Gas Proce!

Sing Developments
Claus plants prove flexible
Key design features can make for ease
of operation under diverse conditions
H. Fischer, Lurgi GmbH, Frankfurt a m Ma in,
W. Germany
LAUS S 1Lf R REC VERY plants pro ide fl xibi lit y to
meet most requir ment s wher hydrog n sulfiqe. must be
convert ed to !em nt ary sulfur. Part -load can b reduced to
less than 5% whil e additional gases cont aining other sulfur
ompounds (i.e., sour water stripp r gas) an be proce sed
wi thout fu rt h r treatment up to a ratio of 2: 1. l-1
2
S to S02 in
the tailgas. ll ydrocarbons, ammonia a nd cyanid can also
b fed in hi gh one ntrati ons without impairing sulfur qual-
ity. Such feeds a re li mi ted onl y by necessa ry a ir surplus sin e
residual oxygen and sulfur di oxid formed in the addi ti onal
gas is comp nsa ted by hydrog n sulfid in the main gas
str am. Hyd rog n sulfide cont ent s in feed gas to the sulfur
recov r y unit can vary t hni ally from almost 100 vol % to
around 5 vol %. Us of oxyg n in additi on t air is of great
advantag in tega rd to product improv mcnt , capacit y in-
crease, or inv stment reduction, not only in ranges below 20
vol % when one oxygen must be used,
1
but also in ranges
above 20 vol % .
The key to mast.ering th se methods of handling sulfurous
g.a s li e in burner equipm nt and c mbusti on chamb r de-
stgn.
FLEXIBLE CAPACITY
An 80 tpd Cla us plant with a Sulfreen tailgas unit is run-
Fig. 1-Ciaus-Sulfreen plant design.
ning troubl e-fro in tit load range of I OO.'f" to less than : %.
Sulfu r yi ld (Tabl e 1) 111 excess of 93.0 % arc obt atll d
from a feedstock of 90 % or more l-1
2
S, I % or le s hydrocar-
bons.
Load range
~ 5 0 %
30.0-36%
20.0-25%
9.5-10%
4.8-5.5%
TABLE 1
Sulfur yield, %
99.25- 99.3
99.3-99.6
99.5- 99.6
95.4-95.5
93.0- 95.0
At load ranges below 20 %, the pl ant (Fi g. 1) op rates
without the Sulfre n tailgas plant. Sour gas fr m a DEA re-
generator is pa sed through a separat or to th combustion
chamber burner. This speci al burner (Fig. 2) cont ains a
number of single burners arranged in a circle around a cen-
tral burner muffl e. Here, sour gas rca ts with appropri ate
quanti ti es of air. At minimum operati on (below 20 % load)
sour gas is rout ed through a separated ontrol system and
burner ti ps are inserted in some of th single burners. An
a ppropriate quant it y of r ' Cycle gas is withdrawn upstream of
the tail gas process through sulfur condenser and separat or
using th blower and preheated in th recycl e gas h ater or
regeneration gas heater. It is th ' n fed to th ingle burners
through the our gas line to keep the ingle burner cooled
and free of sulfur, to permit a suffi ci nt tr am of process gas
to be uniforml y applied to the downstream plant sections,
and to ma intain the operation tt: mperatu te. A suffi ient fire-
Hydrocarbon Processing, April 1985 79
Recyclo gas
An
Pilot burner Combustton chamber
Cornbu ' II n ch rnb r Reaction chamber
Fig. 2-Spectal Claus burner design.
box tcmpera tu rc is mai ntai ned and pla nt heat arc
orn p nsatecl fell by burnin , appropriate quantiti es of fuel
gas when the load fa ll s below 20% of capacity. Fuel gas com-
bustion mus t d finitely be free of soot to ensure production
of quality bri ght yellow sulfur. The quantity of air added
must be r_egulated to maintain an H
2
S/S0
2
ratio at 2/1 up-
stream of the thermal incineration. This air requirement
drop reatl y a th ' sour gas feed decrea es, therefore, at
loads of I . s tha n 10%, fuel must be burned soot free at
I ss tha n 70 If< of stoi biometri c at 5% load .
uit a ble bumers a rra nged in tll<' entral combustion
cha mber pro,i dt' thPs requirement s. Appropri ate steam
provides for n 'C sa ry soot-free combusti o n when fu f' l gases
ontamtn g h ydruca rb n are u cd . Th<' foll owing fuel gas i.-
used in the subject plant:
87.0vol %
6.8 vol %
0 .6 vol '}'(
5.6 , ol %
VVith a non- a rb nitre us gas such as o n containing hy-
dro e n and/or <'l rb n monoxi le, cracking st<'am i not re-
qu i reel .
Sulfttr yi Ids can be increased to more tha n 99% t"ven at
minimum loilcl:s by adapting the pl an t for usc of Sul freen
Tail gas operation . A separate blower musr recycle tailgas
throu h a ga o r hi gh-pressure team heater when the load
ra nge i under 20%. Recycle gas must be drawn off up-
stream of the the rma l incin rati on so that sufficient feed is
upJii ed to th rca tors of the Sulfreen plant. This met hod of
HP
80 Hydro arbon Pro P<; n
minimum op ration a lso appli s to oth r proces comhina-
ti ons such as Claus-Scot (Fig. 3).
DIVERSE FEEDSTOCKS
Claus plants must often poor quali ty feed . Ra"
mattri a l pri ces c::t us wirl swings in fced. l()rk compositi on
while Slatut or y r qu in:tnent funhn influe nce uptimwn uti
li zati on in a market. Thus, incrc:-s . ing quantitils of uyprod-
u ts such as ammoni a. cyanide, nwrcaptans, etc., appea in
sour wa ter tripper gas il lo ng- with important quant iti es
hydrogen sulfide. Howe\Tr, sur h gases dema nd pecial ha n-
clling in a Claus unit. The gas must b burned separately,
pa rticularl y with respect to ammo ni a , in orrln to 'et com-
plete co n,-crsion and to a n>icl bl o king gas fl ow with a mmo-
nium alt s. This is !'specia ll y tnt in t he colder catalytic a rea
or the reco,erv unit.
Use of sour ' water stripper is limited by a\'ailabilit y of
sulfur di oxide and the oxyge n needed for complte combus-
ti on. Each of th se compounds requires two volumes of hy-
drogen sulfid for optimum sulfur yield :
(2H
2
S + S0
2
= 2H
2
0 + 3/n S" or
2H2S + 0 2 = 2H20 + 2/n n)
A Claus-. cot plant is operated feeding a n Aclip wash from
a hydro racker complex run feeding vacuum gas oil and the
sour wate r stripper gas from thi s complex. Th ratio of the
gases , arie sign ificantly to an extreme of 1. 34: I volume o f
Claus gas to sour water strippe r gas. The pl ant capacity
135 tons of sulfur per day. so2 is guaranteed at les
tha n 55 kg/h a nd H
2
S in wa. te gas at below 10 The
mean composition of the gases is as shown in Tab! 2.
H2S
C0
2
co
H2
NH
3
N2
HC
H
2
0
TABLE 2
Claus gas, vol %
96.4
2.6
0. 1
0.2
0.4
03
Saturated at 40C
and p = 1.8 bar abs .
Sour water stripper
gas, vol%
27.2
28.0
0. 1
44.7
ulfur r icld wa tested at 99.8% with H
2
S in the wa te ga'
. fess tha n I ppn1 at an 0
2
content of 3.5 %.
Th i111plified pro e s diagram of thi s plant is shown in
Fig. 3-Ciaus and Sulfreen
combination flow.
Pdol burner Combus11on chomb r
Combust1on chamber ReactiOn chamber
Fig. 4-Ci aus burner adapted for oxygen supply.
Fi ' 3. Ri h Adip s lution fr m the cot absorber 1s rt' -
togethe r with t he rema ining Adip soluti on.
H ydrocarbon cont nt depends upon ori gin and t ype of
wa tc wa te r (leated . O ne C la us- ulfrecn pla nt handles a
s 1u r wat r stripper gas whi ch vari s thmugh the ra nges
shown in Table 3.
TABLE 3
3.6-12.2 vol %
13.2- 23.2 vol %
17.2- 4.5 vol %
66.0- 60. 1 vol %
Furth rmor , a ll hvdro arb n s from
0
::1 r r pre-
sent d in the gas. additi o n , th bus gas which is satu-
ra t d with steam a t 40 a nd a pre ure of 1.5 bar abs lu te ,
flu ctua t a lso. Th s a lso through the range hown in
' ! able 4.
TABLE 4
98.3- 97.4 vol %
1.3- 1.6vol%
0 .4- 1.0 vol %
In spite fth se fluctua t ions th sulfur yield from th plam
(similar to Fi g. I) opera ting a t full load is 9i.l to 9i.S% for
the C la us un it a nd 99. 1 to 9.5 % fo1 the ' lau a nd Sulfreen
units L g thcr.
Pr tlu t is of a good bri r )JI yell ow color. It conta ins the
impuriti s shown i n Table 5.
Ash
Fe
Si0
2
MS
Bitumen
Moisture
TABLE 5
1- 3 ppm
0.6- 1.67 ppm
0.22-0.72 ppm
10- 12 ppm
2-4 ppm
87- 124 ppm
An th r plant is designed fo r a bus gas and a sou r wate r
' ll ipplT ga as shown in Ti1hk 6.
The planr is sma ll with two reactor stages and a therlllal in -
cinera tor. Ca e on1 e fn rn Arni snl " " 'h dcsulfurization ol a
llla l ga. ifi a ti on stream .
:\'mural gas is a\a ilabk fue l ga fo r up the
pl a nt . Tht.: plant is in that it i de to be
hu down <ln wee ke nds. wh ik nl a int ai ning ten1pcraturc. b\
II"( Ulat td ine rt ga . h Co ll ' uppli cl bY em d ct
\' tl hcat<:r.
T h thcrnt a l inrinerati 11 is d es igned with flexibilit\ to
'' llld h e ither total combusti on o f' ta il g;r a lone o r" it h
'->t tl \,,orr r stripp r ga ..
1 ht incinerator is a lso des ig ned to run waste a ir, N I 1-
1
-
c. from a gas pre\\ a h , purg gas a nd analysi ga ;
TABLE 6
Sour water stri pper
Claus gas, vol % gas, vol %
co
2.46 2.27
C02
50.25 51.14
H2
0.98 1.14
CH, + C2H
0.57
N
2
+ Ar
5.95 4.54
H
2
S
34.17 4.54
cos
3.72 1.14
cs1
0.57
HCN
2.47 20.45
NH
3
13.64
CH
3
0H
Traces Traces
H20
Saturated at 40C Saturated at 90C
and p = 1.5 bar and p = 1.6 bar
of whi h the latt e r two cont a in large qual iti s o f hydrogen
hloritlc and hydrog n flu rid . Wast ' gases from this the r-
mal incin rati on are ' U to a large boil er unit at about
4-80 .
VARIABLE H
2
S FEEDS
H ,S conc>ntra ti o ns ca n flu ctuat from 20- iO , ol o/o de-
P ntiing on feed source. as to b clean d and abs rption
unit type I, ch mira! and physica l , or pure hemical)
. and d gr<'c of S'kcti\ity de te r llline the concentration of h -
dr sulfide in t!H.: fct:tl ga . a r iat i n in H
2
COII Ce ntrati n occuts whe re seve ra l ab orpt iun uni t s C , d th
laus unit. In surh cas s, specia l r quire me nt s are plac d
npon burner most nowbly whe n lt yclro a tb ns
of difC ring ompos ition are xpe t d. p ration with nor-
mal ombu tion air is tantl artl in high r H
2
r ang . Atten-
ti n i required to n sure only that good reacta nt mix ing is
obtai ned a nd that ombustion hambe r temperature do not
fa ll below the minimum required fo r usual s condary reac-
ti ons to ccur. How v r, in I wer oncentrat ions. oper ation
wit h pure a ir is only an xp di nt . oluti on e, en whe n ha n-
cll ing Claus gas fe d with indir ct pre heating of Claus ga
a nd combustion a ir, whil e wh n burning fuel gas to mai ntain
the necessar y f ire-box minimum tempe ra ture. Investme nt
costs and utiliti s consumption ri s consi d rably under thes
< onditi ons. A fa r b tt e r solution is to supply oxygen to im-
pr v combusti on . This r duces requ ir em nt s for pro ess
gas by lowering the a mount of air which , in tu rn , pe rmits a n
increase in pl a nt capaci ty. Further, operating te mpe ra tures
a re inereasetl in the ornbustion chambe1 causing a product
sulfur to be a be tt er purit y, e pecia ll y when hydrocarbo ns ar
present in the C la us feed.
Two 50 tpd la u s ot unit showed hi gh capacity after
having been revamped to pe rmit an additi onal supply of ox-
ygen to be used. Tests show that at between 20 a nd 50 vol %
H
2
S in the Claus gas, ca paci ti e a lmost doubled while prod-
uct quali t y improved. sp cia ll y in low con ce ntrati on
ran YC Oxvge n i su pplictl a t ra tes quival e nt to a theoreti -
;11 residua l oxyge n o n te nt in air of betwee n 21 and 45 vol
Pl ant ca p:1city lin1 its ha'T not y t b e n detnrninetl .
Principles of the special bu m -r equipment as used in these
pl :l tU S a n: shown in Fi g. 4.
LITERAl'l:RF. CITED
1
F1M' h4:r, 11. , "'ulfur \,tf\ \\' Uh ff;d,onuhon p, ortssmg. Vo l
'>8. Nn. l . 1\la.rh. l 'li'' J'(J l"lY
The aut hor
H. Fischer is Assistant Senior Manager and
/l ead of the Sulfur Recovery Department of
LURGI GMBH, Gas Technology Division Frank-
furt/Main, Federal Republic of Germany
Hydrocarbon Processi ng, April 1985 81