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WO2008080361A1 - Dispositif d'élaboration de processus catalytiques à fort débit - Google Patents

Dispositif d'élaboration de processus catalytiques à fort débit Download PDF

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Publication number
WO2008080361A1
WO2008080361A1 PCT/CN2007/071391 CN2007071391W WO2008080361A1 WO 2008080361 A1 WO2008080361 A1 WO 2008080361A1 CN 2007071391 W CN2007071391 W CN 2007071391W WO 2008080361 A1 WO2008080361 A1 WO 2008080361A1
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Prior art keywords
reactor
stages
catalyst
reactors
composite
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Inventor
Richard F. Bauman
Rocco A. Fiato
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Accelergy Shanghai R & D Center Co Ltd
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Accelergy Shanghai R & D Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/12—Apparatus specially adapted for use in combinatorial chemistry or with libraries for screening libraries
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00015—Scale-up
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    • 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
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    • B01J2219/00286—Reactor vessels with top and bottom openings
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00389—Feeding through valves
    • 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
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    • B01J2219/00277—Apparatus
    • B01J2219/00477—Means for pressurising the reaction vessels
    • 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
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    • B01J2219/00277—Apparatus
    • B01J2219/00495—Means for heating or cooling the reaction vessels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00585—Parallel processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J2219/0059—Sequential processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J2219/00707—Processes involving means for analysing and characterising the products separated from the reactor apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/0086—Dimensions of the flow channels
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00869—Microreactors placed in parallel, on the same or on different supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00873—Heat exchange
    • 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
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    • B01J2219/00891—Feeding or evacuation
    • 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
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    • B01J2219/00957—Compositions or concentrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/0095—Control aspects
    • B01J2219/00952—Sensing operations
    • B01J2219/00968—Type of sensors
    • B01J2219/00981—Gas sensors

Definitions

  • This invention relates to apparatus for the low cost, accelerated development of catalysts and plug flow catalytic processes from discovery to commercial readiness, and more particularly to plug flow reactor apparatus and methods useful for the accelerated scale-up of catalytic processes.
  • the first step in a traditional scale-up program generally involves the selection, and definition of the intrinsic properties of, the catalyst. This step is typically performed isothermally with a diluted, crushed or powdered catalyst to minimize mass transfer limitations.
  • a process variable study is performed to determine the impact of space velocity, pressure, and residence time on reaction rate and selectivity. Activity and selectivity maintenance are then determined over a six to twelve month operating period.
  • a second process variable study is performed to determine whether these properties have changed during time on stream.
  • the commercial catalyst is of a larger particle size than the crushed catalyst and may have a special shape to minimize pressure drop during operation.
  • the larger particle size generally results in a lower reaction rate and a selectivity loss due to limitations on mass transfer of reactants or products in and out of the catalyst pores.
  • Operations generally consist of performing process variable studies at the beginning and end of an activity and selectivity maintenance run. This operation can be run in a laboratory scale reactor and typically lasts approximately one year.
  • the final step in the scale-up process is to test the commercial catalyst under adiabatic conditions, normally in a demonstration scale reactor containing one or more reactor tubes.
  • the tubes in the demonstration scale reactor would have internal diameter of approximately 1 inch.
  • a configuration containing up to about 6-8 tubes arranged at commercial spacing could be used.
  • the temperature profile depends upon the degree to which heat is continuously removed, as in a tubular reactor, or the reactor is simply a fixed bed reactor without a specific heat removal capability.
  • the temperature profile can have a significant impact on selectivity, reaction rate, and activity maintenance.
  • the test run also provides a measure of the tendency for the catalyst to produce hot spots or temperature runaways. Here again, the operating period can exceed one year.
  • reaction rate and selectivity may be a function of residence time as well as time on stream. This can be the result of changes in the catalyst state or form, due to exposure for extended periods of time, or it may be due to the changing gas and liquid composition from the reactor inlet to the outlet. Examples would include oxidation from water formed during conversion, formation of a support over layer, poisoning, e.g., by reaction with hydrogen sulfide and ammonia, etc.
  • surface catalytic reactions and buildup of feed and products in the pores can result in reductions in mass transfer rate to the catalyst.
  • HTE High Throughput Experimentation
  • the apparatus includes a first laboratory scale plug flow reactor that is operated at a relatively high conversion, e.g., between 60 and 80%.
  • the outlet of the first plug flow reactor is connected through valves to the inlets of the first stages of a plurality of parallel composite multistage series-connected laboratory scale plug flow reactors for feeding controlled amounts of the effluent of the first plug flow reactor to the inlets of the first stages of each of the multistage reactors.
  • Such inlets to the composite multistage series-connected reactors also receive controlled varying amounts of fresh reactant feed.
  • each composite multistage series-connected plug flow reactor includes a set of three or more series-connected plug flow reactor stages.
  • the composite multistage reactor may, for instance, include four or five or six series-connected reactor stages. Sampling valves are connected between each of the reactor stages in order to allow the bleeding off of controlled amounts of reactor stage effluent for analysis.
  • Each reactor stage contains a bed of the catalyst under test usually mixed with inert diluent particles.
  • the internal diameter of a reactor stage should be at least ten times the diameter of the smaller of the catalyst particles and inert diluent particles contained in the catalyst bed in the reactor stage.
  • the composite multistage series-connected reactor in a constant temperature environment, for instance by disposing it in a temperature control device.
  • the temperature control device for use in exothermic reactions may take various forms, for instance, by immersing the composite multistage reactor in a container of boiling water or in a fluidized sand bath.
  • the temperature control device could contain apparatus, such as an electrical heater, to supply heat to the composite multistage series-connected reactor in order to maintain the substantially constant desired temperature.
  • a fluidized sand bath can also be used as a temperature control device for endothermic reactions by immersing the composite multistage reactor therein.
  • all three or more series-connected reactor stages of one of the composite multi-stage reactor can contain beds of the same size catalyst, thereby simulating a single composite catalyst bed made up of the beds in the three or more reactor stages.
  • This permits the collection of data concerning the longitudinal gradients in reactor performance and changes in catalyst characteristics at successive positions along the composite catalyst bed formed by the three or more reactor stages.
  • One of the other parallel composite multi-stage series-connected reactor can contain, e.g., beds of crushed or powdered catalyst, while others can contain beds of commercial size catalyst of one or more shapes or sizes.
  • Such an arrangement permits the investigation of, e.g., longitudinally dependent mass transfer, kinetics and heat transfer characteristics of the composite bed of a fixed bed reactor.
  • the crushed or powdered catalyst results can be considered to represent the Intrinsic Reaction Rate (free of mass transfer and heat transfer limitations) and selectivity of the catalyst at Start of Run. Thereafter, during time on stream, the crushed or powdered catalyst results can be considered to represent a running Intrinsic Reaction Rate for the catalyst in the catalyst bed of that stage that includes the effects of catalyst aging. This is equivalent to an Effectiveness Factor of 1.0, where the Effectiveness Factor is equal to the Observed Reaction Rate divided by the Intrinsic Reaction Rate.
  • selectivity data provides a direct measure of the Intrinsic Selectivity versus conversion for both fresh and aged catalysts.
  • nonane is converted much more rapidly than heptane on all catalysts studied, as a result of the selective uptake (lower volatility) of nonane on the zeolite catalyst.
  • liquid phase at higher pressure such as 100 bar
  • the differences in observed reactivity between nonane and heptane are much smaller, reflecting their higher overall concentration on the catalyst.
  • the observed reactivities better reflect the intrinsic reactivity of the molecules.
  • the stages of a multistage probe reactor may have the same set of catalyst beds as one of the one or more composite multistage series-connected reactors and receive the same gas feed.
  • the use of the multistage probe reactor allows one to measure the transient response of the system to permanent or temporary changes in the feed composition at any stage of a composite multistage series-connected reactor. For instance, in the case of a multistage probe reactor, introduction of a change in gas or liquid input to the third reactor stage of the probe reactor and comparing its performance with that of the corresponding stage of a composite multistage series-connected reactor, allows one to measure the impact of the changed component on the reaction rate and selectivity of the third reactor stage catalyst bed with time. Introduction of the change to the second probe reactor stage allows one to measure the impact on the second and third stage catalyst beds.
  • a plurality of composite multistage series-connected reactors can be operated in parallel in a common constant temperature environment with the each of the composite multistage series-connected reactors containing beds of the same or different catalysts and with the same or different catalyst particle sizes or shapes. This would permit the simultaneous investigation of a plurality of different catalysts and/or of different catalyst sizes or shapes.
  • a plurality of probe reactors can be operated in parallel with one or more composite multistage series-connected reactors in a common constant temperature environment to permit the simultaneous investigation of the response over time of various portions of the composite multistage series-connected reactor or reactors to different changes in feeds.
  • plug flow reactor refers to fixed bed reactors, packed bed reactors, trickle bed reactors and monolithic reactors operating either in a once through or a recycle mode.
  • laboratory scale plug flow reactor refers to a plug flow reactor in which each reactor stage has an internal diameter of less than 4 inches, preferably less than 2 inches, and more preferably less than 1 inch; a length of less than 8 feet, preferably less than 4 feet, more preferably less than 1 foot; and a catalyst charge of less than 800 grams, preferably less than 400 grams, more preferably less than 25 grams (excluding inert diluent particles charged to the reactor).
  • Figure 1 is a schematic representation of a plurality of composite multistage, series-connected plug flow reactors configured to receive controlled variable inputs in accordance with the invention.
  • Figure 2 is a schematic representation of a multistage, composite series-connected, isothermal plug flow reactor in accordance with the invention
  • Figure 3 illustrates an assembled, schematic diagram of reactors and a separator in accordance with one embodiment of the present invention
  • FIG. 4 illustrates an assembled, schematic diagram of the reactors and the separator in accordance with another embodiment of the present invention.
  • Figure 5 illustrates an assembled, schematic diagram of the reactor and the separator in accordance with yet another embodiment of the present invention.
  • the module 151 contains a plurality of parallel plug flow reactor stages 151-1 through 151-n.
  • the module 151 includes a temperature control device 152 surrounding the module 151 for controlling the temperature of the ambient experienced by the reactor stages 151-1 through 151-n.
  • the temperature control device may consist of an enclosure containing circulating boiling water for extracting heat from the reactor stages 151-1 through 151-n.
  • the temperature control device can comprise apparatus, such as an electrical heater, for supplying heat to the reactor stages 151-1 through 151-n.
  • the temperature control device 152 may alternatively comprise a fluidized sand bath heater in which the multistage reactors are immersed.
  • Each of the reactor stages 151-1 through 151-n contain a catalyst bed 153-1 through 153-n.
  • the modules 155 and 157 can be identical to the module 151, and contain a plurality of parallel plug flow reactor stages 155-1 through 155-n and 157-1 through 157-n, respectively.
  • Each of the parallel reactor stages in the modules 155 and 157 contain catalyst beds 159-1 through 159-n and 161-1 through 161-n, respectively.
  • the outlet of each of the reactor stages in module 151 is connected to the inlet of the corresponding reactor stage in module 155
  • the outlet of each of the reactor stages in module 155 is connected to the inlet of the corresponding reactor stage in module 157.
  • the series connected reactors stages 151-1, 155-1 and 157-1 form a composite multistage series-connected fixed bed reactor.
  • the other sets of series connected reactor stages in the modules 151, 155 and 157 also form composite multistage series-connected fixed bed reactors.
  • the modules 151, 155 and 157 may contain any desired number of parallel reactor stages depending upon the application. For instance, each module might contain four or eight or even 16 parallel reactor stages. Is also possible to have additional modules of parallel reactors stages, with each of said parallel reactors stages being connected in series with the corresponding reactor stages of the preceding and succeeding modules. For instance, there might be four or six modules in a given application.
  • the modules 155 and 157 are surrounded by temperature control devices 158 and 160, respectively, that may be the same as, or common with, the temperature control device 152 that surrounds the module 151.
  • Sampling valves 163-1 through 163-n are connected between the outlet of each reactor stage in the module 151 and the inlet of the corresponding reactor stage in module 155.
  • Sampling valves at 165-1 through 165-n are connected between the outlets of each of the reactor stages in module 155 in the inlet of the corresponding reactor stage in module 157.
  • Fresh reactant feed is fed from a source 167 through control valves 169-1 through 169-n to the inlets of each of the reactor stages 151-1 through 151 -n of module 151 for supplying controlled amounts of reactant feed to the inlets of the respective reactor stages.
  • the plug flow reactor 171 also receives fresh reactant feed from the source 167 at its inlet, and has its outlet connected to the inlets of the reactor stages 151-1 through 151 -n through control valves 173-1 through 173-n, respectively, for supplying controlled amounts of effluent from the reactor 171 to the reactors 151-1 through 151-n.
  • the proportion of fresh feed and reaction products and byproducts varies continuously along the length of the catalyst bed. At the inlet there is 100% fresh reactant feed and zero reaction products and byproducts. As the fresh feed is consumed in the catalyst bed of the reactor, the proportion of fresh feed decreases and the proportion of reactant products and byproducts increases longitudinally along the catalyst bed.
  • the multiple parallel-serial reactor arrangement of Figure 1 can be used to perform a number of different kinds of experiments. For instance, all of the reactor stages can contain the same catalyst and the composition of the feed can be varied from stage to stage. Alternatively, the composition size or configuration of the catalyst particles can be varied from reactor stage to reactor stage in each of the reactor stages can receive the same feed.
  • the temperature control devices 152, 158 and 160 may, for an exothermic reaction such as the Fischer-Tropsch reaction, could contain a material, such as circulating boiling water or a fluidized sand bath, for extracting heat from the multistage series-connected reactors in order to maintain the multistage reactors in a substantially constant temperature environment.
  • a material such as circulating boiling water or a fluidized sand bath
  • the temperature control devices could contain apparatus, such as an electrical heater, to supply heat to the composite multistage reactors in order to maintain the substantially constant desired temperature environment.
  • the temperature control devices can consist of a fluidized sand bath heater in which the multistage reactors are immersed.
  • the analysis of the feed and the effluent from the reactor stages can include, e.g., conventional GC/MS or UV or IR characterization of the reactant and product stream(s), and/or analysis of the catalyst system by XRD, diffuse reflectance IR or other spectroscopic techniques that are well known in the art. These studies would allow the performance attributes of the system to be quantified as a function of the longitudinal position in the catalyst bed.
  • Such knowledge would allow the system to be optimized with direct knowledge of the catalytic reaction kinetics and performance attributes of each point and permit the design of catalyst systems in which, e.g., the catalyst particles may have different chemical or physical characteristics in different portions of the catalyst bed so as to operate at peak productivity or selectivity as a function of the local environment.
  • the catalysts are diluted with an inert particulate matter, typically in a ratio of up to about 8-10 to 1.
  • the catalyst For measurements being made with the reactor operating in a substantially adiabatic regime, the catalyst, and depends on the heat of reaction of the process under study and reactor diameter.
  • the ratio of catalyst particles to diluent particles in a catalyst bed depends upon a number of factors, including the amount of heat generated by the reaction and the activity of the catalyst particles in the bed. The appropriate ratio for a given reaction, catalyst, reactor diameter and catalyst particle size can easily be determined by one of ordinary skill in the art by a simple experiment.
  • a commercial-size catalyst in a fixed bed reactor typically has particle size of about 1 to 5mm.
  • the catalyst particles can be in any one or more a variety of shapes, e.g., round, tubular, trilobe, toroidal, etc.
  • the crushed or powdered catalyst which is typically formed by crushing a commercial-size catalyst, typically has a particle size of about 0.10 - 0.20 mm. the crushed or powdered catalyst particles are normally preferably as small as can be obtained while still retaining a performance qualities of the catalyst.
  • the interior diameter of a reactor stage should be about 10 times the diameter of the smaller of the diluent or catalyst particles and the minimum would typically be in the range of about 10 to 50 mm (0.4 to 2 inches) for a bed containing commercial-size catalyst particles and diluent. Crushed or powdered catalyst particles are typically more active than the commercial-size catalyst particles because of lower mass transfer resistance.
  • the ratio of inert diluent particles to catalyst particles in the bed of crushed or powdered catalyst particles normally needs to be higher than that of the bed containing commercial-size catalyst particles in order that the heat release per unit volume of the to catalyst beds is the same.
  • the interior diameter of a reactor containing crushed catalyst can, if desired, be smaller, in the range of about 5 to 12mm, than that of a reactor containing the commercial size catalyst.
  • the crushed catalyst bed may be reduced by the use of a thermally conductive sleeve within the reactor.
  • the minimum height of a reactor stage is determined either by mixing or heat release considerations. For isothermal operation, if mixing is the limiting factor, the height should be sufficient to avoid bypassing. Typically, this would be at least about 50 times the average diameter of the particles, or about 50 to 250 mm (2 to 10 inches) for a reactor stage containing a bed of commercial-size catalyst particles. Because the feed is progressively converted as it traverses the stages of a composite multistage series-connected reactor, the concentration of fresh feed in the successive reactor stages decreases from one stage to the next. If it is desired to have constant conversion in each reactor stage, the lengths of the catalyst beds of the successive series-connected reactor stages can be progressively longer.
  • One or more of the composite multistage reactors formed by of the corresponding series-connected stages of the modules 151, 155 and 157 can be used as a probe reactor to investigate the effects of the addition of various materials to the flow stream of a composite multistage series-connected plug flow reactor. Such materials could be for instance, additional reactant feed, reaction products or byproducts, contaminants or poisonous to the catalyst.
  • the composite multistage series connected reactor formed by a stages 151 -n 155-n and 157-n can be used as a probe reactor receiving such additional inputs from the source 175. That source 175 could be connected to any of the stages of such composite multistage series-connected reactor, or separate sources could be connected to some or all of such series-connected reactor stages.
  • a probe reactor allows one to measure the transient response of the system to permanent or temporary changes in the feed composition at any stage of a composite multistage reactor by comparing the characteristics and performance of the relevant stages of the probe reactor over time in response to the change in input with the characteristics and performance of the corresponding stages of the composite multistage reactor.
  • Introduction of a change in gas or liquid input to the third reactor stage of the probe reactor 157-n allows one to measure the impact of the changed component on the reaction rate and selectivity of the third reactor stage catalyst bed of the relevant composite multistage reactor with time. This is equivalent to measuring the response to a change in conditions of any small segment of the catalyst bed in a commercial-size fixed bed reactor.
  • the source 175 can vary the concentrations of the trace components present in the fresh feed in a selected probe reactor stage, for instance by adding fresh reactant feed having a higher or lower concentration of such trace components, in order to quantify the effect of such trace components on various parts of the composite catalyst bed under a full range of operating conditions. By doing this it would be possible to map the critical longitudinal portions of the composite catalyst bed in a commercial system in which the catalyst is most vulnerable to poisoning or other inhibitory reactions caused by poisons or other natural byproducts of the reaction being practiced.
  • the probe reactor can also be used to investigate the transient response of a reactor to temporary changes in the composition of the feed or prior stage effluent to various points in a composite catalyst bed by temporarily adding the materials of interest to a selected stage of the probe reactor from the source 175 and monitoring the time dependent response of that stage and following stages of the probe reactor to such added materials both during and after the time that such materials are added.
  • the reactant and other material feeds, and reaction products and byproducts in reactor effluents supplied or generated in the embodiments of the invention described herein may be either gaseous, liquid or mixed phase (such as e.g., gas/liquid or two or more immiscible liquids).
  • Feeds and effluents consisting of gases can be handled using well known conventional back pressure regulators and gas flow control systems with mass flow controllers. Controlled amounts of liquids can be pumped in high-pressure environments using known pumps such as a Ruska pump or a Syringe pump. If the effluent from a reactor stage or the feed contains multiple phases, particularly if such phases are immiscible, such as water and hydrocarbons or liquid and gas, it is important to avoid slug flow.
  • sampling valves may consist of e.g., iso-kinetic sampling valves such as available from Proserv AS, or splitters such as described in U.S. Patent No. 4,035,168.
  • the stream may be sampled immediately after a static mixer such as available from Proserv AS, which homogenizes the multiphase stream.
  • a static mixer such as available from Proserv AS, which homogenizes the multiphase stream.
  • static mixers such as available from Proserv AS or from Admix, Inc., Manchester, NH, can also be used. In this case, some simple initial testing may be desirable to confirm that the operating conditions are leading to the homogeneity of the stream passing through the device. If the gas and liquid are well mixed in a transfer line, it is possible, for instance, to take a combined liquid and gas sample in a sample bomb connected to the reactor line via double block valves. The bomb would be at atmospheric pressure or slightly above. The block valves would be opened and liquid and gas would be allowed to flow into the bomb. The two block valves would then be closed, the sample bomb removed from the reactor and the contents analyzed.
  • an inert gas such as Argon in the stream can be used to allow closure of the material balance.
  • an inert gas such as Argon
  • gas/liquid separators and analyze the gas and liquid phases separately with an internal standard such as He or Ar and overall carbon balance analysis to link the two. This could be accomplished e.g., by using a gas sample bomb attached to the top of the line and a liquid sample bomb attached to the bottom of the line.
  • a major area of concern in understanding and controlling the characteristics and performance of a plug flow reactor is the adsorption or reaction of a feed component, product or byproduct with the catalyst surface.
  • materials such as ammonia, carbon monoxide, hydrogen sulfide, can tie up active catalyst sites, reduce reaction rate and adversely impact product selectivity.
  • the reactions caused by these materials can take time to equilibrate and can also take time to be released after removal of the material from the feed stream to the reactor.
  • Ammonia is known to react with cobalt Fischer-Tropsch and hydrocracking catalysts, causing activity to decline and line out.
  • hydrogen can be used to remove the ammonia from the catalyst surface.
  • ammonia can be added to the inlet of any of the stages of probe reactor, thereby replicating the effect of the presence of ammonia in the feed to a selected longitudinal slice of the composite catalyst bed.
  • By controlling the conversion level in a given catalyst slice e.g., by adjusting temperature and/or flow rate and/or reactant partial pressures in a probe reactor stage, it is possible to define the effect of the ammonia under various operating conditions.
  • By varying the hydrogen concentration in the feed to one or more probe reactor stages it is possible, for example, to investigate the effect of increased hydrogen on the ammonia-contaminated catalyst in different portions of the composite catalyst bed, e.g., the bed with the greatest activity decline.
  • Carbon monoxide is tightly held on a cobalt Fischer-Tropsch catalyst, which can reduce available surface for hydrogen, thereby making hydrogen the rate limiting step.
  • concentrations of carbon monoxide and hydrogen in the feed to selected stages of the probe reactor 35 or 101 and comparing performance of the relevant probe reactor stages with the corresponding stages of the multistage reactor 11, it is possible to determine the impact of carbon monoxide and hydrogen concentration on reaction rate and selectivity.
  • the use of a multi-stage probe reactor allows for testing of the impact at various conversion levels by e.g., by adjusting temperature and/or flow rate and/or reactant partial pressures.
  • Conradson carbon is usually utilized in correlations for hydrotreater performance. Wax has a similar impact on Fischer-Tropsch catalysts. In general, carbon and heavy wax deposits on a catalyst inhibit the diffusion of reactants to the catalyst surface and the removal of reaction products from the catalyst surface. This tends to lead to activity reduction via unwanted side reactions with deposits on the catalyst surface or with the diffusion limited reactants or both. In the case of beds containing commercial-size catalyst particles where the diffusion path is the longest, this sort of diffusion limitation can limit overall catalyst life and require costly steps to maintain system performance. Adding different molecular weight fractions of these materials to a selected stage of the probe reactor would allow the determination of what portion of the composite catalyst bed is impacted the most.
  • Polynuclear aromatics are also known to inhibit a catalyst by forming carbonaceous overlayers on catalyst sites that reduce selectivity and activity of hydroprocessing catalysts.
  • the effect of the presence of polynuclear aromatics in the feed at various longitudinal portions of a composite catalyst bed of a plug flow reactor can be determined by adding the polynuclear aromatics to a selected stage of the probe reactor and comparing the characteristics and performance of the relevant stages of the probe reactor with the corresponding stages of the relevant composite multistage series-connected reactor.
  • a layered composite catalyst bed in which the intrinsic behavior of each catalyst layer is matched to the local kinetic and mass transfer environment, so that the overall response of the system is varied longitudinally so as to obtain behavior characteristics in each longitudinal portion of the composite reactor that are optimum for process performance. If a plurality of multistage series-connected plug flow reactors is disposed in separate, independently controllable temperature control devices, a plurality of different heat removal levels can be investigated in parallel.
  • the multistage series-connected reactor of the present invention can be used in accordance with the method of the invention to develop scale-up data for investigating the integral, differential and intrinsic kinetics of a plug flow catalytic reactor system as a function of the longitudinal position along the catalyst bed of the reactor.
  • the catalyst beds in the reactor stages of modules 151, 155 and 157 and the reactor 171 can contain the catalyst intended for use with the system.
  • the parallel reactor stages 151-1 through 151-n in the module 151 receive varying proportions of fresh feed from the source 167 and effluent from the reactor 171.
  • valves 169-1 through 169-n and valves at 173-1 through 173-n can be set such that reactor stage 151-1 receives 100% fresh feed and no effluent, and the reactor stages 151-2 through 151-n receive successively decreasing proportions of fresh feed and increasing proportions of effluent.
  • the successive reactor stages 151-1 through 151-n are equivalent to successive, longitudinally-spaced slices of the catalyst bed of a fixed bed reactor, with reactor stage 151-1 being equivalent to the slice at the inlet of the catalyst bed and reactor stages 151-2 through 151-n operating at conditions equivalent to slices of the catalyst bed positioned at successive longitudinal positions along the composite bed.
  • the reactor stages in modules 155 and 157 can be used to provide data for slices of the catalyst bed being scaled-up that are intermediate the slices of the successive reactor stages in module 151.
  • reactor 171 is operated at 90% conversion, its effluent will contain 10% of the amount of fresh feed at its inlet with the remainder of the effluent being reaction products and byproducts.
  • reactor stage 151-2 receives 88% fresh feed and 12% effluent from the reactor 171, the composition of the feed at the inlet to reactor stage 151-2 will be 89.2% fresh feed with the remainder being reaction products and byproducts.
  • the reactor stages 151-1, 155-1 and 157-1 are each run at 3% conversion, their effluents will contain 97% fresh feed, 94.1% fresh feed and 92.3% fresh feed, respectively, with the remainder being reaction products and byproducts.
  • the compositions and proportions of fresh feed and reaction products and byproducts in the reactor stages in modules 151 155 and 157 are equivalent to those at successive longitudinal slices in the catalyst bed of a fixed bed reactor.
  • the slope at each point along the resulting curve is equal to the Reaction Rate for the system.
  • the reaction rate is then plotted on a log-log plot versus the concentration of the fresh feed along the reactor catalyst bed. If the resulting curve is a straight line, the integral kinetics of the system is a constant along the length of the catalyst bed. If the line is horizontal, the system has first-order kinetics. If the line has a positive slope, the system has positive order kinetics greater than one. If the line has a negative slope, the system has negative order kinetics.
  • the above-described experiment can be run at different temperatures and at different pressures.
  • the experiment can also be run using different size catalysts.
  • the experiment can be run using the intended commercial size and shape catalyst and also with a diluted crushed or powdered catalyst.
  • the intrinsic and differential kinetics, free of mass transfer and heat transfer effects, of the composite multistage series-connected fixed bed catalytic system of the invention can also be investigated for purposes of scale-up to a commercial system using the systems depicted in Figure 1 of the drawings.
  • the catalyst beds of the reactor stages include very finely crushed or powdered catalyst particles in order to avoid mass transfer effects, and the catalyst is highly diluted to avoid heat transfer effects.
  • the diameter of the reactor should preferably be small, typically about 5 to 12 millimeters to further avoid heat transfer effects. This can be accomplished by using a smaller diameter reactor or by using a heat conductive sleeve in each reactor stage to reduce its diameter.
  • the depth of the catalyst bed in each of the reactor stages is typically between about 5 and 10 centimeters.
  • the same series of measurements and calculations are performed as described above for determining the integral kinetics of the system.
  • the amount of conversion in each reactor stage should be very small, e.g. less than 20 percent, preferably about 2 to 5 percent in the case of a Fischer Tropsch reaction.
  • the measurements can be performed at different temperatures and pressures in order to investigate the effects of temperature and pressure on the intrinsic and differential kinetics of the system.
  • a significant advantage of the system of convention is that the use of the reactor 171 to supply the effluent to all of the reactor stages in module 151 means that each of the reactor stages in the module 151 receives exactly the same reaction products and byproducts and trace elements, thereby replicating actual reactor conditions more exactly and eliminating errors resulting from variations in the composition of the feed to the reactor stages. Additionally, the composition of the inputs and outputs from all of the reactor stages can be sampled substantially simultaneously to give a snapshot of the reactor's performance at a given moment.
  • the sampling of the composition of the inputs and outputs from the reactor stages can also be repeated periodically while the reactor system continues to operate thereby investigating the performance of the reactor system as a function of time on stream to see what aspects of the reactor performance change and in what longitudinal zones of the overall catalyst bed the changes occur. This data is useful in investigating the catalyst stability, among other things.
  • the apparatus of the invention can also be used to investigate other operating parameters of a plug flow reactor for scale-up or other purposes in accordance with the method of the invention.
  • the longitudinally dependent activity maintenance of a catalyst bed can be investigated as a function of time on stream under different conditions of temperature, pressure and catalyst shape and size.
  • Other longitudinally dependent process parameters that can be investigated using the method of the invention include the effects of different space velocities, reaction products and by-products, different operating temperatures and pressures, time on stream, and different catalyst sizes and shapes, on matters such as e.g., conversion, productivity, kinetics and selectivity, and on changes in catalyst physical and chemical properties such as active site crystal size, oxidation, and growth of an over-layer of support on the surface of the catalyst active sites.
  • the time for scale-up of the catalytic process from discovery to commercial scale application can be significantly reduced.
  • four multi-stage reactors of the type described above can be operated in parallel.
  • the stages of one of the reactors are loaded with crushed catalyst.
  • This reactor provides Intrinsic Reaction Rate and selectivity data.
  • the stages of the second reactor are loaded with commercial-size catalyst.
  • the data from this second reactor can be used to define the degree of mass transfer limitation (Effectiveness Factor) based on a direct comparison of the relative residence times in the reactors containing the crushed catalyst in the commercial-size catalyst required to achieve a given amount of conversion.
  • a third, probe reactor can be operated in parallel with the previous two reactors.
  • This probe reactor can either be a shallow fixed bed reactor or a back-mixed reactor. Flow can be directed to the appropriate actor from any of the reactor beds in the previous two reactors.
  • additional gases or liquids can be added to the probe reactor to determine the rates of adsorption or surface property changes on the catalyst. This information can provide valuable insight in modeling the fixed bed reactor.
  • an adiabatic reactor can be operated in parallel to test the reactor model developed from the previous reactors.
  • an adiabatic reactor In an adiabatic reactor, it is possible to produce hot spots in the reactor, which may cause the adiabatic reactor to run away. Also, in an adiabatic reactor, because reaction parameters, such as temperature, kinetics parameters, etc., can change continuously, it is difficult to measure the reaction parameters by direct measurement. Dividing an adiabatic reactor into multistage series-connected reactor stages can help determine reaction parameters at different locations along a flow direction of the reactor, but it is difficult to keep continuities of the reaction parameters, especially temperature, between adjacent reactor stages.
  • reaction parameters in an adiabatic reactor it is difficult to directly measure reaction parameters in an adiabatic reactor, and to exactly and securely determine reaction characteristics in the adiabatic reactor, such as kinetics, mass transfer, heat transfer etc.
  • Fig. 2 illustrates a schematic diagram of a composite multistage laboratory scale plug flow reactor 607.
  • the reactor 607 includes first, second and third series-connected reactor stages 61, 63 and 65, each having a catalyst bed 62, 64 and 66.
  • the reactor 607 further includes a fresh reactant conduit 70 which connects an inlet of the first reactor stage 61 to a source 60, so that the source 60 can provide feeds, which are normally fresh reactants, to the first reactor stage 61.
  • the reactor 607 further includes connecting conduits 71 and 72 to connect the first and second reactor stages 61 and 63, and the second and the third reactor stages 63 and 65, respectively.
  • a first sampling valve 67 is disposed between the first and second reactor stages 61 and 63, and has an output 601 to facilitate sampling effluents from the first reactor stage 61.
  • a device is said to be disposed between two stages of the reactor does not necessarily mean that the device is physically disposed between the two stages of the rector but that the device is between the two stages of the reactor along a flow of reactants.
  • a second sampling valve 68 is disposed on the conduit 72 and has an output 602 for sampling effluents from the second reactor stage 63.
  • a third sampling valve 69 is disposed between an outlet of the third reactor stage 65 and a device, such as a fourth reactor stage or a product accumulator (not shown) and has an output 603 for sampling effluents from the third reactor stage 65.
  • a sampling valve connected to the fresh reactant conduit 70 may also be provided in order to permit analysis of the feeds.
  • the reactor stages 61, 63 and 65 are isothermal reactor stages, which are used together to simulate an adiabatic reactor.
  • temperature control devices 604, 605 and 606 are provided to control the temperature of the reactor stages 61, 63 and 65 respectively.
  • a preheater (not shown) may be disposed between the source 60 and the first reactor stage 61 to preheat the feeds from the source 60 so that when the feeds flow into the first reactor stage 61, the feeds have already reached a desired temperature for the feeds.
  • the preheater can also be disposed in the first reactor stage 61.
  • the temperature setting for each of the temperature control devices 604, 605 and 606 should be determined first.
  • the temperature setting for the first temperature control device 604 and temperature variation in the first reactor stage 61 can be determined.
  • the temperature setting of the second temperature control device 605 can also be determined, and so on.
  • the reactor stages 61, 63 and 65 can be used to simulate the characteristics of the adiabatic reactor.
  • the temperature of the temperature control devices 604, 605 and 606 are defined as Tl, T2 and T3, which are different from each other. Different catalytic processes may have different Tl, T2 and T3 settings.
  • a common temperature control device (not shown) can be provided to control the temperatures of reactor stages 61, 63 and 65 together.
  • the isothermal reactor stages 61, 63 and 65 can respectively simulate successive catalyst bed slices of a catalyst bed of a larger adiabatic reactor.
  • the characteristics of the catalyst bed which is simulated by the catalyst beds 62, 64 and 66, are determined.
  • characteristics associated with the larger adiabatic reactor can be determined by simulating the adiabatic reactor using the isothermal reactor stages.
  • the first, second and third reactor stages 61, 63 and 65 can be arranged upright.
  • the effluent from a reactor stage may be in a multiphase state, meaning that it includes one or more gaseous fluids, which are fluids in gas phase (such as gases, vapors or mixtures of gases and vapors), and one or more liquid fluids, which are fluids in one or more liquid phases (such as water phase, oil phase, other immiscible phases and partial emulsion phases, etc.)
  • gas phase such as gases, vapors or mixtures of gases and vapors
  • liquid fluids which are fluids in one or more liquid phases (such as water phase, oil phase, other immiscible phases and partial emulsion phases, etc.)
  • the multiphase fluid is often a multi-component fluid, each component being in its own state, which can be a single-phase state or multiphase state. If the multi-component fluid is in thermodynamic equilibrium, the fluid can be transferred directly by a tube connecting two successive reactor stages.
  • a catalytic process development apparatus includes a composite multistage laboratory scale plug flow reactor 707 which includes first and second series-connected reactor stages 71 and 73.
  • the reactor stages 71 and 73 include catalyst beds 72 and 74, respectively.
  • the catalytic process development apparatus further includes temperature control devices 701 and 702 disposed on the reactor stages 71 and 73 respectively, and a fresh reactant conduit 77.
  • the fresh reactant conduit 77 is connected an inlet of the first reactor stage 71 to a source 70 so that the source 70 can provide feeds which are normally fresh reactants to the first reactor stage 71.
  • the catalytic process development apparatus further includes a separator 703, first and second effluent conduits 78, a gas conduit 75 and a liquid conduit 76.
  • the first conduit 78 is connected an outlet of the first reactor stage 71 to an inlet of the separator 703.
  • the gas conduit 75 and the liquid conduit 76 connect the separator 703 to an inlet of the second reactor stage 73.
  • the second effluent conduit 78 connect an outlet of the second reactor to a following device (not shown), such as another separator.
  • the reactants from the source 70 are fed into the first reactor stage 71.
  • a multiphase effluent fluid from the first reactor stage 71 is sent into the separator 703, wherein gaseous fluid(s) in the multiphase fluid are separated from liquid fluid(s), and both are introduced into the second reactor stage 73 through the gas conduit 75 and the liquid conduit 76 respectively.
  • the catalytic process development apparatus further includes a flow restrictor 705 disposed on the gas conduit 75 to control flow resistance in the gas conduit 75, resulting in a gas pressure difference (pressure drop) ⁇ P between two sides of the flow restrictor 705.
  • a gas pressure in the first reactor 71 and the separator 703 is Pl
  • a gas pressure in the second reactor 73 is P2.
  • Pl> P2 due to the flow restrictor 705, and ⁇ P Pl-P2. .
  • ⁇ P is large enough so that it can drive the liquid fluid in the separator 703 to enter into the liquid conduit 76 and to flow into the second reactor stage 73 but is also small enough so that it can not affect reactions in the second reactor stage 73.
  • the flow restrictor 705 can be a restricting valve, an orifice, or other restricting means etc.
  • the gas conduit 75 can function as the flow restrictor 705.
  • the flow resistance of the gaseous fluid can be adjusted by many ways, such as electrical, electromagnetic, pneumatic, mechanical or thermal ways etc., which are familiar to those ordinary skills in the art. The electromagnetic ways are preferred.
  • the catalytic process development apparatus further includes a differential pressure sensor (not shown) disposed across the flow restrictor 705 or two ends of the gas conduit 75 to measure the ⁇ P. Combined ⁇ P and physical properties of the gaseous fluid, information about a mass flow rate of the gaseous fluid can be determined.
  • the liquid fluid can not flow but accumulate in the separator 703. If ⁇ P is too large, the liquid fluid may keep flowing until all the liquid fluid in the separator 703 is transported to the second reactor stage 73. When the liquid fluid in the separator 703 is drawn out, the gaseous fluid may flow through the liquid conduit 76. Thus, ⁇ P is reduced due to an extra pathway for the gaseous fluid. Then, the liquid fluid begins to accumulate in the separator 703 and blocks the liquid conduit 76. Subsequently, the ⁇ P restores to a desired value little by little, and the liquid fluid starts to flow again. Thus, the flow rates of the gaseous and liquid fluids may fluctuate with respect to time because of fluctuation of the ⁇ P, which is disadvantageous to the second reactor stage.
  • the catalytic process development apparatus includes a liquid level sensor 706 disposed in the separator 703.
  • the liquid lever sensor 706 monitors variation of a liquid level 704 in the separator 703.
  • Liquid sensor signals from the liquid level sensor 706 are used to control the flow restrictor 705 to generate a suitable ⁇ P to drive the liquid fluid in such a manner that the liquid level 704 is maintained at a desired substantially constant level.
  • the fluctuation of the fluids in the separator 703 can be eliminated.
  • the liquid mass flow rate information can also be obtained by using the measured ⁇ P in combination with physical properties of the liquid fluid.
  • a small pressure drop ⁇ P may still be too big to tolerate, especially when the reactor stage is long or there are many reactor stages. Additionally, in the process of adjusting ⁇ P to maintain the liquid level 704 by the liquid level sensor 706 and the flow restrictor 705, the fluctuation of ⁇ P may also affect liquid flow in the first reactor stage 71.
  • Fig. 4 illustrates a similar schematic diagram as the diagram of Fig. 3.
  • the flow restrictor 705 is removed from the gas conduit 75, so, there is no pressure drop ⁇ P on the gaseous fluid.
  • a liquid pump 707 is disposed on the liquid conduit 76.
  • the liquid level signals are used to control the liquid pump 707 to maintain the liquid level 704 at the desired constant level. Additionally, because an output pressure of the liquid pump 707 is approximately equal to its input pressure, it does not create a pressure drop between the first and the second reactor stages 71 and 73.
  • the liquid pump 707 includes a positive displacement pump or a centrifuge pump etc. Additionally, the liquid pump 707 can have metering capability, which can be used to obtain the liquid flow rate information directly.
  • a sprayer or similar spraying devices (not shown) can be adopted inside the reactor stage 73.
  • a check valve (not shown) may be disposed on the liquid conduit 76 and located behind the liquid pump 707 to prevent the liquid fluid in the liquid conduit 76 from reflux.
  • the gaseous fluid and the liquid fluid in the effluent of the first reactor stage 71 are separated in the separator 703, and then transported to the second reactor stage 73.
  • an agitation device (not shown) can be provided to cause homogenization of the multiphase fluid.
  • the agitation device may include a mechanical stirring device, a magnetic stirring device or an ultrasonic stirring device etc.
  • the ultrasonic stirring device is provided, which can be installed near a bottom of the separator 703. The ultrasonic stirring device can provide sufficient homogenization of the liquid fluid, while having minimum interference to the performance of the liquid level sensor 706 and also without significantly increasing liquid temperature.
  • the separator 703 if the separator 703 is operated in a temperature which is higher than that of the first reactor stage 71, portions of volatile species in the liquid phase in the separator 703 may be evaporated and enter into the gas phase so as to alter the states of the species. If the separator 703 is operated in the temperature which is lower than that of the first reactor stage 71, portions of vapors in the gas phase in the separator 703 may be condensed and enter into the liquid phase so as to also alter the states of the species. As a result, variations in the effluent from the first reactor stage 71 can be produced during its transfer to the second reactor stage 73. Therefore, for certain catalytic processes, it is preferred that the temperature of the separator 703 is the same as that of the effluent from the first reactor stage 71. Thus, the states of the species of the effluent are preserved.
  • the separator 703 is integrated into the first reactor stage 71.
  • the integrated first reactor stage 71 and the separator 703 can enjoy operation simplicity and also minimize the potential of altering the states of the components.
  • the composite multistage reactor 707 can include three or more series-connected reactor stages.
  • the outlet of each of the reactor stages can connect to a separator.
  • the separator and the reactor stage can be separate from or integrated with each other. All the reactor stages can also be arranged upright along a vertical line.

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Abstract

Dispositif d'élaboration de processus catalytiques comprenant une pluralité de réacteurs à piston connectés en série multi-étagés, parallèles, composites, à l'échelle du laboratoire, (151-1 à 151-n, 155-1 à 155-n, 157-1 à 157-n), constitués chacun d'au moins trois étages de réaction à piston montés en série, chacun de ces étages présentant une entrée et une sortie et renfermant un lit catalytique (153-1 à 153-n, 159-1 à159-n, 161-1 à 161-n). Un réacteur à piston commun (171) comporte une entrée et une sortie, l'entrée assurant l'alimentation en réactif neuf via un conduit. Une pluralité de soupapes (173-1 à 173-n) relient la sortie dudit réacteur à piston commun (171) aux entrée des premiers étages de chacun des réacteurs multi-niveau composites (151-1 à 151-n), fournissant ainsi des quantités contrôlées distinctes de l'effluent à chacun des réacteurs composites multi-niveau connectés en série (151-1 à 151-n, 155-1 à 155-n, 157-1 à 157-n).
PCT/CN2007/071391 2006-12-29 2007-12-29 Dispositif d'élaboration de processus catalytiques à fort débit Ceased WO2008080361A1 (fr)

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