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1 Overview

Sulfuric acid is a dense clear liquid. It is used for making fertilizers, leaching metallic
ores, refining petroleum, and manufacturing a myriad of chemicals and materials. World-
wide, about 200 million tonnes of sulfuric acid is consumed per year (Apodaca, 2012).
The raw material for sulfuric acid is SO2 gas. It is obtained by:

(a) burning elemental sulfur with air


(b) smelting and roasting metal sulfide minerals
(c) decomposing contaminated (spent) sulfuric acid catalyst.

Elemental sulfur is far and away the largest source.


Table 1.1 describes three typical sulfuric acid plant feed gases. It shows that acid
plant SO2 feed is always mixed with other gases.
Sulfuric acid is almost always made from these gases by:

(a) catalytically reacting their SO2 and O2 to form SO3(g)


(b) reacting (a)’s product SO3 with the H2O(ℓ) in 98.5 mass% H2SO4(ℓ), 1.5 mass% H2O(ℓ)
sulfuric acid.

Industrially, both processes are carried out rapidly and continuously (Fig. 1.1).
The standard state for SO2, SO3, O2, N2, and CO2 is gas in the acid plant. Each is
referenced in this book, for example, as O2 not O2(g). The standard state for H2O, S,
and H2SO4 is gas or liquid in the acid plant. Each is referenced accordingly.

1.1 Catalytic oxidation of SO2 to SO3


O2 does not oxidize SO2 to SO3 without a catalyst. All industrial SO2 oxidation is done
by sending SO2 bearing gas down through “beds” of catalyst (Fig. 1.2). The reaction is:
400-630  C
SO2 þ 0:5O2 ƒƒƒƒƒ! SO3 (1.1)
in dry SO2 , O2 , N2 gas in feed gas catalyst in SO3 , SO2 , O2 , N2 exit gas

It is strongly exothermic (DH 25 C ¼  100 MJ/kg mol of SO3). Its heat of reaction
provides considerable energy for operating the acid plant.

1.1.1 Catalyst
At normal operating temperature, 400-630  C, SO2 oxidation catalyst consists of a molten
film of V, K, Na, Cs pyrosulfate salt on a solid porous SiO2 substrate. The molten film
rapidly absorbs SO2 and O2 and rapidly produces and desorbs SO3 (Chapters 7 and 8).

Sulfuric Acid Manufacture. http://dx.doi.org/10.1016/B978-0-08-098220-5.00001-0


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

Table 1.1 Typical compositions (volume%) of acid plant feed gases entering SO2 oxidation
“converters,” 2013. The gases may also contain small amounts of CO2 and SO3.

Gas Sulfur burning Sulfide mineral smelters Spent acid decomposition


furnace and roasters furnace

SO2 12 10 9
O2 9 11 11
N2 79 79 76

Absorption

Converter

Drying

Furnace

Figure 1.1 Modern 4100 tonnes/day sulfur burning sulfuric acid plant, courtesy PCS
Phosphate Company, Inc. (2012). The main components are the catalytic SO2 oxidation
“converter” (tall, right), twin H2SO4(ℓ) making (“absorption”) towers (middle, right of stack)
and a sulfur burning furnace (middle, bottom). The air dehydration (“drying”) tower is left
of the stack. The catalytic converter is 16.5 m diameter.

1.1.2 Feed gas drying


Equation (1.1) indicates that catalytic oxidation feed gas is almost always dry.1 This
dryness avoids:

(a) accidental formation of H2SO4 by the reaction of H2O(g) with the SO3 product of cat-
alytic SO2 oxidation

1
A small amount of sulfuric acid is made by wet catalysis. This is discussed in Section 1.9 and Chapters 25
and 26.
Overview 3

Catalyst

Catalyst

~20 m
Catalyst

Catalyst ~0.5-1 m

~12 m
Figure 1.2 Catalyst pieces in a catalytic SO2 oxidation “converter.” Converters are typically
20 m high and 12 m diameter. They typically contain four, 0.5- to 1-m-thick catalyst beds.
SO2-bearing gas descends the bed at 3000 Nm3/min. Catalyst pieces are 10 mm in diameter
and length. Copyright 2013 MECS, Inc. All rights reserved. Used by permission of MECS, Inc.

(b) condensation of the H2SO4(ℓ) in cool flues and heat exchangers


(c) corrosion.

The H2O(g) is removed by cooling/condensation (Chapter 4) and by dehydration with


H2SO4(ℓ) (Chapter 6).

1.2 H2SO4 production


Catalytic oxidation’s SO3 product is made into H2SO4(ℓ) by contacting catalytic oxi-
dation’s exit gas with strong sulfuric acid (Fig. 1.3). The reaction is:
80-110  C
SO3 þ H 2 O ðl Þ ƒƒƒƒƒƒƒ! H2 SO4 ðlÞ ,
in SO3 SO2 , O2 , N2 gas in 98:5% H2 SO4 ðlÞ, 1:5% H2 OðlÞ sulfuric acid in strengthened sulfuric acid

DH  25  C  130 MJ=kg mol of SO3 (1.2)

Reaction (1.2) produces strengthened sulfuric acid because it consumes H2O(ℓ) and
makes H2SO4(ℓ).
H2SO4(ℓ) is not made by reacting SO3(g) with pure H2O(ℓ). This is because Reac-
tion (1.2) is so exothermic that the product of the SO3 þ H2O(ℓ) ! H2SO4 reaction
would be hot H2SO4 vapor—which is difficult and expensive to condense.
4 Sulfuric Acid Manufacture

Figure 1.3 Top of H2SO4 making (“absorption”) tower, courtesy MECS (www.mecsglobal.
com). The tower is packed with ceramic saddles. 98.5 mass% H2SO4(ℓ), 1.5 mass% H2O(ℓ)
sulfuric acid is distributed uniformly across this packed bed. Distributor headers and
“downcomer” pipes are shown. The acid flows through slots in the downcomers down across the
bed (see buried downcomers at the right of the photograph). It descends around the saddles,
while SO3-rich gas ascends, giving excellent gas-liquid contact. The result is efficient H2SO4(ℓ)
production by Reaction (1.2). A tower is 7 m diameter. Its packed bed is 4 m deep. About
25 m3 of acid descends per minute, while 3000 Nm3 of gas ascends per minute.

The small amount of H2O(ℓ) and the massive amount of H2SO4(ℓ) in Reac-
tion (1.2)’s input acid avoid this problem. The small amount of H2O(ℓ) limits the
extent of the reaction. The large amount of H2SO4(ℓ) warms only 25  C, while it
absorbs Eq. (1.2)’s heat of reaction.

1.3 Industrial flowsheet


Figure 1.4 is a sulfuric acid manufacture flowsheet. It shows:
(a) the three sources of SO2 for acid manufacture (metallurgical, sulfur burning, and spent
acid decomposition gas)
(b) acid manufacture from SO2 by Reactions (1.1) and (1.2).

(b) is the same for all three sources of SO2. The next three sections describe (a)’s three
SO2 sources.

1.4 Sulfur burning


About 60% of sulfuric acid is made from elemental sulfur (Chapter 3). Virtually, all
the sulfur is obtained as a byproduct from refining natural gas and petroleum.
10-75% SO2 dusty Elemental sulfur Spent sulfuric acid

Overview
metallurgical offgas
Dried air
Spent acid
Gas cooling Sulfur burning furnace
Dilution with low decomposition
S + O2 → SO2
SO2 in-plant gas
8-14% SO2, 2% O2, remainder
CO2, H 2O(g), and N2
Dust removal by electrostatic
12% SO2, 9% O2, 79% N 2
precipitation and aqueous
Gas cooling and aqueous
scrubbing
Gas cooling scrubbing

Gas drying and heating Gas drying and heating


~420 °C
Air Air
Catalyst layers
Gas cooling
SO2 + 0.5O2 → SO3
Gas cooling

Gas cooling

SO3 rich, SO3, SO2, O2, N 2 gas


SO2 (trace), O2, N 2 gas
to environment

SO3 free, SO2, O2, N 2 gas


Gas heating
98.5% H 2SO4 acid 98.5% H 2SO4 acid
SO2 +0.5O2 → SO3
SO3(g) + H 2O in acid → H 2SO4(l) SO3(g) + H 2O in acid → H 2SO4(l)
Packed bed Gas cooling Packed bed

SO2 (trace), SO3, O2, N 2 gas

H 2SO4 strengthened acid to H 2SO4 strengthened acid to


dilution, recycle, and market dilution, recycle, and market

Figure 1.4 Double contact sulfuric acid manufacture flowsheet. The three main SO2 sources are at the top. Sulfur burning is by far the biggest source.
The acid product leaves from two H2SO4(ℓ) making towers at the bottom. Barren tail gas leaves the final H2SO4(ℓ) making tower, right arrow.

5
6 Sulfuric Acid Manufacture

The sulfur is made into SO2 acid plant feed by


(a) melting the sulfur
(b) spraying it into a hot furnace
(c) burning the droplets with dried air.

The reaction is:


1150  C
SðlÞ þ O2 ƒƒƒƒ! SO2 , DH  25  C  300 MJ=kg mol of SðlÞ:
in dry air in SO2 , O2 , N2 gas

(1.3)
Very little SO3 forms at the 1150  C flame temperature of this reaction (Fig. 7.4). This
explains the two-step oxidation shown in Fig. 1.4:
(a) burning of sulfur to SO2

then:
(b) catalytic oxidation of SO2 to SO3, 400-630  C.

The product of sulfur burning is hot, dry SO2, O2, N2 gas. After cooling to 400  C, it
is ready for catalytic SO2 oxidation and subsequent H2SO4(ℓ) making.

1.5 Metallurgical offgas


SO2 in smelting and roasting gas accounts for about 30% of sulfuric acid production
(Chapter 4). The SO2 is ready for sulfuric acid manufacture, but the gas is dusty. If left
in the gas, the dust would plug the downstream catalyst layers and block gas flow.
It must be removed before the gas goes to catalytic SO2 oxidation.
It is removed by combinations of:
(a) settling in heat recovery boilers
(b) electrostatic precipitation
(c) scrubbing with water (which also removes impurity vapors).

After treatment, the gas contains 1 mg of dust per dry Nm3 of gas. It is ready for
drying, heating, catalytic SO2 oxidation, and H2SO4(ℓ) making.

1.6 Spent acid regeneration


A major use of sulfuric acid is as catalyst for petroleum refining and polymer man-
ufacture (Chapter 5). The acid becomes contaminated with water, hydrocarbons,
and other compounds during this use. It is regenerated by:
(a) spraying the acid into a hot (1050  C) furnace—where the acid decomposes to SO2,
O2, and H2O(g)
(b) cleaning, drying, and heating the furnace offgas
(c) catalytically oxidizing the offgas’s SO2 to SO3
Overview 7

(d) making the resulting SO3 into new H2SO4(ℓ) by contact with strong sulfuric acid
(Fig. 1.4).

About 10% of sulfuric acid is made this way. Virtually, all is reused for petroleum
refining and polymer manufacture.

1.7 Sulfuric acid product


Most industrial acid plants have three flows of sulfuric acid—one gas-dehydration
flow and two H2SO4(ℓ)-making flows. These flows are connected through automatic
control valves to:
(a) maintain proper flows and H2SO4(ℓ) concentrations in the three acid circuits
(b) draw off newly made acid.

Water is added where necessary to give prescribed acid strengths.


Sulfuric acid is sold in grades of 93-99 mass% H2SO4(ℓ) according to market
demand. The main product in cold climates is 94% H2SO4(ℓ) because of its low
(35  C) freezing point (Gable et al., 1950). A small amount of oleum (H2SO4(ℓ) with
dissolved SO3) is also produced (King and Forzatti, 2009).
Sulfuric acid is mainly shipped in stainless steel trucks, steel rail tank cars, and
double-hulled steel barges and ships (Louie, 2008). Great care is taken to avoid spillage.

1.8 Recent developments


The three main recent developments in sulfuric acidmaking have been:
(a) improved materials of construction (Chapter 30), specifically more corrosion-resistant
materials
(b) improved SO2 þ 0.5 O2 ! SO3 catalyst, specifically V, Cs, K, Na, S, O, SiO2 catalyst
with low activation temperatures (Christensen and Polk, 2011; Felthouse et al., 2011)
(c) improved techniques for recovering the heat from Reactions (1.1)–(1.3) (Viergutz, 2009).

All of these improve H2SO4 and energy recovery.

1.9 Alternative processes


1.9.1 Wet gas sulfuric acid
An alternative to the conventional acidmaking described above is the Wet gas Sulfuric
Acid (WSA; Laursen and Jensen, 2007) process. This process:
(a) catalytically oxidizes the SO2 in H2O(g), SO2, O2, N2 gas

and:
(b) condenses strong (98 mass% H2SO4(ℓ)  2 mass% H2O(ℓ)) sulfuric acid directly from
this oxidized gas.
8 Sulfuric Acid Manufacture

It is described in Chapters 25 and 26.


In 2013, it is mainly used for removing SO2 from moist, dilute (3 volume% SO2)
waste gases (Chapter 25). It accounts for  3% of world sulfuric acid production.

1.9.2 Sulfacid®
About 20 Sulfacid® installations worldwide produce weak sulfuric acid (10-20%
H2SO4) from very low concentration gases (<1.0 volume% SO2) using an activated
carbon catalytic reactor where SO2 reacts with O2 and H2O(ℓ) at 30-80  C to produce
H2SO4 (Kruger, 2004). The acid is intermittently washed with water from the
catalyst which produces weak sulphuric acid. The cleaned gas is discharged to
the atmosphere.
The sulfuric acid is often used for other on-site processes (e.g., titanium dioxide
production) or sold.

1.10 Summary
About 200 million tonnes of sulfuric acid are produced/consumed per year. The acid is
used for making fertilizer, leaching metal ores, refining petroleum and for
manufacturing a myriad of products.
Sulfuric acid is made from dry SO2, O2, N2 gas. The gas comes from:

(a) burning molten elemental sulfur with dry air (Chapter 3)


(b) smelting and roasting metal sulfide minerals (Chapter 4)
(c) decomposing contaminated (spent) sulfuric acid catalyst (Chapter 5).

Sulfur burning is far and away the largest source.


The SO2 in the gas is made into sulfuric acid by

(a) catalytically oxidizing it to SO3 (Chapters 7 and 8)


(b) reacting this SO3 with the H2O(ℓ) in 98.5 mass% H2SO4(ℓ), 1.5 mass% H2O(ℓ) sulfuric
acid (Chapter 9).

References
Apodaca, L.E., 2012. Sulfur Mineral Commodity Summary. United States Geological Survey,
Washington, DC.
Christensen, K., Polk, P., 2011. SO2 emission reduction by Topse’s new VK-701 LEAP5™
catalyst. Sulfuric Acid Today 17 (1), 23–24.
Felthouse, T.R., DiGiovanni, M.P., Horne, J.R., Richardson, S.A., 2011. Improving sulfuric
acid plant performance with MECS’ new GEAR catalysts. Sulfuric Acid Today 17 (2),
16–18.
Gable, C.M., Betz, H.F., Maron, S.H., 1950. Phase equilibria of the system sulfur trioxide-water.
J. Am. Chem. Soc. 72, 1445–1448.
Overview 9

King, M.J., Forzatti, R.J., 2009. Sulphur based by-products from the non-ferrous metals industry.
In: Liu, J., Peacey, J., Barati, M., Kashani-Nejad, S., Davis, B. (Eds.), Pyrometallurgy of
Nickel and Cobalt 2009: Proceedings of the 48th Conference of Metallurgists of CIM.
CIM METSOC, Montreal, pp. 137–149.
Kruger, B., 2004. Recovery of SO2 from low strength off-gases. In: International Platinum
Conference ‘Platinum Surges Ahead’. The Southern African Institute of Mining and
Metallurgy, Johannesburg, pp. 59–61.
Laursen, J.K., Jensen, F.E., 2007. WSA—meeting industry demands. Sulfur 312, 80–85.
Louie, D.K., 2008. Handbook of sulphuric acid manufacturing, second ed. DKL Engineering
Inc., Richmond Hill, Ontario, Canada.
Viergutz, M.D., 2009. Heat recovery system update. In: Proceedings of the Sulphur and Sulphuric
Acid Conference. The Southern African Institute of Mining and Metallurgy, Johannesburg.

Suggested reading
Louie, D., 2010. Sulphuric acid plant fundamentals. In: Sulfuric Acid Short Course Given at
COM 2010, Vancouver, Canada, October 2-6, 2010.
Sander, U.H.F., Fischer, H., Rothe, U., Kola, R., More, A.I., Sander, U.H.F., Fischer, H.,
Rothe, U., Kola, R., More, A.I., 1984. Sulphur, Sulphur Dioxide and Sulphuric Acid.
The British Sulphur Corporation Ltd, London.