Process for testing catalysts using detection agents

• US 6,605,470 B1
• Filed: 07/10/2000
• Issued: 08/12/2003
• Est. Priority Date: 02/28/1996
• Status: Expired due to Term

• Current Assignee: University of Houston (University of Houston System)
• Original Assignee: University of Houston (University of Houston System)
• Inventors: Willson, Richard C. III
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US09/613,084
• Time in Patent Office: 1,128 Days
• Field of Search: 422/52, 422/62, 422/93, 422/104, 422/196-197, 436/37, 436/147, 436/159, 436/161, 436/164, 436/172, 436/173, 436/183
• US Class Current: 506/4
• CPC Class Codes: B01J 19/0046 Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays synthesis methods per se C40B50/00
• CPC Class Codes: B01J 2219/00286 Reactor vessels with top and bottom openings
• CPC Class Codes: B01J 2219/00315 Microtiter plates
• CPC Class Codes: B01J 2219/00364 Pipettes
• CPC Class Codes: B01J 2219/00527 Sheets
• CPC Class Codes: B01J 2219/00585 Parallel processes
• CPC Class Codes: B01J 2219/00596 Solid-phase processes
• CPC Class Codes: B01J 2219/00659 Two-dimensional arrays
• CPC Class Codes: B01J 2219/00691 using robots
• CPC Class Codes: B01J 2219/00704 integrated with the reactor apparatus
• CPC Class Codes: B01J 2219/00745 Inorganic compounds
• CPC Class Codes: B01J 2219/00747 Catalysts
• CPC Class Codes: C40B 30/08 by measuring catalytic activity
• CPC Class Codes: C40B 40/18 Libraries containing only inorganic compounds or inorganic materials
• CPC Class Codes: G01N 31/10 using catalysis
• CPC Class Codes: Y10T 436/214 Acyclic [e.g., methane, octane, isoparaffin, etc.]
• CPC Class Codes: Y10T 436/24 Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry

Abstract

Methods for evaluating catalysts, in which a multicell holder, e.g., a honeycomb or plate, or a collection of individual support particles, is treated with solutions/suspensions of catalyst ingredients to produce cells, spots or pellets holding each of a variety of combinations of the ingredients, is dried, calcined or treated as necessary to stabilize the ingredients in the cells, spots or pellets, then is contacted with a potentially reactive feed stream or batch, e.g., biochemical, gas oil, hydrogen plus oxygen, propylene plus oxygen, CCl₂F₂ and hydrogen, etc. The reaction occurring in each cell can be measured, e.g., by infrared thermography, spectroscopic detection of products or residual reactants, or by sampling, e.g., multistreaming through low volume tubing, from the vicinity of each combination, followed by analysis, e.g., spectral analysis, chromatography, etc., or by observing temperature change in the vicinity of the catalyst, e.g., by thermographic techniques, to determine the relative efficacy of the catalysts in each combination. Robotic techniques can be employed in producing the cells, spots, pellets, etc.

Claims

1. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being simultaneously contacted with the one or more reactants in a common reactor,

staining or reacting the reaction products or unreacted reactants with a detection agent to form a detectable species, and

detecting the detectable species to determine the relative efficacy of the plurality of candidate catalysts.

2. The method of claim 1 wherein the reaction products or unreacted reactants are simultaneously stained or reacted with a detection agent.

3. The method of claim 1 wherein the detectable species are simultaneously detected.

4. The method of claim 1 wherein the reaction products or unreacted reactants are simultaneously stained or reacted with a detection agent, and the detectable species are simultaneously detected.

5. The method of claim 1 wherein the detectable species are detected by imaging.

6. The method of claim 1 wherein the detectable species are simultaneously detected by imaging.

7. The method of claim 1 wherein the detectable species are simultaneously detected with a camera.

8. The method of claim 1 wherein the plurality of catalyst candidates are chemical conversion catalysts.

9. The method of claim 1 wherein the plurality of catalyst candidates are metals or metal oxides.

10. The method of claim 1 wherein the plurality of catalyst candidates are transition metals or transition metal oxides.

11. The method of claim 1 wherein the plurality of catalyst candidates are supported catalysts.

12. The method of claim 1 wherein the plurality of candidate catalysts comprises fifteen candidate catalysts.

13. The method of claim 1 wherein the plurality of candidate catalysts comprises twenty-four candidate catalysts.

14. The method of claim 1 wherein the plurality of candidate catalysts are formed by calcining catalyst precursors at different temperatures.

19. The method of claims 1 and 15 wherein the plurality of candidate catalysts are provided at a plurality of sites on a common support, each of the plurality of candidate catalysts being is in its own site on the support.

20. The method of claims 1 and 15 wherein the plurality of candidate catalysts are simultaneously contacted with the one or more reactants in parallel reactor comprising a plurality of reaction channels, each of the plurality of candidate catalysts being in its own reaction channel.

21. The method of claim 20 wherein the parallel reactor comprises a plurality of reaction channels in a monolithic support.

22. The method of claim 20 wherein the parallel reactor is a flow reactor and the one or more reactants flow through each of the plurality of reaction channels.

23. The method of claims 1 and 15 wherein at least one reaction is catalyzed by each of the plurality of candidate catalysts.

27. The method of claims 1, 15, 24, 25, or 26 wherein the plurality of candidate catalysts are contacted with the one or more reactants under reaction conditions that include a temperature greater than 100°

C., and additionally, or alternatively, a pressure of greater than 1 bar.

28. The method of claims 1 and 15 wherein each of the plurality of candidate catalysts are tagged or labeled to identify particular catalyst candidates, the method further comprising

collecting candidate catalysts showing catalytic activity, and

analyzing the tag or label of the collected candidate catalysts to determine the catalyst candidates having catalytic activity.

48. The method of claims 1, 15, 29 or 42 wherein the plurality of catalyst Candidates are hydrocarbon conversion catalysts.

49. The method of claims 1, 15, 29 or 42 wherein the plurality of catalyst candidates are inorganic catalysts.

50. The method of claims 1, 15, 29 or 42 wherein the plurality of catalyst candidates are zeolites.

51. The method of claims 1, 15, 29 or 42 wherein the plurality of catalyst candidates are metallocenes.

52. The method of claims 1, 15, 29 or 42 wherein the one or more reactants are in the gas phase.

53. The method of claims 1, 15, 29 or 42 wherein the one or more reactants are in the liquid phase.

15. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being simultaneously contacted with the one or more reactants in a common reactor, and

detecting the reaction products or unreacted reactants by chemiluminescence.

16. The method of claim 15 wherein the reaction products or unreacted reactants are simultaneously detected.

17. The method of claim 15 wherein the reaction products or unreacted reactants are simultaneously detected by reaction with a detection agent to liberate light, and detecting the liberated light.

18. The method of claim 17 wherein the liberated light is detected with a camera.

24. A method of for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being provided at a plurality of sites on a common support, each of the plurality of candidate catalysts being is in its own site on the support, the support being a plate or sheet having a surface comprising the candidate-catalyst-containing sites,

staining or reacting the reaction products or unreacted reactants with a detection agent to form a detectable species, and

detecting the detectable species to determine the relative efficacy of the plurality of candidate catalysts.

25. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being provided at a plurality of sites on a common support, each of the plurality of candidate catalysts being is in its own site on the support, the support being a plate having a plurality of wells as candidate-catalyst-containing sites,

staining or reacting the reaction products or unreacted reactants with a detection agent to form a detectable species, and

detecting the detectable species to determine the relative efficacy of the plurality of candidate catalysts.

26. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being simultaneously contacted with the one or more reactants in a parallel reactor comprising a plurality of reaction channels, each of the plurality of candidate catalysts being in its own reaction channel, the parallel reactor being a parallel batch reactor pressurized with the one or more reactants,

staining or reacting the reaction products or unreacted reactants with a detection agent to form a detectable species, and

detecting the detectable species to determine the relative efficacy of the plurality of candidate catalysts.

29. A method for evaluating a plurality of candidate catalysts, the method comprising

flowing a reactant-containing stream through each of a plurality of reaction channels in a parallel flow reactor, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream, an outlet for discharging a product-containing stream, and a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being in its own reaction channel,

simultaneously contacting the plurality of candidate catalysts with one or more reactants under reaction conditions such that at least one reaction is catalyzed by each of the plurality of candidate catalysts,

staining or reacting reaction products or unreacted reactants in the plurality of product-containing streams with a detection agent to (i) form a detectable species or (ii) liberate light, and

simultaneously detecting (i) the detectable species or (ii) the liberated light, respectively, by imaging using a camera to determine the relative efficacy of the plurality of candidate catalysts.

30. The method of claim 29 further comprising simultaneously discharging product-containing stream from each of the plurality of reaction channels.

31. The method of claim 29 wherein the reaction products or unreacted reactants are stained or reacted with the detection agent in the reaction channel.

32. The method of claim 29 wherein the reaction products or unreacted reactants in the product-containing stream of each of the plurality of reaction channels are simultaneously reacted with the detection agent to form a detectable species.

33. The method of claim 29 wherein the reaction products or unreacted reactants in the product-containing stream of each of the plurality of reaction channels are simultaneously reacted with the detection agent to liberate light, and the liberated light is simultaneously detected.

34. The method of claim 29 wherein the reaction products or unreacted reactants in the product-containing stream of each of the plurality of reaction channels are simultaneously reacted with ozone to liberate light, and the liberated light is simultaneously detected.

35. The method of claim 29 wherein the reaction conditions include a temperature greater than 100°

C., and additionally, or alternatively, a pressure of greater than 1 bar.

36. The method of claim 29 wherein the parallel flow reactor comprises the plurality of reaction channels in a monolithic support.

37. The method of claim 29 wherein the plurality of reaction channels are arranged in an array with a density of at least 9 reaction channels per square inch.

38. The method of claim 29 wherein the parallel flow reactor comprises the plurality of reaction channels arranged in an array in a monolithic support with a density of at least 9 reaction channels per square inch.

39. The method of claim 29 wherein the parallel reactor comprises twenty-four reaction channels and at least four catalyst candidates having differing compositions, each of the twenty-four catalyst compositions being in its own reaction channel.

40. The method of claim 29 wherein the parallel flow reactor is adapted to provide uniform flow of the reactant-containing stream through each of the plurality of reaction channels.

41. The method of claim 29 further comprising

depositing a plurality of catalyst precursors to the plurality of reaction channels, each of the plurality of catalyst precursors being in its own reaction channel, and

drying, and additionally, or alternatively, calcining the catalyst precursors to form the catalyst candidates.

42. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants in a plurality of reaction wells in a parallel batch reactor under reaction conditions such that at least one reaction is catalyzed by each of the plurality of candidate catalysts, each of the plurality of catalyst candidates being in its own reaction well,

staining or reacting reaction products or unreacted reactants with a detection agent to (i) form a detectable species or (ii) liberate light, and

detecting (i) the detectable species or (ii) the liberated light, respectively, to determine the relative efficacy of the plurality of candidate catalysts.

43. The method of claim 42 wherein the reaction products or unreacted reactants are simultaneously reacted with the detection agent to form a detectable species, and the detectable species is simultaneously detected.

44. The method of claim 42 wherein the reaction products or unreacted reactants are simultaneously reacted with the detection agent to liberate light, and the liberated light is simultaneously detected.

45. The method of claim 42 wherein the reaction products or unreacted reactants are simultaneously reacted with ozone to liberate light, and the liberated light is simultaneously detected.

46. The method of claim 42 wherein the reaction conditions include a temperature greater than 100°

C., and additionally, or alternatively, a pressure of greater than 1 bar.

47. The method of claim 42 wherein the parallel batch reactor comprises the plurality of reaction wells in a plate.

54. The method of claim 42 wherein the reactor is a parallel batch stirred autoclave reactor.

55. The method of claim 42 wherein the reactor is a parallel batch reactor comprising a plurality of agitated containers.

56. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being provided at a plurality of sites on a common support, each of the plurality of candidate catalysts being is in its own site on the support, the support being a plate or sheet having a surface comprising the candidate-catalyst-containing sites, and

detecting the reaction products or unreacted reactants by chemiluminescence.

57. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being provided at a plurality of sites on a common support, each of the plurality of candidate catalysts being is in its own site on the support, the support being a plate having a plurality of wells as candidate-catalyst-containing sites, and

detecting the reaction products or unreacted reactants by chemiluminescence.

58. A method for evaluating a plurality of candidate catalysts, the method comprising

simultaneously contacting a plurality of candidate catalysts having differing compositions with one or more reactants under reaction conditions to catalyze at least one reaction, the plurality of candidate catalysts being simultaneously contacted with the one or more reactants in parallel reactor comprising a plurality of reaction channels, each of the plurality of candidate catalysts being in its own reaction channel, the parallel reactor being a parallel batch reactor pressurized with the one or more reactants, and

detecting the reaction products or unreacted reactants by chemiluminescence.