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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:
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.
It is strongly exothermic (DH 25 C 100 MJ/kg mol of SO3). Its heat of reaction
provides considerable energy for operating the acid plant.
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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).
Table 1.1 Typical compositions (volume%) of acid plant feed gases entering SO2 oxidation
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converters, 2013. The gases may also contain small amounts of CO2 and SO3.
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() 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.
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.
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Overview 3
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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.
Reaction (1.2) produces strengthened sulfuric acid because it consumes H2O() and
makes H2SO4().
H2SO4() is not made by reacting SO3(g) with pure H2O(). This is because Reac-
tion (1.2) is so exothermic that the product of the SO3 H2O() ! H2SO4 reaction
would be hot H2SO4 vaporwhich is difficult and expensive to condense.
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4 Sulfuric Acid Manufacture
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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(), 1.5 mass% H2O()
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()
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() and the massive amount of H2SO4() in Reac-
tion (1.2)s input acid avoid this problem. The small amount of H2O() limits the
extent of the reaction. The large amount of H2SO4() warms only 25 C, while it
absorbs Eq. (1.2)s heat of reaction.
(b) is the same for all three sources of SO2. The next three sections describe (a)s three
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SO2 sources.
Overview
metallurgical offgas
Dried air
Spent acid
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Gas cooling
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() making towers at the bottom. Barren tail gas leaves the final H2SO4() making tower, right arrow.
5
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6 Sulfuric Acid Manufacture
(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() making.
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() making.
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) furnacewhere the acid decomposes to SO2,
O2, and H2O(g)
(b) cleaning, drying, and heating the furnace offgas
(c) catalytically oxidizing the offgass SO2 to SO3
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Overview 7
(d) making the resulting SO3 into new H2SO4() by contact with strong sulfuric acid
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(Fig. 1.4).
About 10% of sulfuric acid is made this way. Virtually, all is reused for petroleum
refining and polymer manufacture.
and:
(b) condenses strong (98 mass% H2SO4() 2 mass% H2O()) sulfuric acid directly from
this oxidized gas.
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8 Sulfuric Acid Manufacture
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() 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:
References
Apodaca, L.E., 2012. Sulfur Mineral Commodity Summary. United States Geological Survey,
applicable copyright law.
Washington, DC.
Christensen, K., Polk, P., 2011. SO2 emission reduction by Topses new VK-701 LEAP5
catalyst. Sulfuric Acid Today 17 (1), 2324.
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),
1618.
Gable, C.M., Betz, H.F., Maron, S.H., 1950. Phase equilibria of the system sulfur trioxide-water.
J. Am. Chem. Soc. 72, 14451448.
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Overview 9
King, M.J., Forzatti, R.J., 2009. Sulphur based by-products from the non-ferrous metals industry.
Copyright 2013. Elsevier. All rights reserved. May not be reproduced in any form without permission from the publisher, except fair uses permitted under U.S. or
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. 137149.
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. 5961.
Laursen, J.K., Jensen, F.E., 2007. WSAmeeting industry demands. Sulfur 312, 8085.
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.
applicable copyright law.
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