
S (Eq
22-5) rather than by the Cl aus reaction (Eq 22-6).
2 H
2
S + O
2
2 H
2
O + S
2
Eq 22-5
H @ 25C = 314 500 kJ
2 H
2
S + SO
2
2 H
2
O +
3
2
S
2
Eq 22-6
H @ 25C = +47 500 kJ
However, both l aboratory and pl ant measurements i ndi cate
the more hi ghl y exothermi c oxi dati on of H
2
S to SO
2
(Eq 22-2)
predomi nates and the composi tion of the equi li bri um mi xture
therefore i s determi ned by the sl i ghtl y endothermi c Claus re-
acti on (Eq 22-6).
Fig. 22-2 is a representati on of theoretical equi l i bri um con-
version as a functi on of temperature for
An aci d gas from a well head-type treater, wi th about
3.5 mol % hydrocarbons (Curve 1)
An aci d gas from a refi nery treater, with about 7 mol %
hydrocarbons and 1 mol % mercaptans (Curve 2)
Pure H
2
S (Curve 3)
These curves i ndi cate:
Sul fur recovery would be expected to be lower for a feed
gas from a refi nery than for a well head treater because
of hi gher hydrocarbon content
The cal cul ated equi li bri um conversi on for both aci d gas
feeds fol l ows closel y the i deal i zed curve for pure H
2
S
Conversi on of H
2
S to el emental sul fur i s favored in the
reacti on furnace by hi gher operati ng temperatures of
980C pl us and i n the catal yti c converters by l ower oper -
ati ng temperatures of less than 371C.
To attai n an overall sul fur recovery l evel above about 70%,
the thermal , or combusti on, secti on of the pl ant is fol lowed by
one or more catal yti c reacti on stages. Sul fur i s condensed and
separated from the process gases after the combusti on secti on
and after each catal yti c reacti on stage i n order to i mprove
equi l i bri um conversion. Although Fi g. 22-2 i ndi cates that the
Cl aus reacti on i s favored by l ower temperatures, the process
gases must be reheated pri or to bei ng fed to the catal ytic re-
acti on stage i n order to mai ntai n acceptabl e reaction rates and
to ensure that the process gases remai n above the sul fur dew-
poi nt as addi ti onal sulfur is formed. Fi g. 22-3 i s the fl ow sheet
of an exampl e three-stage Cl aus sul fur recovery pl ant; Fi g.
22-4 shows the mechani cal arrangement of an exampl e smal l ,
package-type, two-stage Cl aus plant.
Gases l eavi ng the final sul fur condensati on and separati on
stage may requi re further processi ng. These requi rements are
establ i shed by local , state, or national regul atory agenci es.
These requi rements can be affected by the si ze of the sulfur
recovery pl ant, the H
2
S content of the plant feed gas, and the
geographi cal l ocati on of the pl ant.
CLAUS PROCESS CONSIDERATIONS
The Cl aus sul fur recovery process i ncl udes the fol l owing
process operations:
Combusti on burn hydrocarbons and other combusti -
bl es and 1/3 of the H
2
S in the feed.
Waste Heat Recovery cool combusti on products. Be-
cause most Cl aus pl ants produce 1030-3450 kPa (ga)
steam at 185-243C, the temperature of the cooled proc-
ess gas stream i s usual ly about 315-370C.
Sul fur Condensi ng cool outl et streams from waste
heat recovery uni t and from catal ytic converters. Low
FIG. 22-2
Theoretical Equilibrium Percent Conversion of Hydrogen Sulfide to Sulfur
3
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
pressure steam at at 345-480 kPa (ga) i s often produced
and the temperature of the cool ed gas stream i s usuall y
about 177C or 127-149C for the l ast condenser.
Reheating Reheat process stream, after sul fur conden-
sation and separ ati on, to a temper ature high enough to
remai n suffi ci entl y above the sulfur dewpoi nt, and gen-
eral l y, for the fi rst converter, hi gh enough to promote hy-
drol ysi s of COS and CS
2
to H
2
S and CO
2
.
COS + H
2
O CO
2
+ H
2
S Eq 22-7
CS
2
+ 2 H
2
O CO
2
+ 2 H
2
S Eq 22-8
Catal yti c Conversi on Promote reacti on of H
2
S and SO
2
to form elemental sul fur (Eq 22-3)
Process Variations
Several vari ati ons of the basi c Cl aus process have been de-
vel oped to handl e a wi de range of feed gas composi ti ons. Some
of these are shown i n Fig. 22-5. Strai ght-through operati on
resul ts i n the hi ghest overal l sul fur recovery effi ciency and i s
chosen whenever feasi bl e.
Fig. 22-6 can be used as a gui de in Cl aus process sel ecti on.
Combustion Operation
Most Claus plants operate in the "straight-through" mode. The
combustion is carried out in a reducing atmosphere with only enough
air (1) to oxidize one-third of the H
2
S to SO
2
, (2) to burn hydrocarbons
and mercaptans, and (3) for many refinery Claus units, to oxidize
ammonia and cyanides. Air is supplied by a blower and the combus-
tion is carried out at 20-100 kPa (ga), depending on the number of
converters and whether a tail gas unit is installed downstream of the
Claus plant.
Numerous si de reacti ons can al so take pl ace duri ng the com-
busti on operati on, resul ti ng i n such products as hydrogen
(H
2
), carbon monoxide (CO), carbonyl sul fide (COS), and carb-
on di sul fi de (CS
2
). Thermal decompositi on of H
2
S appears to
be the most l ikel y source of hydrogen si nce the concentrati on
of H
2
in the product gas i s roughl y proportional to the concen-
trati on of H
2
S i n the feed gas. Formati on of CO, COS, and CS
2
i s rel ated to the amounts of CO
2
and/or hydrocarbons present
i n the feed gas. Pl ant tests i ndi cate concentrati ons of H
2
and
FIG. 22-5
Claus Process Variations
Feed H2S
Concentration, Mol%
Claus Variation
Suggested
55 - 100 Str ai ght-thr ough
30 - 55 Str ai ght-thr ough or str ai ght-
through wi th aci d gas and/or ai r
preheat
15 - 30 Spl i t-fl ow or str ai ght-thr ough
wi th feed and/or ai r pr eheat
10 - 15 Spl i t-fl ow wi th aci d gas and/or ai r
preheat
5 - 10 Spl i t-fl ow wi th fuel added or wi th
aci d gas and ai r pr eheat, or di r ect
oxi dati on or sul fur r ecycl e
< 5 Sul fur recycl e or var i ati ons of
di r ect oxi dati on or other sul fur
recover y pr ocesses.
FIG. 22-6
Claus Plant Configurations
22-4
CO i n the product gas to be approxi matel y at equi li bri um at
reacti on furnace temperatures; Fig. 22-7 indicates potential COS
and CS
2
formation in the Claus furnace.
Heavy hydrocarbons, ammonia, and cyanides are difficult to burn
completely in a reducing atmosphere. Heavy hydrocarbons may
burn partially and form carbon which can cause deactivation of the
Claus catalyst and the production of off-color sulfur. Ammonia and
cyanides can burn to form nitric oxide (NO) which catalyzes the
oxidation of sulfur dioxide (SO
2
) to sulfur trioxide (SO
3
); SO
3
causes
sulfation of the catalyst and can also cause severe corrosion in cooler
parts of the unit. Unburned ammonia may form ammonium salts
which can plug the catalytic converters, sulfur condensers, liquid
sulfur drain legs, etc. Feed streams containing ammonia and cya-
nides are sometimes handled in a special two-combustion stage
burner or in a separate burner to ensure satisfactory combustion.
Flame stability can be a problem with low H
2
S content feeds (a
flame temperature of about 980C appears to be the minimum for
stable operation). The split flow, sulfur recycle, or direct oxidation
process variations often are utilized to handle these H
2
S-lean feeds;
but in these process schemes, any hydrocarbons, ammonia, cya-
nides, etc. in all or part of the feed gas are fed unburned to the first
catalytic converter. This can result in the cracking of heavy
hydrocarbons to form carbon or carbonaceous deposits and the
formation of ammonium salts, resulting in deactivation of the
catalyst and/or plugging of equipment. A method of avoiding
these problems while still improving flame stability is to pre-
heat the combustion air and/or acid gas, and to operate
"straight-through". An example of such an arrangement is
shown in Fig. 22-8. Steam-, hot oil-, or hot gas-heated ex-
changers and direct fired heaters have been used. The air and acid
gas are usually heated to about 230-260C. Other methods of im-
proving flame stability are to use a high intensity burner, add fuel
gas to the feed gas, or to use oxygen or oxygen-enriched air for com-
bustion.
Waste Heat Recovery Operation
Most Cl aus pl ants cool the process gases l eavi ng the com-
bustion section by generating steam in a fire-tube waste heat
boiler. Steam pressures usually range between 1035 and 3450 kPa
(ga). The waste heat boiler outlet temperature is therefore nor-
mally above the sulfur dewpoint of the process gases; however,
some sulfur may condense, especially during partial loads, and
provision should be made to drain this sulfur from the process
stream (or the piping should be arranged so the sulfur will drain
through downstream equipment).
Other methods of cooling the hot combustion gases include the
use of glycol-water mixtures, amine solutions, circulating cooling
water (no boiling), and oil baths. The utilization of one of these
alternate cooling fluids can be especially advantageous at loca-
tions where good quality boiler feed water is not available, or
where steam generation is not desired.
Some small Claus units use a closed steam system. Steam is
generated at 140-210 kPa (ga), condensed with air in an elevated
condenser, and the steam condensate returned by gravity to the
boiler as feed water.
Sulfur Condenser Operation
Sul fur i s condensed ahead of the first catal ytic converter
(except i n the case of spl it-fl ow operation) and fol l owing each
catalyti c converter i n order to promote the Claus reaction.
These condensers (other than the one fol l owing the last cata-
l yti c converter) are typi cal l y desi gned for outl et temperatures
of 166-182C which resul ts i n a condensed li quid sul fur of rea-
sonabl y l ow viscosi ty and a metal ski n temperature (on the
process gas si de) above the sulfurous/sul furic aci d dewpoi nt.
The final sul fur condenser outl et temperature can be as low
as 127C, dependi ng on the cool ing medi um avai l abl e. A l arge
temperature di fference between process gases and cool i ng me-
dium shoul d be avoi ded, however, because of the possi bl e for -
mation of sul fur fog; thi s i s especial l y i mportant for the fi nal
sul fur condenser.
Reheating Operation
The temperature of the process gas at the i nl et of the cata-
l yti c converters shoul d be such that the effluent gas tempera-
ture i s
About 14-17C higher than the expected outl et sulfur
dewpoint
As low as possi ble to maxi mi ze H
2
S conversi on but high
enough to obtai n a satisfactory Cl aus r eacti on rate
Hi gh enough for hydrol ysi s of COS and CS
2
(for the fi rst
catalyti c converter onl y)
Feed composition, mol%
COS, CS2
formation, % of
sulfur in feed
a,b
Hydrocarbon
(as C3H8)
Water CO2 H2S
0 6 4 90 0.5
0 6 14 80 1.5
0 6 24 70 2.5
0 6 34 60 3.5
0 6 44 50 4.5
0 6 54 40 5.5
0 6 64 30 6.5
0 6 74 20 7.5
2 6 4 88 2.0
2 6 14 78 3.0
2 6 24 68 4.5
2 6 34 58 6.0
2 6 44 48 7.0
2 6 54 38 9.0
2 6 64 28 11.0
2 6 74 18 14.0
4 6 4 86 3.5
4 6 14 76 5.0
4 6 24 66 6.0
4 6 34 56 8.0
4 6 44 46 10.0
4 6 54 36 12.0
4 6 64 26 14.0
4 6 74 16 18.0
a
Maxi mum. Actual pr oducti on var i es wi th operati ng
temper ature and pr essur e, r esi dence ti me, burner mi xi ng
and bur ner effi ci ency.
b
Uni ts feedi ng <30% H2S may operate other than "strai ght
thr ough," causi ng r educed COS and CS2 pr oducti on
pr opor ti onal to amount fed to mai n bur ner .
FIG. 22-7
Potential COS and CS
2
Formation in Claus Furnaces
19
22-5
Fig. 22-9 shows the methods of reheat commonl y used.
The hot gas bypass method takes a sl i p-stream of hot
process gases from the waste heat recovery uni t, usuall y
at 480-650C, and mixes thi s stream wi th the sul fur con-
denser outl et gases upstream of the catal yti c converter.
The di rect fi red method of reheati ng uses i nli ne burners
burni ng ei ther fuel gas or acid gas, wi th the combusti on
products bei ng mi xed wi th the sul fur condenser outl et
gases.
The indirect reheat methods use direct fi red heaters or
heat exchangers to heat the sul fur condenser outl et
gases; hi gh pressure steam, hot oi l, and hot process gases
have been used. El ectri cal reheati ng has al so been used.
Hot gas bypass reheati ng i s normal ly the l owest cost al ter -
nati ve, is relativel y si mpl e to control , and results in low pres-
sure drop. I ts disadvantage i s l ower overal l sul fur recovery,
parti cul arl y at reduced throughput. The hot gas bypass
method is someti mes used for the fi rst two catalyti c converters
and an indirect method of reheat used for the thi rd converter.
Direct fi red reheati ng uses an i nl ine burner which usuall y
burns a porti on of the Cl aus pl ant feed gas but whi ch some-
times burns fuel gas. Thi s r eheati ng method can be desi gned
to heat the process gases to any desi red temperature l evel .
Pressure drop is also rel ati vel y l ow. Potenti al di sadvantages
of i nl i ne burners are the possi bl e formati on of SO
3
, i f aci d gas
i s burned (sul fates deacti vate the catalyst) and of soot, i f fuel
gas i s burned (soot can pl ug and al so deactivate the catal yst).
A wel l-mi xed, hi gh-i ntensi ty burner capabl e of operati ng sub-
stoichiometri cal l y wi thout producing soot shoul d be util i zed
for burning fuel gas. Burner requirements are less stringent
for burni ng aci d gas; the H
2
S:SO
2
ratio in the i nli ne burner
outl et gases i s usual l y maintai ned at about 1:2 to 1:3. Precau-
tions must be taken, however, to avoi d oxygen breakthrough
from the inl i ne burners. Oxygen i n as l ow a concentrati on as
30 ppmv can rapi dly sul fate the catal yst.
I ndi rect reheati ng, whi ch i nvolves a heat exchanger ahead
of each catal yti c converter, i s the most expensi ve al ternati ve
and resul ts i n the hi ghest pressure drop. I n additi on, con-
verter inl et temperatures are l i mi ted by the temperature of
the heati ng medi um. For exampl e, the use of 4140 kPa steam
at 254C as the heat source woul d l imit the converter inl et
temperature to a maximum of about 243C. Thus, catal yst re-
juvenation i s usual ly not possibl e and COS and CS
2
hydrol ysi s
may be more di ffi cul t. However, i ndi rect reheati ng usual l y re-
sul ts i n the highest overall sul fur recovery, and deacti vati on
of the catal yst (because of sul fation, carbon deposi ts, etc.) i s
l ess l i kely to occur.
Catalyst Converter Operation
The Claus reaction i s exothermi c at converter temperatures,
and the reaction equi l ibrium i s favored by l ower tempera-
tures. However, carbonyl sul fi de (COS) and carbon di sul fi de
(CS
2
) hydrol yze more compl etel y at hi gher temperatures as
shown by Fig. 22-10. The fi rst catal yti c converter i s therefore
frequentl y operated at temperatures hi gh enough to promote
the hydrol ysi s of COS and CS
2
; the second and thi rd catalyti c
converters are operated at temperatures only high enough to
FIG. 22-8
Sulfur Recovery Process with Acid Gas and Air Preheat
22-6
obtai n acceptable reacti on rates and to avoi d l i qui d sulfur
deposi ti on. A three converter Claus unit wi ll uti l ize i nl et tem-
peratures in the fol lowi ng range: (1) fi rst converter, 232-
249C; (2) second converter, 199-221C; (3) thi rd converter,
188-210C.
A temperature ri se occurs across each catalyti c converter
because both the Cl aus and COS/CS
2
hydrolysis reactions are
exothermi c. The temperature ri se wi l l general ly be 44-100C
for the fi rst converter, 14-33C for the second converter, and
3-8C for the thi rd converter. Because of heat losses, measured
temperatures for the thi rd converter wil l often show a small
temperature drop.
MECHANICAL CONSIDERATIONS
Combustion Operation
Combusti on i s carri ed out i n the reacti on furnace whi ch may
be ei ther external (separate from waste heat recovery faci li ty)
or i nternal (combined wi th waste heat recovery faci l i ty). At the
normal operating temperature of 980-1370C, external fur -
naces requi re a refractory l ini ng to protect the steel shel l , but
wi th i nternal furnaces, the steel fi re tunnel (i .e. fi retube) i s
surrounded by the cool i ng medium, and refractory i s not re-
quired. For smal l Cl aus units, an i nternal furnace i s l ess ex-
pensi ve. For units l arger than about 30 t/d, an external fur -
nace i s usual ly more economi cal .
Reacti on furnaces are desi gned for a resi dence ti me of at
l east 0.5 seconds; pl ant tests i ndi cate thi s i s adequate to reach
equi l i bri um. Feed gases richer in H
2
S generall y require l ess
residence ti me than l eaner feeds.
The refractory i n the external reacti on furnace serves to re-
si st the hi gh fl ame temperatures and to protect the steel shel l .
Refractori es capabl e of withstandi ng hi gh temperatures nor -
mal l y have a hi gh alumi na content, e.g., 85-90% al umina.
However, these refractori es have rel ati vel y poor i nsulating
properti es and wi ll not provi de adequate protecti on for the
steel shel l. Therefore, an insul ati ng refractory l ayer is nor -
mal l y pl aced agai nst the steel shel l , and a l ayer of high al u-
mi na refractory covers the insul ati ng refractory. Occasi onal l y,
three di fferent refractori es have been used i n reacti on fur-
naces. (See Secti on 8 for addi tional i nformati on regardi ng re-
fractori es.)
Refractory sel ecti on and desi gn i s i mportant because the
steel shell can be overheated (above 343C) resul ting in di rect
sul fi de (H
2
S) attack, or can be cool ed bel ow the dewpoi nt of
SO
2
and SO
3
, resul ti ng i n acid condensati on and rapid corro-
si on. External i nsulation or shrouding for personal protecti on
i s often i nstal l ed to all ow metal temperatures above about
204C, which i s generall y safely above the aci d dewpoi nt.
FIG. 22-9
Alternate Methods of Reheating
3
22-7
I nteri or refractory checker wal l s are someti mes i nstal l ed i n
external -type reacti on furnaces to i mprove mi xi ng and to
serve as a heat buffer. Thi s i s of greater i mportance i f ammonia
or cyani des or high concentrations of hydrocarbons are present
i n the feed gas.
Waste Heat Recovery Operation
For most i nternal reacti on furnace-type waste heat recovery
units, the acid gas burner i s i nstal l ed i nsi de a singl e, l arge,
first-pass fi retube (radi ant secti on) and the process gas then
flows through one or more addi ti onal tube passes (convecti on
secti on). The fi rst pass fi retube is cool ed external l y and there-
fore does not requi re refractory protecti on; however, pass
plates and other uncool ed metal surfaces exposed to the proc-
ess gases at temperatures above about 343C shoul d be pro-
tected with refractory. Tube si zes for the convecti on secti on
passes range from 25-150 mm wi th a tube mass vel oci ty of
10-24 kg/(s m
2
).
External reacti on furnace-type waste heat recovery units
are usuall y si ngl e pass exchangers wi th smal l tubes (50-75
mm). The i nl et ends of these tubes are exposed to the hot com-
busti on gases (and possi bly to the fl ame). To ensure a reason-
able tube l ife, the i nl et end of each tube i s protected by
i nserting a cerami c ferrul e that extends about 75-150 mm be-
yond the insi de of, and about 75 mm outsi de of the tube sheet.
Thi s prevents the hot gases from di rectl y contacti ng the tube
at the cri ti cal junction of tube and tubesheet. These cerami c
ferrul es shoul d al so be wrapped wi th a thin l ayer of i nsul ati on
(3-10 mm thi ck). The i nl et tube sheet shoul d be protected by
a refractory overlay, usual l y about 75 mm thick.
Waste heat recovery uni ts are usual ly desi gned to meet pres-
sure contai nment requi rements accordi ng to Section I of the
ASME Code rather than to TEMA standar ds. A two-pass tube
wel di ng procedure i s normal l y used. Conventi onal practi ce i s
to appl y the first-pass wel d before tube rol li ng (or after a l i ght
rol l i ng), whi ch al l ows venti ng to eli mi nate gas traps. The first-
pass wel d i s usuall y pressure tested to l ocate al l wel d pi nhol es
for repairi ng prior to subsequent tube rol l ing and final wel d-
i ng. After final wel di ng, the compl eted tube attachment i s
l i ghtl y rol l ed. Duri ng the fi nal hydrotest, the tube wel d sur -
faces should be i nspected wi th a dye-penetrant test.
Tube si zes range between 50 and 150 mm. Tube spaci ng i s
based on a mi ni mum l igament (di stance between outer edge
of each tube) di mensi on of 19-25 mm. The desi gn mass
vel oci ty i n these tubes ranges between 5 kg/(s m
2
) and 39
kg/(s m
2
). For most i nstal l ati ons, the tube mass vel oci ty wi ll
be 10 to 24 kg/(s m
2
). All owabl e tube si de pressure drop often
determi nes tube vel oci ty.
Both kettl e-type and natural circul ati on-type waste heat
boil ers are used as hori zontal uni ts to ensure total submer -
gence of the tubes.
The advantages of the natural circul ati on-type unit whi ch
has a separate el evated steam di sengaging drum, i ncl ude:
I mproved steam qual ity because of surface bl owdown ca-
pabi l ity and more sophi sti cated steam/water separati on
devi ces.
More water hol dup above the hot process tubes whi ch
provi des addi tional ti me to react to emergency condi tions
and l essens the chance of tube fai l ure from overheati ng.
Better steam/water ci rcul ati on at the cri tical tube/tu-
besheet juncti on.
The advantages of the kettl e-type boil ers i ncl ude:
Lower i nstal l ed cost
Abi li ty to handl e a much wi der range of load condi ti ons
Both kettl e-and natural circul ati on-type waste heat boi l ers
should be consi dered as severe-servi ce appl i cations. Some
earl y boi l ers were desi gned to TEMA standards and the re-
sul ti ng thi ck tubesheets together wi th the hi gh heat fl ux re-
sul ted i n fai lures at the tube-tubesheet juncture.
The tubesheet desi gn i s based upon the thermal , mechani cal
stresses at the tube-tubesheet attachment. Tubesheets are
usuall y thi n (19-38 mm) resul ti ng i n acceptabl e temperature
profi l es at the tube weld, the l i gaments between tubes, and
the porti on of tubesheet not cool ed by water. The deflecti on of
these thi n tubesheets duri ng operati on reduces the stress
transmi tted to the tube-tubesheet attachment. Natural ci rcu-
l ati on-type units have tube patterns arranged to accommodate
the bendi ng stress at the patterns outer boundari es, whi le
kettl e-type uni ts have stayrods to sti ffen the porti ons of the
tubesheet wi thout tubes. Waste heat boi l ers uti li zi ng fl exi bl e,
thi n tubesheets have extremel y good servi ce hi stori es.
Sulfur Condenser Operation
Sul fur condensers may be si ngl e pass or mul ti -pass uni ts.
Both natural ci rcul ati on- and kettl e-type condensers are used;
hori zontal uni ts are recommended. Condensers are desi gned
wi th a mi nimum tube di ameter of 25 mm. Normal l y 12 BWG
steel tubes are used, install ed with a 13-19 mm li gament be-
tween tubes.
Sul fur condensers operate at much l ower heat fluxes than
waste heat boil ers and usuall y operate at l ower shel l si de pres-
sures. Both of these factors signi fi cantly reduce the mechani -
FIG. 22-10
Hydrolysis of COS and CS
2
in Sulfur Converter
COS + H2O = H2S + CO2
CS2 + 2 H2O = 2 H2S + CO2
22-8
cal design requi rements for tubesheets and tube attachments.
Sul fur condensers are desi gned to meet either ASME Secti on I
or Secti on VI I I Codes. Tubes are typi cal ly rol l ed, seal wel ded,
and re-rol l ed.
The design mass vel oci ty for the sul fur condenser tubes var -
i es from 15 to 39 kg/(s m
2
) wi th a typical mi ni mum mass ve-
l oci ty at design condi ti ons of 24 kg/(s m
2
). The desi gn mass
vel oci ty shoul d be suffici ently hi gh to prevent sulfur fogging
from occurring duri ng turndown condi ti ons.
21
I f sul fur fog-
gi ng does occur, the l iqui d sul fur wi ll not adequately separate
from the process gas in the separator downstream of the con-
denser. The tube vel oci ty i s al so l i mi ted by the al lowable tube
si de pressure drop, which i s usuall y about 2-4 kPa.
Sul fur condensers are subject to pl uggi ng wi th sol i d sulfur.
I n the design of the pl ant pipi ng system, the condensers shoul d
be the low poi nts in the system and shoul d al so slope toward
the outl et end. Thi s al lows any l iqui d sul fur present upstream
of the condenser, as well as that formed i n the condenser, to
drai n i nto the l i qui d-vapor separator chamber and out
through the sulfur drai n.
To all ow access to the tubes for cl eani ng and i nspecti on, sul -
fur condensers should have inspection ports and manways at
both ends. Addi ti onal access to the tubes shoul d be provi ded
by usi ng bol ted cover (end) plates.
Vapor-l iqui d separator chambers are i nstal l ed downstream
of the sul fur condensers to separate the li quid sul fur from the
process gases and to al l ow the l i qui d sul fur to drain from the
system. These separator chambers can be i ntegral parts of the
condenser or separate vessel s and may be provi ded wi th wire-
mesh type mi st el i mi nators or i mpingement pl ates to reduce
l i qui d sul fur entrainment. A superfi ci al gas vel oci ty of 6-9 m/s
i s commonly used as a basi s for sizi ng the separator chambers.
Sul fur condensers are usual ly desi gned to generate low
pressure steam of about 140-700 kPa (ga) on the shel l si de.
The fi nal sulfur condenser i s often used to heat boi ler feed
water, but car e must be taken not to over cool the str eam and
sol i di fy sulfur. Someti mes 100 kPa (ga) steam is generated,
condensed and returned i n a closed ci rcui t.
Reheating Operation
Hot Gas Bypass Method Pi pi ng and val ves are usu-
al ly of stai nless steel (although someti mes refractory-li ned
pipi ng i s used) in order to handle the hot corrosi ve process gas
rangi ng from 480 to 650C. An addi ti onal val ve i s someti mes
i nstal l ed i n the process stream downstream of the hot gas by-
pass extraction poi nt in order to improve turndown capabi li ty.
Direct (Inline Burner) Method I nl i ne burners are
usuall y desi gned to rai se the temperature of the process gas
at l east 28C above the normal operati ng i nl et temperature of
the catal ytic converter. Thi s extra heat rel ease capacity i s use-
ful during a "heat soak" or catal yst rejuvenati on operation.
Usual l y, a porti on of the aci d gas i s burned i n the i nl i ne burner;
however, other fuel s, such as natural gas, can be used. The
burner i s install ed i n a refractory l i ned combusti on chamber
and the hot combustion gases are mi xed wi th the process gas
to reach the reactor i nl et temperature. The retenti on ti me i n
the mixi ng chamber is usual l y between 0.1 and 0.3 seconds.
Indirect (Heating Exchanger) Method Heat ex-
changers used for reheati ng are normal l y constructed to the
same mechanical requirements as sul fur condensers. These
exchangers should sl ope toward the i nl et end so any l iqui d
sul fur present can drai n back i nto the l i qui d-vapor separator
l ocated downstream of the upstream sul fur condenser.
Catalyst Converter Operation
Catalytic converters are usually designed for a flow at operat-
ing conditions of 20-40 Sm
3
/h of process gas per m
3
of catalyst
bed. Because of pressure drop considerations, this usually results
in a bed depth of 915-1525 mm. The catalyst is activated alumina
(Al
2
O
3
) or promoted activated alumina which is installed on top
of a 75-150 mm thick layer of more dense support material. Cata-
lyst density is about 720-850 kg/m
3
; the support medium, which
usually has a density of 1360-1600 kg/m
3
, reduces migration of
catalyst and/or catalyst fines from the reactor bed to the sulfur
condenser downstream. These catalyst fines can plug the sulfur
drain legs and condenser tubes. The catalyst and support mate-
rial are installed on top of stainless steel wire screens which are
tied to carbon steel grating. A minimum of 75 mm of the support
material may be placed on top of the catalyst bed to serve as a
gas flow distributor.
For Cl aus uni ts small er than about 100 t/d, the catalyst beds
are frequently install ed in a singl e hori zontal vessel , wi th i n-
ternal parti ti on pl ates. For l arger uni ts, i ndi vi dual catalyst
bed vessel s are used. Verti cal (stacked) beds are someti mes
used but thi s i s usual l y not economi cal for uni ts smal l er than
about 800 t/d. I nternal refractory li ni ng of these vessels i s not
necessary unless i t i s pl anned to regenerate the catal yst in
place; i n thi s case the grati ng fl oor desi gn must al so be ade-
quate for the expected el evated temperatures. I f i nternal re-
fractory i s not used, a mi ni mum of 75 mm external i nsul ati on
i s recommended. I f a refractory l i ni ng is i nstal l ed, the outsi de
i nsul ation thi ckness can be reduced to 25-50 mm. Most con-
verters have internal refractory from the bottom to about
150 mm above the top of the catal yst bed, whi ch protects
against hi gh-temperature upsets.
Nozzl es i n the bottom of the catal yst bed vessel s shoul d be
i nstal l ed flush wi th the vessel i nteri or.
Piping
The pipi ng systems in Cl aus pl ants which requi re speci al
attenti on are li quid sul fur l ines and vapor process l i nes. Si nce
sul fur freezes at about 118C, li quid sul fur l i nes must be ade-
quately heated and i nsulated. Process l i nes are al so i nsul ated
to prevent sul fur from condensing and/or desubl i mi ng to the
sol i d form and to keep the metal temperature above the dew-
poi nts of sul furous/sul furi c aci ds. Process l ines operating at
temperatures above 343C are often l ined wi th refractory or,
especi al l y in smal l er uni ts, are of stai nl ess steel . Vapor process
pipi ng must al so have proper all owance for thermal expan-
si on. Either convol uted expansi on joi nts or expansi on "loops"
are used. Convol uted joi nts should be constructed of seri es 300
stainl ess steel , and insul ated to prevent ei ther water and/or
sul fur condensati on. The expansi on joi nts should be i nstal l ed
i n verti cal pipe runs so, if condensati on does occur, the l iqui d
can drai n freel y. I f l i qui d sulfur does not drai n, i t coul d sol i di fy,
causi ng the convol utes to be inoperabl e. Undrai ned water re-
sul ts i n corrosi on because of the aci ds formed.
Carbon steel process pi pi ng i s normall y adequate. Because
a Cl aus pl ant operates bel ow 103 kPa (ga) pressure, sched-
ul e 40 pi pe i s normal l y used for smal l l i nes. For 350 mm or
l arger l ines, standard weight pipe i s adequate. For process
l i nes over 750 mm i n diameter, the pi ping thi ckness can be the
same as the catal yst bed vessel wal l s.
Val ves shoul d be steel and ful l y jacketed. Smal l er val ves
usuall y have i ntegral jackets; l arge val ves may have fabri -
22-9
cated jackets. Val ves i n l i qui d sul fur servi ce shoul d be ful l -
openi ng gate or pl ug type to permi t roddi ng out. Li qui d sul fur
normal l y drains by gravi ty from the condensers i nto a sulfur
col l ection pi t or storage vessel wi th a li quid sul fur seal on each
drai n l ine to prevent gases from escapi ng to atmosphere. Sul -
fur drai n li nes often include both horizontal and verti cal sec-
tions of pi pi ng. Because of potential pluggi ng of these li nes,
faci li ties shoul d be install ed to cl ean-out (usuall y by roddi ng)
these li nes to prevent a pl ugged sul fur drai n from causi ng pre-
mature uni t shutdown. As shown i n Fig. 22-11, these "roddi ng-
out" faci l iti es usual ly i ncl ude both hori zontal and verti cal
crosses at each change i n pipi ng di recti on. The crosses are
often equi pped wi th external val ves. Valves are also often
placed in the hori zontal secti ons of the sul fur drai n l i nes to
al low easy cl eani ng of these segments, ei ther mechani cal l y or
wi th steam, whi l e the uni t conti nues to operate.
Each sul fur l i qui d/vapor separator shoul d have a separate
drai n li ne and sul fur seal to facil i tate detecti on of pl uggi ng.
Each sul fur seal shoul d be equi pped wi th a sight port (ori ented
away from si dewal ks, etc.) so the sul fur draini ng i nto the stor -
age pi t can be observed. When the fl ow of l iqui d sulfur stops,
remedi al acti on can be taken to el i mi nate the restri cti on or
plug so as not to cause additi onal damage to the pl ant.
Steam-jacketi ng is the preferred method of heati ng l iqui d
sul fur li nes. I nternal (gut) steam l ines are sometimes used,
especi al l y for l onger l i nes. Ski n Effect Current Traci ng (SECT)
whi ch uti l izes the skin effect phenomenon exhi bi ted when an
al ternati ng current passes through a steel pi pe has al so been
used to heat l ong pi pel i nes. For short l ines, steam traci ng may
be satisfactory. Steam i s the most common heati ng medi um,
but hot oi l can al so be used. The l i qui d sul fur li nes shoul d be
designed to mai ntai n the sul fur at a mi ni mum temperature of
138C whi ch corresponds to a steam pressure of at l east 345
kPa (ga). Hi gh pressure steam above about 690 kPa (ga) or
superheated steam shoul d normal l y not be used because of the
possi bi l i ty of heati ng the sulfur i nto the hi ghl y vi scous region.
(Fig. 22-15)
Si nce the l i qui d sulfur i s used as a seal to prevent process
vapors from bei ng vented to the atmosphere, the "net" l iqui d
col umn head must be l arge enough to wi thstand the maxi mum
expected operati ng pressure. For most pl ants this maxi mum
operati ng pressure i s the same as the ai r bl ower maxi mum
discharge pressure. The densi ty of l i qui d sul fur is about 1800
kg/m
3
, so for a 69 kPa seal , the required "net" sulfur seal depth
is 3.9 m. Minimum safety factors would require at least a 4.0 m
seal depth, and often an extra 150-300 mm i s added to the
cal cul ated depth to all ow for upsets, l ower sulfur densi ty, etc.
CLAUS UNIT TAIL GAS HANDLING
The tai l gas from a Cl aus uni t contai ns N
2
, CO
2
, H
2
O, CO,
H
2
, unreacted H
2
S and SO
2
, COS, CS
2
, sul fur vapor, and en-
trai ned li quid sul fur. Because of equil i bri um li mi tati ons and
other sul fur l osses, overal l sul fur recovery effi ci ency i n a Claus
unit usual l y does not exceed 96-97%. Venti ng of thi s tail gas
stream wi thout further processi ng i s sel dom permi tted; the
mi ni mum requi rement i s normal ly i nci nerati on, the pri nci pal
purposes of whi ch are to reduce H
2
S concentrati ons to a low
l evel (whi ch value wil l depend on the l ocal regul ati ons) and to
provi de the thermal l ift for di spersi on of SO
2
upon release to
atmosphere through a stack. Dependi ng upon the si ze of the
Cl aus unit, the H
2
S content of the feed gas, and the geographi -
cal locati on, a tai l gas cleanup process may be required i n order
to reduce emissi ons to the atmosphere.
Incineration
I nci nerati on of the H
2
S (as wel l as the other forms of sul fur)
i n the Claus plant tai l gas to SO
2
can be done thermall y or
catalyti cal ly. Thermal oxi dati on normal l y is carri ed out at
temperatures between 480C and 815C i n the presence of ex-
cess oxygen. Most thermal i nci nerators are natural draft op-
erating at sub-atmospheri c pressure with ai r fl ow control l ed
wi th dampeners; the excess oxygen level vari es between 20%
and 100%. Al though the Cl aus uni t tail gas contai ns some
combusti bl es for exampl e, H
2
S, COS, CO, CS
2
, H
2
, and el e-
mental sul fur (i n the case of "spl i t-fl ow" pl ants, some hydro-
carbons) these combusti bl es are at too l ow a concentrati on
to burn si nce they general l y amount to l ess than 3% of the total
tai l gas stream. The entire tai l gas stream must therefore be
i nci nerated at a hi gh enough temperature for oxi dati on of sul -
fur and sul fur compounds to SO
2
.
I nci nerator fuel consumpti on can be reduced si gni fi cantl y
by uti l i zing catal yti c incineration. Thi s i nvolves heati ng the
tai l gas stream to about 316-427C wi th fuel gas and then
passi ng the heated gas along wi th a control l ed amount of ai r
through a catal yst bed. Catal yti c i nci nerators are normall y
forced draft, operati ng at a posi ti ve pressure in order to mai n-
tai n cl oser control of excess ai r. Catalyti c i nci nerati on i s a pro-
pri etary process which shoul d be consi dered where fuel costs
for conventi onal (thermal ) incineration are hi gh.
Another method of i mprovi ng overal l fuel economy i nvol ves
recoveri ng heat from the i nci nerator outl et gases. Saturated
steam at pressures ranging between 345 and 3100 kPa (ga)
has been produced, and saturated steam has been super -
heated, usi ng waste heat from the i nci nerator outl et gases.
The effect of lower emi ssi on temperature upon di spersi on of
the outl et stream, and therefore upon the requi red stack
height, must be consi dered i n eval uati ng thi s al ternative. I n-
cinerators wi th waste heat recovery are normal l y forced draft
operati ng at a positi ve pressure.
Fuel requi red for thermal i nci nerati on i s determi ned by the
amount of heat needed to heat the Cl aus tail gas, ai r, and fuel
to the requi red temperature. Normal l y the incinerator i s si zed
for at least 0.5 second resi dence ti me, and someti mes for as
FIG. 22-11
Typical Relationship of Sulfur Seal and Drain
22-10
much as 1.5 seconds resi dence ti me. General l y, the l onger the
residence ti me, the l ower the i nci nerator temperature needed
to meet the envi ronmental requi rements. Thi s i s i l l ustrated
by Fi g. 22-12 whi ch shows the rel ati onship between resi dence
time and temperature for a typi cal install ati on to meet a maxi -
mum H
2
S requi rement of 10 ppmv.
The i nci nerator and stack can sometimes be combi ned i nto
a si ngl e vessel. The i nci nerator is the enl arged base, and the
smal l er di ameter stack is mounted on top of the i nci nerator.
The burner is normal l y mounted hori zontal l y i n the si de of the
i nci nerator. The tai l gas i s someti mes fed through the burner,
but it can also be fed into the incinerator adjacent to the burner.
Both the i nci nerator and stack are refractory l i ned to protect
the steel from the hi gh temperatures. Thi s refractory is not as
el aborate as that used for the reacti on furnace at the front of
the Claus uni t, because of l ower operating temperatures. The
i nci nerator is normal ly desi gned for a maxi mum operating
temperature of 1095C. Refractories rated as low as 1205C
have been used i n i nci nerator-stack i nstal l ati ons; one l ayer of
refractory is general l y suffici ent. The refractory is usual l y an
i nsulating castabl e rated for servi ce condi ti ons of 1205C or
above, except where flame i mpi ngement is anti cipated. A high
al umina castabl e (above 60% al umina) i s used i n the area of
flame i mpi ngement.
For vertical i nci nerators i nstal led at the base of the stack,
protecti on for the i nci nerator steel fl oor is i mportant. The best
method to protect the fl oor is to all ow for ambi ent (cool i ng) ai r
circul ati on below the fl oor even though the fl oor i s refractory
l i ned. I f there i s no cool i ng below the floor, or if the space i s
too restricted (too close to grade), the floor refractory usuall y
wi l l not provide adequate protection.
The steel components (fl oor, wal l s, stack shel l ) shoul d be
kept bel ow 343-371C and above 149C. This requi res careful
design of both the i nside refractory l i ning and outsi de insul a-
tion. Normall y the refractory thi ckness to protect the i nci n-
erator shell (ei ther verti cal or horizontal type) wil l be between
50 and 100 mm, with an average of about 75 mm. The i nci n-
erator fl oor on the verti cal styl e uni ts normal l y has refractory
thi cknesses rangi ng between 100 and 150 mm.
The i nci nerator and stack shoul d be i nsul ated on the outsi de
to prevent l ow shel l temperatures. Thi s i nsul ati on can be in
the form of an air gap (usual l y 75-100 mm) wi th either a stai n-
l ess steel or al umi num sheathi ng, or can be a thi n (25 mm
thi ck) l ayer of bl anket type i nsul ation covered with ei ther an
al uminum or a stai nl ess steel overl ay. Care should be taken
not to over-i nsul ate because overheati ng of the steel shel l can
then resul t.
Another method of handl i ng potential corrosi on of the out-
si de shel l of the stack is to make the most criti cal secti on of
the stack (say the top 4.6 m) of unl ined and uni nsul ated stai n-
l ess steel.
Stacks can be desi gned as free-standi ng, guyed, or derri ck-
supported structures. Sel ecti on of the type of stack is di ctated
by the required stack hei ght di ameter and by windload and/or
sei smi c cri teri a for the parti cul ar i nstal lation si te. A guyed
FIG. 22-12
Typical Relationship Between Incinerator Residence Time and Required Temperature
22-11
stack i s often the most economi cal desi gn; however, this re-
quires plot space for guy anchors and cables. A free standing
steel stack i s a common design for hei ghts not exceedi ng 76 m.
Stacks tal l er than about 107 m are usual l y derri ck-supported
steel stacks or are free-standi ng, rei nforced concrete stacks.
Typi cal desi gn stack vel oci ties are between 12 m/s and 30 m/s
wi th al l owabl e pressure drop generall y determi ni ng the de-
si gn stack vel oci ty.
Most governmental ai r control bodies (federal, state, and/or
l ocal ) requi re that the emi ssi ons from the i nci nerator-stack
system be moni tored on a periodic basi s. I n some areas, stack
emi ssi ons must be monitored and recorded conti nuousl y. The
stack should therefore be equi pped wi th platforms, sample
nozzles, and uti li ties l ocated at an appropri ate el evation.
These desi gn detail s are specifi ed i n current state or Envi ron-
mental Protecti on Agency regul ati ons. This equipment per -
mi ts a peri odi c measurement of the stack fl ow rate and stack
gas compositi on, which can be used to determine a reasonabl y
accurate emi ssion rate. Atmospheri c emi ssi ons usual l y are ex-
pressed in total kg/h of sulfur dioxi de, or expressed as SO
2
concentrati on i n ppmv reported on a water and oxygen free
basi s. The detai led stack sampl ing procedures are covered in
EPA or state and/or l ocal regul ati ons and procedures.
Where conti nuous monitori ng i s requi red, stack gas anal yz-
ers (which measure the amount of SO
2
i n the stack gas) are
i nstal l ed on the stack. These i nstruments are often coupl ed
wi th a flow measuri ng i nstrument so there i s a conti nuous
record of both the fl ow and SO
2
content of the stack gas. Thi s
al lows the total dail y emi ssion l evel to be determi ned.
Tail Gas Clean-up Processes
Fig. 22-13 i s a summary of some of the avai l abl e Cl aus tail
gas cl eanup (TGCU) processes, not al l of whi ch are proven
commercial l y. Al l of these processes fi t roughly i nto four cate-
gori es:
Processes based primari ly on the conti nuation of the
Cl aus reacti on to produce additi onal sul fur under more
favorabl e equi l i bri um conditi ons than normal l y found in
the Claus uni ts, ei ther through operation at tempera-
tures bel ow the sul fur dewpoi nt or i n the li quid phase at
a temperature above the mel ting point of sul fur.
Processes based on converti ng al l the sul fur components
i n the tai l gas to SO
2
and recoveri ng the SO
2
for further
processing.
Processes based on converti ng all the sul fur i n the Claus
unit tai l gas to H
2
S, then recoveri ng sulfur from thi s H
2
S.
Processes that directly oxi di ze the tai l -gas H
2
S to sul -
phur.
Continuation Processes
The dry-bed subdewpoi nt processes i ncl ude CBA (Cold Bed
Adsorpti on) of the United States, Cl i nsul f of Germany, MCRC
(Maximum Cl aus Recovery Concept) of Canada, and Sul freen
of France. General ly, the l i censors of these processes report
sul fur recoveri es of 99-99.5%. The processes have not been
wi del y used in the U.S. because the attai nabl e sulfur recovery
l evel wi l l sel dom meet l ocal ai r quali ty requi rements. I nci n-
eration of the resi due gas i s sti l l required and the stack gases
from tai l gas treaters of thi s type general l y contain 1200-
2000 ppmv SO
2
.
The I FP process Cl auspol I I conti nues the Cl aus reacti on
al so at sub-dewpoi nt, but i n the presence of a catal yst contai n-
i ng l i qui d sol vent, whi ch is fed counter-currently with the i n-
coming Cl aus tai l gas i n a packed tower. The process operates
above the mel ti ng poi nt of sul fur so the product sul fur i s re-
covered as a l i qui d. Any l i qui d and vapor sulfur present i n the
Cl aus tail gas i s al so recovered. I FP reports sulfur recoveri es
to 99.8%.
A typi cal subdewpoi nt sul fur plant wi l l resembl e a conven-
tional Cl aus pl ant i n the process flow through the waste heat
boil er, the fi rst catalyti c converter, the fi rst condenser, and the
first reheat uni t. At thi s poi nt in the process fl ow, the subdew-
poi nt plant differs si gni ficantl y from the conventi onal Claus
plant and even di fferent types of subdewpoi nt pl ants (CBA,
Cl i nsul f, MCRC, and Sul freen) di ffer i n the downstream proc-
ess sequenci ng. Generall y one converter i n the subdewpoi nt
plants i s operati ng bel ow the dewpoi nt temperature of sulfur.
Other converters may be operati ng i n a cool i ng or i n a regen-
erati on mode. Bed swi tchi ng i s a common feature of these
plants so the subdewpoi nt bed i s regenerated peri odi cal l y. The
subdewpoi nt catal ytic converter temperature means a si gni fi -
cantly hi gher equil i bri um constant for the Cl aus reaction,
thus resul ting i n l ess unreacted H
2
S and SO
2
i n the tai l gas.
Li ke the I FP process, cl ose control of the H
2
S:SO
2
rati o i s es-
senti al for effective subdewpoint operation; and any COS and
CS
2
present i n process gas pass through to the pl ant tai l gas
i nci nerator.
Although the pri nci pl es of the dry-bed subdewpoint proc-
esses are si mi l ar, each process cl aims to have uni que and de-
si rabl e features. The li censors of these processes shoul d be
consul ted for detai l s.
SO
2
Recovery Processes
The SO
2
recovery processes i nvolve i nci nerati on of the Claus
tai l gas as the fi rst step. Thi s converts essential l y al l the forms
of sulfur to SO
2
.
The Well man-Lord Process invol ves usi ng a basi c sol u-
tion to absorb the SO
2
whi ch i s generall y recovered from
the sol uti on as essenti al ly pure SO
2
. Thi s SO
2
i s avail able
as a l i qui d or a vapor.
For small Cl aus uni ts, a solution of NaOH may be used
to scrub SO
2
from the i nci nerator outl et stream; the re-
sul ti ng sul fi te solution after further oxidati on to sul fate
wi th ai r (or another oxidi zing agent such as hydrogen
peroxide) can be di sposed of underground or at an ap-
proved di sposal faci li ty.
H
2
S Recovery Processes
I n these processes, essenti al l y al l forms of sul fur i n the
Cl aus tail gas are converted to H
2
S by hydrogenati on and hy-
drol ysi s. The Beavon-Stretford process then recovers el emen-
tal sul fur directly from the H
2
S i n thi s tai l gas stream i n a
Stretford uni t. The ARCO (Atlanti c Ri chfiel d), BSR (Beavon
Sul fur Removal )-MDEA, Exxon, Resul f and SCOT processes
remove the H
2
S using an amine solution that i s selecti ve for
H
2
S over CO
2
. The H
2
S and any coabsorbed CO
2
from the re-
generated sol uti on are recycl ed to the front end of the Claus
unit.
BSR-Stretford can reduce the H
2
S content i n the absorber
off gas to 10 ppmv. General l y the ami ne-based processes (i .e.
SCOT et al .), usi ng generi c ami nes such as MDEA wi thout
addi ti ves, are l i mi ted to about 100-150 ppmv. However, using
propri etary ami nes (such as Dows GAS/SPEC, Exxons FLEX-
SORB SE, Shel ls SCOT-LSS or Union Carbi des UCARSOL
HS 102), these processes can also achieve 10 ppmv H
2
S. Al l of
these processes resul t i n overal l sulfur recovery i n excess of
99.9%. BSR-MDEA was devel oped by Parsons and Unocal
22-12
(Unocal s versi on sold to UOP), SCOT by Shel l , and Resul f by
TPA.
Direct Oxidation Processes
MODOP (Mobi l Oil Di rect Oxidati on Processes)
27
and SU-
PERCLAUS 99 and 99.5
28
are Cl aus TGCU processes that i n-
clude air oxi dation of tai l gas H
2
S to sul fur usi ng speci al
catalysts. I n MODOP, al l forms of sulfur i n the Cl aus tai l gas
are converted to H
2
S i n a sulfur-reducti on (i .e., hydrogena-
tion/hydrolysis) uni t. Cool ing of the reducti on-unit effl uent i n-
cludes di rect contact wi th reci rcul ati ng water whi ch reduces
the water vapor i n the effl uent to about 5-9%. The effluent
combi nes with ai r, and enters a MODOP reactor where the
H
2
S i s oxi di zed to sul fur wi th the ai d of ti tani um-dioxi de cata-
l yst. The pri or removal of water vapor i n the reducti on uni t
i ncreases the conversi on to sul fur. MODOP can achi eve 99.5%
overal l recovery by using three Cl aus stages fol l owed by sulfur
reduction and one MODOP stage, or by usi ng two Cl aus stages
fol l owed by sul fur reducti on and two MODOP stages.
SUPERCLAUS 99 does not i ncl ude a sulfur-reducti on unit.
Cl aus tai l gas i s reheated and mi xed wi th Cl aus-bl ower ai r,
and i s processed i n a SUPERCLAUS reactor empl oying a pro-
pri etary catal yst. SUPERCLAUS 99 achi eves up to 99% recov-
ery dependi ng upon the qual ity of the acid gas and whether
there are two or three Cl aus converters. SUPERCLAUS 99.5
does include a sulfur-reducti on uni t, and can achi eve an over -
al l sulfur recovery of 99.5%. I ts descri ption i s si mi l ar to the
MODOP descri pti on; however, di rect-contact cool i ng of reduc-
tion-uni t effluent, wi th the associ ated water-vapor removal , i s
unnecessary because water does not i mpede SUPERCLAUS
catalysis.
Fi nal sel ecti on of a tai l gas treati ng process shoul d con-
si der the appl i cabl e pol l uti on regul ati ons, i ni ti al i nvest-
ment, l ong ter m (conti nui ng) operati ng costs, and the
oper ati ng advantages and di sadvantages of each process.
Si nce these tai l gas treati ng processes are propri etary, the
pr ocess devel oper or a contractor author i zed to desi gn and
i nstal l these systems shoul d be consul ted for more defi ni -
ti ve i nfor mati on.
Liquid Redox
Liqui d redox sulfur recovery processes al l share the fol l ow-
i ng major operati ons:
Removal of the aci d gas, H
2
S, from a gas stream by ab-
sorption i nto an al kal ine sol uti on to form the ions S

and 2H
+
;
Conversi on (i .e. oxidati on) of the S

to el emental sulfur
(S) by the acti on of a redox reagent (i .e. catalyst) such
as iron attached to a l egend (also cal l ed chel ant)(i .e.
Fe
+++
L) whi ch keeps the i ron i n sol uti on:
S

+ 2H
+
+ 2Fe
+++
L S + 2H
+
+ 2Fe
++
L
The reagent is sai d to be "spent" and the i ron "reduced."
Separati on and recovery of soli d sul fur. Dependi ng on the
regenerati on process, thi s may precede or succeed the
next step.
Regenerati on of the spent redox reagent (i.e. Fe
++
L) by
reacti ng i t wi th oxygen dissolved i n the sol uti on:

1
/
2
O
2
+ 2H
+
+ 2Fe
++
L H
2
O + 2Fe
+++
L
The i ron i s said to be "oxidi zed."
Thus the reagent i s reduced as i t converts H
2
S to sul fur and
i s oxi dized as it i s regenerated wi th oxygen/air, and hence the
ter m "redox."
Redox processes can remove and convert to sul fur up to
99.9% of the H
2
S i n sour natural gas and acid gas. Thei r turn-
down capabi l i ti es are very good, and they can be desi gned for
l arge vari ati ons i n H
2
S concentrati ons. However, the sulfur
col or i s a brown/tan yel low rather than the bri ght yell ow pro-
duced in Claus pl ants. The redox sol uti ons are corrosi ve, and
much of the equi pment must be al l oy or coated. Al so, chemi cal
consumpti on can be high, and di sposal of spent chemi cal s can
be a probl em. The sol uti on must usual ly be anal yzed dail y
wi th addi ti on of chemicals.
Neverthel ess, redox can be consi dered for vari ous combi na-
tions of the fol l owing:
Natural gas or aci d gas contai ning l ess than 20 t/d of
sul fur.
Sour natural gas for whi ch CO
2
does not have to be re-
moved.
Acid gas wi th very l ow concentrati ons of H
2
S.
Establ ished redox processes i ncl ude the fol lowi ng:
Stretford li censed by Bri ti sh Gas, uses a vanadiam redox
reagent.
ARI -LO-CAT I I l i censed by Wheel abrator Clean Air Sys-
tems, SulFerox li censed by Dow, and Sul fi nt l i censed by
I FP. Al l employ i ron redox reagents.
Claus Tail Gas Cleanup Processes
Extend Cl aus Reacti on on Sol i d Bed (sub-dew-
poi nt)
CBA (Amoco/Pri tchard/Ortl off)
Cl i nsulf SDP (Linde AG)
MCRC (Delta Hudson)
Sul freen (Lurgi Bamag /SNEA(P))
Extend Cl aus Reacti on in Li quid Phase Cata-
l yst (sub-dewpoi nt)
Cl auspol 300 (I FP)
Di rect Oxi dati on to Sul fur
Supercl aus 99 (Stork Compri mo)
Oxi di ze to SO
2
, Absorb and Recycle to Cl aus
Chiyoda Thoroughbred (CT121)
El sorb (Elkem Technol ogy)
Wel l man-Lord (Lurgi Bamag)
Reduce to H
2
S, Absorb and Recycl e to Claus
ARCO (ARCO/Pri tchard)
BSR/MDEA (Parsons/UPO)
Cl i ntox (Linde AG)
Exxon
HCR (Nuovo I GI )
Resulf (TPA)
SCOT (Shel l )
Reduce to H
2
S and React/Oxi di ze to Sul fur
BSR/Sel ectox (Parsons/UOP)
MODOP (Mobi l Oil )
Supercl aus 99.5 (Stork Compri mo)
FIG. 22-13
Claus Tail Gas Clean Up Processes
22-13
PROPERTIES OF SULFUR
Sul fur i s a sol i d at ambi ent temperatures; i t exi sts in two
octatomi c crystal l i ne forms (rhombi c and monocli ni c) and an
amorphous form. Up to about 96C, rhombi c crystal s are the
stabl e form; above thi s temperature and up to i ts mel ti ng
poi nt, monocl ini c sulfur i s the stable vari ety. Both crystal l i ne
forms consi st basi cal ly of ei ght-membered rings, but the ar -
rangement of the ri ngs and the i nteratomic di stances are di f-
ferent. Amorphous sulfur i s prepared by rapi dly chi l l ing l iqui d
sul fur whi ch has been heated to near its boi l ing point. Amor -
phous sulfur, whi ch sl owly changes to the rhombi c crystal l i ne
form at ambi ent temperatures, i s al so referred to as "rubber"
sul fur and i ts presence i s not desi red. The approxi mate den-
si ty of each sol i d sulfur form is as fol l ows:
Rhombic 2066 kg/m
3
Monocl i ni c 1954 kg/m
3
Amorphous 1922 kg/m
3
The heat capaci ty of sol i d sulfur i s shown i n Fi g. 22-14.
The mel ting points of soli d sul fur range from 113C for
rhombi c sul fur to 120C for amorphous sul fur. Pure crystal s
of monocl ini c sul fur melt at 115C. When mel ted, sul fur be-
comes a browni sh-yel l ow, transparent l iqui d (l ambda sul fur),
whose mol ecul ar structure i s al so octatomi c. As l i qui d sul fur
i s heated to about 160C, the structure of the l i qui d undergoes
an abrupt change; its col or becomes a dark reddi sh brown and
i ts vi scosi ty i ncreases si gnifi cantl y. Long chai n pol ymers, (
sul fur), exi st i n equi l ibrium with octatomic sul fur mol ecul es.
Fi g. 22-15 shows how the vi scosi ty of pure li quid sulfur
changes wi th temperature and Fi g. 22-16 shows how di ssol ved
H
2
S affects the vi scosity of li quid sulfur. As the temperature
i s i ncreased above 160C, the col or of l i qui d sul fur darkens and
turns to a browni sh-bl ack above 250C and remai ns dark up
to the boi li ng poi nt of 444C. Fi g. 22-17 and Fi g. 22-18 show
how the density and heat capaci ty, respecti vely, of li quid sulfur
change wi th temperature.
Several sul fur molecul es are present i n the vapor phase, but
the pri nci pal sul fur speci es are S
2
, S
6
, and S
8
. Fi g. 22-19 shows
the di stri bution of sulfur speci es as a function of temperature.
I n sul fur plant vapors, the distributi on of sul fur speci es i s
si mi l ar but not identi cal to that shown in Fi g. 22-19 because
of the presence of components other than sul fur. Thi s sulfur
speci es distributi on was used to cal cul ate (1) the equi val ent
vapor pressure of sul fur shown i n Fig. 22-20 and (2) the l atent
heat of condensi ng sul fur vapors shown in Fi g. 22-21. The S
1
equi val ent vapor pressure and latent heat curves are conven-
i ent to use i n process calculations al though they may not be
rigorous when components other than sul fur are present. The
vi scosity of sulfur vapors i s shown i n Fi g. 22-22; the heat ca-
paci ty of sul fur vapors is shown in Fi g. 22-23.
SULFUR STORAGE AND HANDLING
Sul fur can be stored and handl ed as a l i qui d (at about 138C)
or as a sol id (at ambi ent temperature). A Cl aus sul fur recovery
plant wil l usuall y be provi ded with a rundown tank or pi t
(whi ch may be ei ther of steel or of acid-resi stant concrete)
si zed for 3-5 days producti on. I f the sul fur i s handl ed as a
l i qui d, i t can be pumped from the rundown tank ei ther di rectl y
to tank truck or rai l road tank car or to i ntermediate l iqui d
sul fur storage. I f the sul fur i s handled as a sol i d, it i s pumped
to storage block (where the sul fur i s all owed to cool and soli d-
i fy) or to sul fur-formi ng faci li ties such as a fl aker, a pri l l ing
tower, etc.
Seri ous envi ronmental and/or safety probl ems can occur in
the handl ing of l i qui d sulfur produced i n Claus uni ts. As
shown i n Fi g. 22-24, the total solubi li ty of H
2
S i n li quid sulfur
i ncreases wi th temperature because of the formati on of hydro-
gen pol ysul fi des (H
2
S
x
). Sul fur i s produced i n Cl aus uni ts at
temperatures of 138-154C but i n storage, or during transpor -
tati on, the temperature of the sulfur may drop as l ow as 127C.
Under these conditi ons, H
2
S i s emi tted and accumul ates i n the
vapor space above the l i qui d sul fur.
Concentrati ons of H
2
S exceedi ng i ts l ower expl osive or fl am-
mabi li ty l i mi t of 3.5 mol % (i n ai r) have been measured i n the
vapor space of rai l road tank cars. Emi ssi on of H
2
S from l iqui d
sul fur duri ng sol id sul fur formi ng operations can also present
serious operati ng and/or envi ronmental probl ems.
The H
2
S/H
2
S
x
content of Cl aus sul fur i s dependent on the
parti al pressure of H
2
S i n the process stream and the operat-
i ng temperature. Typical measured concentrati ons (as H
2
S)
are as fol lows:
From 1st Condenser 500-700 mg/kg
From 2nd Condenser 180-280 mg/kg
From 3rd Condenser 70-110 mg/kg
From 4th Condenser 10-30 mg/kg
From Fi nal Coalescer 5-10 mg/kg
FIG. 22-14
Heat Capacity of Solid Sulfur at Constant Pressure
4
22-14
FIG. 22-15
Viscosity of Liquid Sulfur
12
22-15
Degasi ficati on faci li ties handl ing Cl aus sul fur are normall y
designed on the basi s of an average val ue of 250 to 300 ppmw
total H
2
S.
Tests usi ng rail road tank cars wi th li quid sulfur contai ning
7 ppmw, 15 ppmw, and 100 ppmw of total H
2
S i ndi cated that
15 ppmw H
2
S is the upper l i mi t for safe handl ing of l iqui d
sul fur and, therefore, degasi ficati on faci li ties should be de-
si gned for a maximum of 10 ppmw H
2
S.
17, 24
Commercial de-
gasi fi cati on processes are avail able from Amoco, El f
Aquitaine, Exxon, Procor, and Shel l.
CLAUS PLANT STARTUP AND
SHUTDOWN PROCEDURES
Initial Startup
For the i ni ti al startup, three i mportant procedures must be
fol l owed before putti ng a Cl aus sul fur recovery pl ant i n serv-
i ce. These are:
Curi ng of al l refractory (i n combustion chamber, pi pi ng,
i nli ne burners, incinerator, stack, etc.)
Cl eani ng of the waste heat boi l er and other steam-pro-
duci ng equi pment
Heati ng of the catal yst beds and al l other equi pment to
proper operating temperatures
Curi ng of the refractory, whi ch i nvolves careful l y control l ed
heati ng, i s necessary because, i f wet refractory i s heated too
quickl y, the contai ned water wil l vapori ze too rapidl y, damag-
i ng the refractory. The manufacturer of the refractory (or re-
fractori es) shoul d be consulted regardi ng suitabl e curing
procedures.
Cleaning of the waste heat boi l er and other steam-producing
equi pment is necessary to remove oi l and grease. The equi p-
ment can be boi l ed out wi th water pl us boi l -out chemi cal s
(such as sodi um hydroxide and sodi um carbonate) or it can be
cleaned chemi cal l y. I f a chemi cal cl eani ng procedure i s chosen,
any steam produced duri ng the refractory curi ng can be fed to
the pl ant steam headers; if a boi l -out procedure is fol l owed,
any steam produced shoul d be vented to atmosphere. Under
ei ther procedure, the steam-produci ng equi pment shoul d be
fil l ed wi th water to prevent tube damage before refractory cur -
i ng and/or boi l ing-out are commenced and either the pi l ot
burners or the mai n gas burners are l i t.
Heati ng the catal ytic converters and al l other equi pment to
near normal operati ng temperatures by burni ng fuel gas i s
necessary to prevent condensati on of li quid sul fur on the cata-
l yst beds when aci d gas i s fed to the uni t. The pi l ot burners
are l i t first and after about 30 mi nutes, the mai n burners are
used to gradual l y rai se the temperatures of the refractory and
al l the equipment. Each catal ytic converter shoul d be heated
unti l the outlet temperature i s about 204C. Usuall y the Claus
plant i s ready for startup when the catal yti c converters are
hot. Aci d gas i s then fed to the pl ant whi l e conti nui ng to burn
fuel gas. When combusti on of the aci d gas i s assured, the fuel
gas rate i s gradual ly reduced to zero. The ai r rate is then ad-
justed to give opti mum sul fur recovery.
Subsequent Startups
Claus pl ant startups after the pl ant has been i n operati on
are ei ther hot startups or col d startups. A hot startup i s when
the catal yst bed temperatures have not dropped bel ow about
204C and other temperatures i n the uni t have not dropped
FIG. 22-16
Effects of Hydrogen Sulfide on the Viscosity
of Molten Sulfur
12, 18
FIG. 22-17
Density of Liquid Sulfur
26
22-16
below about 149C; a cold startup is when the uni t tempera-
tures have dropped bel ow these val ues.
A hot startup does not requi re that the pl ant be heated wi th
fuel gas. The fuel gas pi l ots are l it and aci d gas i s fed to the
plant. When stabl e aci d gas combusti on has been establ i shed,
the pi lots are turned off and the air rate adjusted for opti mum
sul fur recovery. Excess ai r shoul d not be used.
A col d startup requi res that the pl ant be heated wi th fuel
gas as in the ini ti al startup procedure with two excepti ons.
The refractory need not be cured (unless refractory repairs
have been made) nor the steam-produci ng equi pment boi l ed
out. Second, excess ai r shoul d normal l y not be used duri ng the
heati ng procedure, unless the unit has been compl etel y purged
of al l sul fur and sul fur compounds as part of a planned shut-
down.
Shutdowns
The procedures to be foll owed duri ng a pl anned shutdown
of a Cl aus sul fur recovery uni t are an i mportant part of pl ant
operati ons.
I f the pl ant i s bei ng shutdown for only a few hours (for ex-
ample, for reasons unrel ated to the sul fur plant operati on) the
procedure may only invol ve
Rai si ng the catalyst bed temperatures by 17-22C, i n or -
der to provi de added assurance that sul fur condensati on
wi l l not occur duri ng the shutdown peri od
Shutti ng off the ai r and aci d gas
Bl ocki ng i n (isol ati ng) the pl ant to prevent the entrance
of ai r.
I f a l onger shutdown period i s pl anned, the ai r rate i s re-
duced (after the catal yst bed temperatures have been rai sed)
to give an H
2
S/SO
2
rati o at the front end of 2.5/1 to 3/1 and the
plant is operated in thi s manner for several hours to rejuve-
nate the catal yst beds. Fuel gas i s then added to the burner
and as soon as the fuel gas fl ame is establ ished, the acid gas
i s gradual l y shut off. The ai r rate i s then adjusted to provi de
(as cl ose as possi bl e) the stoi chi ometri c requi rement for com-
busti on of the fuel gas. I nsuffici ent ai r, which can resul t in
carbon formati on and foul i ng of the unit, shoul d be avoi ded;
excess air i s more acceptabl e but because sul fur fi res within
the uni t are possi ble even wi th a smal l amount of excess ai r,
temperatures shoul d be cl osel y moni tored and the combusti on
products should be anal yzed regul arl y. Control of the combus-
tion temperature (to prevent damagi ng the refractory) i s ob-
tai ned by i njecti ng an i nert gas (usual l y steam, al though
ni trogen and carbon dioxi de can be used). Thi s purgi ng of the
plant by combusti on of fuel gas shoul d be conti nued at l east
unti l sul fur stops drai ni ng from the uni t. I f i t i s pl anned to
enter the uni t for mai ntenance or other work, the fuel gas i s
then shut off, but the fl ow of ai r is conti nued unti l the unit i s
suffi ci entl y cooled and thoroughl y purged of hazardous mate-
rial s; i f entry to the uni t i s not scheduled, both ai r and fuel gas
are shut off, and the uni t is blocked i n.
FIG. 22-18
Heat Capacity of Liquid Sulfur
5
22-17
Emergency shutdowns can cause seri ous problems i f proper
precauti ons are not taken. I f the plant cannot be pl aced i n
operati on soon after an emergency shutdown, an inert gas
should be fed to purge the pl ant. Otherwi se, sul fur i n the uni t
may sol idi fy and damage the plant, or requi re repl acement of
the catal yst beds, and manual cleaning of the waste heat boi l er
and sul fur condenser tubes.
CLAUS PROCESS CALCULATION
Process calculations for a Claus sulfur recovery unit are com-
pl icated by the existence of vari ous species of gaseous sulfur
(S
2
, S
3
, S
4
, S
5
, S
6
, S
7
, and S
8
) whose equil ibrium concentrations
i n relation to each other are often not precisely known, and by
the number of side reacti ons i nvolving other feed gas compo-
nents such as CO
2
, hydrocarbons, ammoni a, etc., which take
pl ace si mul taneously. These calculati ons are usuall y carried
out by computer wi th equi l i bri um condi ti ons and composi tions.
A data base which is often util ized for these Cl aus plant cal -
culati ons is the JANAF (Joint Army Navy Air Force) tabl es.
8
Reasonabl y accurate process cal cul ati ons can be carri ed out
manual l y, however, i f side reacti ons are i gnored. The fol l owing
exampl e i l l ustrates a si mpl i fi ed method of calculating the si g-
ni fi cant process parameters for a 100 t/d (feed) Cl aus pl ant.
Example 22-1
Feed Gas @ 43.3C & 143 kPa (abs) Ambi ent Condi ti ons
mol % kmol s/h Dr y Bul b
Temperatur e 37.8C
H2S 60.65 132.06
CO2 32.17 70.05 Wet Bul b
Temperatur e 23.9C
H2O 6.20 13.50
Hydr ocar bons
(as C1) 0.98 2.14
Ai r Bl ower Di schar ge
Temperatur e 82.2C
100.00 217.75
FIG. 22-19
Distribution of Sulfur Vapor Species
2
22-18
FIG. 22-20
Vapor Pressure of Sulfur
9, 20
22-19
FIG. 22-21
Heat of Vaporization of Sulfur
9
FIG. 22-22
Viscosity of Sulfur Vapor
12
22-20
Step 1 Combustion/Reaction Section
Cal cul ate air requi red to burn
1

3
of the H
2
S i n the feed and
for total combusti on of hydrocarbons
H
2
S + 1
1

2
O
2
H
2
O + SO
2
From Eq 22-2
H @ 25C = 518 822 kJ
CH
4
+ 2O
2
CO
2
+ 2 H
2
O Eq 22-9
H @ 25C = 802 587 kJ
Fi nd oxygen required:
H
2
S SO
2
(
1

3
) (
3

2
) (132.06)
Hydrocarbons (as C
1
) 2 (2.14)
Total
=
=
=
66.03 kmols / h O
2
4.28 kmols / h O
2
__________________
70.31 kmols / h O
2
Assume x = kmol s of H
2
S reacti ng
2 H
2
S
x

+

SO
2
1

2
x



2 H
2
O
x

+

3

2
S
2
3

4
x
From Eq 22-6
H @ 25C = +47 386 kJ
Materi al Bal ance (Combustion/Reaction Secti on)
Feed Gas
kmol s/h
Ai r
kmol s/h
H2S 132.06
CO2 70.05
H2O 13.50 9.94
SO2
N2 264.36
O2 70.31
S2
S6
S8
Hydr ocarbons (as C1) 2.14
217.75 344.61
Combusti on
Pr oducts
kmol s/h
Reacti on
Pr oducts
kmol s/h
H2S 88.04 88.04 x
CO2 72.19 72.19
H2O 71.73 71.73 + x
SO2 44.02 44.02
1

2
x
N2 264.36 264.36
S2
3

4
x
S6
S8
Hydr ocarbons (as C1)
540.34 540.34 +
1

4
x
Assume P through the burner and furnace i s 11 kPa. Then P
= 131.6 kPa (abs).
At equi l ibrium,
K
p
=
[H
2
O]
2
[S
2
]
3/2
[H
2
S]
2
[SO
2
]

total mol s

3
2
1
=
[71.73 + x]
2
[
3

4
x]
3/2
[88.04 x]
2
[44.02
1

2
x]

[131.6]
[540.34 +
1

4
x]

1/2
x, kmol s/h
(assumed)
Kp
(cal cul ated)
Equi l i br i um
Temperatur e
(fr om Fi g. 22-25)
59.0 199 1027C
61.3 279 1143C
63.5 398 1310C
Determi ne fl ame temperature by heat bal ance for each val ue
of x usi ng the thermodynami c data i n Fi g. 22-26. For exampl e,
at x = 59 kmols/h.
FIG. 22-23
Heat Capacity of Equilibrium Sulfur Vapors
7, 10, 16
22-21
FIG. 22-24
H
2
S and H
2
S
x
to Total H
2
S Solubility
(at 1 bar H
2
S vapor pressure)
22-22
kmol s/h
Feed Gas
H @ 43.3C
kJ/kmol kJ/h
H2S 132.06 1474 194 656
CO2 70.05 1606 112 500
H2O 13.50 1456 19 656
Hydrocar bons (as C1) 2.14 1549 3 315
217.75 330 127
kmol s/h
Combusti on Ai r
H @ 82.2C
kJ/kmol kJ/h
O2 70.31 2425.9 170 565
N2 264.36 2396.6 633 565
H2O 9.94 2770.5 27 539
344.61 831 669
kmol s/h
Reacti on Pr oducts
H @ 1149C
kJ/kmol kJ/h
H2S 29.06 48 876 1 420 336
CO2 72.19 58 154 4 198 137
H2O 130.71 45 272 5 917 503
SO2 14.53 58 572 851 051
N2 264.36 36 436 9 632 221
S2 44.24 41 482 1 835 164
555.09 23 854 412
Reacti on Pr oducts
H @ 1204C
kJ/kmol kJ/h
H2S 51 666 1 501 414
CO2 61 386 4 431 455
H2O 47 830 6 251 859
SO2 61 665 895 992
N2 38 343 10 136 355
S2 43 551 1 926 713
25 143 788
Heat in, kJ/h:
Feed Gas = 330 127
Combusti on Ai r = 831 669
H2S Combusti on (44.02 kmol s/h) (518 822) = 22 838 527
HC Combusti on (2.14 kmol s/h) (802 587) = 1 717 535
Cl aus Reacti on (58.98/2 kmol s/h) (47 387) = 1 397 413
24 320 445
By i nterpol ati on, fl ame temperature i s approxi matel y 1168C.
Si mi l arl y for x = 61.25 kmol s/h, the cal cul ated fl ame tem-
perature i s 1166C, and for x = 63.52 kmol s/h, 1164C. Pl otting
the assumed val ues of x versus cal cul ated equi l ibrium tem-
perature and fl ame temperatures (Fi g. 22-27) gi ves a value of
x = 61.7 kmols/h (equi val ent to 70.1% conversi on) and a tem-
perature of 1166C whi ch meet both thermodynami c equil i b-
rium and heat bal ance conditi ons.
Step 2 Waste Heat Boiler Duty
Assume that 1723 kPa (ga) steam i s generated i n the waste
heat boi l er and therefore that the temperature of the cool ed
combusti on products i s 371C. From Fi g. 22-19, the di stri bu-
tion of sul fur vapor speci es at 371C i s approxi matel y 0.5 mol
% S
2
, 45 mol % S
6
, and 54.5 mol % S
8
. The cooled combusti on
product compositi on and waste heat boil er heat bal ance are
therefore as foll ows:
kmol s/h
Reacti on Pr oducts
H @ 1166C
kJ/kmol kJ/h
H2S 26.33 49 713 1 308 943
CO2 72.19 59 123 4 268 089
H2O 133.44 46 039 6 143 444
SO2 13.17 59 500 783 615
N2 264.36 37 008 9 783 435
S2 46.28 42 103 1 948 516
S6
S8
555.77 24 235 042
kmol s/h
Cool ed Reacti on Pr oducts
H @ 371C
kJ/kmol kJ/h
H2S 26.33 13 477 354 849
CO2 72.19 15 939 1 150 636
H2O 133.44 12 956 1 728 849
SO2 13.17 16 697 219 899
N2 264.36 10 959 2 897 121
S2 0.0635 12 784 812
S6 5.889 32 565 191 775
S8 7.137 42 384 302 495
522.58 6 846 436
H: 24 235 042 6 846 436 = 17 388 600 kJ/h
From Fi g. 22-28
S
2
(vapor) S
6
(vapor) (5.889) (279 026) = 1 643 186 kJ/h
From Fi g. 22-28
S
2
(vapor) S
8
(vapor) (7.137) (414 624) = 2 959 171 kJ/h
Total heat duty
17 388 606 + 1 643 186 + 2 959 171 = 21 990 963 kJ/h
Note: Parti al pressure of sulfur vapor
=
S
2
+ S
6
+ S
8
Total Mol s
(Total Pressure)
=
0.0635 + 5.889 + 7.137
522.58
(131.7) = 3.34 kPa
From Fig. 22-20, the vapor pressure of sul fur at 371C i s ap-
proxi matel y 30.4 kPa, so no sul fur is condensed.
Step 3 1st Sulfur Condenser
Assume a pressure drop through the condenser of 3.44 kPa,
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
is below the sulfur dewpoint. From Fig. 22-19, the distribution of
sulfur species is 14.5 mol % S
6
and 85.5 mol % S
8
. I f no conden-
sation took place, there would be 1.74 kmols/h of S
6
and 10.26
kmols/h of S
8
. [Note: (6)(1.74) + (8)(10.26) @ (2)(46.28)]
22-23
FIG. 22-25
Equilibrium Constant for Claus Reaction
22-24
Enthalpies of Paraffin Hydrocarbons, C1-C6 kJ/kg-mole
C C1 C2 C3 nC4 iC4 nC5 nC6
16 545 787 1088 1473 1429 1832 2195
25 881 1279 1773 2396 2328 2977 3566
38 1340 1962 2731 3680 3591 4573 5473
93 3429 5175 7243 9732 9504 12098 14484
149 5652 8781 12421 16580 16356 20587 24607
204 8071 12774 18206 24179 23993 29982 35811
260 10676 17133 24514 30401 32355 40263 48039
316 13468 21867 31331 41473 41356 51312 61227
371 16433 26944 38658 51032 50963 63104 75253
427 19576 32331 46380 61151 61104 75572 90063
482 22858 37984 54545 71757 71780 88621 105600
538 26354 43915 63058 82806 82899 102228 121766
593 29959 50102 71920 94296 94459 116347 138490
649 33704 56499 106159 81108 106415 130977 155819
704 37611 63104 118393 90574 118696 146026 173682
760 41612 69896 100274 130977 131349 161494 192058
816 45729 76967 110322 143956 144328 177427 210898
871 49939 84178 120580 157214 157703 193709 230111
927 54312 91505 131047 170728 171356 210154 249789
982 58755 98995 141723 184522 185150 227111 269816
1038 63290 106694 152493 198571 199082 244230 290192
1093 67896 114462 163564 212759 213271 261628 310870
1149 72594 122348 174636 227087 227739 279585 331874
1204 77246 130396 186010 241695 242346 297263 352971
1316 87039
1538 107112
1649 117416
1927 143910
2204 170821
Enthalpies of Combustion Gases kJ/kg-mole
C N2 O2 Air H2 CO CO2 H2O
16 453 456 453 446 453 565 521
25 726 733 727 719 729 912 839
38 1101 1109 1100 1088 1101 1391 1268
93 2721 2756 2721 2698 2724 3552 3147
149 4345 4426 4350 4329 4354 5836 5050
204 5978 6127 5992 5955 5996 8227 6980
260 7622 7860 7650 7578 7657 10716 8936
316 9283 9623 9327 9164 9334 13291 10932
371 10962 11416 11025 10823 11035 15945 12960
427 12660 13235 12744 12444 12756 18668 15026
482 14379 15082 14484 14091 14500 21455 17129
538 16117 16952 16245 15749 16266 24300 19269
593 17878 18841 18027 17373 18054 27196 21450
649 18962 20750 19827 19029 19864 30145 23669
704 21462 22674 21650 20683 21692 33122 25928
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
1093 34518 36518 34820 32564 34937 54963 42752
1149 36448 38519 36751 34378 36867 58173 45287
1204 38356 40542 38705 36216 38821 61406 47846
1260 40333 42589 40658 38053 40775 64663 50451
1316 42287 44636 42612 39868 42752 67942 53056
1371 44241 46683 44589 41728 44729 71222 55708
1649 54149 57034 54368 50893 54708 87807 69268
1927 64198 67570 64686 60523 64802 104717 83317
2204 74316 78293 74874 70431 74990 121882 97739
2482 84527 89179 85178 80387 85271 139141 112439
2760 94808 95575 90737 95599 156540 127395 100251
3038 105158 106042 101134 105973 174031 142514 111439
3316 115532 122766 116579 111671 116393 191662 157796
3593 125953 134210 127186 122417 126837 209387 173147
Enthalpies of Sulfur Compounds kJ/kg-mole
C S2 SO2 SO3 H2S CS2 COS S6 S8
16 501 611 768 526 699 506 1304 1695
25 805 986 1233 846 1127 1025 2098 2728
38 1223 1499 1919 1283 1718 1571 3175 4129
93 3066 3798 4919 3198 4357 3980 7904 10279
149 4952 6203 8141 5154 7104 6510 12700 16519
204 6873 8706 11618 7157 9944 9148 17566 22851
260 8823 11300 15259 9211 12863 11842 22502 29275
316 10797 13965 19073 11318 15849 14638 27505 35781
371 12788 16703 23062 13481 18889 17517 32576 42398
427 14791 19506 27168 15703 21978 20432 37718 49100
482 16810 22351 31354 17980 25098 23400 42926 55891
538 18838 25214 35658 20311 28261 26400 48206 62774
593 20874 28145 40030 22695 31471 29447 53554 69750
704 24958 34099 49055 27610 37937 35425 64456 83976
760 27005 37100 53661 30145 41193 38798 70010 91228
816 29075 40124 58313 32704 44473 41961 73632 98569
871 31145 43147 63035 35309 47776 45148
927 33192 46194 67780 37960 51079 48358
982 35262 49265 72618 40635 54405 51591
1038 37332 52358 43357 57755 54801
1093 39402 55475 46101 61104 58103
1149 41496 58592 48893 64453 61360
1204 43566 61686 51684 67803 64663
1371 49800 71059 60220 77944 74572
1649 60243 86853
1927 70710 102763
2204 81224 118696
2482 91737 134699
2760 102297 150678
Note: Val ues ar e based upon datum of 0.0 kJ/kg-mol e @ 0C
FIG. 22-26
Enthalpies of Paraffin Hydrocarbons, Combustion Products and Sulfur Compounds
11
(Based on datum of 0.0 kJ/kg-mole @ C)
Uncondensed sul fur
=

0.111
128.15 0.111

[522.58 (1.74 + 10.26)]

= 0.444 kmol s / h
S
6
: 0.145 (0.444) = 0.0644 kmol s/h uncondensed
1.74 0.0644 = 1.676 kmol s/h condensed
S
8
: 0.853 (0.444) = 0.3787 kmol s/h uncondensed
10.26 0.3787 = 9.88 kmols/h condensed
kmol s/h
Condenser Outl et Condi ti ons
H @ 177C
kJ/kmol kJ/h
H2S 26.33 6154 162 035
CO2 72.19 7029 507 424
H2O 133.44 6013 802 375
SO2 13.17 7452 98 143
N2 264.36 5160 1 364 098
S2 (vapor)
S6 (vapor) 1.74 15 129 26 324
S8 (vapor) 10.26 19 680 201 917
521.49 3 162 316
H: 6 846 436 3 162 316 = 3 684 120 kJ/h
22-25
Fi g. 22-29 H:
S
6
(vapor) S
l iq
(1.676) (92 288) = 154 675 kJ/h
Fi g. 22-29 H:
S
8
(vapor) S
l iq
(9.88) (80 987) = 800 156 kJ/h
Fi g. 22-28 H:
S
2
(vapor) S
6
( vapor ) (0.00227) (275 771) = 626 kJ/h
Fi g. 22-28 H:
S
2
(vapor) S
8
(vapor ) (0.014 065) (409 741) = 5763 kJ/h
Total Duty
3 684 120 + 154 675 + 800 156 + 626 + 5763
= 4 645 340 kJ/h
Step 4 1st Reheater
One of the pri nci pal purposes of reheati ng i s to maintai n the
process gas above the sul fur dewpoi nt throughout the catalyst
bed. To esti mate the dewpoint temperature at the bed outl et,
assume that 20% of the H
2
S i n the feed wil l be converted to
sul fur i n the fi rst catal yst bed. Total sul fur (as S
1
) at the bed
outl et wi l l then be
0.0644 (6) + 0.3787 (8) + 0.2 (132.06) = 29.83 kmol s/h vapor
as S
1
assumi ng a pressure drop for the reheater and cata-
l yst bed of 6.89 kPa,
Sul fur vapor pressure (as S
1
) then i s:
29.84
512.4
(121.3) = 7.06 kPa (abs)
From Fi g. 22-20, the vapor pressure of sulfur at 229.4C i s
about 7.1 kPa. The preheater outl et temperature i s therefore
set 16.7C hi gher or 246C.
kmol s/h
H @ 246C H @ 177C
kJ/kmol kJ/h kJ/h
H2S 26.33 8 694.7 228 931 162 035
CO2 72.19 10 090 728 397 507 424
H2O 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
Reheater Heat Duty = 4 142 123 2 942 536
= 1 199 587 kJ/h
Note: At 246C, the molecul ar di stri buti on of sul fur vapor
speci es (Fig. 22-19) i s 0.255 S
6
and 0.745 S
8
.
Step 5 1st Catalytic Converter
I n the temperature range of 204C-371C prevai l ing i n the
catalyti c reactors, the Cl aus reacti on equil i bri um invol ving
formati on of S
2
, S
6
, and S
8
should al l be used i n equi li bri um
cal cul ati ons. However, a good approxi mati on i s obtai ned (usu-
al ly wi thi n 1% total overal l conversi on) if onl y the reacti on to
form S
8
i s consi dered.
Assume y mol s of H
2
S react.
2 H
2
S
y

+

SO
2
1

2
y



2 H
2
O
y

+

3

8
S
8
3

16
y
H @ 25C = 104 774 kJ
Feed Gas @ 246C
Outl et Condi ti ons
kmol s/h
kmol s/h
H2S 26.33 26.33 y
CO2 72.19 72.19
H2O 133.44 133.44 + y
SO2 13.17 13.17 y/2
N2 264.36 264.36
S6 0.12
S
8
0.34 0.43 + (
3

16
)y
509.95 509.92 0.3125y
at equi li bri um
K
p
=
[H
2
O]
2
[S
8
]
3/8
[H
2
S]
2
[SO
2
]

total mol s

3
8
1
=
[133.44 + y]
2
[0.43 + (
3

16
) y]
3/8
[26.33 y]
2
[13.17 y/2]

[121.59]
[509.92 0.3125y]

5/8
FIG. 22-27
Calculation of Reaction Furnace Temperature
22-26
y, mol s/h
(assumed)
Kp
(cal cul ated)
Equi l i br i um
Temperatur e
(fr om Fi g. 22-25)
16.33 31 507 313.9C
17.24 43 274 304.4C
18.15 60 910 296.7C
For each assumed value of y, calculate the total outl et
stream enthal py (usi ng the data i n Fi g. 22-26) and the overall
converter heat bal ance. For example, for y = 17.24 kmol s/h
Outl et Str eam
kmol s/h
H @ 304.4C
kJ/kmol kJ/h
H2S 9.09 10 894 99 026
CO2 72.19 12 772 922 011
H2O 150.68 10 528 1 586 359
SO2 4.55 13 428 61 097
N2 264.36 8 947 2 365 229
S6 1.41 26 496 37 359
S8 2.61 34 471 89 970
504.89 5 161 051
Heat Bal ance
Heat I n (fr om Step 4) = 4 142 123 kJ/h
Cl aus Reacti on (17.24/2)(104 774) = 903 152 kJ/h
Total Heat Out = 5 045 275 kJ/h
NOTE: At 304.4C, the mol ecul ar di stri buti on of sul fur spe-
cies (Fi g. 22-19) is 0.35 S
6
and 0.65 S
8
.
These calculated values are plotted in Fig. 22-30. By interpo-
lation, a value of y = 17.6 kmols/h meets both equilibrium and
thermodynamic conditions and the converter outlet temperature
is 301.7C (K
p
48 220). [NOTE: At 304.4C, the molecular dis-
tribution of sulfur species is 0.345 S
6
and 0.655 S
8
.]
Conver ter Outl et
kmol s/h
H@ 301.7C
kJ/kmol kJ/h
H2S 8.775 10 789 94 673
CO2 72.187 12 642 912 588
H2O 150.998 10 431 1 575 060
SO2 4.387 13 296 58 330
N2 264.360 8 866 2 343 816
S6 1.384 26 245 36 323
S8 2.627 34 153 89 720
504.718 5 110 510
Step 6 2nd Sulfur Condenser
Repeat procedure of Step 3.
Step 7 2nd Reheater
Repeat procedure of Step 4.
Step 8 2nd Catalyst Converter
Repeat procedure of Step 5.
These cal cul ati on steps are conti nued for the number of
catalyti c converter stages being uti l ized. For thi s exampl e, a
three-stage pl ant i s assumed and the total cal cul ated conver -
si on effi ci ency i s about 98%. Total recovery effi ci ency, after
FIG. 22-28
Heat of Dissociation of Sulfur Vapor Species
22-27
al lowi ng for sul fur vapor l osses and about
1

2
% for l i qui d sulfur
entrai nment, i s about 97% and the tai l gas composi ti on i s ap-
proxi matel y as fol l ows:
kmol s/h
H @ 148.9C
kJ/kmol kJ/h
H2S 1.76 5 153 9 069
CO2 72.19 5 834 421 156
H2O 158.01 5 048 797 634
SO2 0.88 6 201 5 457
N2 264.36 4 344 1 148 380
S6 (vapor ) 0.009 12 696 114
S8 (vapor ) 0.010 16 514 165
Sli q (as S1) 0.635 8 871 5 633
497.85 2 376 342
Thi s is the feed to the incinerator. Assumi ng 50% excess ai r
(based upon combustibl es) and an outl et temperature of
538C, the fuel gas requi rement and stack gas vol ume can be
cal cul ated as fol l ows:
Step 1. Calculate oxygen required for combustibles in feed gas
H
2
S +
3

2
O
2
H
2
O + SO
2
from Eq 22-2
H @ 25C = 518 757 kJ
S
1
+ O
2
SO
2
Eq 22-10
H @ 25C = 595 489 kJ
H
2
S: 1.5 (1.76) = 2.640 kmols/h O
2
S
1
: 1.0 (1.488) = 1.488 kmols/h O
2
4.128 kmols/h O
2
+ 50% = 6.192 kmols/h O
2
Feed Ai r
kmol s/h kmol s/h
H @ 37.8C
kJ/kmol kJ/h
H2S 1.76
CO2 72.19
H2O 158.01 0.876 1 267.9 1 111
SO2 0.88
N2 264.36 23.28 1 100.5 25 620
S (as S1) 1.488
O2 6.19 1 108.4 6 861
498.69 30.35 33 592
FIG. 22-29
Molar Heat of Condensation of S
6
and S
8
22-28
Products
kmol s/h
H @ 538C
kJ/kmol kJ/h
H2S
CO2 72.19 24 292 1 753 639
H2O 160.65 19 262 3 094 440
SO2 4.13 25 205 104 097
N2 287.65 16 111 4 634 329
S (as S1)
O2 2.06 16 946 34 909
526.68 9 621 414
Heat Balance
Heat Out 9 621 444 kJ/h
Heat In
Feed @ 148.9C 2 376 342 kJ/h
Ai r @ 37.8C 33 592 kJ/h
H
2
S Combusti on 1.76 (518 757) = 913 012 kJ/h
S
1
Combustion 1.488 (595 489) = 886 088 kJ/h
4 209 034 kJ/h
Heat Gai ned by Feed Gas 5 412 380 kJ/h
Step 2. Cal cul ate net heat rel ease for fuel (assumed to be meth-
ane) at 50% excess ai r, using 10 mol s/h as the base rate.
CH
4
+ 2 O
2
CO
2
+ 2 H
2
O
H @ 25C = 802 596 kJ
Fuel
kmol s/h
H @ 37.8C
kJ/kmol kJ/h
CH4 10.0 1340 13 400
CO2
O2
N2
H2O
10.0 13 400
Ai r
kmol s/h
H @ 37.8C
kJ/kmol kJ/h
CH4
CO2
O2 30.0 1108.4 33 252
N2 112.81 1100.5 124 147
H2O 4.24 1267.9 5 376
147.05 162 775
Combusti on Pr oducts
kmol s/h
H @ 538C
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
Heat Balance
Heat In
Fuel 13 400 kJ/h
Air 162 775 kJ/h
C
1
Combusti on 10 x 802 596 8 025 960 kJ/h
8 202 135 kJ/h
Heat Out 2 696 773 kJ/h
Net Heat Rel ease of Fuel 5 505 362 kJ/h
Step 3. Calcul ate fuel requirement and stack gas rate and com-
posi tion
Fuel required =
Heat gained by feed gas
Net Heat Release of Fuel
(10 mol s / h)
=
5 412 380
5 505 362
(10) = 9.83 kmol s / h
Stack Gas
kmol s/h mol %
CO
2
82.01 12.04
H
2
O 184.47 27.09
SO
2
4.13 0.61
N
2
398.52 58.51
O
2
11.89 1.75
681.03 100.00
FIG. 22-30
Calculation of Converter Outlet Temperature
22-29
Total Heat Rel ease
Fuel = 9.83 (802 596) = 7 889 579 kJ/h
H
2
S (From Step 1) 913 240 kJ/h
S (From Step 1) 886 211 kJ/h
9 688 970 kJ/h
SULFUR PRODUCT SPECIFICATIONS
A sul fur product meeti ng the fol lowi ng specifi cati ons wi ll
normal l y sati sfy the requi rements of the major consumers of
sul fur such as manufacturers of sul furic aci d, chemi cal s, fer -
til i zers, etc.:
Puri ty 99.5%-99.9% by wei ght (dry basi s)
Acidi ty (as H
2
SO
4
) Less than 0.01% by wei ght
Moi sture Less than 1.0% by weight
Ash Less than 0.05% by wei ght
Carbonaceous Matter Less than 0.025% by wei ght
Arseni c, Tel lurium,
Seleni um Commerci all y Free*
Col or (see Note bel ow) Bright yell ow at ambi ent
temperature
*Contents of l ess than 0.25 ppmw of arsenic and 2.0 ppmw of
sel eni um and tel lurium are usual l y consi dered as "commer -
cial l y free."
NOTE: The col or of sul fur i s an i mportant property because
i t gi ves an i mmedi ate i ndi cati on of product purity. The sul fur
i s a bright yel l ow i f the i mpurity content i s less than about
0.02% by wei ght. Small amounts of carbon (soot) change the
bri ght yel l ow col or to dull yel low or green; "dark" sul fur in
whi ch the yel l ow col or has a shade of gray or brown usuall y
contai ns 0.1%-0.5% by wei ght of carbon. For sul furi c aci d
manufacturers, however, sul fur color i s usual ly less i mportant
than ash and heavy metal contents.
INSTRUMENTATION
Si nce the quanti ty of aci d gas being handl ed by the sulfur
recovery uni t is determined by upstream sweeteni ng faci l i ti es,
the sul fur plant feed gas rate i s normal ly not control l ed. How-
ever, duri ng startup or i n an emergency, part or all of the feed
gas can be di rected to fl are.
For the mai n burner, the vol ume of feed gas is measured and
the amount of ai r i s control led in rati o wi th the amount of aci d
gas. Both feed-forward
25
, i n whi ch the measured feed gas flow
rate and assumed composi ti on are used, and feed-back, in
whi ch the measured ratio of H
2
S:SO
2
i n the pl ant tai l gas i s
used, can be uti li zed to adjust the ai r/feed gas rati o for maxi -
mum sulfur recovery. A combi nati on feed-forward/feed-back
control system, i n whi ch the feed gas fl ow rate i s used to con-
trol a mai n ai r valve and to set an approxi mate air/feed gas
rati o and the rati o of H
2
S:SO
2
i n the tai l gas i s used to control
a tri m ai r val ve, i s often uti l i zed.
For i nl i ne burners, the process stream temperature i s nor -
mal l y used to adjust the combusti on air rate and the amount
of fuel (ei ther aci d gas or fuel gas) i s control l ed i n rati o wi th
the amount of ai r. Because these burners normal l y operate
wi th a near substoi chi ometri c ai r, thi s control system wi ll re-
sul t i n a more rapid response to changes i n process require-
ments.
Although conventi onal ori fi ce meters can be used for aci d
gas and ai r measurement, the venturi meter i s often more sui t-
able. Thermocouples are used for most temperature measure-
ments and a mul ti poi nt stri p chart temperature recorder can
be useful to operati ons by indicati ng trends. Tai l gas anal yzers
(for H
2
S and SO
2
) are usual l y of the ul travi ol et type al though
chromatographi c anal yzers have been util i zed successful l y.
Except at the front of the pl ant and on ai r, aci d gas or fuel gas
systems, pressure gauges are not normal l y i nstal l ed. Sample
connections shoul d be as short as possi ble; sample val ves
should be plug val ves. Sampl e connections and val ves shoul d
be ful l y steam-jacketed.
Measurement of reacti on furnace temperature i s someti mes
used as an indicati on of satisfactory ai r/aci d gas control . Both
thermocoupl es and i nfra-red type i nstruments have been uti l -
i zed; however, thermocoupl e l i fe i s short (6-9 months reported)
and the response ti me for i nfra-red i nstruments can be poor.
Conventi onal i nfra-red instruments often can be util i zed as
flame moni tori ng devi ces for both the mai n burner and the
i nli ne burners; combi nati on i nfra-red/ul travi ol et (fl icker-type)
i nstruments have also been used successful ly.
OPERATIONAL ASPECTS
Overall Cl aus pl ant conversi on effi ciency i s maxi mi zed by
mai ntai ni ng the stoi chi ometri c H
2
S:SO
2
rati o of 2:1 in the
process gas to the catalyti c converter s. The most sui table poi nt
for thi s determi nati on i s at the outlet of the l ast sul fur con-
denser because a sl i ght change i n the ai r:acid gas rati o at the
front of the pl ant wi l l resul t i n a signi fi cant change i n the
H
2
S:SO
2
ratio i n the tai l gas and in the theoretical overall
sul fur recovery (Fi g. 22-31). An H
2
S:SO
2
rati o i n the tai l gas
of between 1:1 and 3:1 can be consi dered normal al though the
desired goal shoul d be a 2:1 rati o.
A si mpl e method of determi ni ng the H
2
S:SO
2
rati o i s by the
use of stai n tubes. Thi s determinati on shoul d be done at l east
once every 8 hours duri ng startup, pl ant test runs, and when-
ever signi fi cant changes i n pl ant operati ng vari abl es are ob-
served. Other anal ytical procedures invol ving wet chemistry,
chromatography, or UV photometry are also sui tabl e for ad-
justing pl ant operations.
Because of the effect of temperature upon the Claus reacti on
equi l i bri um, control of temperatures at vari ous poi nts i n the
process sequence i s i mportant. Unexpected changes i n oper -
ati ng temperatures usual l y denote changes i n conversi on ef-
fici ency. For exampl e, a decrease in the temperature ri se
across a catalyti c converter bed i s an indicati on of decl i ning
catalyst acti vi ty which may be caused by adsorption of el emen-
tal sul fur on the acti ve surface area of the catal yst. Operating
the catalyst bed at a temperature 28-56C hi gher than normal
for 24-48 hours wi l l remove this sulfur from the catalyst and
can restore its acti vi ty.
CLAUS PLANT MAINTENANCE
Maintenance and repai r of Cl aus pl ant equi pment requi res
speci al precautions because of the physical properti es of sulfur
and the potenti al hazards and/or toxici ty of many pl ant proc-
ess streams. Equi pment handl i ng l iqui d sulfur shoul d be
drai ned compl etel y and other equipment shoul d be purged of
al l hazardous materi als (see shutdown porti on of this secti on).
22-30
A sati sfactory wel di ng procedure can i nvol ve sandbl asting
and/or grinding to a bare metal surface, extensi ve preheati ng,
and the use of Type 309 stai nl ess steel rod.
REFERENCES
1. Maddox, R. N., Vol . 4, Gas and Liquid Sweetening, Campbel l Pe-
tr ol eum Seri es, Apr i l 1977
2. Gamson, B. W. and El ki ns, R. H., "Sul fur fr om Hydr ogen Sul fi de",
Chemi cal Engi neeri ng Progress, Vol . 49, No. 4, Apri l 1953, 203-
215
3. Val des, A. R., "A New Look at Sul fur Pl ants", Hydrocar bon Pr oc-
essi ng and Petr ol eum Refi ner, Vol . 43, 104-108, (Mar ch 1964),
122-124, (Apr i l 1964)
4. Eastman, E. D. and McGavock, W. C., J. Am. Chem. Soc., Vol . 59,
145-151 (1937)
5. Lewi s, G. N. and Randal l , M., J. Am. Chem. Soc., Vol . 33, 476-488
(1911)
6. Dal i n, G. A. and West, J. R., J. Phys. and Col l oi d Chem., Vol . 54,
1215-1221 (1950)
7. Stul l , D. R., I nd. Eng. Chem., Vol . 41, 1468-1473 (1949)
8. Stul l , D. R., Pr ophet, H., et al , JANAF Ther mochemi cal Tabl es,
Nati onal Bureau of Standards (1971)
9. West, W. A., and Menzi es, A. W. C., J. Phys. Chem., Vol . 33, 1880-
1892 (1929)
10. Kel l ey, K. K., The Ther modynami c Pr operti es of Sul phur and I ts
I nor gani c Compounds, Bul l eti n 406, U.S. Bur eau of Mi nes (1937)
11. Kobe, K. A. and Long, E. G., Petr ol eum Refi ner, Vol . 28, No. 2,
113-116 (Feb. 1949); Vol . 28, No. 11, 127-132 (Nov. 1949); Vol . 29,
No. 1, 126-130 (Jan. 1950)
12. Fanel l i , R., I nd. Eng. Chem., Vol . 38, 39 (1946) and Vol . 41, 2031
(1949)
13. Lagas, J. A., Stop Emi ssi ons fr om Li qui d Sul fur, Hydrocar bon
Processi ng, Vol . 61, 85-89 (October 1982)
14. Goar, B. G., Sul fur Formi ng and Degassi ng Processes, 1984 Gas
Condi ti oni ng Confer ence, Uni ver si ty of Okl ahoma
15. Goar, B. G., and Sames, J. A., Tai l Gas Cl ean Up Pr ocesses A
Revi ew, 1983 Gas Condi ti oni ng Confer ence, Uni versi ty of Okl a-
homa
16. West, J. R., I nd. Eng. Chem., Vol . 42, 713-718 (Apr i l 1950)
17. Ki ng, F. W., Oi l & Gas J., Vol . 72, 164-165 (June 3, 1974)
18. Ruber o, P. A., J. Chem. Eng. Data, Vol . 9, 481-484 (1964)
19. Par nel l , D. C., Hydr ocar bon Pr ocessi ng, Vol . 64, 114-118 (Sept.
1985)
20. For d, G. P., and LaMer, V. K., J. Phys. Chem., Vol . 72, 1959-1964
(1950)
21. Johnston, H. E., Kel l ey, M. D., and McKi nl ey, D. L., I nd. Eng.
Chem., Vol . 42, No. 11, 2298-2302 (1950)
22. Wi ewi orowski , T. K. and Tour o, F. J., J. Phys. Chem., Vol . 70,
No. 1, 234-238 (1966)
23. Ando, M. and Kawahara, H., Hydr ocar bon Pr ocessi ng, Vol . 55,
90-92 (December 1976)
24. Sol i nhac, J., Fr Patent No. 1435788 (1964)
25. Dougherty, J. F. and Mor gan, D. J., Oi l & Gas J., Vol . 78, 68-70
(May 26, 1980)
26. Kel l as, A. M., J. Chem. Soc., Vol . 113, 903-922 (1918)
27. Kettner, R., Li er mann, N., New Cl aus Tai l -Gas Pr ocess Proved
i n Ger man Oper ati ons, Oi l & Gas Jour nal , Jan. 11, 1988, p 63-
66.
28. Ber ben, P.H., Bor sboom, J., Lagas, J.A., SUPERCLAUS, the An-
swer to Cl aus Pl ant Li mi tati ons, 38th Canadi an Chemi cal En-
gi neer i ng Confer ence, Oct. 2-5, 1988.
BIBLIOGRAPHY
1. Lewi s, G., Randal l , M., Ther modynami cs and the Fr ee Ener gi es
of Chemi cal Substances, pp. 530-550, McGr aw Hi l l (1923)
2. Tul l er, Wi l l i am N. (Edi tor ), The Sul phur Data Book, McGr aw Hi l l
(1954)
3. Gr ekel , H., Pal m, J. W., and Ki l mer, J. W., Oi l & Gas J., Vol . 66,
88, 93-95, 97, 98, 101 (October 28, 1968)
4. Gr ekel , H., Kunkel , L. V., and McGal l i ar d, R. L., Chem. Engr.
Prog., Vol . 61, 70-73 (September 1965)
5. Opekar, P. C. and Goar, B. G., Oi l & Gas J., Vol . 64, 86-89 (May 2,
1966)
6. Nor man, W. S., Oi l & Gas J., Vol . 74, 55-60 (November 15, 1976)
7. Kni ght, W. P., Hydr ocar bon Pr ocessi ng, Vol . 57, 239-241 (May
1978)
8. Chute, A., Hydrocar bon Processi ng, Vol . 56, 119-124 (Apr i l 1977)
9. Tr an, J. C., Hydr ocarbon Pr ocessi ng, Vol . 61, 91-97 (January
1982)
10. Taggar t, G. W., Hydr ocar bon Pr ocessi ng, Vol . 60, 155-157 (Mar ch
1981)
11. Taggar t, G. W., Hydr ocarbon Pr ocessi ng, Vol . 59, 135-137 (Apr i l
1980)
12. Chao, J., Hydr ocar bon Pr ocessi ng, Vol . 59, 217-223 (November
1980)
13. Mei sen, L. and Bennett, H., Hydr ocar bon Pr ocessi ng, Vol . 53,
171-174 (November 1974)
14. Goar, B. G., Hydr ocar bon Pr ocessi ng. Vol . 53, 129-132 (Jul y 1974)
FIG. 22-31
Plot Showing That a Slight Change in Air to Acid Gas
Ratio at the Head End of the Plant Will Make a Significant
Change in the Tail Gas Ratio, H
2
S:SO
2
22-31
15. Pal m, J. W., Hydr ocar bon Pr ocessi ng, Vol . 51, 105-108 (Mar ch
1972)
16. Sol omon, P., Oi l & Gas J., Vol . 71, 85-90 (August 27, 1973)
17. Goar, B. G., Hydr ocar bon Pr ocessi ng, Vol . 47, 248-252 (Septem-
ber 1968)
18. Sudduth, L. F., Far mer, S. K., and Gr ekel , H., Oi l & Gas J., Vol . 68
(December 14, 1970)
19. Raymont, M. E. D., Hydrocar bon Pr ocessi ng, Vol . 54, 177-179
(May 1975)
20. Ker r, R. K. and Paskal l , H. G., Ener gy Pr ocessi ng/Canada, 38-44
(Nov.-Dec. 1976)
21. Ker r, R. K. and Ber l i e, E. M., Energy Processi ng/Canada, 42-46
(May-June 1977)
22. Fi scher, H., Hydr ocar bon Pr ocessi ng, Vol . 58, 125-129 (Mar ch
1979)
23. Pearson, M. J., Ener gy Processi ng/Canada, 38-42 (Jul y-August
1976)
24. Ker r, R. K., Paskal l , H. G. and Bal l ash, N., Ener gy Pr ocess-
i ng/Canada, 40-51 (Jan.-Feb. 1977)
25. Ker r, R. K., Energy Pr ocessi ng/Canada, 28-34 (Jul y-August
1976)
26. Fi scher, H., Hydr ocar bon Pr ocessi ng, Vol . 53, 125-130 (October
1974)
27. Par nel l , D. C., Chem. Eng. Pr og., Vol . 69, 89-92 (August 1973)
28. Hayfor d, J. S., Hydr ocarbon Pr ocessi ng, Vol . 52, 95-96 (October
1973)
29. Hyne, J. B., Proc. 51st Annual Conventi on NGPA, 85-94 (1972)
30. Bal l , F. J., Br own, G. N., Davi s, J. E., Repi k, A. J., and Tor r ence,
S. L., Hydr ocar bon Pr ocessi ng, Vol . 51, 125-127 (October 1972)
31. Zey, A., Whi te, S. and Johnson, D., Chem. Eng. Prog., Vol . 76,
76-78 (October 1980)
32. Goddi n, C. S., Hunt, E. B. and Pal m, J. W., Pr oc. 53r d Annual
Conventi on GPA (1974)
33. Nobl es, J. E., Pal m, J. W., Knudtson, D. K., Hydrocar bon Pr oc-
essi ng, Vol . 56, 143-145 (Jul y 1977)
34. Andr ews, E. J. and Kouzel , B., Pr oc. 53rd Annual Conv. GPA
(1974)
22-32