Supercritical Fluids ( Condensed Matter Research and Technology )

Publication series :Condensed Matter Research and Technology

Author: Marcel R. Belinsky  

Publisher: Nova Science Publishers, Inc.‎

Publication year: 2017

E-ISBN: 9781617284205

P-ISBN(Paperback): 9781607419303

Subject: L No classification

Keyword: 暂无分类

Language: ENG

Access to resources Favorite

Disclaimer: Any content in publications that violate the sovereignty, the constitution or regulations of the PRC is not accepted or approved by CNPIEC.

Supercritical Fluids

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

6. Conclusions

Acknowledgment

References

Chapter 2

The Critical Properties of a Binary Aqueous and CO2 Containing Mixtures and the Krichevskii Parameter

Abstract

1. Introduction

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. Experimental Methods

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

6. Conclusions

Acknowledgments

References

Appendix 1: Compilation of the Critical Properties of Binary Mixtures Containing Carbon Dioxide

Appendix 2: Compilation of the Critical Properties of Binary Aqueous Solutions

Chapter 3

Modeling the Fluid Phase Behavior of Systems Involving High Molecular Weight Compounds and Supercritical Fluids Using Cubic and Non-Cubic Equations of State

1. Abstract

2. Introduction

3. Thermodynamic Models

3.1. Perturbed Chain - Statistical Associating Fluid Theory, PC-SAFT

3.2. Sánchez-Lacombe, SL

3.3. Peng-Robinson, PR

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

5.3.6. PS + CO2 systems

5.3.7. p(MMA) + CO2 systems

5.3.8. p(BMA) + CO2 systems

5.3.9. p(DMS) + CO2 systems

5.3.10. PC + 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

5.5.1. PLAG + DME system

5.5.2. PLAG + CO2 system

5.5.3. PLAG + CDFM system

5.5.4. PLAG + TFM 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

5.7.1.1. PBD/PS blends

5.7.1.2. PVME/PS blends

5.7.1.3. PPG/PEGE blends

5.7.1.4. PEO/PES blends

5.7.2. Fluid phase behavior of ps/pvme blend + co2 systems

6. Conclusions

Acknowledgments

References

Chapter 4

Supercritical Fluid Technology Applied to the Manufacture of Prebiotic Carbohydrates

Abstract

1. Introduction

1.1. Lactulose

1.2. Tagatose

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

4.1. SFE of Duphalac®

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

Conclusion

References

Appendix A: Measurement of the Carbohydrate Solubility in different Liquid Alcohols and in SCCO2 + Ethanol:Water Cosolvent

Samples and Reagents

Solubility of Carbohydrates in Liquid Alcohols

Solubility of Carbohydrates in SCCO2 + Ethanol:Water Cosolvent

Solubility of CGOS Mixture in Liquid Ethanol:Water Mixtures

GC Analysis

Appendix B: A-UNIFAC Parameters and Sugar Physical Properties Employed in the Calculation of Carbohydrate Solubility in Liquid Alcohols, Water and Ethanol: Water Mixtures

Chapter 5

Design of Supercritical Fluid Processes for High Molecular Mass Petrochemicals

Abstract

1. Introduction

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

6.3.1. Density

6.3.2. Viscosity

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. Case Studies

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

11. Conclusion

12. Nomenclature

Acknowledgments

References

Chapter 6

Considerations for the Design of High-Pressure Phase Equilibrium and Solubility Measurements Equipment

Abstract

Introduction

Classification of Experimental Equipment

Synthetic Equipment

Static Analytical Equipment

Dynamic Analytical Equipment

Flow Equipment

Continuous-Flow Equipment

Semi-Flow Equipment

Circulation Equipment

Single-Phase Circulation Equipment

Multi-Phase Circulation Equipment

Detailed Design Considerations

Mixing

Mixing in Static Systems

Mixing in Circulation Systems

Mixing in Flow Systems

Identification of Equilibrium

Sampling

Sampling Capillaries

Multi-Port Sampling Valves

ROLSITM and Microsamplers

The Rapid Online Sampler Injector

Microsamplers

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

Analysis Method

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

Pressure Measurement

Temperature Control and Measurement

Observation Windows

Degassing of Liquids and Solids

Mechanical Design and Construction

Additional Thermodynamic and Physical Data

Density Measurements

Excess Molar Enthalpy Measurements

Sound Velocity Measurements

Interfacial Tension Measurements

The Way Forward

Conclusion

Acknowledgments

References

Chapter 7

Non-Fluorous, Hydrocarbon-Based, Highly CO2-Soluble Materials

Abstract

1. Introduction

1.1. Properties of Supercritical Carbon Dioxide

1.2. Non-fluorous CO2-philies

2. CO2 Solution

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

3.5. End Groups

3.6. Poly(Dimethyl Siloxanes) (PDMS)

4. Modeling Aided Design

5. Applications of CO2-Philes

6. Summary

References

Chapter 8

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

Abstract

Introduction

1. Problems in the Design of Industrial Plants for FAME Production and Detailed Analyses of Energy Consumption

1.1. Background

1.1.1. Homogeneous Alkali Catalyzed Alcoholysis (HACA)

1.1.2. Supercritical Alcoholysis (SCA)

1.2. Process Simulation

1.2.1. Key Component, Thermodynamic Models and Kinetic Data

1.3. Process Design

1.3.1. Description of Process Flowsheet of SCA

1.3.1.1. Alcoholysis

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

1.3.2.1. Alcoholysis

1.3.2.2. Methanol Recovery

1.3.2.3. Water Washing

1.3.2.4. FAME Purification

1.3.2.5. Alkali Removal

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

1.4.4. FAME Purification

1.4.5. Glycerol Purification

1.4.6. Comparison of Calculated Energy Consumption

1.5. Conclusion

2. The Best Route for Reducing the Energy Consumption

2.1. Process Simulation, Thermodynamic Models and Kinetic Data

2.2. Process Design

2.3. Results

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

2.5. Conclusion

3. Techno-Economical Analysis of Supercritical Synthesis

Conclusion

References

Chapter 9

Modelling and Analysis of Global Phase Diagrams in CO2 + 1-Alkanols Binary Mixtures Using PC–SAFT

Abstract

Introduction

Classification of Phase Behavior for Binary Mixtures

Phase Behavior for CO2 + Alkanols Binary Mixtures

Pc–Saft Equation of State

Results and Discussion

Pure Compounds

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

Conclusion

References

Chapter 10

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 Ducts

SFE from Secretory Cavities and Cells

New Trends in Pre-treatment and Processing of Plant Material

References

Chapter 11

Heterogeneous Reaction Media Using Dense Phase Carbon Dioxide for Catalytic Selective Hydrogenation

Abstract

Introduction

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

Conclusions

Acknowledgments

References

Chapter 12

Fundamental Properties and Chemical Reactions of Supercritical Methanol

1. Introduction

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

Summary

References

Chapter 13

Polymeric Materials Modification with Supercritical CO2 Both as Solvent and Swelling Agent

1. Introduction

2. Polymer/Nanoscopic Metal Particles Composites

3. Polymer Blends

4. Extrusion Modification

5. Surface Modification

6. Bulk Graft-Modifications of Polymeric Materials

7. Conclusions and Outlook

Acknowledgment

References

Chapter 14

Why Is Naphthalene Extensively Used for Solubility Comparison?

Abstract

1. Introduction

2. Density-Based Models

3. Results and Discussion

4. Conclusion

Acknowledgments

References

Chapter 15

Supercritical Extraction of Seed Oil: Analysis and Comparison of Up-To-Date Models

Abstract

1. Introduction

2. The Models

2.1. The BIC Model

2.2. The SC Model

2.3. The BIC-SC Model

3. The Free Oil Amount

4. Model Comparison

4.1. Prediction of the Extraction Kinetics

4.2. Evaluation of the Internal Mass Transport Coefficient

5. Conclusion

Nomenclature

Greek Letters

References

Chapter 16

Hydrogenation of Terpene in Highly Dense CO2 – Significance of Phase Equilibria

Abstract

1. Introduction

2. CO2-Expanded Fluids and Phase Behaviour Driven by the Thermodynamics

3. Hydrogenation of Terpenes and the Overriding Factors

4. Conclusion

5. Perspectives in Catalytical Hydrogenation of Terpenes Using Highly-Dense CO2

References

Chapter 17

Stereoselective Hydrogenation of Alkylphenols over Charcoal-Supported Rhodium Catalyst in Supercritical Carbon Dioxide Solvent

1. Introduction

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

2.4. Conclusion

References

Chapter 18

Extraction of Metal Cations with Complexing Agent Solutions in Supercritical Fluids and Liquefied Gases

Introduction

Experiment Technique

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

Conclusion

References

Index

The users who browse this book also browse


No browse record.