Tethered catalyst processes in microchannel reactors and systems containing a tethered catalyst or tethered chiral auxiliary

• US 20040132613A1
• Filed: 08/14/2003
• Published: 07/08/2004
• Est. Priority Date: 08/15/2002
• Status: Active Grant

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Jarosch, Kai, Brophy, John H.
• Granted Patent: US 8,338,325 B2
• Time in Patent Office: Days
• US Class Current: 502/150
• CPC Class Codes: B01J 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 2219/00783 Laminate assemblies, i.e. the reactor comprising a stack of plates
• CPC Class Codes: B01J 2219/00788 Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
• CPC Class Codes: B01J 2219/00822 Metal
• CPC Class Codes: B01J 2219/00824 Ceramic
• CPC Class Codes: B01J 2219/00826 Quartz
• CPC Class Codes: B01J 2219/00835 Comprising catalytically active material
• CPC Class Codes: B01J 2219/0086 Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 2219/00891 Feeding or evacuation
• CPC Class Codes: B01J 2231/12 Olefin polymerisation or copolymerisation
• CPC Class Codes: B01J 2231/20 Olefin oligomerisation or telomerisation
• CPC Class Codes: B01J 2231/32 Addition reactions to C=C or C-C triple bonds
• CPC Class Codes: B01J 2231/321 Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
• CPC Class Codes: B01J 2231/325 Cyclopropanations
• CPC Class Codes: B01J 2231/341 1,2-additions, e.g. aldol or Knoevenagel condensations
• CPC Class Codes: B01J 2231/342 Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
• CPC Class Codes: B01J 2231/348 1,4-additions, e.g. conjugate additions
• CPC Class Codes: B01J 2231/40 Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
• CPC Class Codes: B01J 2231/4205 : C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
• CPC Class Codes: B01J 2231/4211 : Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
• CPC Class Codes: B01J 2231/4261 : Heck-type, i.e. RY + C=C, in which R is aryl
• CPC Class Codes: B01J 2231/4266 : Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
• CPC Class Codes: B01J 2231/52 : Isomerisation reactions
• CPC Class Codes: B01J 2231/543 : alkene metathesis
• CPC Class Codes: B01J 2231/643 : of R2C=O or R2C=NR (R= C, H)
• CPC Class Codes: B01J 2231/72 : Epoxidation
• CPC Class Codes: B01J 2531/80 : Complexes comprising metals of Group VIII as the central metal
• CPC Class Codes: B01J 2531/824 : Palladium
• CPC Class Codes: B01J 31/0212 : Alkoxylates
• CPC Class Codes: B01J 31/0237 : Amines
• CPC Class Codes: B01J 31/08 : Ion-exchange resins
• CPC Class Codes: B01J 31/1633 : covalent linkages via silicon containing groups
• CPC Class Codes: B01J 31/1815 : with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• CPC Class Codes: B01J 31/185 : Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/1855 : Triamide derivatives thereof
• CPC Class Codes: B01J 31/20 : Carbonyls
• CPC Class Codes: B01J 31/226 : Sulfur, e.g. thiocarbamates
• CPC Class Codes: B01J 31/24 : Phosphines , i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• CPC Class Codes: B01J 31/2404 : Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• CPC Class Codes: C07B 37/00 : Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
• CPC Class Codes: C07B 37/02 : Addition
• CPC Class Codes: C07B 37/04 : Substitution
• CPC Class Codes: C07B 61/00 : Other general methods
• CPC Class Codes: C07C 205/45 : the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
• CPC Class Codes: C07C 253/30 : by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/41 : the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
• CPC Class Codes: C07C 45/38 : being a primary hydroxyl group
• CPC Class Codes: C07C 45/39 : being a secondary hydroxyl group
• CPC Class Codes: C07C 45/46 : Friedel-Crafts reactions
• CPC Class Codes: C07C 67/343 : by increase in the number of carbon atoms
• CPC Class Codes: C07C 69/618 : having unsaturation outside the six-membered aromatic ring
• CPC Class Codes: F28F 2260/02 : having microchannels
• CPC Class Codes: Y02P 20/50 : Improvements relating to the production of bulk chemicals

Abstract

The invention provides systems and methods for conducting reactions in which a reactant contacts a tethered catalyst and/or tethered chiral auxiliary in a microchannel and is converted to product.

Claims

1. A catalytic system comprising a tethered catalyst composition or a tethered chiral auxiliary disposed in a microchannel.

3. The catalytic system of claim 1 wherein the system comprises a tethered catalyst composition, and the tethered catalyst composition defines at least one wall of a bulk flow path in the microchannel.

4. The catalytic system of claim 3, wherein at least one heat transfer microchannel is adjacent to at least one wall of the microchannel.

5. The catalytic system of claim 1 wherein said tethered catalyst composition or tethered chiral auxiliary is provided as, or part of, a porous insert.

6. The catalytic system of claim 5, wherein said porous insert is adjacent at least one wall of the microchannel, and at least one heat transfer microchannel is adjacent said at least one wall of a microchannel.

7. The catalytic system of claim 1, wherein said tethered catalyst composition or tethered chiral auxiliary comprises a solid support selected from the group consisting of:

solid inorganic oxide, carbon, polymer, silica, alumina, clay, zeolite and mesoporous solid.

8. The catalytic system of claim 1, wherein the system comprises a tethered catalyst composition in which a tether comprises at least a three atom chain that connects a metal center with a surface oxygen.

9. The catalytic system of claim 8, wherein the tethered catalyst composition comprises one or more member selected from the group consisting of metal, metal coordination complex, organometallic complex, oxidant, reductant, acid, and base.

11. The system of claim 1 further comprising a micromixer positioned to mix reactants prior to passage into the microchannel.

24. The catalytic system of claim 1 wherein the microchannel comprises at least one wall and a tethered catalyst or a tethered chiral auxiliary is coated on the wall of the microchannel.

28. The system of claim 1 wherein the microchannel comprises a chiral auxiliary.

32. The catalytic system of claim 1, wherein the system comprises a tethered catalyst composition comprises a dendritic catalyst.

2. A method of converting a reactant to a product, comprising

passing a reactant fluid composition into a microchannel;

wherein the microchannel contains a tethered catalyst or a tethered chiral auxiliary; and

reacting the reactant to form a product.

10. The method of claim 2 further characterized by either (1) superior mass transfer characteristics, or (2) superior control of residence time, or (3) superior yield.

12. The method of claim 2 wherein the microchannel comprises a tethered catalyst composition and further comprising the step of quenching the product immediately after passing in contact with the tethered catalyst.

13. The method of claim 2 comprising C—

C bond formation.

14. The method of claim 13 comprising a Friedel Crafts reaction.

15. The method of claim 13 comprising a Heck reaction.

16. The method of claim 13 comprising oligomerization or polymerization.

17. The method of claim 2 comprising a reduction.

18. The method of claim 17 wherein a chiral compound is formed in greater than 90% enantioselectivity.

19. The method of claim 2 comprising an enantiomeric addition with a greater than 70% enantioselectivity.

20. The method of claim 2 comprising an oxidation.

21. The method of claim 2 comprising an epoxidation.

22. The method of claim 13 comprising a Knoevenagel condensation.

23. The method of claim 2 comprising a reaction selected from the group consisting of:

hydrogenation, dehydrogenation, hydrogenolysis, hydroformylation, hydrosilation, oxidation, reduction, isomerization, aromatization, hydrocyanation, olefin metathesis, carbonylation, decarbonylation, carboxylation, epoxidation, oxygen insertion reactions, oxidation of alcohols to carbonyls and carboxylic acids, olefin polymerization, oxygen transfer, hydrogen transfer, hydrogenation of imines, nitrogen transfer, Heck Reaction, alkylation, amination, cyclopropanation, addition reactions, condensation, hydration, dihydroxylation of olefins, dehydration, Suzuki reaction, Buchwald-Hartig Reaction, Sonogashira Reaction, cross coupling reactions, and esterification.

25. The method of claim 2 wherein a chiral compound is formed in greater than 90% enantioselectivity.

26. The method of claim 13 comprising a Michael addition.

27. The method of claim 2 wherein the microchannel comprises a chiral auxiliary.

29. The method of claim 2 wherein the system comprises a tethered catalyst composition in which a tether comprises at least a three atom chain that connects a metal center with a surface oxygen.

30. The method of claim 29 comprising a reaction selected from the group consisting of:

hydrogenation, dehydrogenation, hydrogenolysis, hydroformylation, hydrosilation, oxidation, reduction, isomerization, aromatization, hydrocyanation, olefin metathesis, carbonylation, decarbonylation, carboxylation, epoxidation, oxygen insertion reactions, oxidation of alcohols to carbonyls and carboxylic acids, olefin polymerization, oxygen transfer, hydrogen transfer, hydrogenation of imines, nitrogen transfer, Heck Reaction, alkylation, amination, cyclopropanation, addition reactions, condensation, hydration, dihydroxylation of olefins, dehydration, Suzuki reaction, Buchwald-Hartig Reaction, Sonogashira Reaction, cross coupling reactions, and esterification.

31. The method of claim 13 comprising a Suzuki reaction.

33. The method of claim 2 wherein the reactant fluid composition is a liquid having a diffusivity (D_eff) of 0.5×

10<sup>−

5</sup> cm²/s to 3.5×

10<sup>−

5</sup> cm²/s, and the method is carried out with a capture number 100 or less and a residence time of 10,000 s or less.