CHECAL2 SULFUR and its Compounds

Dr. Susan A. Roces AY 2017-2018

SULFUR AND ITS COMPOUNDS

Sources of Sulfur:
☻ Sulfur is usually found in meteorites.
☺ Dark area near the crater Aristarchus is a sulfur deposit.
☻ Occurs in the vicinity of volcanoes and hot springs.

Production of Sulfur:
☺ commercially recovered from wells sunk into the salt domes
along the Gulf Coast in the U. S.
☻ Frasch process uses heated water forced into the wells in order
to melt the sulfur which is then brought to the surface.
☻ occurs in natural gas and petroleum crudes
☺ large amounts of sulfur are recovered from Alberta gas fields

Uses of Sulfur:
☺ used to produce sulfuric acid, and one of the most important
and basic raw materials in the chemical process industries
☻ component of black gunpowder
☺ used in the vulcanization of natural rubber and a fungicide
☻ used extensively in making phosphatic fertilizers
☺ used to make sulfite paper and other papers, to fumigate, and
to bleach dried fruits
☺ essential to life, and it is a minor constituents of fats, body
fluids and skeletal minerals.

Types of sulfur:
1. free state as Raw Sulfur
2. combined in ores such as Pyrites

Sulfur Compounds:
Before conversion into its other compounds Raw Sulfur or Pyrites
are burned to give SO2 or SO3. The operations are similar in

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

principle to the combustion of carbon compounds, although

special furnaces have to be employed. Among the most important
applications of sulfur is in the manufacture of Sulfuric Acid,
Oleum and Bisulfites.

Burning of Raw Sulfur:

Raw sulfur is a combination of pure S and inert materials. When

sulfur is burned, the following reactions take place:

Main Reaction:
S + O2 = SO2 MW SO2 = 64

Side Reaction:
S + 3/2 O2 = SO3 MW SO3 = 80

Theoretical O2 calculations may be based on any of the above

reactions:

Theo O2 (S conversion to SO2) = Total at-S

Theo O2 (S conversion to SO3) = Total at-S x 3/2

The determination of the Excess O2 and % excess O2 should

identify whether the calculations are based on the conversion of
Sulfur to SO2 or SO3.

O2 from air  theo O2 S to SO2 

% Excess O2 (S to SO2)  theo O2 S to SO2 
x100

O2 from air  theo O2 S to SO3 

% Excess O2 (S to SO3)  theo O2 S to SO3 
x100

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CHECAL2 SULFUR and its Compounds
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Case I: Calculations based on Raw Sulfur Analysis

Since raw sulfur contains inerts, these are unburned during the
combustion and separates into the CINDER. Sometimes some
unburned elemental sulfur may be lost in the cinder resulting in
incomplete gasification of the S charged.

The gases from the burner consist of SO2, O2, N2, SO3 and
water. These gases are effectively analyzed in an Orsat Analyzer.
However SO3 is soluble in water and thus as water is not included
in an orsat analysis, so too is SO3 eliminated in the results of the
orsat analysis.

Examples:
1. Raw Sulfur analyzing 95% S and 5% inerts is burned with 65%
excess air (S to SO2). Air is supplied at 30oC, 740 mm Hg with
60% RH. Analysis of the cinder shows 10% S and 90% inerts.
88% of the S gasified burns to SO2, the rest to SO3. Calculate:
a) % excess air (S to SO3)
b) m3 air/kg raw S c) Complete analysis of the burner gas

Solution: Basis: 100 kg raw S

AIR
30oC 60 % RH
740 mm Hg STACK GAS
65% x’ss

FUEL BURNER
Raw S
95% S
5% inerts CINDER
10% S
90% inerts
a) Total at S = 95/32 = 2.96875
Theo O2 (S to SO2) = 2.96875

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O2 from air = (1.65)(2.96875) = 4.898

N2 from air = 4.898 (79/21) = 18.427
Theo O2 (S to SO3) = 2.96875 (3/2) = 4.453

% excess O2 (S to SO3)= [(4.898 - 4.453) / 4.453] x 100 = 10 %

b) At 30oC: logVP = 7.96681 - 1668.21/(228+30)

VP = 31.7 mm Hg

 4.898  18.427 x
0.6 x31.7
 0.615
moles H2O from air 740  0.631.7 

3
m air
4.898  18.427  0.615x22.4 x 760 x 273  30
 740 273
kg raw S 100 = 6.1127

c) Inert bal: 0.9 x wt. Cinder = 5

wt. Cinder = 5.555

At S gasified = 2.96875 - (0.1 x 5.555)/32 = 2.951

At S converted to SO2 = 0.88 x 2.951 = 2.596
At S converted to SO3 = 0.12 x 2.951 = 0.355

O2 used up = O2 for SO2 + O2 for SO3 = 2.596 + 0.355(3/2) = 3.127

Free O2 = O2 from air - O2 used up = 4.898 - 3.127 = 1.771

c) gas n %
SO2 2.596 10.93
O2 1.771 7.45
N2 18.427 77.54
SO3 0.355 1.49
H2O 0.615 2.58
23.764

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Case II: Calculations based on Analysis of Burner Gas

In the orsat analysis of the burner gas, SO3 is not included.

To find the moles of SO3, a comparison of the oxygen in the
burner gas and that supplied by air will show an oxygen
unaccounted for which is present as the combined oxygen in SO3.
This could therefore be used to compute for any SO3 formed
during combustion. The O2 from the air can be determined from
the N2 in the burner gas since all of these come from air.

2. Raw sulfur analyzing 88 % S and 12 % inerts when burned

produces a gas with an orsat analysis of 9.79 % SO2, 9.16 % O2
and 81.05 % N2. Dry air is supplied at 25oC and 745 mm Hg while
the burner gas is supplied at 250 oC and 760 mm Hg. Calculate:
a) % excess air (S to SO2)
b) % excess air (S to SO3)
c) m3 burner/m3 air

Solution: Basis: 100 moles dry SO3 free Burner gas

BURNER GAS
AIR 250oC
25oC 760 mm Hg
745 mm Hg 9.79% SO2
dry 9.16% O2
81.05% N2
FUEL BURNER
Raw S CINDER
88% S
12% inerts

O2 from air = (81.05) (21/79) = 21.54

O2 for SO3 = 21.54 - (9.79 + 9.16) = 2.59
O2 SO3 2
S + 3/2 O2 = SO3;  SO3  O2
3/ 2 1 3

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moles SO3 formed = 2.59 x (2/3) = 1.727 = at S converted to SO3

Total at S = at S converted to SO2+ at S converted to SO3

= 1.727 + 9.79 = 11.517

Theo O2 (S to SO2) = 11.517

Theo O2 (S to SO3) = 11.517 (3/2) = 17.28

a) % ex’ss air (S to SO2) = [(21.54 - 11.517)/11.517] x 100 = 87.03%

b) % ex’ss air (S to SO3) = [(21.54 - 17.28)/17.28] x100 = 24.65%

3
m Burner gas
100  1.727x22.4 x 760 x 273  250
 760 273
21.54  81.05x22.4 x 760 x 273  25
c) 3
m air = 1.706
745 273

Roasting of Iron Pyrites:

Iron pyrites refer to the sulfide ore most commonly burned

for SO2 manufacture. It consists primarily of Iron Sulfide (FeS2),
small amounts of metallic sulfides and appreciable amounts of
totally incombustible materials. These incombustible materials are
reported as GANGUE in the analysis.

The following reactions take place in the combustion of pyrites:

Main Reaction: 4 FeS2 + 11 O2 = 2 Fe2O3 + 8 SO2

Side Reaction: 4 FeS2 + 15 O2 = 2 Fe2O3 + 8 SO3

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As in the burning of raw S, the theoretical O2 and % excess air

have to be defined as to whether based on conversion of FeS2 to
SO2 or SO3.
Theo O2 (FeS2 to SO2) = Total moles FeS2 x 11/4
Theo O2 (FeS2 to SO3) = Total moles FeS2 x 15/4

During burning, the gangue and the iron oxide goes to the cinder.
Unburned FeS2 may also be present and possibly a small amount
of the divalent oxide may also be formed. The latter is small
enough and may be neglected in a well operated furnace. Thus the
main Sulfur compounds in the cinder are SO3 which is absorbed
on the cinder by the trivalent oxide, and unburned FeS2.

Case I: Calculations based on Pyrite Analysis

3. Pyrite Fines containing 85 % FeS2 and 15 % gangue are

charged to a burner. An analysis of the cinder shows 11.11%
FeS2, 66.63 % Fe2O3, 2.67 % SO3 and 19.6 % gangue. Air is
supplied 17.33 % in excess (FeS2 to SO3) at 25oC, 740 mm Hg
and 80 % RH. If 8 % of the SO3 formed is absorbed in the
cinder, calculate:
a). % excess air (FeS2 to SO2)
b). % of the FeS2 charged lost in the cinder
c). Orsat analysis of the burner gas
d). m3 of burner gas at 350oC and 750 mm Hg / kg pyrite
BURNER GAS
AIR 350oC
25oC
750 mm Hg
740 mm Hg
80% RH
17.33% x’ss CINDER
BURNER 11.11% FeS2
FUEL 66.63% Fe2O3
Pyrite 2.67% SO3
85% FeS2 19.6% gangue
15% gangue Note: 8 % SO3
formed is absorbed in
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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

Basis: 100 kg pyrite

a) moles FeS2 = 85/120 = 0.70833

theo O2 (FeS2 to SO2) = 0.70833 x 11/4 = 1.948
theo O2 (FeS2 to SO3) = 0.70833 x 15/4 = 2.656

O2 from air = 1.1733 x 2.656 = 3.1163

N2 from air = 3.1163 x (79/21) = 11.723

% ex’ss O2 (FeS2 to SO2) = [(3.1163-1.948)/1.948]x100 = 59.97 %

b). Gangue bal:

0.196 x wt of cinder = 15
wt of cinder = 76.53

wt of FeS2 in cinder = 0.1111 (76.53) = 8.503

% FeS2 lost in the cinder = (8.503/85) x 100 = 10 %

c). moles of SO3 in the cinder = (0.0267) (76.53) / 80 = 0.0255

0.08 (moles SO3 formed) = 0.0255

moles of SO3 formed = 0.0255/0.08 = 0.31927

In the reaction:
4 FeS2 + 15 O2 = 2 Fe2O3 + 8 SO3
0.1596 0.5986 0.0798 0.31927

moles FeS2 converted to SO2

= n FeS2 - n (FeS2 to SO3) – n FeS2 in cinder
= 0.70833 - 0.1596 - (8.503/120) = 0.4777

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CHECAL2 SULFUR and its Compounds
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In the reaction: 4 FeS2 + 11 O2 = 2 Fe2O3 + 8 SO2

0.4777 1.3136 0.2389 0.9554

Free O2 = (O2)air - (O2)SO3 - (O2)SO2

= 3.1163 - 0.5986 - 1.3136 = 1.2041

Orsat Analysis
GAS n %
SO2 0.9554 6.89
O2 1.2041 8.67
N2 11.723 84.44
13.8825

d). Vapor pressure at 25oC = 23.61 mm Hg

H2O from air

= (3.1163 + 11.723) x [(23.61 x 0.8)/(740 - 23.61(0.8))]
= 0.388

SO3 in the Burner Gas = (SO3)formed - (SO3)cinder

= 0.31927 - 0.0255 = 0.29377

760 273  350

3 (13.8825  0.388  0.29377) x 22.4 x x
m Burner Gas 750 273

kg pyrite 100
= 7.54

Case II: Calculations based on Gas Analysis

4. Dry pyrite fines containing 82 % FeS2 and 18 % gangue are

burned in a Herreshoff Burner. The cinder produced contains
3.06 % SO3 and no unburned FeS2. Orsat analysis on the burner
gas showed 8.15 % SO2, 8.46 % O2 and 83.38 % N2. Calculate:

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

a) % of the FeS2 charged converted to SO2

b) % excess air (FeS2 to SO2)
c) Complete analysis of the burner gas

Solution: Basis: 100 moles SO3 free Burner Gas

BURNER GAS
8.15 % SO2
AIR 8.46 % O2
83.38 % N2

FUEL
Pyrites
BURNER
82 % FeS2 CINDER no unburned FeS2
18 % gangue 3.06 % SO3
Fe2O3
Gangue
a) O2 from air = 83.38 x (21/79) = 22.164

SO2 in the burner gas = 8.15

In the reaction: 4 FeS2 + 11 O2 = 2 Fe2O3 + 8 SO2

4.075 11.206 2.0375 8.15

O2 for SO3 = (O2)air - (O2)SO2 - free O2

= 22.164 - 11.206 - 8.46 = 2.498

In the reaction: 4 FeS2 + 15 O2 = 2 Fe2O3 + 8 SO3

0.666 2.498 0.333 1.3323

% FeS2 charged converted to SO2

= [4.075 / (4.075 + 0.666)] x 100 = 85.95%

b) Theo O2 (FeS2 to SO2) = (4.075 + 0.666) (11/4)

= 13.038

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% ex’ss air (FeS2 to SO2) = [(22.164 - 13.038) / 13.038) x 100

= 70 %

c) Cinder Analysis:
82 (4.075  0.666) (120)

18 Gangue
weight of Gangue = (4.075 + 0.666)(120)(18/82) = 124.88

wt wt %
Fe2O3 = (2.0375 + 0.333)160 379.28 96.94 %
Gangue = (4.075 + 0.666)(120)(18/82) 124.88
SO3 ? 3.06

3.06 Wt of SO3 in the cinder


96.94 379.28  124.88

wt of SO3 in the cinder = (379.28 + 124.88) x (0.0306 / 0.9694)

= 15.9

moles SO3 in the burner gas = (SO3)formed - (SO3)cinder

= 1.3323 - (15.9/80)
= 1.13355

Complete Analysis of Burner Gas

GAS n %
SO2 8.15 8.06
O2 8.46 8.37
N2 83.38 82.45
SO3 1.13355 1.12
101.12375

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CHECAL2 SULFUR and its Compounds
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Production of Sulfuric Acid and Oleum

Sulfuric Acid has historically been produced by two methods,

the Contact Process and the Chamber Process. Both of these
methods involve the formation of SO2 in a burner using either
Raw S or Pyrite; followed by conversion of the SO2 to SO3; and
absorption of SO3 in water to give Sulfuric Acid or Oleum.

a) Contact Process

The contact process involves the catalytic oxidation of SO2 to

SO3 using Vanadium Pentoxide or Platinum dispersed in asbestos
or silica gel as catalyst under appropriate conditions in an
equipment known as a Converter. The reaction is:

SO2 + ½ O2 = SO3

Two or more converters may be in series, and extra air (called

Secondary Air) may be supplied.

The SO3 from the gases in the converters is absorbed by

countercurrent passage of the gases (upward) and absorbing liquid
(downward) in Ceramic Packed Towers. Sulfuric Acid is formed
by the reaction:
SO3 + H2O = H2SO4

This absorption cannot be satisfactorily accomplished by water

alone, because the vapor pressure of water is sufficiently high to
cause the formation of an acid mist that hinders absorption. Thus
it is customary to feed sulfuric acid solution. 98% acid has been
found to be the most efficient absorbing agent to produce fuming
sulfuric acid, otherwise known as Oleum. Water is added to the
product acid to give grades of lower concentration.

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CHECAL2 SULFUR and its Compounds
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Different concentrations of acids will be used as absorbing

agents. If the absorbing agent is dilute acid, it will be assumed that
concentrated sulfuric is formed; if the absorbing agent is
concentrated acid, it will be assumed that oleum is formed. A 20
% oleum product means that it contains 20 % SO3 and 80 %
H2SO4.

In the absorbers it may be possible that additional oxidation

of the SO2 to SO3 may take place before absorption. To check
this, the O2 in the converter gases is compared with the O2 in the
wastes gases.

The flow diagram for the Contact Process is illustrated below:

Sulfuric Acid
Waste Gas Sol’n

Primary Air Secondary Air a) Dilute Acid

b) Conc. Acid

Burner CATALYTIC GAS

Pyrite or CONVERTER ABSORBER
Raw S

Cinder
Converter Gas a) Conc. Acid
b) Oleum

b) Chamber Process

Aside from the burner, the process involves the use of a

Glover Tower, and the Chambers and Gay Lussac’s Tower. The
hot gases from the burner passes up through the Glover Tower
where SO2 is converted to H2SO4. This comprises about 15 % of
the total H2SO4 production. The balance of the conversion takes
place in the chambers. The chamber process produces a weak
sulfuric acid (70 % H2SO4).

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CHECAL2 SULFUR and its Compounds
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The contact process is the more popular method for sulfuric

acid production, it shall be the only one to be considered in the
computational analysis.

5. Raw Sulfur, 96 % pure is burned in dry excess air producing a

gas with an orsat analysis of 18 % SO2, 0.50 % O2 and 81.50 %
N2. The burner gases are fed to a catalytic converter together
with 20 % excess secondary air resulting in the oxidation of 60
% of the SO2 to SO3. The gases from the converter enter an
absorber to produce the acid. Assuming no further oxidation of
the SO2 taking place in the absorber, calculate: a) Complete
analysis of the burner gas; b) Complete analysis of the
converter gas; c) Wt of an 85 % concentrated H2SO4 solution
per kg raw S charged if the absorbing acid is 40 % H2SO4; d)
Wt of a 5 % oleum formed per kg raw S charged if the
absorbing acid is a 90 % H2SO4 solution.
Sulfuric Acid
Waste Gas solution
Secondary Air (20 % excess)
Primary Air a) 40% Acid
60% SO2 SO3 b) 90% Acid
Burner Gas
Burner CATALYTIC GAS
18%SO2 CONVERTER ABSORBER
Raw S 0.5%O2
96% pure 81.5% N2
4 % inert
Cinder
Inert a) 85% Conc. Acid
Converter Gas b) 5% Oleum

Basis: 100 moles SO3 free Burner Gas

a). Burner Analysis

Primary O2 from air = 81.5 x (21/79) = 21.66

O2 unaccounted for = 21.66 – 18 – 0.5 = 3.16

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S converted to SO3 = 3.16 x (2/3) = 2.10

= moles SO3 formed in BG

0.96 (wT raw S) = wt of S to form SO2 + wt of S to form SO3

wT of raw S = (2.10 + 18.0) (32) (1/0.96)
= 670

Complete Analysis of Burner Gas

GAS n %
SO2 18 17.63
O2 0.5 0.49
N2 81.5 79.82
SO3 2.1 2.06
102.1

b) Converter Analysis: SO2 + ½ O2 = SO3

(theo. O2)sec.air = (theo. O2)SO2 to SO3 - (free O2)burner gas

= ½ x moles SO2 – moles free O2 in burner gas
= ½ x 18 – 0.5
= 8.5

secondary O2 from air = 8.5 x (1.2) = 10.2

secondary N2 from air = 10.2 x (79/21) = 38.37

SO2 converted to SO3 = 0.6 x 18 = 10.8

The reaction is: SO2 + ½ O2 = SO3

10.8 5.4 10.8

SO2 unreacted = 18 – 10.8 = 7.2

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O2 after reaction = free O2 + (O2)sec. air - (O2)SO3 formed

= 0.5 + 10.2 – 5.4 = 5.3

N2 after reaction = 81.5 + 38.37 = 119.87

SO3 after reaction = 2.1 + 10.8 = 12.9

Complete Analysis of Converter Gas

GAS n %
SO2 7.2 4.96
O2 5.3 3.65
N2 119.87 82.51
SO3 12.9 8.88
145.27

c) Absorber Analysis:
SO3 + H2O = H2SO4

Let: y = wt of 85 % H2SO4 solution formed

wt. SO3 in CG + wt of 40 % H2SO4 = wt of 85 % H2SO4

12.9 (80) + wt of 40 % H2SO4 = y

wt of 40 % H2SO4 used = y – 12.9 (80) = y – 1032

H2SO4 Balance:

40 % (wt of 40 % H2SO4 used) + wt of SO3 (MW H2SO4/MW SO3)

= 85 % (wt of 85 % H2SO4)

0.4 (y – 1032) + 1032 (98/80) = 0.85 y

y = 1892 kg / 100 moles SO3 free BG

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wt of 85 % acid/kg raw S = 1892 / 670 = 2.823

d) Let: z = wt of 5 % oleum formed

wt. SO3 in CG + wt of 90 % H2SO4 = wt of 5 % oleum

12.9 (80) + wt of 90 % H2SO4 = z
wt of 90 % H2SO4 acid used = z – 1032

SO3 Balance:

90 % (wt of 90 % H2SO4) (MW SO3 /MW H2SO4) + SO3 in CG

= 5%(wt of 5 % SO3 in oleum) + 95%(wt of 5%SO3 in oleum)(MW SO3
/MW H2SO4)
0.9 (z – 1032) (80/98) + 1032 = 0.05 z + 0.95 z (80/98)
z = 3014.83 kg / 100 moles SO3 free BG

wt of 5 % oleum / kg raw S = 3014.83 / 670 = 4.5

6. 1000 kg/hr Pyrites analyzing 81 % FeS2 and 19 % gangue is

burned in excess air to produce a burner gas with an orsat
analysis of 5.84 % SO2, 9.72 % O2 and 84.44 % N2. Analysis of
the cinder shows 8.29 % unburned FeS2 and 3.81 % SO3. The
gases from the burner enter the catalytic converter where SO2 is
oxidized to SO3. Partial orsat analysis of the converter gas
shows 1.87 % SO2. No additional secondary air is supplied in
the converter. The converter gases are then sent to an absorber
where contact with acid takes place. The waste gas from the
absorbers analyze 0.95 % SO2, 7.82 % O2 and 91.23 % N2.
Calculate: a) Complete Analysis of the Burner Gas; b) %
conversion of SO2 to SO3 in the converter; c) wt of a 60 %
H2SO4 needed to produce a concentrated 90 % H2SO4 solution /
hr.; d) wt of an 88 % H2SO4 acid need to produce 12 %
oleum/hour

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Basis: 100 moles dry SO3 free Burner Gas

0.95 % SO2
7.82 % O2
Sulfuric Acid
91.23 % N2
5.84 %SO2 Waste Gas Sol’n
9.72 %O2
Primary Air 84.44 % N2 a) 60% Acid
Burner Gas b) 88% Acid

Burner CATALYTIC GAS

Pyrite CONVERTER ABSORBER
1000 kg/hr
81 % FeS2
19 % gangue
Cinder
8.29 % FeS2 a) 90% Conc. Acid
Converter Gas b) 12% Oleum
3.81 % SO3 1.87 % SO2

a) Burner Analysis:
O2 from air = 84.44 x (21/79) = 22.446

For the Reaction:

4 FeS2 + 11 O2 = 2 Fe2O3 + 8 SO2
2.92 8.03 1.46 5.84

O2 for conversion of FeS2 to SO3 = 22.446 – 8.03 – 9.72 = 4.696

For the Reaction:

4 FeS2 + 15 O2 = 2 Fe2O3 + 8 SO3
1.2522 4.696 0.6261 2.5045

Cinder Analysis:
wt %
FeS2 = (w moles) 120 120w 8.29
Fe2O3 = (1.46 + 0.6261)(160) 333.776
Gangue = (2.92 + 1.2522 + w)(120)(19/81) 117.44 + 28.148w
SO3 = a moles 80a 3.81
total wt of cinder 100

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total wt of cinder = 451.216 + 148.148w + 80a

Solving simultaneously:
120 w 8.29 80 a 3.81
 (1)  (2)
wT cinder 100 wT cinder 100

w = 0.36268, a = 0.25

0.81 (wtT of Pyrite) = (nT of FeS2) (MW FeS2)

wt of pyrite = (2.92 + 1.2522 + 0.36268)(120)/0.81 = 671.34

wt of pyrite / 100 moles SO3 free BG = 671.34

SO3 in BG = (SO3)total - (SO3)cinder = 2.5045 – 0.25 = 2.2545

Complete Analysis of BG
GAS n %
SO2 5.84 5.71
O2 9.72 9.51
N2 84.44 82.58
SO3 2.2545 2.2
102.2545
b) Converter Analysis:

Let: b = moles SO2 converted to SO3 in converter

The reaction is: SO2 + ½ O2 = SO3

b 0.5b b

GAS n %
SO2 5.84 - b 1.87
O2 9.72 – 0.5b
N2 84.44____
100 – 1.5b

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5.84  b 1.87
for SO2 :   0.0187
100  1.5b 100
b = 4.0846

% conversion of SO2 to SO3 = (4.0846/5.84) x 100 = 70 %

Converter Gas n
SO2 = 5.84 – 4.0846 1.7554
O2 = 9.72 – 0.5(4.0846) 7.6777
N2 = 84.44
SO3 = 2.2545 + 4.0846 6.3391
100.2122
c) Absorber Analysis:

Note:
84.44 mols N2 in BG = 84.44 mols N2 in CG = 84.44 mols N2 in WG

91.23 % N 2 (Waste Gas)T = 84.44

(Waste Gas)T = 84.44 /0.9123 = 92.55

O2 in waste gas = 92.55 x 0.0782 = 7.238

O2 reacting = 7.6777 – 7.238 = 0.44

For the reaction: SO2 + ½ O2 = SO3

0.88 0.44 0.88

SO3 available for absorption = 6.3391 + 0.88 = 7.2191

Let: y = wt of 60 % H2SO4 acid charged

wt of 90 % H2SO4 formed = y + 7.2191 (80) = y + 577.528

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

SO3 Balance:
y(0.6)(80/98) + 577.528 = (y + 577.528) (80/98) (0.9)
y = 625.655
625.655 wt of dilute 60 % acid

671.834 1000

wt of dilute 60 % acid/hr = (625.655 / 671.834) x 1000

= 931.26

d) Let: z = wt of 88 % acid

z + 577.528 = wt of 12 % oleum

H2SO4 Balance:
0.88 z + 577.528 (98/80) = (0.12) (z + 577.528) (98/80)
+ 0.88( z + 577.528)
z = 777.895

wt of 88 % acid/hr = (777.895/671.834) x 1000

= 1157.87

BISULFITE LIQUOR PRODUCTION:

In bisulfite liquor production, the gases from the sulfur
burner are passed through a cooler, an entrainment separator and
then into an absorption tower. In the tower, it is made to come
into contact with Milk of Lime or Slaked Lime (lime mixed with
water) to form the bisulfite. Lime is essentially a mixture of CaO,
MgO and inerts. The following reactions take place.

slaked lime
SLAKER: CaO + H2O = Ca(OH)2
MgO + H2O = Mg(OH)2

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

ABSORPTION TOWER:

Main Reactions: Bisulfite

Ca(OH)2 + 2 SO2 = Ca(HSO3)2
Mg(OH)2 + 2 SO2 = Mg(HSO3)2

Side Reactions: Sulfate

Ca(OH)2 + SO3 = CaSO4 + H2O
Mg(OH)2 + SO3 = MgSO4 + H2O
H2O + SO3 = H2SO4
SO2 + ½ O2 = SO3

To determine if oxidation of SO2 to SO3 takes place in the

absorber, the waste gases are compared with the cooled burner
gases. If the O2 in the waste gases is less than the O2 in the cooled
burner gas, oxidation took place.

The mixture of Ca and Mg bisulfites, Ca and Mg sulfates,

H2SO4, inerts and water make up the Bisulfite liquor. The
analysis of the bisulfite liquor is usually reported in terms of the
% SO2 it contains, both “free” and present as bisulfites; e.g. A
bisulfite liquor contains 10 % SO2 of which 3 % is “free” and the
rest are present as bisulfites.

7. Using the Pyrites and Burner Gas in Example (6), the burner
gases are cooled and made to come into contact with Milk of
Lime in an absorption tower. The dolomitic lime used is 82 %
CaO, 16 % MgO and 2 % inerts. The bisulfite liquor produced
contains 7.05 % total SO2 of which 1.15 % is “free” and the rest
5.9 % being present as bisulfites. An analysis of the dry waste gas
shows that it contains only O2 and N2. Assuming no further
oxidation of SO2 to SO3 and formation of H2SO4 in the tower,
calculate:

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

a) wt. of the bisulfite liquor/hr

b) wt. of lime consumption / hr
c) wt. of water used for slaking / hr

Solution: From Ex.6, Basis: 100 moles SO3 free Burner Gas
Lime
O2 82% CaO
N2 16% MgO
2% Inerts
Waste Gas
5.84 %SO2 SLAKER
9.72 %O2 H2O
Primary Air 84.44 % N2
Burner Gas
Burner Cooler GAS
Pyrite ABSORBER
1000 kg/hr
81% FeS2
19 % gangue
Cinder
8.29 % FeS2 Cooler Gas
3.81 % SO3 Bisulfite Liquor
1.15 % free SO2
7.05 % SO2
5.9 % Bisulfites
a) wt pyrite / 100 moles SO3 free BG = 671.834

Burner Gas: 5.84 moles SO2

9.72 moles O2
84.44 moles N2
2.2545 moles of SO3, from Example (6)

Let: y = wt of the bisulfite liquor

SO2 Balance: 0.0705 y = 5.84 (64)

y = 5301.56 kg

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

wt. bisulfite liquor/hr =  5301.56 kg bisulfite liquor  671.834 kg pyrite

1000 kg pyrite / hour

= 7891.17

b). moles CaO & MgO converted to Bisulfites

1mol Ca( HSO3 ) 5301.56 x 0.059 1
 nSO2 x = x  2.444
2 mols SO2 64 2

moles CaO & MgO converted to Sulfates = moles SO3 = 2.2545

total moles CaO & MgO supplied = 2.444 + 2.2545 = 4.6985

For 100 kg lime:

moles CaO and MgO = 82/56 + 16/40.3 = 1.86

100 kg wt. lim e


1.86 4.6985
wt. lime = (100/1.86) x 4.6985 = 252.6 / 100 moles burner gas

wt. of lime/hr = 252.6 x (1000/671.834) = 375.986

c) OMB in the Absorber:

wt cooler gas + wt lime + wt H2O for slaking
= wt waste gas + wt Bisulfite liquor

SO2 + SO3 + O2 + N2 + lime + H2O for slaking = O2 + N2 + BL

but: O2 and N2 in burner gas = O2 and N2 in waste gas

5.84 (64) + 2.2545 (80) + 252.6 + H2O for slaking = 5301.56
H2O for slaking = 4494.84

wt. water for slaking/hr = 4494.84 x (1000/671.34) = 6695.32

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

Problem Set:
1. Raw Sulfur which is 75 % pure is burned in excess air supplied at the rate of 4.713 m3/kg of
raw Sulfur at 25 oC. 745 mm Hg with 80 % RH. If 87 % of the sulfur charged burns to SO2 and
the rest to SO3, calculate:
a. % excess air (S to SO2) (65%)
b. % excess air (S to SO3) (10%)
c. complete analysis of the burner gas (10.88% SO2, 7.32% O2, 1.63% SO3, 2.56% H2O)

2. The burner gas from a sulfur burner analyzes 9.2 % SO2, 7.13 % O2 and 83.67 % N2. The raw
sulfur charged contains 82 % pure sulfur and analysis of the cinder shows 20% unburned sulfur.
Calculate:
a. % excess air (S to SO2) (60%)
b. % excess air (S to SO3) (6.67%)
c. m3 of saturated air (28oC, 750 torrs) / kg raw S (5.076)
3 o
d. m of burner gas (300 C, 730 torrs) / kg raw S (9.75)

3. Pyrite analyzing 78 % FeS2 and 22 % gangue is burned at the rate of 1000 kg/hr. Analysis of
the cinder shows 11.87 % FeS2 and 7.22 % S as unburned FeS2 and SO3 absorbed by Fe2O3. Air
supplied is 70 % in excess based on conversion of FeS2 to SO2. The ratio of SO2 to SO3 in the
burner gas is 3.48:1. Calculate:
a. % excess air (FeS2 to SO3) (24.67%)
b. % of the FeS2 charged lost in the cinder (12%)
c. complete analysis of the burner gas (6.26% SO2, 9.57% O2, 82.35% N2, 1.82% SO3)

4. In the burning of pyrite containing 92 % FeS2 and 8 % gangue, 13 % of the FeS2 charged is lost
in the cinder. A partial analysis of the cinder also shows 5.31 % SO3. The orsat analysis of the
burner gases shows 6.75 % SO2, 6.88 % O2 and 86.38 % N2. Air supplied is at 23 oC, 743 mm
Hg and 88 % RH. Calculate:
a. % excess air (FeS2 to SO) (40%)
b. % excess air (FeS2 to SO3) (2.676%)
c. m3 air/kg pyrite (3.58)
d. m3 burner gas (250oC, 750 mm Hg)/kg pyrite (5.922)

5. Raw sulfur containing 83 % pure S is burned together with 80 % excess air (S to SO 2). An
analysis of the cinder shows 20 % unburned sulfur and 80 % inerts. 90 % of the S gasified
burns to SO2 and the rest to SO3. Air is supplied saturated at 30 oC and 750 mm Hg. The gases
from the burner enter a converter where catalytic oxidation of SO2 to SO3 takes place. A partial
orsat analysis of the converter gas shows 1.37 % SO2. The gases from the converter enter an
absorber where after absorption in acid solution forms a waste gas analyzing 0.55 % SO2, 11.99
% O2 and 87.46 % N2. Calculate per 100 kg raw sulfur:
a. complete analysis of the burner gas (9.59% SO2, 9.03% O2, 1.07% SO3, 4.25% H2O)
b. % of the SO2 entering the converter that is converted to SO3 (88.3%)
c. weight of a 60 % dilute H2SO4 needed to produce an 87 % H2SO4 (248.04)
d. if the absorbing acid is in 94 % H2SO4, what weight of a 14 % oleum is formed? (587.61)

6. Pyrite containing 80 % FeS2 and 20 % gangue is burned in excess air to produce a gas with a
complete analysis of 7.78 % SO2, 1.39 % O2, 82.06 % N2, 4.92 % SO3, and 3.85 % H2O.
Analysis of the cinder shows a total sulfur content of 6.46 % due to the presence of unburned

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CHECAL2 SULFUR and its Compounds
Dr. Susan A. Roces AY 2017-2018

FeS2 and SO3 absorbed by Fe2O3. Air supplied is at 27oC, 745 mm Hg and saturated vapor. The
burner gases then enter a converter together with 30% excess secondary air (supplied at the
same conditions as primary air) based on the complete conversion of all SO2 to SO3. 75 % of
the SO2 actually burns to SO3. The converter gases enter an absorber and absorbed in acid
solution. The waste gases formed has a partial orsat analysis of 0.7 % SO 2. Calculate per kg of
pyrite:
a. % excess air (S to SO2) (10.17)
b. complete analysis of the converter gas (1.72% SO2, 1.52% O2, 9.51% SO3, 3.91% H2O)
c. kg of an 80 % H2SO4 acid formed from a 40 % acid charged (1.84)
d. kg of a 75 % H2SO4 needed to produce 10 % oleum (0.663)

7. The roasting of pyrites analyzing 85 % FeS2 and 15 % gangue utilizes 40 % excess air (FeS2 to
SO2) supplied at the rate of 358 m3/hr at 23 oC, 743 mm Hg and 88 % RH. A partial analysis of
the cinder showed 25.92 % FeS2 and 17.83 % gangue. Only 65 % of the FeS2 gasified is
converted to SO2 and the rest to SO3. The burner gases are cooled and charged to a converter
together with slaked lime from a dolomitic lime containing 75 % CaO, 25 % MgO. If 850 kg/hr
of bisulfite liquor are produced with no oxidation of SO2 to SO3 taking place. Assume all SO2
converted to bisulfite. Calculate:
a. kg/hr of lime (35.59)
b. kg/hr of water for slaking (740.69)
c. complete analysis of the burner gas (5.4% SO2, 8.6% O2, 2.4% SO3, 2.6% H2O)

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