Sulfuric Acid Manufacture - 2nd Edition - ISBN: 9780080982205, 9780080982267

Sulfuric Acid Manufacture

2nd Edition

Analysis, Control and Optimization

Authors: Matt King Michael Moats William Davenport
Hardcover ISBN: 9780080982205
eBook ISBN: 9780080982267
Imprint: Elsevier
Published Date: 29th May 2013
Page Count: 608
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By some measure the most widely produced chemical in the world today, sulfuric acid has an extraordinary range of modern uses, including phosphate fertilizer production, explosives, glue, wood preservative and lead-acid batteries. An exceptionally corrosive and dangerous acid, production of sulfuric acid requires stringent adherence to environmental regulatory guidance within cost-efficient standards of production.

This work provides an experience-based review of how sulfuric acid plants work, how they should be designed and how they should be operated for maximum sulfur capture and minimum environmental impact. Using a combination of practical experience and deep physical analysis, Davenport and King review sulfur manufacturing in the contemporary world where regulatory guidance is becoming ever tighter (and where new processes are being required to meet them), and where water consumption and energy considerations are being brought to bear on sulfuric acid plant operations. This 2e will examine in particular newly developed acid-making processes and new methods of minimizing unwanted sulfur emissions.

The target readers are recently graduated science and engineering students who are entering the chemical industry and experienced professionals within chemical plant design companies, chemical plant production companies, sulfuric acid recycling companies and sulfuric acid users. They will use the book to design, control, optimize and operate sulfuric acid plants around the world.

Key Features

  • Unique mathematical analysis of sulfuric acid manufacturing processes, providing a sound basis for optimizing sulfuric acid manufacturing processes
  • Analysis of recently developed sulfuric acid manufacturing techniques suggests advantages and disadvantages of the new processes from the energy and environmental points of view
  • Analysis of tail gas sulfur capture processes indicates the best way to combine sulfuric acid making and tailgas sulfur-capture processes from the energy and environmental points of view
  • Draws on industrial connections of the authors through years of hands-on experience in sulfuric acid manufacture


Chemists, Chemical Engineers, Industrial Engineers, Chemical plant operators, chemical manufacturers; Any researcher, scientist, and student with an interest in sulfuric acid

Table of Contents


1. Overview

1.1 Catalytic oxidation of SO2 to SO3

1.2 H2SO4 production

1.3 Industrial flowsheet

1.4 Sulfur burning

1.5 Metallurgical offgas

1.6 Spent acid regeneration

1.7 Sulfuric acid product

1.8 Recent developments

1.9 Alternative processes

1.10 Summary


Suggested reading

2. Production and consumption

2.1 Uses

2.2 Acid plant locations

2.3 Price

2.4 Summary


Suggested reading

3. Sulfur burning

3.1 Objectives

3.2 Sulfur

3.3 Molten sulfur delivery

3.4 Sulfur atomizers and sulfur burning furnaces

3.5 Product gas

3.6 Heat recovery boiler

3.7 Summary


Suggested reading

4. Metallurgical offgas cooling and cleaning

4.1 Initial and final SO2 concentrations

4.2 Initial and final dust concentrations

4.3 Offgas cooling and heat recovery

4.4 Electrostatic collection of dust

4.5 Water scrubbing (Tables 4.5 and 4.6)

4.6 H2O(g) removal from scrubber exit gas (Tables 4.5 and 4.6)

4.7 Summary


Suggested reading

5. Regeneration of spent sulfuric acid

5.1 Spent acid compositions

5.2 Spent acid handling

5.3 Decomposition

5.4 Decomposition furnace product

5.5 Optimum decomposition furnace operating conditions

5.6 Preparation of offgas for SO2 oxidation and H2SO4 making

5.7 Summary


Suggested Reading

6. Dehydrating air and gases with strong sulfuric acid

6.1 Chapter objectives

6.2 Dehydration with strong sulfuric acid

6.3 Dehydration reaction mechanism

6.4 Residence times

6.5 Recent advances

6.6 Summary


7. Catalytic oxidation of SO2 to SO3

7.1 Objectives

7.2 Industrial SO2 oxidation

7.3 Catalyst necessity

7.4 SO2 oxidation “heatup” path (Chapter 11)

7.5 Industrial multicatalyst bed SO2 oxidation (Tables 7.2–7.7)

7.6 Industrial operation (Table 7.2)

7.7 Recent advances

7.8 Summary


8. SO2 oxidation catalyst and catalyst beds

8.1 Catalytic reactions

8.2 Maximum and minimum catalyst operating temperatures

8.3 Composition and manufacture

8.4 Choice of size and shape

8.5 Catalyst bed thickness and diameter

8.6 Gas residence times

8.7 Catalyst bed temperatures

8.8 Catalyst bed maintenance

8.9 Summary


Suggested reading

9. Production of H2SO4(ℓ) from SO3(g)

9.1 Objectives

9.2 Sulfuric acid rather than water

9.3 Absorption reaction mechanism

9.4 Industrial H2SO4 making (Tables 9.3–9.8)

9.5 Choice of input and output acid compositions

9.6 Acid temperature

9.7 Gas temperatures

9.8 Operation and control

9.9 Double contact H2SO4 making (Tables 19.3 and 23.2)

9.10 Intermediate versus final H2SO4 making

9.11 Summary


Suggested reading


10. Oxidation of SO2 to SO3—Equilibrium curves

10.1 Catalytic oxidation

10.2 Equilibrium equation

10.3 KE as a function of temperature

10.4 KE in terms of % SO2oxidized

10.5 Equilibrium % SO2 oxidized as a function of temperature

10.6 Discussion

10.7 Summary

10.8 Problems


11. SO2 oxidation heatup paths

11.1 Heatup paths

11.2 Objectives

11.3 Preparing a heatup path—The first point

11.4 Assumptions

11.5 A specific example

11.6 Calculation strategy

11.7 Input SO2, O2, and N2 quantities

11.8 Sulfur, oxygen, and nitrogen molar balances

11.9 Enthalpy balance

11.10 Calculating level L quantities

11.11 Matrix calculation

11.12 Preparing a heatup path

11.13 Feed gas SO2 strength effect

11.14 Feed gas temperature effect

11.15 Significance of heatup path position and slope

11.16 Summary

11.17 Problems

12. Maximum SO2 oxidation: Heatup path-equilibrium curve intercepts

12.1 Initial specifications

12.2 % SO2 oxidized-temperature points near an intercept

12.3 Discussion

12.4 Effect of feed gas temperature on intercept

12.5 Inadequate % SO2 oxidized in first catalyst bed

12.6 Effect of feed gas SO2 strength on intercept

12.7 Minor influence—Equilibrium gas pressure

12.8 Minor influence—O2 strength in feed gas

12.9 Minor influence—CO2 in feed gas

12.10 Catalyst degradation, SO2 strength, and feed gas temperature

12.11 Maximum feed gas SO2 strength

12.12 Exit gas composition ≡ intercept gas composition

12.13 Summary

12.14 Problems

13. Cooling first catalyst bed exit gas

13.1 First catalyst bed summary

13.2 Cooldown path

13.3 Gas composition below equilibrium curve

13.4 Summary

13.5 Problem


14. Second catalyst bed heatup path

14.1 Objectives

14.2 % SO2 oxidized redefined

14.3 Second catalyst bed heatup path

14.4 A specific heatup path question

14.5 Second catalyst bed input gas quantities

14.6 S, O, and N molar balances

14.7 Enthalpy balance

14.8 Calculating 760 K (level L) quantities

14.9 Matrix calculation and result

14.10 Preparing a heatup path

14.11 Discussion

14.12 Summary

14.13 Problem

15. Maximum SO2 oxidation in a second catalyst bed

15.1 Second catalyst bed equilibrium curve equation

15.2 Second catalyst bed intercept calculation

15.3 Two bed SO2 oxidation efficiency

15.4 Summary

15.5 Problems


16. Third catalyst bed SO2 oxidation

16.1 2-3 Cooldown path

16.2 Heatup path

16.3 Heatup path-equilibrium curve intercept

16.4 Graphical representation

16.5 Summary

16.6 Problems

17. SO3 and CO2 in feed gas

17.1 SO3

17.2 SO3 effects

17.3 CO2

17.4 CO2 effects

17.5 Summary

17.6 Problems

18. Three catalyst bed acid plant

18.1 Calculation specifications

18.2 Example calculation

18.3 Calculation results

18.4 Three catalyst bed graphs

18.5 Minor effect—SO3 in feed gas

18.6 Minor effect—CO2 in feed gas

18.7 Minor effect—Bed pressure

18.8 Minor effect—SO2 strength in feed gas

18.9 Minor effect—O2 strength in feed gas

18.10 Summary of minor effects

18.11 Major effect—Catalyst bed input gas temperatures

18.12 Discussion of book’s assumptions

18.13 Summary


19. After-H2SO4-making SO2 oxidation

19.1 Double contact advantage

19.2 Objectives

19.3 After-H2SO4-making calculations

19.4 Equilibrium curve calculation

19.5 Heatup path calculation

19.6 Heatup path-equilibrium curve intercept calculation

19.7 Overall SO2 oxidation efficiency

19.8 Double/single contact comparison

19.9 Summary

19.10 Problems


20. Optimum double contact acidmaking

20.1 Total % SO2 oxidized after all catalyst beds

20.2 Four catalyst beds

20.3 Improved efficiency with five catalyst beds

20.4 Input gas temperature effect

20.5 Best bed for Cs catalyst

20.6 Triple contact acid plant

20.7 Summary


21. Enthalpies and enthalpy transfers

21.1 Input and output gas enthalpies

21.2 H2SO4 making input gas enthalpy

21.3 Heat transfers

21.4 Heat transfer rate

21.5 Summary

21.6 Problems

22. Control of gas temperature by bypassing

22.1 Bypassing principle

22.2 Objective

22.3 Gas to economizer heat transfer

22.4 Heat transfer requirement for 480 K economizer output gas

22.5 Changing heat transfer by bypassing

22.6 460 K Economizer output gas

22.7 Bypassing for 460, 470, and 480 K economizer output gas

22.8 Bypassing for 470 K economizer output gas while input gas temperature is varying

22.9 Industrial bypassing

22.10 Summary

22.11 Problems

23. H2SO4 making

23.1 Objectives

23.2 Mass balances

23.3 SO3 input mass

23.4 H2O(g) input from moist acid plant input gas

23.5 Water for product acid

23.6 Calculation of mass water in and mass acid out

23.7 Interpretations

23.8 Summary

23.9 Problem

24. Acid temperature control and heat recovery

24.1 Objectives

24.2 Calculation of output acid temperature

24.3 Effect of input acid temperature

24.4 Effect of input gas temperature

24.5 Effect of input gas SO3 concentration on output acid temperature

24.6 Adjusting output acid temperature

24.7 Acid cooling

24.8 Target acid temperatures

24.9 Recovery of acid heat as steam

24.10 Steam production principles

24.11 Double-packed bed absorption tower

24.12 Steam injection

24.13 Sensible heat recovery efficiency

24.14 Materials of construction

24.15 Summary

24.16 Problems


25. Making sulfuric acid from wet feed gas

25.1 Chapter objectives

25.2 WSA feed Gas

25.3 WSA flowsheet

25.4 Catalyst bed reactions

25.5 Preparing the oxidized gas for H2SO4(ℓ) condensation

25.6 H2SO4(ℓ) condenser

25.7 Product acid composition

25.8 Comparison with conventional acidmaking

25.9 Appraisal

25.10 Alternatives

25.11 Summary


Suggested reading

26. Wet sulfuric acid process fundamentals

26.1 Wet gas sulfuric acid process SO2 oxidation

26.2 Injection of nanoparticles into cooled process gas

26.3 Sulfuric acid condensation

26.4 Condenser temperature choices

26.5 Condenser acid composition up the glass tube

26.6 Condenser re-evaporation of H2O(ℓ)

26.7 Condenser acid production rate

26.8 Condenser appraisal

26.9 Summary


Suggested reading

27. SO3 gas recycle for high SO2 concentration gas treatment

27.1 Objectives

27.2 Calculations

27.3 Effect of recycle extent

27.4 Effect of recycle gas temperature on recycle requirement

27.5 Effect of gas recycle on first catalyst SO2 oxidation efficiency

27.6 Effect of first catalyst exit gas recycle on overall acid plant performance

27.7 Recycle equipment requirements

27.8 Appraisal

27.9 Industrial SO3 gas recycle

27.10 Alternatives to gas recycle

27.11 Summary


28. Sulfur from tail gas removal processes

28.1 Objectives

28.2 Environmental standards

28.3 Acid plant tail gas characteristics

28.4 Industrial acid plant tail gas treatment methods

28.5 Technology selection (after Hay et al., 2003)

28.6 Capital and operating costs

28.7 Summary


29. Minimizing sulfur emissions

29.1 Industrial catalytic SO2+0.5O2→SO3 oxidation

29.2 Methods to lower sulfur emissions

29.3 Summary


Suggested reading

30. Materials of construction

30.1 Chapter objectives

30.2 Corrosion rate factors for sulfuric acid plant equipment

30.3 Sulfuric acid plant materials of construction

30.4 Summary


31. Costs of sulfuric acid production

31.1 Investment costs

31.2 Production costs

31.3 Summary


Appendix A. Sulfuric acid properties

A.1 Sulfuric acid specific gravity at constant temperature

A.2 Specific gravity of sulfuric acid at elevated temperatures

A.3 Sulfuric acid freezing points

A.4 Oleum specific gravity

A.5 Electrical conductivity of sulfuric acid

A.6 Absolute viscosity of sulfuric acid

Appendix B. Derivation of equilibrium equation (10.12)

B.1 Modified equilibrium equation

B.2 Mole fractions defined

B.3 Feed and oxidized gas molar quantities

B.4 Mole fractions in oxidized gas

B.5 Equation applicability

B.6 Equilibrium equation

B.7 Equilibrium constant and molar quantities

B.8 Equilibrium and ΦE

Appendix C. Free energy equations for equilibrium curve calculations

C.1 Production of SO3(g) from SO2(g) and O2(g)

C.2 Production of H2SO4(g) from SO3(g) and H2O(g)

Appendix D. Preparation of Fig. 10.2’s equilibrium curve

D.1 Integer temperature calculations

D.2 Second and third catalyst bed equilibrium curves

Appendix E. Proof that volume%=mol% (for ideal gases)

E.1 Definitions

E.2 Characterization of partial volumes

E.3 Equality of volume% and mol%

Appendix F. Effect of CO2 and Ar on equilibrium equations (none)

F.1 CO2

F.2 Ar

F.3 Conclusions

Appendix G. Enthalpy equations for heatup path calculations

G.1 An example—Enthalpy of SO3(g) at 600 K

G.2 Preparation of equations


Appendix H. Matrix solving using Tables 11.2 and 14.2 as examples

Appendix I. Enthalpy equations in heatup path matrix cells

I.1 Example results

Appendix J. Heatup path-equilibrium curve: Intercept calculations

J.1 Calculation strategy

J.2 Worksheet

J.3 Intercept worksheet preparation instructions

J.4 Goal Seek instructions

J.5 Another example

Appendix K. Second catalyst bed heatup path calculations

Appendix L. Equilibrium equation for multicatalyst bed SO2 oxidation

L.1 Proof

L.2 Inapplicability

Appendix M. Second catalyst bed intercept calculations

M.1 Calculation strategy

M.2 Specifications (Fig. 14.2)

M.3 Worksheet

M.4 Goal Seek instructions

Appendix N. Third catalyst bed heatup path worksheet

Appendix O. Third catalyst bed intercept worksheet

Appendix P. Effect of SO3 in Fig. 10.1’s feed gas on equilibrium equations

P.1 Molar balances

P.2 Total kg mol of oxidized gas

P.3 Mole fractions in oxidized gas

P.4 New equilibrium equation

P.5 % SO2 oxidized in equilibrium equation

P.6 Equilibrium % SO2 oxidized as a function of temperature

Appendix Q. SO3-in-feed-gas intercept worksheet

Appendix R. CO2- and SO3-in-feed-gas intercept worksheet

Appendix S. Three-catalyst-bed “converter” calculations

S.1 First catalyst bed calculations (cells A1 through M47)

S.2 Second catalyst bed calculations (cells AA1 through AM47)

S.3 Third catalyst bed calculations (cells BA1 through BM47)

Appendix T. Worksheet for calculating after-intermediate-H2SO4-making heatup path-equilibrium curve intercepts

Appendix U. After-H2SO4-making SO2 oxidation with SO3 and CO2 in input gas

U.1 Equilibrium equation with SO3 in after-H2SO4-making input gas

U.2 H2SO4 making input gas quantity specification

U.3 H2SO4 making exit gas quantity calculation

U.4 Calculation of H2SO4 making exit gas volume percents

U.5 Worksheet construction and operation

U.6 Calculation of % SO2 oxidized after all catalyst beds

Appendix V. Moist air in H2SO4 making calculations

V.1 Calculation

Appendix W. Calculation of H2SO4 making tower mass flows

W.1 Input and output gas specifications

W.2 Input SO3(g) equation

W.3 Input and output acid composition equations

W.4 Total mass balance equation

W.5 Sulfur balance equation

W.6 Solving for flows

W.7 Effect of output acid mass% H2SO4 on input and output acid flows

Appendix X. Equilibrium equations for SO2, O2, H2O(g), N2 feed gas

X.1 Equilibrium equations

X.2 Modified equilibrium equations

X.3 Mole fractions defined

X.4 Feed and oxidized gas molar quantities

X.5 Preparing Eqs. (X.1) and (X.2) from Eqs. (X.19) and (X.21)

Appendix Y. Cooled first catalyst bed exit gas recycle calculations

Y.1 Exit gas temperature without recycle

Y.2 Recycle calculation setup

Y.3 Recycle matrix (Table Y.2)

Y.3.2 Result

Y.4 Recalculation to steady state

Y.5 Different feed and recycle temperatures

Y.6 Third catalyst bed exit gas recycle calculations

Answers to numerical problems

Chapter 10

Chapter 11

Chapter 12

Chapter 13

Chapter 14

Chapter 15

Chapter 16

Chapter 17

Chapter 19

Chapter 21

Chapter 22

Chapter 23

Chapter 24



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About the Author

Matt King

Michael Moats

Affiliations and Expertise

University of Utah, UT, USA

William Davenport

Professor William George Davenport is a graduate of the University of British Columbia and the Royal School of Mines, London. Prior to his academic career he worked with the Linde Division of Union Carbide in Tonawanda, New York. He spent a combined 43 years of teaching at McGill University and the University of Arizona.

His Union Carbide days are recounted in the book Iron Blast Furnace, Analysis, Control and Optimization (English, Chinese, Japanese, Russian and Spanish editions).

During the early years of his academic career he spent his summers working in many of Noranda Mines Company’s metallurgical plants, which led quickly to the book Extractive Metallurgy of Copper. This book has gone into five English language editions (with several printings) and Chinese, Farsi and Spanish language editions.

He also had the good fortune to work in Phelps Dodge’s Playas flash smelter soon after coming to the University of Arizona. This experience contributed to the book Flash Smelting, with two English language editions and a Russian language edition and eventually to the book Sulfuric Acid Manufacture (2006), 2nd edition 2013.

In 2013 co-authored Extractive Metallurgy of Nickel, Cobalt and Platinum Group Metals, which took him to all the continents except Antarctica.

He and four co-authors are just finishing up the book Rare Earths: Science, Technology, Production and Use, which has taken him around the United States, Canada and France, visiting rare earth mines, smelters, manufacturing plants, laboratories and recycling facilities.

Professor Davenport’s teaching has centered on ferrous and non-ferrous extractive metallurgy. He has visited (and continues to visit) about 10 metallurgical plants per year around the world to determine the relationships between theory and industrial practice. He has also taught plant design and economics throughout his career and has found this aspect of his work particularly rewarding. The delight of his life at the university has, however, always been academic advising of students on a one-on-one basis.

Professor Davenport is a Fellow (and life member) of the Canadian Institute of Mining, Metallurgy and Petroleum and a twenty-five year member of the (U.S.) Society of Mining, Metallurgy and Exploration. He is recipient of the CIM Alcan Award, the TMS Extractive Metallurgy Lecture Award, the AusIMM Sir George Fisher Award, the AIME Mineral Industry Education Award, the American Mining Hall of Fame Medal of Merit and the SME Milton E. Wadsworth award. In September 2014 he will be honored by the Conference of Metallurgists’ Bill Davenport Honorary Symposium in Vancouver, British Columbia (his home town).

Affiliations and Expertise

University of Arizona, Tuscon, AZ, USA


"The 2006 first edition has been updated with seven new chapters, and one additional author, Moats…They consider such topics as metallurgical offgas cooling and cleaning, the catalytic oxidation of S2 to S3, the second catalyst bed heatup path, the three catalyst bed acid plant, acid temperature and control and heat recovery, wet sulfuric acid process fundamentals, and the cost of sulfuric acid production." --Reference & Research Book News, December 2013