Process for testing catalysts using mass spectroscopy

• US 6,623,969 B1
• Filed: 07/10/2000
• Issued: 09/23/2003
• Est. Priority Date: 02/28/1996
• Status: Expired due to Term

• Current Assignee: University of Houston Law Center (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:
  US09/613,082
• Time in Patent Office: 1,170 Days
• Field of Search: 250/281-282, 250/288, 422/62, 422/83, 422/93, 422/104, 422/196-197, 436/37, 436/147, 436/159, 436/161, 436/164, 436/172-173, 436/183
• US Class Current: 506/11
• 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, and

detecting reaction products or unreacted reactants using mass spectrometry to determine the relative efficacy of the plurality of candidate catalysts.

2. The method of claim 1 wherein the plurality of candidate catalysts are 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.

3. The method of claim 2 wherein the parallel reactor comprises a plurality of reaction channels in a monolithic support.

4. The method of claim 2 wherein the parallel reactor is a flow reactor and the one or more reactants flow through each of the plurality of reaction channels.

5. The method of claim 1 wherein at least one reaction is catalyzed by each of the plurality of candidate catalysts.

6. The method of claim 1 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.

7. The method of claim 1 wherein the reaction products or unreacted reactants corresponding to the reaction catalyzed by each of the plurality of candidate catalysts are simultaneously detected using a corresponding plurality of mass spectrometers to determine the relative efficacy of the plurality of candidate catalysts.

8. The method of claim 1 wherein the reaction products or unreacted reactants corresponding to the reaction catalyzed by each of the plurality of candidate catalysts are simultaneously detected by multistreaming or sampling into a corresponding plurality of mass spectrometers to determine the relative efficacy of the plurality of candidate catalysts.

21. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are chemical conversion catalysts.

22. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are hydrocarbon conversion catalysts.

23. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are inorganic catalysts.

24. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are zeolites.

25. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are metallocenes.

26. The method of claim 1, 9 or 18 wherein the plurality of catalyst candidates are supported catalysts.

27. The method of claim 1, 9 or 18 wherein the one or more reactants are in the gas phase.

28. The method of claim 1, 9 or 18 wherein the one or more reactants are in the liquid phase.

29. The method of claim 1, 8 or 18 wherein the plurality of candidate catalysts comprises twenty-four candidate catalysts.

30. The method of claim 1, 9 or 18 wherein the plurality of candidate catalysts are formed by calcining catalyst precursors at different temperatures.

31. The method of claim 1 or 18 wherein the plurality of catalyst candidates are metals or metal oxides.

32. The method of claim 1 or 18 wherein the plurality of catalyst candidates are transition metals or transition metal oxides.

33. The method of claim 1 or 18 wherein the plurality of candidate catalysts comprises fifteen candidate catalysts.

34. The method of claim 1 or 18 wherein the reactor is a parallel batch stirred autoclave reactor.

35. The method of claim 1 or 18 wherein the reactor is a parallel batch reactor comprising a plurality of agitated containers.

9. 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 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, such that

the plurality of candidate catalysts are simultaneously contacted with one or more reactants under reaction conditions and at least one reaction is catalyzed by each of the plurality of candidate catalysts, and

detecting reaction products or unreacted reactants in the plurality of product-containing streams using mass spectrometry to determine the relative efficacy of the plurality of candidate catalysts,

wherein the flow reactor further comprises a plurality of sampling tubes adapted to provide fluid communication between the plurality of reaction channels and a plurality of mass spectrometers for multistream detection of a reaction product or unreacted reactant in each of the plurality of discharged product-containing streams.

10. The method of claim 9 wherein the reaction products or unreacted reactants in the plurality of product-containing streams are simultaneously detected using mass spectrometry.

11. The method of claim 9 wherein the reaction conditions include a temperature greater than 100°

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

12. The method of claim 9 wherein the flow reactor comprises the plurality of reaction channels in a monolithic support.

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

14. The method of claim 9 wherein the 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.

15. The method of claim 9 wherein the reactor comprises twenty-four reaction channels and twenty-four catalyst candidates having differing compositions, each of the twenty-four catalyst compositions being in its own reaction channel.

16. The method of claim 9 wherein the flow reactor is adapted to provide uniform flow of the reactant-containing stream through each of the plurality of reaction channels.

17. The method of claim 9 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.

18. 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 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,

sampling the reaction product mixtures in each of the plurality of reaction wells, and

detecting reaction products or unreacted reactants in the sampled reaction product mixtures using mass spectroscopy to determine the relative efficacy of the plurality of candidate catalysts.

19. The method of claim 18 wherein the reaction products or unreacted reactants in the plurality of product-containing streams are simultaneously sampled and simultaneously detected using mass spectrometry.

20. The method of claim 18 wherein the reaction conditions include a temperature greater than 100°

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

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

flowing a reactant-containing stream through each of at least twenty four reaction channels in a parallel flow reactor, each of the at least twenty four reaction channels comprising an inlet for receiving a reactant-containing stream, an outlet for discharging a product-containing stream, and at least twenty four catalyst candidates having differing compositions, each of the at least twenty four catalyst candidates being a metal or a metal oxide in its own reaction channel, the parallel flow reactor being adapted to provide uniform flow of the reactant-containing stream through each of the at least twenty four reaction channels, such that

the at least twenty four candidate catalysts are simultaneously contacted with one or more reactants under reaction conditions and at least one reaction is catalyzed by each of the at least twenty four candidate catalysts, the reaction conditions including a temperature greater than 100°

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

discharging the product-containing stream from each of the at least twenty four reaction channels

sampling the product-containing streams of each of the plurality of reaction channels through an array of tubes, the array of tubes comprising a plurality of sampling tubes in fluid communication with a plurality of mass spectrometers, and

detecting the discharged reaction products or unreacted reactants in the at least twenty four product-containing streams using the plurality of mass spectrometers to determine the relative efficacy of the plurality of candidate catalysts.