V.

Sulfur and Sulfur Compounds

sulfur one of the important basic raw materials in the chemical industry

sulfur compounds used in the manufacture of wood pulp, insecticides,

bleaching agents, vulcanized rubber, detergents, pharmaceutical products, dyes

A. Sources of Sulfur

1. Mined, as either
a. raw sulfur pure sulfur plus inert materials
b. sulfide ores, e.g. pyrite (FeS2), sphalerite (ZnS), chalcopyrite (CuFeS2)

Frasch method process for extracting sulfur developed by Herman

Frasch and first used in 1894
three pipes, one inside another, are sunk to the bottom
of the sulfur bed. Water heated under pressure to a temperature well
above the melting point of the sulfur (>160C) is conducted down the outer
pipe, and air under pressure down through the innermost pipe. The heated
water melts the sulfur and the compressed air forces it through the middle
pipe to the surface.

2. Obtained as H2S from the desulfurization of crude oil and natural gas. The
H2S is converted to pure S using the Claus process. At present, more than
half of the worlds supply of sulfur is recovered from this process.

B. Processes

Sulfur is usually burned to SO2 and SO3 first before it is converted into
other compounds.
 air

sulfur SO2 SO2

SO3 catalytic more SO3
(raw sulfur burner
O2 converter O2
or pyrite)
N2 N2

absorption contact
tower tower

bisulfites sulfuric acid solution

(Ca(HSO3)2, Mg(HSO3)2) (H2SO4, H2O)
sulfates oleum
(CaSO4, MgSO4) (H2SO4, SO3)

Summary of processes:

1. Burning of raw sulfur

2. roasting of pyrites
3. Bisulfite and sulfate production
4. Conversion of SO2 to SO3
5. Sulfuric acid production

Table 6-1, page 167: heats of formation of sulfur compounds

Figure 6-1: page 168: average molal heat capacities

C. Burning of Raw Sulfur

Under normal furnace conditions, much of the sulfur is oxidized to SO2. A

small percentage (2 to 10%) may be further oxidized to SO3.

S + O2 SO2
3
S + O2 SO3
2

During analysis, the SO3 in the product gases condenses in the presence
of H2O.

SO3 + H2O H2SO4

The resulting analysis is usually reported on an SO3-free basis.

 theoretical/excess oxygen based on the conversion of S to either SO2
or SO3, which must be clearly stated in the problem

e.g. Raw sulfur analyzing 95% S and 5% inerts is burned with 65% excess air
(SSO2). Analysis of the cinders shows 10% S and 90% inerts. 88% of the S
gasified burns to SO2, the rest to SO3. Determine the analysis of the burner
gases on an SO3-free basis. Also, determine its complete analysis.

Given:
air
65% xs (SSO2)

raw sulfur burner gases

95% S burner 88% SSO2
5% inerts

cinders
10% S
90% inerts
Required: a. analysis burner gases, SO3-free
b. complete analysis burner gases

Solution:

Basis: 100 lb raw sulfur

lb MW mol
S 95 32 2.97
inerts 5 - -
total 100 - -

1 lbmol O2
mol theo O 2 = 2.97 lbmol S
lbmol S
= 2.97 lbmol O2
mol O2 supplied = 1.65 2.97 lbmol O2
= 4.90 lbmol O2

Inerts balance:

5 lb = 0.90 mass cinders

mass cinders = 5.56 lb
 mass S in cinders = 0.10 5.56 lb
= 0.56 lb S
mass S gasified = 95 lb 0.56 lb
= 94.44 lb S
1 lbmol
mol S gasified = 94.44 lb S
32 lb
= 2.95 lbmol S
Burner gases:
1 lbmol SO2
mol SO2 = 0.88 2.95 lbmol S
lbmol S
= 2.60 lbmol SO2
1 lbmol SO3
mol SO3 = 0.12 2.95 lbmol S
lbmol S
= 0.35 lbmol SO3
O2 balance:
1 lbmol O2 3 lbmol O2
4.90 lbmol O2 = 2.60 lbmol SO2 + 0.35 lbmol SO3 +
lbmol SO2 2 lbmol SO3
mol free O2
mol free O2 = 1.78 lbmol O2

N2 balance:
0.79 lbmol N2
4.90 lbmol O2 = mol N2 in burner gas
0.21 lbmol O2
18.43 lbmol N2 = mol N2 in burner gas

Orsat analysis burner gas, SO3-free:

mol mol %
SO2 2.60 11.40
O2 1.78 7.80
N2 18.43 80.80
total 22.81 100 a

Complete Orsat analysis burner gas:

mol mol %
SO2 2.60 11.23
SO3 0.35 1.51
O2 1.78 7.69
N2 18.43 79.58
total 23.16 100.01 b
e.g. Burner gases resulting from the burning of sulfur have the following dry
analysis: 9.14% SO2, 10.66% O2, and 80.20% N2. Calculate the percent
conversion of S to SO2 and the percent excess air used (SSO2).

Given:
air

burner gases
dry, SO2-free basis:
S burner SO2 9.14%
O2 10.66%
N2 80.20%

cinders
Required: a. % conversion SSO2
b. % xs air (SSO2)

Solution:

Basis: 100 lbmol dry SO3-free burner gas

mol mol O2
SO2 9.14 9.14
O2 10.66 10.66
N2 80.20 -
total 100 19.80

No N2 from feed. N2 balance:

mol N2 from air = 80.20 lbmol N2

0.21 lbmol O2
mol O2 supplied = 80.20 lbmol N2
0.79 lbmol N2
= 21.32 lbmol O2
mol O2 unaccounted for = 21.32 lbmol O2 19.80 lbmol O2
= 1.52 lbmol O2
= mol O2 in SO3
2 lbmol SO3
mol SO3 = 1.52 lbmol O2
3 lbmol O2
= 1.01 lbmol SO3

Assume all S in feed gasified.

S balance:
1 lbmol S 1 lbmol S
mol S in feed = 9.14 lbmol SO2 + 1.01 lbmol SO3
lbmol SO2 lbmol SO3
= 10.15 lbmol S
1 lbmol S
9.14 lbmol SO2
lbmol SO2
% S SO2 = 100
10.15 lbmol S
= 90.05% a

1 lbmol O2
mol theo O 2 ( S SO2 ) = 10.15 lbmol S
lbmol S
= 10.15 lbmol O2
21.32 lbmol O2 10.15 lbmol O2
% x's O2 ( S SO2 ) = 100
10.15 lbmol O2
= 11 0.05% b

e.g. A plant burns sulfur which is 99.4% pure at the rate of 680 lb per hour. The
average air temperature is 60F. The gases emerge from the burner at 760C
and are found to contain 17.4% SO2 and 2.7% O2 when analyzed in the usual
way. The gases then pass to a cooler, which reduces their temperature to 70F
by means of water which rises from 58F to 90F. Calculate:
a. the percent of the sulfur burned to SO3
b. the pounds per hour of SO2 leaving the burner
c. the air consumption in cubic feet per minute
d. the cubic feet per minute of gas leaving the burner and the cubic feet per
minute leaving the cooler
e. the heat dissipated from the burner in BTU per hour
f. the water used in the cooler in gallons per hour

Given:
air, 60F water, 58F

raw sulfur
680 lb/hr burner cooler burner gases
99.4% S burner gases 70F
760C
SO2 17.4%
cinders O2 2.7% water, 90F
Required: a. % S burned to SO3
b. lb/hr SO2
c. ft3 /min air
d. ft3/min burner gases leaving the burner, ft3/min burner gases
leaving the cooler
e. heat loss from burner, BTU/hr
f. gal/hr water

Solution:

Basis: 100 lbmol dry, SO3-free burner gases

mol mol O2
SO2 17.4 17.40
O2 2.7 2.70
N2 79.9 -
total 100 20.10

No N2 from raw sulfur. N2 balance:

mol N2 from air = 79.90 lbmol N2

0.21 lbmol O2
mol O2 supplied = 79.90 lbmol N2
0.79 lbmol N2
= 21.24 lbmol O2
mol O2 unaccounted for = 21.24 lbmol O2 20.10 lbmol O2
= 1.14 lbmol O2
= mol O2 in SO3
2 lbmol SO3
mol SO3 = 1.14 lbmol O2
3 lbmol O2
= 0.76 lbmol SO3

Assume all S in raw sulfur gasified.

S balance:
1 lbmol S 1 lbmol S
mol S in raw sulfur = 17.4 lbmol SO2 + 0.76 lbmol SO3
lbmol SO2 lbmol SO3
= 18.16 lbmol S
1 lbmol S
0.76 lbmol SO3
lbmol SO3
% S SO3 = 100
18.16 lbmol S
= 4.19% a
Basis: 1 hr operation

total mass raw sulfur = 680 lb

Raw sulfur:

lb MW mol
S 675.92 32 21.12
inerts 4.08 - -
total 680 - -

% S SO2 = 100% 4.19%

= 95.81%
1 lbmol SO2
mol SO2 in burner gases = 0.9581 21.12 lbmol S
lbmol S
= 20.24 lbmol SO2
64 lb
20.24 lbmol SO2
mass SO2 lbmol
=
hr 1 hr
1,295.36 lb
= b
hr
100 lbmol burner gases
mol burner gases (SO3 -free) = 20.24 lbmol SO2
17.4 lbmol SO2
= 116.32 lbmol

Burner gases:

mol
SO2 20.24
O2 3.14
N2 92.94
total 116.32

mol N2 from air = 92.94 lbmol N2

1 lbmol dry air
mol dry air = 92.94 lbmol N2
0.79 lbmol N2
= 117.65 lbmol

Assume: Air supplied is dry, PT = 1 atm

 359 ft 3 ( 60 + 460R )
117.65 lbmol
vol dry air lbmol 492R 1 hr
=
min 1 hr 60 min
744 ft 3
= c
min

1 lbmol SO3
mol SO3 in burner gases = 0.0419 21.12 lbmol S
lbmol S
= 0.88 lbmol SO3
total mol burner gases = 116.32 lbmol + 0.88 lbmol
= 117.20 lbmol

9
Tburner gases = 760C + 32
5
= 1400F
359 ft 3 (1400 + 460R )
117.20 lbmol
vol burner gases lbmol 492R 1 hr
=
min 1 hr 60 min
2651 ft 3
= d
min
vol cooled burner gases 2651 ft 3 70 + 460R
=
min min 1400 + 460R
3
755 ft
= d
min

Energy balance around burner:

air, 60F
heat loss

burner burner gases

raw sulfur 1400F

cinders

Hformation = Hburner gases + Qloss

Qloss = Hformation Hburner gases
Heats of formation from (Table 6-1):

70,920 cal
S + O2 SO2
gmol
3 93,900 cal
S + O2 SO3
2 gmol

Basis: 1 hr

mol SO2 = 20.24 lbmol SO2

mol SO3 = 0.88 lbmol SO3
454.5 gmol 70,920 cal 1 BTU
Hformation = 20.24 lbmol SO2 +
lbmol gmol 252 cal
454.5 gmol 93,900 cal 1 BTU
0.88 lbmol SO3
lbmol gmol 252 cal
= 2,737,917 BTU

Enthalpy burner gases at 1400F:

Figure 6-1: cpave of SO2, SO3

Figure 1-3: cpave of O2, N2

n cpave, 1400F ncpave(1400-60)

SO2 20.24 11.7 317,323
SO3 0.88 17.0 20,046
O2 3.14 7.7 32,399
N2 92.94 7.3 909,139
total 117.2 - 1,278,907

Hburner gases, 1400F = 1,278,907 BTU

Qloss = 2,737,917 BTU 1,278,907 BTU
1,459,010 BTU
= e
hr

Energy balance around cooler:

Assume: No heat loss

 water
58F

burner gases cooler burner gases

1400F 70F

water
90F
Hburner gases, 1400F + Hwater , 58F = Hburner gases, 70F + Hwater , 90F
Hwater , 90F Hwater , 58F = Hburner gases, 1400F Hburner gases, 70F

Assume: cp of water is constant

Hwater , 58F90F = Hburner gases, 1400F Hburner gases , 70F

Enthalpy burner gases at 70F:

n cpave, 70F ncpave(70-60)

SO2 20.24 9.4 1,903
SO3 0.88 11.8 104
O2 3.14 7.0 220
N2 92.94 7.0 6,506
total 117.2 - 8,733

Hburner gases , 70 F = 8,733 BTU

Hwater , 58 F90F = 1,278,907 BTU 8,733 BTU
= 1,270,174 BTU
= mwater cp T
1,270,174 BTU
mwater =
BTU
1 ( 90F 58F )
lb F
= 39, 693 lb
ft 3 7.48 gal
39,693 lb
vol water 62.3 lb ft 3
=
hr 1 hr
4,766 gal
= f
hr