CA1337235C - Chemical reactions in reverse micelle systems - Google Patents
Chemical reactions in reverse micelle systemsInfo
- Publication number
- CA1337235C CA1337235C CA000584081A CA584081A CA1337235C CA 1337235 C CA1337235 C CA 1337235C CA 000584081 A CA000584081 A CA 000584081A CA 584081 A CA584081 A CA 584081A CA 1337235 C CA1337235 C CA 1337235C
- Authority
- CA
- Canada
- Prior art keywords
- reactant
- reverse
- fluid
- microemulsion
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000693 micelle Substances 0.000 title claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- 239000012530 fluid Substances 0.000 claims abstract description 62
- 239000000376 reactant Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 239000001294 propane Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 36
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 22
- 239000012071 phase Substances 0.000 description 20
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 13
- 239000011162 core material Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- KTTSJTVLWUJJMN-UHFFFAOYSA-L cadmium(2+);dichlorate Chemical compound [Cd+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O KTTSJTVLWUJJMN-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FBELJLCOAHMRJK-UHFFFAOYSA-L disodium;2,2-bis(2-ethylhexyl)-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCC(CC)CC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CC(CC)CCCC FBELJLCOAHMRJK-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/10—Dispersions; Emulsions
- A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
- A61K9/1075—Microemulsions or submicron emulsions; Preconcentrates or solids thereof; Micelles, e.g. made of phospholipids or block copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/04—Specific aggregation state of one or more of the phases to be mixed
- B01F23/043—Mixing fluids or with fluids in a supercritical state, in supercritical conditions or variable density fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
- B01F23/4105—Methods of emulsifying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
- C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
- C01G5/02—Halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/02—Alkyl sulfonates or sulfuric acid ester salts derived from monohydric alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
- B01F23/414—Emulsifying characterised by the internal structure of the emulsion
- B01F23/4143—Microemulsions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00058—Temperature measurement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00054—Controlling or regulating the heat exchange system
- B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
- B01J2219/00065—Pressure measurement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00191—Control algorithm
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/925—Phase inversion
Abstract
This invention is directed to conducting chemical reactions in reverse micelle or microemulsion systems comprising a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a microemulsion promoter, typically a surfactant, for facilitating the formation of reverse micelles in the system. The system further includes a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. Thus, the microemulsion system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The method of carrying out chemical reactions generally comprises forming a first reverse micelle system including an aqueous fluid including reverse micelles in a water-insoluble fluid in the supercritical state. Then, a first reactant is introduced into the first reverse micelle system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse micelles. A second reactant can also be incorporated in the first reverse micelle system which is capable of reacting with the first reactant to form a product.
Description
~ CHEMICAL REACTIONS IN REVERSE MICELLE SYSTEMS
BACKGROUND OF THE INVENTION
The subject invention is directed to a method for forming chemical products by reacting chemical reactants in reverse micelle or microemulsion systems at a supercritical or near critical state.
SUMMARY OF THE INVENTION
This invention relates to the conduct of chemical reactions in reverse micelle or reverse microemulsion systems. The micelles or microemulsions formed are referred to as "reverse micelles" or "reverse microemulsions" to distinguish them from the normal micelles or microemulsions of non-water-soluble fluids in aqueous liquids.
The method of carrying out chemical reactions generally comprises forming a first system including an aqueous fluid including reverse microemulsions or reverse micelles in a water-insoluble fluid in the near critical or supercritical state. Then, a first reactant is introduced into the first system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse microemulsions or reverse micelles. A second reactant can also be incorporated in the first system which is capable of reacting with the first reactant to form a product. The first and/or the second reactant can be capable of diffusing into or out of the reverse microemulsions or reverse micelles for conducting the subject chemical reactions. The reverse micelles or microemulsions typically comprise water and a surfactant.
The method of the present invention can also include the step of introducing a chemical catalyst, such as dispersed metallic particles or metallic compounds, or an energy source for initiating and/or driving the chemical reaction, such as radiation energy. Such chemical catalysts can include, for example, Pt, Pd, and Rh ,,,~ ~
_ - 2 - l 33 72 35 particles, or the borides of Ni, Co, and Fe, added to the system or formed in situ.
The first reactant can also be incorporated into the water-insoluble fluid for conducting the chemical reaction.
Although the product formed can be soluble in either of the phases present, it is typically insoluble in water, in the supercritical fluid, or in the water and the supercritical fluid, respectively.
In a preferred method, the second reactant is incorporated into a second system typically comprising an aqueous fluid in a water-insoluble fluid in the supercritical or near critical state. The second system can then be added to the first system. For instance, a precipitation reaction may be provided employing solute species present in two distinct systems. In any case, the exchange of core materials occurs rapidly in the systems, ensuring complete mixing of the reactants. Two supercritical reverse micelle or microemulsion solutions can be prepared, each of which contains a water-soluble salt or other soluble reactant species dissolved in the aqueous cores of such solutions.
More specifically, although products which are soluble in the continuous or discontinuous phase may be formed by the method of this invention, this invention also relates to the formation of very fine particles by the reaction of a substance contained in the reverse microemulsion or micelles with a reactant added to the supercritical fluid which diffuses into the microemulsion or micelles and reacts with the substance to give a product insoluble in either water or supercritical fluid, or both.
The two solutions can comprise some combination of cations and anions which will produce an insoluble precipitate. The first and/or second reactant can comprise a water-soluble salt, such as sodium chloride, silver chloride, iron chloride, silver nitrate, barium hydroxide, calcium hydroxide, cadmium chloride, cadmium nitrate, cadmium chlorate, cadmium sulfide, cobalt chloride, cobalt B
_ _ 3 _ l 33 723 5 sulfide, zinc sulfide, lead sulfide, and copper sulfide.
It can also comprise an acidic material in aqueous solution such as an aqueous solution of sulfuric acid, a basic material in aqueous solution, and the water-insoluble fluid itself, or a reactant dissolved in the water-insoluble fluid such as an alkene or alkane. Further reactants may include a monomeric material or monomeric precursor material, such as tetraethoxysilane, dissolved in the water-insoluble or aqueous fluid, such as a hydrolysis/polymerization reaction catalyzed by an acidic or basic aqueous solution or other initiator in the reverse micelle system.
Still more specifically, it relates to a first reactant which is aqueous aluminum nitrate, a second reactant which is aqueous ammonia, and a reaction product which is aluminum hydroxide, and a particular method which comprises the production of submicron particles of aluminum hydroxide by forming reverse micelles of aluminum nitrate, water, and a surfactant, in supercritical propane and introducing ammonia into the propane phase.
The ability to form reverse micelles, or molecular assemblages consisting of surfactant shells with aqueous cores, in continuous nonpolar phases operated above their critical temperatures and pressures has recently been reported[1]. In this specification we describe the formation of inorganic, submicron particles in a supercritical hydrocarbon solution containing reverse micelles. A fine powder consisting of 0.5-micron-diameter aluminum hydroxide particles was precipitated from aqueous Al(NO3)3 solutions present in micelle cores by the diffusion of ammonia, a component in the binary supercritical fluid continuous phase, into the aqueous core. This work represents not only the first report of particle production using supercritical fluid micelles but is also the first example of a chemical reaction occurring within reverse micelles dispersed in a supercritical fluid.
S ~
- _ 4 _ l 3 3 7 235 Reverse micelles in liquids have been shown to offer a wide range of potential applications in the areas of chromatography, separations, and reaction processes[2~5]. In addition, chemical reactions involving species present in the reverse micelle cores have allowed the production of colloidal-size particles (3 to 10 nm) for use in catalytic and semiconductor applications[6 8] . Chemical processes utilizing systems in which reverse micelles exist in supercritical fluid regimes are expected to expand the scope of potential applications for micellar systems by utilizing the unique properties of supercritical fluids.
These include such pressure-dependent variables as viscosity, density, and diffusion rate, as well as the ability to readily manipulate the P-T-phase behavior in the multicomponent micelle systems. Supercritical fluid reverse micelle phase stability is strongly dependent on the fluid pressure, and the amount of water that can be contained in the micelle core increases with the pressure applied to the fluid. At 100 bar and 103`C, the maximum water-to-AOT molar ratio for reverse micelles in a propane continuous phase is 4. This value increases to 12 at the same temperature and 300 bar[9].
Typically, the subject chemical reactions in reverse micelle or microemulsion systems comprises a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a micelle or microemulsion promoter, preferably a surfactant, for facilitating the formation of a reverse microemulsion or reverse micelles in the system.
The system, which for purposes of this invention can be a reverse micelle or inverse microemulsion system, can further include a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. A fluid is in a supercritical state when its temperature and pressure exceed its critical temperature and pressure. Thus, the B
system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The non-polar or low-polarity fluid can also be maintained in a near 5 critical state up to the critical temperature thereof.
The preferred temperature is in a range from about 90`C
below the critical temperature thereof up to the critical temperature.
BRIEF DESCRIPTION OF THE DRAWING
In the drawing: The single figure is a scanning electron micrograph of aluminum hydroxide particles produced by addition of ammonia to reverse micelles containing 0.1 M Al(NO3)3 in a supercritical propane solution at 100`C and 200 bar.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
In this research aluminum hydroxide particles were prepared in a 25-ml high-pressure reaction vessel incorporating two 13-mm thick, 25-mm diameter sapphire windows through which the various steps in the reaction process could be observed. Before pressurizing with propane, the solid surfactant, sodium bis (2-ethylhexyl) sulfosuccinate (AOT), and the aqueous reaction solution, Al(NO3)3 9H20 in water were charged into the vessel at a molar water to AOT ratio (W) of 5. In all experiments the AOT concentration was 50mM. Three different Al(NO3)3 concentrations were used; 0.1 M, 0.05 M and .01 M Al(NO3)3 9H20 in water. After reaching the desired reaction temperature, 100`C in all cases, the system was pressurized to 200 bar with propane (Tc = 96.8`C, Pc = 42 atmospheres) by means of a high-pressure syringe pump. After several minutes of agitation with a magnetic stir bar, optically clear solutions were obtained, which contained the aqueous Al(NO3)3 solution dispersed in the reverse micelle phase.
In other experiments without the addition of AOT to the system, two phases, consisting of supercritical propane and ;
~ - 6 - l 337235 the liquid aqueous phase, remained in the view cell under the same temperature and pressure conditions. Once temperature in the cell was stabilized, approximately 40 uL
of dry ammonia was injected through a short length of small-bore (100-um-i.d.) tubing connected to a second syringe pump. Ammonia is known to exhibit considerable solubility in many supercritical hydrocarbons, including propane[10]. The ammonia was clearly evident (by the appearance of a milky plume which rapidly dissipated) as it was introduced into a reverse micelle solution consisting of pure water, AOT and supercritical propane. Addition of ammonia to a pure supercritical propane system produced a clear plume, suggesting that the milky plume produced in the micelle systems resulted from alteration of micelle phase behavior due to the locally high ammonia concentrations. Subsequent to addition of the ammonia, fluid in the view cell containing the 0.1 M Al(NO3)3 solution became turbid after approximately one minute but remained clear in the systems containing more dilute Al(NO3)3 solutions. To collect and characterize particles formed in the supercritical fluid system, flow was established across a 0.5-um stainless steel frit mounted in-line to a flow restrictor through which the fluid in the cell was vented. Pressure was held constant in the cell during sample collection by the gradual addition of propane from a syringe pump.
Aluminum hydroxide particles precipitated by introduction of ammonia into a reverse micelle system containing 0.1 M Al(NO3)3 are shown in FIG. 1. Mean particle sizes are on the order of 0.5 um, with some evidence of "necking" between particles or minor agglomeration. It is not clear whether this behavior results from interactions in the solution prior to the particle deposition, or whether it is an artifact of collecting the sample on a porous frit where interactions between the high surface energy particles would be enhanced. The product particles collected from the system I
- 7 _ l 337235 utilizing a 0.05 M Al(NO3)3 solution were significantly smaller (<0.1 um) and exhibited a much higher degree of agglomeration. No product was collected from the system utilizing the 0.01 M Al(NO3)3 solution, perhaps because any individual particles formed in that system were too small to be collected on the frit surface.
The particles shown in the figure are considerably larger than the reverse micelles present in the supercritical propane prior to introduction of the ammonia (5 to 10 nm). The phenomenon of particles far exceeding the sizes of micelles from which they were formed has also been observed during the formation of colloidal catalyst particles from reverse micelle phases in liquid systemsl7~8].
This behavior has been attributed to the rapid exchange of contents between micelle cores, which could promote the coalescence of angstrom- or nanometer-size precipitated nuclei to form the much larger particles actually observed in the collected product.
The use of reaction processes in supercritical micelle solutions for powder production offers a number of potential advantages over existing technologies. The ability to manipulate the concentrations of reactants involved in the particle formation may allow the capability to finely control the particle size. Operation in the supercritical fluid regime may also allow high mass transfer rates of reactants to and across the micelle membranes, and should relax rate limitations when one of the reactants is a gas. Increased reaction rates are expected for diffusion limited reactions. High diffusion rates may reduce polydispersity of the particles produced by minimizing local concentration gradients due to the incomplete mixing. The pressure dependence of the phase and density behavior in supercritical fluid systems may also allow additional advantages to be gained in the area of particle separation from the continuous fluid phase in which it is produced.
, ~
, ., ~, , - - 8 - ~ 33 7235 Three examples of the chemical reactions of this invention are described below which were performed in reverse micelle systems in which propane was used as the water-insoluble fluid and aerosol-OT (AOT) was the surfactant. Each of the reactions described below was performed using system conditions of 100`C and approximately 300 atm pressure, which is above the critical temperature and pressure of propane.
Example 1 This example describes the reaction between reactants present in two distinct reverse micelle systems at supercritical conditions.
Two reverse micelle systems were made independently in high pressure viewcells. Both were prepared such that the final solution would have a final AOT concentration of approximately 50 mM. In one of the cells, 0.lM NaOH was added to make a water-to-surfactant ratio of approximately 11. The system was heated, pressurized, and stirred to form a clear, single-phase solution. In the other view cell, AOT was added and the system was pressurized and heated to the desired conditions. A quantity of 0.lM
Cu(NO3) 2 solution was added to the second cell from a high pressure hand-crank pump to make a reverse micelle solution having a water-to-surfactant ratio of approximately 13.
The solution formed in the viewcell containing copper nitrate solution was one-phase and appeared slightly yellow in color.
When the supercritical fluid solutions had been prepared in both cells, a valve between them was opened.
Pressure was vented slowly through a restrictor at the outlet of one of the cells so that a pressure differential existed between the cells and solution from one cell was transported into the other. Pressure was maintained in the upstream cell by adding propane from a high pressure syringe pump. After 25~ of the solution in the downstream cell had been vented, the valves were closed and the ..
B~
:
- 9 ~ 337235 solution was allowed to set for several minutes. The reaction resulting from the mixing of copper and hydroxide solutions was evidenced by the visible observation of fine particles (copper hydroxide) in the cell containing the mixed solutions.
Example 2 This example describes the reaction between reactants present in a reverse micelle system at supercritical conditions and a water soluble reactant added to the system.
In a high pressure viewcell, AOT and 0.lM KC1 solution were added in sufficient quantities to prepare a solution having an AOT concentration of approximately 75 mM and containing a water-to-surfactant ratio of approximately 3.
The system was heated and pressurized to form a clear, single phase reverse micelle solution at supercritical conditions. A small amount of 0.lM AgNO3 solution was added to the system using a high pressure hand-crank pump to raise the water-to-surfactant ratio of the system to between 5 and 7. After allowing the solution to set for several minutes, fine solid particles (silver chloride) were visually observed in the viewcell.
Example 3 This example describes the reaction between reactants present in the supercritical fluid reverse micelle system and reactants dissolved in the continuous phase. The reaction was catalyzed by material present in the reverse micelle.
In a high pressure viewcell, AOT and 0.lM NaOH were added in appropriate quantities such that, when pressurized with supercritical propane, the resulting solution had an AOT concentration of approximately 50 mM and a water-to-surfactant ratio of 10. On achieving a clear solution at100`C and 300 atm, tetraethoxysilane (TEOS) was added to the cell at approximately ten times the water content using r - lo 1 337235 a high pressure hand-crank pump. TEOS is an alkane-soluble, water-insoluble silicate precursor to form interlinked Si-O-Si networks which are generated via hydrolysis of the TEOS monomer and subsequent polycondensation reactions. The reaction is catalyzed by the presence of either an acid or a base. This hydrolysis/condensation reaction was evidenced by visual observation of solid particles in the viewcell after approximately an hour. Fourier-transform infrared spectra taken on the supercritical fluid solution containing TEOS
also provided evidence for an increasing concentration of Si-O-Si linkages in the system with time.
REFERENCES
1. Gale, R.W., J.L. Fulton, R.D. Smith. J. Am. Chem.
Soc. 109. 1986. p. 920.
BACKGROUND OF THE INVENTION
The subject invention is directed to a method for forming chemical products by reacting chemical reactants in reverse micelle or microemulsion systems at a supercritical or near critical state.
SUMMARY OF THE INVENTION
This invention relates to the conduct of chemical reactions in reverse micelle or reverse microemulsion systems. The micelles or microemulsions formed are referred to as "reverse micelles" or "reverse microemulsions" to distinguish them from the normal micelles or microemulsions of non-water-soluble fluids in aqueous liquids.
The method of carrying out chemical reactions generally comprises forming a first system including an aqueous fluid including reverse microemulsions or reverse micelles in a water-insoluble fluid in the near critical or supercritical state. Then, a first reactant is introduced into the first system, and a chemical reaction is carried out with the first reactant to form a reaction product. In general, the first reactant can be incorporated into, and the product formed in, the reverse microemulsions or reverse micelles. A second reactant can also be incorporated in the first system which is capable of reacting with the first reactant to form a product. The first and/or the second reactant can be capable of diffusing into or out of the reverse microemulsions or reverse micelles for conducting the subject chemical reactions. The reverse micelles or microemulsions typically comprise water and a surfactant.
The method of the present invention can also include the step of introducing a chemical catalyst, such as dispersed metallic particles or metallic compounds, or an energy source for initiating and/or driving the chemical reaction, such as radiation energy. Such chemical catalysts can include, for example, Pt, Pd, and Rh ,,,~ ~
_ - 2 - l 33 72 35 particles, or the borides of Ni, Co, and Fe, added to the system or formed in situ.
The first reactant can also be incorporated into the water-insoluble fluid for conducting the chemical reaction.
Although the product formed can be soluble in either of the phases present, it is typically insoluble in water, in the supercritical fluid, or in the water and the supercritical fluid, respectively.
In a preferred method, the second reactant is incorporated into a second system typically comprising an aqueous fluid in a water-insoluble fluid in the supercritical or near critical state. The second system can then be added to the first system. For instance, a precipitation reaction may be provided employing solute species present in two distinct systems. In any case, the exchange of core materials occurs rapidly in the systems, ensuring complete mixing of the reactants. Two supercritical reverse micelle or microemulsion solutions can be prepared, each of which contains a water-soluble salt or other soluble reactant species dissolved in the aqueous cores of such solutions.
More specifically, although products which are soluble in the continuous or discontinuous phase may be formed by the method of this invention, this invention also relates to the formation of very fine particles by the reaction of a substance contained in the reverse microemulsion or micelles with a reactant added to the supercritical fluid which diffuses into the microemulsion or micelles and reacts with the substance to give a product insoluble in either water or supercritical fluid, or both.
The two solutions can comprise some combination of cations and anions which will produce an insoluble precipitate. The first and/or second reactant can comprise a water-soluble salt, such as sodium chloride, silver chloride, iron chloride, silver nitrate, barium hydroxide, calcium hydroxide, cadmium chloride, cadmium nitrate, cadmium chlorate, cadmium sulfide, cobalt chloride, cobalt B
_ _ 3 _ l 33 723 5 sulfide, zinc sulfide, lead sulfide, and copper sulfide.
It can also comprise an acidic material in aqueous solution such as an aqueous solution of sulfuric acid, a basic material in aqueous solution, and the water-insoluble fluid itself, or a reactant dissolved in the water-insoluble fluid such as an alkene or alkane. Further reactants may include a monomeric material or monomeric precursor material, such as tetraethoxysilane, dissolved in the water-insoluble or aqueous fluid, such as a hydrolysis/polymerization reaction catalyzed by an acidic or basic aqueous solution or other initiator in the reverse micelle system.
Still more specifically, it relates to a first reactant which is aqueous aluminum nitrate, a second reactant which is aqueous ammonia, and a reaction product which is aluminum hydroxide, and a particular method which comprises the production of submicron particles of aluminum hydroxide by forming reverse micelles of aluminum nitrate, water, and a surfactant, in supercritical propane and introducing ammonia into the propane phase.
The ability to form reverse micelles, or molecular assemblages consisting of surfactant shells with aqueous cores, in continuous nonpolar phases operated above their critical temperatures and pressures has recently been reported[1]. In this specification we describe the formation of inorganic, submicron particles in a supercritical hydrocarbon solution containing reverse micelles. A fine powder consisting of 0.5-micron-diameter aluminum hydroxide particles was precipitated from aqueous Al(NO3)3 solutions present in micelle cores by the diffusion of ammonia, a component in the binary supercritical fluid continuous phase, into the aqueous core. This work represents not only the first report of particle production using supercritical fluid micelles but is also the first example of a chemical reaction occurring within reverse micelles dispersed in a supercritical fluid.
S ~
- _ 4 _ l 3 3 7 235 Reverse micelles in liquids have been shown to offer a wide range of potential applications in the areas of chromatography, separations, and reaction processes[2~5]. In addition, chemical reactions involving species present in the reverse micelle cores have allowed the production of colloidal-size particles (3 to 10 nm) for use in catalytic and semiconductor applications[6 8] . Chemical processes utilizing systems in which reverse micelles exist in supercritical fluid regimes are expected to expand the scope of potential applications for micellar systems by utilizing the unique properties of supercritical fluids.
These include such pressure-dependent variables as viscosity, density, and diffusion rate, as well as the ability to readily manipulate the P-T-phase behavior in the multicomponent micelle systems. Supercritical fluid reverse micelle phase stability is strongly dependent on the fluid pressure, and the amount of water that can be contained in the micelle core increases with the pressure applied to the fluid. At 100 bar and 103`C, the maximum water-to-AOT molar ratio for reverse micelles in a propane continuous phase is 4. This value increases to 12 at the same temperature and 300 bar[9].
Typically, the subject chemical reactions in reverse micelle or microemulsion systems comprises a substantially discontinuous phase including a polar fluid, typically an aqueous fluid, and a micelle or microemulsion promoter, preferably a surfactant, for facilitating the formation of a reverse microemulsion or reverse micelles in the system.
The system, which for purposes of this invention can be a reverse micelle or inverse microemulsion system, can further include a substantially continuous phase including a non-polar or low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and which is generally a water-insoluble fluid in a near critical or supercritical state. A fluid is in a supercritical state when its temperature and pressure exceed its critical temperature and pressure. Thus, the B
system is maintained at a pressure and temperature such that the density of the non-polar or low-polarity fluid exceeds the critical density thereof. The non-polar or low-polarity fluid can also be maintained in a near 5 critical state up to the critical temperature thereof.
The preferred temperature is in a range from about 90`C
below the critical temperature thereof up to the critical temperature.
BRIEF DESCRIPTION OF THE DRAWING
In the drawing: The single figure is a scanning electron micrograph of aluminum hydroxide particles produced by addition of ammonia to reverse micelles containing 0.1 M Al(NO3)3 in a supercritical propane solution at 100`C and 200 bar.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
In this research aluminum hydroxide particles were prepared in a 25-ml high-pressure reaction vessel incorporating two 13-mm thick, 25-mm diameter sapphire windows through which the various steps in the reaction process could be observed. Before pressurizing with propane, the solid surfactant, sodium bis (2-ethylhexyl) sulfosuccinate (AOT), and the aqueous reaction solution, Al(NO3)3 9H20 in water were charged into the vessel at a molar water to AOT ratio (W) of 5. In all experiments the AOT concentration was 50mM. Three different Al(NO3)3 concentrations were used; 0.1 M, 0.05 M and .01 M Al(NO3)3 9H20 in water. After reaching the desired reaction temperature, 100`C in all cases, the system was pressurized to 200 bar with propane (Tc = 96.8`C, Pc = 42 atmospheres) by means of a high-pressure syringe pump. After several minutes of agitation with a magnetic stir bar, optically clear solutions were obtained, which contained the aqueous Al(NO3)3 solution dispersed in the reverse micelle phase.
In other experiments without the addition of AOT to the system, two phases, consisting of supercritical propane and ;
~ - 6 - l 337235 the liquid aqueous phase, remained in the view cell under the same temperature and pressure conditions. Once temperature in the cell was stabilized, approximately 40 uL
of dry ammonia was injected through a short length of small-bore (100-um-i.d.) tubing connected to a second syringe pump. Ammonia is known to exhibit considerable solubility in many supercritical hydrocarbons, including propane[10]. The ammonia was clearly evident (by the appearance of a milky plume which rapidly dissipated) as it was introduced into a reverse micelle solution consisting of pure water, AOT and supercritical propane. Addition of ammonia to a pure supercritical propane system produced a clear plume, suggesting that the milky plume produced in the micelle systems resulted from alteration of micelle phase behavior due to the locally high ammonia concentrations. Subsequent to addition of the ammonia, fluid in the view cell containing the 0.1 M Al(NO3)3 solution became turbid after approximately one minute but remained clear in the systems containing more dilute Al(NO3)3 solutions. To collect and characterize particles formed in the supercritical fluid system, flow was established across a 0.5-um stainless steel frit mounted in-line to a flow restrictor through which the fluid in the cell was vented. Pressure was held constant in the cell during sample collection by the gradual addition of propane from a syringe pump.
Aluminum hydroxide particles precipitated by introduction of ammonia into a reverse micelle system containing 0.1 M Al(NO3)3 are shown in FIG. 1. Mean particle sizes are on the order of 0.5 um, with some evidence of "necking" between particles or minor agglomeration. It is not clear whether this behavior results from interactions in the solution prior to the particle deposition, or whether it is an artifact of collecting the sample on a porous frit where interactions between the high surface energy particles would be enhanced. The product particles collected from the system I
- 7 _ l 337235 utilizing a 0.05 M Al(NO3)3 solution were significantly smaller (<0.1 um) and exhibited a much higher degree of agglomeration. No product was collected from the system utilizing the 0.01 M Al(NO3)3 solution, perhaps because any individual particles formed in that system were too small to be collected on the frit surface.
The particles shown in the figure are considerably larger than the reverse micelles present in the supercritical propane prior to introduction of the ammonia (5 to 10 nm). The phenomenon of particles far exceeding the sizes of micelles from which they were formed has also been observed during the formation of colloidal catalyst particles from reverse micelle phases in liquid systemsl7~8].
This behavior has been attributed to the rapid exchange of contents between micelle cores, which could promote the coalescence of angstrom- or nanometer-size precipitated nuclei to form the much larger particles actually observed in the collected product.
The use of reaction processes in supercritical micelle solutions for powder production offers a number of potential advantages over existing technologies. The ability to manipulate the concentrations of reactants involved in the particle formation may allow the capability to finely control the particle size. Operation in the supercritical fluid regime may also allow high mass transfer rates of reactants to and across the micelle membranes, and should relax rate limitations when one of the reactants is a gas. Increased reaction rates are expected for diffusion limited reactions. High diffusion rates may reduce polydispersity of the particles produced by minimizing local concentration gradients due to the incomplete mixing. The pressure dependence of the phase and density behavior in supercritical fluid systems may also allow additional advantages to be gained in the area of particle separation from the continuous fluid phase in which it is produced.
, ~
, ., ~, , - - 8 - ~ 33 7235 Three examples of the chemical reactions of this invention are described below which were performed in reverse micelle systems in which propane was used as the water-insoluble fluid and aerosol-OT (AOT) was the surfactant. Each of the reactions described below was performed using system conditions of 100`C and approximately 300 atm pressure, which is above the critical temperature and pressure of propane.
Example 1 This example describes the reaction between reactants present in two distinct reverse micelle systems at supercritical conditions.
Two reverse micelle systems were made independently in high pressure viewcells. Both were prepared such that the final solution would have a final AOT concentration of approximately 50 mM. In one of the cells, 0.lM NaOH was added to make a water-to-surfactant ratio of approximately 11. The system was heated, pressurized, and stirred to form a clear, single-phase solution. In the other view cell, AOT was added and the system was pressurized and heated to the desired conditions. A quantity of 0.lM
Cu(NO3) 2 solution was added to the second cell from a high pressure hand-crank pump to make a reverse micelle solution having a water-to-surfactant ratio of approximately 13.
The solution formed in the viewcell containing copper nitrate solution was one-phase and appeared slightly yellow in color.
When the supercritical fluid solutions had been prepared in both cells, a valve between them was opened.
Pressure was vented slowly through a restrictor at the outlet of one of the cells so that a pressure differential existed between the cells and solution from one cell was transported into the other. Pressure was maintained in the upstream cell by adding propane from a high pressure syringe pump. After 25~ of the solution in the downstream cell had been vented, the valves were closed and the ..
B~
:
- 9 ~ 337235 solution was allowed to set for several minutes. The reaction resulting from the mixing of copper and hydroxide solutions was evidenced by the visible observation of fine particles (copper hydroxide) in the cell containing the mixed solutions.
Example 2 This example describes the reaction between reactants present in a reverse micelle system at supercritical conditions and a water soluble reactant added to the system.
In a high pressure viewcell, AOT and 0.lM KC1 solution were added in sufficient quantities to prepare a solution having an AOT concentration of approximately 75 mM and containing a water-to-surfactant ratio of approximately 3.
The system was heated and pressurized to form a clear, single phase reverse micelle solution at supercritical conditions. A small amount of 0.lM AgNO3 solution was added to the system using a high pressure hand-crank pump to raise the water-to-surfactant ratio of the system to between 5 and 7. After allowing the solution to set for several minutes, fine solid particles (silver chloride) were visually observed in the viewcell.
Example 3 This example describes the reaction between reactants present in the supercritical fluid reverse micelle system and reactants dissolved in the continuous phase. The reaction was catalyzed by material present in the reverse micelle.
In a high pressure viewcell, AOT and 0.lM NaOH were added in appropriate quantities such that, when pressurized with supercritical propane, the resulting solution had an AOT concentration of approximately 50 mM and a water-to-surfactant ratio of 10. On achieving a clear solution at100`C and 300 atm, tetraethoxysilane (TEOS) was added to the cell at approximately ten times the water content using r - lo 1 337235 a high pressure hand-crank pump. TEOS is an alkane-soluble, water-insoluble silicate precursor to form interlinked Si-O-Si networks which are generated via hydrolysis of the TEOS monomer and subsequent polycondensation reactions. The reaction is catalyzed by the presence of either an acid or a base. This hydrolysis/condensation reaction was evidenced by visual observation of solid particles in the viewcell after approximately an hour. Fourier-transform infrared spectra taken on the supercritical fluid solution containing TEOS
also provided evidence for an increasing concentration of Si-O-Si linkages in the system with time.
REFERENCES
1. Gale, R.W., J.L. Fulton, R.D. Smith. J. Am. Chem.
Soc. 109. 1986. p. 920.
2. Sheu, E., K.E. Goklen, T.A. Hatton, S. H. Chen.
Biotechnol. Prog. 2. 1986. p. 175.
Biotechnol. Prog. 2. 1986. p. 175.
3. Reverse Micelles. Eds. P.L. Luisi, B.E. Straub.
Plenum Press, New York. 1984.
Plenum Press, New York. 1984.
4. Luisi, P.L., Angew. Chem., Int. Ed. Engl. 24. 1985.
p. 439.
p. 439.
5. Goklen, K.E., T.A. Hatton. Biotechnol. Prog. 1.
1985. p. 69.
1985. p. 69.
6. Meyer, M., C. Wallberg, K. Curihara, J.H. Fendler. J.
Chem. Soc., Chem. Commun. 1984. p. 90.
Chem. Soc., Chem. Commun. 1984. p. 90.
7. Nagy, J.B., A. Gourgue, E.G. Derouane. Preparation of CatalYsts III. Eds. G. Poncelet, P. Grange, P.A.
Jacobs, P.A. Elsevier, Amsterdam. 1983. p. 193.
Jacobs, P.A. Elsevier, Amsterdam. 1983. p. 193.
8. Lufimpadio, N., J.B. Nagy, E.G. Derouane. Surfactants in Solution, Vol. 3. Eds. K.L. Mittal, B. Lindman.
Plenum, New York. 1984. p. 1483.
Plenum, New York. 1984. p. 1483.
9. Gale, R.W., J.L. Fulton, R.D. Smith. Anal. Chem. 59.
1987. p. 1977.
1987. p. 1977.
10. Lentz, H., E.U. Franck. Extraction with Supercritical Gases. Eds. G.M. Schneider, E. Stahl, G. Wilke.
Verlag Chemie, Weinheim. 1980. p. 83.
~, ~ .~
While we have described one example in detail, it will be obvious to those skilled in the art that various changes can be made. We, therefore, wish our invention to be limited solely by the scope of the appended claims.
Verlag Chemie, Weinheim. 1980. p. 83.
~, ~ .~
While we have described one example in detail, it will be obvious to those skilled in the art that various changes can be made. We, therefore, wish our invention to be limited solely by the scope of the appended claims.
Claims (25)
1. A method of carrying out chemical reactions which comprises forming a first reverse micelle or reverse microemulsion system comprising a polar fluid in a non-polar or low-polarity fluid in a near-critical or supercritical state including reverse micelles or reverse microemulsions;
introducing a first reactant to said first system; and carrying out a chemical reaction with said first reactant to form a reaction product.
introducing a first reactant to said first system; and carrying out a chemical reaction with said first reactant to form a reaction product.
2. The method of claim 1, which includes the step of incorporating said first reactant in the reverse micelles or reverse microemulsion.
3. The method of claim 1, which includes the step of forming said product in the reverse micelles or reverse microemulsion.
4. The method of claim 1, which includes the further step of adding a second reactant to said first system, said second reactant being capable of reacting with said first reactant to form a product.
5. The method of claim 4, wherein said second reactant is capable of diffusing into or out of said reverse micelles or reverse microemulsions for conducting said chemical reaction.
6. The method of claim 1, which includes the step of introducing an energy source into said first system for either one of initiating and driving said chemical reaction.
7. The method of claim 1, which includes the step of incorporating said first reactant into said water-insoluble fluid for conducting said chemical reaction.
8. The method of claim 7, which includes the step of incorporating a chemical catalyst into said system for initiating said chemical reaction.
9. The method of claim 1, wherein said first reactant is a water soluble salt.
10. The method of claim 1, wherein said product is insoluble in water, in the supercritical fluid, or in the water and the supercritical fluid, respectively.
11. The method of claim 1, wherein said reverse micelles comprise an aqueous fluid and a surfactant.
12. The method of claim 1, wherein said first reactant is aluminum nitrate, and said second reactant is ammonia, and said reaction product comprises submicron particles of aluminum hydroxide.
13. The method of claim 1, which includes the further step of incorporating a second reactant into a second system comprising a polar fluid in a non-polar or low-polarity fluid in the supercritical or near critical state;
and adding said second system to said first system.
and adding said second system to said first system.
14. The method of claim 13, wherein said first reactant comprises one of a water-soluble salt, an acidic material and a basic material.
15. The method of claim 14, wherein said second reactant comprises one of a water-soluble salt, an acidic material and a basic material.
16. The method of claim 15, wherein said first reactant is sodium hydroxide, and said second reactant is copper nitrate.
17. The method of claim 13, wherein said polar phase comprises an aqueous fluid and a surfactant.
18. The method of claim 1, wherein said second reactant comprises said supercritical or near critical fluid.
19. A method of carrying out a chemical reaction, which comprises forming a reverse micelle or reverse microemulsion system comprising an aqueous fluid in a water-insoluble fluid in the supercritical state;
incorporating a first reactant in said system; and adding a second reactant to said system, said second reactant being water-soluble and being capable of diffusing into said reverse micelles or reverse microemulsion and carrying out a reaction with said first reactant to form a reaction product.
incorporating a first reactant in said system; and adding a second reactant to said system, said second reactant being water-soluble and being capable of diffusing into said reverse micelles or reverse microemulsion and carrying out a reaction with said first reactant to form a reaction product.
20. The method of claim 19, wherein said chemical reactions will form a product in said reverse micelles or reverse microemulsion.
21. A process for carrying out a chemical reaction, which comprises forming a reverse micelle microemulsion system comprising a first substantially continuous phase including a low-polarity fluid material which is a gas under standard temperature and pressure and has a critical density, and a second substantially discontinuous phase including a polar fluid and a microemulsion or micelle promoter for facilitating the formation of reverse micelles or a reverse microemulsion in said first phase;
maintaining the system at a pressure and temperature such the density of the low-polarity fluid exceeds the critical density thereof;
forming reverse micelles or a reverse microemulsion in said second phase;
introducing a first reactant into said microemulsion system; and carrying out a chemical reaction with said first reactant to form a reaction product.
maintaining the system at a pressure and temperature such the density of the low-polarity fluid exceeds the critical density thereof;
forming reverse micelles or a reverse microemulsion in said second phase;
introducing a first reactant into said microemulsion system; and carrying out a chemical reaction with said first reactant to form a reaction product.
22. The process of claim 21, wherein said reaction is conducted at a temperature at least equal to the supercritical temperature of said fluid material.
23. The process of claim 21, wherein said promoter comprises a surfactant which is substantially soluble in said second phase.
24. The process of claim 21, wherein said fluid material is at least one lower alkane.
25. The process of claim 24, wherein said lower alkane is at least one of ethane, propane and butane.
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US07/125,842 | 1987-11-24 | ||
US12584287A | 1987-11-27 | 1987-11-27 | |
US15225688A | 1988-02-04 | 1988-02-04 | |
US07/152,256 | 1988-02-04 |
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CA000584081A Expired - Fee Related CA1337235C (en) | 1987-11-24 | 1988-11-24 | Chemical reactions in reverse micelle systems |
CA000584080A Expired - Fee Related CA1333316C (en) | 1987-11-24 | 1988-11-24 | Processes for microemulsion polymerization employing novel microemulsion systems |
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CA000583781A Expired - Lifetime CA1337750C (en) | 1987-11-24 | 1988-11-22 | Supercritical fluid reverse micelle separation |
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CA000584080A Expired - Fee Related CA1333316C (en) | 1987-11-24 | 1988-11-24 | Processes for microemulsion polymerization employing novel microemulsion systems |
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EP (3) | EP0343233B1 (en) |
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CA (3) | CA1337750C (en) |
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EP0387307A1 (en) | 1990-09-19 |
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