The present invention relates generally to systems for analysis of materials by contacting a plurality of solid members with a test fluid, and more particularly, to an apparatus and method for evaluating solid catalysts that have a size suitable for industrial scale processes in a laboratory scale reactor having hydrodynamics that perform comparably to a pilot or industrial scale fixed bed reactor.
In traditional catalyst development, researchers synthesize relatively small amounts of a candidate compound. They then test the compound to determine whether it warrants further study. For solid phase catalysts, this initial testing typically involves confining the compound in a crushed and sieved form in a vessel, such as a micro-reactor, and then contacting the compound with one or more fluid phase reactants at a particular temperature, pressure and flow rate. If the compound produces some minimal level of conversion to a desired product, the compound undergoes more thorough characterization in a later step.
The later step includes manufacturing the catalyst into shaped crystals, such as spheres, cylinders, or rings. These shaped catalysts are then evaluated in a bench top reactor for more thorough analysis. However, these reactions typically are not able to achieve ideal displacement conditions and/or are not conducted under real flow reaction conditions, such as those used in a pilot plant or industrial reactor. Typical reaction conditions for the bench top reactors include a lower fluid flow rate, a lower linear velocity, a diluted bed, and/or back-mixing.
It has been found that, in order for a fixed bed reactor, such as a tube, having a bed of catalyst grains, to have ideal displacement conditions, the diameter of the tube needs to be at least approximately 10 times greater, and the length of the bed needs to be at least approximately 30 times greater than the particle diameter. Thus, an industrial or pilot plant fixed bed reactor utilizing particles having a mass of at least 1 gram will require a large amount of catalyst material for reaction. This is not ideal for catalyst research, where amounts of material may be small, and a researcher needs to work in a laboratory, not a pilot plant.
M. I. Temkin, Laboratory Reactor With Ideal Displacement, Kinetika i Kataliz, vol. 10 no. 2, pp. 461-463 (1969), describes a laboratory-scale reactor in which a cylindrical reaction cavity is filled with industrial form catalyst beads that are spaced apart with inert cylinders. The reactor emulates a plug flow reactor by assembling a series of continuous stirred tank reactors. A large number of continuous stirred tank reactors in series behave as a plug flow reactor. However, under certain conditions, transport effects arising from poor mixing in stagnant zones in the reactor can impede accurate kinetic measurements.
Thus, there is a need for a reactor that can be used to obtain accurate kinetic information for industrial-form catalysts using minimal catalyst material while approximating large-scale reactor hydrodynamics as well as heat and mass transfer characteristics.
It is therefore an object of the present invention to provide an apparatus and method for obtaining kinetic information for commercial-form catalysts using minimal catalyst material while approximating large-scale reactor hydrodynamics and heat and mass transfer.
Briefly, therefore, the present invention is directed to a chemical processing system comprising a plug flow reactor that comprises a surface defining a reaction cavity for carrying out a chemical reaction and containing industrial form catalyst particles, an inlet port in fluid communication with the reaction cavity, and an outlet port in fluid communication with the reaction cavity. The reaction cavity has a volume of not more than about 1 liter, and in some applications, not more than about 500 ml, 100 ml, 50 ml, 10 ml, 5 ml, 1 ml, 100 μl, 10 μl or 1 μl. A fluid distribution system can supply one or more reactants from one or more external reactant sources to the inlet port of the reaction cavity and can discharge a reactor effluent from the outlet port of the reaction cavity to one or more external effluent sinks.
The present invention is directed to single and parallel (e.g., multi-channel) chemical processing systems, especially, laboratory-scale chemical systems that approximate industrial scale process conditions. Specifically, the invention is directed to a laboratory-scale reactor system that approximates plug-flow behavior for industrial form catalysts while achieving space velocities and velocities over the surface of the catalyst particles comparable to those used in industrial processes. Although primarily discussed and exemplified herein in the context of laboratory-scale reactors, including parallel reactors, it is to be understood that the invention has applications in other chemical processing systems (e.g., mixing systems, separation systems, material-processing systems, etc.), some of which are discussed in varying detail below.
Briefly, therefore, in one embodiment, the present invention is directed to a method for evaluating catalysts, which includes flowing a reactant fluid through a reactor, wherein the reactant fluid contacts a plurality of solid catalyst particles located in a reaction cavity of the reactor under reaction conditions such that a flow characteristic of the reactant fluid through the reaction cavity of the reactor is a Peclet number for axial dispersion greater than 100 and in some aspects, greater than 125, 150, 175, 200, 225, 250, 275 or 300. The reactor includes a surface defining the reaction cavity, which has a volume less than 1 liter.
In another embodiment, the present invention is directed to a heterogeneous catalysis process, which includes contacting a gas stream in a reactor with a plurality of solid catalyst particles located in a reaction cavity of the reactor, the catalyst particles having dimensions suitable for industrial scale processes, under reaction conditions such that the gas stream has a substantially uniform velocity at all points over substantially the entire surface of each of the plurality of solid catalyst particles. The reactor includes a surface defining the reaction cavity, which has a volume less than 1 liter.
In another embodiment, the present invention is directed to a method for evaluating catalysts, which includes flowing a reactant fluid through a reactor that comprises a surface defining an internal cavity, and an insert located in the internal cavity. The insert includes a fluid inlet for receiving a fluid from a fluid source, a fluid outlet for discharging the fluid as an effluent, a surface defining a plurality of reaction cells connected via conduits, and a plurality of industrial form solid catalyst particles located in the reaction cells. Each reaction cell is adapted to hold a single catalyst particle. The reactant fluid flows through the reaction cells, and contacts the plurality of solid catalyst particles located in the reaction cells under reaction conditions.
In another embodiment, the present invention is directed to a system for contacting solid catalyst particles with a fluid. The system includes a reactor adapted to hold a plurality of solid catalyst particles, and includes a surface defining an internal cavity, and an insert located in the internal cavity. The insert includes a fluid inlet for receiving a fluid, a fluid outlet for discharging the fluid, and a surface defining a plurality of reaction cells connected via conduits. Each reaction cell is adapted to hold a single catalyst particle.
In another embodiment, the present invention is directed to a reactor system, which includes a vessel comprising an inlet for receiving a fluid, an outlet for discharging the fluid as an effluent, a surface defining a reaction cavity having a volume less than 1 liter, and a plurality of industrial form catalyst particles located in the reaction cavity. The reaction cavity is adapted to provide a substantially uniform velocity of the fluid over the surface of each of the catalyst particles under reaction conditions.
In another embodiment, the present invention is directed to a reactor system for evaluating catalysts. The reactor includes a vessel comprising an inlet for receiving a fluid, an outlet for discharging the fluid, a surface defining a reaction cavity, and a plurality of solid catalyst particles all having approximately the same geometry and dimensions located in the reaction cavity. The reaction cavity has a cross sectional area no greater than twice a cross-sectional area of a single catalyst particle of the plurality of catalysts, and a length adapted to accommodate the plurality of catalyst particles. The reaction cavity is adapted to provide a substantially uniform velocity of the fluid over substantially the entire surface of each of the plurality of catalyst particles under reaction conditions.
In another embodiment, the present invention is directed to a parallel flow reactor system for evaluating a plurality of industrial form catalyst particles. The reactor has a plurality of surfaces defining a plurality of reaction cavities, each of the plurality of reaction cavities having an inlet for receiving a reactant-containing stream and an outlet for discharging a product-containing stream. Each reaction cavity has a plurality of industrial form solid catalysts contained therein. The reactor system is adapted such that each reactant-containing stream can be fed through the plurality of reaction cavities simultaneously to contact the catalyst particles under reaction conditions and each reaction cavity is adapted to provide a substantially uniform velocity of the reactant-containing stream over substantially the entire surface of each of the plurality of catalyst particles under reaction conditions.
In some embodiments, by designing the geometry of a reaction cavity in a small scale reactor to accommodate industrial form solid catalyst particles and by controlling the hydrodynamics of the reaction to model an ideal plug flow reactor, relevant performance characteristics and accurate kinetic data can be obtained using a small-scale reactor. Thus, catalysts that would typically be run in a pilot plant can be evaluated on a much smaller scale, and the data obtained can be useful in predicting the performance of the same catalyst particles in larger reactors.
In some embodiments, the reaction cavity has a shape that that roughly follows the contour of the catalyst particles such that a fluid velocity and residence time behaves in a plug flow manner. Some embodiments utilize a cavity chain reactor, which is a plurality of reaction cavities or reaction cells, arranged in a chain formation. Each cavity or cell in the chain is designed to hold a catalyst particle and has a shape that that roughly follows the contour of the catalyst particle.
One advantage of the present invention is that the hydrodynamics perform comparably to a pilot or industrial scale fixed bed reactor. The velocity of the reaction fluid over the surface of the catalyst is similar to a pilot or industrial scale reactor at a given space velocity such that the heat and mass transfer characteristics are attained on a laboratory-scale. With this reactor an average linear velocity greater than 1 meter/second can be obtained at a space velocity at 5000 per hour.
Another advantage of the present invention is a very fast experiment turnaround. Catalysts can be changed and the reactor can be cleaned and/or re-started typically in less than 30 minutes.
The present invention also provides the ability to monitor individual catalyst temperatures in-situ, thus yielding additional kinetic and transport phenomena information.
The present invention provides a bench top reactor providing more uniform mass transfer over the entire surface of the catalyst particles than do other bench top reactors for evaluating industrial form catalysts.
Other features, objects and advantages of the present invention will be in part apparent to those skilled in art and in part pointed out hereinafter. All references cited in the instant specification are incorporated by reference for all purposes. Moreover, as the patent and non-patent literature relating to the subject matter disclosed and/or claimed herein is substantial, many relevant references are available to a skilled artisan that will provide further instruction with respect to such subject matter.
The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawings will be provided by the Office upon request and payment of the necessary fee.
The present invention provides an apparatus and method for reacting a plurality of industrial form catalysts in a laboratory scale reactor while closely approximating industrial or pilot plant reactor conditions. This is accomplished by controlling the hydrodynamics to model an ideal plug flow reactor. “Plug flow” characterizes the manner in which materials move through a reactor. Due to the configuration and/or operation of the reactor, any particular selected plug of material traversing the reactor has minimal axial mixing with an adjacent plug of material even though there may be radial mixing within the plug.
One way of characterizing flow characteristics of a fluid through a reactor is by the Peclet number for axial dispersion. The Peclet number for axial dispersion (a dimensionless number) is a ratio comparing the relative effects of convective fluid flow versus axial dispersion. When the ratio is low, the Peclet number for axial dispersion is low, and dispersion is more pronounced. Dispersion results in a spread of the residence time that different slices, or plugs, of the fluid spend in the reactor. In the context of chemical reactions, higher dispersion can result in lower conversions. Hence, the lower the Peclet number for axial dispersion, the lower the maximum conversion that can be attained in the reactor.
Chemical reactors are classified by the type of mixing as plug flow reactors (little or no intermixing of fluid) and continuous stirred tank reactors (CSTR) (complete mixing). An ideal plug flow reactor has a very high Peclet number for axial dispersion, typically greater than 100. Because pilot plant and large-scale packed beds exhibit plug-flow behavior with very few exceptions, plug flow is desired in a laboratory scale reactor. Thus, the Peclet number for axial dispersion is used to characterize how close a reactor is to a plug flow reactor for the reactions of interest to the present invention.
Another characteristic of importance in reactors of the present invention is having a substantially uniform velocity of the fluid at all points over the surface of each catalyst particle at a given space velocity. Velocity of the fluid at a given point is defined as the volumetric flow rate of the fluid divided by the cross-sectional area of the fluid path at that point. Space velocity is defined as the volumetric flow rate of the fluid divided by the volume of the catalyst particle. Reactors of the present invention are able to run at space velocities comparable to space velocities run in industrial reactors, while maintaining a substantially uniform velocity of the fluid at all points over the surface of each catalyst particle comparable to those attained in industrial reactors.
In one aspect, the invention simulates the hydrodynamics of large scale reactors using industrial-form catalyst particles in a laboratory-scale reactor. In one embodiment, this is accomplished by using a modular ball cavity chain reactor. The reactor can test industrial-form catalysts (beads, cylinders, extrudates, etc.) without diluent while maintaining plug-flow characteristics under reaction conditions.
By “industrial form catalyst particles” it is intended to mean catalyst particles having dimensions suitable for industrial scale processes. This includes catalyst particles having a mass of at least 1 g, and/or having a diameter of at least 3 mm. In preferred embodiments, catalyst particles are spherical and have a diameter between about 3 mm and 10 mm, and more preferably between about 3 mm and 8 mm.
In one embodiment, reaction is achieved by providing a laboratory-scale or bench top reactor having a reaction space geometry designed to have a shape that roughly follows the contours of the catalyst particles such that the fluid residence time behaves in a plug flow manner. Reactions can be simultaneous for two or more pluralities of catalysts located in a plurality of reaction cavities, or carried out in a rapid serial manner. Changes in the fluid resulting from contact with the catalysts are used to evaluate the catalysts. In the following disclosure, the term “fluid” refers to any substance that will deform continuously under the action of a shear force, including both gases and liquids.
The apparatus and method can be used to evaluate catalysts based on any property that can be discerned by detecting or measuring changes in a test fluid following contact with a plurality of catalyst particles. Thus, for example, the catalyst particles can be evaluated for catalytic activity by contacting the catalyst particles with a reactive fluid and detecting conversion or selectivity.
The disclosed invention is not limited to evaluating catalysts, but can be used for reaction of many different types of materials. For example, the method and apparatus can be used to evaluate solid particles based on their ability to filter out or adsorb a specific gas species. The concentration of that gas species in a fluid stream following contact with a plurality of solid particles is inversely proportional to the particular material's performance. Similarly, for example, polymeric materials can be evaluated for thermal stability by measuring the concentration of gaseous decomposition products in an inert fluid stream in contact with heated library members. The amount of decomposition product evolved by a particular polymeric material is a measure of that material's thermal stability.
The invention is described in further detail below with reference to the Figures, in which like items are numbered the same in the several figures.
Reactor Configurations
The reaction cavity 18 shape can be designed based on the geometry of the solid catalyst particles 24 contained therein. For example, the embodiment shown in
In other embodiments, as shown in
The reactor 10 of the invention can be utilized in several different ways. For example, in one embodiment, as shown in
In another embodiment, as shown in
The reactor 10 of this embodiment can be utilized in several ways. For example, the reactor 10 can be utilized to run two reactions simultaneously in a parallel fashion, by running two separate feeds, either from separate fluid sources or from a common fluid source through the reaction cavities 1828, and running the effluent streams to a parallel or rapid serial detector. Alternatively, the reactor 10 can be utilized to run two reactions in a serial fashion, running the reactant gas through the first reaction cavity 18, then switching to the second reaction cavity 28 after the first reaction is through.
In another embodiment, as shown in
While the embodiment shown and described in
Body
Insert
The resulting insert may then be slid into a sleeve 64 as shown in
Like the body 12, the insert and sleeve 64 are preferably constructed of materials that are machinable, have good thermal conductivity, and are relatively chemically inert, with aluminum being preferred.
The reaction cavity 18 of the reactor is designed so as to hold the catalyst particles and have a reaction pathway around each catalyst particle so that under reaction conditions, a Peclet number for axial dispersion greater than 100, specifically more than 125, more than 150, more than 175, more than 200, more than 250, and more than 300 is achieved. Space velocities such as those run in industrial reactors are achieved, and at those space velocities, there is a substantially uniform velocity at all points over the surface of each catalyst particle. The insert design of
The design of the insert as described above, in combination with the use of spherical catalyst particles sized appropriately to the reaction cavity size, allows for ideal plug flow conditions during reaction and a substantially uniform velocity at all points over the surface of each catalyst particle at space velocities run in industrial and pilot plant reactors. In a preferred embodiment, the cross sectional area of the reaction cavity at any point is less than three times, preferably less than twice, the cross-sectional area of the largest catalyst particle located in the reaction cavity. In preferred embodiments, the catalysts are industrial form catalysts all having approximately the same dimensions, geometry, and chemical compositions. It may be desirable however, to react catalysts having different geometries, dimensions and/or chemical compositions, and this is within the scope of the invention. The embodiments described herein are suitable for reacting spherical catalyst particles, preferably having a diameter from 3-8 mm.
End Caps
In some embodiments of the present invention, reactors 10 have end caps for providing various connections for the reaction cavities in the body 12 of the reactor 10. Various end cap designs are illustrated in
An inlet/outlet end cap 440 located at each end 1517 of the body 12 provides a variation of the configuration described in
An inlet/outlet end cap 440 located at the first end 15 of the body 12 and a bypass end cap 460 located at the second end 17 of the body 12 provides the configuration described in
Four Reaction Cavity Pathway Configuration
In operation, the chemical processing systems of the invention, can operate over various ranges of temperature, pressure, contact times and space velocities. For a chemical reaction system: the reactor temperature can generally range from about 0° C. to about 1000° C., and preferably from about 20° C. to about 500° C., and more preferably from about 100° C. to about 500° C.; the reactor pressure can range from about 1 bar to about 200 bar, and preferably from about 1 bar to about 10 bar; residence times can range from about 1 μsec to about 100 sec, preferably from about 1 μsec to about 10 seconds, and most preferably from about 0.2 seconds to about 5 seconds; and space velocities can range from about 1,000 hr−1 to about 100,000 hr−1, and preferably from about 1,000 hr−1 to about 50,000 hr−1, and more preferably from about 1,000 hr−1 to about 10,000 hr−1. For explosive reactants (e.g., hydrocarbons and oxygen), explosion limits should be observed.
The accompanying Figures and this description depict and describe embodiments of the reactor system and method of the present invention, and features and components thereof. Fastening, mounting, attaching or connecting the components of the present invention to form the apparatus or device as a whole, unless specifically described otherwise, are intended to encompass conventional fasteners such as machine screws, nut and bolt connectors, machine threaded connectors, snap rings, clamps such as screw clamps and the like, rivets, nuts and bolts, toggles, pins and the like. Components may also be connected by welding, friction fitting or deformation, if appropriate. Unless specifically otherwise disclosed or taught, materials for making components of the present invention are selected from appropriate materials such as metal, metallic alloys, fibers, plastics and the like, and appropriate manufacturing or production methods including casting, extruding, molding and machining may be used.
Any references herein to front and back, right and left, top and bottom, upper and lower and horizontal and vertical are intended for convenience of description only, not to limit the present invention or its components to any one positional or spatial orientation. Such terms are to be read and understood with their conventional meanings. In the Figures, elements common to the embodiments of the invention are commonly identified.
It is contemplated that various changes may be made without deviating from the spirit and scope of the present invention. Accordingly, it is intended that the scope of the present invention not be limited strictly to that of the above description of the present invention.
The following examples illustrate the principles and advantages of the invention.
A modular ball reactor, such as that described above, having 7 mm diameter reaction cells, was used to confirm that the hydrodynamics of the reactor of the present invention perform comparably to a pilot or industrial scale fixed bed reactor. Calculated Peclet numbers for axial dispersion were used as a comparison. Helium gas was initially run through the reactor, and at time=0, the gas was switched to nitrogen. The time it took for the nitrogen to be detected at the outlet of the reactor corresponds to the residence time distribution (RTD) data listed in
Results indicate a Pe=300 (±50) for 28×6 mm Glass Beads (One body) and a Pe=150 (±25) for 56×6 mm Glass Beads (Two bodies) (2× residence time)
This example shows that plug flow behavior can be obtained in the laboratory scale modular ball reactor using commercial form catalyst pellets.
Residence time distribution in this example shows that the hydrodynamics perform comparably to a pilot or industrial scale fixed bed reactor.
In this example, experiments were conducted to determine and compare the residence time distribution (RTD) and velocity profiles in the prior art reactor described by Temkin as shown in
The experiments were performed using FLUENT computational fluid dynamics software. Both 2D and 3D simulations were performed on both designs and after validating the 2D results with the 3D results, the 2D models were used to reduce computation time.
Nitrogen was used as the process gas to model fluid flow and was run at 1 liter/minute. The RTD experiments were performed as step experiments. While the system was at steady state, flow was switched from a tracer nitrogen species (having exactly the same physical properties as nitrogen) to nitrogen and the concentration of nitrogen in the gas was measured at the inlet and outlet of the reactor.
Experiments were performed using 14 6 mm diameter beads in each reactor, the beads representing catalyst particles, and the results were convoluted to determine the RTD for an increasing number of beads.
The mole fractions of nitrogen at the inlet and outlet of the reactor of the invention as a function of time is shown in
The results were convoluted to determine the RTD for the reactor of the invention using an increasing number of beads (representing catalyst particles). The results are shown in
The same procedures were then run on the reactor shown in
The results were convoluted to determine the RTD for the prior art reactor using an increasing number of beads (representing catalyst particles). The results are shown in
Peclet numbers were then calculated and compared for an increasing number of beads used in the reactor of the invention as compared to the prior art reactor.
With this data and the reactor designs, velocity profiles were simulated using Fluent computational fluid dynamics software.
The reactor of the present invention showed a nearly uniform velocity profile over the catalyst bead under reaction conditions. No dead zones were present, whereas the velocity profiles for the reactor described by the prior art showed the presence of dead zones and non-uniform velocity distribution over the surface of the catalyst bead under similar reaction conditions. The reactor of the present invention showed a better residence time distribution with higher Peclet numbers indicating better plug flow behavior in comparison to the reactor described by Temkin. Thus, the reactor design of the present invention is superior to the reactor described by Temkin in terms of velocity distribution, plug flow behavior and external mass transport.
In light of the detailed description of the invention and the example presented above, it can be appreciated that the several objects of the invention are achieved.
The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. Those skilled in the art may adapt and apply the invention in its numerous forms, as may be best suited to the requirements of a particular use. Accordingly, the specific embodiments of the present invention as set forth are not intended as being exhaustive or limiting of the invention.
This application claims the benefit of U.S. Provisional Application No. 60/640,428, filed Dec. 30, 2004, which is incorporated herein by reference for all purposes.
Number | Date | Country | |
---|---|---|---|
60640428 | Dec 2004 | US |