Supercritical and near-critical CO2 in green chemical synthesis and processing

Abstract Carbon dioxide is often promoted as a sustainable solvent, as CO 2 is non-flammable, exhibits a relatively low toxicity and is naturally abundant. However, injudicious use of carbon dioxide in a process or product can reduce rather than enhance overall sustainability. This review specifically examines the use of CO 2 to create greener processes and products, with a focus on research and commercialization efforts performed since 1995. The literature reveals that use of CO 2 has permeated almost all facets of the chemical industry and that careful application of CO 2 technology can result in products (and processes) that are cleaner, less expensive and of higher quality.

[1]  K. Johnston,et al.  Organic Synthesis in Water/Carbon Dioxide Microemulsions , 1999 .

[2]  K. E. J. Barrett,et al.  Dispersion polymerization in organic media , 1974 .

[3]  W. Leitner,et al.  Activation, Tuning, and Immobilization of Homogeneous Catalysts in an Ionic Liquid/Compressed CO2 Continuous-Flow System. , 2001, Angewandte Chemie.

[4]  K. Johnston,et al.  Solubility of homopolymers and copolymers in carbon dioxide , 1998 .

[5]  J. Schwartz,et al.  Organometallics , 1987, Science.

[6]  E. G. Hope,et al.  Effects of the ponytails of arylphosphines on the hydroformylation of higher olefins in supercritical CO2 , 2000 .

[7]  J. King,et al.  Hydrogenation of vegetable oils using mixtures of supercritical carbon dioxide and hydrogen , 2001 .

[8]  C. Eckert,et al.  Carbon dioxide as a solubility "switch" for the reversible dissolution of highly fluorinated complexes and reagents in organic solvents: application to crystallization. , 2002, Inorganic chemistry.

[9]  P. Ehrlich,et al.  Fundamentals of the free-radical polymerization of ethylene , 1970 .

[10]  J. DeSimone,et al.  Crystallization and Solid-State Polymerization of Poly(bisphenol A carbonate) Facilitated by Supercritical CO2 , 2000 .

[11]  A. Klibanov.  Why are enzymes less active in organic solvents than in water? , 1997, Trends in biotechnology.

[12]  P. Canu,et al.  Catalytic Hydrogenation in Supercritical CO2: Kinetic Measurements in a Gradientless Internal-Recycle Reactor , 1997 .

[13]  E. Beckman,et al.  Dispersion Polymerization of Methyl Methacrylate in Supercritical CO2 , 1997 .

[14]  U. Chatterjee,et al.  Effect of unconventional feeds on production cost, growth performance and expression of quantitative genes in growing pigs , 2022, Journal of the Indonesian Tropical Animal Agriculture.

[15]  C. Hall,et al.  Phase behavior of PVAC–PTAN block copolymer in supercritical carbon dioxide using SAFT , 2002 .

[16]  J. Gladysz,et al.  Fluorous catalysis without fluorous solvents: a friendlier catalyst recovery/recycling protocol based upon thermomorphic properties and liquid/solid phase separation. , 2001, Journal of the American Chemical Society.

[17]  T Herskovitz.  Organic and Bio-organic Chemistry of Carbon Dioxide , 1983 .

[18]  T. Casimiro,et al.  Transition-metal-mediated activation of arylisocyanates in supercritical carbon dioxide , 2001 .

[19]  John A. Hyatt,et al.  Liquid and supercritical carbon dioxide as organic solvents , 1984 .

[20]  Michael R. Nelson,et al.  Ab Initio Calculations on CO 2 Binding to Carbonyl Groups , 1998 .

[21]  W. Leitner,et al.  Iridium-Catalyzed Enantioselective Hydrogenation of Imines in Supercritical Carbon Dioxide , 1999 .

[22]  S. Nolan,et al.  Synthetic, Thermochemical, and Catalytic Studies of Fluorinated Tertiary Phosphine Ligands R2PRf [R = Cy, Ph, iPr; Rf = CH‘2CH2(CF2)5CF3] in Rhodium Systems , 1999 .

[23]  J. Texter,et al.  Reactions And Synthesis In Surfactant Systems , 2001 .

[24]  W. H. Hauthal,et al.  Advances with supercritical fluids [review] , 2001 .

[25]  Y. Hsiao,et al.  Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide: Influence of helium concentration on particle size and particle size distribution , 1997 .

[26]  A. Baiker,et al.  Enantioselective hydrogenation of ethyl pyruvate in supercritical fluids , 1995 .

[27]  Michel Perrut,et al.  Supercritical Fluid Applications: Industrial Developments and Economic Issues , 2000 .

[28]  P. Stark,et al.  A Comparison of Liquid and Supercritical Carbon Dioxide as an Extraction Solvent for Plating Bath Treatment , 1998 .

[29]  K. Johnston,et al.  Water-in-Carbon Dioxide Microemulsions with a Fluorocarbon-Hydrocarbon Hybrid Surfactant , 1994 .

[30]  D. Canelas,et al.  Dispersion Polymerization of Styrene in Supercritical Carbon Dioxide: Importance of Effective Surfactants , 1996 .

[31]  V. Krukonis,et al.  Effect of molecular architecture on the phase behavior of fluoroether-functional graft copolymers in supercritical CO2 , 1997 .

[32]  C. Michels,et al.  Isotherms of COFormula between 70 and 3000 Atmospheres (Amagat Densities between 200 and 600) , 1935 .

[33]  W. Arlt,et al.  Separations and Material Processing in Solutions with Dense Gases , 1998 .

[34]  M. Arai,et al.  Supercritical carbon dioxide as reaction medium : examination of its solvent effects in the near-critical region , 1992 .

[35]  Chunmei Shi,et al.  Remediation of Metal-Bearing Aqueous Waste Streams via Direct Carbonation , 2001 .

[36]  Maj-Britt Macher,et al.  Hydrogenation of palm oil in near‐critical and supercritical propane , 2001 .

[37]  B. Subramaniam,et al.  Coking of solid acid catalysts and strategies for enhancing their activity , 1999 .

[38]  Yigui Li,et al.  Prediction of phase equilibria for CO2–C2H5OH–H2O system using the SAFT equation of state , 2000 .

[39]  Mark A. McHugh,et al.  Solubility of Polymers and Copolymers in Supercritical CO2 , 1996 .

[40]  S. Allada.  Solubility parameters of supercritical fluids , 1984 .

[41]  Ch. Schneider.  Supercritical Fluid Science and Technology (ACS Symposium Series 406). Herausgegeben von K. P. Johnston und J. M. L. Penninger. 550 Seiten, zahlr. Abb. und Tab. Preis: 119,95 $ (USA und Canada 99,95 $) , 1990 .

[42]  Walter Leitner,et al.  Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO2 , 1995 .

[43]  Robert C. Reid,et al.  SUPERCRITICAL FLUID EXTRACTION. , 1983 .

[44]  D. Canelas,et al.  Dispersion polymerizations in carbon dioxide using siloxane-based stabilizers , 1996 .

[45]  Dorian A. Canelas,et al.  Dispersion Polymerizations of Styrene in Carbon Dioxide Stabilized with Poly(styrene-b-dimethylsiloxane) , 1997 .

[46]  A. Akgerman,et al.  Styrene Hydroformylation in Supercritical Carbon Dioxide: Rate and Selectivity Control , 2001 .

[47]  T. Sakakura,et al.  Hydrosilation of polyfluoroolefin in dense carbon dioxide , 2001 .

[48]  C. Eckert,et al.  Phase-Transfer Catalysis in Supercritical Carbon Dioxide: Kinetic and Mechanistic Investigations of Cyanide Displacement on Benzyl Chloride , 1998 .

[49]  C. Erkey.  Supercritical carbon dioxide extraction of metals from aqueous solutions: a review , 2000 .

[50]  Gina L. Weibel,et al.  E‐Beam Patterning of Hot‐Filament CVD Fluorocarbon Films Using Supercritical CO2 as a Developer , 2001 .

[51]  P. Debenedetti,et al.  Mathematical modeling of nucleation and growth of particles formed by the rapid expansion of a supercritical solution under subsonic conditions , 2002 .

[52]  C. Eckert,et al.  In Situ Formation of Alkylcarbonic Acids with CO2 , 2001 .

[53]  E. Beckman,et al.  Production of Hydrogen Peroxide in Liquid CO2. 3. Oxidation of CO2-Philic Anthrahydroquinones , 2000 .

[54]  Hideomi Koinuma,et al.  Copolymerization of carbon dioxide and epoxide , 1969 .

[55]  S. Inoue,et al.  Alternating copolymerization of carbon dioxide and epoxide catalyzed by the aluminum porphyrin-quaternary organic salt or -triphenylphosphine system. Synthesis of polycarbonate with well-controlled molecular weight , 1986 .

[56]  P. Debenedetti,et al.  Numerical Modeling of Mass Transfer in the Supercritical Antisolvent Process , 1999 .

[57]  A. Russell,et al.  Biocatalytic synthesis of acrylates in organic solvents and supercritical fluids: I. Optimization of enzyme environment , 1992, Biotechnology and bioengineering.

[58]  M. Shirai,et al.  Heck reactions using water-soluble metal complexes in supercritical carbon dioxide , 1999 .

[59]  乾 智行.  Advances in chemical conversions for mitigating carbon dioxide : proceedings of the fourth International Conference on Carbon Dioxide Utilization, Kyoto, Japan, September 7-11, 1997 , 1998 .

[60]  E. Beckman,et al.  Generation of hydrogen peroxide directly from H2 and O2 using CO2 as the solvent , 2001 .

[61]  P. Anastas,et al.  Green Chemistry , 2018, Environmental Science.

[62]  Dorian A. Canelas,et al.  Design of Nonionic Surfactants for Supercritical Carbon Dioxide , 1996, Science.

[63]  R. Smith,et al.  Supercritical fluids in separation science--the dreams, the reality and the future. , 1999, Journal of chromatography. A.

[64]  S. Howdle,et al.  Solubilization in nonionic reverse micelles in carbon dioxide , 1994 .

[65]  D. Richardson,et al.  Equilibria, Kinetics, and Mechanism in the Bicarbonate Activation of Hydrogen Peroxide: Oxidation of Sulfides by Peroxymonocarbonate , 2000 .

[66]  Eckhard Schollmeyer,et al.  Past, present and future of supercritical fluid dyeing technology – an overview , 2002 .

[67]  R. Gupta,et al.  Fundamentals of polymers , 1998 .

[68]  C. Stafford,et al.  Expansion of Polystyrene Using Supercritical Carbon Dioxide: Effects of Molecular Weight, Polydispersity, and Low Molecular Weight Components , 1999 .

[69]  Jianliang Xiao,et al.  Carbonylated Phosphines as Ligands for Catalysis in Supercritical CO2 , 2001 .

[70]  Joseph M. DeSimone,et al.  Synthesis of Tetrafluoroethylene-Based, Nonaqueous Fluoropolymers in Supercritical Carbon Dioxide , 1995 .

[71]  B. Shekunov,et al.  CRYSTALLIZATION PROCESSES IN PHARMACEUTICAL TECHNOLOGY AND DRUG DELIVERY DESIGN , 2000 .

[72]  M. Halmann.  Chemical Fixation of Carbon Dioxide: Methods for Recycling CO2 into Useful Products , 1993 .

[73]  P. D. Brown,et al.  Clean preparation of nanoparticulate metals in porous supports: a supercritical route , 2002 .

[74]  D. H. Busch,et al.  CO(2)-expanded solvents: unique and versatile media for performing homogeneous catalytic oxidations. , 2002, Journal of the American Chemical Society.

[75]  Stephen K. Ritter.  ALKYLATE RISING: Solid acid catalysis is leading the way toward environmentally friendlier gasoline and cleaner air , 2001 .

[76]  Richard D. Smith,et al.  Solubility of fluorinated metal diethyldithiocarbamates in Supercritical carbon dioxide , 1991 .

[77]  J. Tanko,et al.  Free-Radical Side-Chain Bromination of Alkylaromatics in Supercritical Carbon Dioxide , 1994, Science.

[78]  E. Beckman,et al.  Radical Reactions with Alkyl and Fluoroalkyl (Fluorous) Tin Hydride Reagents in Supercritical CO2 , 1997 .

[79]  J. Matsuo,et al.  Friedel-Crafts Reactions Catalyzed by Rare Earth Metal Trifluoromethanesulfonates , 2000 .

[80]  C. Eckert,et al.  Quantitative Equilibrium Constants between CO2 and Lewis Bases from FTIR Spectroscopy , 1996 .

[81]  J. Watkins,et al.  Deposition of Conformal Copper and Nickel Films from Supercritical Carbon Dioxide , 2001, Science.

[82]  M. Paulaitis,et al.  Swelling and sorption in polymer-CO2 mixtures at elevated pressures , 1987 .

[83]  Alfons Baiker,et al.  Supercritical Fluids in Heterogeneous Catalysis. , 1999, Chemical reviews.

[84]  M. Poliakoff,et al.  Selective catalytic hydrogenation of organic compounds in supercritical fluids as a continuous process , 1998 .

[85]  E. A. Brignole,et al.  Modeling and simulation tools for supercritical fluid processes , 2000 .

[86]  P. Debenedetti,et al.  Mathematical modeling of aerosol formation by rapid expansion of supercritical solutions in a converging nozzle , 1993 .

[87]  H. Elias.  Principles of Polymerization , 1977 .

[88]  D. Vlachos,et al.  Reactive Deposition of Metal Thin Films within Porous Supports from Supercritical Fluids , 2001 .

[89]  M. Z. Yates,et al.  Ambidextrous surfactants for water-dispersible polymer powders from dispersion polymerization in supercritical CO2 , 1999 .

[90]  Amparo Galindo,et al.  Study of the high pressure phase behaviour of CO2+n-alkane mixtures using the SAFT-VR approach with transferable parameters , 2002 .

[91]  K. Johnston,et al.  Buffering the Aqueous Phase pH in Water-in-CO2 Microemulsions , 1999 .

[92]  Jean-Noël Jaubert,et al.  The Group Contribution Concept: A Useful Tool To Correlate Binary Systems and To Predict the Phase Behavior of Multicomponent Systems Involving Supercritical CO2 and Fatty Acids , 1999 .

[93]  Jong Sung Lim,et al.  Solubility of vinylidene fluoride polymers in supercritical CO2 and halogenated solvents , 2000 .

[94]  L. Blomberg,et al.  Synthesis of fatty alcohol mixtures from oleochemicals in supercritical fluids , 2000 .

[95]  E. Weidner,et al.  Measurement and modelling of high-pressure phase equilibria in the systems polyethyleneglycol (PEG)–propane, PEG–nitrogen and PEG–carbon dioxide , 2000 .

[96]  M. Shirai,et al.  The selective formation of unsaturated alcohols by hydrogenation of α,β-unsaturated aldehydes in supercritical carbon dioxide using unpromoted Pt/Al2O3 catalyst , 1999 .

[97]  A. Russell,et al.  Rational Control of Polymer Molecular Weight and Dispersity during Enzyme-Catalyzed Polyester Synthesis in Supercritical Fluids , 1995 .

[98]  E. Beckman,et al.  Effect of structure on the cloud-point curves of silicone-based amphiphiles in supercritical carbon dioxide , 1993 .

[99]  Leitner,et al.  Steel-promoted oxidation of olefins in supercritical carbon dioxide using dioxygen in the presence of aldehydes , 2000, Chemistry.

[100]  J. DeSimone,et al.  Continuous Polymerizations in Supercritical Carbon Dioxide: Chain-Growth Precipitation Polymerizations , 1999 .

[101]  J. K.,et al.  Industrial Organic Chemistry , 1938, Nature.

[102]  A. Akgerman,et al.  Hydroformylation of propylene in supercritical carbon dioxide , 1997 .

[103]  E. Beckman,et al.  Copolymerization of 1,2-Epoxycyclohexane and Carbon Dioxide Using Carbon Dioxide as Both Reactant and Solvent , 1997 .

[104]  W. Sachse,et al.  Effects of high‐pressure CO2 on the glass transition temperature and mechanical properties of polystyrene , 1982 .

[105]  S. Schneider,et al.  Stille couplings in supercritical CO 2 catalyzed with perfluoro-tagged and un-tagged Pd complexes , 2001 .

[106]  B. Subramaniam,et al.  Fixed-bed hydrogenation of organic compounds in supercritical carbon dioxide , 2001 .

[107]  D. Richardson,et al.  Epoxidation of Alkenes with Bicarbonate-Activated Hydrogen Peroxide , 2000 .

[108]  C. Eckert,et al.  Asymmetric hydrogenation and catalyst recycling using ionic liquid and supercritical carbon dioxide. , 2001, Journal of the American Chemical Society.

[109]  Will Conley,et al.  157 nm resist materials: Progress report , 2000 .

[110]  John Oscar Pande,et al.  Ammonia plant NII: Explosion of hydrogen in a pipeline for CO2 , 2001 .

[111]  E. Beckman,et al.  H2O2 in CO2: Sustainable production and green reactions , 2002 .

[112]  B. Waller,et al.  Dissolution of Metal Species in Supercritical FluidsPrinciples and Applications , 2000 .

[113]  C. B. Roberts,et al.  Subcritical solvent effects on a parallel Diels-Alder reaction network , 1999 .

[114]  M. W. George,et al.  How does the critical point change during a chemical reaction in supercritical fluids? A study of the hydroformylation of propene in supercritical CO(2). , 2001, Journal of the American Chemical Society.

[115]  T. Long,et al.  Solvent-Free Polymerizations and Processes: Minimization of Conventional Organic Solvents , 1999 .

[116]  D. H. Gibson,et al.  The Organometallic Chemistry of Carbon Dioxide. , 1996, Chemical reviews.

[117]  D. Darensbourg,et al.  Catalytic Activity of Zinc(II) Phenoxides Which Possess Readily Accessible Coordination Sites. Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide , 1995 .

[118]  E. Beckman,et al.  Affinity Extraction into CO2. 2. Extraction of Heavy Metals into CO2 from Low-pH Aqueous Solutions , 1998 .

[119]  Gary R. List,et al.  Supercritical fluid technology in oil and lipid chemistry , 1996 .

[120]  E. Beckman,et al.  Phase behavior of fluoroether-functional amphiphiles in supercritical carbon dioxide , 1993 .

[121]  Dean W. Matson,et al.  Production of powders and films by the rapid expansion of supercritical solutions , 1987 .

[122]  J. Kadla,et al.  Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents. , 2001, Journal of the American Chemical Society.

[123]  T. J. McCarthy,et al.  Preparation and Characterization of Microcellular Polystyrene Foams Processed in Supercritical Carbon Dioxide , 1998 .

[124]  E. Beckman,et al.  Affinity Extraction into Carbon Dioxide. 1. Extraction of Avidin Using a Biotin-Functional Fluoroether Surfactant , 1997 .

[125]  Jean-Pierre Wauquier,et al.  Crude oil, petroleum products, process flowsheets , 1995 .

[126]  J. R. Royer,et al.  High-pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships , 2000 .

[127]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[128]  Jean W. Tom,et al.  Particle formation with supercritical fluids—a review , 1991 .

[129]  F. Gasparrini,et al.  CARBON-CARBON BOND FORMING REACTIONS IN SUPERCRITICAL CARBON DIOXIDE IN THE PRESENCE OF A SUPPORTED PALLADIUM CATALYST , 1999 .

[130]  M. Shamsipur,et al.  Extraction of uranium from solid matrices using modified supercritical fluid CO2 , 2001 .

[131]  D. Kiserow,et al.  Reaction Kinetics of the Solid-State Polymerization of Poly(bisphenol A carbonate) Facilitated by Supercritical Carbon Dioxide , 2001 .

[132]  P. Debenedetti,et al.  Numerical modeling of mass transfer in the supercritical antisolvent process: miscible conditions , 2000 .

[133]  Alan R. Berens,et al.  Application of compressed carbon dioxide in the incorporation of additives into polymers , 1992 .

[134]  R. Carbonell,et al.  Opportunities for pollution prevention and energy efficiency enabled by the carbon dioxide technology platform , 2000 .

[135]  W. Leitner,et al.  Catalytic asymmetric hydroformylation in the presence of compressed carbon dioxide , 1998 .

[136]  Walter Leitner,et al.  Chemical synthesis using supercritical fluids , 1999 .

[137]  V. Barocas,et al.  Mechanism Governing Microparticle Morphology during Precipitation by a Compressed Antisolvent: Atomization vs Nucleation and Growth , 2000 .

[138]  W. Kuran.  Coordination polymerization of heterocyclic and heterounsaturated monomers , 1998 .

[139]  K. Jordan,et al.  CO2−Fluorocarbon and CO2−Hydrocarbon Interactions from First-Principles Calculations , 1998 .

[140]  E. Beckman,et al.  Design of ligands for the extraction of PtCl62- into liquid CO2 , 2001 .

[141]  R. Crooks,et al.  Dendrimer-Encapsulated Metals and Semiconductors: Synthesis, Characterization, and Applications , 2001 .

[142]  T. Bruno,et al.  Solubilities of Copper(II) and Chromium(III) Beta-Diketonates in Supercritical Carbon-Dioxide , 1995 .

[143]  Michael Mccoy.  ROHM AND HAAS JOINS LOW-K PACK , 2001 .

[144]  E. Beckman,et al.  Nucleation and growth in microcellular materials: Supercritical CO2 as foaming agent , 1995 .

[145]  C. Wai,et al.  Supercritical fluid extraction: metals as complexes , 1997 .

[146]  J. E. Lyons,et al.  Catalysis research of relevance to carbon management: progress, challenges, and opportunities. , 2001, Chemical reviews.

[147]  R. Enick,et al.  ‘Gel’ formation in carbon dioxide-semifluorinated alkane mixtures and phase equilibria of a carbon dioxide-perfluorinated alkane mixture , 1989 .

[148]  C. D. Pearson,et al.  Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions , 1993 .

[149]  R. M. Izatt,et al.  Accomplishment of difficult chemical separations using solid phase extraction , 1996 .

[150]  C. Wai,et al.  Synthesizing and Dispersing Silver Nanoparticles in a Water-in-Supercritical Carbon Dioxide Microemulsion. , 1999, Journal of the American Chemical Society.

[151]  S. Howdle,et al.  Free radical polymerization of methyl methacrylate in supercritical carbon dioxide using a pseudo-graft stabilizer : Effect of monomer, initiator, and stabilizer concentrations , 2000 .

[152]  W. Hoelderich,et al.  The greening of nylon , 2001 .

[153]  Y. Xiong,et al.  Miscibility, density and viscosity of poly(dimethylsiloxane) in supercritical carbon dioxide , 1995 .

[154]  Dorian A. Canelas,et al.  Polymerizations in Supercritical Carbon Dioxide. , 1999, Chemical reviews.

[155]  Masahito Miyamoto,et al.  A review of particulate design for pharmaceutical powders and their production by spouted bed coating , 2000 .

[156]  Miss A.O. Penney.  (b) , 1974, The New Yale Book of Quotations.

[157]  G. Montero,et al.  Scale‐up and economic analysis for the design of supercritical fluid extraction equipment for remediation of soil , 1996 .

[158]  M. McHugh,et al.  Phase Behavior and Modeling of Supercritical Carbon Dioxide−Organic Acid Mixtures , 2000 .

[159]  C. Eckert,et al.  Tuning Solvents for Sustainable Technology , 2000 .

[160]  K. Manabe,et al.  Green Lewis acid catalysis in organic synthesis , 2000 .

[161]  C. Michels,et al.  Isotherms of COFormula between 0 degrees and 150 degrees and Pressures from 16 to 250 Atm (Amagat Densities 18-206) , 1935 .

[162]  A. Cooper,et al.  Synthesis of Macroporous Polymer Beads by Suspension Polymerization Using Supercritical Carbon Dioxide as a Pressure-Adjustable Porogen , 2001 .

[163]  C. Erkey,et al.  Kinetics of the homogeneous catalytic hydroformylation of 1-octene in supercritical carbon dioxide with HRh(CO)[P(p-CF3C6H4)3]3 , 1999 .

[164]  M. McHugh,et al.  Phase Behavior of Polymers in Supercritical Fluid Solvents. , 1999, Chemical reviews.

[165]  T. J. McCarthy,et al.  Polymer/metal nanocomposite synthesis in supercritical CO2 , 1995 .

[166]  Kang-ming Nie,et al.  An investigation of a Friedel-Crafts alkylation reaction in homogeneous supercritical CO2 and under subcritical and splitphase reaction conditions , 2000 .

[167]  Z. Guan,et al.  Synthesis of Fluoropolymers in Supercritical Carbon Dioxide , 1992, Science.

[168]  C. Y. Tsang,et al.  Phase equilibria in the H2/CO2 system at temperatures from 220 to 290 K and pressures to 172 MPa , 1981 .

[169]  E. Beckman,et al.  Solvent-free generation of poly(vinyl acetals) directly from poly(vinyl acetate) , 1999 .

[170]  Huanfeng Jiang,et al.  Wacker reaction in supercritical carbon dioxide , 2000 .

[171]  C. Erkey,et al.  Hydroformylation of Higher Olefins in Supercritical Carbon Dioxide with HRh(CO)[P(3,5-(CF3)2−C6H3)3]3 , 2000 .

[172]  F. Solymosi,et al.  Surface interaction between H2 and CO2 over palladium on various supports , 1985 .

[173]  G. D. Holder,et al.  Supercritical Fluid Solubilization of Catalyst Precursors : The Solubility and Phase Behavior of Molybdenum Hexacarbonyl in Supercritical Carbon Dioxide and Application to the Direct Liquefaction of Coal , 1992 .

[174]  A. Ravve,et al.  Principles of Polymer Chemistry , 1995 .

[175]  John Howard Perry,et al.  Chemical Engineers' Handbook , 1934 .

[176]  T. Aida,et al.  Synthesis of polyether-polycarbonate block copolymer from carbon dioxide and epoxide using a metalloporphyrin catalyst system , 1982 .

[177]  Frank V. Bright,et al.  Specific Intermolecular Interaction of Carbon Dioxide with Polymers , 1996 .

[178]  Richard D. Smith,et al.  Observations on the solubility of surfactants and related molecules in carbon dioxide at 50°C , 1990 .

[179]  S J Prestrelski,et al.  Biopharmaceutical powders: particle formation and formulation considerations. , 2000, Current pharmaceutical biotechnology.

[180]  Bala Subramaniam,et al.  Enhancing the stability of porous catalysts with supercritical reaction media , 2001 .

[181]  Charles N. Satterfield,et al.  Heterogeneous catalysis in practice , 1980 .

[182]  Dan Hancu,et al.  Green processing using ionic liquids and CO2 , 1999, Nature.

[183]  J. Kolis,et al.  Oxidation of Alkenes in Supercritical Carbon Dioxide Catalyzed by Molybdenum Hexacarbonyl , 1998 .

[184]  K. Johnston,et al.  Glass transitions of polymers with compressed fluid diluents : type II and III behavior , 1994 .

[185]  C. Stoldt,et al.  Formation of Aqueous Small Droplet Aerosols Assisted by Supercritical Carbon Dioxide , 1999 .

[186]  R. Koningsveld,et al.  Liquid-Liquid Phase Separation in Multicomponent Polymer Systems. 18. Effect of Short-Chain Branching , 1980 .

[187]  M. McHugh,et al.  Cosolvency effect of SF6 on the solubility of poly(tetrafluoroethylene‐co‐19 mol % hexafluoropropylene) in supercritical CO2 and CHF3 , 1999 .

[188]  A. Russell,et al.  Solubilization of subtilisin in CO2 using fluoroether-functional amphiphiles. , 1998, Biotechnology and bioengineering.

[189]  T. Bruno,et al.  Solubilities of Cerium(IV), Terbium(III), and Iron(III) β-Diketonates in Supercritical Carbon Dioxide† , 2001 .

[190]  B. Subramaniam,et al.  Environmentally benign multiphase catalysis with dense phase carbon dioxide , 2002 .

[191]  P. Mitchell.  Hydrodemetallisation of crude petroleum: fundamental studies , 1990 .

[192]  M. N. Ponte,et al.  The influence of phase behavior on reactions at supercritical conditions : The hydrogenation of α-pinene , 2001 .

[193]  J. Watkins,et al.  Reactive Deposition of Conformal Palladium Films from Supercritical Carbon Dioxide Solution , 2000 .

[194]  Kenji Ogino,et al.  Low-Surface-Energy Fluoromethacrylate Block Copolymers with Patternable Elements , 2000 .

[195]  A. Behr.  Carbon Dioxide Activation by Metal Complexes , 1988 .

[196]  J. DeSimone,et al.  Dispersion polymerization of glycidyl methacrylate in supercritical carbon dioxide , 2001 .

[197]  M. N. Myers,et al.  High Pressure Gas Chromatography of Nonvolatile Species , 1968 .

[198]  K. Johnston,et al.  Supercritical Fluid Science and Technology , 1989 .

[199]  M. Mukhopadhyay,et al.  Influence of the thermodynamic state on cyclohexane oxidation kinetics in carbon dioxide medium , 1997 .

[200]  J. DeSimone,et al.  Dispersion Polymerizations in Supercritical Carbon Dioxide , 1994, Science.

[201]  R. J. Klingler,et al.  Propylene hydroformylation in supercritical carbon dioxide , 1991 .

[202]  L. Lake,et al.  Enhanced Oil Recovery , 2017 .

[203]  Peter York,et al.  Phase Behavioral Effects on Particle Formation Processes Using Supercritical Fluids , 1999, Pharmaceutical Research.

[204]  J. Watkins,et al.  Chemical Fluid Deposition: A Hybrid Technique for Low‐Temperature Metallization , 2000 .

[205]  C. Tanford.  Macromolecules , 1994, Nature.

[206]  Frank V. Bright,et al.  Water-in-Carbon Dioxide Microemulsions: An Environment for Hydrophiles Including Proteins , 1996, Science.

[207]  P. Debenedetti.  Homogeneous nucleation in supercritical fluids , 1990 .

[208]  R. Wiebe,et al.  The Solubility of Carbon Dioxide in Water at Various Temperatures from 12 to 40° and at Pressures to 500 Atmospheres. Critical Phenomena* , 1940 .

[209]  E. Reverchon.  SUPERCRITICAL ANTISOLVENT PRECIPITATION OF MICRO- AND NANO-PARTICLES , 1999 .

[210]  Michael E. Paulaitis,et al.  GLASS TRANSITIONS IN POLYMER/CO2 MIXTURES AT ELEVATED PRESSURES , 1991 .

[211]  W. Tumas,et al.  Asymmetric catalytic hydrogenation reactions in supercritical carbon dioxide. , 1995 .

[212]  L. Archer,et al.  Principles of Polymer Systems , 1982 .

[213]  C. Wai,et al.  Solubility of chelating agents and metal-containing compounds in supercritical fluid carbon dioxide. , 1997, Talanta.

[214]  Paul T. Anastas,et al.  Green chemical syntheses and processes , 2000 .

[215]  C. Eckert,et al.  In situ Spectroscopy of Polymers Subjected to Supercritical CO2: Plasticization and Dye Impregnation , 1997 .

[216]  E. Beckman,et al.  Microemulsions in near-critical and supercritical carbon dioxide , 1991 .

[217]  E. Beckman,et al.  H2O2 in CO2/H2O Biphasic Systems: Green Synthesis and Epoxidation Reactions , 2002 .

[218]  F. Solymosi,et al.  Catalytic hydrogenation of CO2 over supported palladium , 1986 .

[219]  Rafiqul Gani,et al.  Design and analysis of supercritical extraction processes , 1997 .

[220]  C. Manke,et al.  Rheology of molten polystyrene with dissolved supercritical and near‐critical gases , 1999 .

[221]  O. Crosby.  Microspheres. , 2020, Archives of internal medicine.

[222]  Berth-Jan Deelman,et al.  Homogeneous Reactions in Supercritical Carbon Dioxide Using a Catalyst Immobilized by a Microporous Silica Membrane. , 2001, Angewandte Chemie.

[223]  Suresh Valiyaveettil,et al.  Supercritical CO2 Processing for Submicron Imaging of Fluoropolymers , 2000 .

[224]  Andrew G. Glen,et al.  APPL , 2001 .

[225]  M. McHugh,et al.  Comparison of the Solubility of PVF and PVDF in Supercritical CH2F2 and CO2 and in CO2 with Acetone, Dimethyl Ether, and Ethanol , 1999 .

[226]  J. DeSimone,et al.  Ring-Opening Metathesis Polymerizations in Carbon Dioxide , 1996 .

[227]  The Fluid Phase , 2022 .

[228]  A. McGowin,et al.  Selectivity of 1,3-dipolar cycloaddition of methyl propiolate to 3-phenylsydnone in near- or supercritical carbon dioxide , 2000 .

[229]  M. Radosz,et al.  Phase behavior of poly(ethylene−1-butene) in subcritical and supercritical propane : ethyl branches reduce segment energy and enhance miscibility , 1995 .

[230]  R. J. Klingler,et al.  HIGH-PRESSURE NMR INVESTIGATION OF HYDROGEN ATOM TRANSFER AND RELATED DYNAMIC PROCESSES IN OXO CATALYSIS , 1994 .

[231]  G. Coates,et al.  Single-site beta-diiminate zinc catalysts for the alternating copolymerization of CO2 and epoxides: catalyst synthesis and unprecedented polymerization activity. , 2001, Journal of the American Chemical Society.

[232]  W. Tumas,et al.  Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide , 1999 .

[233]  Cationic Polymerization of Vinyl and Cyclic Ethers in Supercritical and Liquid Carbon Dioxide , 1995 .

[234]  P. Canu,et al.  Kinetic experiments and modeling of a three-phase catalytic hydrogenation reaction in supercritical CO2 , 1999 .

[235]  K. Nicholas,et al.  Palladium-Catalyzed Carboxylation of Allyl Stannanes , 1997 .

[236]  Gerardo A. Montero,et al.  Supercritical Fluid Technology in Textile Processing: An Overview , 2000 .

[237]  Jianliang Xiao,et al.  Asymmetric hydrogenation of α,β-unsaturated carboxylic acids in supercritical carbon dioxide , 1996 .

[238]  J. B. Cain,et al.  High-Pressure NMR of Polymers Dissolved in Supercritical Carbon Dioxide , 1997 .

[239]  P. Jessop,et al.  HOMOGENEOUS CATALYSIS IN SUPERCRITICAL FLUIDS : HYDROGENATION OF SUPERCRITICAL CARBON DIOXIDE TO FORMIC ACID, ALKYL FORMATES, AND FORMAMIDES , 1996 .

[240]  J. Brennecke,et al.  Esterification of acetic acid with ethanol in carbon dioxide , 2001 .

[241]  T. J. McCarthy,et al.  Chemical Fluid Deposition: Reactive Deposition of Platinum Metal from Carbon Dioxide Solution , 1999 .

[242]  W. D. Marshall,et al.  Dechlorination of pentachlorophenol in supercritical carbon dioxide with a zero-valent silver–iron bimetallic mixture , 2001 .

[243]  E. Beckman,et al.  Generation of Microcellular Biodegradable Polymers Using Supercritical Carbon Dioxide , 1999 .

[244]  M. Moshfeghian,et al.  Evaluation of vapor—liquid equilibrium of CO2 binary systems using UNIQUAC-based Huron—Vidal mixing rules , 1997 .

[245]  J. DeSimone,et al.  Precipitation Polymerization of Acrylic Acid in Supercritical Carbon Dioxide , 1995 .

[246]  M. Härröd,et al.  Hydrogenation of oleochemicals at supercritical single-phase conditions: influence of hydrogen and substrate concentrations on the process , 2001 .

[247]  C. Eckert,et al.  Olefin Epoxidations Using Supercritical Carbon Dioxide and Hydrogen Peroxide without Added Metallic Catalysts or Peroxy Acids , 2002 .

[248]  W. Tumas,et al.  Enhanced catalyst reactivity and separations using water/carbon dioxide emulsions [5] , 1999 .

[249]  Chen,et al.  Palladium-catalyzed synthesis of aqueous, fluorous, and supercritical CO2-soluble phosphines , 2000, Organic letters.

[250]  J. Kennedy,et al.  Carbocationic polymerizations in supercritical carbon dioxide , 1994 .

[251]  J. DeSimone,et al.  Decomposition of polymerisation initiators in supercritical CO2 : a novel approach to reaction kinetics using a CSTR , 2000 .

[252]  M. Z. Yates,et al.  Emulsion Stabilization and Flocculation in CO2. 1. Turbidimetry and Tensiometry , 1997 .

[253]  A. Russell,et al.  Biocatalytic synthesis of acrylates in organic solvents and supercritical fluids: III. Does carbon dioxide covalently modify enzymes? , 1995, Biotechnology and bioengineering.

[254]  Martin Palmer,et al.  Applications for supercritical fluid technology in food processing , 1995 .

[255]  N. Foster,et al.  Solubilities of solid mixtures in supercritical carbon dioxide: a review , 2000 .

[256]  Coking and activity of a reforming catalyst in near-critical and dense supercritical reaction mixtures , 1994 .

[257]  M. Abraham,et al.  Evaluation of catalyst support effects during rhodium-catalyzed hydroformylation in supercritical CO2 , 2001 .

[258]  Huanfeng Jiang,et al.  Selective carbonylation of norbornene in scCO2 , 1999 .

[259]  Kishimoto,et al.  Supercritical carbon dioxide as a reaction medium for silane-mediated free-radical carbonylation of alkyl halides , 2000, The Journal of organic chemistry.

[260]  V. Krukonis,et al.  Supercritical fluid technology , 1985 .

[261]  A. Akgerman,et al.  DETERMINATION OF SELECTIVITY FOR PARALLEL REACTIONS IN SUPERCRITICAL FLUIDS , 1999 .

[262]  J. Tester,et al.  Kinetic Correlation of Diels−Alder Reactions in Supercritical Carbon Dioxide , 1996 .

[263]  C. B. Roberts,et al.  Supercritical fluid and compressed solvent effects on metallic nanoparticle synthesis in reverse micelles , 2000 .

[264]  I. Velasco,et al.  Representation for binary mixtures of n-alcohols + sub and supercritical CO2 by a group-contribution method , 2001 .

[265]  Lou Massa.  BEYOND THE DOUBLE HELIX , 2002 .

[266]  Hwang,et al.  Catalytic Intermolecular Pauson - Khand Reactions in Supercritical Ethylene. , 2000, Angewandte Chemie.

[267]  J. Kennedy,et al.  Carbocationic polymerization in supercritical carbon dioxide , 1994 .

[268]  Yuehe Lin,et al.  STUDIES ON IN-SITU CHELATION/SUPERCRITICAL FLUID EXTRACTION OF LANTHANIDES AND ACTINIDES USING A RADIOTRACER TECHNIQUE , 2001 .

[269]  Stephen K. Ritter.  THE CHANGING FACE OF CHEMICAL ENGINEERING: Century-old discipline is ripe for expansion into materials and biomedical product development , 2001 .

[270]  Jennifer Jung,et al.  Particle design using supercritical fluids: Literature and patent survey , 2001 .

[271]  M. Härröd,et al.  Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical conditions , 1999 .

[272]  Daniel Koch,et al.  Rhodium-Catalyzed Hydroformylation in Supercritical Carbon Dioxide , 1998 .

[273]  C. Erkey,et al.  Effect of Ligand Modification on Rhodium-Catalyzed Homogeneous Hydroformylation in Supercritical Carbon Dioxide , 2000 .

[274]  Y. Oshima,et al.  Aerobic Oxidation of Cyclohexane Catalyzed by Fe(III)(5,10,15,20-tetrakis(pentafluorophenyl)porphyrin)Cl in Sub- and Super-Critical CO2 , 1997 .

[275]  C. Erkey,et al.  Homogeneous Catalytic Hydroformylation of 1-Octene in Supercritical Carbon Dioxide Using a Novel Rhodium Catalyst with Fluorinated Arylphosphine Ligands , 1998 .

[276]  Esteban A. Brignole,et al.  Optimal design of supercritical fluid processes , 2000 .

[277]  M. N. Myers,et al.  Dense Gas Chromatography at Pressures to 2000 Atmospheres , 1969 .

[278]  J. Shim,et al.  Molecular thermodynamics of solute‐polymer‐supercritical fluid systems , 1991 .

[279]  L. T. Taylor,et al.  Metallized poly(etherether ketone) films achieved by supercritical fluid impregnation of a silver precursor followed by thermal curing , 2002 .

[280]  E. Samulski,et al.  Fluorocarbons Dissolved in Supercritical Carbon Dioxide. NMR Evidence for Specific Solute−Solvent Interactions , 1998 .

[281]  J. Shim,et al.  Adjustable solute distribution between polymers and supercritical fluids , 1989 .

[282]  R. Marr,et al.  Use of supercritical fluids for different processes including new developments—a review , 2000 .

[283]  E. Beckman,et al.  Toward the Development of “CO2-philic” Hydrocarbons. 1. Use of Side-Chain Functionalization to Lower the Miscibility Pressure of Polydimethylsiloxanes in CO2 , 1999 .

[284]  Eric J. Beckman,et al.  Non-fluorous polymers with very high solubility in supercritical CO 2 down to low pressures , 2000, Nature.

[285]  J. Tester,et al.  Concerning the Regiochemical Course of the Diels-Alder Reaction in Supercritical Carbon Dioxide. , 1997, The Journal of organic chemistry.

[286]  H. Koinuma,et al.  Copolymerization of carbon dioxide and epoxide with organometallic compounds , 1969 .

[287]  Zachary Evenhouse,et al.  Supercritical fluids. , 1982, Environmental science & technology.

[288]  Xu,et al.  The Gelation of CO(2): A Sustainable Route to the Creation of Microcellular Materials. , 1999, Science.

[289]  M. Abraham,et al.  Rhodium supported on activated carbon as a heterogeneous catalyst for hydroformylation of propylene in supercritical carbon dioxide , 2000 .