26 Wet sulfuric acid process

fundamentals

Chapter 25 described the Haldor Tops
e Wet gas Sulfuric Acid (WSA) process. This
chapter focuses on three key aspects of the process:
(a) Catalytic oxidation of SO2 to SO3 and H2SO4(g) in the presence of O2 and H2O(g)
(b) Injection of nanoparticles to increase H2SO4(g) condensation efficiency
(c) Condensation of strong (
98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ)) sulfuric acid from
H2SO4(g)-rich gas in a vertical, glass tube condenser.

26.1 Wet gas sulfuric acid process SO2 oxidation

The first major step in wet sulfuric acidmaking is catalytic SO2 oxidation (Fig. 25.1).
The reaction is:

vanadium
catalyst
SO2 þ 0:5O2 ƒƒƒƒ! SO3 (1.1)
in SO2 , H2 OðgÞ, O2 in feed gas and in SO3 , SO2 , H2 OðgÞ, O2
N2 , CO2 , feed gas in added air N2 , CO2 , product gas

It is carried out in one, two, or three sequential
1 m thick catalyst beds with gas cool-
ing between and after the beds. It is quite similar to conventional SO2 oxidation.
The chemical composition of the catalyst is similar to that used for dry SO2 oxi-
dation (Tables 26.1 and 8.1). The catalyst substrate is, however, considerably stronger
than its dry gas equivalent in order to withstand the erosive effect of H2O(g) (Haldor
Tops
e, 2008). It is made from modified porous diatomaceous earth ore.

26.1.1 SO2 oxidation objective

As with conventional SO2 oxidation, the objective of WSA process oxidation is max-
imum SO2 to SO3 oxidation. It is achieved by:
(a) using active alkali-promoted vanadium catalyst and
(b) adequate gas-in-catalyst-bed residence time.

Together, these lead to near-equilibrium conditions at the exit from each catalyst bed.

Sulfuric Acid Manufacture. http://dx.doi.org/10.1016/B978-0-08-098220-5.00027-7

© 2013 Elsevier Ltd. All rights reserved.
296 Sulfuric Acid Manufacture

Table 26.1 Characteristics of SO2 þ 0.5O2 ! SO3 oxidation catalysts used in wet
sulfuric acid processing (Haldor Tops
e, 2008)

Designation VK-WSA VK-WSX VK-WH VK-WL

Type Potassium Potassium- Cesium promoted Cesium-

promoted promoted promoted
high high
vanadium vanadium
Ignition 360 340 320 320
temperature ( C)
Continuous 400-630 370-450 370-500 370-450
operating
temperature
range ( C)
Maximum 650 650 650 650
allowable
temperature ( C)
Size and shape 12 and 25 mm 9 mm 12 mm diameter 9 mm
diameter daisies diameter daisy diameter
(Fig. 8.1) daisy daisy
Application All WSA beds, Last WSA Upper layer of first For WSA-
dust capture in bed for bed for increased DC plants
first bed efficient SO2 operational
oxidation flexibility

In addition, equilibrium should be achieved at the coolest possible temperature,

consistent with the catalyst being active. This is because, thermodynamically, SO3
formation increases with decreasing reaction temperature (Fig. 7.3).
Any SO2 not oxidized during catalytic SO2 oxidation is not condensed to H2SO4(ℓ).
It must be scrubbed from the gas before leaving the WSA plant. Tail gas scrubbing is
described in Chapter 28.

26.1.2 Effect of H2O(g) in the oxidation converter

Wet sulfuric acid feed gas always contains H2O(g) (Table 25.2). This H2O(g) leads to
a second reaction in the catalyst beds. It is H2SO4(g) formation, i.e.:

H2 OðgÞ þ SO3 ! H2 SO4 ðgÞ (26.1)

in feed gas produced in in catalyst bed
catalyst beds exit gas

H2O(g) and H2SO4(g) do not condense at the active operational temperature of the
vanadium catalyst or in the subsequent heat exchanger, >300  C, ensuring condensa-
tion/corrosion problems do not occur in or after the catalyst beds.
The H2SO4(g) formed by Reaction 26.1 eventually ends up as condensed acid at
the bottom of the WSA condenser (Fig. 25.1). The remaining SO3 reacts to
Wet sulfuric acid process fundamentals 297

H2SO4(g) in Fig. 26.1’s gas flue and condenser. It also condenses to sulfuric acid in the
condenser.
Feed gas H2O(g) concentrations are kept in excess of the 1:1 molar stoichiometric
ratio shown in Reaction 26.1. This ensures complete hydration of SO3 to H2SO4(g).
Steam is sometimes added to the feed gas to maintain excess H2O(g).

26.1.3 Extent of H2SO4(g) formation during catalytic SO2 oxidation

The equilibrium quantity of H2SO4(g) in the last catalyst bed exit gas is calculated
from:

(a) the equilibrium constants for Reactions (1.1) and (26.1) as determined from tabulated
thermodynamic data
(b) molar S, H, O, and N balances.

Appendix X describes the method of calculation. The results are shown in

Figs. 26.1–26.3.

26.1.4 H2SO4(g) formation

Figure 26.1 indicates that 15-20% of the feed gas’s SO2 reacts to H2SO4(g) in
Fig. 25.1’s catalyst beds. SO3 accounts for the remainder. This is consistent with
observed industrial values.
Figure 26.1 also shows that H2SO4(g) formation increases with decreasing exit gas
temperature, while the residual SO3 decreases to compensate. This is because Reac-
tion 26.1 is increasingly favored with decreasing temperature (Fig. 25.2).

100
3 volume% SO2
% of feed SO2 oxidized to H2SO4 and SO3

8 volume% H2O(g)
13 volume% O2 in feed gas
80 SO3
after last catalyst bed

60

40

20
H2SO4(g)

0
400 405 410 415 420
Last catalyst bed exit gas temperature (°C)
Figure 26.1 Oxidation of SO2 in H2O(g)-bearing catalytic converter feed gas. Calculated
amounts of SO3 and H2SO4(g) formation are shown. They are similar to those obtained
industrially. As predicted thermodynamically, H2SO4(g) formation increases with decreasing
last catalyst bed exit gas temperature. The calculations are described in Appendix X.
298 Sulfuric Acid Manufacture

100

% of feed SO2 reacted to SO3 and H2SO4

8 volume% H2O(g) 400 °C after last catalyst bed
13 volume% O2 in feed gas
after last catalyst bed 80
SO3

60

40

20
H2SO4(g)

0
1 2 3 4 5
Volume% SO2 in feed gas
Figure 26.2 Oxidation of SO2 in H2O(g)-bearing catalytic converter feed gas. Calculated
amounts of SO3 and H2SO4(g) formation are shown. They are barely affected by SO2
concentration in feed gas.

Figure 26.2 shows that H2SO4(g) formation is independent of SO2-in-feed-gas

concentration.

26.1.5 Total SO2 oxidation

Figure 26.3 shows that total SO2 oxidation increases slightly when the feed gas con-
tains H2O(g). This is because Reaction 26.1 consumes some SO3, thereby shifting
Reaction (1.1) slightly to the right. The effect is quite small.
100
3 volume% SO2 in feed gas
% of feed SO2 oxidized to H2SO4 + SO3

13 volume% O2 in feed gas

99.8
after last bed

99.6
8 volume% H2O(g) in feed gas

99.4
No H2O(g) in feed gas

99.2

99
400 405 410 415 420
Last catalyst bed exit gas temperature (°C)
Figure 26.3 Oxidation of SO2 in H2O(g)-bearing and dry catalytic converter feed gas. Total
SO2 oxidation is increased slightly by the presence of H2O(g) in feed gas. The calculations are
described in Appendix X.
Wet sulfuric acid process fundamentals 299

26.1.6 Thermal behavior with H2SO4(g) formation

Production of H2SO4(g) in the catalytic converter produces more heat of reaction than
production of SO3 alone. This is beneficial because:

(a) additional heat can be exported from the catalytic converter for uses around the plant
or
(b) weaker SO2 feed gas (3 volume% SO2) can be treated without fossil-fuel-combustion
preheating the first catalyst bed feed gas, i.e., by preheating with the converter’s extra
heat of reaction.

26.2 Injection of nanoparticles into cooled process gas

The product gas from the SO2 þ 0.5O2 ! SO3 oxidation converter leaves the last cat-
alyst bed at 390-400  C (Fig. 26.1). It typically contains:

2-5 volume% SO3,

0.2-0.5 volume% H2SO4(g),
4-8 volume% H2O(g),
5-13 volume% O2,

remainder N2 (mostly) and CO2.

It is cooled to 270-290  C and continuously sent to sulfuric acid condensation
through a stainless steel flue.

26.2.1 Nanoparticle injection

The first step in treating the cooled gas from SO2 þ 0.5O2 ! SO3 oxidation is injection
of solid silica nanoparticles, 2-100 nm (2  109 to 100  109 m) diameter. These
particles provide condensation sites for H2SO4(g) produced by the following reaction:
260-90 C
SO3 þ H2 OðgÞ ƒƒƒƒƒ! H2 SO4 ðlÞ (26.2)
in SO3 , H2 SO4 ðgÞ, in condensed
H2 OðgÞ, O2 , N2 , CO2 sulfuric acid
oxidation exit gas

They also serve as condensation sites for the H2SO4(g) already in the converter exit
gas, i.e.,
260-90 C
H2 SO4 ðgÞ ƒƒƒƒƒ! H2 SO4 ðlÞ (26.3)
in SO3 , H2 SO4 ðgÞ, in condensed
H2 OðgÞ, O2 , N2 , CO2 sulfuric acid
oxidation exit gas

The sulfuric acid condenses mainly on the injected particles (Christensen, 2008;
Schoubye, 1982). It also condenses on the glass tube walls and to a much lesser extent,
homogeneously.
300 Sulfuric Acid Manufacture

26.2.2 Nanoparticle injection method

Industrial nanoparticle injection is typically accomplished by:

(a) burning of silicone oil in air with other fuels, such as natural gas or propane, in a burner
adjacent to the converter-condenser flue
(b) blowing the resulting silica particle smoke into the flue (Fig. 26.4).

To environment

Photometric
aerosol meter
Air flow rate
control valve Electronic
signal Condenser exit gas

Secondary filter
droplet-catching filters

Combustion air

Sulfuric acid
condenser

Silicone oil / fuel Burner

mixture
Nanoparticles

SO3, H2O(g), H2SO4(g),

O2, N2, CO2, process gas
from oxidation converting
Sulfuric acid product
Figure 26.4 Control system for minimizing sulfuric acid emission to the environment. It
operates continuously. A condensation particle counter (top) senses acid droplet concentration
in the exit gas (TSI, 2012). It sends an electronic signal to the combustion air flow controller—
telling it to increase or decrease air flow rate. This in turn decreases or increases the
concentration of nanoparticles in the burner exit gas (represented by mass% smoke in Fig. 26.5)
as needed to minimize acid droplet-in-exit gas emission. The physical location of the system in
the wet sulfuric acid flowsheet is indicated in Fig. 25.1.
Wet sulfuric acid process fundamentals 301

26.2.3 Optimum smoke concentration

Figure 26.5 shows the effect of smoke concentration in flue gas on H2SO4(ℓ) emission
into the environment. The presence of an optimum at about 1.5 mass% smoke is nota-
ble. The next section describes how this optimum concentration is attained.

100
Parts per million H2SO4 after filter

80

60

40

20

0
0 2 4 6 8 10
Mass% smoke from oil burner
Figure 26.5 H2SO4(ℓ) concentration in condenser offgas as a function of particle (smoke)
concentration in condenser input gas (Schoubye, 1993). Minimum H2SO4(ℓ) emission at
1.5
mass% smoke is notable. It is obtained industrially by continuously measuring H2SO4(ℓ)
concentration in offgas and automatically adjusting smoke production rate (Fig. 26.4).

26.2.4 Adjusting smoke-in-flue gas concentration

Smoke concentration in flue gas is varied by adjusting the:
air input rate
fuel input rate
ratio into the particle injection burner. Generally speaking, reduction of the air input
rate at a constant fuel input rate increases % smoke in flue gas.
26.2.5 Finding and maintaining the optimum
The optimum mass% smoke in flue gas (i.e., minimum H2SO4 emission) is found and
maintained by Fig. 26.4’s control system. It:

(a) continuously measures acid droplet concentration (hence H2SO4 concentration) in con-
denser offgas
(b) automatically adjusts:

air input rate

fuel input rate
302 Sulfuric Acid Manufacture

ratio until acid droplet concentration in offgas reaches its minimum. It then maintains
the optimum as flue gas conditions change.

26.2.6 Size of injected particles

The above-described injected particles are typically 2-100 nm (2  109 to
100  109 m) diameter. They provide an adequate surface area for condensation
while minimizing contamination of the final acid product (Table 26.2). Particle size
is readily measured by means of scanning mobility particle sizer™ spectrometers
(TSI, 2012). This is, however, in no way required in industrial plants.
Particle size is adjusted by using an appropriate silicone oil in Fig. 26.4’s burner fuel.
These size data are provided by the manufacturer and are not measured in the plant.

26.2.7 Particle concentration in flue gas

Mass percent smoke in flue gas is a nebulous term. This section discusses particle con-
centration in more scientific terms, number of particles per Nm3 of flue gas. Particle
concentration is readily measured by means of condensation particle counters and
spectrometers (TSI, 2012).
Industrial measurements indicate that efficient sulfuric acid condensation during
wet sulfuric acidmaking requires

1  1010 to 1  1013

nanoparticles per Nm3 of process gas per volume% of [SO3 þ H2SO4(g)] in the
process gas.
This concentration is chosen to produce condensed droplets that are large enough to
be efficiently caught in the droplet-catching filters atop Fig. 26.4’s glass condenser
tubes.
A smaller concentration does not efficiently prevent fine droplet acid mist forma-
tion by homogeneous condensation. These fine mist particles tend to escape through
the droplet-catching filters.
A greater concentration produces an excessive number of small droplets which also
tend to pass through the droplet-catching filters (Schoubye, 1993).

26.2.8 Particle-in-acid contamination

The degree of seed particle-in-acid contamination is very small, typically 1  105
mass% (Table 26.2). It decreases with decreasing initial particle size.

26.3 Sulfuric acid condensation

The last step in wet sulfuric acidmaking is sulfuric acid condensation. It entails two
reactions:
Wet sulfuric acid process fundamentals 303

Table 26.2 Calculation of sulfuric acid contamination by silica nanoparticle seeds

Data
Input particle diameter (d) (m) 1  108
Fully grown droplet diameter (D) (m) 3  106 (Schoubye, 1993)
Silica particle density (kg/m3) 2600
3
Sulfuric acid density (kg/m ) 1600

Equations
Sphere mass (kg) ¼ sphere volume (m3) * material density (kg/m3)
Mass of silica sphere ¼ (p/6) * (d)3 * 2600 ¼ (p/6) * (1  108)3 * 2600 ¼ 1.4  1021 kg
Mass of fully grown acid droplet ¼ (p/6)  (D)3 * 1600 ¼ (p/6) * (3  106)3 * 1600
¼ 2.3  1014 kg
Mass% silica
in fully grown ¼ ½mass silica=ðmass acid þ mass silicaÞ  100
acid droplet  
¼ 1:4  1021 kg=ð2:3  1014 kg þ 1:4  1021 kgÞ  100
¼ 6  106 mass% silicaa or 6 ppm mass silica
It shows that 10 nm (1  108m) diameter silica particles cause very little contamination.
a
Note that when the original silica particle diameter is 1  107 m, the silica content in the fully grown acid drop
is 6  103 mass%.

H2 SO4 ðgÞ ! H2 SO4 ðlÞ (26.3)

in SO3 , H2 OðgÞ in condensed
O2 , N2 , CO2 sulfuric acid ð260-90 CÞ
oxidation exit gas ð270-290 CÞ

and
H 2 O ð gÞ ! H2 OðlÞ (26.4)
in H2 SO4 ðgÞ, SO3 , in sulfuric acid ð260-90 CÞ
O2 , CO2
condenser feed gas ð270-290 CÞ

The process starts with hot 270-290  C feed gas and condenses sulfuric acid by cooling
the gas in air-cooled glass tubes (Fig. 26.6). Reaction (26.3) predominates under these
conditions because H2SO4(ℓ) condenses at a much higher temperature than H2O(ℓ).
H2O(ℓ) absorption in acid only becomes significant near the top of the condenser where:
(a) most of the H2SO4(g) has already condensed
(b) the gas has been cooled to
110  C.

The result is the production of:

(a) high-strength [98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ)] sulfuric acid at the bottom of the
condenser
(b) SO3, H2SO4(g)-depleted gas at the top of the condenser.
304 Sulfuric Acid Manufacture

To environment

H2O, O2, N2, CO2, tail gas

100-120 °C
H2SO4
condensation
Secondary filter
droplet filters
Dust-free
cooling air
25-60 °C

Glass condenser tubes

Warm air
190-230 °C

270-290 °C Dripping acid

Condenser feed gas

98 mass% H2SO4,
2 mass% H2O acid to
cooling and market
Figure 26.6 Sulfuric acid condenser. Hot feed gas enters bottom left and ascends the glass
condensation tubes. Hot condensed sulfuric acid leaves at the bottom. Cool sulfur-depleted gas
departs at the top. Cool cooling air enters top left. Warmed cooling air leaves bottom left.
Note how the cooling air is forced to move around the tubes as it moves down the condenser.
The glass tubes are 0.04 m outside diameter, 0.0046 m thick, and 6.8 m tall. An industrial
condenser typically contains 1000-10,000 tubes.

The product acid composition is mostly independent of:

(a) the total S concentration of the feed gas

(b) the H2O/S concentration ratio of the feed gas
(c) the temperature in the condenser.

This is the essence of the wet sulfuric acid process, i.e., its use of condensation to pro-
duce high-strength sulfuric acid from H2O(g)-bearing, low SO2 strength acid plant
feed gas.
Wet sulfuric acid process fundamentals 305

26.3.1 Industrial condenser operation

Figure 26.6 sketches a wet sulfuric acid plant condenser. The major flows are:

(a) input of nanoparticle-laden H2SO4(g), H2O(g), O2, N2, CO2, process gas 270-290  C
(lower left)
(b) output of liquid 98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ) sulfuric acid
250  C (bottom)
(c) output of H2SO4(g)—depleted H2O(g), O2, N2, CO2, offgas 100-120  C (top).

Two other flows are:

(a) input of cool air coolant 25-60  C (top left)

(b) output of warmed air coolant 190-230  C (bottom left).

26.3.2 Borosilicate glass

Borosilicate glass is the material of choice for the condenser tubes. It is the only mate-
rial that:

(a) can withstand long-term exposure to hot (up to
270  C) sulfuric acid
and
(b) has a low coefficient of thermal expansion so that it avoids expansion stresses top
(110  C) to bottom (270  C) in the glass tubes.

26.4 Condenser temperature choices

The purpose of the glass tube condenser is to condense virtually all the input gas’s
H2SO4(g) as sulfuric acid during the gas’s passage up the glass condenser tubes.
The next four subsections describe condenser temperatures chosen to achieve this
purpose.

26.4.1 Input process gas temperature

The temperature of the input process gas must be higher than the sulfuric acid dew
point of the gas. Otherwise, sulfuric acid will condense in and corrode the process
gas input flue and the upstream gas heat exchanger. The input flue gas temperature
is typically 270-290  C. This temperature is usually kept 20-30  C above the acid
dew point, which increases with increasing feed gas SO2 concentration.

26.4.2 Output process gas temperature

The output process gas temperature is chosen so that the gas contains very little uncon-
densed H2SO4(g). Specifically, it is chosen so that the H2SO4(g) vapor pressure of the con-
densing acid at the top of the condensing tube is
2  106 bar, which is equivalent to

2  104 volume% H2SO4(g) in the gas. The output gas temperature is typically 110  C.
306 Sulfuric Acid Manufacture

26.4.3 Input cooling air temperature

The input cooling air must be cooler than the temperature specified for the exiting
H2SO4(g)-barren process gas. Industrial condenser operates with the additional spec-
ification that the input cooling must not be more than 90  C cooler than the exiting
process gas. This is to avoid homogeneous sulfuric acid mist condensation near the
top of the gas tubes—and consequent mist escape through the top filters. Cooling
air input temperature is usually ambient, or slightly higher, i.e., 25-60  C.

26.4.4 Output cooling air temperature

Output cooling air temperature must be lower than the process gas input temperature.
This ensures that the process gas is being cooled over the whole length of the glass
condenser tubes. However, the process gas must not be so cool that sulfuric acid
mist condenses homogeneously inside the glass tubes (Schoubye, 1993). This restricts
exit cooling air temperature to above
190  C.
The sensible heat in this warmed exit cooling air is not wasted. It is recovered by
using it for combustion and heating duties around the plant.

26.4.5 Condenser reactions

Condenser feed gas enters the condenser at 270-290  C. It is cooled by indirect air
cooling through the glass tube walls. Once the gas is cooled below its sulfuric acid
dewpoint, liquid acid begins to condense:
(a) on the feed gas’s silica seed particles
(b) on the glass walls and descending cool acid
(c) homogeneously.

(a) is the largest contributor to condensation because of the large surface area of the
seeds. Wall condensation (b) is second.
Homogeneous condensation (c) is a small contributor because the process gas tem-
perature is controlled to always be only slightly below the acid dewpoint temperature.
This thermodynamically favors heterogeneous condensation.

26.4.6 Acid collection

The condensed acid-on-silica droplets are mainly collected in the filters atop each gas
tube. There the acid droplets combine and flow down the tube walls to the collection area
at the bottom of the condenser. Additional droplets are caught in the descending acid.
Much of the acid flows down on top of a 0.003-m gas spiral attached to the tube’s
inside wall for this purpose.
Wet sulfuric acid process fundamentals 307

26.5 Condenser acid composition up the glass tube

26.5.1 Condenser feed gas first condensate (near the bottom of
the glass tubes)
The acid that first condenses near the bottom of the glass tubes is
98 mass%
H2SO4(ℓ)  2 mass% H2O(ℓ). This occurs at
250  C which is much hotter than the
dewpoint temperature of H2O(ℓ). The net result is that:

(a) H2SO4(ℓ) condensation is strongly favored over H2O(ℓ) condensation

(b) the feed gas’s first condensate is mostly H2SO4(ℓ).

26.5.2 Last condensate (near the top of the glass tubes)

The last acid to condense (where the cooling air enters) contains
75 mass% H2SO4(ℓ)
and 25 mass% H2O(ℓ) (Schoubye, 1993). It is diluted in H2SO4(ℓ) because:

(a) most of the H2SO4(g) in the original condenser feed gas has already condensed lower in
the glass tubes
(b) the gas temperature at the top of the glass tubes is low (
110  C) allowing more H2O to
be absorbed into the acid.

The results are considerable H2O(ℓ) condensation, less H2SO4(ℓ) condensation, and 75
mass% H2SO4(ℓ)-25 mass% H2O(ℓ) condensate.

26.6 Condenser re-evaporation of H2O(ℓ)

The previous section indicates that 75 mass% H2SO4(ℓ)  25 mass% H2O(ℓ) acid
condenses near the top of the condenser tubes. Yet the product of the condenser is
almost always
98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ) acid.
This strengthening is caused by re-evaporation of H2O(g) from the weak acid
condensate as it flows down to the hot bottom of the condenser.
This explains the high H2SO4(ℓ)-strength product of the condenser in spite of a high
H2O(g) concentration in its feed gas.
It should be noted that with extremely low feed gas SO2 concentrations
0.2-0.4
volume% SO2, the product acid contains 94-95 mass% H2SO4 (Laursen and Jensen,
2007). This acid concentration is suitable for sale and use in most industries.

26.6.1 Evaporation limit—The H2SO4(ℓ)-H2O(ℓ) azeotrope

The H2SO4(ℓ)-H2O(ℓ) system has an azeotrope at 98.8 mass% H2SO4(ℓ)  1.2 mass%
H2O(ℓ) (Bolsaitis and Elliott, 1990). The weak condensate from the top of the glass
condenser cannot be strengthened by evaporation beyond this composition. This is
308 Sulfuric Acid Manufacture

because at the azeotrope composition the evaporate (gas) composition is the same as
the liquid composition.
This explains the almost constant composition of the condenser product in spite of
varying condenser feed gas composition.

26.7 Condenser acid production rate

Table 26.3 calculates glass tube acid production rate. It indicates that each glass tube
produces
2 kg of 98 mass% H2SO4 acid per hour.
For a 1000-tube condenser, this is equivalent to 2 tonnes (2000 kg) per hour or

50 tonnes per day.
For a 10,000-tube condenser, it is equivalent to
500 tonnes of 98 mass% H2SO4
acid per day.

Table 26.3 Acid condensation rate calculation. It indicates that each condenser tube produces

2 kg of acid per hour, depending on feed gas composition.
Specifications
Feed gas flow rate into each condenser tube ¼ 15 Nm3/h (industrial estimate)
Feed gas composition specification ¼ 3 volume (mole)% [SO3(g) þ H2SO4(g)]
Product acid composition specification ¼ 98 mass% H2SO4(ℓ), 2 mass% H2O(ℓ)
Calculations
Equivalent
kg mol of feed gas ¼ 15 Nm3 feed gas per hour=22:4 Nm3 of gas per kg mol of gas
per hour
¼ 0:67 kg mol of feed gas per hour
Equivalent
kg mol of
¼ ð3%½SO3 þ H2 SO4 ðgÞ=100%Þ  0:67 kg mol of gas per hour
S in feed gas
per hour
¼ 0:02 kg mol S per hour
Virtually, all this S ends up in condensed H2SO4(ℓ) so that the H2SO4(ℓ) condensation rate
is 0.02 kg mol H2SO4(ℓ) per hour
Mass calculations
Mass H2 SO4 ðlÞ=h ¼ 0:02 kg mol of H2 SO4 ðlÞ=h  98 kg per kg mol of H2 SO4 ðlÞ
¼ 1:96 kg H2 SO4 ðlÞ=h
Equivalent
mass of 98 mass% ¼ 1:96 kg H2 SO4 ðlÞ=h=½98 mass% H2 SO4 ðlÞ in acid=100%
H2 SO4 ðlÞ acid
¼ 2 kg acid per hour per glass tube
Wet sulfuric acid process fundamentals 309

26.7.1 Condenser gas velocity and residence time

Table 26.4 calculates gas velocity and gas residence time in the condenser tubes. The
residence time is
0.7 s.
This indicates that near-complete acid condensation from nanoparticle laden gas is
quite rapid.

Table 26.4 Gas velocity and gas residence time in glass condenser tubes. Gas residence
time is shown to be about 0.7 s.
Specifications
Glass condenser tube dimensions, inside 6.8 m tall (h)  0.03-m diameter (d)
Feed gas flow rate into each condenser tube 15 Nm3/h  4.2  103 Nm3/s
(industrial information)
Feed gas entry temperature 270  C (543 K)
Gas exit temperature 110  C (383 K)
Gas average temperature 190  C (463 K)

Calculations
Average gas

flow ratea ðm3 =sÞ ¼ feed gas flow rate Nm3 =s  ½gas average temperature ðKÞ=273 K
¼ 4:2  103 Nm3 =s  ð463 K=273 KÞ ¼ 7:1  103 m3 =s
Average gas
¼ average gas flow rateðm3 =sÞ=tube crosssectional areaðm2 Þ
velocity ðm=sÞ 

¼ 7:1  103 m3 =s= p  d2 =4 m2 ¼ 7:1  103 m3 =s½p  ð0:03Þ22=4
¼ 10 m=s
Gas residence time ¼ tube length ðmÞ=average gas velocity ðm=sÞ
¼ 6:8 m=10 m=s ¼ 0:7 s
a
Assumes pressure in tube ¼ atmospheric pressure.

26.8 Condenser appraisal

Condensation produces strong sulfuric acid from H2O(g)-laden, weak [SO3 þ
H2SO4(g)] (2-3 volume%) gas. This makes it indispensable as the last step in treating
S-bearing hydrocarbon wastes and moist SO2-bearing sulfide concentrate hearth
roaster exit gases.
It is also used to treat gases containing
6.5 volume% [SO3(g) þ H2SO4(g)]. How-
ever, these gases can also be treated by conventional acidmaking so that condensation
is not indispensible.
Gases containing much more than
6.5 volume% [SO3 þ H2SO4(g)] cannot be
treated by condensation because the acid dewpoint temperature of these gases is quite
high, e.g., 270-300  C. The materials utilized in the WSA condenser are less suitable
at these high temperatures.
310 Sulfuric Acid Manufacture

The proposed WSA-DC process overcomes these limitations by using two acid
condensation steps (Rosenberg, 2009). The first WSA-DC plant is expected to
start-up in China in early 2014.

26.9 Summary
The first major step in wet sulfuric acidmaking is SO2 þ 0.5O2 ! SO3 oxidation. It is
similar to dry gas SO2 oxidation, but with physically stronger catalyst.
15-20% of the SO3 produced by SO2 oxidation reacts with feed gas H2O(g) to form
H2SO4(g). H2SO4(g) does not condense at catalytic converter operating temperatures
so its formation does not cause a problem.
The SO3 þ H2O(g) ! H2SO4(g) reaction beneficially produces heat for the use
throughout the acid plant.
Condensation of sulfuric acid from SO3, H2O(g), H2SO4(g), O2, N2, CO2 gas
requires prior injection of solid nanoparticles into the gas. Without these particles:
(a) condensation takes place homogeneously in very small droplets (acid mist) that are very
difficult to separate
(b) H2SO4(ℓ), as fine acid mist, is emitted into the environment.

An effective way to inject nanoparticles into the gas is to:

(a) burn silicone oil with other fuel and air and
(b) blow the resulting smoke into the process gas flue.

Automatic control of this combustion system maximizes acid condensation and min-
imizes sulfur emission to the environment.
Condensation is the last step in producing high-strength sulfuric acid from H2O(g)-
bearing, low SO2(g) strength gases.
It starts with silica nanoparticle-laden H2SO4(g), H2O(g), SO3, O2, N2, CO2 gas and
produces:
(a)
98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ) sulfuric acid and
(b) sulfur-depleted offgas.

The condensation is achieved by:

(a) blowing hot (270-290  C) nanoparticle-laden gas up through 0.04-m diameter glass con-
denser tubes
(b) cooling this process gas to
110  C by indirect counter current air cooling as the process
gas rises up the tubes
(c) condensing sulfuric acid on the silica nanoparticle seeds during this cooling
(d) catching the condensed acid droplets in filters atop the condenser tubes
(e) allowing the condensed acid droplets to combine and flow down the condenser tube walls
(f) collecting the condensed acid at the bottom of the condenser
(g) releasing filtered sulfur-depleted exit gas from the top of the tubes to the environment.

The acid from the process almost always contains
98 mass% H2SO4(ℓ)  2 mass%
H2O(ℓ).
Wet sulfuric acid process fundamentals 311

References
Bolsaitis, P., Elliott, J.F., 1990. Thermodynamic activities and equilibrium partial pressures for
aqueous sulfuric acid solutions. J. Chem. Eng. Data 35 (1), 69–85.
Christensen, K.A., 2008. Process for the production of sulfuric acid. U.S. Patent 7,361,326 B2.
Laursen, J.Kr., Jensen, F.E., 2007. Meeting industry demands. Sulphur 312, 80–85.
Rosenberg, H., 2009. WSA-DC—next generation Topsoe WSA technology for stronger SO2
gases and very high conversion. In: Sulphur and Sulphuric Acid Conference 2009,
Johannesburg, South Africa: SAIMM, pp. 27–35.
Schoubye, P.C.S., 1982. Process for the preparation of sulfuric acid. U.S. Patent 4,348,373.
Schoubye, P., 1993. Condensing sulfuric acid vapors to produce sulfuric acid. U.S. Patent
5,198,206.
Haldor Tops
e, 2008. VK-W series wet gas sulphuric acid catalysts. Retrieved on October 19,
2012 from http://www.topsoe.com/business_areas/sulphuric_acid/
/media/PDF%20files/
WSA/Topsoe_VK%20W_catalyst_series.ashx
TSI, 2012. TSI Particle Technology. TSI Incorporated, Shoreview, Minnesota.

Suggested reading
Degerman, M., Nilsson, B., Odenbrand, I., Almvist, M., Andersson, N., Holmqvist, A.,
Jonsson, J., 2008. Simulation of a WSA process of SO2 containing off gases from the
metallurgical industry. Project report, Lund University, Faculty of Engineering, Depart-
ment of Chemical Engineering, May 13, 2008.
Laursen, J.Kr., Karavanov, A.N., 2006. Processes for sulfur recovery regeneration of spent acid,
and reduction of NOx emissions. Chem. Pet. Eng. 42 (5-6), 229–234.