CA2247259C - Catalyst testing process and apparatus - Google Patents
Catalyst testing process and apparatus Download PDFInfo
- Publication number
- CA2247259C CA2247259C CA002247259A CA2247259A CA2247259C CA 2247259 C CA2247259 C CA 2247259C CA 002247259 A CA002247259 A CA 002247259A CA 2247259 A CA2247259 A CA 2247259A CA 2247259 C CA2247259 C CA 2247259C
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- reactor
- candidate
- catalysts
- infrared
- 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
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00279—Features relating to reactor vessels
- B01J2219/00281—Individual reactor vessels
- B01J2219/00286—Reactor vessels with top and bottom openings
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00279—Features relating to reactor vessels
- B01J2219/00306—Reactor vessels in a multiple arrangement
- B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
- B01J2219/00315—Microtiter plates
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00351—Means for dispensing and evacuation of reagents
- B01J2219/00364—Pipettes
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00497—Features relating to the solid phase supports
- B01J2219/00527—Sheets
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00585—Parallel processes
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00596—Solid-phase processes
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00659—Two-dimensional arrays
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/0068—Means for controlling the apparatus of the process
- B01J2219/00686—Automatic
- B01J2219/00691—Automatic using robots
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/0068—Means for controlling the apparatus of the process
- B01J2219/00702—Processes involving means for analysing and characterising the products
- B01J2219/00704—Processes involving means for analysing and characterising the products integrated with the reactor apparatus
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/00745—Inorganic compounds
-
- 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
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/00745—Inorganic compounds
- B01J2219/00747—Catalysts
-
- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B30/00—Methods of screening libraries
- C40B30/08—Methods of screening libraries by measuring catalytic activity
-
- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
- C40B40/18—Libraries containing only inorganic compounds or inorganic materials
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/21—Hydrocarbon
- Y10T436/214—Acyclic [e.g., methane, octane, isoparaffin, etc.]
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/24—Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
Abstract
A multicell holder (10) e.g. a honeycomb or plate, or a collection of individual support particles, is treated with solutions/suspensions of catalyst ingredients to produce a plurality of cells, spots, or pellets (12) each having a different composition. The plurality of cells, spots, or pellets are dried, calcined or treated to stabilize the ingredients and contacted with a potentially reactive feed stream or batch of reactants. The reaction occurring in each cell (12) is measured or analyzed to determine the relative efficacy of the catalysts in each combination. The measurement or analysis is done through a number of different methods including infrared thermography (14), spectroscopy of products or residual reactants or sampling for further analysis.
Robotic techniques can be employed in producing the cells, spots or pellets (12).
Robotic techniques can be employed in producing the cells, spots or pellets (12).
Description
Catalyst Testing process and ,ApZaa~atus Backg~rour~.d of the Iraventiors T . Fiel.d of the Invention The preser~.t ira.5rentxon relates t:o the general field of catalyst test3.ng.
~.o II. Problems Presented by Prior Art Catalyst testing is conventionally accomplished in bench scale or larger pilot plants in which the feed is contacted with a catalyst under reac.~:ion conditions, 15 generally with effluent products being sampled, often with samples being analyzed and results subjected to data resolution techniques. S~u.ch procedures can take a day or more for a single run on a single catalyst. While such technigues will have value in fine-tuning the optimum 2Q matrices, pellet shape, etc., the present invention permits the scanning of dozens of catalysts in a single set-up, often in less time than required for a single catalyst to be evaluated by conventional methods. Further, when. practiced in its preferred robotic embodiments, the invention. can 25 sharply reduce the labor costs per catalyst-scxeened.
1a Further details with respect to the prior art can be found in the following references:
(a) "Proceedings of the 5~" International Congress of Catalysis," Vol. 2, 1977, pages 796-805, Jensen J.V., ~~t al., 'A deactivation reactor for catalyst screening and evaluation,' which relates to a deactivatian reactor for catalyst screening and evaluation using a multitube converter for simultaneous aging of catalyst samples followed by determination of fundamental kinetic parameters in a separate reactor.
The fundamental kinetic parameters of both fresh and spent catalysts are determined by measurement in a conventional recirculation reactor.
(b) US-A-4 877 584 which relates to temperature programmed spectrometry wherein particles of a substrate under investigation are attached in a non-overlapping manner to a heating filament. Gases from the filament desorbed at increased temperatures are commonly measured by a quadruple mass spectrometer and are not individually selectively determined.
(c) "International Journal of Hydrogen Energy", Vol. 7, No. 9, 1982, pages 729-736, Haruta M. et al., 'Catalytic combustion of hydrogen, II. An experimental investigation of fundamental conditions for burner design,' which relates to catalytic combustion of hydrogen. A catalyst body carrying four types of catalysts tested is inserted into a chamber and st:pot temperature and spot compositions of gas mixtures on the front surface of the catalysts are measured with nine chromel-alumel thermocouples connected to a digital multi-temperature recorder, and with nine microprobes for gas sampling connected to a gas chromatograph.
(d) JP-A-08015139 which relates to a gas adsorptionldesorption measuring method of catalyst for automobile. A cell containing a single sample under constant flow rate of reactant is investigated.
~.o II. Problems Presented by Prior Art Catalyst testing is conventionally accomplished in bench scale or larger pilot plants in which the feed is contacted with a catalyst under reac.~:ion conditions, 15 generally with effluent products being sampled, often with samples being analyzed and results subjected to data resolution techniques. S~u.ch procedures can take a day or more for a single run on a single catalyst. While such technigues will have value in fine-tuning the optimum 2Q matrices, pellet shape, etc., the present invention permits the scanning of dozens of catalysts in a single set-up, often in less time than required for a single catalyst to be evaluated by conventional methods. Further, when. practiced in its preferred robotic embodiments, the invention. can 25 sharply reduce the labor costs per catalyst-scxeened.
1a Further details with respect to the prior art can be found in the following references:
(a) "Proceedings of the 5~" International Congress of Catalysis," Vol. 2, 1977, pages 796-805, Jensen J.V., ~~t al., 'A deactivation reactor for catalyst screening and evaluation,' which relates to a deactivatian reactor for catalyst screening and evaluation using a multitube converter for simultaneous aging of catalyst samples followed by determination of fundamental kinetic parameters in a separate reactor.
The fundamental kinetic parameters of both fresh and spent catalysts are determined by measurement in a conventional recirculation reactor.
(b) US-A-4 877 584 which relates to temperature programmed spectrometry wherein particles of a substrate under investigation are attached in a non-overlapping manner to a heating filament. Gases from the filament desorbed at increased temperatures are commonly measured by a quadruple mass spectrometer and are not individually selectively determined.
(c) "International Journal of Hydrogen Energy", Vol. 7, No. 9, 1982, pages 729-736, Haruta M. et al., 'Catalytic combustion of hydrogen, II. An experimental investigation of fundamental conditions for burner design,' which relates to catalytic combustion of hydrogen. A catalyst body carrying four types of catalysts tested is inserted into a chamber and st:pot temperature and spot compositions of gas mixtures on the front surface of the catalysts are measured with nine chromel-alumel thermocouples connected to a digital multi-temperature recorder, and with nine microprobes for gas sampling connected to a gas chromatograph.
(d) JP-A-08015139 which relates to a gas adsorptionldesorption measuring method of catalyst for automobile. A cell containing a single sample under constant flow rate of reactant is investigated.
Scary of th.~ ~r~.ver'.ta.~a~.
General 5tatemeat of the Ir~.ver~.tiorj.
According to the invention, a multisample holder (support) e.g.. a honeycomb or plate, ar a collection of individual support particles, is treated with solutions/suspensions of catalyst ingredients to fill wells in plates, or to produce cells, spots or pellets, holding each of a variety of combinations of the ingredients, is ~°ied, calcined or otherwise treated as necessary to stabilize the ingredients in the r~ells, spots or pelhets, then is contacted with a potentially reactive feedstream or batch e.g_, to catalyze biochemical reactions catalyzed by proteins, cells,. enzymes; gas oil,. hydrogen plus oxygen, l5 eahylene or other polymerizable monomer, propylene plus oxygen, or CC12F2 and hydrogen. The reaction occurring in each cell is measured, e.g. by infrared thermography, spectroscopic, electrochemical, photometric, thermal conductivity or other method of detection of products or residual reacta~.zts, or by sampling, e.g. by multistreaming through low volume tubing, from the vicinity of each combination, followed by analysis ~.g. spectral analysis, chromatography etc, or by obsezvin.c~ temperature change in the vicinity of the catalyst e.g. by thermographic 25 techniques, to determine the relative efficacy of the catalysts in each combination. Robotic techniques can be employed i:rt producing the cells, spots. pellets, ete.:.
2a The invention also concerns a method of simultaneously testing a plurality of candidate catalyst formulations, the method comprising, supporting a plurality of catalyst formulations an one or more supports, simultaneously contacting the formulations witr~ a reactant or reactant mixture under reaction conditions in a common reactor; and determining the relative efficacy of the plurality of candidate catalyst formulations by simultaneously (i) observing heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, or (ii) analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts by chromatography or spectroscopy.
In another aspect the invention concerns an apparatus for evaluating a plurality of differing candidate catalyst formulations for catalysis, the apparatus comprising a parallel reactor comprising a plurality of reaction sites, each of the ph~rality of reaction sites being adapted for containing a different candidate catalyst, the reactor being adapted such that the plurality of candidate catalysts can be simultaneously contacted with one or more reactants under reaction conditions, and a detector for determining the relative efficacy of the plurality of candidate catalyst formulations, characterized in that the detector is a parallel detector adapated for simultaneous analysis of the reactions, reaction products or unreacted reactants, and in that: (i) the detector comprises means adpated to observe the heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, the means being selected from (a) an infrared camera for observing radiation emitted from or absorbed by the reactions through one or more infra-red transparent windows, or (b) temperature sensors arranged for determining the temperature of the reactions, or (ii) the parallel detector comprises spectrometers or chromatographs for simultaneously analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts using spectroscopy or chromatography, respectively.
$ach of these parameters is discussed beloi~r:
Catalysts: Biotechnology catalysts include proteins,. cells, enzymes, etc. Chemical conversion catalysts include most of the elements of the .periodic table urh.ich are solid at the reaction conditions. Hydrocarbon conversion catalysts include Bi, Sn, S3~a, '~i, Zr, Pt, the rare earths, and many possible candidates whose potential :has not yet been recognized for the specific reaction_ Many synergistic combinations will be useful. Supported metals and metal 1o com'Plexes are preferred. The chemical catalysts can be added to the substrate (support) as elements, as organic or inorganic compounds which decompose under the temperature of the stabilizing step, depositing the element or its oxide onto the substrate, or as stable compounds.
Supports: Supports can be inert clays, zeolites, ceramics, carbon, plastics, e.g. reactive plastics, stable, nonreactive metals, or combinations o.f the foregoing. Their shape can be porous honeycomb penetrated by channels, particles (pellets), or plates onto' which patches (spots) of 2fl catalyst candidates are deposited or dells in plates.
Conventional. catalyst matrix materials such as .zeol.ites e.g.
WO 97!32208 PCT/US97/02756 zeolite USY, kaolin., alumina, etc. are particularly preferred as they can simulate commercial catalysts.
Preparation: The catalyst candidate precursors can be deposited onto the supports by any convenient technique, preferably by pipette or absorbing stamp (like a rubber stamp), or silk screen. In preferred embodiments, the deposition process will be under robotic control, similar to that used to load multicell plates in biochemical assays.
2p Many of the spots of catalyst will be built up by several separate depositions e.g. a channel penetrating a honeycomb can be plugged at one third of its length and the channel filled with a catalyst solution in its upper third, then the plug can be moved to the two-thirds point in the channel and a second catalyst pipetted in, then the plug can be removed and a third catalyst solution added, resulting in a channel in which reactants contact three catalysts successively as they flow through the channel. Catalyst can also be added by ion exchange, solid deposition, impregnation, or co~ination of these. The techniques of combinatorial chemical or biological preparation can preferably be utilized to prepare an array of candidate catalysts with the invention. Coprecipitates of two or mare catalysts can be slurried, applied to the support, then activated as necessary. Catalysts can be silk screened onto a support plate or inside of a support conduit, and successive screenings can be used to add different catalyst combinations to different spots.
Stabilizing Step: Once the catalysts are in place on the , 3p support, any suitable technique known to the art can be used to stabilize, and/or activate the particular catalysts ~ CA 02247259 1998-08-25 W~ 97132208 PCTIUS97/02756 chosen, so they will remain in place during the reaction step. Calcining, steaming, melting, drying, precipitation and reaction in place will be particularly preferred.
5 Reactants: The invention has utility with any reaction which can be enhanced by the presence of a catalyst, including biological reactions and inorganic and organic chemical reactions. Chemical reactions include polymerization reactions, halogenation, oxidation, hydrolysis, ~~ esterification, reduction and any other conventional reaction which can benefit from a catalyst. Hydrocarbon conversion reactions, as used in petroleum refining are an important use of the inventions and include reforming, fluid catalytic cracking, hydrogenation, hydrocracking, 1,5 hydrotreating, hydrodesulfurizing, alkylation and gasoline sweetening .
Sensors: The sensors used to detect catalytic activity in the candidate catalysts are not narrowly critical but will preferably be as simple as practical. Chromatographs, 2p temperature sensors, and spectrometers will be particularly preferred, especially those adapted to measure temperature and/or products near each specific catalyst spot e.g. by multistreaming, multitasking, sampling, fiber optics, or laser techniques. Thermography, as by an infrared camera 25 recording the temperature at a number of catalyst sites simultaneously, is particularly preferred. Other suitable sensors include electrochemical, fluorescence detectors, NMR, NIR, FTNIR, Raman, flame ionization, thermal conductivity, mass, viscosity and stimulated electron or 3Q X-ray emission Sensors can detect products in a gas or . liquid stream or on the surface of the support. Endothermic reactions exhibit reduced temperature at best catalysts.
Some sensors employ an added detection reagent, e.g. ozone to impart chemiluminesce.
Taggants: Optionally taggants (labels) can be added to identify particular catalysts, particularly where particles are employed as the supports for the catalysts. These taggants can be conventional as discussed in the literature.
Taggants can be chemicals which are stable at reaction conditions or can be radioactive with distinctive emissions.
The techniques of combinatorial chemistry will beapplicable with taggants as well as with catalysts chosen to suit the particular reaction to be enhanced by the catalyst.
Batch or Continuous: While the invention will be preferred on a flow basis, with reactants flowing by the catalyst spots under reaction conditions, batch testing e.g. in a stirred autoclave or agitated containers, can be employed, particularly in biological reactions.
Temperatures, pressures, space velocities and other reaction conditions: These will be determined by the reactants and reaction. Elevated pressures can be provided as reaction conditions by encasing the support in a reaction chamber with a sapphire or similar window for observation by the sensing means, or with pressure-tight leads extending through the reactor walls.
II. Utility of the Ir~ventiori The present invention is useful in the testing of catalysts for biotechnology, for promotion of gas phase and liquid phase reactions; under batch or, preferably, continuous flowstream conditions; at elevated, reduced or atmospheric Wf) 97132208 PCTlUS97102756 pressure; and saves both elapsed time and labor in screening for improved catalysts to promote a desired reaction.
Brief Description of the Drawings Figure 1 is a schematic diagram of a preferred honeycomb support with a robotic pipetting device depositing different combinations of catalyst ingredients into each of the channels running through the honeycomb, which is thereafter calcined to stabilize the catalysts in each ZO channel.
Figure 2 is shows schematically the honeycomb of Fig.
lbeing contacted by reactants flowing through the channels.
Figures 3a and 3b are alternative schematic diagrams of one channel of the honeycomb of Fig. 2 with a detector sensing the products exiting the channel by measuring absorption in a laser beam directed through the products or the channel.
Figure 4a shows a channel plugged at its midpoint prior to receiving a solution of catalyst and Figure 4b shows the plug moved to the end of the channel, so as to form a channel having one catalyst in one half its length and another catalyst in its other half.
Figure 5 shows schematically a sheet of support onto which 15 spots of different catalyst combinations have been deposited, as discussed in example 1.
Figure 6a shows an array of particles (pellets) of support in place in a reactor after having been ion exchanged with different catalyst combinations on different pellets (denoted schematically by different markings on the pellets in. the Figure). Figure 6b shows a packed reactor . which is less preferred because upstream pellets see fresh feed, while downstream pellets see partial3.y reacted feed.
D~scrz tiori, of the Pref~rre ~mbod~tn ~xampLe 1.
Referring to Figure 5, a. sheet of alpha alumina 10 3.s wash coated with particles of porous gamma-alumina by standard methods. Solutions of oxalate salts of 12 different transition metal elements are prepared in the wells of a 24 well itL'LCrotiter dish made of polystyrene . A
Bec7QnanBiornek2000 robotic automatedliquid handling system is used to prepare dilutions and mixtures from the original stocks, again in the.wells of microtiter style plates. The robot is used to deposit 20 mi:croliter aliquots of each of _ the resulting solutions at. def~.ried positions (spots) 12 on the surface of the alumina support 10, which is. then dried, calcined and inserted into a reactor capable of'temperature control at temperatures from 100 to 350 degrees, centirgrade.
After reduction, a potentially reactive mixture of oxygen.
and hydrogen is fed to the reactor_ An Agetaa M infra.-red sensitive camera 14 is ~.sed to observe the alumi.aa support through infra-red-transparent sapphire windows via a polished metal mirror. The camera is set so that the lower end of its dynamic range corresponds to a temperature of about 40 degrees C be3ow the feed temperature and the ~imum signal is associated with a temperature aboua 200 degrees higher. Compositions catalyzing the reaction are revealed by the local3.zed temperature increases (decreases for endothermic reactions) around spots ~.2 of that composition, as shown on photograph 18.
Example la.
Catalysts are alternatively identified by conducting the reaction in the presence of strong ultraviolet and/or visible light illumination, with infra-red thermography being conductea~. immediately after the illumination is turned off, or through the use of a short pass filter on tYie illumination source to eliminate,contaminating infra-red radiation.
zo Example 2..
Refering to Figure 2, a porous alurnina monolith 20 (Carning~ having square or circular cross-section channels extending in a regular array through its entire thickness is treated in each channel with a solutions of catalyst Precursors of differing compostions, With each composition bea..ng segregated in its own channel. After drying, calcination, etc., the activated monolith is placed in contact with a flowing potentially :reactive mixture at an elevated temperature, and observed in the infra-red using an 2p Agema~ model camera. The enthalpy of reaction produces localized temperature differences in the vicinity of composition exhibiting catalytic activity and these are observed as temperature variations near the exits of the channels_ Exa~cnp 3. a 3 .
Referring to Figures 2 and 3, a porous c;eramie monolith. 2t~ of the type described in Example 2, bearing various catalyst compositions in its channels a.s installed in a reactor {not shown) in such a way the entire length of each channel can p be observed. through sapphire windows at the ends of the Zo reactor. A broad-spectrum thermal infra-red source is installed at one end of the reactor, giving an areal infra-red energy flux density. An~~A.gem~ TR-sensitive camera is positioned in such a way as to observe the infra-red source directly through a signifir_ant fraction of the pores.
An interferometric or other filter is installed on one side of the reactor between the camera and the infra-red source such that the light reaching the camera from the source is lp substantially limited to wavelengths between 4 and 4.5 microns_ Observation of absorbency at this wavelength range is used to compare candidate catalyst compositions on the basis of their production of carbon dioxide, an undesired side product of the intended reaction. Catalyst Z5 compositions chosen for low carbon dioxide formation tin combination with high overall conversion activity ass measured by infra-red absorbance of the desired product or by infra-red thermography) are found to have high selectivity for the desired product over the carbon dioxide 2p side product.
Exatngl a A collection of catalyst precursor compositions is produced by automated liquid handling device, and a catalyst support particle is contacted with each composition. After zg further treatment to stabilize and activate the catalyst precursors, catalyst pellets are arrayed on a surface, exposed to a poter~tial2y reactive environment and their activity determined by infrared thermography.
~X3t'~11~ ~. a WO 97132208 PCTlUS97102'756 Solutions of combinations of catalyst precursors are prepared in a variety of separate vessels. Each composition also contains a small quantity of a labeling material (e. g., stable isotopes of the element carbon or sulfur in varying ratios). Catalyst support particles are contacted with catalyst precursor preparations, and activated. Pellets are then contacted one at a time with a potentially reactive mixture (for examples, by elutriation into an enclosed Volume) and their activity measured (by thermography, by spectroscopic measurement of products, or sampling of the surrounding vapor or liquid phase). Particles showing activity are collected and individually analyzed for their content of the labeling material so as to determine the composition giving the desired catalytic activity.
Example 6.
Example 2 is repeated except that only a portion of the pare length is coated with a catalyst candidate so as to allow for observation of unmodified monolith pore wall as a control reference standard foroptical uniformity.
Example 7.
The emissivity of the support monolith pores of the support of Example 2 is mapped at a wavelength of interest by holding the monolith at the intended experimental temperature in the absence of reactants. Digitally stored maps of the emissivity are used to normalize the infra-red energy flux measured under experimental conditions, to improve the accuracy with which local temperatures can be estimated.
Example 8.
A surface of high, substantially uniform emissivity is located at the end of the monolith of Example 2, away from the camera, in close radiative heat transfer/contact with ' the monolith channel material. The temperature of the portion of the surface closest to the open end of each channel is observed. In this case, it is necessary that gas be admitted into the channels past the uniform radiative 1p surface, either by means of pores or by means of a small offset between the radiative surface and the monolith.
Example 9.
Alternatively, spots of catalysts can be deposited on the inner surface of a reactor e.g. a tube formed of the support material, and temperature of the corresponding spots on the outside of the reactor can be measured to determine by conduction whether the respective catalyst has increased or decreased in temperature under the reaction.
Example 10.
The process of Example 1 is repeated except that the reactants are in the liquid phase and a liquid phase assay is used to detect the activity of individual catalyst candidates.
Example 11.
The experiment of Example 4 is repeated except that the metal loading is directly measured by dissolving the pellet and directly analyzing the metal loading.
Example 12.
A sheet of alpha alumina is wash coated with particles of porous gamma-alumina by standard methods. Solutions of oxalate salts of 3.2 different transition metal elements are prepared in the wells of a 24 wel:1 micro titer dish made of polystyrene. A Beckman Biomek2000 automated liquid handling system is used to prepare dilutions anal mixtures of the original stocks, again in the wells of microtiter style p3.ates. The Hiomekrobot is used to deposit 40 microliter aliquots of each of the resulting solutions at defined positions on the surface of the alumina support, which is then dried, calcined and inserted into a reactor controlled at a temperature of 200 degrees centigrade. A gaseous mixture of hydrogen (97.5x) and oxygen (2.5%) is fed at a temperature of 200 degrees centigrade. An infra-red s~sitive camera is used to observe the alumina-support through infra-red-trax~sparent sapphire windows.. The camera is set so that its lower range corresponds to the feed temperature and the maximum signal is associated with a temperature degrees 20 degrees higher. Compositions catalyzing the reaction are revealed by the localized temperature increases around spots of that composition.
example 13.
A porous alumina monolith having square pores extending in a regular array through its entire thickness at a density of 25 per square inch is washcoated with alumina particles.
The channels are then partially filled with solutions of differing compositions, each containing one or more metal oxalate or nitrate salts, with each composition being segregated in its own channel or set: of channels. After ~'Ying and activation in the presence of hyrogen gas, the _ . . .. ~ _,, ~ ~ ~ ,. , e., .~, .. ..~....,~ ~~...~.~.~. .~ .,~..~~.,.~~:~.-a.~ ~_~.u,~.. ,.~.~w ... .._._..__. .__ __..._ ...._w_ _...__ _...
WO 97!32208 PCT/US97/02756 activated monolith is placed into a sapphire-window-equipped reactor in which it can be observed in the infrared using an IR-sensitive camera. The camera is positioned in such a way as to observe the walls of the support. The relative emissivity of the support at each pixel is determined by imaging the monolith in the IR while holding the reactor and ' monolith at each of several constant temperatures while flowing nitrogen gas through the reactor.
The reactor is then fed with a gas mixture of 2.5 mole % oxygen in hydrogen. The reactor and feed temperatures are originally set to 40 degrees centigrade, and are gradually increased while the catalyst-bearing monolith is repeatedly imaged in the IR. The temperature in each cell may be judged by observing the cell at a position adjacent to the end of the catalyst-precursor-coated section of the channel, or by normalizing the observed IR energy emission by the emissivity calculated from the images taken under nanreactive conditions. The compositions in the cells ~0 showing the earliest temperature increase above the reactor temperature are useful as hydrogen oxidation catalysts.
Example 14.
A porous alumina monolith having square channels in a regular array extending through its entire 10 centimeter thickness at a density of 25 per square inch is washcoated with alumina particles. The channels are then partially filled with solutions of differing compositions, each containing one or more metal salts and in some cases also candidate modifiers such as barium, cesium or potassium ' compounds, each composition being segregated in its own i Vd0 97)32208 PCT/LTS97102756 channel or set of channels.
After drying and reduction in the presence of hydrogen gas, the activated monolith is placed into a 5 reactor in which it can be observed through a sapphire window using an IR-sensitive camera. This first window is positioned 0.5 centimeter from the surface of the monolith.
The camera is positioned in such a way as to look through the window, through the channels of the support and through 10 a second sapphire window toward a source of TR radiation.
The reactor is then fed with methane gas, mixed with oxygen and argon, in such a way that the gas flows through the channels of the monolith toward the camera. An optical filter which selectively passes IR radiation at 4.3 microns, 15 a wavelength which is strongly absorbed by carbon dioxide, is inserted between the IR source and the camera. The effective concentration of carbon dioxide in each channel is inferred from the IR intensity at 4.3 microns seen in that channel. The reading at 4.3 microns for each pixel is divided by the reading taken through a filter selective for an IR wavelength which is near 4.3 microns, but which is not absorbed strongly by carbon dioxide, methane or water, to compensate for potential optical artifacts.
Compositions giving high concentrations of carbon dioxide after long exposures to operating conditions are useful in catalytic oxidation of methane.
Example 15.
Solutions of combinations of catalyst precursors are prepared in a variety of separate vessels. Each composition 3p also contains a smallquantity of a labeling material (e. g., Z
stable isotopes .vf the element sulfur in varying ratios unique to each composition). catalyst support particles are contacted with the preparations of catalyst precursors compositions, and activated. Pellets are then contacted one at a time with a potentially reactive mixture (for examples, by elutriation into an enclosed volume) and their activity measured (by thermography, by spectroscopic measurement of products, or sampling of the surrounding vapor or liquid lp phase). Particles showing activa.ty are collected and individually analyzed for their content of the labeling material so as to deternii.ne the composition giving the desired catalytic activity.
$xampla ~.6.
A Tefloxz block having square channels in a regular array extending through its entire thickness at.a density of 9 per square inch is prepared in such a way that a shallow well exists at the bottom of each channel. $ach well is charged with a different polymer preparatior~. bearing 2p sulfonic acid groups on its surface, and a porous retaining mesh installed to keep th~.e polymer samples in place.
The catalyst-charged monolith is placed into a reactor in which it can be abserved through. a window positioned 0_5 centimeter from the surface of the block. A
camera is positioned in such a way as to look via through the sapphire window, through the channels of the support and through a second wa.ndow, toward a source of polarized light.
A polarizer is installed between the block and the camera.
A sucrose solution is fed to the reactor in such a waY as to flow through the channels of the block. The angle WC? 97732208 PCT/US97J027S6 i~
of rotation of polarized light in passing through the liquid in. each channel is measured by rotating the polarizer to various angles, and observingthe variation in brightness of the light passing through each channel. The candidate catalysts found in channels giving the greatest change in the angle of rotation are useful as catalysts of sucrose hydrolysis.
Example 17.
Catalysts for photooxidation of hexane are identified by conducting the reaction in the apparatus of Example 1& in the presence of strong ultraviolet and/or visible light illumination, with infra-red thermography being conducted immediately after the illumination is turned off, or through the use of a short pass filter on the illumination source to eliminate contaminating infrared radiation.
Example 18.
Samples of cyanogen bromide-activated cross linked agarose beads are exposed to solutions of alcohol oxidase at 2p varied pH's, salt concentrations, and enzyme concentrations.
After coupling of the enzyme, residual active groups are quenched with ethanolamine, the beads are washed, and each sample placed in a separate well of a multiwell plate. The plate is exposed to a flowing air stream containing ethanol vapor and observed with an Amber infrared-sensitive camera.
The samples showing the greatest temperature increase are selected as highly active immobilized alcohol oxidase catalysts.
Example 19.
3p Samples of cyanogen bromide activated cross linked agarose beads are exposed to solutions of anti-alcohol oxidase antibodies at varied pH's, salt concentrations, and antibody concentrations.
After coupling of the enzyme, residual active groups are , quenchedwith ethanolamine. The beads are washed, exposed to a solution of alcohol oxidase, washed again, and each sample placed in a separate well of a multiwell plate. The plate is exposed to a flowing air stream containing ethanol vapor and observed with an Amber infrared-sensitive camera. The samples showing the greatest temperature increase are selected as highly active immobilized alcohol oxidase catalysts.
Example 20.
A ceramic monolith having channels arranged in perpendicular row/column format passing through its entire thickness is washcoated with porous alumina particles and all the channels in each column are treated with the same catalyst precursors, which are activated. A potentially 2p reactive stream is flowed through the channels of the monolith, and a multiwavelength beam of radiation is passed over the surface of the monolith, parallel to each column, to a detector situated at the end of the column. The composition of the stream leaving the pores in that column is estimated by processing the detector output, including Fourier transformation and/or weighted summation/differencing of the intensities at different wavelengths.
Example 21. ' Pellets bearing catalytically-active groups capable of , catalyzing the conversion of both the D-and L-stereoisomers of a reactant are treated with a variety of substances potentially capable of preferentially suppressing (temporarily or permanently) the conversion of the L-stereoisomer of that compound by that catalyst. The pellets are distributed among the wells of a multiwellplate and exposed to a mixture of the isomers of the compound to be modified. Pellets treated with the suppressor giving the Jreatest reduction in the activity for conversion of the L-isomer are useful in stereoselective modification of the D-isomer.
Example 22.
A ceramic monolith having channels arranged in Z5 perpendicular row/coiumn format passing through its entire thickness is washcoated with porous alumina particles and the channels treated with catalyst precursors, which are activated. A potentially reactive stream is flowed through the channels of the monolith. A manifold consisting of an 2p array of tubes, each smaller than the dimensions of an individual channel, is used to introduce a stream containing ozone into the stream flowing through each channel, near its outlet. Reaction of the introduced ozone with the desired product liberates light, which is detected by a camera ~5 directed at the monolith. The catalyst composition giving the strongest light output is a useful catalyst for conversion of the reactants to the ozone-reactive desired product.
Example 23.
30 A ceramic monolith having channels arranged in perpendicular row/column format passing through its entire thickness is washcoated with porous alumina particles and the channels treated with catalyst precursors, which are 5 activated and then exposed to a potential-deactivating , substance. A potentially-reactive stream isflowed through the channels of the monolith. A manifold consisting of an ' array of tubes, each smaller than the dimensions of an individual channel, is used to sample the stream flowing ~p within each channel. Samples from each channel in turn are introduced into a gas chromatograph-mass spectrometer combination through an arrangement of switching valves, and catalyst compositions giving the highest yield of desired products are useful in conversion of that reactive stream.
15 MOC~lf lCa.'t1011S
Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variations on these compositions, methods, or embodiments are readily 20 apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
For example, statistically-designed experiments, and automated, iterative experimental process methods can be employed to obtain further reductions in, time for testing.
Attachment/arraying of preformed catalytic elements (especially precipitates, also single molecules and complexes such as metallocenes) onto a support, preferably by precipitating or deposition is useful in many cases.
Detection can involve addition of some reagent to the W(Y 97132208 PCT/US97102756 stream leaving each candidate, the reagent allowing detection of a catalyst product through staining or reaction to give a detectable product, light, etc.
The supports can comprise arrays with special arrangements for uniform flow distribution, e.g., a header . of multiple delivery tubes inserted into each channel in a block.
The detection means can comprise electrochemical means, or a gamma camera for metals accumulation measurement, imaging elemental analysis by neutron activation and imaging by film or storage plate of emitted radioactivity, temperature measurement by acoustic pyrometry, bolometry, electrochemical detection, conductivity detection, liquid phase assay, preferably dissolving the support pellet and directly analyzing the metal loading; measuring refractive index in the liquid phase; observing the IR emissions of product gases directly, without the usual source and using instead the radiation hot gases emit at characteristic wavelengths.
Other modifications can include testing for selectivity after deliberately poisoning some sites, especially in chiral catalysis, etc.
The formulations can be supported in the form of spots or layers on. the surface of a support containing wells or channels or channels extending across the entire extent of the support. The support can comprise a form of carbon, zeolite and/or plastic. The plastic can comprise a reactant. The support can hold a form of catalyst made by coprecipitation, or aluminum, or particles.
At least one of the formulations can preferably comprise a material selected from the group consisting of transition metals, platinum, iron, rhodium, manganese, metallocenes, zinc, copper, potassium chloride, calcium, zinc, molybdenum, silver, tungsten, cobalt and mixtures of the foregoing.
The label can comprise different isotopes or different mixtures of isotopes. The reaction conditions can comprise a pressure greater than one bar absolute pressure and the contact can be at a temperature greater than l00 degrees centigrade.
The method can comprise detection of temperature changes in the vicinity of a respective formulation due to reaction endotherm or exotherm. The method can comprise treatment with a reducing agent. The contacting step can be carried out in the presence of compounds which modify the distribution of the metal within the porous support. The candidate catalyst formulations can be contacted in the form of spots or layers on the surface of a support containing a washcoat supported by an underlayer.
The stabilizing step can be carried out with a temperature gradient or other means whereby certain candidate catalyst formulations are exposed to different temperatures. The stabilizing can comprise calcining, steaming, drying, reaction, ion exchange and/or precipitation. The detection of temperature changes due to reaction can employ a correction for emissivity variations associated with differences in chemical composition.
The array of formulations to be tested can comprise preformed metallocenes or other catalytic complexes fixed to a support. , The infrared radiation can be detected through the use of nondispersive infrared spectroscopy, or infrared-sensitive photographic film. The detector means can comprise means for physically scanning over an array of candidate formulations.
Observations at:~ multiple wavelengths can be procea sed by mathematical manipulation a.g. transformation, weighted summation and/or suY:~traction, etc. Reaction activity, reactants, or produc:~ts can be detected through the use of an added reaction which. signals the presence of_ reaction or particular compounds or classes of compounds.
Chemiluminescence can be used as an indicator of reaction activity, or particular compounds or classes of compounds. A
substantially collimated radiation source can be employed in product detection/imaging. Multa-tube sampling can be used to lead into a mass :upectrometer, chromatograph, or optical monitor. To simulate aging, etr~_, the formulations can exposed to a deleterious agent which reduces the activity of at least one formulation by at least 10~k, and then optionally exposed tc~ steam, heat, ~L2, air, liquid water or other different subst:ance(s) oz- condition (s) which increase the activity of at lt.>,ast one member o~ the collection by at least 10~ over its pr°eviously-reduced activity whereby regenerabili.ty, react.ivatability, decaking, or other catalyst property is treasured. The deleterious agent ca:n comprise elevated temperature, V, Pb, Ni, As, Sb, Sn, Hg, Fe, S or other metals, H~S, chlorine, oxygen, C1, and/o_r carbon monoxide.
General 5tatemeat of the Ir~.ver~.tiorj.
According to the invention, a multisample holder (support) e.g.. a honeycomb or plate, ar a collection of individual support particles, is treated with solutions/suspensions of catalyst ingredients to fill wells in plates, or to produce cells, spots or pellets, holding each of a variety of combinations of the ingredients, is ~°ied, calcined or otherwise treated as necessary to stabilize the ingredients in the r~ells, spots or pelhets, then is contacted with a potentially reactive feedstream or batch e.g_, to catalyze biochemical reactions catalyzed by proteins, cells,. enzymes; gas oil,. hydrogen plus oxygen, l5 eahylene or other polymerizable monomer, propylene plus oxygen, or CC12F2 and hydrogen. The reaction occurring in each cell is measured, e.g. by infrared thermography, spectroscopic, electrochemical, photometric, thermal conductivity or other method of detection of products or residual reacta~.zts, or by sampling, e.g. by multistreaming through low volume tubing, from the vicinity of each combination, followed by analysis ~.g. spectral analysis, chromatography etc, or by obsezvin.c~ temperature change in the vicinity of the catalyst e.g. by thermographic 25 techniques, to determine the relative efficacy of the catalysts in each combination. Robotic techniques can be employed i:rt producing the cells, spots. pellets, ete.:.
2a The invention also concerns a method of simultaneously testing a plurality of candidate catalyst formulations, the method comprising, supporting a plurality of catalyst formulations an one or more supports, simultaneously contacting the formulations witr~ a reactant or reactant mixture under reaction conditions in a common reactor; and determining the relative efficacy of the plurality of candidate catalyst formulations by simultaneously (i) observing heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, or (ii) analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts by chromatography or spectroscopy.
In another aspect the invention concerns an apparatus for evaluating a plurality of differing candidate catalyst formulations for catalysis, the apparatus comprising a parallel reactor comprising a plurality of reaction sites, each of the ph~rality of reaction sites being adapted for containing a different candidate catalyst, the reactor being adapted such that the plurality of candidate catalysts can be simultaneously contacted with one or more reactants under reaction conditions, and a detector for determining the relative efficacy of the plurality of candidate catalyst formulations, characterized in that the detector is a parallel detector adapated for simultaneous analysis of the reactions, reaction products or unreacted reactants, and in that: (i) the detector comprises means adpated to observe the heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, the means being selected from (a) an infrared camera for observing radiation emitted from or absorbed by the reactions through one or more infra-red transparent windows, or (b) temperature sensors arranged for determining the temperature of the reactions, or (ii) the parallel detector comprises spectrometers or chromatographs for simultaneously analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts using spectroscopy or chromatography, respectively.
$ach of these parameters is discussed beloi~r:
Catalysts: Biotechnology catalysts include proteins,. cells, enzymes, etc. Chemical conversion catalysts include most of the elements of the .periodic table urh.ich are solid at the reaction conditions. Hydrocarbon conversion catalysts include Bi, Sn, S3~a, '~i, Zr, Pt, the rare earths, and many possible candidates whose potential :has not yet been recognized for the specific reaction_ Many synergistic combinations will be useful. Supported metals and metal 1o com'Plexes are preferred. The chemical catalysts can be added to the substrate (support) as elements, as organic or inorganic compounds which decompose under the temperature of the stabilizing step, depositing the element or its oxide onto the substrate, or as stable compounds.
Supports: Supports can be inert clays, zeolites, ceramics, carbon, plastics, e.g. reactive plastics, stable, nonreactive metals, or combinations o.f the foregoing. Their shape can be porous honeycomb penetrated by channels, particles (pellets), or plates onto' which patches (spots) of 2fl catalyst candidates are deposited or dells in plates.
Conventional. catalyst matrix materials such as .zeol.ites e.g.
WO 97!32208 PCT/US97/02756 zeolite USY, kaolin., alumina, etc. are particularly preferred as they can simulate commercial catalysts.
Preparation: The catalyst candidate precursors can be deposited onto the supports by any convenient technique, preferably by pipette or absorbing stamp (like a rubber stamp), or silk screen. In preferred embodiments, the deposition process will be under robotic control, similar to that used to load multicell plates in biochemical assays.
2p Many of the spots of catalyst will be built up by several separate depositions e.g. a channel penetrating a honeycomb can be plugged at one third of its length and the channel filled with a catalyst solution in its upper third, then the plug can be moved to the two-thirds point in the channel and a second catalyst pipetted in, then the plug can be removed and a third catalyst solution added, resulting in a channel in which reactants contact three catalysts successively as they flow through the channel. Catalyst can also be added by ion exchange, solid deposition, impregnation, or co~ination of these. The techniques of combinatorial chemical or biological preparation can preferably be utilized to prepare an array of candidate catalysts with the invention. Coprecipitates of two or mare catalysts can be slurried, applied to the support, then activated as necessary. Catalysts can be silk screened onto a support plate or inside of a support conduit, and successive screenings can be used to add different catalyst combinations to different spots.
Stabilizing Step: Once the catalysts are in place on the , 3p support, any suitable technique known to the art can be used to stabilize, and/or activate the particular catalysts ~ CA 02247259 1998-08-25 W~ 97132208 PCTIUS97/02756 chosen, so they will remain in place during the reaction step. Calcining, steaming, melting, drying, precipitation and reaction in place will be particularly preferred.
5 Reactants: The invention has utility with any reaction which can be enhanced by the presence of a catalyst, including biological reactions and inorganic and organic chemical reactions. Chemical reactions include polymerization reactions, halogenation, oxidation, hydrolysis, ~~ esterification, reduction and any other conventional reaction which can benefit from a catalyst. Hydrocarbon conversion reactions, as used in petroleum refining are an important use of the inventions and include reforming, fluid catalytic cracking, hydrogenation, hydrocracking, 1,5 hydrotreating, hydrodesulfurizing, alkylation and gasoline sweetening .
Sensors: The sensors used to detect catalytic activity in the candidate catalysts are not narrowly critical but will preferably be as simple as practical. Chromatographs, 2p temperature sensors, and spectrometers will be particularly preferred, especially those adapted to measure temperature and/or products near each specific catalyst spot e.g. by multistreaming, multitasking, sampling, fiber optics, or laser techniques. Thermography, as by an infrared camera 25 recording the temperature at a number of catalyst sites simultaneously, is particularly preferred. Other suitable sensors include electrochemical, fluorescence detectors, NMR, NIR, FTNIR, Raman, flame ionization, thermal conductivity, mass, viscosity and stimulated electron or 3Q X-ray emission Sensors can detect products in a gas or . liquid stream or on the surface of the support. Endothermic reactions exhibit reduced temperature at best catalysts.
Some sensors employ an added detection reagent, e.g. ozone to impart chemiluminesce.
Taggants: Optionally taggants (labels) can be added to identify particular catalysts, particularly where particles are employed as the supports for the catalysts. These taggants can be conventional as discussed in the literature.
Taggants can be chemicals which are stable at reaction conditions or can be radioactive with distinctive emissions.
The techniques of combinatorial chemistry will beapplicable with taggants as well as with catalysts chosen to suit the particular reaction to be enhanced by the catalyst.
Batch or Continuous: While the invention will be preferred on a flow basis, with reactants flowing by the catalyst spots under reaction conditions, batch testing e.g. in a stirred autoclave or agitated containers, can be employed, particularly in biological reactions.
Temperatures, pressures, space velocities and other reaction conditions: These will be determined by the reactants and reaction. Elevated pressures can be provided as reaction conditions by encasing the support in a reaction chamber with a sapphire or similar window for observation by the sensing means, or with pressure-tight leads extending through the reactor walls.
II. Utility of the Ir~ventiori The present invention is useful in the testing of catalysts for biotechnology, for promotion of gas phase and liquid phase reactions; under batch or, preferably, continuous flowstream conditions; at elevated, reduced or atmospheric Wf) 97132208 PCTlUS97102756 pressure; and saves both elapsed time and labor in screening for improved catalysts to promote a desired reaction.
Brief Description of the Drawings Figure 1 is a schematic diagram of a preferred honeycomb support with a robotic pipetting device depositing different combinations of catalyst ingredients into each of the channels running through the honeycomb, which is thereafter calcined to stabilize the catalysts in each ZO channel.
Figure 2 is shows schematically the honeycomb of Fig.
lbeing contacted by reactants flowing through the channels.
Figures 3a and 3b are alternative schematic diagrams of one channel of the honeycomb of Fig. 2 with a detector sensing the products exiting the channel by measuring absorption in a laser beam directed through the products or the channel.
Figure 4a shows a channel plugged at its midpoint prior to receiving a solution of catalyst and Figure 4b shows the plug moved to the end of the channel, so as to form a channel having one catalyst in one half its length and another catalyst in its other half.
Figure 5 shows schematically a sheet of support onto which 15 spots of different catalyst combinations have been deposited, as discussed in example 1.
Figure 6a shows an array of particles (pellets) of support in place in a reactor after having been ion exchanged with different catalyst combinations on different pellets (denoted schematically by different markings on the pellets in. the Figure). Figure 6b shows a packed reactor . which is less preferred because upstream pellets see fresh feed, while downstream pellets see partial3.y reacted feed.
D~scrz tiori, of the Pref~rre ~mbod~tn ~xampLe 1.
Referring to Figure 5, a. sheet of alpha alumina 10 3.s wash coated with particles of porous gamma-alumina by standard methods. Solutions of oxalate salts of 12 different transition metal elements are prepared in the wells of a 24 well itL'LCrotiter dish made of polystyrene . A
Bec7QnanBiornek2000 robotic automatedliquid handling system is used to prepare dilutions and mixtures from the original stocks, again in the.wells of microtiter style plates. The robot is used to deposit 20 mi:croliter aliquots of each of _ the resulting solutions at. def~.ried positions (spots) 12 on the surface of the alumina support 10, which is. then dried, calcined and inserted into a reactor capable of'temperature control at temperatures from 100 to 350 degrees, centirgrade.
After reduction, a potentially reactive mixture of oxygen.
and hydrogen is fed to the reactor_ An Agetaa M infra.-red sensitive camera 14 is ~.sed to observe the alumi.aa support through infra-red-transparent sapphire windows via a polished metal mirror. The camera is set so that the lower end of its dynamic range corresponds to a temperature of about 40 degrees C be3ow the feed temperature and the ~imum signal is associated with a temperature aboua 200 degrees higher. Compositions catalyzing the reaction are revealed by the local3.zed temperature increases (decreases for endothermic reactions) around spots ~.2 of that composition, as shown on photograph 18.
Example la.
Catalysts are alternatively identified by conducting the reaction in the presence of strong ultraviolet and/or visible light illumination, with infra-red thermography being conductea~. immediately after the illumination is turned off, or through the use of a short pass filter on tYie illumination source to eliminate,contaminating infra-red radiation.
zo Example 2..
Refering to Figure 2, a porous alurnina monolith 20 (Carning~ having square or circular cross-section channels extending in a regular array through its entire thickness is treated in each channel with a solutions of catalyst Precursors of differing compostions, With each composition bea..ng segregated in its own channel. After drying, calcination, etc., the activated monolith is placed in contact with a flowing potentially :reactive mixture at an elevated temperature, and observed in the infra-red using an 2p Agema~ model camera. The enthalpy of reaction produces localized temperature differences in the vicinity of composition exhibiting catalytic activity and these are observed as temperature variations near the exits of the channels_ Exa~cnp 3. a 3 .
Referring to Figures 2 and 3, a porous c;eramie monolith. 2t~ of the type described in Example 2, bearing various catalyst compositions in its channels a.s installed in a reactor {not shown) in such a way the entire length of each channel can p be observed. through sapphire windows at the ends of the Zo reactor. A broad-spectrum thermal infra-red source is installed at one end of the reactor, giving an areal infra-red energy flux density. An~~A.gem~ TR-sensitive camera is positioned in such a way as to observe the infra-red source directly through a signifir_ant fraction of the pores.
An interferometric or other filter is installed on one side of the reactor between the camera and the infra-red source such that the light reaching the camera from the source is lp substantially limited to wavelengths between 4 and 4.5 microns_ Observation of absorbency at this wavelength range is used to compare candidate catalyst compositions on the basis of their production of carbon dioxide, an undesired side product of the intended reaction. Catalyst Z5 compositions chosen for low carbon dioxide formation tin combination with high overall conversion activity ass measured by infra-red absorbance of the desired product or by infra-red thermography) are found to have high selectivity for the desired product over the carbon dioxide 2p side product.
Exatngl a A collection of catalyst precursor compositions is produced by automated liquid handling device, and a catalyst support particle is contacted with each composition. After zg further treatment to stabilize and activate the catalyst precursors, catalyst pellets are arrayed on a surface, exposed to a poter~tial2y reactive environment and their activity determined by infrared thermography.
~X3t'~11~ ~. a WO 97132208 PCTlUS97102'756 Solutions of combinations of catalyst precursors are prepared in a variety of separate vessels. Each composition also contains a small quantity of a labeling material (e. g., stable isotopes of the element carbon or sulfur in varying ratios). Catalyst support particles are contacted with catalyst precursor preparations, and activated. Pellets are then contacted one at a time with a potentially reactive mixture (for examples, by elutriation into an enclosed Volume) and their activity measured (by thermography, by spectroscopic measurement of products, or sampling of the surrounding vapor or liquid phase). Particles showing activity are collected and individually analyzed for their content of the labeling material so as to determine the composition giving the desired catalytic activity.
Example 6.
Example 2 is repeated except that only a portion of the pare length is coated with a catalyst candidate so as to allow for observation of unmodified monolith pore wall as a control reference standard foroptical uniformity.
Example 7.
The emissivity of the support monolith pores of the support of Example 2 is mapped at a wavelength of interest by holding the monolith at the intended experimental temperature in the absence of reactants. Digitally stored maps of the emissivity are used to normalize the infra-red energy flux measured under experimental conditions, to improve the accuracy with which local temperatures can be estimated.
Example 8.
A surface of high, substantially uniform emissivity is located at the end of the monolith of Example 2, away from the camera, in close radiative heat transfer/contact with ' the monolith channel material. The temperature of the portion of the surface closest to the open end of each channel is observed. In this case, it is necessary that gas be admitted into the channels past the uniform radiative 1p surface, either by means of pores or by means of a small offset between the radiative surface and the monolith.
Example 9.
Alternatively, spots of catalysts can be deposited on the inner surface of a reactor e.g. a tube formed of the support material, and temperature of the corresponding spots on the outside of the reactor can be measured to determine by conduction whether the respective catalyst has increased or decreased in temperature under the reaction.
Example 10.
The process of Example 1 is repeated except that the reactants are in the liquid phase and a liquid phase assay is used to detect the activity of individual catalyst candidates.
Example 11.
The experiment of Example 4 is repeated except that the metal loading is directly measured by dissolving the pellet and directly analyzing the metal loading.
Example 12.
A sheet of alpha alumina is wash coated with particles of porous gamma-alumina by standard methods. Solutions of oxalate salts of 3.2 different transition metal elements are prepared in the wells of a 24 wel:1 micro titer dish made of polystyrene. A Beckman Biomek2000 automated liquid handling system is used to prepare dilutions anal mixtures of the original stocks, again in the wells of microtiter style p3.ates. The Hiomekrobot is used to deposit 40 microliter aliquots of each of the resulting solutions at defined positions on the surface of the alumina support, which is then dried, calcined and inserted into a reactor controlled at a temperature of 200 degrees centigrade. A gaseous mixture of hydrogen (97.5x) and oxygen (2.5%) is fed at a temperature of 200 degrees centigrade. An infra-red s~sitive camera is used to observe the alumina-support through infra-red-trax~sparent sapphire windows.. The camera is set so that its lower range corresponds to the feed temperature and the maximum signal is associated with a temperature degrees 20 degrees higher. Compositions catalyzing the reaction are revealed by the localized temperature increases around spots of that composition.
example 13.
A porous alumina monolith having square pores extending in a regular array through its entire thickness at a density of 25 per square inch is washcoated with alumina particles.
The channels are then partially filled with solutions of differing compositions, each containing one or more metal oxalate or nitrate salts, with each composition being segregated in its own channel or set: of channels. After ~'Ying and activation in the presence of hyrogen gas, the _ . . .. ~ _,, ~ ~ ~ ,. , e., .~, .. ..~....,~ ~~...~.~.~. .~ .,~..~~.,.~~:~.-a.~ ~_~.u,~.. ,.~.~w ... .._._..__. .__ __..._ ...._w_ _...__ _...
WO 97!32208 PCT/US97/02756 activated monolith is placed into a sapphire-window-equipped reactor in which it can be observed in the infrared using an IR-sensitive camera. The camera is positioned in such a way as to observe the walls of the support. The relative emissivity of the support at each pixel is determined by imaging the monolith in the IR while holding the reactor and ' monolith at each of several constant temperatures while flowing nitrogen gas through the reactor.
The reactor is then fed with a gas mixture of 2.5 mole % oxygen in hydrogen. The reactor and feed temperatures are originally set to 40 degrees centigrade, and are gradually increased while the catalyst-bearing monolith is repeatedly imaged in the IR. The temperature in each cell may be judged by observing the cell at a position adjacent to the end of the catalyst-precursor-coated section of the channel, or by normalizing the observed IR energy emission by the emissivity calculated from the images taken under nanreactive conditions. The compositions in the cells ~0 showing the earliest temperature increase above the reactor temperature are useful as hydrogen oxidation catalysts.
Example 14.
A porous alumina monolith having square channels in a regular array extending through its entire 10 centimeter thickness at a density of 25 per square inch is washcoated with alumina particles. The channels are then partially filled with solutions of differing compositions, each containing one or more metal salts and in some cases also candidate modifiers such as barium, cesium or potassium ' compounds, each composition being segregated in its own i Vd0 97)32208 PCT/LTS97102756 channel or set of channels.
After drying and reduction in the presence of hydrogen gas, the activated monolith is placed into a 5 reactor in which it can be observed through a sapphire window using an IR-sensitive camera. This first window is positioned 0.5 centimeter from the surface of the monolith.
The camera is positioned in such a way as to look through the window, through the channels of the support and through 10 a second sapphire window toward a source of TR radiation.
The reactor is then fed with methane gas, mixed with oxygen and argon, in such a way that the gas flows through the channels of the monolith toward the camera. An optical filter which selectively passes IR radiation at 4.3 microns, 15 a wavelength which is strongly absorbed by carbon dioxide, is inserted between the IR source and the camera. The effective concentration of carbon dioxide in each channel is inferred from the IR intensity at 4.3 microns seen in that channel. The reading at 4.3 microns for each pixel is divided by the reading taken through a filter selective for an IR wavelength which is near 4.3 microns, but which is not absorbed strongly by carbon dioxide, methane or water, to compensate for potential optical artifacts.
Compositions giving high concentrations of carbon dioxide after long exposures to operating conditions are useful in catalytic oxidation of methane.
Example 15.
Solutions of combinations of catalyst precursors are prepared in a variety of separate vessels. Each composition 3p also contains a smallquantity of a labeling material (e. g., Z
stable isotopes .vf the element sulfur in varying ratios unique to each composition). catalyst support particles are contacted with the preparations of catalyst precursors compositions, and activated. Pellets are then contacted one at a time with a potentially reactive mixture (for examples, by elutriation into an enclosed volume) and their activity measured (by thermography, by spectroscopic measurement of products, or sampling of the surrounding vapor or liquid lp phase). Particles showing activa.ty are collected and individually analyzed for their content of the labeling material so as to deternii.ne the composition giving the desired catalytic activity.
$xampla ~.6.
A Tefloxz block having square channels in a regular array extending through its entire thickness at.a density of 9 per square inch is prepared in such a way that a shallow well exists at the bottom of each channel. $ach well is charged with a different polymer preparatior~. bearing 2p sulfonic acid groups on its surface, and a porous retaining mesh installed to keep th~.e polymer samples in place.
The catalyst-charged monolith is placed into a reactor in which it can be abserved through. a window positioned 0_5 centimeter from the surface of the block. A
camera is positioned in such a way as to look via through the sapphire window, through the channels of the support and through a second wa.ndow, toward a source of polarized light.
A polarizer is installed between the block and the camera.
A sucrose solution is fed to the reactor in such a waY as to flow through the channels of the block. The angle WC? 97732208 PCT/US97J027S6 i~
of rotation of polarized light in passing through the liquid in. each channel is measured by rotating the polarizer to various angles, and observingthe variation in brightness of the light passing through each channel. The candidate catalysts found in channels giving the greatest change in the angle of rotation are useful as catalysts of sucrose hydrolysis.
Example 17.
Catalysts for photooxidation of hexane are identified by conducting the reaction in the apparatus of Example 1& in the presence of strong ultraviolet and/or visible light illumination, with infra-red thermography being conducted immediately after the illumination is turned off, or through the use of a short pass filter on the illumination source to eliminate contaminating infrared radiation.
Example 18.
Samples of cyanogen bromide-activated cross linked agarose beads are exposed to solutions of alcohol oxidase at 2p varied pH's, salt concentrations, and enzyme concentrations.
After coupling of the enzyme, residual active groups are quenched with ethanolamine, the beads are washed, and each sample placed in a separate well of a multiwell plate. The plate is exposed to a flowing air stream containing ethanol vapor and observed with an Amber infrared-sensitive camera.
The samples showing the greatest temperature increase are selected as highly active immobilized alcohol oxidase catalysts.
Example 19.
3p Samples of cyanogen bromide activated cross linked agarose beads are exposed to solutions of anti-alcohol oxidase antibodies at varied pH's, salt concentrations, and antibody concentrations.
After coupling of the enzyme, residual active groups are , quenchedwith ethanolamine. The beads are washed, exposed to a solution of alcohol oxidase, washed again, and each sample placed in a separate well of a multiwell plate. The plate is exposed to a flowing air stream containing ethanol vapor and observed with an Amber infrared-sensitive camera. The samples showing the greatest temperature increase are selected as highly active immobilized alcohol oxidase catalysts.
Example 20.
A ceramic monolith having channels arranged in perpendicular row/column format passing through its entire thickness is washcoated with porous alumina particles and all the channels in each column are treated with the same catalyst precursors, which are activated. A potentially 2p reactive stream is flowed through the channels of the monolith, and a multiwavelength beam of radiation is passed over the surface of the monolith, parallel to each column, to a detector situated at the end of the column. The composition of the stream leaving the pores in that column is estimated by processing the detector output, including Fourier transformation and/or weighted summation/differencing of the intensities at different wavelengths.
Example 21. ' Pellets bearing catalytically-active groups capable of , catalyzing the conversion of both the D-and L-stereoisomers of a reactant are treated with a variety of substances potentially capable of preferentially suppressing (temporarily or permanently) the conversion of the L-stereoisomer of that compound by that catalyst. The pellets are distributed among the wells of a multiwellplate and exposed to a mixture of the isomers of the compound to be modified. Pellets treated with the suppressor giving the Jreatest reduction in the activity for conversion of the L-isomer are useful in stereoselective modification of the D-isomer.
Example 22.
A ceramic monolith having channels arranged in Z5 perpendicular row/coiumn format passing through its entire thickness is washcoated with porous alumina particles and the channels treated with catalyst precursors, which are activated. A potentially reactive stream is flowed through the channels of the monolith. A manifold consisting of an 2p array of tubes, each smaller than the dimensions of an individual channel, is used to introduce a stream containing ozone into the stream flowing through each channel, near its outlet. Reaction of the introduced ozone with the desired product liberates light, which is detected by a camera ~5 directed at the monolith. The catalyst composition giving the strongest light output is a useful catalyst for conversion of the reactants to the ozone-reactive desired product.
Example 23.
30 A ceramic monolith having channels arranged in perpendicular row/column format passing through its entire thickness is washcoated with porous alumina particles and the channels treated with catalyst precursors, which are 5 activated and then exposed to a potential-deactivating , substance. A potentially-reactive stream isflowed through the channels of the monolith. A manifold consisting of an ' array of tubes, each smaller than the dimensions of an individual channel, is used to sample the stream flowing ~p within each channel. Samples from each channel in turn are introduced into a gas chromatograph-mass spectrometer combination through an arrangement of switching valves, and catalyst compositions giving the highest yield of desired products are useful in conversion of that reactive stream.
15 MOC~lf lCa.'t1011S
Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variations on these compositions, methods, or embodiments are readily 20 apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
For example, statistically-designed experiments, and automated, iterative experimental process methods can be employed to obtain further reductions in, time for testing.
Attachment/arraying of preformed catalytic elements (especially precipitates, also single molecules and complexes such as metallocenes) onto a support, preferably by precipitating or deposition is useful in many cases.
Detection can involve addition of some reagent to the W(Y 97132208 PCT/US97102756 stream leaving each candidate, the reagent allowing detection of a catalyst product through staining or reaction to give a detectable product, light, etc.
The supports can comprise arrays with special arrangements for uniform flow distribution, e.g., a header . of multiple delivery tubes inserted into each channel in a block.
The detection means can comprise electrochemical means, or a gamma camera for metals accumulation measurement, imaging elemental analysis by neutron activation and imaging by film or storage plate of emitted radioactivity, temperature measurement by acoustic pyrometry, bolometry, electrochemical detection, conductivity detection, liquid phase assay, preferably dissolving the support pellet and directly analyzing the metal loading; measuring refractive index in the liquid phase; observing the IR emissions of product gases directly, without the usual source and using instead the radiation hot gases emit at characteristic wavelengths.
Other modifications can include testing for selectivity after deliberately poisoning some sites, especially in chiral catalysis, etc.
The formulations can be supported in the form of spots or layers on. the surface of a support containing wells or channels or channels extending across the entire extent of the support. The support can comprise a form of carbon, zeolite and/or plastic. The plastic can comprise a reactant. The support can hold a form of catalyst made by coprecipitation, or aluminum, or particles.
At least one of the formulations can preferably comprise a material selected from the group consisting of transition metals, platinum, iron, rhodium, manganese, metallocenes, zinc, copper, potassium chloride, calcium, zinc, molybdenum, silver, tungsten, cobalt and mixtures of the foregoing.
The label can comprise different isotopes or different mixtures of isotopes. The reaction conditions can comprise a pressure greater than one bar absolute pressure and the contact can be at a temperature greater than l00 degrees centigrade.
The method can comprise detection of temperature changes in the vicinity of a respective formulation due to reaction endotherm or exotherm. The method can comprise treatment with a reducing agent. The contacting step can be carried out in the presence of compounds which modify the distribution of the metal within the porous support. The candidate catalyst formulations can be contacted in the form of spots or layers on the surface of a support containing a washcoat supported by an underlayer.
The stabilizing step can be carried out with a temperature gradient or other means whereby certain candidate catalyst formulations are exposed to different temperatures. The stabilizing can comprise calcining, steaming, drying, reaction, ion exchange and/or precipitation. The detection of temperature changes due to reaction can employ a correction for emissivity variations associated with differences in chemical composition.
The array of formulations to be tested can comprise preformed metallocenes or other catalytic complexes fixed to a support. , The infrared radiation can be detected through the use of nondispersive infrared spectroscopy, or infrared-sensitive photographic film. The detector means can comprise means for physically scanning over an array of candidate formulations.
Observations at:~ multiple wavelengths can be procea sed by mathematical manipulation a.g. transformation, weighted summation and/or suY:~traction, etc. Reaction activity, reactants, or produc:~ts can be detected through the use of an added reaction which. signals the presence of_ reaction or particular compounds or classes of compounds.
Chemiluminescence can be used as an indicator of reaction activity, or particular compounds or classes of compounds. A
substantially collimated radiation source can be employed in product detection/imaging. Multa-tube sampling can be used to lead into a mass :upectrometer, chromatograph, or optical monitor. To simulate aging, etr~_, the formulations can exposed to a deleterious agent which reduces the activity of at least one formulation by at least 10~k, and then optionally exposed tc~ steam, heat, ~L2, air, liquid water or other different subst:ance(s) oz- condition (s) which increase the activity of at lt.>,ast one member o~ the collection by at least 10~ over its pr°eviously-reduced activity whereby regenerabili.ty, react.ivatability, decaking, or other catalyst property is treasured. The deleterious agent ca:n comprise elevated temperature, V, Pb, Ni, As, Sb, Sn, Hg, Fe, S or other metals, H~S, chlorine, oxygen, C1, and/o_r carbon monoxide.
Claims (52)
1. A method of simultaneously testing a plurality of candidate catalyst formulations, the method comprising:
supporting a plurality of catalyst formulations on one or more supports, simultaneously contacting the formulations with a reactant or reactant mixture under reaction conditions in a common reactor; and determining the relative efficacy of the plurality of candidate catalyst formulations by simultaneously (i) observing heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, or (ii) analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts by chromatography or spectroscopy.
supporting a plurality of catalyst formulations on one or more supports, simultaneously contacting the formulations with a reactant or reactant mixture under reaction conditions in a common reactor; and determining the relative efficacy of the plurality of candidate catalyst formulations by simultaneously (i) observing heat liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, or (ii) analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts by chromatography or spectroscopy.
2. The method of claim 1 wherein the relative efficacy of the plurality of candidate catalyst formulations is determined by analyzing the reaction products or unreacted reactants in the vicinity of the respective formulations.
3. The method of claim 1 wherein the relative efficacy of the plurality of candidate catalyst formulations is determined by taking a sample in proximity to the respective formulations, and analyzing the sample for product or reactant composition by chromatography or spectroscopy.
4. The method of claim 1 wherein the formulations are contacted while in the form of an array of reaction sites on the surface of a common support.
5. The method of claim 1 further comprising identifying the respective formulations by their position in an arrangement of different catalyst formulations on a common support.
6. The method of claim 1 further comprising identifying the respective formulations by analysis of a unique label physically associated with each of the formulations.
7. The method of claim 1 further comprising, exposing the catalyst formulations to substances or conditions that reduce the activity of at least one formulation by at least 10%, and thereafter measuring the activity of the plurality of catalyst formulations.
8. The method of claim 1 wherein the supported catalyst formulations are formed by contacting a porous support with a solution comprising a metal salt.
9. The method of claim 1 further comprising exposing certain of the candidate catalyst formulations to different temperatures, calcining, steaming, drying, reaction, ion-exchange or precipitation conditions.
10. The method of claim 1 wherein the relative efficacy of the candidate catalyst formulations is determined by detecting infrared radiation emitted or absorbed from the reactions.
11. The method of claim 10 wherein the common reactor comprises an infrared-transparent window, and the infrared raditaion is detected through the infrared-transparent window.
12. The method of claim 10 comprising:
providing the plurality of candidate catalysts having differing compositions at a plurality of sites on a common support, encasing the support in a reaction chamber of a parallel reactor, the reaction chamber having an infrared-transparent window, simultaneously contacting the plurality of candidate catalysts with one or more reactants under reaction conditions to catalyze at least one reaction, and simultaneously detecting infrared radiation emitted from or absorbed by the reaction at each of the plurality of sites with an infrared camera through the infrared-transparent window during the course of the reaction to determine the relative efficacy of the plurality of candidate catalysts.
providing the plurality of candidate catalysts having differing compositions at a plurality of sites on a common support, encasing the support in a reaction chamber of a parallel reactor, the reaction chamber having an infrared-transparent window, simultaneously contacting the plurality of candidate catalysts with one or more reactants under reaction conditions to catalyze at least one reaction, and simultaneously detecting infrared radiation emitted from or absorbed by the reaction at each of the plurality of sites with an infrared camera through the infrared-transparent window during the course of the reaction to determine the relative efficacy of the plurality of candidate catalysts.
13. The method of claim 10 further comprising correcting for emissivity variations associated with differences in chemical composition of the plurality of catalyst formulations.
14. The method of claim 13 wherein the emissivity variations associated with differences in composition of the candidate catalysts are determined by detecting infrared radiation emitted from each of the plurality of candidate-catalyst-containing sites under nonreactive conditions.
15. The method of claim 13 wherein the observed infrared emissions are corrected by a method that includes determining the relative emissivity associated with each of the plurality of candidate-catalyst-containing sites under nonreactive conditions at each of several constant temperatures, and normalizing the observed infrared emissions with the determined relative emissivity at the reaction temperature.
16. The method of claim 13 wherein the observed infrared emissions are corrected by a method that includes observing infrared radiation emitted from the support material as a control reference, and normalizing the infrared emissions observed from each of the plurality of candidate-catalyst-containing sites to the control reference.
17. The method of any one of claims 10 to 16 wherein the radiation emitted during the course of the reaction is detected by imaging with an infrared-sensitive camera.
18. The method of claim 1 wherein the relative efficacy of the candidate catalyst formulations is determined by detecting temperature changes due to the reactions.
19. The method of claim 18 wherein the temperature of the reaction is determined during the course of the reaction by sensing with a temperature sensor.
20. The method of claim 1 wherein the relative efficacy of the plurality of candidate catalyst formulations is determined by spectral analysis of the reaction products or unreacted reactants at multilple wavelengths.
21. The method of claim 1 wherein the reactor is a parallel reactor comprising the plurality of candidate catalysts, a plurality of reaction sites with each of the plurality of candidate catalysts being in its own reaction site, and one or more radiation-transparent windows, the reaction products or unreacted reactants are irradiated with radiation through the one or more radiation-transparent windows, and reaction products or unreacted reactants are detected by spectroscopic methods through the one or more radiation-transparent windows to determine the relative efficacy of the plurality of candidate catalysts.
22. The method of claim 21 wherein the parallel reactor is a parallel batch reactor.
23. The method of claim 21 wherein the parallel reactor is a parallel flow reactor.
24. The method of claim 23 wherein the parallel flow reactor is adapted to provide uniform flow of the reactant-containing stream through each of the plurality of reaction sites.
25. The method of claim 21 wherein the parallel reactor comprises a plurality of reaction channels as reaction sites.
26. The method of claim 25 wherein the parallel reactor comprises the plurality of reaction channels in a monolithic support.
27. The method of any one of claims 1, 21, 22, 23, 24, 25, or 26, wherein the reaction products or unreacted reactants are detected with a technique selected from the group consisting of infrared spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, Raman spectroscopy, laser spectroscopy and optical spectroscopy.
28. The method of claim 1 wherein the reactor is a parallel flow reactor comprising the plurality of candidate catalysts, a plurality of reaction sites with each of the plurality of candidate catalysts being in its own reaction site, and a plurality of sampling tubes adapted to provide fluid communication between the plurality of reaction sites and a plurality of spectrometers or chromatographs for multistream detection of a reaction product or unreacted reactant in each of the plurality of discharged product-containing streams.
29. The method of claim 1 wherein the reactor is a parallel flow reactor comprising the plurality of candidate catalysts, a :plurality of reaction sites with each of the plurality of candidate catalysts being in its own reaction site, a plurality of tubes for sampling the product-containing streams of each of the plurality of reaction sites, and an arrangement of switching valves for introducing the plurality of product-containing streams into a plurality of spectrometers or chromatographs.
30. The method of claim 1 wherein the reactor is a parallel flow reactor comprising an array of tubes for sampling the product-containing streams of each of the plurality of reaction channels, the method further comprising physically scanning over the array of tubes to introduce the plurality of product-containing streams into a spectrometer or chromatograph.
31. A method according to claim 1 wherein said detecting step comprises measuring the angle of rotation of polarized light.
32. The method of any one of claims 1 to 31 wherein the plurality of catalyst candidates or precursors are selected from at least one of chemical conversion catalysts, hydrocarbon conversion catalysts, inorganic catalysts, metals or metal oxides, transition metals or transition metal oxides, zeolites, metallocenes, and supported catalysts.
33. The method of any one of claims 1 to 32 wherein the reaction conditions include a temperature greater than 100°C, and additionally, or alternatively, a pressure of greater than 1 bar.
34. The method of any one of claims 1 to 33 wherein the one or more reactants are in the gas phase.
35. The method of any one of claims 1 to 34 wherein the one or more reactants are in the liquid phase.
36. An apparatus for evaluating a plurality of differing candidate catalyst formulations for catalysis, the apparatus comprising:
a parallel reactor comprising a plurality of reaction sites, each of the plurality of reaction sites being adapted for containing a different candidate catalyst, the reactor being adapted such that the plurality of candidate catalysts can be simultaneously contacted with one or more reactants under reaction conditions, and a detector for determining the relative efficacy of the plurality of candidate catalyst formulations, characterized in that the detector is a parallel detector adapated for simultaneous analysis of the reactions, reaction products or unreacted reactants, and in that: (i) the detector comprises means adpated to observe the heat Liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, the means being selected from (a) an infrared camera for observing radiation emitted from or absorbed by the reactions through one or more infra-red transparent windows, or (b) temperature sensors arranged for determining the temperature of the reactions, or (ii) the parallel detector comprises spectrometers or chromatographs for simultaneously analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts using spectroscopy or chromatography, respectively.
a parallel reactor comprising a plurality of reaction sites, each of the plurality of reaction sites being adapted for containing a different candidate catalyst, the reactor being adapted such that the plurality of candidate catalysts can be simultaneously contacted with one or more reactants under reaction conditions, and a detector for determining the relative efficacy of the plurality of candidate catalyst formulations, characterized in that the detector is a parallel detector adapated for simultaneous analysis of the reactions, reaction products or unreacted reactants, and in that: (i) the detector comprises means adpated to observe the heat Liberated or absorbed during the course of the reactions catalyzed by the plurality of candidate catalysts, the means being selected from (a) an infrared camera for observing radiation emitted from or absorbed by the reactions through one or more infra-red transparent windows, or (b) temperature sensors arranged for determining the temperature of the reactions, or (ii) the parallel detector comprises spectrometers or chromatographs for simultaneously analyzing the reaction products or unreacted reactants of the reactions catalyzed by the plurality of candidate catalysts using spectroscopy or chromatography, respectively.
37. The apparatus of claim 36 wherein the parallel reactor further comprises a common support having reaction sites for the plurality of candidate catalysts formulations.
38. The apparatus of claim 36 wherein the parallel reactor comprises a plurality of candidate catalysts having differing compositions, a reaction chamber encasing the plurality of candidate catalysts, the reaction chamber being adapted such that the reaction chamber can be pressurized with a gas comprising one or more reactants to simultaneously contact the plurality of candidate catalysts under reaction conditions, and an infrared-transparent window in the reaction chamber, the infrared-transparent window and reactor chamber being adapted to allow for detection of infrared radiation emitted from the reaction catalyzed by each of the plurality of candidate catalysts through the infrared-transparent window during the course of a reaction to determine the relative efficacy of the plurality of candidate catalysts.
39. The apparatus of claim 36 wherein the apparatus further comprises a radiation source adapted for simultaneously irradiating a plurality of reaction products with radiation through the one or more radiation-transparent windows, and the detector is adapted for simultaneously determining radiation absorbed or emitted by a reaction product or unreacted reactant through the one or more radiation-transparent windows during the course of a reaction.
40. The apparatus of claim 39 wherein the parallel reactor comprises a plurality of reaction channels, each of the plurality of reaction channels comprising a different candidate catalyst, a first infrared-transparent window, and a second infrared-transparent window, the radiation source is adapted for simultaneously irradiating a plurality of reaction products with radiation through the first infrared-transparent window, and the detector is adapted for simultaneously determining radiation absorbed by a reaction product or unreacted reactant through the second infrared-transparent window during the course of a reaction to determine the relative efficacy of the plurality of candidate catalysts.
41. The apparatus of claim 40 wherein the radiation source is an infrared radiation source and the detector is an infrared-sensitive camera.
42. The apparatus of claim 39 wherein the radiation source is a. polarized light source adapted for simultaneously irradiating a plurality of reaction products with polarized light, and the detector comprises a polarizes for determining an angle of rotation of the polarized light during the course of a reaction to determine the relative efficacy of the plurality of candidate catalysts.
43. The apparatus of claim 42 further comprising a camera for simultaneously detecting the polarized light.
44. The apparatus of any one of claims 36 to 43 wherein the parallel reactor is a parallel batch reactor.
45. The apparatus of any one of claims 36 to 44 wherein the parallel reactor is a parallel flow reactor.
46. The apparatus of any one of claims 36 to 45 wherein the reactor is a parallel flow reactor further comprising a fluid distribution system for providing uniform flow of the reactant-containing stream through each of the plurality of reaction channels.
47. The apparatus of claim 36 or 39 wherein the parallel reactor is a parallel flow 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.
48. The apparatus of claim 36 wherein the reactor is a parallel flow reactor comprising the plurality of candidate catalysts, a plurality of reaction sites with each of the plurality of candidate catalysts being in its own reaction site, and a plurality of sampling tubes adapted to provide fluid communication between the plurality of reaction sites and a plurality of spectrometers or chromatographs for multistream detection of a reaction product or unreacted reactant in each of the plurality of discharged product-containing streams.
49. The apparatus of claim 36 wherein the reactor is a parallel flow reactor comprising the plurality of candidate catalysts, a plurality of reaction sites with each of the plurality of candidate catalysts being in its own reaction site, a plurality of tubes for sampling the product-containing streams of each of the plurality of reaction sites, and an arrangement of switching valves for introducing the plurality of product-containing streams into a plurality of spectrometers or chromatographs.
50. The apparatus of claim 36 wherein the reactor is a parallel flow reactor comprising an array of tubes for sampling the product-containing streams of each of the plurality of reaction sites, and means for physically scanning over the array of tubes to introduce the plurality of product-containing streams into a spectrometer or chromatograph.
51. The apparatus of any one of claims 36 to 50 wherein the reactor is adapted for providing reaction conditions that include a temperature greater than 100°C, and additionally, or alternatively, a pressure of greater than 1 bar.
52. The apparatus of any one of claims 36 to 51 wherein the parallel detector comprises an infrared-sensitive camera, Raman spectrometer, FTIR spectrometer, gas chromatograph or liquid chromatograph.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002465957A CA2465957A1 (en) | 1996-02-28 | 1997-02-25 | Catalyst testing process and apparatus |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1245796P | 1996-02-28 | 1996-02-28 | |
US60/012,457 | 1996-06-17 | ||
US08/664,836 US6063633A (en) | 1996-02-28 | 1996-06-17 | Catalyst testing process and apparatus |
US08/664,836 | 1996-06-17 | ||
PCT/US1997/002756 WO1997032208A1 (en) | 1996-02-28 | 1997-02-25 | Catalyst testing process and apparatus |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002465957A Division CA2465957A1 (en) | 1996-02-28 | 1997-02-25 | Catalyst testing process and apparatus |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2247259A1 CA2247259A1 (en) | 1997-09-04 |
CA2247259C true CA2247259C (en) | 2004-08-31 |
Family
ID=26683580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002247259A Expired - Fee Related CA2247259C (en) | 1996-02-28 | 1997-02-25 | Catalyst testing process and apparatus |
Country Status (8)
Country | Link |
---|---|
US (11) | US6063633A (en) |
EP (1) | EP0883806B2 (en) |
JP (1) | JP2000506265A (en) |
CN (1) | CN100430725C (en) |
AU (1) | AU1967997A (en) |
CA (1) | CA2247259C (en) |
DE (1) | DE69725429T3 (en) |
WO (1) | WO1997032208A1 (en) |
Families Citing this family (201)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6030917A (en) | 1996-07-23 | 2000-02-29 | Symyx Technologies, Inc. | Combinatorial synthesis and analysis of organometallic compounds and catalysts |
US6440745B1 (en) | 1994-10-18 | 2002-08-27 | Symyx Technologies | Combinatorial synthesis and screening of organometallic compounds and catalysts |
US7166470B2 (en) | 1994-10-18 | 2007-01-23 | Symyx Technologies, Inc. | Formation of combinatorial arrays of materials using solution-based methodologies |
US6419881B1 (en) | 1994-10-18 | 2002-07-16 | Symyx Technologies, Inc. | Combinatorial arrays of organometallic compounds and catalysts |
US5985356A (en) | 1994-10-18 | 1999-11-16 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
US6063633A (en) * | 1996-02-28 | 2000-05-16 | The University Of Houston | Catalyst testing process and apparatus |
US6738529B1 (en) | 1996-10-09 | 2004-05-18 | Symyx Technologies, Inc. | Analysis of chemical data from images |
US6720186B1 (en) | 1998-04-03 | 2004-04-13 | Symyx Technologies, Inc. | Method of research for creating and testing novel catalysts, reactions and polymers |
US6536944B1 (en) * | 1996-10-09 | 2003-03-25 | Symyx Technologies, Inc. | Parallel screen for rapid thermal characterization of materials |
DE69735411T2 (en) * | 1996-10-09 | 2006-09-07 | Symyx Technologies, Inc., Santa Clara | INFRARED SPECTROSCOPY AND LIBRARY IMAGING |
DE19642261A1 (en) * | 1996-10-11 | 1998-04-16 | Hoechst Ag | Method and device for detecting the catalytic activity of solids |
US6576906B1 (en) | 1999-10-08 | 2003-06-10 | Symyx Technologies, Inc. | Method and apparatus for screening combinatorial libraries for semiconducting properties |
GB2327754B (en) * | 1997-07-26 | 2000-03-15 | Johnson Matthey Plc | Improvements in catalyst testing |
PL339834A1 (en) * | 1997-10-10 | 2001-01-02 | Bp Chem Int Ltd | Radiant activation and screening of catalyst libraries for evaluation of catalysts and reactors therefor |
US6426226B1 (en) * | 1997-10-10 | 2002-07-30 | Laboratory Catalyst Systems Llc | Method and apparatus for screening catalyst libraries |
US6242262B1 (en) * | 1997-10-24 | 2001-06-05 | The University Of North Carolina At Chapel Hill | Method and apparatus for screening catalyst libraries |
DE19826303A1 (en) * | 1998-06-12 | 1999-12-16 | Studiengesellschaft Kohle Mbh | A method for the comparative determination of physically or chemically induced heat coloration using infrared camera imaging |
WO1999034206A1 (en) * | 1997-12-23 | 1999-07-08 | Studiengesellschaft Kohle Mbh | Method for combinatorial material development using differential thermal images |
DE19805719A1 (en) * | 1998-02-12 | 1999-08-19 | Basf Ag | Array of heterogeneous catalysts, or precursors, each arranged in separate channel, used to screen for activity, selectivity or long-term stability |
EP1054727A1 (en) * | 1998-02-12 | 2000-11-29 | Basf Aktiengesellschaft | Method for the combinatorial production and testing of heterogeneous catalysts |
DE19809477C2 (en) * | 1998-03-06 | 2002-04-11 | Hte Ag High Throughput Experim | Arrangement for testing the catalytic activity of solids exposed to a reaction gas |
DE19861355B4 (en) * | 1998-03-06 | 2007-02-08 | Hte Ag The High Throughput Experimentation Company | Catalyst test unit facilitates the simultaneous and sequential testing of a large number of solid material catalyst samples |
DE19861316B4 (en) * | 1998-03-06 | 2005-10-06 | Hte Ag The High Throughput Experimentation Company | Catalyst test unit facilitates the simultaneous and sequential testing of a large number of solid material catalyst samples |
US6406632B1 (en) | 1998-04-03 | 2002-06-18 | Symyx Technologies, Inc. | Rapid characterization of polymers |
DE19822077A1 (en) * | 1998-05-16 | 1999-11-18 | Studiengesellschaft Kohle Mbh | Preparation of library of spatially separted solids by wet-chemical methods on a removable reaction plate, used e.g. to screen for new catalysts or materials |
US6149882A (en) * | 1998-06-09 | 2000-11-21 | Symyx Technologies, Inc. | Parallel fixed bed reactor and fluid contacting apparatus |
KR20010052741A (en) * | 1998-06-12 | 2001-06-25 | 야마모토 카즈모토 | Analyzer |
DE19830607C2 (en) * | 1998-07-09 | 2002-08-01 | Hte Ag The High Throughput Exp | Process for the detection of a product in the downstream of a catalytic material of a variety of catalytic materials |
US6528026B2 (en) | 1998-08-13 | 2003-03-04 | Symyx Technologies, Inc. | Multi-temperature modular reactor and method of using same |
US6864092B1 (en) | 1998-08-13 | 2005-03-08 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6455316B1 (en) | 1998-08-13 | 2002-09-24 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6548026B1 (en) | 1998-08-13 | 2003-04-15 | Symyx Technologies, Inc. | Parallel reactor with internal sensing and method of using same |
US6306658B1 (en) * | 1998-08-13 | 2001-10-23 | Symyx Technologies | Parallel reactor with internal sensing |
US6410332B1 (en) | 1998-09-08 | 2002-06-25 | Symyx Technologies, Inc. | Sampling and analysis of reactions by trapping reaction components on a sorbent |
US6535284B1 (en) * | 1998-10-19 | 2003-03-18 | Symyx Technologies, Inc. | Rheo-optical indexer and method of screening and characterizing arrays of materials |
US6240790B1 (en) | 1998-11-09 | 2001-06-05 | Agilent Technologies, Inc. | Device for high throughout sample processing, analysis and collection, and methods of use thereof |
MXPA01004785A (en) * | 1998-11-12 | 2002-05-06 | Bp Chem Int Ltd | Method and apparatus for screening catalyst libraries. |
US6485692B1 (en) | 1998-12-04 | 2002-11-26 | Symyx Technologies, Inc. | Continuous feed parallel reactor |
EP1149282A2 (en) | 1998-12-18 | 2001-10-31 | Symyx Technologies, Inc. | Apparatus and method for characterizing libraries of different materials using x-ray scattering |
US7491677B2 (en) * | 1999-01-15 | 2009-02-17 | Basf Catalysts Llc | Combinatorial synthesis |
US6797516B1 (en) * | 1999-01-22 | 2004-09-28 | Thales Technologies Ag | Mass spectrometric screening of catalysts |
JP3997642B2 (en) * | 1999-02-24 | 2007-10-24 | トヨタ自動車株式会社 | Carbon monoxide concentration detection apparatus and carbon monoxide concentration detection method |
EP1129772A3 (en) * | 1999-03-03 | 2001-11-07 | Symyx Technologies, Inc. | Fluid distribution for chemical processing microsystems |
US6749814B1 (en) | 1999-03-03 | 2004-06-15 | Symyx Technologies, Inc. | Chemical processing microsystems comprising parallel flow microreactors and methods for using same |
US20020042140A1 (en) * | 1999-03-03 | 2002-04-11 | Alfred Hagemeyer | Methods for analysis of heterogeneous catalysts in a multi-variable screening reactor |
US7150994B2 (en) | 1999-03-03 | 2006-12-19 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
US6436292B1 (en) | 1999-04-02 | 2002-08-20 | Symyx Technologies, Inc. | Parallel high-performance liquid chromatography with post-separation treatment |
DE19918956A1 (en) * | 1999-04-27 | 2000-11-02 | Studiengesellschaft Kohle Mbh | Process for the automated investigation of catalytic and spectroscopic properties of the components of combinatorial libraries |
FR2795512B1 (en) * | 1999-06-28 | 2001-08-03 | Inst Francais Du Petrole | AUTOMATIC MULTI-REACTOR METHOD AND DEVICE FOR EVALUATING CATALYSTS WITH IN-LINE ANALYSIS WITHOUT LIQUID / GAS SEPARATION |
FR2795513B1 (en) * | 1999-06-28 | 2001-08-03 | Inst Francais Du Petrole | AUTOMATIC MULTI-REACTOR METHOD AND DEVICE FOR EVALUATING CATALYSTS WITH A HEAVY LOAD |
WO2001034660A2 (en) * | 1999-11-09 | 2001-05-17 | Sri International | Screening and analysis of polymers, specialty chemicals and catalysts using radiography |
AU1591301A (en) * | 1999-11-09 | 2001-06-06 | Sri International | Workstation, apparatus, and methods for the high-throughput synthesis, screeningand characterization of combinatorial libraries |
US7033840B1 (en) * | 1999-11-09 | 2006-04-25 | Sri International | Reaction calorimeter and differential scanning calorimeter for the high-throughput synthesis, screening and characterization of combinatorial libraries |
DE19959973A1 (en) * | 1999-12-13 | 2001-06-21 | Basf Ag | Process for combinatorial production and testing of heterogeneous catalysts |
DE19959974A1 (en) * | 1999-12-13 | 2001-06-21 | Basf Ag | Process for the production of material libraries by electrochemical deposition |
US6576196B1 (en) | 1999-12-15 | 2003-06-10 | Uop Llc | Multiple parallel catalytic reactor assembly |
US6627445B1 (en) * | 1999-12-15 | 2003-09-30 | Uop Llc | Process for simultaneously evaluating a plurality of catalysts |
US6342185B1 (en) * | 1999-12-15 | 2002-01-29 | Uop Llc | Combinatorial catalytic reactor |
US6776963B1 (en) | 1999-12-15 | 2004-08-17 | Uop Llc | Multiple parallel catalytic reactor assembly |
US6368865B1 (en) * | 1999-12-15 | 2002-04-09 | Uop Llc | Combinatorial process for performing catalytic chemical reactions |
US6770245B2 (en) * | 1999-12-15 | 2004-08-03 | Uop Llc | Multiple parallel processing assembly |
DE10004816A1 (en) | 2000-02-04 | 2001-08-09 | Hte Gmbh | Method and device for the combinatorial production and testing of material libraries using photoacoustic analysis methods |
ES2166310B1 (en) * | 2000-02-08 | 2003-10-16 | Univ Valencia Politecnica | AUTOMATIC DIPOSITIVE AND MULTIPLE CATALYTIC TEST METHOD |
US6627571B1 (en) * | 2000-03-01 | 2003-09-30 | Symyx Technologies, Inc. | Method and system for the situ synthesis of a combinatorial library of supported catalyst materials |
US6881585B1 (en) | 2000-03-06 | 2005-04-19 | General Electric Company | Method and apparatus for rapid screening of volatiles |
WO2001066245A2 (en) | 2000-03-07 | 2001-09-13 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
DE10012847A1 (en) * | 2000-03-16 | 2001-09-27 | Hte Gmbh | Combinatorial properties inspection method for building blocks of material libraries, e.g. catalyst, involves measuring different parameters of two building blocks by infrared thermography and mass spectrometry |
US7216113B1 (en) * | 2000-03-24 | 2007-05-08 | Symyx Technologies, Inc. | Remote Execution of Materials Library Designs |
US20010051376A1 (en) * | 2000-04-14 | 2001-12-13 | Jonker Robert Jan | Apparatus and method for testing samples of a solid material |
DE10019976A1 (en) * | 2000-04-24 | 2001-10-31 | Gwp Ges Fuer Werkstoffpruefung | Parallel preparation and testing of individual heterogeneous catalysts in multiple reactor comprises carrying out renewed preparation/testing |
US6994827B2 (en) * | 2000-06-03 | 2006-02-07 | Symyx Technologies, Inc. | Parallel semicontinuous or continuous reactors |
US20050048614A1 (en) * | 2000-06-13 | 2005-03-03 | Children's Medical Center Corporation | Biosynthetic oncolytic molecules and uses therefor |
US7078164B1 (en) | 2000-06-19 | 2006-07-18 | Symyx Technologies, Inc. | High throughput screen for identifying polymerization catalysts from potential catalysts |
AU2001273317A1 (en) | 2000-07-07 | 2002-01-21 | Symyx Technologies, Inc. | Methods for analysis of heterogeneous catalysts in a multi-variable screening reactor |
AU2001271747A1 (en) | 2000-07-08 | 2002-01-21 | Uop Llc | Method of screening compositions for electrocatalytic activity in a gas diffusion electrode |
WO2002004527A2 (en) * | 2000-07-11 | 2002-01-17 | Sri International | Encoding methods using up-converting phosphors for high-throughput screening of catalysts |
US7018589B1 (en) * | 2000-07-19 | 2006-03-28 | Symyx Technologies, Inc. | High pressure parallel reactor |
DE10036633B4 (en) * | 2000-07-27 | 2005-03-10 | Hte Ag The High Throughput Exp | Arrangement in a modular design and method for the parallel testing of a plurality of components of a material library |
US6701774B2 (en) * | 2000-08-02 | 2004-03-09 | Symyx Technologies, Inc. | Parallel gas chromatograph with microdetector array |
DE10038495A1 (en) * | 2000-08-08 | 2002-02-21 | Abb Research Ltd | Device for testing catalytic material comprises channels for testing elements coated with catalytic material |
AU2001283076A1 (en) * | 2000-08-14 | 2002-02-25 | Chevron U.S.A. Inc. | Use of microchannel reactors in combinatorial chemistry |
US6864091B1 (en) | 2000-08-31 | 2005-03-08 | Symyx Technologies, Inc. | Sampling probe |
DE10131581B4 (en) * | 2000-09-12 | 2008-04-03 | Robert Bosch Gmbh | Method and device for generating and checking composite arrangements |
AU2002212828A1 (en) * | 2000-10-13 | 2002-04-22 | Avantium International B.V. | Method and apparatus for screening of polycondensation catalysts |
DE10052511B4 (en) * | 2000-10-23 | 2005-12-29 | Henkel Kgaa | System for monitoring chemical reactions and its use |
US20020132360A1 (en) * | 2000-11-17 | 2002-09-19 | Flir Systems Boston, Inc. | Apparatus and methods for infrared calorimetric measurements |
US6821787B2 (en) * | 2000-11-17 | 2004-11-23 | Thermogenic Imaging, Inc. | Apparatus and methods for infrared calorimetric measurements |
US20040110301A1 (en) * | 2000-11-17 | 2004-06-10 | Neilson Andy C | Apparatus and methods for measuring reaction byproducts |
DE10059890A1 (en) * | 2000-12-01 | 2002-06-20 | Hte Ag | Method for producing a large number of building blocks of a material library |
DE10101118C2 (en) * | 2001-01-05 | 2002-12-19 | Inst Angewandte Chemie Berlin | Method for evaluating the performance of solid catalysts for a reaction network |
US7118917B2 (en) * | 2001-03-07 | 2006-10-10 | Symyx Technologies, Inc. | Parallel flow reactor having improved thermal control |
DE10118782A1 (en) * | 2001-04-18 | 2002-10-31 | Bosch Gmbh Robert | Catalyst testing process involves exposing catalyst emissions to radiation temperature detector in side-chamber |
US6844198B2 (en) | 2001-04-27 | 2005-01-18 | Uop Llc | Adsorptive method for determining a surface property of a solid |
US6808928B1 (en) | 2001-04-27 | 2004-10-26 | Uop Llc | Desorptive method for determining a surface property of a solid |
US20040197920A1 (en) * | 2001-04-27 | 2004-10-07 | Swenson Lasalle R. | Desorptive method for determining a surface property of a solid |
US20070092974A1 (en) * | 2001-04-27 | 2007-04-26 | Swenson Lasalle R | Desorptive Method for Determining a Surface Property of a Solid |
US20020197732A1 (en) * | 2001-06-20 | 2002-12-26 | Carnahan James Claude | Method and apparatus for combinatorial screening of polymer compositions |
US6838052B2 (en) | 2001-06-29 | 2005-01-04 | Symyx Technologies, Inc. | In-situ injection and materials screening device |
DE10132252B4 (en) * | 2001-07-04 | 2007-04-19 | Basf Ag | Device for carrying out catalytic tests |
US6923939B1 (en) * | 2001-07-05 | 2005-08-02 | Uop Llc | Heat activated membrane introduction apparatus and method for screening materials |
US20030012700A1 (en) * | 2001-07-11 | 2003-01-16 | Carnahan James Claude | Systems and methods for parallel testing of catalyst performance |
DE10143517A1 (en) * | 2001-09-05 | 2003-03-27 | Hte Ag The High Throughput Exp | Analysis of fluid medium for, e.g. determining performance properties of building blocks of material libraries, by guiding fluid medium on microsensors, and monitoring the microsensors regarding change of properties |
US7390463B2 (en) * | 2001-09-07 | 2008-06-24 | Corning Incorporated | Microcolumn-based, high-throughput microfluidic device |
US6808685B2 (en) | 2001-09-17 | 2004-10-26 | Uop Llc | Apparatus and method for generating a plurality of isolated effluents |
US20030064006A1 (en) * | 2001-10-02 | 2003-04-03 | Carnahan James Claude | Methods and systems for sealed parallel reactions |
US6673237B2 (en) | 2001-11-28 | 2004-01-06 | Corning Incorporated | High performance monolith treater for gasoline upgrade |
US20030141253A1 (en) * | 2001-12-07 | 2003-07-31 | Bihan Thierry Le | Apparatus for efficient liquid chromatography/mass spectrometry processing |
DE10209177A1 (en) * | 2002-03-01 | 2003-09-18 | Studiengesellschaft Kohle Mbh | A high-throughput screening method to determine the enantioselectivity of catalysts, biocatalysts and agents |
US20030173205A1 (en) | 2002-03-12 | 2003-09-18 | Arne Karlsson | Process vessel with integral evaporator |
US7063982B1 (en) | 2002-03-12 | 2006-06-20 | Uop Llc | Process of vaporizing and reacting a liquid feed |
US6989131B2 (en) | 2002-03-12 | 2006-01-24 | Uop Llc | Catalytic reactor with integral evaporator |
US6949267B2 (en) | 2002-04-08 | 2005-09-27 | Engelhard Corporation | Combinatorial synthesis |
US7122159B2 (en) * | 2002-04-29 | 2006-10-17 | Symyx Technologies, Inc. | High pressure parallel reactor with individually sealable vessels |
GB0210237D0 (en) * | 2002-05-03 | 2002-06-12 | Bp Chem Int Ltd | Injector system |
US20030219363A1 (en) * | 2002-05-17 | 2003-11-27 | Kobylecki Ryszard J. | Examining chemical reactions |
US20030224105A1 (en) * | 2002-05-30 | 2003-12-04 | Symyx Technologies, Inc. | Apparatus and methods for forming films on substrates |
US20040071888A1 (en) * | 2002-05-30 | 2004-04-15 | Symyx Technologies, Inc. | Apparatus and method of research for creating and testing thin films |
DE10225994B3 (en) * | 2002-06-12 | 2004-03-11 | Robert Bosch Gmbh | Device and method for testing numerous, different material samples |
US20040002162A1 (en) * | 2002-06-27 | 2004-01-01 | Leugers Mary Anne | Transmission infrared spectroscopy array and method |
ES2199080B1 (en) * | 2002-07-16 | 2005-02-16 | Universidad Politecnica De Valencia | ROTARY SUPPORT AND APPARATUS FOR SPECTROSCOPIC MULTIPLE CHARACTERIZATION OF SAMPLES OF SOLID MATERIALS. |
EP1386664B1 (en) * | 2002-07-31 | 2016-05-11 | Ineos Technologies (Vinyls) Limited | A hollow parallelepiped pellet suitable as carrier of catalysts for selective exothermic reactions |
US20040033609A1 (en) * | 2002-08-13 | 2004-02-19 | Hai-Ying Chen | Catalyst testing method |
US7141217B2 (en) | 2002-12-05 | 2006-11-28 | Uop Llc | Elevated pressure apparatus and method for generating a plurality of isolated effluents |
US7160513B2 (en) * | 2002-12-20 | 2007-01-09 | Symyx Technologies, Inc. | Batch reactor with injection system |
US7267987B2 (en) * | 2003-01-06 | 2007-09-11 | Uop Llc | Process and assembly for simultaneously evaluating a plurality of catalysts |
US20040136873A1 (en) * | 2003-01-09 | 2004-07-15 | Argonaut Technologies, Inc. | Modular reactor system |
US20040232075A1 (en) * | 2003-01-31 | 2004-11-25 | Jason Wells | Microfiltration device and method for washing and concentrating solid particles |
US7134459B2 (en) * | 2003-06-12 | 2006-11-14 | Symyx Technologies, Inc. | Methods and apparatus for mixing powdered samples |
US6805175B1 (en) | 2003-06-12 | 2004-10-19 | Symyx Technologies, Inc. | Powder transfer method and apparatus |
US7255474B2 (en) | 2003-07-28 | 2007-08-14 | Symyx Technologies, Inc. | Parallel infrared spectroscopy apparatus and method |
CA2537271A1 (en) * | 2003-08-28 | 2005-03-17 | Teva Pharmaceutical Industries, Ltd. | Process for preparation of rosuvastatin calcium |
WO2005040739A2 (en) * | 2003-10-22 | 2005-05-06 | Softmax, Inc. | System and method for spectral analysis |
US7745161B2 (en) * | 2003-12-19 | 2010-06-29 | Palo Alto Research Center Incorporated | Amplification of enzymatic reactions for use with an enthalpy array |
FR2865821B1 (en) * | 2004-01-30 | 2006-07-21 | Novalyst Discovery | USEFUL PROCESS FOR CHARACTERIZING THE CATALYTIC REACTIVITY OF CATALYST (S) |
AU2005234067A1 (en) * | 2004-04-14 | 2005-10-27 | Catalyst Design, Inc. | Smart combinatorial operando spectroscopy catalytic system |
US7589041B2 (en) | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
MX2007003084A (en) | 2004-09-15 | 2007-05-16 | Bp Oil Int | Process for evaluating a refinery feedstock. |
US8882914B2 (en) * | 2004-09-17 | 2014-11-11 | Intermolecular, Inc. | Processing substrates using site-isolated processing |
US20060292846A1 (en) * | 2004-09-17 | 2006-12-28 | Pinto Gustavo A | Material management in substrate processing |
US20060060301A1 (en) * | 2004-09-17 | 2006-03-23 | Lazovsky David E | Substrate processing using molecular self-assembly |
US7749881B2 (en) * | 2005-05-18 | 2010-07-06 | Intermolecular, Inc. | Formation of a masking layer on a dielectric region to facilitate formation of a capping layer on electrically conductive regions separated by the dielectric region |
US8084400B2 (en) * | 2005-10-11 | 2011-12-27 | Intermolecular, Inc. | Methods for discretized processing and process sequence integration of regions of a substrate |
US7390739B2 (en) * | 2005-05-18 | 2008-06-24 | Lazovsky David E | Formation of a masking layer on a dielectric region to facilitate formation of a capping layer on electrically conductive regions separated by the dielectric region |
US7879710B2 (en) * | 2005-05-18 | 2011-02-01 | Intermolecular, Inc. | Substrate processing including a masking layer |
WO2006058034A2 (en) * | 2004-11-22 | 2006-06-01 | Intermolecular, Inc. | Molecular self-assembly in substrate processing |
WO2006073117A1 (en) * | 2005-01-07 | 2006-07-13 | Kyoto University | Optical sensor and process for producing the same |
GB0501102D0 (en) | 2005-01-19 | 2005-02-23 | Bp Chem Int Ltd | Process |
WO2007008151A1 (en) * | 2005-07-08 | 2007-01-18 | Portendo Ab | Sensor structures, methods of manufacturing them and detectors including sensor structures |
US7544574B2 (en) * | 2005-10-11 | 2009-06-09 | Intermolecular, Inc. | Methods for discretized processing of regions of a substrate |
US7955436B2 (en) * | 2006-02-24 | 2011-06-07 | Intermolecular, Inc. | Systems and methods for sealing in site-isolated reactors |
US8776717B2 (en) * | 2005-10-11 | 2014-07-15 | Intermolecular, Inc. | Systems for discretized processing of regions of a substrate |
WO2007071575A1 (en) * | 2005-12-21 | 2007-06-28 | Tecan Trading Ag | Method and device for checking whether a liquid transfer has been successful |
US8772772B2 (en) * | 2006-05-18 | 2014-07-08 | Intermolecular, Inc. | System and method for increasing productivity of combinatorial screening |
KR101388389B1 (en) * | 2006-02-10 | 2014-04-22 | 인터몰레큘러 인코퍼레이티드 | Method and apparatus for combinatorially varying materials, unit process and process sequence |
EP1842587A1 (en) * | 2006-04-03 | 2007-10-10 | Sika Technology AG | The use of infrared thermography as a means for determining the hardening behaviour of a two-component composition |
EP2104755A4 (en) | 2006-10-26 | 2011-01-12 | Symyx Solutions Inc | High pressure parallel fixed bed reactor and method |
ES2319007B1 (en) * | 2006-12-07 | 2010-02-16 | Rive Technology, Inc. | METHODS FOR MANUFACTURING MESOSTRUCTURED ZEOLITICAL MATERIALS. |
US8011317B2 (en) * | 2006-12-29 | 2011-09-06 | Intermolecular, Inc. | Advanced mixing system for integrated tool having site-isolated reactors |
DE102007005618A1 (en) * | 2007-01-31 | 2008-08-07 | Institut für Automation und Kommunikation (ifak) e. V. Magdeburg | Device and method for determining the amount of substance in small cavities |
WO2008140874A1 (en) * | 2007-05-09 | 2008-11-20 | Dow Global Technologies Inc. | System and method for high-throughput turbidity measurements |
US7807109B2 (en) | 2007-05-14 | 2010-10-05 | Freeslate, Inc. | Parallel batch reactor with pressure monitoring |
US7655191B2 (en) * | 2007-05-14 | 2010-02-02 | Symyx Solutions, Inc. | Methods for chemical reactions in a parallel batch reactor |
US20080286170A1 (en) * | 2007-05-14 | 2008-11-20 | Symyx Technologies, Inc. | Parallel batch reactor |
US7960313B2 (en) * | 2007-06-14 | 2011-06-14 | Intermolecular, Inc. | Combinatorial processing including stirring |
ATE490457T1 (en) * | 2007-06-15 | 2010-12-15 | Bp Chem Int Ltd | METHOD FOR ONLINE ANALYSIS OF A GAS PHASE PROCESS STREAM |
US20090046535A1 (en) | 2007-07-25 | 2009-02-19 | Carlson Eric D | Systems and methods for mixing materials |
US7785172B2 (en) * | 2007-08-14 | 2010-08-31 | Intermolecular, Inc. | Combinatorial processing including rotation and movement within a region |
US8206498B2 (en) * | 2007-10-25 | 2012-06-26 | Rive Technology, Inc. | Methods of recovery of pore-forming agents for mesostructured materials |
US9044774B2 (en) * | 2007-12-18 | 2015-06-02 | Intermolecular, Inc. | Vented combinatorial processing cell |
US8884237B2 (en) * | 2008-02-12 | 2014-11-11 | Nova Scientific, Inc. | Neutron detection |
US8586801B2 (en) * | 2008-09-04 | 2013-11-19 | Albemarle Corporation | Cobalt-molybdenum sulfide catalyst materials and methods for stable alcohol production from syngas |
US20100127022A1 (en) * | 2008-11-21 | 2010-05-27 | Symyx Technologies, Inc. | Dispensing valve |
US8926317B2 (en) * | 2008-12-15 | 2015-01-06 | Exxonmobil Research And Engineering Company | System and method for controlling fired heater operations |
US8524625B2 (en) | 2009-01-19 | 2013-09-03 | Rive Technology, Inc. | Compositions and methods for improving the hydrothermal stability of mesostructured zeolites by rare earth ion exchange |
US8486369B2 (en) | 2009-01-19 | 2013-07-16 | Rive Technology, Inc. | Introduction of mesoporosity in low Si/Al zeolites |
US8563325B1 (en) | 2009-09-29 | 2013-10-22 | Sandia Corporation | Coaxial microreactor for particle synthesis |
US8685875B2 (en) | 2009-10-20 | 2014-04-01 | Rive Technology, Inc. | Methods for enhancing the mesoporosity of zeolite-containing materials |
DE202010001754U1 (en) * | 2010-02-02 | 2011-06-09 | Süd-Chemie AG, 80333 | Device for identifying empty and partially filled tubes of a tube bundle reactor |
US20110231966A1 (en) * | 2010-03-17 | 2011-09-22 | Ali Passian | Scanning probe microscopy with spectroscopic molecular recognition |
US8448261B2 (en) * | 2010-03-17 | 2013-05-21 | University Of Tennessee Research Foundation | Mode synthesizing atomic force microscopy and mode-synthesizing sensing |
GB201008716D0 (en) * | 2010-05-25 | 2010-07-07 | Whitley Don Scient Ltd | System and method for monitoring the atmoshpere of an anaerobic workstation |
US8080796B1 (en) * | 2010-06-30 | 2011-12-20 | Ut-Battelle, Llc | Standoff spectroscopy using a conditioned target |
WO2012052149A2 (en) * | 2010-10-22 | 2012-04-26 | Hte Aktiengesellschaft | Device and method for testing catalysts with variable process pressure adjustment |
AU2012240093B2 (en) | 2011-04-08 | 2015-06-11 | W. R. Grace & Co.-Conn. | Mesoporous framework-modified zeolites |
US9376324B2 (en) | 2012-01-13 | 2016-06-28 | Rive Technology, Inc. | Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment |
CN103930369A (en) | 2012-01-13 | 2014-07-16 | 瑞弗科技有限公司 | Introduction of mesoporosity into low silica zeolites |
US9068954B1 (en) * | 2012-03-28 | 2015-06-30 | Catalytic Combustion Corporation | Monolith catalyst test system and method for its use |
US9562880B1 (en) | 2012-03-28 | 2017-02-07 | Catalytic Combustion Corporation | Monolith catalyst test system and method for its use |
US8663397B1 (en) | 2012-10-22 | 2014-03-04 | Intermolecular, Inc. | Processing and cleaning substrates |
US8765660B1 (en) | 2013-03-08 | 2014-07-01 | Rive Technology, Inc. | Separation of surfactants from polar solids |
GB2511772B (en) | 2013-03-12 | 2019-01-30 | Ceramex Ltd | Testing catalytic efficiency of an exhaust component |
US9662640B2 (en) | 2013-12-27 | 2017-05-30 | Rive Technology, Inc. | Introducing mesoporosity into zeolite materials with a modified acid pre-treatment step |
FR3017058B1 (en) * | 2014-02-06 | 2017-08-18 | Centre Nat Rech Scient | DEVICE FOR EVALUATING AT LEAST ONE PERFORMANCE CRITERION OF HETEROGENEOUS CATALYSTS |
CN107001056B (en) | 2014-12-11 | 2019-04-02 | 瑞弗科技有限公司 | Mesoporous zeolite is prepared with the processing of reduction |
CN104483442A (en) * | 2014-12-16 | 2015-04-01 | 河北盛华化工有限公司 | Evaluation device and evaluation method of acetylene hydrochlorination reaction catalyst |
US10626019B2 (en) | 2014-12-30 | 2020-04-21 | W. R. Grace & Co.-Conn. | Methods for preparing zeolites with surfactant-templated mesoporosity and tunable aluminum content |
WO2016205495A1 (en) * | 2015-06-16 | 2016-12-22 | Multicore Photonics, Inc. | System and method for determining one or more fluid concentrations in a fluid stream |
CA3065774A1 (en) * | 2017-06-02 | 2018-12-06 | Univation Technologies, Llc | Method of determining a relative decrease in catalytic efficacy of a catalyst in a catalyst solution |
CN110927326A (en) * | 2019-12-06 | 2020-03-27 | 潍柴动力股份有限公司 | Method and device for predicting desulfurization catalyst failure time |
EP3961195A1 (en) * | 2020-08-28 | 2022-03-02 | Siemens Aktiengesellschaft | Measuring device for determining the calorific value of a hydrocarbon-containing fuel gas |
WO2023163965A1 (en) * | 2022-02-22 | 2023-08-31 | Northwestern University | Reactive thin film coatings on catalyst libraries for high throughput screening |
Family Cites Families (174)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE160855C (en) * | ||||
DE234941C (en) * | ||||
US2604438A (en) * | 1949-05-23 | 1952-07-22 | Shell Dev | Catalytic dehydrogenation of hydrocarbon oils |
US2947163A (en) * | 1956-03-20 | 1960-08-02 | Robert L Stone | Material testing apparatus and method |
US2896442A (en) * | 1956-07-02 | 1959-07-28 | Florent H Bailly | Mineralogical analysis |
US3010880A (en) | 1959-05-08 | 1961-11-28 | Media Inc | Device for determining bacterial sensitivities |
US3227522A (en) | 1961-09-19 | 1966-01-04 | Ankh Lab Inc | Assaying apparatus |
US3283560A (en) * | 1962-12-24 | 1966-11-08 | Du Pont | Differential thermal analysis apparatus |
US3339398A (en) * | 1964-03-30 | 1967-09-05 | Chevron Res | High sensitivity differential thermal analysis apparatus and method |
US3536452A (en) | 1965-04-21 | 1970-10-27 | Marathon Oil Co | Multiple reactor apparatus |
US3537294A (en) * | 1965-06-25 | 1970-11-03 | Tracor | Differential thermal analysis |
CH430663A (en) * | 1966-05-25 | 1967-02-28 | Lonza Ag | Reactor for catalytic gas reactions |
US3431077A (en) * | 1966-07-18 | 1969-03-04 | Joseph D Danforth | Analytical apparatus |
US3441383A (en) * | 1966-10-26 | 1969-04-29 | Francis C Moore | Multiple cup tray |
DE1547277A1 (en) * | 1967-03-13 | 1969-12-18 | Euratom | Microscope heating table for precision measurements |
US3474004A (en) | 1967-09-21 | 1969-10-21 | Aaron J Fink | Disposable culture device |
US3429944A (en) * | 1967-12-27 | 1969-02-25 | Universal Oil Prod Co | Preparation of normal mono-olefins |
CA849014A (en) * | 1968-10-25 | 1970-08-11 | Ichikawa Yataro | Apparatus for continuous gas-liquid contact and process for refining crude terephthalic acid |
GB1306365A (en) * | 1969-05-21 | 1973-02-07 | ||
US3609296A (en) * | 1970-03-27 | 1971-09-28 | Fuel Engineering | Electrically heated autoclave apparatus |
SE384271B (en) | 1971-01-07 | 1976-04-26 | J Guigan | LIQUID DISTRIBUTION DEVICE FOR SAME DISTRIBUTION OF CALIBRATED QUANTITIES OF A LIQUID TO SECONDARY CONTAINERS |
US3812254A (en) | 1971-06-25 | 1974-05-21 | Ppg Industries Inc | Control of pythium spp.and sclerotium spp.using azides |
US3760831A (en) | 1971-11-01 | 1973-09-25 | Ford Motor Co | Gas flow control system for an analytical instrument |
US3819490A (en) | 1971-12-08 | 1974-06-25 | E Klingstrom | Testing device for use when making bacteriological tests |
US3881872A (en) | 1972-08-15 | 1975-05-06 | Jeol Ltd | Automatic analyzing device |
US3933044A (en) * | 1973-03-15 | 1976-01-20 | Chevron Research Company | Method and apparatus for monitoring temperatures during catalytic regeneration |
US3919589A (en) | 1973-04-06 | 1975-11-11 | Rca Corp | Electroluminescent cell with a current-limiting layer of high resistivity |
US3944826A (en) | 1973-07-19 | 1976-03-16 | Applied Research Laboratories Limited | Methods and apparatus for analyzing mixtures |
FR2245249A5 (en) * | 1973-09-25 | 1975-04-18 | Erap Elf Entr Rech Activ Petro | |
NL7403568A (en) * | 1974-03-18 | 1975-09-22 | Stamicarbon | Fluidised bed reactor temperature control - by monitoring the infra-red emission with a television camera |
DE2414888C2 (en) * | 1974-03-27 | 1983-08-25 | Siemens AG, 1000 Berlin und 8000 München | Device for temperature measurement |
JPS521916B2 (en) * | 1974-09-20 | 1977-01-18 | ||
US3948213A (en) * | 1974-10-21 | 1976-04-06 | Universal Oil Products Company | Coating-impregnating chamber for catalyst support members |
GB1528192A (en) * | 1975-03-10 | 1978-10-11 | Secr Defence | Surface treatment of iii-v compound crystals |
US4342407A (en) | 1975-07-11 | 1982-08-03 | Dynatech Laboratories, Incorporated | Liquid dispensing apparatus |
US4021898A (en) * | 1976-05-20 | 1977-05-10 | Timex Corporation | Method of adjusting the frequency of vibration of piezoelectric resonators |
US4099923A (en) * | 1977-01-17 | 1978-07-11 | The Standard Oil Company | Automatic catalytic screening unit |
US4195131A (en) * | 1977-03-09 | 1980-03-25 | Papas Gary R | Environmentally controlled unit |
US4200614A (en) * | 1978-02-17 | 1980-04-29 | National Distillers And Chemical Corporation | Turbine mixer |
US4325914A (en) * | 1980-09-02 | 1982-04-20 | Autoclave Engineers, Inc. | Laboratory pressure vessel |
US4521975A (en) * | 1981-05-04 | 1985-06-11 | Marquest Medical Products, Inc. | Lyophilizing and forming biologicals having a predetermined unit dosage |
US4399361A (en) * | 1981-05-29 | 1983-08-16 | Rca Corporation | Device for multisample infrared analysis of materials in microgram quantity |
US4391780A (en) * | 1981-07-06 | 1983-07-05 | Beckman Instruments, Inc. | Container for sample testing |
US4496698A (en) * | 1982-07-26 | 1985-01-29 | The Dow Chemical Company | Process for producing polyethylene having constant physical and chemical properties |
IT1192490B (en) * | 1982-08-10 | 1988-04-13 | Diesse Diagnostica Senese Srl | APPARATUS FOR THE DETERMINATION OF THE SPEED OF ERITROSEDIMENTATION OF THE BLOOD (ESR) ON A MULTIPLE OF SAMPLES |
US4877584A (en) * | 1982-09-10 | 1989-10-31 | Yates Jr John T | Temperature programmed spectroscopy techniques |
JPS59178358A (en) * | 1983-03-29 | 1984-10-09 | Hiroyoshi Inoue | Tester of performance of catalyst |
JPS6010890A (en) * | 1983-06-29 | 1985-01-21 | Fujitsu Ltd | Picture display system |
US4598049A (en) * | 1983-08-31 | 1986-07-01 | Systec Inc. | General purpose gene synthesizer |
US5106756A (en) | 1984-03-02 | 1992-04-21 | The United States Of America As Represented By The United States Department Of Energy | Method and system for gathering a library of response patterns for sensor arrays |
DE3565986D1 (en) | 1984-05-02 | 1988-12-08 | Brendan James Hamill | An apparatus for the chemical synthesis of oligonucleotides |
US4945079A (en) * | 1984-11-13 | 1990-07-31 | Aluminum Company Of America | Catalyst of nickel and molybdenum supported on alumina |
US4626412A (en) * | 1984-12-14 | 1986-12-02 | Monsanto Company | Method and apparatus for carrying out catalyzed chemical reactions and for studying catalysts |
US5009849A (en) * | 1984-12-14 | 1991-04-23 | Monsanto Company | Apparatus for carrying out catalyzed chemical reactions and for studying catalysis |
GB8500294D0 (en) * | 1985-01-07 | 1985-02-13 | Martin W J | Automatic chemistry machine |
US5045916A (en) | 1985-01-22 | 1991-09-03 | Fairchild Semiconductor Corporation | Extended silicide and external contact technology |
DD234942A1 (en) * | 1985-02-28 | 1986-04-16 | Leuna Werke Veb | METHOD AND ARRANGEMENT FOR CATALYST ACTIVITY DETERMINATION |
DD234941A1 (en) * | 1985-02-28 | 1986-04-16 | Leuna Werke Veb | METHOD AND ARRANGEMENT FOR CATALYST ACTIVITY DETERMINATION |
DE3631862A1 (en) * | 1986-09-19 | 1988-03-31 | Strahlen Umweltforsch Gmbh | DEVICE FOR ANALYTICAL DETERMINATION OF ORGANIC SUBSTANCES |
US4670404A (en) * | 1985-04-22 | 1987-06-02 | Fike Corporation | Micro-scale chemical process simulation methods and apparatus useful for design of full scale processes, emergency relief systems and associated equipment |
US4653935A (en) * | 1985-05-13 | 1987-03-31 | Daily Jeffrey N | Thermocouple containment chamber |
GB2176932A (en) | 1985-05-28 | 1987-01-07 | Agricultural Genetics Co | Sample plate for immunosorbent electron microscopy |
US4682890A (en) * | 1985-05-31 | 1987-07-28 | Health Research, Incorporated | Microsample holder and carrier therefor |
EP0207537B1 (en) | 1985-06-28 | 1993-01-13 | Shell Internationale Researchmaatschappij B.V. | Chromatographic analyzer |
US4676951A (en) * | 1985-07-01 | 1987-06-30 | American Hospital Supply Corp. | Automatic specimen analyzing system |
JPH0619311B2 (en) | 1985-10-19 | 1994-03-16 | 株式会社堀場製作所 | Gas analyzer for multi-component simultaneous measurement |
US5104621A (en) * | 1986-03-26 | 1992-04-14 | Beckman Instruments, Inc. | Automated multi-purpose analytical chemistry processing center and laboratory work station |
GB2194847A (en) | 1986-09-05 | 1988-03-16 | Marconi Co Ltd | Image converter |
US4895706A (en) * | 1986-10-28 | 1990-01-23 | Costar Corporation | Multi-well filter strip and composite assemblies |
US5198401A (en) | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5306411A (en) | 1989-05-25 | 1994-04-26 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
US5364765A (en) | 1987-05-28 | 1994-11-15 | Abbott William A | Method and reagent system for assaying isoenzyme profiles |
DE3722680A1 (en) * | 1987-07-09 | 1989-01-19 | Leybold Ag | Melting furnace with weight-dependent control of the melting block |
US5011663A (en) * | 1987-07-22 | 1991-04-30 | S E A C S.R.L. | Multitest-tube for clinical chemistry analysis for several simultaneous tests |
US5011779A (en) * | 1988-01-21 | 1991-04-30 | Long Island Jewish Medical Center | Apparatus for rapid deposition of test samples on an absorbent support |
US5035866A (en) | 1988-02-16 | 1991-07-30 | Wannlund Jon C | Luminescence reaction test apparatus |
EP0342155A3 (en) * | 1988-05-13 | 1990-06-27 | Agrogen-Stiftung | Laboratory device for optional heating and cooling |
SE8802403D0 (en) | 1988-06-28 | 1988-06-28 | Pharmacia Ab | MUST BE USED IN EXCLUSIVE EPIC TESTING TO PAVISA CONTACT ALERGY |
AU3869289A (en) | 1988-07-14 | 1990-02-05 | Baylor College Of Medicine | Solid phase assembly and reconstruction of biopolymers |
US5281540A (en) | 1988-08-02 | 1994-01-25 | Abbott Laboratories | Test array for performing assays |
US5240604A (en) | 1988-09-13 | 1993-08-31 | The Dow Chemical Company | Multidimensional chromatographic system |
US4865986A (en) * | 1988-10-06 | 1989-09-12 | Coy Corporation | Temperature control apparatus |
US5024992A (en) | 1988-10-28 | 1991-06-18 | The Regents Of The University Of California | Preparation of highly oxidized RBa2 Cu4 O8 superconductors |
US5215889A (en) | 1988-11-18 | 1993-06-01 | The Regents Of The University Of California | Catalytic and reactive polypeptides and methods for their preparation and use |
US4967084A (en) * | 1989-02-02 | 1990-10-30 | The University Of Michigan | Multi-sample scintillation counter using position-sensitive detector |
US5053454A (en) * | 1989-02-15 | 1991-10-01 | Sri International | Multiple polymer synthesizer |
US4924923A (en) * | 1989-05-17 | 1990-05-15 | Vernay Laboratories, Inc. | Fuel filler pipe seal |
US4990076A (en) * | 1989-05-31 | 1991-02-05 | Halliburton Company | Pressure control apparatus and method |
US5424186A (en) | 1989-06-07 | 1995-06-13 | Affymax Technologies N.V. | Very large scale immobilized polymer synthesis |
US5744101A (en) | 1989-06-07 | 1998-04-28 | Affymax Technologies N.V. | Photolabile nucleoside protecting groups |
US5143854A (en) | 1989-06-07 | 1992-09-01 | Affymax Technologies N.V. | Large scale photolithographic solid phase synthesis of polypeptides and receptor binding screening thereof |
IL90970A (en) | 1989-07-13 | 1993-07-08 | Univ Ramot | Mass spectrometer method and apparatus for analyzing materials |
US4990312A (en) * | 1989-07-18 | 1991-02-05 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | High-pressure promoted combustion chamber |
US4996387A (en) | 1989-07-20 | 1991-02-26 | Phillips Petroleum Company | Dehydrogenation process |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US5198670A (en) * | 1989-09-29 | 1993-03-30 | Packard Instrument Company | Scintillation counting system for in-situ measurement of radioactive samples in a multiple-well plate |
JPH0650460B2 (en) * | 1989-10-17 | 1994-06-29 | アプライド バイオシステムズ インコーポレイテッド | Robot interface |
US5277871A (en) | 1989-10-20 | 1994-01-11 | Hitachi, Ltd. | Liquid chromatographic analyzer, sample feeder and prelabeling reaction treating method |
US5108928A (en) | 1989-11-13 | 1992-04-28 | General Dynamics Corporation | Method and apparatus for delivering a sample to multiple analytical instruments |
GB8928917D0 (en) | 1989-12-21 | 1990-02-28 | Vg Instr Group | Method and apparatus for surface analysis |
CA2031912A1 (en) * | 1989-12-22 | 1991-06-23 | Robert Fred Pfost | Heated cover device |
US5288644A (en) * | 1990-04-04 | 1994-02-22 | The Rockefeller University | Instrument and method for the sequencing of genome |
WO1991016675A1 (en) * | 1990-04-06 | 1991-10-31 | Applied Biosystems, Inc. | Automated molecular biology laboratory |
US5205845A (en) | 1990-09-28 | 1993-04-27 | The Regents Of The University Of Michigan | Mechanical gas chromatography injection valves and column multiplexing techniques |
ATE130209T1 (en) | 1990-10-09 | 1995-12-15 | Dow Chemical Co | MULTIDIMENSIONAL ON-LINE CHROMATOGRAPHY SYSTEM FOR SUPERCRITICAL FLUID CHROMATOGRAPHY. |
KR100236506B1 (en) * | 1990-11-29 | 2000-01-15 | 퍼킨-엘머시터스인스트루먼츠 | Apparatus for polymerase chain reaction |
DE4038829A1 (en) * | 1990-12-05 | 1992-06-11 | Emitec Emissionstechnologie | DETERMINATION OF A REACTION ZONE IN A CATALYST |
ES2155822T3 (en) | 1990-12-06 | 2001-06-01 | Affymetrix Inc | COMPOUNDS AND ITS USE IN A BINARY SYNTHESIS STRATEGY. |
AU9172991A (en) | 1990-12-07 | 1992-07-08 | Cnc Development, Inc. | Catalytic chemical reactor |
US5262130A (en) | 1990-12-07 | 1993-11-16 | Baker Hughes Inc. | Fixed bed chemical reactor |
ATE135358T1 (en) | 1990-12-27 | 1996-03-15 | Exxon Chemical Patents Inc | TRANSITION METAL AMIDE COMPOUND AND CATALYST SYSTEM FOR PRODUCING ISOTACTIC PROPYLENE |
US5077470A (en) | 1991-01-11 | 1991-12-31 | Jeol Ltd. | Mass spectrometer |
US5190734A (en) * | 1991-02-22 | 1993-03-02 | Frushour Robert H | Modified end assembly for high pressure, high temperature reaction vessels |
US5246665A (en) * | 1991-06-03 | 1993-09-21 | Abbott Laboratories | Heat and air flow control for assay carrier |
US5200023A (en) | 1991-08-30 | 1993-04-06 | International Business Machines Corp. | Infrared thermographic method and apparatus for etch process monitoring and control |
US5294198A (en) | 1991-10-01 | 1994-03-15 | Cincinnati Electronics Corporation | Infrared inspection system and method employing emissivity indications |
IL103674A0 (en) | 1991-11-19 | 1993-04-04 | Houston Advanced Res Center | Method and apparatus for molecule detection |
US5412087A (en) | 1992-04-24 | 1995-05-02 | Affymax Technologies N.V. | Spatially-addressable immobilization of oligonucleotides and other biological polymers on surfaces |
US5384261A (en) | 1991-11-22 | 1995-01-24 | Affymax Technologies N.V. | Very large scale immobilized polymer synthesis using mechanically directed flow paths |
AU675054B2 (en) | 1991-11-22 | 1997-01-23 | Affymetrix, Inc. | Combinatorial strategies for polymer synthesis |
FI915731A0 (en) * | 1991-12-05 | 1991-12-05 | Derek Henry Potter | FOERFARANDE OCH ANORDNING FOER REGLERING AV TEMPERATUREN I ETT FLERTAL PROV. |
US5183564A (en) * | 1991-12-05 | 1993-02-02 | Hong Chin Chen | Stirring device for facilitating dialysis |
US5344236A (en) | 1992-01-23 | 1994-09-06 | Fishman Iiya M | Method for evaluation of quality of the interface between layer and substrate |
DE4244712C2 (en) * | 1992-02-14 | 1996-09-05 | Degussa | Coating dispersion for the production of coatings promoting an alkaline, structure-strengthening body |
JPH07509120A (en) * | 1992-03-20 | 1995-10-12 | セルシス・インターナショナル・パブリック・リミテッド・カンパニー | Biological substance analysis method and device |
US5587128A (en) | 1992-05-01 | 1996-12-24 | The Trustees Of The University Of Pennsylvania | Mesoscale polynucleotide amplification devices |
JPH0634546A (en) * | 1992-07-17 | 1994-02-08 | Tosoh Corp | Fluorescene detector |
GB9218357D0 (en) * | 1992-08-28 | 1992-10-14 | Oxford Instr Uk Ltd | X-ray spectrometry detector |
US5338488A (en) * | 1992-09-10 | 1994-08-16 | Council Of Scientific Research | Process for the production of synthesis gas by oxidative converson of methane (or natural gas) using composite catalyst containing transitional and alkine earth metal oxides |
US5288514A (en) | 1992-09-14 | 1994-02-22 | The Regents Of The University Of California | Solid phase and combinatorial synthesis of benzodiazepine compounds on a solid support |
US5324483B1 (en) * | 1992-10-08 | 1996-09-24 | Warner Lambert Co | Apparatus for multiple simultaneous synthesis |
US5714127A (en) * | 1992-10-08 | 1998-02-03 | Warner-Lambert Company | System for multiple simultaneous synthesis |
US5601141A (en) * | 1992-10-13 | 1997-02-11 | Intelligent Automation Systems, Inc. | High throughput thermal cycler |
US5356756A (en) * | 1992-10-26 | 1994-10-18 | The United States Of America As Represented By The Secretary Of Commerce | Application of microsubstrates for materials processing |
US5679548A (en) | 1993-02-02 | 1997-10-21 | The Scripps Research Institute | Methods for producing polypeptide metal binding sites and compositions thereof |
US5342581A (en) * | 1993-04-19 | 1994-08-30 | Sanadi Ashok R | Apparatus for preventing cross-contamination of multi-well test plates |
US5376335A (en) * | 1993-04-30 | 1994-12-27 | Gleaves; John T. | Apparatus for study and analysis of products of catalytic reaction |
US5766875A (en) | 1993-07-30 | 1998-06-16 | Molecular Devices Corporation | Metabolic monitoring of cells in a microplate reader |
US5472672A (en) * | 1993-10-22 | 1995-12-05 | The Board Of Trustees Of The Leland Stanford Junior University | Apparatus and method for polymer synthesis using arrays |
US6165778A (en) * | 1993-11-02 | 2000-12-26 | Affymax Technologies N.V. | Reaction vessel agitation apparatus |
US5503805A (en) * | 1993-11-02 | 1996-04-02 | Affymax Technologies N.V. | Apparatus and method for parallel coupling reactions |
US5451524A (en) * | 1994-02-01 | 1995-09-19 | The Gillette Company | In vitro chamber for human organ tissue samples |
JPH07226884A (en) | 1994-02-14 | 1995-08-22 | Mitsubishi Electric Corp | Solid-state image pickup device |
ATE156911T1 (en) | 1994-03-04 | 1997-08-15 | Waters Investments Ltd | METHOD FOR DETECTING POLYMERS IN A SOLUTION, DETECTOR SYSTEM AND A CHROMATOGRAPHY DEVICE INCLUDING SUCH A DETECTOR SYSTEM |
US6015880A (en) | 1994-03-16 | 2000-01-18 | California Institute Of Technology | Method and substrate for performing multiple sequential reactions on a matrix |
DK0751950T3 (en) | 1994-03-23 | 2001-01-29 | Penn State Res Found | Method for identifying elements of combinatorial libraries |
US5519220A (en) * | 1994-06-28 | 1996-05-21 | Janos Technology Inc. | FTIR chemical reaction monitor |
JPH0815139A (en) * | 1994-07-02 | 1996-01-19 | Horiba Ltd | Gas adsorption/desorption measuring method of catalyst for automobile |
US5428118A (en) * | 1994-07-15 | 1995-06-27 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase fluidized bed polyolefin polymerization process using gas or gas-solids tangential flow |
US5498545A (en) * | 1994-07-21 | 1996-03-12 | Vestal; Marvin L. | Mass spectrometer system and method for matrix-assisted laser desorption measurements |
US5508197A (en) * | 1994-07-25 | 1996-04-16 | The Regents, University Of California | High-speed thermal cycling system and method of use |
US5595712A (en) | 1994-07-25 | 1997-01-21 | E. I. Du Pont De Nemours And Company | Chemical mixing and reaction apparatus |
JP3035169B2 (en) * | 1994-09-16 | 2000-04-17 | 株式会社堀場製作所 | Catalyst adsorption species measurement device |
US5985356A (en) * | 1994-10-18 | 1999-11-16 | The Regents Of The University Of California | Combinatorial synthesis of novel materials |
US5492831A (en) | 1994-11-15 | 1996-02-20 | Lachat Instruments | Shared peripheral analytical system |
US5467635A (en) | 1994-12-12 | 1995-11-21 | Shimadzu Corporation | Gas chromatograph |
US5891742A (en) | 1995-01-19 | 1999-04-06 | Chiron Corporation | Affinity selection of ligands by mass spectroscopy |
US5603899A (en) | 1995-04-12 | 1997-02-18 | Pharmacia Biotech, Inc. | Multiple column chromatography assembly |
US5609826A (en) * | 1995-04-17 | 1997-03-11 | Ontogen Corporation | Methods and apparatus for the generation of chemical libraries |
US6171555B1 (en) * | 1995-04-17 | 2001-01-09 | Ontogen Corporation | Reaction block docking station |
US5716584A (en) * | 1995-09-07 | 1998-02-10 | Pathogenesis Corporation | Device for the synthesis of compounds in an array |
US5888830A (en) * | 1995-09-22 | 1999-03-30 | Berlex Laboratories, Inc. | Apparatus and process for multiple chemical reactions |
US5772874A (en) | 1995-11-02 | 1998-06-30 | Cohesive Technologies, Inc. | High performance liquid chromatography method and apparatus |
US5859700A (en) | 1995-11-22 | 1999-01-12 | Kairos Scientific, Inc. | High resolution imaging microscope (HIRIM) and uses thereof |
DE29519713U1 (en) * | 1995-12-12 | 1996-02-01 | Erweka Gmbh | Dissolution tester |
EP0821788B1 (en) | 1996-02-20 | 2006-02-01 | Waters Investments Limited | Capillary electrophoresis detector apparatus |
US6063633A (en) * | 1996-02-28 | 2000-05-16 | The University Of Houston | Catalyst testing process and apparatus |
AU741049B2 (en) * | 1996-05-09 | 2001-11-22 | Life Technologies Corporation | Microplate thermal shift assay and apparatus for ligand development and multi-variable protein chemistry optimization |
DE69735411T2 (en) * | 1996-10-09 | 2006-09-07 | Symyx Technologies, Inc., Santa Clara | INFRARED SPECTROSCOPY AND LIBRARY IMAGING |
US5852498A (en) | 1997-04-04 | 1998-12-22 | Kairos Scientific Inc. | Optical instrument having a variable optical filter |
US6456734B1 (en) | 1997-06-05 | 2002-09-24 | Kairos Scientific, Inc. | Calibration of fluorescence resonance energy transfer in microscopy |
US5914245A (en) | 1998-04-20 | 1999-06-22 | Kairos Scientific Inc. | Solid phase enzyme kinetics screening in microcolonies |
FI106409B (en) | 1998-05-15 | 2001-01-31 | Fortum Oil & Gas Oy | Arrangement and Method for Testing Heterogeneous Catalysts for Short Contact Reactions |
US6106024A (en) * | 1998-06-04 | 2000-08-22 | Cooper Cameron Corporation | Riser joint and apparatus for its assembly |
-
1996
- 1996-06-17 US US08/664,836 patent/US6063633A/en not_active Expired - Lifetime
-
1997
- 1997-02-25 CA CA002247259A patent/CA2247259C/en not_active Expired - Fee Related
- 1997-02-25 CN CNB971920168A patent/CN100430725C/en not_active Expired - Fee Related
- 1997-02-25 AU AU19679/97A patent/AU1967997A/en not_active Abandoned
- 1997-02-25 JP JP9531028A patent/JP2000506265A/en not_active Ceased
- 1997-02-25 DE DE69725429T patent/DE69725429T3/en not_active Expired - Lifetime
- 1997-02-25 WO PCT/US1997/002756 patent/WO1997032208A1/en active IP Right Grant
- 1997-02-25 EP EP97907768A patent/EP0883806B2/en not_active Expired - Lifetime
-
2000
- 2000-02-08 US US09/499,956 patent/US6333196B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/613,877 patent/US6623970B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/613,879 patent/US6630111B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/613,084 patent/US6605470B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/612,857 patent/US6623968B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/613,082 patent/US6623969B1/en not_active Expired - Lifetime
- 2000-07-10 US US09/612,853 patent/US6623967B1/en not_active Expired - Lifetime
- 2000-11-28 US US09/727,890 patent/US6514764B1/en not_active Expired - Lifetime
-
2001
- 2001-12-21 US US10/029,891 patent/US6908768B2/en not_active Expired - Fee Related
-
2005
- 2005-03-16 US US11/081,429 patent/US20050158865A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
DE69725429D1 (en) | 2003-11-13 |
US6063633A (en) | 2000-05-16 |
EP0883806B2 (en) | 2010-11-24 |
DE69725429T2 (en) | 2004-05-19 |
US6623967B1 (en) | 2003-09-23 |
US20020127725A1 (en) | 2002-09-12 |
CN100430725C (en) | 2008-11-05 |
US6623968B1 (en) | 2003-09-23 |
US6514764B1 (en) | 2003-02-04 |
US6630111B1 (en) | 2003-10-07 |
US20050158865A1 (en) | 2005-07-21 |
WO1997032208A1 (en) | 1997-09-04 |
US6623969B1 (en) | 2003-09-23 |
CA2247259A1 (en) | 1997-09-04 |
US6605470B1 (en) | 2003-08-12 |
AU1967997A (en) | 1997-09-16 |
DE69725429T3 (en) | 2011-06-30 |
US6623970B1 (en) | 2003-09-23 |
US6908768B2 (en) | 2005-06-21 |
EP0883806A4 (en) | 2001-09-12 |
US6333196B1 (en) | 2001-12-25 |
EP0883806A1 (en) | 1998-12-16 |
CN1226966A (en) | 1999-08-25 |
JP2000506265A (en) | 2000-05-23 |
EP0883806B1 (en) | 2003-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2247259C (en) | Catalyst testing process and apparatus | |
US6667009B1 (en) | Apparatus for sampling and analysis of reactions by trapping reaction components on a sorbent | |
US6627445B1 (en) | Process for simultaneously evaluating a plurality of catalysts | |
US6873414B2 (en) | Method and apparatus for the combinatorial preparation and testing of material libraries by photoacoustic analytical methods | |
Schüth et al. | High-throughput experimentation in oxidation catalysis | |
US7374942B2 (en) | Process and apparatus for the combinatorial production and testing of catalyst material libraries by using at least two analytical methods | |
Murphy et al. | High-throughput approaches to catalyst discovery | |
US7229832B2 (en) | Heat activated membrane introduction apparatus and method for screening materials | |
EP1609526A1 (en) | Catalyst testing process and apparatus | |
EP1384995A1 (en) | Catalyst testing process and apparatus | |
CA2465957A1 (en) | Catalyst testing process and apparatus | |
CN101363820A (en) | Catalyst testing process and apparatus | |
DE29724908U1 (en) | Simultaneous testing or selecting of catalyst formulations - by stabilising individual formulations to support(s), contacting with reactant(s) and measuring and/or analysing e.g. heat liberated |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20170227 |