Aspen Technology Aspen Process Manual Contents www.aspentech.com   support.aspentech.com 
Web site | Process Manual > Solids and separation > Crystallization | Word index

CR 5: Crystallizer Applications

CR 5: Crystallizer Applications
     Part 1: Cooling Crystallization by Direct Contact Heat Transfer
         1. INTRODUCTION
             1.1 Scope
             1.2 Contents of Report
         2. MAIN TYPES OF DIRECT CONTACT CRYSTALLIZATION PROCESSES
             2.1 Introduction
             2.2 Immiscible coolant with no change of phase
             2.3 Immiscible coolant with change of phase
             2.4 Miscible coolant with no change of phase
             2.5 Miscible coolant with change of phase
             2.6 "Reacting" coolant systems
         3. THEORETICAL ASPECTS OF DIRECT CONTACT CRYSTALLIZATION
             3.1 Introduction
             3.2 Phase equilibrium considerations
                 3.2.1 Immiscible coolant with no change of phase
                 3.2.2 Immiscible coolant with change of phase
                 3.2.3 Miscible coolant with no change of phase
                 3.2.4 Miscible coolant with change of phase
                 3.2.5 Reacting coolant systems
             3.3 Effects of coolant on the Crystallisation Process
                 3.3.1 Effect of coolant on solubility of crystallising product
                 3.3.2 Effect of coolant on operating conditions and thermals economy
                 3.3.3 Recovery and removal of coolant
                 3.3.4 Effect of coolant on crystal habit and crystallisation kinetics
             3.4 Effect of Hydrodynamics and Interfacial Phenomena on Crystallisation Kinetics
             3.5 Phase Inversion in Immiscible Systems
         4. EXISTING DIRECT CONTACT CRYSTALLIZATION PROCESSES
             4.1 Introduction
             4.2 Dewaxing of Oils
             4.3 Desalination and Dewatering by Freezing
             4.4 Organic Products
             4.5 Inorganic Products
         5. THE EFFECTS OF HEAT TRANSFER MODE ON THE CRYSTALLIZATION PROCESS
             5.1 Introduction
             5.2 Crystal Size and Purity
             5.3 Crystallisation kinetics and crystal habit
             5.4 Coolant recovery and removal
             5.5 Refrigerant cycle and equipment considerations
             5.6 Crystal/Mother liquor separation
             5.7 Scope for application of direct contact heat transfer to crystallisation processes
         6. CONCLUSIONS
             6.1 Introduction
             6.2 Areas of Uncertainty and Requirements for Future Work
                 6.2.1 Effects of the coolant as an 'impurity' upon the crystallisation process
                 6.2.2 Process hydrodynamics, interfacial effects and effects of phase inversion
                 6.2.3 The recovery and removal of coolant from process streams
                 6.2.4 The effects of residual coolant on subsequent process steps
                 6.2.5 Economics
         7. REFERENCES
     Part 2: Melt crystallisation
         1. INTRODUCTION
         2. EQUILIBRIUM
         3. FUNDAMENTAL ASPECTS
             3.1 Kinetics of Crystallization
                 3.1.1 Introduction
                 3.1.2 Crystal nucleation
                 3.1.3 Crystal growth mechanisms
                 3.1.4 Mass transfer
                 3.1.5 Final product quality; suspension and layer crystallization
             3.2 Design Calculations
                 3.2.1 Zone refining
                 3.2.2 Column crystallizers
                 3.2.3 Roll crystallizers
         4. EQUIPMENT AND PROCESSES
             4.1 Equipment - Introduction and Classification
             4.2 Equipment for Layer Crystallization Processes
                 4.2.1 Introduction
                 4.2.2 Static crystallization
                 4.2.3 Dynamic or falling film crystallization
                 4.2.4 Other operational aspects
                 4.2.5 Industrial applications
                 4.2.6 Other layer crystallization techniques
             4.3 Equipment for Suspension Crystallization Processes
                 4.3.1 Scraped surface devices, with conventional separation means
                 4.3.2 Wash columns and column crystallizers
             4.4 Processes for Specific Applications
                 4.4.1 The historic Phillips process for paraxylene
                 4.4.2 Other xylene separation processes
                 4.4.3 Processes for manufacture of para-dichlorobenzene
                 4.4.4 Combined distillation and melt crystallization process for MDI
                 4.4.5 Dilchill process for lubricating oils
                 4.4.6 Newton Chambers process for benzene
         5. CONCLUSIONS
         6. NOMENCLATURE
         7. REFERENCES
     Part 3: Precipitation
         1. INTRODUCTION
             1.1 Precipitation as a Unit Operation
             1.2 Definition of Terms
             1.3 Scope of the Report
         2. EQUILIBRIUM AND NON-EQUILIBRIUM PROPERTIES
             2.1 Phase Equilibria and Transformations
             2.2 Polymorphism and Other Properties
             2.3 Solution Composition
             2.4 Supersaturation
             2.5 Interactions in Solutions
                 2.5.1 Activity coefficients and ionic strength
                 2.5.2 Ionic association and dissociation
                 2.5.3 Effects on supersaturation
             2.6 Sparingly Soluble Salts
                 2.6.1 Solubility products
                 2.6.2 The common ion effect
                 2.6.3 Temperature effects
             2.7 Metastability
             2.8 Ostwald's Rule of Stages
             2.9 The Size Solubility Effect
         3. CHARACTERISTICS OF SOLID-LIQUID SYSTEMS
             3.1 Introduction
             3.2 Kinetic Properties
                 3.2.1 Brownian movement
                 3.2.2 Viscosity
             3.3 Electrokinetic Properties
             3.4 Stability of Sols
                 3.4.1 The effect of electrolytes on hydrophobic sols
                 3.4.2 The effect of electrolytes on hydrophilic sols
             3.5 Macroparticle Behaviour
             3.6 Expression of Slurry Densities
             3.7 Particle Size Analysis
                 3.7.1 Equivalent diameters
                 3.7.2 Mean sizes
                 3.7.3 MS/CV classification
                 3.7.4 Measurement of particle size
         4. KINETICS OF PRECIPITATION
             4.1 Introduction
             4.2 Nucleation
                 4.2.1 Types of nucleation
                 4.2.2 Primary nucleation
                 4.2.3 Secondary nucleation
                 4.2.4 Metastable zone widths
                 4.2.5 Induction periods
                 4.2.6 Precipitation diagrams
                 4.2.7 Effect of impurities
             4.3 Crystal Growth
                 4.3.1 Fundwnental mechanisms
                 4.3.2 Growth of very small crystals
                 4.3.3 Effect of impurities
         5. DEVELOPMENT OF PRECIPITATES
             5.1 Ripening
             5.2 Agglomeration
             5.3 Phase Transformations
             5.4 Precipitate Morphology
             5.5 Amorphous Precipitates
             5.6 Co-Precipitation
                 5.6.1 Adsorption phenomena
                 5.6.2 Solid solution formation
                 5.6.3 Incorporation of solvent
         6. TECHNIQUES OF PRECIPITATION
             6.1 Precipitation by Direct Mixing
             6.2 Reaction Precipitation
             6.3 Precipitation from Homogeneous Solution
             6.4 Salting-Out
                 6.4.1 General
                 6.4.2 Organic liquid precipitants
                 6.4.3 Gaseous and solid precipitants
             6.5 Fractional Precipitation
             6.6 Batch Versus Continuous Operation
             6.7 Analysis of Continuous Precipitation
                 6.7.1 Concept of the population balance
                 6.7.2 Crystal size distributions
                 6.7.3 Assessment of experimental data
             6.8 Analysis of Batch Precipitation
         7. PRECIPITATION AS AN INDUSTRIAL PROCESS
             7.1 Methods and Equipment
             7.2 Specific Applications
                 7.2.1 Recovery of salts from brines
                 7.2.2 Calcium carbonate
                 7.2.3 Calcium sulphate
                 7.2.4 Alumina trihydrate
                 7.2.5 Magnesium hydroxide
                 7.2.6 Sucrose
                 7.2.7 Pigments and dyestuffs
                 7.2.8 Protein precipitation
                 7.2.9 Photographic chemicals
                 7.2.10 Precipitation fouling
                 7.2.11 Monodispersed colloids
         8. AREAS FOR DEVELOPMENT
         9. REFERENCES
         10. NOMENCLATURE
     Part 4: Freeze Crystallization
         1. INTRODUCTION
             1.1 Purpose and Scope
             1.2 History
             1.3 Potential
             1.4 Principles of Freezing
                 1.4.1 Phase Equilibrium
                 1.4.2 Energy Efficiency
         2. FREEZING PROCESS DESCRIPTIONS
             2.1 General Description
             2.2 Vacuum Freezing
                 2.2.1 Vacuum Freezing Vapour Compression (VFVC)
                 2.2.2 Vacuum Freezing Absorption
                 2.2.3 Vacuum Freezing Ejector Absorption (VFEA)
             2.3 Secondary Reftigerant Freezing
                 2.3.1 General Description
                 2.3.2 Refrigerants
                 2.3.3 Development with Pilot Plants
             2.4 Indirect Freezing
                 2.4.1 General Description
                 2.4.2 Sheet and Block freezing
                 2.4.3 Scraped Surface Indirect Freezing
             2.5 Eutectic Freezing
         3. PATENTS
         4. PROCESS UNIT OPERATIONS
             4.1 Heat Transfer Processes
                 4.1.1 Crystallizers
                 4.1.2 Melters
                 4.1.3 Feed Heat Exchangers
                 4.1.4 Condensers
             4.2 Crystal Separation
                 4.2.1 Centrifuges
                 4.2.2 Wash Columns
             4.3 Primary Refrigeration Systems
                 4.3.1 Mechanical Compression for Vacuum Freezing
                 4.3.2 Ejector Compression for Vacuum Freezing
                 4.3.3 Conventional Refrigeration
                 4.3.4 Absorption Refrigeration
             4.4 Crystal Growth
                 4.4.1 Nucleation Effects
                 4.4.2 Growth
                 4.4.3 Application to Industrial Crystailizers
             4.5 Heat Removal
             4.6 Vacuum Systems
             4.7 Deaeration
             4.8 Secondary Refrigerant Stripping
         5. OTHER PROCESS AND EQUIPMENT CONSIDERATIONS
             5.1 Materials and Corrosion
             5.2 Pumps
             5.3 Piping
             5.4 Ice Adherence
             5.5 Controls
         6. ECONOMICS
             6.1 Previous Economic Studies
             6.2 Basis of Economic Analysis by CSI
                 6.2.1 Capital Costs
                 6.2.2 Economic Parameters
             6.3 Sugar Concentration
             6.4 Coffee Extract Concentration
             6.5 Acetic Acid Waste Processing
             6.6 Cost and Energy Consumption Sensitivity to Operating Parameters
         7. APPLICATIONS
             7.1 Food Industry
             7.2 Pulp and Paper Industry
             7.3 Chemical Industry
             7.4 Desalination
             7.5 Waste Processing
         8. SUMMARY OF FUTURE RESEARCH NEEDS
         9. CONCLUSIONS
         10. REFERENCES
     Part 5: Novel Crystallization Techniques
         Section 1: Chiral Crystallization
             1. INTRODUCTION
             2. CHEMICAL AND CRYSTALLOGRAPHIC CHIRALITY
                 2.1 Principles of Molecular Asymmetry.
                 2.2 Crystallization of Optically Active Compounds.
             3. PHYSICAL PROPERTIES OF CRYSTALLINE ENANTIOMER MIXTURES
                 3.1 Phase Diagrams for Crystallization from Melts and Solutions.
                 3.2 Conglomerates.
                 3.3 Racemic Crystals.
                 3.4 Pseudoracemates or Solid Solutions.
                 3.5 Polymorphism in Chiral Crystal Systems.
                 3.6 Experimental Methods for Characterizing Crystalline Enantiomer Mixtures and Phase Relationships.
             4. RESOLUTION AND SEPARATION OF ENANTIOMER MIXTURES BY DIRECT CRYSTALLIZATION
                 4.1 Conversion of Racemic Crystal Systems to Conglomerates.
                 4.2 Simultaneous and Separate Crystallization.
                 4.3 Preferential Crystallization or 'Entrainment'.
                 4.4 Crystallization from Optically Active Solvents.
                 4.5 Replacing Crystallization.
             5. RESOLUTION OF RACEMATES BY DIASTEREOMER FORMATION AND SEPARATION
                 5.1 Salts Formed from Chiral Acids and Bases.
                 5.2 Other Methods of Resolution via Diastereomer Salt Formation.
                 5.3 Metal Coordination Complexes.
                 5.4 Lewis Acid-Base Adducts.
                 5.5 Crystalline Inclusion Compounds.
                 5.6 Covalent Diastereomer Derivatives.
                 5.7 Separation of Diastereomer Adducts.
             6. ASYMMETRIC TRANSFORMATIONS INDUCED BY CRYSTALLIZATION.
                 6.1 Enantiomer Yield Enhancement by Combined Resolution and Racemisation.
                 6.2 Topochemically Controlled Reactions.
             7. REFERENCES
             8. APPENDIX 1. LIST OF RACEMIC MIXTURES CRYSTALLIZING AS CONGLOMERATES.
             9. APPENDIX 2. LIST OF RACEMIC MIXTURES CRYSTALLIZING AS PSEUDORACEMATES.
         Section 2: Sonocrystallization
             1. INTRODUCTION
             2. PHYSICAL EFFECTS OF ULTRASOUND ON CRYSTALLIZING SOLUTIONS AND SUSPENSIONS.
                 2.1 Stable and Unstable Cavitation in Liquids.
                 2.2 Effects of Cavitation in Continuous Liquids.
                 2.3 Cavitation at Solid-Liquid Interfaces.
             3. IMPACT OF ULTRASOUND ON CRYSTALLIZATION PROCESSES.
                 3.1 Nucleation.
                 3.2 Crystal Growth, Habit and Size Distribution.
                 3.3 Reported Applications.
             4. SONOCRYSTALLIZATION EQUIPMENT.
                 4.1 Laboratory Scale Equipment.
                 4.2 Process Scale Equipment.
             5. RECOMMENDED STRATEGY FOR DEVELOPMENT AND EXPLOITATION.
             6. REFERENCES

Volume V covers the various specific crystallization processes such as precipitation and freeze crystallization. The volume concentrates on the mechanisms and processes relevant to the crystallization technique rather than equipment design.

Volume CR V  Part 1 Cooling crystallization by direct contact heat transfer. When the vapour pressure of a solvent is too low for evaporative cooling of a liquor during crystallization, the usual cooling method adopted is to use a jacketed vessel or similar device as a heat exchanger. There is an alternative method, however, where the coolant is in direct contact with the crystallizing liquid; this is termed direct contact heat transfer. The main types of direct contact heat transfer are reviewed in this report, followed by a discussion of the theoretical aspects which specifically apply to direct contact crystallization. The importance of the interaction between the crystallizing liquor and the coolant is highlighted. Several processes which have been proposed for commercial application are discussed as examples. The use of direct contact cooling will also affect the crystal product quality and the report, therefore, discusses its effects on parameters such as crystal size, purity and habit.


Volume CR V  Part 2 Melt crystallization. Melt crystallization was originally developed as a small-scale process for ultra-pure chemical production, but it is increasingly used on a large scale. The boundary between melt crystallization and solution crystallization is somewhat difficult to define, but there are, practical differences in the growth and nucleation kinetics and the factors affecting crystallizer design. Various types of melt crystallization systems are discussed, such as Zone Refining, Column and Roll crystallizers. Design calculations for each of these are provided, highlighting the particular aspects of crystallization theory relevant to that process. The available equipment is reviewed, and several examples of industrial melt crystallization processes are also discussed.
Volume CR V  Part 3 Precipitation. Precipitation (or fast reaction crystallization) is used to produce a wide variety of products. Although the same fundamental mechanisms as normal solution crystallization are involved, their relative importance is different and this report looks at the processes from the viewpoint of precipitation. Since the processes are very rapid, the equilibrium and non-equilibrium properties of the system are important, particularly effects such as Ostwald Ripening which are not normally encountered with slow solution crystallization. Brownian motion and inter-particle forces become more important at the small particle sizes encountered in precipitating systems. With the high supersaturation levels generated, primary nucleation is usually dominant over secondary, and this is discussed along with crystal growth. Various techniques for precipitation can be used (such as mixing, reaction and salting-out), and the equipment required and the advantages and disadvantages of each are discussed. The report also contains a review of the use of precipitation in the industrial production of various chemicals such as magnesium hydroxide and proteins.
Volume CR V  Part 4 Freeze crystallization. Freeze crystallization is used as an alternative to evaporation or distillation, and involves the cooling of liquor below the freezing point of the solute. Cooling can be generated by evaporation, or the use of a refrigerant either in direct contact with the liquor, or indirectly using a heat exchanger. These methods are discussed, and examples of industrial processes using them are given. Eutectic freezing is also discussed (where the solute and solvent both crystallize, but as separate rather than mixed crystals). The report reviews the various process operations for freeze crystallization including the design of heat transfer systems, the separation of product crystals, and the design of refrigeration cycles. The report also discusses the economics and possible applications of freeze crystallization.
Volume CR V  Part 5 Novel crystallization techniques.

In this new manual part a range of novel or new crystallization techniques will be reviewed. Topics covered will include:

Section 1 : Chiral crystallization
Section 2 : Sonocrystallization
Section 3 : Supercritical crystallization
Section 4 : High pressure crystallization
Section 5 : Spherical & liquid membrane emulsion crystallization