CN101363820A - Catalyst determination method and device - Google Patents

Abstract

A method of testing or selecting a plurality of catalyst formulations capable of catalytically converting a given reactant or mixture of reactants from a set of at least two candidate formulations is disclosed, the method comprising a combination of the steps of: a) separating the formulations supported on one or more supports; b) contacting the plurality of supported formulations with one or more reactants under reaction conditions; and c) determining the relative relative strength of the plurality of candidate catalyst formulations by Efficiency: Simultaneously staining or reacting a reaction product with a detection agent to form a detectable product or light, and detecting the detectable product or light. The present application also discloses an apparatus for evaluating the catalytic efficiency of a number of different candidate catalyst formulations.

Description

Catalyst determination method and device

field of invention

The present invention relates to the field of determination of catalysts in general, and the invention is generally classified in US Patent Classification No. 502 or 252. The present invention relates to the field of determination of catalysts in general, and the invention is generally classified in US Patent Classification No. 502 or 252.

Introduction to existing technology

The prior art includes: C&E News, 1/8/96, page 30, which teaches reactive plastics and many catalyst testing apparatus and methods known to the petroleum refining field; J. "Phosphatase catalysts developed via combinatoriol organic chemistry" by F.M. Menger, A.V. Eliseev and V.A. Migulin, Org. Chem pp. 6666-667; Xiang, 268 Science 1738 and Briceno, 270 Science 273, both on combinatorial libraries of solid-state compounds; Sullivan for Combinatorial Technologies, Today's Chem.At Work 14; Nessler 59 J.Org.Chem. for Combinatorial Libraries 4723; Baldwin, 117 J. for Combinatorial Libraries 5588. Amer. Chem. Soc.

Problems with Existing Technology

Routine catalyst testing is done at laboratory scale or in larger pilot plants where the feed and catalyst are contacted under reaction conditions and the effluent product is typically sampled and the sample is often analyzed and the results reviewed. Data analysis technology processing. Such a procedure may take a day or more for a single experimental run for a catalyst. While the techniques described above are important in fine-tuning optimal arrays, pellet shapes, etc., the present invention enables scanning of dozens of catalysts in a single selection, typically less time than would be required to evaluate a single catalyst using traditional methods less. Furthermore, the present invention, when practiced in its preferred robotic embodiment, significantly reduces the labor cost of each catalyst screening.

Introduction to the invention

General description of the invention

According to the invention, a multi-sample support (support), such as a honeycomb body or a flat plate, or a collection of individual support particles is treated with a solution/suspension of catalyst components to fill the wells on the plate, or to create a grid ( cells), spots (spots) or pellets to support each of the various combinations of catalyst components, the carrier is dried, calcined, or otherwise treated as necessary to stabilize the components in the grids, spots or pellets, and then the carrier is combined with Possible reaction feed streams or _batches (e.g., gas oil, hydrogen and oxygen, ethylene or other polymerizable monomers, propylene plus oxygen, or _CCl2F2 and hydrogen) are contacted to catalyze a biochemical reaction consisting of Protein, cell, enzyme catalysis. The reactions taking place in each grid are detected for example by infrared thermometry, spectrometry, electrochemical methods, photometry, thermal conductivity or other methods to detect products or remaining reactants, or by e.g. multi-streaming small Volume sample tube method, sampling from the vicinity of each composition, and then analyzing, such as spectral analysis, chromatographic analysis, etc., or measuring by observing the temperature change near the catalyst, such as thermosensitive technology, to determine the catalyst in each composition relative efficiency. Automatic control techniques can be employed in forming grids, spots, pellets, etc.

These parameters are discussed below:

Catalysts: Biotechnology catalysts include proteins, cells, enzymes, etc. Chemical transformation catalysts include most of the elements of the periodic table that are solid under the reaction conditions. Hydrocarbon conversion catalysts include Bi, Sn, Sb, Ti, Zr, Pt, rare earths, and many other possible catalyst candidates whose potential for specific reactions has not been recognized. Many synergistic combinations are useful. Supported metals and metal complexes are preferred. The chemical catalyst can be added to the substrate (support) as an element, or as an organic or inorganic compound that decomposes at the temperature of the stabilization step to deposit the element or its oxide on the substrate, or as a stable compound.

Support: The support can be an inert clay, zeolite, ceramic, carbon, plastic such as a reactive plastic, a stable non-reactive metal, or a combination of the above. They can be in the shape of porous honeycombs penetrated by channels, particles (pellets), or flat plates on which many small pieces (spots) of catalyst candidates are deposited, or depressions in a flat plate. Common catalyst substrate materials such as zeolites such as zeolite USY, kaolinite, alumina, etc. are particularly preferably used because they can simulate commercial catalysts.

Preparation: The precursor of the candidate catalyst can be deposited on the support by any convenient technique, preferably by pipette or absorbing stamp (like a rubber stamp) or wire mesh. In a preferred embodiment, the deposition process can be performed under automated control, as is the case with catalyst loading on multigrid plates in biochemical assays. Many spots of catalyst can be obtained by several separate depositions, such as the passage through the honeycomb body can be blocked at one-third of its length, the upper third of the passage is filled with catalyst solution, and then the plug Moving two-thirds of the way down the channel, the straw sucks in the second catalyst, then the blockage is removed and a solution of the third catalyst is added, resulting in a channel where, as the reactants flow through the channel, they come into contact with the three catalysts in sequence. Catalysts can also be added by ion exchange, solid deposition, impregnation, or combinations of these methods. Combinatorial chemical or biological preparation techniques are preferably utilized to prepare the catalyst candidates for the arrays of the invention. Co-precipitates of two or more catalysts can be slurried and coated onto a support, and reactivated if necessary. Catalysts can be supported by wire mesh on the support plate or inside the channels of the support, and different catalyst compositions can be applied to different spots by sequential masking.

Stabilization step: Once the catalyst is supported on the support, any suitable technique known in the art can be used to stabilize and/or activate the particular catalysts selected so that they remain in place during the reaction steps. It is especially preferred to perform firing, steaming, melting, drying, depositing and reacting in situ.

Reactants: The present invention has utility for any reaction that can be promoted in the presence of a catalyst, including biological reactions and inorganic and organic chemical reactions. Chemical reactions include polymerization, halogenation, oxidation, hydrolysis, esterification, reduction, and any other conventional reaction that would benefit from a catalyst. Hydrocarbon conversion reactions such as those used in petroleum refining are an important application of the present invention, including reforming, fluid catalytic cracking, hydrogenation, hydrocracking, hydrotreating, hydrodesulfurization, alkylation and gasoline desulfurization deal with.

Sensors: The number of sensors used to detect catalytic activity in a candidate catalyst is not strictly limited, but is preferably simple and practical. The use of multiple chromatographs, multiple temperature sensors, and multiple spectrometers is particularly preferred, especially those suitable for measuring near each specific The temperature of the catalyst spots and/or those of the product. Particular preference is given to thermometry in which the temperature is recorded simultaneously at several catalyst sites by means of an infrared camera. Other suitable sensors include electrochemical sensors, fluorescence detectors, NMR detectors, NIR detectors, FTNIR detectors, Raman detectors, flame ionization detectors, thermal conductivity detectors, mass detectors, viscosity detectors, and Exciton or X-ray emission detectors. Multiple sensors detect gas or liquid flow or products on the surface of the carrier. The endothermic reaction manifests itself as a decrease in temperature at the best catalysts. Some sensors use additional detection reagents such as ozone to generate chemiluminesce.

Labels: Labels (tracers) may optionally be added to identify a particular catalyst, especially in the case of particles as catalyst supports. These markers may be conventional markers as already discussed in the literature. The label can be a chemical that is stable under the reaction conditions, or it can be a radioactive substance with a characteristic emission. The techniques of combinatorial chemistry allow the adaptation of markers and selected catalysts to specific reactions enhanced by the catalyst.

Batch or Continuous: While the invention is preferably based on flow, where reactants flow through catalyst spots under reaction conditions, batch tests such as in agitated autoclaves or stirred vessels may also be used, especially in biological reactions middle.

Temperature, Pressure, Space Velocity, and Other Reaction Conditions: These conditions are determined by the reactants and the reaction. High pressure reaction conditions can be provided by placing the carrier in a reaction chamber with a sapphire or similar window for viewing by the sensing device or a pressure-tight lead along the reactor wall.

use of invention

The present invention can be used for the test of the catalyst of the biotechnology that promotes gas phase or liquid phase reaction; Be suitable for testing the catalyzer under intermittent or preferred continuous material flow condition; Be applicable to test under high pressure, low pressure or normal pressure condition; The present invention saves The time and labor spent screening for improved catalysts to promote desired reactions.

Brief introduction to the drawings

Figure 1 is a schematic diagram of a preferred honeycomb support. Automatically controlled pipetting equipment deposits a composition of different catalyst components in each channel passing through the honeycomb support, and then calcines the support to stabilize the catalyst in each channel. .

Figure 2 is a schematic illustration of the honeycomb carrier of Figure 1 in contact with reactants flowing through the channels.

Figures 3a and 3b are alternative schematic views of one channel of the honeycomb carrier of Figure 2, the detector detecting the product leaving the channel by measuring the absorption of a laser beam passing through the product or channel.

Figure 4a schematically shows a channel plugged at the midpoint before receiving catalyst solution, and Figure 4b shows the plug moving to the end of the channel, thus forming a channel with one catalyst half its length and one catalyst at the other. Channels with another catalyst in half the length.

Figure 5 schematically shows a sheet of support on which 15 spots of different catalyst compositions, as discussed in Example 1, were deposited.

Figure 6a shows an array of particles (pellets) of the support in place in a reactor after different pellets (shown with different labels on the pellets in the figure) have been ion-exchanged with different catalyst compositions state. Figure 6b shows a packed reactor, which is not preferred because the upstream pellets are exposed to fresh feed, while the downstream pellets are partially exposed to reacted feed.

Description of the preferred embodiment

Example 1

Referring to Figure 5, a sheet of alpha alumina 10 was wash coated with porous gamma alumina particles by standard methods. The oxalate solutions of 12 different transition metal elements were prepared in the wells of a 24-well microtiter plate made of polystyrene. Dilutions and mixtures were prepared from the stock again in wells of microtiter plates using a Beckman Biomek 2000 automated liquid handling system. A robotic device was used to deposit 20 microliter aliquots of each of the resulting solutions at defined locations 12 (spots) on the surface of an alumina support 10 which was then dried, calcined and inserted into a temperature range between 100 and 350 degrees Celsius. in a temperature-controlled reactor. After reduction, a possible reaction mixture of oxygen and hydrogen is fed into the reactor. The Agema infrared sensor camera 14 was used to view the alumina support with a polished metal mirror through an infrared transparent sapphire window. Set up the camera so that the lower limit of its dynamic range corresponds to a temperature about 40 °C lower than the feed temperature, and the maximum signal involves a temperature about 200 °C higher than the feed temperature. An increase in the local temperature around the spot 12 of the catalyst composition (decrease for an endothermic reaction) reveals that the composition catalyzes the reaction, as shown in photograph 18.

Example 1a

Catalysts were alternately identified by reacting under intense UV and/or visible light irradiation, where infrared temperature measurements were taken immediately after irradiation ceased, or by using short-circuit filters on the irradiation source to eliminate infrared contamination.

Example 2

Referring to FIG. 2, a porous alumina monolith 20 (Corning) has square or circular cross-sectional channels extending in a regular array through its entire thickness, the monolith 20 using a different composition of catalyst in each channel Precursor solution processing where each composition is isolated in its own channel. After drying, calcination, etc., at high temperature, the activated monolith is brought into contact with a flowing possible reaction mixture and observed with an Agema type camera in the infrared region. The enthalpy of the reaction produces local temperature differences near the composition exhibiting catalytic activity, and these are observed as temperature changes near the outlet of the channel.

Example 3

Referring to FIG. 3, the porous ceramic monolith 20 described in Example 2, having different catalyst compositions in its channels, is mounted in a reactor (not shown) in such a manner that each The entire length of each channel can be observed through a sapphire window at the end of the reactor. A broad-spectrum thermal infrared source is installed at one end of the reactor to generate regional infrared energy flux density. The Agema IR sensitive camera is positioned in such a way that it can directly observe the infrared light source through most of the holes. An interference filter or other filter is mounted on the side of the reactor between the camera and the infrared light source so that the light reaching the camera from the light source is substantially limited to wavelengths between 4 and 4.5 microns. The observation of absorbance in this wavelength range was used to compare candidate catalyst compositions based on the amount of _CO2 produced, an undesired by-product of the target reaction. The catalyst composition selected for low carbon dioxide generation (combined with high overall conversion activity, as measured by infrared absorption or infrared thermometry of the desired product) was found to have a high effect on the desired product compared to the _CO2 by-product. selective.

Example 4

A collection of catalyst precursor compositions is prepared by automated liquid handling equipment, and catalyst support particles are contacted with each composition. After further processing to stabilize and activate the catalyst precursors, the catalyst pellets are arranged on the surface, exposed to a potentially reactive environment, and their activity is determined by infrared thermometry.

Example 5

A solution of the catalyst precursor composition is prepared in a number of separate containers. Each composition also includes small amounts of tracer materials (eg, stable isotopes of elemental carbon or sulfur in varying proportions). The catalyst support particles are contacted with the formulation of catalyst precursor and activated. The pellet is then contacted at some point with a possible reaction mixture (e.g. by elutriation into a closed volume) and its activity measured (by thermometry, by spectroscopic measurement of the product, or sampling around the gas or liquid phase) . Particles showing activity are collected and individually analyzed for tracer material content in order to determine the composition giving the desired catalytic activity.

Example 6

The procedure of Example 2 was repeated, except that only a portion of the pore length was coated with the candidate catalyst, so that the observation of the pore walls of the unmodified monolith served as a reference for optical uniformity.

Example 7

The emissivity of the pores of the support monolith of the support of Example 2 was plotted over a useful wavelength range by maintaining the monolith at the desired experimental temperature in the absence of reactants. The digitally stored thermal emissivity map is used to normalize the infrared energy flux measured under experimental conditions to increase the precision of the estimated local temperature.

Example 8

The high, substantially uniform thermally emissive surface is located at the end of the monolith of Example 2, away from the camera, near the point of 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 to pass the gas into the channel through a uniform radiating surface, which can be achieved by means of pores or by means of a small offset between the radiating surface and the monolith.

Example 9

As an alternative, spots of catalyst can be deposited on the inner surface of a reactor such as a tube formed by a support material, and the temperature of the corresponding spot on the outside of the reactor can be measured, thereby determining by heat conduction the individual catalysts in the reaction. Whether the temperature is raised or lowered.

Example 10

The procedure of Example 1 was repeated, except that the reactants were in the liquid phase, and liquid phase analysis was used to determine the activity of each catalyst candidate.

Example 11

The experiment of Example 4 was repeated except that the metal loading was measured directly by dissolving the pellets and analyzing the metal loading directly.

Example 12

The flakes of alpha alumina were washed with particles of porous gamma alumina by standard methods. The oxalate solutions of 12 different transition metal elements were prepared in the wells of a 24-well microtiter plate made of polystyrene. Dilutions and mixtures were prepared from the stock, again in the wells of a microtiter plate, using a Beckman Biomek 2000 automated liquid handling system. A Biomek robot was used to deposit 40 microliter aliquots of each of the resulting solutions at defined locations on the surface of an alumina support, which was then dried, calcined, and inserted into a reactor controlled at 200°C middle. A gaseous mixture of hydrogen (97.5%) and oxygen (2.5%) was added at 200°C. An infrared sensing camera is used to observe the alumina support through an infrared transparent sapphire window. The camera is set so that the lower limit corresponds to the feed temperature and the maximum signal corresponds to a temperature 20 degrees above the feed temperature. The composition catalyzes the reaction as shown by a local temperature rise near the spot of the composition.

Example 13

A porous alumina monolith having square pores extending in a regular array throughout its thickness, the pores distributed at a density of 25 per square inch, was washcoated with alumina particles. The channels are then partially filled with solutions of different compositions, each composition comprising one or more metal oxalates or nitrates, each composition separated in its own channel or group of channels. After drying and activation in the presence of hydrogen, the activated monolith is placed in a reactor equipped with a sapphire window where it can be observed in the infrared using an infrared sensing camera. Position the camera so that the carrier wall can be observed. The relative thermal emissivity of the support at each pixel is determined by imaging the monolith in the infrared while holding the reactor and monolith at each of several constant temperatures while nitrogen gas is passed through the reactor .

The reactor was then fed with a gas mixture containing 2.5 mole percent oxygen in hydrogen. Reactor and feed temperatures were initially set at 40°C and then gradually increased while the catalyst-loaded monolith was repeatedly imaged in the infrared. The temperature in each grid can be obtained by observing the grid near the end of the catalyst precursor coated area of the channel, or by making the observed infrared It can be judged by launching normalization. It was shown that the composition in the grid that was heated first above the reactor temperature could be used as a hydrogen oxidation catalyst.

Example 14

A porous alumina monolith having square channels extending in a regular array along its entire 10 cm thickness at a density of 25 channels per square inch was wash-coated with alumina particles. The channels are then partially filled with solutions of different compositions, each composition comprising one or more metal salts and, in some cases, candidate modifiers such as barium, cesium, or potassium compounds, each combination Objects are separated in their own channel or channel group.

After drying and reduction in the presence of hydrogen, the activated monolith is placed in a reactor where it can be observed by using an infrared camera through a sapphire window. The first viewing window is located 0.5 cm from the surface of the monolith. The camera was set up to view through the window, through the channel of the carrier and through the second sapphire window towards the source of infrared radiation.

Methane gas mixed with oxygen and argon was then passed through the reactor and flowed through the channels of the monolith towards the camera. An optical filter was inserted between the infrared light source and the camera to selectively pass infrared radiation at a wavelength of 4.3 microns, which is strongly absorbed by carbon dioxide. The effective concentration of carbon dioxide in each channel can be deduced from the infrared intensity at 4.3 microns in that channel. The reading for each pixel at 4.3 microns is divided by the reading from the filter for infrared wavelengths near 4.3 microns that are not strongly absorbed by carbon dioxide, methane, or water to correct for the effects of possible optical artifacts Be selective.

Compositions with high concentrations of carbon dioxide are useful for the catalytic oxidation of methane after prolonged exposure to operating conditions.

Example 15

Solutions of the catalyst precursor compositions were prepared in various separate containers. Each composition also includes a small amount of tracer material (eg, a stable isotope of elemental sulfur in varying proportions unique to each composition). The catalyst support particles are contacted with the formulation of the catalyst precursor composition and activated. The pellet is then contacted at some point with a possible reaction mixture (e.g. by elutriation into a closed volume) and its activity is measured (by thermometry, by spectroscopic measurement of the product, or sampling around the gas or liquid phase) . Particles showing activity are collected and analyzed individually for tracer material content and then determine the composition giving the desired catalytic activity.

Example 16

A polytetrafluoroethylene block having square channels extending in a regular array along its entire thickness and a density of 9 channels per square inch was prepared in such a way that a shallow hole existed at the bottom of each channel. Each hole is filled with a different polymer formulation with sulfonic acid groups on its surface, and is fitted with a perforated positioning screen to hold the polymer sample in place.

The catalyst-loaded monolith was placed in a reactor where it could be observed through a window located 0.5 cm from the surface of the monolith. The camera is configured so that it can be viewed through the sapphire window, through the channel of the carrier and through the second window towards the polarized light source, with a polarizer mounted between the block and the camera.

A sucrose solution was supplied to the reactor so that it flowed through the channels of the block. The angle at which polarized light is rotated as it passes through the liquid in each channel is measured by rotating the polarizer to different angles and observing the change in brightness of the light passing through each channel. Candidate catalysts found in the channel with the largest change in rotation angle can be used as catalysts for the hydrolysis of sucrose.

Example 17

Catalysts for the photooxidation of hexane were identified by performing reactions in the apparatus of Example 16 in the presence of intense UV and/or visible light irradiation, where infrared temperature measurements were taken immediately after the irradiation had ceased, or by using Shorting filter to eliminate contamination of infrared rays.

Example 18

Samples of cyanogen bromide-activated cross-linked agarose beads were exposed to solutions of alcohol oxidase at different pH values, salt concentrations and enzyme concentrations. After enzyme coupling, residual reactive groups were inhibited with ethanolamine, the beads were washed, and each sample was placed in a separate well of a multi-well plate. The plate was exposed to a flowing air stream containing ethanol vapor and viewed with an Amber infrared sensor camera. The sample whose temperature increased the most was selected as the highly active immobilized alcohol oxidase catalyst.

Example 19

Samples of cyanogen bromide-activated cross-linked agarose beads were exposed to anti-alcohol oxidase antibody solutions at various pH values, salt concentrations, and antibody concentrations. After enzyme coupling, residual reactive groups were inhibited with ethanolamine. The pellets were washed, exposed to a solution of alcohol oxidase, washed again, and each sample was placed in a separate well of a multi-well plate. The plate was exposed to a flowing air stream containing ethanol vapor and viewed with an Amber infrared sensor camera. The sample whose temperature increased the most was selected as the highly active immobilized alcohol oxidase catalyst.

Example 20

A ceramic monolith having channels arranged in an orthogonal row/column format across its entire thickness is washcoated with porous alumina particles, with all channels in each column being activated by treating them with the same catalyst precursor. The possible reactant streams flow through the channels of the monolith, and the multi-wavelength radiation beams pass through the surface of the monolith in parallel with each column to a detector at the end of the column. The composition of the stream leaving that column of pores is estimated by processing the detector output including Fourier transform and/or weighted summation/difference of intensities at different wavelengths.

Example 21

Pellets bearing catalytically active groups capable of catalyzing the conversion of the D- and L-stereoisomers of the reactants are treated with various substances which may preferentially inhibit (temporarily or permanently) the conversion of the L-stereoisomer of the compound by the catalyst to process. The pellets are distributed in the wells of a multi-well plate and exposed to the mixture of isomers of the compound to be modified. The pellets treated with the inhibitor that gave the greatest decrease in conversion activity to the L-isomer were used for stereoselective improvement of the D-isomer.

Example 22

A ceramic monolith having channels arranged in an orthogonal row/column format across its entire thickness is washed coated with porous alumina particles, the channels being activated by treating them with a catalyst precursor. Possible reactant streams flow through the channels of the monolith. A manifold consisting of an array of tubes, each of which is smaller in size than the individual channels, is used to direct the ozone-containing stream into the stream flowing through each channel near its outlet. The reaction of the introduced ozone with the desired product emits light, which can be detected by a camera directed towards the monolith. Catalyst compositions that emit the most intense light output are very useful catalysts for the conversion of reactants to ozone-reactive desired products.

Example 23

A ceramic monolith having channels arranged in an orthogonal row/column format across its entire thickness is washed coated with porous alumina particles, the channels are treated with a catalyst precursor, activated, and then exposed to potentially deactivating species. Possible reactant streams flow through the channels of the monolith. A manifold consisting of an array of tubes, each of which is smaller in size than the individual channels, is used to sample the stream flowing through each channel. Samples from each channel are directed sequentially through an on-off valve arrangement to the coupled gas chromatograph-mass spectrometer, and the catalyst composition that provides the greatest yield of the desired product can be used for conversion of the reactant stream.

change implementation

The specific compositions, methods or embodiments discussed herein are merely illustrative of the invention disclosed in this specification. It is easy for those skilled in the art to make changes to these compositions, methods or embodiments on the basis of the teachings of this specification, so these changes are also included in the disclosed part of the present invention. Methods such as statistically designed experiments and automated iterative trial procedures can be used to further reduce test times. The option of attaching/arranging preformed catalytic elements (in particular precipitates, but also single molecules and complexes such as metallocenes) on the support, preferably by precipitation or deposition methods, is useful in many cases.

Detection may involve the addition of reagents to the stream leaving each candidate that detect the catalyst product by staining or reacting to provide a detectable product such as light.

The carrier may comprise a specially arranged array designed to distribute the flow evenly, such as a header of multiple delivery tubes inserted into each channel of the block.

Detection devices may include electrochemical devices, or gamma cameras for metal accumulation measurements; analysis of imaged elements by neutron activation and imaging by film or emissive radioactive storage plates; temperature measurements by acoustic pyrometry, bolometery , electrochemical detection, conductivity detection, liquid phase determination, preferably dissolution of carrier pellets and direct analysis of metal loading; measurement of the refractive index in the liquid phase; use of radiation emitted at a characteristic wavelength instead of the usual emission source Hot gas to directly observe the infrared emission of the product gas.

Other variations may include selectivity testing after deliberate poisoning of some sites, especially in chiral catalysis and the like.

The formulation may be supported in the form of spots or layers on the surface of the support comprising pores or channels, or channels through the entire extent of the support. The support may comprise carbon, zeolites and/or plastics. The plastic may include reactants. The support may support the form of a catalyst made of coprecipitate or aluminum or particles.

At least one formulation may preferably include 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 their mixtures.

Tracers may comprise different isotopes or different mixtures of isotopes. Reaction conditions may include pressures greater than 1 bar absolute and may be contacted at temperatures greater than 100 degrees Celsius.

The method may include detecting a change in temperature in the vicinity of each formulation due to a reaction endotherm or exotherm. The method may include treatment with a reducing agent. The contacting step may be performed in the presence of a compound that alters the distribution of the metal within the porous support. Candidate catalyst formulations may be contacted in spots or layers on the surface of a support comprising a washcoat supported by an underlayer.

The stabilization step can be performed under a temperature gradient or by other means whereby certain candidate catalyst formulations are exposed to different temperatures. Stabilization includes calcination, steaming, drying, reaction, ion exchange and/or precipitation. Correction for thermoemissivity errors associated with differences in chemical composition can be utilized when detecting temperature changes due to reactions.

Arrays of formulations to be tested may include pre-formed metallocene or other catalytic complexes immobilized on supports.

Infrared rays can be detected by non-dispersive infrared spectroscopy or by infrared-sensing photographic films. The detector means includes means for physically scanning across the array of candidate formulations.

Observations at multiple wavelengths can be processed through mathematical processing such as conversion, weighted summation, and/or subtraction. Reactivity, reactants or products can be detected by additional reactions that can signal the reaction or the presence of a particular compound or compound species. Chemiluminescence can be used as an indicator of reactivity or a specific compound or class of compounds. A substantially collimated emission source can be used for product detection/imaging. Multitube sampling introduces samples into a mass spectrometer, chromatograph, or optical monitor. To simulate aging, etc., the formulations may be exposed to a noxious agent that reduces the activity of at least one formulation by at least 10%, and then optionally exposed to water vapor, heat, hydrogen, air, liquid water, or other different substances or Under conditions, these substances or conditions can increase the activity of at least one component of the collection by at least 10% from the previously reduced activity, thereby allowing measurement of regenerated, reactivated, decoking or other catalyst performance. Hazardous agents may include high temperature, V, Pb, Ni, As, Sb, Sn, Hg, Fe, S or other metals, _H2S , chlorine, oxygen, Cl and/or carbon monoxide.

Patents or documents referred to in this specification are incorporated herein by reference.

Claims (30)

1. test or select can the given reactant of catalyzed conversion or the method for a plurality of catalyst formulations of reaction-ure mixture, the combination that this method may further comprise the steps from the set of at least two kinds of candidates prescription:

A) described prescription is separately loaded on one or more carriers;

B) prescription of described a plurality of loads is contacted with one or more reactants; With

C) measure the relative efficiency of described a plurality of candidate's catalyst formulations by the following method: make reaction product form detectable product or light simultaneously, and detect detectable product or light with detection agent dyeing or with the detection agent reaction.

2. the process of claim 1 wherein that described a plurality of prescription is touched with the form at the lip-deep array reactive site of common carrier.

3. the process of claim 1 wherein that described a plurality of catalyst formulation loads on the carrier into inertia clay, zeolite, pottery, carbon or plastics, that the shape of described carrier can be that passage runs through is cellular, the pit in particle, plate or the plate.

4. the process of claim 1 wherein each prescription in arranging by they different catalysts prescriptions on carrier the position and/or identify by analyzing with each relevant unique tag thing of physics of filling a prescription.

5. the method for claim 1 comprises that also described a plurality of catalyst formulations are exposed to the activity that makes at least a prescription to descend in one or more materials of at least 10% or under one or more conditions, measure activity then and come measurement stability.

6. the process of claim 1 wherein that described load step comprises makes porous carrier contact with the solution of slaine or contacts with hydrogen.

7. the method for claim 1 also comprises some candidate's catalyst formulation is exposed under the condition of different temperature, roasting, decatize, drying, reaction, ion-exchange and/or precipitation.

8. the method for claim 1, the prescription of wherein said a plurality of loads contacts in comprising the common reactor of infrared transmission form, and a plurality of reactions are launched or the relative efficiency of the infrared-ray mensuration candidate catalyst formulation of absorption by detecting, and this infrared-ray passes the infrared transmission form and detects.

9. the method for each of claim 1-8, wherein the ray of being emitted in course of reaction is by detecting with infrared-sensitive type camera imaging.

10. the process of claim 1 wherein the relative efficiency of determining candidate's catalyst formulation by the spectral analysis that a plurality of reaction product or a plurality of unreacted reactant are carried out multi-wavelength.

11. the method for claim 1, wherein said reactor is a reactor in parallel, it comprises described a plurality of candidate's catalyzer, each candidate's catalyzer a plurality of reactive sites and the one or more ray-transmission form at its own reactive site, a plurality of reaction product or a plurality of unreacted reactant pass the irradiation of one or more rays-transmission form by ray, and pass that one or more rays-transmission form detects a plurality of reaction product or a plurality of unreacted reactant and the relative efficiency of determining a plurality of candidate's catalyzer by spectroscopic methodology.

12. the process of claim 1 wherein that a plurality of products or a plurality of reactant are by being selected from infrared spectrum, NMR (Nuclear Magnetic Resonance) spectrum (NMR), Raman spectrum, laser spectrum, optical spectroscopy and mass spectral technology for detection.

13. the method for claim 1, wherein said reactor is a flow reactor in parallel, it comprises candidate's catalyzer, each candidate's catalyzer is at a plurality of reactive sites of its own reactive site, with a plurality of stopple coupons that are used for the logistics that comprises product at each position of a plurality of reactive sites is taken a sample, and a plurality of stopple coupons are applicable to: (i) provide fluid to be communicated with between a plurality of spectrometers that the multichannel that is used for reaction product or unreacted reactant in a plurality of reactive sites and each logistics in the logistics that contains product of a plurality of outflows detects or chromatograph, or (ii) send into a plurality of spectrometers or chromatographic cross-over valve at a plurality of reactive sites with a plurality of logistics that contain product and provide the fluid connection between arranging.

14. the method for claim 1, wherein reactor is a flow reactor in parallel, it comprises and is used for a series of pipes that the logistics of product is taken a sample are contained in each duct in a plurality of reactions duct that this method comprises that also the described a series of pipes of physical scan are sent to a plurality of logistics that contain product in spectrometer or the chromatograph.

15. the process of claim 1 wherein that described detection step comprises the rotation angle of measuring polarized light.

16. aforesaid right requires each method, wherein reaction conditions comprises and is higher than 100 ℃ temperature and comprises pressure greater than 1bar extraly or selectively.

17. the process of claim 1 wherein that described a plurality of catalyst formulation loads on various product holder.

18. the method for claim 17 also comprises the catalyst formulation of handling a plurality of loads on various product holder, contacts with reactant or reaction mixture at the catalyst formulation after making a plurality of processing under the reaction conditions on various product holder simultaneously then.

19. be used to estimate the equipment of a plurality of different candidate's catalyst formulation catalytic efficiencies, this equipment comprises:

Reactor in parallel, it comprises a plurality of reactive sites, and each position of a plurality of reactive sites all is fit to comprise different candidate's catalyzer, and this reactor adapted makes a plurality of candidate's catalyzer contact with one or more reactants under reaction conditions simultaneously; With

Be used to measure the detecting device of a plurality of candidate's catalyst formulation relative efficiencies, it is characterized in that:

This detecting device is the suitable detecting device of analyzing the parallel connection of a plurality of reactions, a plurality of reaction product or a plurality of unreacted reactants simultaneously, and be: this detecting device comprises makes reaction product form detectable product or light with the dyeing detection agent or with the detection agent reaction, and detects the device of detectable product or light.

20. the equipment of claim 19, wherein Bing Lian reactor also comprises the common carrier with a plurality of reactive sites that are used for a plurality of candidate's catalyst formulations.

21. the equipment of claim 19 or 20, wherein Bing Lian reactor comprises a plurality of different candidate's catalyzer of forming that have, with the reaction chamber that is surrounded by a plurality of candidate's catalyzer, this reaction chamber is fit to make it can bear the pressure of the gas that comprises one or more reactants so that it contacts a plurality of candidate's catalyzer simultaneously under reaction conditions.

22. the equipment of claim 19, wherein this equipment comprises that also being fit to pass one or more rays-transmission form shines the emissive source of a plurality of reaction product simultaneously with ray, and suitable being determined at simultaneously of this detecting device passed the ray that one or more rays-transmission form is absorbed or launched by reaction product or unreacted reactant in the course of reaction.

23. the equipment of claim 22, reactor that wherein should parallel connection comprises a plurality of reactions duct, each duct in a plurality of reactions duct all comprises different candidate's catalyzer, this reactor also comprises the first infrared transmission form and the second infrared transmission form, this emissive source is fit to pass the first infrared transmission form with ray and shines a plurality of reaction product simultaneously, and this detecting device is fit to be determined at simultaneously and passes ray that the second infrared transmission form absorbs by reaction product or unreacted reactant in the course of reaction to determine the relative efficiency of a plurality of candidate's catalyzer.

24. the equipment of claim 22, wherein emissive source is that infrared emitter and detecting device are infrared-sensitive type cameras.

25. the equipment of claim 22, wherein emissive source is to be fit to shine the polarized light source of a plurality of reaction product simultaneously with polarized light, and this detecting device is included in the polarizer of measuring the polarized light rotation angle in the course of reaction, to determine the relative efficiency of a plurality of candidate's catalyzer.

26. the equipment of each of claim 19-25, wherein reactor is a flow reactor in parallel, and it also is included as each duct that the logistics that contains reactant flows through a plurality of reactions duct the fuid distribution system that evenly flows is provided.

27. the equipment of claim 19, wherein reactor is a flow reactor in parallel, it comprises candidate's catalyzer, each of a plurality of candidate's catalyzer is at a plurality of reactive sites of its oneself reactive site, and is adapted at being used in a plurality of reactive sites and each logistics in the material that contains product of a plurality of outflows a plurality of stopple coupons of providing fluid to be communicated with between a plurality of spectrometers that multichannel detects or the chromatograph.

28. the equipment of claim 19, wherein reactor is a flow reactor in parallel, it comprises a plurality of candidates' catalyzer, each of a plurality of candidate's catalyzer is at a plurality of reactive sites of its oneself reactive site, be used for a plurality of pipes of taking a sample from the logistics that contains product at each position of a plurality of reactive sites and a plurality of logistics that contain product introduced a plurality of spectrometers or chromatographic cross-over valve is arranged.

29. the equipment of claim 19, wherein reactor is a flow reactor in parallel, it comprises that a series of pipes and a series of pipes of physical scan that are used for from the logistics that contains product at each position of a plurality of reactive sites is taken a sample introduce spectrometer or chromatographic devices with a plurality of logistics that contain product.

30. each equipment of claim 19-29, wherein reactor adapted provides and comprises and be higher than 100 ℃ temperature and comprise reaction conditions greater than the pressure of 1bar extraly or selectively.

Images