Phosphoric Acid: Purification, Uses, Technology, and Economics

356 Pages·2013·18.72 MB·English

by  Rodney Gilmour

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Phosphoric Acid
Purification, Uses, Technology,
and Economics

Phosphoric Acid
Purification, Uses, Technology,
and Economics
Rodney Gilmour
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Contents
Preface....................................................................................................................xiii
Acknowledgments ....................................................................................................xv
Author ....................................................................................................................xvii
Terminology and Units ...........................................................................................xix
Chapter 1 An Introduction to the Industrial Phosphates Industry ........................1
1.1 History and Background ............................................................1
1.2 Chemistry and Process Overview ...........................................25
1.2.1 Introduction ................................................................25
1.2.2 Simplified Reaction Equations ...................................28
1.2.3 Phosphorus .................................................................28
1.2.4 Phosphoric Acid .........................................................29
1.2.5 Fertilizers ...................................................................30
1.2.6 Purified Phosphoric Acid ...........................................33
1.2.7 Derivative Phosphates ................................................34
1.2.8 Phosphate Rock ..........................................................37
1.2.9 Wet Process Acid .......................................................44
1.2.9.1 Mass Balance ..............................................53
1.2.9.2 Reaction Slurry Assumptions .....................54
1.2.9.3 Mass Balance Calculations .........................54
1.2.10 Thermal Acid .............................................................59
1.2.11 Kiln Process Acid (KPA) ...........................................61
1.3 Economics ...............................................................................61
1.3.1 Production Costs of Phosphorus and Phosphoric Acid .....63
References ..........................................................................................67
Chapter 2 Purification of Phosphoric Acid .........................................................71
2.1 Introduction .............................................................................71
2.2 Chemical Purification ..............................................................79
2.3 Solvent Extraction–Based Processes .......................................84
2.3.1 Introduction ................................................................84
2.3.1.1 Dispersion and Coalescence .......................97
2.3.1.2 Solvent Selection .......................................100
2.3.2 Pretreatment Processes: Desulfation ........................101
2.3.3 Crude Defluorination ................................................105
2.3.4 Crude Dearsenication ...............................................106
2.4 Solvent Extraction Processes .................................................111
2.4.1 Albright & Wilson Process ......................................113
2.4.2 Budenheim Process ..................................................133
2.4.3 FMC Process ............................................................135
vii
viii Contents
2.4.4 IMI Processes ...........................................................141
2.4.5 Prayon Process .........................................................146
2.4.6 Rhône–Poulenc Process ...........................................149
2.4.7 Other Processes Including Bateman (Wengfu)
and Prado (AFB, Turkey) .........................................154
2.5 Solvent Extraction Equipment ...............................................155
2.5.1 Davy Powergas Mixer–Settler ..................................155
2.5.2 IMI Mixer–Settler ....................................................156
2.5.3 Kühni Column ..........................................................157
2.5.3.1 Introduction ..............................................157
2.5.3.2 Scale-Up ...................................................158
2.5.3.3 Process Control .........................................159
2.5.4 Bateman Pulsed Column ..........................................161
2.6 Posttreatment .........................................................................162
2.6.1 Solvent Stripping ......................................................162
2.6.2 Dearsenication ..........................................................165
2.6.3 Decolorization ..........................................................165
2.6.4 Concentration ...........................................................166
2.6.5 Defluorination ...........................................................168
2.7 Crystallization .......................................................................169
2.7.1 Introduction ..............................................................169
2.7.2 Freezing Point Curve of Phosphoric Acid ................169
2.7.3 Crystallization Design Considerations .....................171
2.8 Membrane Separation ............................................................176
2.9 Purification Technology Comparison ....................................177
References ........................................................................................178
Chapter 3 Polyphosphoric Acid ........................................................................183
3.1 Introduction ...........................................................................183
3.2 Chemistry ..............................................................................184
3.3 Production Processes .............................................................187
3.3.1 Solid P O Route ......................................................188
2 5
3.3.2 Thermal Route ..........................................................189
3.3.3 Hot Gas Route ..........................................................190
3.3.4 Electroheat Route .....................................................192
3.3.5 Microwave Route ......................................................195
3.4 Uses .......................................................................................196
3.4.1 Polyphosphoric Acid as a Reagent in Organic
Chemistry .................................................................196
3.4.1.1 Cyclization Reactions ...............................197
3.4.1.2 Rearrangements ........................................197
3.4.1.3 Dehydration ..............................................198
3.4.1.4 Hydrolysis .................................................198
3.4.1.5 Polymerization ..........................................198