Parallel flow reactor and apparatus for testing catalysts

• US 6,623,968 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 (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:
  US09/612,857
• Time in Patent Office: 1,170 Days
• Field of Search: 250/281, 250/282, 422/62, 422/93, 422/104, 422/52, 436/37, 436/147, 436/159, 436/161, 436/164, 436/172-173
• US Class Current: 506/37
• 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

Apparatus for evaluating catalysts, including 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 parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels arranged in an array with a density of at least 9 reaction channels per square inch, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream and 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,

the reactor being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the catalyst candidates under reaction conditions that include a temperature greater than 100°

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

3. The parallel flow reactor of claims 1 or 2 further comprising a sampling system for sampling the product-containing streams of each of the plurality of reaction channels.

4. The parallel flow reactor of claims 1 or 2 further comprising a manifold comprising an array of tubes for sampling the product-containing streams of each of the plurality of reaction channels.

5. The parallel flow reactor of claims 1 or 2 further comprising a sensor for detecting catalytic activity of the candidate catalysts, an array of tubes for sampling the product-containing streams of each of the plurality of reaction channels, and an arrangement of switching valves for introducing the product-containing streams into the sensor.

7. The parallel flow reactor of claims 1, 2, or 6 wherein the plurality of catalyst candidates are hydrocarbon conversion catalysts.

8. The parallel flow reactor of claims 1, 2 or 6 wherein at least twenty-four reaction channels comprise at least twenty-four catalyst candidates having differing compositions, each of the at least twenty-four catalyst compositions being in its own reaction channel.

9. The parallel flow reactor of claims 1, 2 or 6 wherein the plurality of reaction channels are arranged in an array with a density of at least 25 reaction channels per square inch.

10. The parallel flow reactor of claims 1, 2 or 6 wherein the plurality of reaction channels are circular or square in cross-section.

11. The parallel flow reactor of claims 1, 2 or 6 wherein the plurality of reaction channels are defined by tubes or pores.

12. The parallel flow reactor of claims 1, 2 or 6 further comprising a fluid distribution system for providing uniform flow of the reactant-containing stream through each of the plurality of reaction channels.

13. The parallel flow reactor of claims 1 or 6 wherein the plurality of catalyst candidates are inorganic catalysts.

14. The parallel flow reactor of claims 1 or 6 wherein the plurality of catalyst candidates are metals or metal oxides.

15. The parallel flow reactor of claims 1 or 6 wherein the plurality of catalyst candidates are transition metals or transition metal oxides.

16. The parallel flow reactor of claims 1 or 6 wherein the plurality of catalyst candidates are zeolites.

17. The parallel flow reactor of claims 1 or 6 wherein the plurality of catalyst candidates are supported catalysts.

18. The parallel flow reactor of claims 1 or 6 wherein each of the plurality of reaction channels further comprises a porous retaining mesh to keep the candidate catalysts in place in the reaction channel.

24. An apparatus for evaluating a plurality of differing compositions for catalysis, the apparatus comprising

the parallel flow reactor of claims 1, 2, 19, 20 or 21 and

a sensor for detecting catalytic activity in candidate catalysts.

25. The apparatus of claim 24 wherein the sensor is selected from the group consisting of a gas chromatograph, a temperature sensor, an optical monitor and a spectrometer.

26. The parallel flow reactor of claim 25 wherein the optical monitor is an infrared detector.

27. The apparatus of claim 24 wherein the reactor further comprises an array of tubes for introducing a detection agent to the product-containing streams.

34. A method for evaluating a plurality of differing compositions for catalysis, the method comprising

flowing a reactant-containing stream through each of a plurality of reaction channels in a parallel flow reactor of claims 1, 2, 6, 19, 21, 28, 31 or 33 to simultaneously contact the catalyst candidates under the reaction conditions, and

sensing a product-containing stream to detect catalytic activity of the plurality of candidate catalysts.

35. The method of claim 34 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,

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

2. A parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels arranged in an array with a density of at least 9 reaction channels per square inch, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream and 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 a metal or a metal-complex in its own reaction channel,

the reactor being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the catalyst candidates under reaction conditions.

6. An apparatus for evaluating a plurality of differing compositions for catalysis, the apparatus comprising

a plurality of reaction channels arranged in an array, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream and an outlet for discharging a product-containing stream,

a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being in its own reaction channel,

the apparatus being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the catalyst candidates under reaction conditions that include a temperature greater than 100°

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

a plurality of sensors for detecting catalytic activity of the candidate catalysts, and

a plurality of sampling tubes providing fluid communication between the plurality of reaction channels and the plurality of sensors for simultaneous, multistream detection of a reaction product in each of the plurality of discharged product-containing streams, each of the plurality of sensors being selected from the group consisting of a spectrometer and a chromatograph.

19. A parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels in a monolithic support, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream and an outlet for discharging a product-containing stream, and

a plurality of catalyst-candidates having differing compositions, the plurality of reaction channels being at least partially coated with the catalyst candidates such that each of the plurality of catalyst candidates is in its own reaction channel,

the reactor being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the plurality of catalyst candidates under reaction conditions that include a temperature greater than 100°

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

32. An apparatus for preparing and evaluating a plurality of differing compositions for catalysis, the apparatus comprising

an automated liquid handling system for preparing a plurality of candidate catalysts or candidate catalyst precursors having different compositions,

a monolithic support for receiving the plurality of candidate catalysts or candidate catalyst precursors from the automated liquid handling system, and

the parallel flow reactor of claims 2, 6, 19, 21, 28 or 31 adapted to evaluate the candidate catalysts on the monolithic support.

20. An apparatus for preparing and evaluating a plurality of differing compositions for catalysis, the apparatus comprising

an automated liquid handling system for preparing a plurality of candidate catalysts or candidate catalyst precursors having different compositions,

a monolithic support comprising a plurality of reaction channels for receiving the plurality of candidate catalyst or candidate catalyst precursors from the automated liquid handling system, the plurality of reaction channels being arranged in an array with a density of at least 9 reaction channels per square inch, and

a parallel flow reactor adapted to evaluate the candidate catalysts on the monolithic support and configured such that each of the plurality of reaction channels comprises an inlet for receiving a reactant-containing stream and 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, the reactor being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the plurality of catalyst candidates under reaction conditions that include a temperature greater than 100°

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

21. An apparatus for evaluating a plurality of differing compositions for catalysis, the apparatus comprising

an automated liquid handling system for preparing a plurality of candidate catalysts or candidate catalyst precursors having different compositions,

a monolithic support comprising a plurality of reaction channels for receiving the plurality of candidate catalyst or candidate catalyst precursors from the automated liquid handling system, and

a parallel flow reactor adapted to evaluate the candidate catalysts on the monolithic support and configured such that each of the plurality of reaction channels comprises an inlet for receiving a reactant-containing stream and an outlet for discharging a product-containing stream, a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being in its own reaction channel, a plurality of sensors for detecting catalytic activity of the candidate catalysts, and an array of tubes for sampling the product-containing streams of each of the plurality of reaction channels, the sampling tubes being in fluid communication with the plurality of sensors for simultaneous, multistream detection of a reaction product in each of the plurality of discharged product-containing streams, the reactor being adapted such that the reactant-containing stream can be fed through the plurality channels to simultaneously contact the plurality of catalyst candidates under reaction conditions that include a temperature greater than 100°

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

22. The apparatus of claims 6 or 21 wherein the sensors are selected from the group consisting of a mass spectrometer and a gas chromatograph.

23. The apparatus of claims 6 or 21 wherein the sensor is selected from the group consisting of a gas chromatograph, a temperature sensor, an optical monitor and a spectrometer.

28. A parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels in a monolithic support, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing stream, a well adjacent the channel for containing a candidate catalyst, and an outlet for discharging a product-containing stream,

a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being in the well of its own reaction channel,

a distribution system for providing uniform flow of the reactant-containing stream through each of the plurality of reaction channels, such that the reactant-containing stream simultaneously contacts the catalyst candidates under reaction conditions that include a temperature greater than 100°

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

a sensor for detecting catalytic activity of the candidate catalysts.

29. The parallel flow reactor of claim 28 wherein each of the plurality of reaction channels further comprises a porous retaining mesh installed to keep the candidate catalyst in place.

30. The parallel flow reactor of claim 28 wherein the candidate-catalyst-containing well is at the bottom of each of the plurality of reaction channels.

31. A parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels in a monolithic support, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing gas stream, an outlet for discharging a product-containing gas stream, and a porous retaining mesh to keep a candidate catalyst in place in the reaction channels,

a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being a supported metal or a metal oxide catalyst in its own reaction channel,

a distribution system adapted for providing uniform flow of the reactant-containing gas stream through each of the plurality of reaction channels, such that the reactant-containing gas stream simultaneously contacts the catalyst candidates under reaction conditions that include a temperature greater than 100°

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

an array of tubes for sampling the product-containing gas streams of each of the plurality of reaction channels,

an arrangement of switching valves for introducing the product-containing streams into a sensor, and

a sensor for detecting catalytic activity of the candidate catalysts.

33. A parallel flow reactor for evaluating a plurality of differing compositions for catalysis, the reactor comprising

a plurality of reaction channels, each of the plurality of reaction channels comprising an inlet for receiving a reactant-containing gas stream and an outlet for discharging a product-containing gas stream,

a plurality of catalyst-candidates having differing compositions, each of the plurality of catalyst candidates being a supported metal or a metal oxide catalyst in its own reaction channel, each of the plurality of reaction channels being at least partially coated with the candidate catalysts,

a distribution system adapted for providing uniform flow of the reactant-containing gas stream through each of the plurality of reaction channels, such that the reactant-containing gas stream simultaneously contacts the catalyst candidates under reaction conditions that include a temperature greater than 100°

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

an array of tubes for sampling the product-containing gas streams of each of the plurality of reaction channels,

a sensor for detecting catalytic activity of the candidate catalysts, and optionally,

an arrangement of switching valves for introducing the product-containing streams into the sensor.