Sulfuric Acid Manufacture [Kõva köide]

Preface		v
Overview		1	(10)
Catalytic Oxidation of SO2 to SO3		2	(2)
H2SO4 Production		4	(1)
Industrial Flowsheet		5	(1)
Sulfur Burning		5	(1)
Metallurgical Offgas		5	(2)
Spent Acid Regeneration		7	(1)
Sulfuric Acid Product		7	(1)
Recent Developments		8	(1)
Alternative Process		8	(1)
Summary		8	(3)
Suggested Reading		9	(1)
References		9	(2)
Production and Consumption		11	(8)
Uses		13	(2)
Acid Plant Locations and Costs		15	(1)
Price		15	(1)
Summary		16	(3)
Suggested Reading		16	(1)
References		17	(2)
Sulfur Burning		19	(12)
Objectives		19	(1)
Sulfur		20	(1)
Molten Sulfur Delivery		20	(2)
Sulfur Atomizers and Sulfur Burning Furnaces		22	(4)
Product Gas		26	(2)
Summary		28	(3)
References		29	(2)
Metallurgical Offgas Cooling and Cleaning		31	(16)
Initial and Final SO2 Concentrations		31	(2)
Initial and Final Dust Concentrations		33	(1)
Offgas Cooling and Heat Recovery		34	(1)
Electrostatic Collection of Dust		35	(4)
Water Scrubbing		39	(3)
H2O(g) Removal from Scrubber Exit Gas		42	(1)
Summary		43	(4)
Suggested Reading		44	(1)
References		44	(3)
Regeneration of Spent Sulfuric Acid		47	(12)
Spent Acid Compositions		49	(1)
Spent Acid Handling		49	(1)
Decomposition		50	(2)
Decomposition Furnace Product		52	(1)
Optimum Decomposition Furnace Operating Conditions		52	(2)
Preparation of Offgas for SO2 Oxidation and H2SO4 Making		54	(2)
Summary		56	(3)
Suggested Reading		56	(1)
References		56	(3)
Dehydrating Air and Gases with Strong Sulfuric Acid		59	(12)
Objectives		61	(1)
Dehydration with Strong Sulfuric Acid		61	(3)
Residence Times		64	(1)
Recent Advances		64	(5)
Summary		69	(2)
Suggested Reading		69	(1)
References		69	(2)
Catalytic Oxidation of SO2 to SO3		71	(18)
Objectives		71	(1)
Industrial SO2 Oxidation		72	(2)
Catalyst Necessity		74	(2)
SO2 Oxidation `Heatup' Path		76	(1)
Industrial Multi Catalyst Bed SO2 Oxidation		77	(3)
Industrial Operation		80	(8)
Recent Advances		88	(1)
Summary		88	(1)
Suggested Reading		88	(1)
References		88	(1)
SO2 Oxidation Catalyst and Catalyst Beds		89	(10)
Catalytic Reactions		90	(1)
Maximum and Minimum Catalyst Operating Temperatures		91	(1)
Composition and Manufacture		91	(2)
Choice of Size and Shape		93	(1)
Choice of Chemical Composition		93	(1)
Catalyst Bed Thickness and Diameter		94	(2)
Gas Residence Times		96	(1)
Catalyst Bed Maintenance		97	(1)
Summary		97	(2)
Suggested Reading		98	(1)
References		98	(1)
Production of H2SO4(l) from SO3(g)		99	(20)
Objectives		100	(1)
Sulfuric Acid Rather than Water		100	(2)
Industrial H2SO4 Making		102	(2)
Choice of Input and Output Acid Compositions		104	(1)
Acid Temperatures		105	(1)
Gas Temperatures		105	(1)
Operation and Control		105	(2)
Double Contact H2SO4 Making		107	(2)
Intermediate vs. Final H2SO4 Making		109	(7)
Summary		116	(3)
Suggested Reading		116	(1)
References		116	(3)
Oxidation of SO2 to SO3 -- Equilibrium curves		119	(10)
Catalytic Oxidation		119	(2)
Equilibrium Equation		121	(1)
KE as a Function of Temperature		122	(1)
KE in Terms of % SO2 Oxidized		123	(1)
Equilibrium % SO2 Oxidized as a Function of Temperature		124	(2)
Discussion		126	(1)
Summary		127	(2)
Reference		127	(1)
Problems		127	(2)
SO2 Oxidation Heatup Paths		129	(18)
Heatup Paths		129	(1)
Objectives		130	(1)
Preparing a Heatup Path - the First Point		130	(1)
Assumptions		131	(1)
A Specific Example		131	(1)
Calculation Strategy		132	(1)
Input SO2, O2 and N2 Quantities		132	(1)
Sulfur, Oxygen and Nitrogen Molar Balances		133	(2)
Enthalpy Balance		135	(3)
Calculating Level L Quantities		138	(1)
Matrix Calculation		138	(2)
Preparing a Heatup Path		140	(1)
Feed Gas SO2 Strength Effect		141	(2)
Feed Gas Temperature Effect		143	(1)
Significance of Heatup Path Position and Slope		144	(1)
Summary		145	(2)
Problems		145	(2)
Maximum SO2 Oxidation: Heatup Path-Equilibrium Curve Intercepts		147	(12)
Initial Specifications		147	(1)
% SO2 Oxidized-Temperature Points Near an Intercept		148	(1)
Discussion		149	(1)
Effect of Feed Gas Temperature on Intercept		150	(1)
Inadequate % SO2 Oxidized in 1st Catalyst Bed		151	(1)
Effect of Feed Gas SO2 Strength on Intercept		151	(1)
Minor Influence - Equilibrium Gas Pressure		152	(1)
Minor Influence - O2 Strength in Feed Gas		152	(1)
Minor Influence - CO2 in Feed Gas		153	(1)
Catalyst Degradation, SO2 Strength, Feed Gas Temperature		154	(1)
Maximum Feed Gas SO2 Strength		155	(1)
Exit Gas Composition Intercept Gas Composition		155	(1)
Summary		156	(3)
Problems		157	(2)
Cooling 1st Catalyst Bed Exit Gas		159	(6)
1st Catalyst Bed Summary		160	(1)
Cooldown Path		161	(2)
Gas Composition Below Equilibrium Curve		163	(1)
Summary		163	(2)
Problem		163	(2)
2nd Catalyst Bed Heatup Path		165	(12)
Objectives		165	(1)
% SO2 Oxidized Re-defined		165	(1)
2nd Catalyst Bed Heatup Path		166	(1)
A Specific Heatup Path Question		167	(1)
2nd Catalyst Bed Input Gas Quantities		168	(1)
S, O and N Molar Balances		169	(1)
Enthalpy Balance		170	(1)
Calculating 760 K (level L) Quantities		171	(1)
Matrix Calculation and Result		172	(1)
Preparing a Heatup Path		172	(2)
Discussion		174	(1)
Summary		174	(3)
Problem		174	(3)
Maximum SO2 Oxidation in a 2nd Catalyst Bed		177	(6)
2nd Catalyst Bed Equilibrium Curve Equation		177	(2)
2nd Catalyst Bed Intercept Calculation		179	(2)
Two Bed Oxidation Efficiency		181	(1)
Summary		181	(2)
Problems		182	(1)
3rd Catalyst Bed SO2 Oxidation		183	(6)
2-3 Cooldown Path		184	(1)
Heatup Path		184	(2)
Heatup Path-Equilibrium Curve Intercept		186	(1)
Graphical Representation		186	(2)
Summary		188	(1)
Problems		188	(1)
SO3 and CO2 in Feed Gas		189	(10)
SO3		189	(4)
SO3 Effects		193	(1)
CO2		193	(4)
CO2 Effects		197	(1)
Summary		197	(2)
Problems		198	(1)
3 Catalyst Bed Acid Plant		199	(12)
Calculation Specifications		199	(1)
Example Calculation		199	(1)
Calculation Results		200	(1)
3 Catalyst Bed Graphs		200	(2)
Minor Effect -- SO3 in Feed Gas		202	(1)
Minor Effect -- CO2 in Feed Gas		202	(2)
Minor Effect -- Bed Pressure		204	(1)
Minor Effect -- SO2 Strength in Feed Gas		205	(1)
Minor Effect -- O2 Strength in Feed Gas		206	(1)
Summary of Minor Effects		207	(1)
Major Effect -- Catalyst Bed Input Gas Temperatures		207	(2)
Discussion of Book's Assumptions		209	(1)
Summary		210	(1)
Reference		210	(1)
After-H2SO4-Making SO2 Oxidation		211	(18)
Double Contact Advantage		213	(1)
Objectives		213	(1)
After-H2SO4-Making Calculations		213	(1)
Equilibrium Curve Calculation		214	(3)
Heatup Path Calculation		217	(1)
Heatup Path-Equilibrium Curve Intercept Calculation		217	(4)
Overall SO2 Oxidation Efficiency		221	(1)
Double/Single Contact Comparison		222	(1)
Summary		223	(6)
References		223	(1)
Problems		223	(6)
Optimum Double Contact Acidmaking		229	(6)
Total % SO2 Oxidized After All Catalyst Beds		230	(1)
Four Catalyst Beds		230	(1)
Improved Efficiency with 5 Catalyst Beds		231	(2)
Input Gas Temperature Effect		233	(1)
Best Bed for Cs Catalyst		233	(1)
Triple Contact Acid Plant		234	(1)
Summary		234	(1)
Enthalpies and Enthalpy Transfers		235	(8)
Input and Output Gas Enthalpies		236	(3)
H2SO4 Making Input Gas Enthalpy		239	(1)
Heat Transfers		239	(2)
Heat Transfer Rate		241	(1)
Summary		241	(2)
Problems		242	(1)
Control of Gas Temperature by Bypassing		243	(10)
Bypassing Principle		243	(1)
Objective		243	(2)
Gas to Economizer Heat Transfer		245	(1)
Heat Transfer Requirement for 480 K Economizer Output Gas		246	(1)
Changing Heat Transfer by Bypassing		246	(1)
460 K Economizer Output Gas		247	(1)
Bypassing for 460, 470 and 480 Economizer Output Gas		248	(1)
Bypassing for 470 K Economizer Output Gas While Input Gas Temperature is Varying		248	(1)
Industrial Bypassing		249	(1)
Summary		250	(3)
Problems		251	(2)
H2SO4 Making		253	(18)
Objectives		254	(1)
Mass Balances		255	(1)
SO3 Input Mass		255	(1)
H2O(g) Input from Moist Acid Plant Input Gas		256	(1)
Water for Product Acid		257	(1)
Calculation of Mass Water In and Mass Acid Out		258	(3)
Interpretations		261	(3)
Summary		264	(7)
Problem		265	(6)
Acid Temperature Control and Heat Recovery		271	(16)
Objectives		271	(1)
Calculation of Output Acid Temperature		271	(5)
Effect of Input Acid Temperature		276	(1)
Effect of Input Gas Temperature		277	(1)
Effect of Output Acid H2SO4 Concentration on Output Acid Temperature		278	(1)
Effect of Input Gas SO3 concentration on Output Acid Temperature		278	(2)
Acid Cooling		280	(1)
Target Acid Temperatures		281	(1)
Recovery of Acid Heat as Steam		281	(3)
Summary		284	(3)
References		284	(1)
Problems		285	(2)
Appendices		287	(96)
A. Sulfuric Acid Properties		287	(6)
B. Derivation of Equilibrium Equation (10.12)		293	(11)
C. Free Energy Equations for Equilibrium Curve Calculations		304	(2)
D. Preparation of Fig. 10.2 Equilibrium Curve		306	(3)
E. Proof that Volume% = Mole% (for Ideal Gases)		309	(2)
F. Effect of CO2 and Ar on Equilibrium Equations (None)		311	(5)
G. Enthalpy Equations for Heatup Path Calculations		316	(5)
H. Matrix Solving Using Tables 11.2 and 14.2 as Examples		321	(1)
I. Enthalpy Equation in Heatup Path Matrix Cells		322	(4)
J. Heatup Path-Equilibrium Curve Intercept Calculations		326	(7)
K. 2nd Catalyst Bed Heatup Path Calculations		333	(3)
L. Equilibrium Equation for Multi-Catalyst Bed SO2 Oxidation		336	(3)
M. 2nd Catalyst Bed Intercept Calculations		339	(5)
N. 3rd Catalyst Bed Heatup Path Worksheet		344	(2)
O. 3rd Catalyst Bed Intercept Worksheet		346	(2)
P. Effect of SO3 in Fig. 10.1 Feed Gas on Equilibrium Equations		348	(8)
Q. SO3-in-Feed-Gas Intercept Worksheet		356	(2)
R. CO2-and SO3-in-Feed-Gas Intercept Worksheet		358	(2)
S. 3-Catalyst-Bed `Converter' Calculations		360	(7)
T. Worksheet for Calculating After-Intermediate-H2SO4-Making Heatup Path Equilibrium Curve Intercepts		367	(3)
U. After-H2SO4-Making SO2 Oxidation with SO3 and CO2 in Input Gas		370	(5)
V. Moist Air in H2SO4 Making Calculations		375	(3)
W. Calculation of H2SO4 Making Tower Mass Flows		378	(5)
Answers to Numerical Problems		383	(12)
Author Index		395	(2)
Index		397

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 Companys 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 Dodges 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 Davenports 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).

Matthew J. King has over 25 years experience in copper smelter operations and sulfuric acid plant projects. The first eight years of his career were spent in various operations roles at a copper smelter. During that period, he completed his PhD focused on control and optimisation of metallurgical sulphuric acid plants. His career since then has been based in Australia, focusing mainly on sulfuric acid plant design and operations with some work in copper smelting, off-gas handling and steam systems design. Matthew is a co-author of five technical monographs, including the latest editions of Elsevier titles Sulfuric Acid Manufacture and Extractive Metallurgy of Copper.