Chapter
3.3. The Microstructure and Morphology of Membranes
3.4. Comparison between Different Solvent Extraction
4. Membrane of Polymer Blends by SCCO2
4.1. Polymer Blending in SCCO2
4.2. Strategy of Modification for Polymer/Substrate Blends
4.3. Preparation of Polymer Blend Membranes
4.4. Characterization of Polymer Blend Membranes
4.5. Copolymerizations of Styrene and Maleic Anhydride
5. Surface Modification of Membrane in SCCO2
5.1. Surface-Grafted Membrane
5.2. Mechanism for Graft Modification of Polymer Membrane
5.3. Graft Copolymerization of Man/St onto the Surface of PVDF Membrane
5.4 Characterization of the Grafted Chains
5.5. Morphologies and Structure of the SMA-grfted PVDF Membrane
5.6. Surface Properties of the SMA-Based Membrane
Surface hydrophilicity of the SMA-Based Membrane
Surface biocompatibility of the SMA-Based Membrane
The Critical Properties of a Binary Aqueous and CO2 Containing Mixtures and the Krichevskii Parameter
1.1. Technological Applications of the Supercritical Fluid Mixtures Containing CO2
1.2. Technological Applications of the Supercritical Fluid Mixtures Containing H2O
1.3. Scientific Applications of the Supercritical Fluid Mixtures
2. The Critical Properties of Binary Mixtures and Related Thermodynamic Properties
2.1. The Critical Properties of Binary Mixtures and The Krichevskii Parameter
2.2. Partial Molar Volume, Henry’s Constant,Distribution Coefficient, Solubility, and Structurtal Properties of Dilute Mixtures and Krichevskii Parameter
2.3. The Critical Curves Shape Behavior and Asymptotic Scaling Properties of Binary Mixtures near the Critical Points of Pure Solvent
3.1. Method-1. Observation of the Appearance and Disappearance of Meniscus at the Vapor-Liquid Interface. “Sealed Tube” Method
3.2. Method-2. Law of Rectilinear Diameter
3.3. Method-3. PVT Relations, ((P/(V)T = (( 2P/(V2)T =0
3.4. Method-4. Pulse Heating Method
3.5. Method -5. Flow Apparatus
3.6. Method-6. Acoustic Method of Determination of the Critical Points
3.7. Method-7. Method of Quasi-Static Thermograms
4. The Critical Properties of Binary CO2+Solute Mixtures
4.1. The Critical Properties of Binary CO2+Alcohol Mixtures
4.2. The Critical Properties of Binary CO2+n-alkane Mixtures
4.3. The Critical Properties of Binary CO2+Aromatic Hydrocarbon Mixtures
4.4. The Critical Properties of Binary CO2+H2O Mixtures
4.5. The Critical Properties of Binary CO2+Monatomic Gas (He, Ar, Kr, and Xe) Mixtures
4.6. The Critical Properties of Binary CO2+Two Atomic Gases (O2, N2, H2 )
4.7. The Critical Properties of CO2+ Poly-atomic Fluid (H2S, SO2, N2O, SF6, NH3) Mixtures
4.8. The Critical Properties of CO2+Refrigerant (CHF3, CH2F2, R134a) Mixtures
4.9. The Critical Properties of Binary CO2+(Ethylene, Acetylene, Cyclohexane, and Isomers)
4.10. The Critical Properties of Binary CO2+ (Pyridine, Ethanoic Acid, Acetone, Chloroform, Acetonitrile, and Tetrahydrofuran) Mixtures
5. The Critical Properties of Binary Aqueous Solutions
5.1. The Critical Properties of Binary Aqueous Salt Solutions
5.2. The Critical Properties of Binary Aqueous Alcohol Solutions
5.3. The Critical Properties of Binary Aqueous Gas Solutions
5.4. The Critical Properties of Binary Aqueous Hydrocarbon Solutions
5.5. The Critical Properties of H2O+D2O
Appendix 1: Compilation of the Critical Properties of Binary Mixtures Containing Carbon Dioxide
Appendix 2: Compilation of the Critical Properties of Binary Aqueous Solutions
Modeling the Fluid Phase Behavior of Systems Involving High Molecular Weight Compounds and Supercritical Fluids Using Cubic and Non-Cubic Equations of State
3.1. Perturbed Chain - Statistical Associating Fluid Theory, PC-SAFT
4. Phase Equilibrium at High-Pressures
5. Results and Discussions
5.1. EoS Pure-Component Parameters
5.1.1. Low molecular weight pure-component parameters
5.1.2. High molecular weight pure-component parameters
5.2. PS + Supercritical Fluid Systems
5.2.1. Pure-component parameters
5.2.2. Binary interaction parameters
5.2.3. Modeling solubility pressures of binary systems
5.2.3.1. PS + supercritical fluid systems
5.2.3.2. PS + chlorofluorocarbon fluid systems
5.2.3.3. PS + hydrochlorofluorocarbon and ps + hydrofluorocarbon fluid systems
5.3. Molten Polymer + CO2 Systems
5.3.1. Evaluation of EoS pure-component parameters
5.3.2. Correlation of GLE data
5.3.3. HDPE + CO2 and LDPE + CO2 systems
5.3.4. i-PP + CO2 systems
5.3.5. p(VAc) + CO2 Systems
5.3.7. p(MMA) + CO2 systems
5.3.8. p(BMA) + CO2 systems
5.3.9. p(DMS) + CO2 systems
5.4. Modeling of Binary and Ternary Systems Involving a Biodegradable Polymer, a Copolymer and a Supercritical Fluid
5.4.1. Polymer + fluid and copolymer + fluid equilibrium
5.4.1.1. PLA + DME system
5.4.1.2. PLA + CO2 system
5.4.1.3. PLA + CDFM system
5.4.1.4. PLA + DFM system
5.4.1.5. PLA + TFM System
5.4.1.6. PLA + TFE system
5.4.1.7. PBS + CO2 system
5.4.1.8. PBSA + CO2 system
5.4.2. Polymer + Fluid 1 + Fluid 2 Equilibrium
5.4.2.1. PLA + CO2 + DME System
5.5. Biodegradable Copolymer + Supercritical Fluid Systems
5.5.3. PLAG + CDFM system
5.6. Block Copolymer + Supercritical CO2 Systems
5.6.1. p(EO-b-BO) + CO2 system
5.6.2. p(EO-b-PO) + CO2 system
5.6.3. p(VAc-b-AHO) + CO2 system
5.7. Polymer Blends and Polymer Blend + CO2 Systems
5.7.1. Cloud points temperature of blends
5.7.2. Fluid phase behavior of ps/pvme blend + co2 systems
Supercritical Fluid Technology Applied to the Manufacture of Prebiotic Carbohydrates
1.3. Galactooligosaccharides
2. Solubility of Pure Carbohydrates
2.1. Solubility of Pure Carbohydrates in Liquid Alcohols
2.2. Solubility of Pure Carbohydrates in SCCO2 with Ethanol: Water Cosolvent
3. Selective Fractionation of Binary Carbohydrate Mixtures by SFE
3.1. Supercritical Fluid Extraction
3.2. Results and Discussion
3.2.1. SFE of tagatose + galactose solid mixtures
3.2.2. SFE of lactulose + lactose solid mixtures
4. Fractionation of Complex Sugar Mixtures by Sfe
4.2. SFE of Commercial GOS (CGOS) Mixture
4.2.1. Solubility behavior of the CGOS mixture in ethanol:water liquid solvents
4.2.2.2. Commercial GOS mixture SFE using CO2 + ethanol:water cosolvents
Appendix A: Measurement of the Carbohydrate Solubility in different Liquid Alcohols and in SCCO2 + Ethanol:Water Cosolvent
Solubility of Carbohydrates in Liquid Alcohols
Solubility of Carbohydrates in SCCO2 + Ethanol:Water Cosolvent
Solubility of CGOS Mixture in Liquid Ethanol:Water Mixtures
Appendix B: A-UNIFAC Parameters and Sugar Physical Properties Employed in the Calculation of Carbohydrate Solubility in Liquid Alcohols, Water and Ethanol: Water Mixtures
Design of Supercritical Fluid Processes for High Molecular Mass Petrochemicals
2. Suitable SC Solvents for Processing of High Molecular Mass Petrochemicals
3. Evaluation of Phase Behaviour
3.1. Availability of Phase Behaviour Data
3.2. Trends Observed in Phase Behaviour Data
3.3. Application of Phase Behaviour Data
3.4. Use of Phase Behaviour in Solvent Selection
3.5. Conclusions with Regard to Phase Behaviour
4. Applicability and Implementation of Short-Cut Methods
5. Evaluation of the Ability to Simulate a SCF Process
5.1. Thermodynamic Modelling of High Pressure Phase Behaviour
5.2. Estimation of Derived Thermodynamic Properties
5.3. Simulation of SCF Processing of Petrochemicals
6. The Hydrodynamics of SCF Processing
6.1. Hydrodynamics of Packed Columns
6.1.1. Calculation of packed height
6.1.2. Calculation of column diameter
6.2. Hydrodynamics of Tray Columns
6.3. Transport Properties
6.3.3. Diffusion coefficients
6.3.4. Interfacial tension
7. Pilot Plant Data: An Alternative to Simulation and Hydrodynamic Characterisation
8. Economics of SCF Processing
9.1. Fractionation of Paraffin and Synthetic Waxes
9.2. Fractionation of Wax-Like Alcohol Ethoxylates
10. The future of SCF Processing in the Petrochemical Industry
Considerations for the Design of High-Pressure Phase Equilibrium and Solubility Measurements Equipment
Classification of Experimental Equipment
Static Analytical Equipment
Dynamic Analytical Equipment
Continuous-Flow Equipment
Single-Phase Circulation Equipment
Multi-Phase Circulation Equipment
Detailed Design Considerations
Mixing in Circulation Systems
Identification of Equilibrium
Multi-Port Sampling Valves
ROLSITM and Microsamplers
The Rapid Online Sampler Injector
Continuous- and Semi-Flow Systems
Additional Sampling Considerations
Measuring Three-Phase Equilibria
Sample Extraction Sequence
Sample Homogenisation and Preparation
During the Sampling Procedure
After the Sampling Procedure
Direct Chromatographic Analyses
Phase Separation of Samples Prior to Further Analyses
In Situ Spectroscopic Analyses
Injection, Compression, Pressure Control and Measurement
Circulation and Static Systems
Continuous- and Semi-Flow Systems
Temperature Control and Measurement
Degassing of Liquids and Solids
Mechanical Design and Construction
Additional Thermodynamic and Physical Data
Excess Molar Enthalpy Measurements
Sound Velocity Measurements
Interfacial Tension Measurements
Non-Fluorous, Hydrocarbon-Based, Highly CO2-Soluble Materials
1.1. Properties of Supercritical Carbon Dioxide
1.2. Non-fluorous CO2-philies
2.1. Solvent Properties of CO2
2.2. Thermodynamic Fundamentals of Sub/Supercritical CO2 Solution
3. Exploratory Research on Identification and Design of Non-Fluorous CO2 Soluble Materials
3.1. The Presence of Acetate Groups
3.2. Attention on Ether Group
3.3. Flexible Chains and High Free Volume
3.4. Weaker Self-Interactions
3.6. Poly(Dimethyl Siloxanes) (PDMS)
5. Applications of CO2-Philes
Biodiesel Production: The Problems in Software Design at Supercritical and Subcritical Conditions
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade, Republic Serbia
1. Problems in the Design of Industrial Plants for FAME Production and Detailed Analyses of Energy Consumption
1.1.1. Homogeneous Alkali Catalyzed Alcoholysis (HACA)
1.1.2. Supercritical Alcoholysis (SCA)
1.2.1. Key Component, Thermodynamic Models and Kinetic Data
1.3.1. Description of Process Flowsheet of SCA
1.3.1.2. Methanol Recycling
1.3.1.3. FAME Purification
1.3.1.4. Glycerol Purification
1.3.2. Description of Alkali Catalyzed Process
1.3.2.2. Methanol Recovery
1.3.2.4. FAME Purification
1.3.2.6. Glycerol Purification
1.4. Comparisons of SCA and HACA Processes
1.4.1. Reaction of Alcoholysis
1.4.2. Methanol Distillation
1.4.3. Washing Column and Catalyst Neutralisation
1.4.5. Glycerol Purification
1.4.6. Comparison of Calculated Energy Consumption
2. The Best Route for Reducing the Energy Consumption
2.1. Process Simulation, Thermodynamic Models and Kinetic Data
2.3.1. The Influence of Temperature and Pressure on Energy
Consumption Necessary for FAME Synthesis
2.3.2. The Influence of Decreased Methanol to
Oil Molar Ratio on Total Energy Consumption
2.4. Application of Heterogeneous Catalyst for FAME Synthesis
3. Techno-Economical Analysis of Supercritical Synthesis
Modelling and Analysis of Global Phase Diagrams in CO2 + 1-Alkanols Binary Mixtures Using PC–SAFT
Classification of Phase Behavior for Binary Mixtures
Phase Behavior for CO2 + Alkanols Binary Mixtures
Pc–Saft Equation of State
CO2 + Methanol or + Ethanol :Type I Behavior
CO2 + 1-Propanol or + 1-Butanol: Type II Behavior
CO2 + 1-Pentanol: Type IV Behavior
CO2 + Higher 1-Alkanols: Type III Behavior
Pre-Treatment of Herbaceous Matrix in a Process of Supercritical Fluid Extraction
Supercritical Fluid Extraction of Seed Oil
Supercritical Fluid Extraction of Essential Oil
SFE from Glandular Trichomes
SFE from Secretory Cavities and Cells
New Trends in Pre-treatment and Processing of Plant Material
Heterogeneous Reaction Media Using Dense Phase Carbon Dioxide for Catalytic Selective Hydrogenation
Hydrogenation of -Unsaturated Aldehydes
(a) Interaction between CO2 and the Substrate
(b) Expansion of Liquid Phase by Dissolution of CO2
(c) Enhancement of the H2 Dissolution into CO2-Dissolved Liquid Phase
Hydrogenation of Nitro Compounds
(a) Interaction with the Catalyst Surface
(b) Molecular Interactions of CO2 with Reacting Species
Hydrogenation of Other Substrates
Fundamental Properties and Chemical Reactions of Supercritical Methanol
2. Microscopic Properties of Supercritical Methanol
(1) Apparatus for UV/Vis Absorption Spectroscopy
(2) Microscopic Properties of Subcritical and SC Methanol and Mixture of SC Carbon Dioxide and Methanol
(a) Microscopic Properties * and of Subcritical and SC Methanol
(b) Microscopic Parameters and of Mixture of SC Carbon Dioxide and Methanol
(c) Local Density Augmentation of SC Methanol Around a Solute
3. Decomposition of Polyethylene Terephthalate (PET) to Monomers
4. Recycling of Silane Crosslinked Polyethylene
5. Alkylation and Acetal Formation without Catalyst
6. Shape-Selective Methylation of 4-Methylbiphenyl to 4,4’-Dimethylbiphenyl over Zeolite Catalysts
Polymeric Materials Modification with Supercritical CO2 Both as Solvent and Swelling Agent
2. Polymer/Nanoscopic Metal Particles Composites
4. Extrusion Modification
6. Bulk Graft-Modifications of Polymeric Materials
7. Conclusions and Outlook
Why Is Naphthalene Extensively Used for Solubility Comparison?
3. Results and Discussion
Supercritical Extraction of Seed Oil: Analysis and Comparison of Up-To-Date Models
4.1. Prediction of the Extraction Kinetics
4.2. Evaluation of the Internal Mass Transport Coefficient
Hydrogenation of Terpene in Highly Dense CO2 – Significance of Phase Equilibria
2. CO2-Expanded Fluids and Phase Behaviour Driven by the Thermodynamics
3. Hydrogenation of Terpenes and the Overriding Factors
5. Perspectives in Catalytical Hydrogenation of Terpenes Using Highly-Dense CO2
Stereoselective Hydrogenation of Alkylphenols over Charcoal-Supported Rhodium Catalyst in Supercritical Carbon Dioxide Solvent
2. 4-Alkylphenol Hydrogenation
2.1. 4-tert-Butylphenol Hydrogenation
2.2. Carbon Dioxide Pressure Effect
2.3. Addition of Hydrochloric Acid
2.3. Effect of Substituent in 4-Alkylphenol
Extraction of Metal Cations with Complexing Agent Solutions in Supercritical Fluids and Liquefied Gases
Extraction of Microamounts of Metals
Effect of Water on SFE of Microamounts of Metals
Extraction of Macroamounts of Actinides
Features of the Extraction of Metals Cations with Solutions of Complexing Agents in L СО2
Extraction of Cesium and Strontium With Solutions of Complexing Agents in SC and L CO2
Extraction of Actinides with TBP Solutions in Freons