WO2001089681A2 - Systeme de production chimique modulaire utilisant un microreacteur - Google Patents
Systeme de production chimique modulaire utilisant un microreacteurInfo
- Publication number
- WO2001089681A2 WO2001089681A2 PCT/US2001/015738 US0115738W WO0189681A2 WO 2001089681 A2 WO2001089681 A2 WO 2001089681A2 US 0115738 W US0115738 W US 0115738W WO 0189681 A2 WO0189681 A2 WO 0189681A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- module
- modular system
- heat transfer
- transfer media
- fluid
- Prior art date
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Classifications
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00801—Means to assemble
- B01J2219/0081—Plurality of modules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00819—Materials of construction
- B01J2219/00835—Comprising catalytically active material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00867—Microreactors placed in series, on the same or on different supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00869—Microreactors placed in parallel, on the same or on different supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00871—Modular assembly
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00873—Heat exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00891—Feeding or evacuation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00984—Residence time
Definitions
- This invention generally relates to a modular chemical production system, and more specifically, to a miniaturized modular chemical production system that incorporates a microreactor, and which enables modules to be added or removed from the system to accommodate the type and quantity of chemical produced thereby.
- microreactors are of tremendous potential use to the pharmaceutical industry. Aside from providing safety benefits, and providing the ability to ease the transition from research to full-scale commercial production, microreactors utilize small volumes of chemicals efficiently. Often the chemicals used in drug research are costly and unavailable in significant quantity. Thus, the ability to perform research using small volumes of chemicals efficiently is important.
- microreactors whether in a research setting or a production setting, desire not just a microreactor, but an integrated system that enables an end user to easily and effectively exploit the full potential of microreactors.
- many computer users purchase a complete computer system, rather than just the microprocessor, which is at the heart of a computer system, many research and production facilities will desire to purchase a microreactor system that enables the end user to efficiently produce a variety of desired chemicals in almost any desired quantity, by making changes in the system, to scale the production as appropriate.
- a patent issued to Bard (U.S. Patent No. 5,580,523) describes a modular microreactor that includes a series of reactor modules connected in fluid communication, each reactor module having a particular function. Bard specifically teaches that the plurality of microreactor modules are mounted laterally on a support structure, and that individual microreactor modules can be replaced as needed. These reactor modules disclosed in the Bard patent minimally include a reactor module, a separator module, and an analyzer module, and additional microreactor modules can be added in series or parallel. Bard specifically teaches that separate mixing modules and reaction volume modules are used. This patent also teaches that a variety of generic components, such as computerized controls, pumps, valves, flow channels and manifolds can be included in such an apparatus.
- Diffusion mixing can be achieved by forcing fluids to flow in a laminar flow pattern within small fluid channels and is characterized by being extremely rapid and efficient, more so than mixing achieved by creating turbulence or agitation. It would further be desirable to provide a reaction module in which the microreactor is replaceable, so that a different type of chemical product can be produced without requiring the replacement of the entire reaction module.
- control module that includes an intuitive user interface, enabling a user to select from a stored menu of desired chemical products, so that after selecting a desired amount of a particular product, the user is only required to connect the system to a source of the required chemicals, and the control unit will control the system according to stored processing parameters, such as flow rates, temperature, and pressure, to produce the selected product.
- a pump module in such a system should provide sufficient pumping capacity so that flow rates of reactants into the reaction module can be increased to the maximum capacity of the reaction module without requiring replacement of the pump module with a higher rated output pump module.
- the pump module should be configured to be readily replaced with a pump module capable of providing the required flow rate.
- All the processing modules prefferably have housings of a consistent size and shape.
- Any inlet and outlet ports incorporated into the housings of the processing modules should be located in the same positions on all the processing modules, and all connections between processing modules should be of a quick connect type to enable the rapid replacement or addition of processing modules when changing the configuration of the system. Such connections should preferably be self closing to prevent spills when processing modules are replaced.
- the user should have an option to select processing modules adapted for either parallel fluidic heat transfer or serial fluidic heat transfer, when temperature control of a chemical process is required.
- a modular system for producing a desired chemical product from a plurality of reactants.
- the reactor system includes a control module and a reaction module. Different chemical products can be produced by replacing the reaction module or reconfiguring the modular system, as appropriate.
- the control module is adapted to monitor and control a production of the desired chemical product by controlling the flow of each reactant from a reactant supply source.
- the control module includes a memory, a processor, and a user interface. Stored in the memory are machine instructions that are executed by the processor to enable the control module to carry out its control functions.
- the control module also controls a reaction module that is in fluid communication with each reactant supply source and which includes a microreactor in which the desired chemical product is produced by a reaction between the reactants.
- the microreactor includes a mixing volume and a reaction volume.
- the plurality of reactants are preferably fluids, and may be in a gaseous state.
- the modular system includes a pump module, which is also controlled by the control module.
- the pump module is in fluid communication with each reactant supply source, and with the reaction module and enables and controls the flow of fluids within the modular system under the direction of the control module.
- an additional processing module can be included in fluid communication with the reaction module.
- the additional processing module comprises a residence time module that includes a capillary passage of a selected length, the length controlling a residence time of the desired chemical product in the residence time module.
- the residence time module also includes a proportional valve that is controllably connected to the control module to enable the control module to selectively vary a pressure within the modular system.
- the modular system can also include additional reaction modules, each including a microreactor, and each microreactor is designed to achieve a single step in a multi-step reaction.
- a chemical product that can be made by carrying out two different processing steps can be produced using a modular system in accord with the present invention that incorporates two reaction modules, each reaction module including a microreactor adapted to facilitate a single step in the two step process.
- Each reaction module will be controllably connected to the control module. Fluid from each reactant supply source will be directed through the pump module (unless no pump modules is used, as can be the case when the reactants are gases) and into a first reaction module, in which the first step in the reaction is achieved.
- the second reaction module is in fluid communication with the outlet of the first reaction module, and the partially reacted fluids will flow from the first reaction module to the second reaction module, where the second step in the reaction will be achieved. If required, residence time modules can be placed between the first and second reaction modules.
- microreactors are configured to facilitate the completion of a specific class of chemical reactions, and each microreactor can be removed from its reaction module and replaced with a different microreactor configured to facilitate the completion of a different chemical reaction, thus enabling the system to selectively complete a variety of different chemical reactions, thereby producing a wide variety of different chemical products.
- each microreactor is configured to enable at least one process relating to the production of a desired chemical product.
- microreactors will enable a plurality of reagents to be mixed together to form a desired product. It is preferred that each microreactor be able to achieve a precise temperature control of the plurality of reagents and the product within the microreactor.
- Each microreactor will be designed to facilitate a particular type of chemical reaction, such as a liquid/liquid reaction, a gas/liquid reaction, or a gas/gas reaction. It is envisioned that microreactors enabling additional processes relating to the chemical reaction will be useful. Such microreactors can be achieved by incorporating various types of features relating to the reaction process.
- such features are likely to include enabling processes such as diffusion based mixing, catalytic based processing, and/or providing and manipulating one or more of the following: a source of electromagnetic radiation, a source of sonic radiation, a source of alpha radiation, a source of beta radiation, a source of gamma radiation, a source of X-ray's, a source of radioactive particles, a source of charged particles, a source of light, an electric field, and a magnetic field.
- a system including a replaceable microreactor is suitable for facilitating the production of a wide variety of different chemical products.
- the resulting system will enable at least one process, and optionally, will enable additional processes, such as temperature control.
- additional processes such as temperature control.
- the flexibility of such a system enables a user to selectively produce a desired product, by selecting a microreactor incorporating features appropriate for the function. While a wide variety of microreactors, each incorporating specialized features, can be fabricated, it is expected that a liquid/liquid type microreactor, incorporating only temperature control and mixing features, can be beneficially employed to produce a substantial variety of desirable chemical products.
- the reaction module includes a housing with a first side that has a plurality of ports.
- One port enables the reaction module to be controllably connected to the control module and other ports enable it to be in fluid communication with each reactant supply.
- a second side of the housing includes a plurality of ports that enable the reaction module to be connected in fluid communication with the additional processing module or with a product reservoir.
- a mounting frame for the microreactor is also included in the housing.
- the reaction module includes means for promoting the production of the desired chemical product, such as a temperature sensor, a mixing volume in which a stacked laminar flow of said plurality of reactants is enabled, and a reaction volume.
- the modular system includes a plurality of fluid paths, including a fluid path for each of the plurality of reactants, a fluid path for the desired product, at least one fluid path for heat transfer media, and at least one fluid path for spent heat transfer media.
- the heat transfer media fluid paths can be configured in one of a parallel fluidic system and a serial fluidic system.
- the pump module includes at least one pump that is controllably connected to the control module. The pump is in fluid communication with both a heat transfer media fluid supply and the reaction module. Or, the pump is in fluid communication with at least one of the plurality of reactants, and the reaction module.
- the pump module includes an individual pump for each of the plurality of reactants, each individual pump being in fluid communication with a supply of a different one of the plurality of reactants, and with the reaction module.
- the pump module further preferably includes valves controllably connected to the control module, for controlling the flow of the plurality of reactants to the reaction module.
- the pump module also includes a filter for each reactant, to remove undesired material from the plurality of reactants before the reactants flow to the reaction module.
- the pump module includes a housing having a first side that includes a plurality of ports adapted to enable the pump module to be controllably connected to the control module and to be in fluid communication with each reactant supply, and a second side that includes a plurality of ports adapted to enable the pump module to be in fluid communication with the reaction module.
- all connections between modules are preferably achieved using quick connect type connectors that enable rapid connection and disconnection of the modules.
- Another aspect of the present invention is directed to a modular system adapted for producing a desired chemical product using only a single reactant, rather than a plurality of reactants. In such a modular system the reactor module will facilitate a single component reaction, for example, photochemically or pyrolytically.
- the modular system includes elements that are generally consistent with the elements of the modular system described above.
- Yet another aspect of the present invention is directed to a method for producing a desired chemical product with a modular system. The method includes steps that are generally consistent with the functions of the modular system described above.
- FIGURE 1 is a view of a simplified process flow diagram for a modular microreactor system that includes a control module, a pump module, and a reaction module, in accord with the present invention
- FIGURE 2 is a simplified process flow diagram for a modular microreactor system that includes a control module and a reaction module;
- FIGURE 3 is a simplified block diagram illustrating the functional elements of a control module
- FIGURE 4 is a simplified schematic diagram showing a personal computer used as a control module
- FIGURE 5 is a process flow diagram illustrating functional elements of a pump module for use in an embodiment of the present invention
- FIGURE 6 is a process flow diagram illustrating functional elements of a reaction module used in an embodiment of the present invention.
- FIGURE 7 is a process flow diagram illustrating functional elements of an additional process module employed in a preferred embodiment of the present invention for increasing a residence time
- FIGURE 8 is a side elevational view of a housing for use with pump modules, reaction modules, and other process modules in an embodiment of the present invention
- FIGURE 9 is a side elevational view of an interior of the reaction module of FIGURE 6;
- FIGURE 10 is an isometric view of the reactor bracket in the reaction module of FIGURE 9, showing the microreactor secured within the bracket;
- FIGURE 11 is an isometric view of the reactor bracket of FIGURE 10, showing the microreactor positioned to be removed from the bracket;
- FIGURE 12 is a side elevational view of an interior of the residence time process module of FIGURE 7;
- FIGURE 13 is a simplified process flow diagram of a serial heat transfer media fluidic system for use in the preferred embodiment of the present invention;
- FIGURE 14 is a simplified process flow diagram of a parallel heat transfer media fluidic system for use in the preferred embodiment of the present invention
- FIGURE 15 is a simplified process flow diagram for a preferred embodiment of a modular microreactor system that utilizes a serial heat transfer media fluidic system in accord with the present invention.
- a modular system for producing a chemical product from a plurality of reactants and includes a plurality of replaceable modular units.
- a control module enables automated control of parameters such as concentration, flow rates, temperature, pressure, pH values, and residence time.
- the system is configured for continuous operation and in its simplest form, can be used in chemical research facilities for the continuous production of small volumes of specialty chemicals required for research applications.
- Individual modules can be replaced to modify the performance of the system, and reaction modules can be replaced with reaction modules having a different configuration to enable the completion of different classes or types of reactions.
- a single reaction module is preferably capable of facilitating a plurality of processes relating to the production of a desired product from a plurality of reagents, and the system enables a user to select from those plurality of processes which processes are appropriate to produce a desired product from a given set of reagents.
- the reactor portion of the reaction module can be removed and replaced with a reaction module optimized for a particular class of reactions (such as liquid/liquid reactions). Reactors optimized for a particular class of reactions can be further optimized to enable different processes related to completing a reaction to be facilitated, such as diffusion based mixing, and temperature control.
- FIGURE 1 illustrates a simplified process diagram for a modular chemical process system 10.
- System 10 includes a control module 12, a pump module 14, a reaction module 18, and may optionally include one or more additional process modules 20.
- System 10 includes a fluid supply source 16, which supplies the system with all of the reactants required, as well as any heat transfer 'media that will be used in the system. It should be understood that the number of reactant fluids required varies with the type of reaction being implemented. Many chemical reactions can be achieved using two reactants, while some reactions require additional reactants. Generally, the reactants will be liquids, though gases may also be used. Solid reactants will generally be dissolved or suspended in a fluid for ease of processing in the system. It is preferred that any heat transfer media be fluidic in nature also.
- Fluid supply source 16 can also include a solvent fluid used to flush the fluid passages of system 10 to remove any potential contaminants before the reactants are introduced into the system.
- the particular design of fluid supply source 16 is not critical. It is contemplated that standard chemical product containers and/or laboratory glassware can be beneficially employed to serve as fluid supply source 16. It is further contemplated that fluid supply source 16 will include a plurality of different fluid containers, including a separate container for each different reactant used, a container for solvent, and a container for heat transfer media.
- Control module 12 is connected to control pump module 14, reaction module 18, any additional process modules 20, and fluid supply source 16. Reactants and heat transfer media flow from fluid supply source 16 to the pump module. Control module 12 controls the flow of fluids from fluid supply source 16, as well as controlling the pumping rate of pump module 14. Heat transfer media and reactants flow from pump module 14 to reaction module 18, where the desired chemical reaction takes place, and the desired product is produced. The product exits reaction module 18 and flows either to one or more additional process modules 20, or to a product collection vessel 22. Additional process modules 20 can carry out a variety of functions. In one embodiment, the additional process module comprises a residence time chamber to provide additional time for the reagents to complete their reaction before the product they produce is collected at product recovery vessel 22.
- additional process module 20 can comprise an additional reaction module 18, for example, as would be required for a two-step reaction process in which the product of the first reaction module is combined with a reagent to produce the final desired product.
- FIGURE 2 illustrates a modular chemical production system 24 that does not include a separate pump module.
- the reactants are gases, and the flow rates of the reactants are controllable using valves.
- System 24 includes a reactant gas supply 16a and a heat transfer media supply 16b. Again, most commonly, two different reactants will be used, though some reactions will require more. Those of ordinary skill in the art will readily understand how the selection of a desired product and the reaction used to obtain that product necessitates a specific set of two or more reactants be employed in the system.
- Reactant gas supply 16a and heat transfer media supply 16b are connected in fluid communication with reaction module 18. Both reactant gas supply 16a and heat transfer media supply 16b are controlled by control module 12, to which they are connected, and the control module adjusts the flow rates of the reactant gases by controlling valves (not separately shown) associated with the reactant gas supply. As noted above, for modest flow rates, use of a pressurized source for reactant gas supply 16a avoids the need for a separate pump module. Standard gas bottles or commercial grade gas cylinders are expected to be useful in serving as reactant gas supply 16a.
- heat transfer media supply 16b will incorporate its own pump, which is controlled by control module 12, so that the flow rates of the heat transfer media can be controlled.
- the pump required to control the flow of the heat transfer media is simpler than that used in pump module 14.
- pump module 14 is employed to pump a plurality of reactants, as well as heat transfer media; thus, a more complicated pumping system is required in pump module 14 for system 10 in FIGURE 1.
- control module 12 includes a processor 25, an optional reaction database 26, and a user interface 28.
- reaction database 26 includes detailed information relating to a plurality of different chemical products that can be produced by the modular chemical reaction system of the present invention.
- the detailed information preferably includes various chemical products that can be produced, the required starting materials, the relative volumes of starting materials required to produce a desired volume of each product, specified process condition parameters, such as temperature and flow rates for the reactants and any heat transfer media used, and an identification of the types of pump modules, reaction modules, and any additional process modules required to produce each product.
- the detailed information also preferably includes machine language instructions for execution by processor 25 that enable automatic control the system according to the stored parameters specific to each included reaction.
- user interface 28 will comprise a graphic display designed such that a user can navigate from a menu that includes a plurality of options. From the display, the user can select a desired chemical product and be provided with details regarding specific types of pump modules, reaction modules (or microreactors used therein), and any additional process modules required.
- the user can ensure that the modular chemical production system is properly configured to produce the desired product.
- the user would ensure that all fluid supplies and fluid connections within the system are provided and then would activate a start command on using user interface 28, causing processor 25 to control the reaction based on the process control parameters stored within reaction database 26 for the reaction selected by the user. If optional reaction database 26 is not used, the user would manually enter the reaction parameters using user interface 28.
- FIGURE 4 illustrates an alternative preferred embodiment of a control module 12a, in which control module 12a comprises a personal computer (PC) 30.
- PC 30 includes processor 25, optional reaction database 26 (if so desired), which when present, is preferably stored on a hard drive 31, and the user interface (a display 28 of computer 30).
- PC 30 is employed as the control module, the PC is coupled to an appropriate connector on at least one of the modules of the system through a cable connected to a data port on the PC, such as its serial port, parallel port, or universal serial bus port (none of which are shown in the Figures).
- FIGURE 5 is a process flow diagram illustrating the components associated with pump module 14.
- This flow diagram for an exemplary embodiment of pump module 14 has been configured to support the processing of a two component reaction.
- pump module 14 can readily be modified to support specific chemical processes that require more than two reactants or more heat transfer fluids.
- a generally conventional power supply 32 provides electrical power to control module 12. Both electrical power and data are conveyed through conductors 49 that electrically and operatively couple control module 12 to pump module 14.
- Pump module 14 can alternatively can be coupled to a separate power supply 32' that provides its required electrical power.
- pump module 14 For systems in which the electrical demands of pump module 14 are modest, it is more convenient for pump module 14 to be energized with electrical current supplied from power supply 32 via the control module and conductors 49. When the electrical demand of pump module 14 is relatively high, it is more convenient to couple pump module 14 to separate power source 32'.
- Control module 12 is operatively connected to a Reactant 1 supply 16c, a solvent supply 16d, a Reactant 2 supply 16e, and heat transfer media supply 16b.
- Reactant 1 and Reactant 2 will be mixed in reaction module 18 to achieve the desired chemical product.
- Solvent supply 16d is used to flush out all the fluid lines and passages in pump module 14 and subsequent modules to ensure that any reagent residue left over from previous reactions is flushed from the system and will not interfere in the current operation of the system in the present reaction.
- solvent supply 16d can be provided at a desired temperature, in order to pre-warm or pre-chill the fluid pathways within the modular chemical reaction system.
- Control module 12 is operatively connected through a data/power bus 48 to all controllable elements within pump module 14. For example, control module 12 sends a control signal to a valve 34a, which is in fluid communication with Reactant 1 supply 16c and solvent supply 16d. Initially, the signal sent by control module 12 causes valve 34a to. allow solvent from solvent supply 16d to flow through the system and flush out the fluid passages lines, as previously described.
- Control module 12 is similarly operatively connected through power/data bus 48 to a valve 34b, which is in fluid communication with solvent supply 16d and Reactant 2 supply 16e. Again, control module 12 sends a control signal through power/data bus 48 to valve 34b, enabling the solvent to flow to flush the fluid passages and lines within the system with solvent from solvent supply 16d. After a desired interval has passed, control module 12 sends a signal to both valves 34a and 34b to shut off the flow of solvent, and to change state so as to allow the desired volumes of both Reactant 1 and Reactant 2 to flow into the system.
- Reactant 1 flows through a fluid line 36a into a pump 38, which is also operatively connected to control module 12 via power/data bus 48. Simultaneously, the desired amount of Reactant 2 flows through a fluid line 36b to a pump 40.
- Control module 12 controls the pumping rates of pumps 38 and 40 to achieve the desired flow rates of both Reactants 1 and 2.
- Pressure sensors 44 are included down stream of pumps 38 and 40 to provide confirmation to control module 12 that the reactants are flowing.
- Filters 46 are in fluid communication with fluid lines 36a and 36b and are employed to filter any particulate matter that may have contaminated Reactant 1 supply 16c or Reactant 2 supply 16e.
- control module 12 is programmed to alert a user to check the filters when pressure sensors 44 indicate a change in pressure in the system, as such a pressure change may be indicative of a clogged filter.
- pressure sensors 44 and filters 46 can be disposed before pumps 38 and 40, although the preferred embodiment is as illustrated, with pressure sensors 44 disposed behind the pumps, and filters 46 disposed behind pressure sensors 44.
- Control module 12 is further controllably connected to heat transfer media supply 16b. Based on the control parameters stored within reaction database 26, control module 12 will cause heat transfer media supply 16b to release the desired volume or control the flow rate of heat transfer media fluid through a fluid line 36c. Fluid line 36c is connected in fluid communication with a heat transfer media pump 42. Pump 42 is controllably connected to control module 12 to enable the flow rate of the heat transfer media fluid through the system to be controlled.
- Reactant 1, Reactant 2, and the heat transfer media all exit pump module 14 and flow through fluid lines 36a, 36b, and 36c, respectively, to reaction module 18.
- Spent heat transfer media flowing from reaction module 18 returns to pump module 14 via a fluid line 36d.
- Fluid line 36d is in fluid connection with a heat transfer media return vessel 16f, and it should be noted that pump module 14 performs no operations on fluid line 36d. Fluid line 36d merely passes through the pump module to reach heat transfer media return vessel 16f. Thus, fluid line 36d could alternatively be routed to flow directly from reaction module 18 to heat transfer media return vessel 16f without flowing through pump module 14.
- the modular reaction system has been designed so that all fluids used in the process flow from one module to the next, to minimize the number of fluid lines and control lines that are external to the modules.
- FIGURE 6 provides details on the functional elements included within the preferred embodiment of reaction module 18.
- Reaction module 18 is in both electrical and fluid communication with pump module 14 and also includes power/data bus 48.
- Conductors 49 connect the power/data bus in pump module 14 to power/data bus 48 in reaction module 18, enabling the bi-directional flow of data to and from control module 12 through the pump module.
- conductors 49 also connect the power/data bus 48 of reaction module 18 to any optional additional process module 20 that is used in the system.
- the fluid connections between pump module 14 and reaction module 18 include Reactant 1 fluid line 36a, Reactant 2 fluid line 36b, heat transfer fluid line 36c, and spent heat transfer fluid line 36d.
- Reactant 1 flows into reaction module 18 through fluid line 36a, and then into a microreactor 52.
- Reactant 2 flows into reaction module 18 through fluid line 36b, and then similarly flows into microreactor 52. It should be noted that FIGURE 6 does not attempt to illustrate the fluid paths of Reactants 1 and 2 within microreactor 52. The two reactants flow into the microreactor, and a single product exits the microreactor via a product fluid line 36e.
- Product line 36e is shown by the dash line to be in fluid communication with any optional process module. If no optional process module is required for the process carried out by the system, fluid line 36e flows directly to product recovery vessel 22, as indicated by the solid line in the Figure.
- Heat transfer media fluid enters the microreactor via heat transfer fluid line 36c and then exits the microreactor, and the reaction module, through fluid line 36c, which is coupled in fluid communication with any optional additional process module. If no additional process modules are included, fluid line 36c is connected directly to spent heat transfer fluid line 36d, which returns the spent heat transfer fluid to spent heat transfer fluid vessel 16f.
- microreactors can be beneficially employed in the present invention.
- Each microreactor may be designed for only a specific chemical reaction, but will more likely be designed to support the production of a specific class or type of chemical products, since one design configuration is normally useable to produce various chemical products in which the reaction processes are similar in nature.
- a particularly useful microreactor is described in a commonly assigned co-pending U.S. Patent Application, U.S. Serial No. 09/496,999, entitled "MINIATURIZED REACTION APPARATUS,” which was filed February 3, 2000, the specification and drawings of which are hereby specifically incorporated herein by reference.
- the reactor within reaction module 18 is a microreactor
- a non-micro-scale reactor could alternatively be used in conjunction with the present invention.
- Microreactors are generally characterized as incorporating fluidic structures of less than 1 mm in size, especially with respect to reactant fluid pathways.
- the present invention is not limited only to modular systems in which reaction modules must include a microreactor, as the reaction module can incorporate a reactor whose fluidic structures are larger in size than the microscale fluidic structures generally associated with microreactors.
- a reactor with larger scale fluidic structures can be used, as long as the overall size and shape of the reactor is adaptable to fit within the reaction module.
- microreactors designed for only a specific chemical reaction, or a specific class or type of chemical reactions
- beneficial microreactors will incorporate the ability to facilitate a plurality of different processes related to the production of a desired product from a plurality of reagents.
- microreactors will facilitate the mixing of a plurality of reagents. It should be noted however, that not all reactions require the mixing of reagents, such as reactions involving passing one or more reagents over a catalyst impregnated surface, or photochemical reactions that are initiated by the application of light of the appropriate wavelength.
- Preferable microreactors will enable the precise temperature control of the reagents and the product, so that yield and product quality can be enhanced.
- process control parameters that can be beneficially incorporated into microreactors for use in the present invention include magnetic, piezoresistive, piezoelectric, shape memory, radioactive, catalytic, optical, electromagnetic, and electrostatic control parameters. Any such control parameter is preferably capable of being controlled by control module 12.
- control module 12 the selection of a specific desired chemical product by a user navigating through optional reaction database 26 will determine which of the plurality of processes supported by the microreactor will be utilized by control module 12 to produce the desired product.
- the user will manually enter known control parameters for the reaction (via user interface 28), enabling control module 12 to selectively control the required processes to achieve the desired product.
- Reaction module 18 preferably includes a plurality of temperature sensors 54. These temperature sensors are electrically connected to control module 12 via power/data bus 48 in both reaction module 18 and pump module 14 and via conductors 49. Control module 12 uses data derived from the signals produced by the plurality of temperature sensors to adjust the flow rates of the heat transfer fluid (using pump 42 of pump module 14) to maintain the desired temperature parameters within microreactor 52. It should be noted that either more or fewer temperature sensors can be beneficially employed within the reaction module than the three illustrated in FIGURE 6.
- FIGURE 7 illustrates a preferred embodiment of an additional process module.
- the additional process module is a residence time module 20a, designed to increase the residence time of the product within the system to ensure that the product is completely reacted before being sent to product recovery vessel 22.
- Residence time module 20a is in fluid communication with reaction module 18 and with any additional process module 20 disposed downstream of residence time module 20a.
- Residence time module 20a is electrically connected to reaction module 18, as well as any additional downstream processing modules 20, via conductors 49.
- residence time module 20a includes power/data bus 48.
- the power/data buses included in each module are all electrically connected to control module 12, and thus enable control module 12 to control components within any of the modules.
- Capillary passage 56 is wound around an inner cylindrical core 60, which is covered by an outer shell 58, thereby forming a heat exchanger. Heat transfer media from reaction module 18 and fluid line 36c flows within the region defined by the inner core and outer shell, thus bathing capillary passage 56 in a flow of heat transfer fluid.
- capillary passage 56 is of sufficient length to achieve a 45-minute residence time at a flow rate of one milliliter per minute. Generally, a residence time of 45 minutes is sufficient for the majority of most chemical reactions to reach completion. If it is known that a particular chemical reaction can benefit from an increased residence time, an additional residence time module can be added downstream of residence time module 20a, or a longer capillary passage can be used in place of capillary passage 56.
- Several possible reactions can be performed in the system that are pressure dependent. These reactions include, for example, those involving decreasing volumes, increasing boiling points, and increasing gas concentrations in a liquid phase. Thus, specific positive effects can be achieved by causing a reaction to occur at a predefined pressure.
- To increase the pressure in the reaction path requires a throttle at the distal end of the reaction path. Closing the throttle makes the pumps in the pump module generate a higher pressure in the reaction module in order to maintain a constant flow rate.
- the throttle comprises a proportional valve 62. Proportional valve 62 is electrically connected to, and thus operatively controlled by, control module 12.
- FIGURE 8 illustrates a preferred embodiment of the housing for pump module 14, reaction module 18, and any additional process modules 20 (or 20a).
- each of pump module 14, reaction module 18, and additional process modules 20 include fluid inlets on one side of the module and fluid outlets on an opposing side of the module.
- these inlets and outlets are consistently located at the same point along the sides of each module regardless of the function of the module.
- a user knows exactly where fluid connections are required, and modules can be interchanged with other modules because the fluid connections are always consistently located at the same point.
- FIGURE 8 illustrates only one side of a module
- the opposing side of the module incorporates the same fluid ports as illustrated in FIGURE 8, with male connections provided on one side and corresponding female connections on the other.
- These ports include a combination data/power port 64, two heat transfer media ports 66 and two reactant/product ports 68.
- Power/data ports 64 are used to connect conductors 49 to the internal power/data bus 48 of each individual module, thus enabling control module 12 to be operatively connected to all of the modules.
- One of the heat transfer media ports 66 is used to bring heat transfer media into the module, while the second heat transfer media port 66 is used to enable spent heat transfer media to exit the module, to be collected in spent heat transfer media vessel 16f.
- the fluidic connections are of the self-sealing, quick connect type.
- both reactant/product fluid ports 68 are not required, as only product passes through those sides of the modules. However, both reactant/product fluid ports 68 are included to maintain consistency relative to the configuration of these ports in all modules.
- both reactant fluid ports 68 are required so that Reactant 1 and Reactant 2 can be pumped from the pump module to the reaction module.
- two reactant/product fluid ports 68 are required so that Reactant 1 and Reactant 2 can be directed to microreactor 52.
- Reactant 1 and Reactant 2 are mixed within microreactor 52, only a single one of the two reactant/product fluid ports 68 on the outlet side of reaction module 18 is used. In any additional processing modules 20, only the product, and not Reactants 1 and 2, flow through these modules, thus only one of the two reactant/product fluid ports 68 is used. It is envisioned that quick connecting bayonet type female/male connectors will be used to make the fluid connections between the fluid ports of adjacent modules. A bayonet connection 72 that encompasses the fluid ports and the power/data ports is also provided to maintain the individual fluid and power/data ports coupled and to provide a further fluid tight enclosure.
- Bayonet connection 72 is locked to the corresponding bayonet connection of an adjacent module by actuating a bayonet actuating lever 74.
- the bayonet actuating lever is included on each side of the housing to lock the bayonet connections together when the respective ports on adjacent sides of the modules are coupled together.
- FIGURE 9 is a side elevational view that provides interior details of a preferred embodiment for reaction module 18. From this view, it can be seen housing 50 includes two bayonet connections 72 on opposite sides, each of which includes a power/data port 64, two heat transfer fluid ports 66, and two reactant/product ports 68. Within the interior of reaction module 18, microreactor 52 is disposed in a mounting bracket 76.
- Mounting bracket 76 is secured by a plurality of mounting bolts 80.
- a corresponding plurality of springs 82 are inserted over the plurality of mounting bolts and provide a biasing force that is used to secure microreactor 52 and mounting bracket 76 in a desired position.
- Guide pins 78 are preferably included to help properly position the reactor within reaction module 18.
- Reaction module 18 is designed such that microreactor 52 can readily be removed from the reaction module and replaced with a different microreactor designed to carryout a different chemical reaction or with the same design of microreactor, if the previous microreactor was found to be defective.
- a reactor of the proper size and shape that does not include microscale fluidic channels can also be beneficially employed.
- power/data bus 48 does not pass through microreactor 52, but is instead routed around microreactor 52. While not shown in this view, it should be understood that power/data bus 48 is electrically connected to temperature sensors 54, as can clearly be seen in FIGURE 6. Temperature sensors 54 record temperatures both within microreactor 52, and within the interior volume of reaction module 18. The purpose of temperature sensors 54 is to provide control module 12 with current information regarding the temperature conditions within the microreactor and reaction module. Those of ordinary skill in the art will readily understand that different locations of the temperature sensors 54 can be used as long as information is provided to control module 12 relating to the temperature conditions in the reaction module, so that control module 12 can maintain the temperature parameters at the desired levels.
- FIGURE 9 illustrates heat transfer fluid paths 36c and 36d being routed through microreactor 52.
- the fluidic system for the heat transfer can be arranged in either a serial or a parallel fashion.
- Heat transfer media fluid line 36c must pass through microreactor 52 to provide heat exchange within the reactor.
- spent heat transfer media fluid line 36d is not routed through microreactor 52, but is instead routed through housing 50 to avoid any interference with microreactor 52.
- Reactant 1 fluid line 36a and Reactant 2 fluid line 36b enter the reaction module and are directed to microreactor 52.
- the reactant fluids flowing through these two fluid paths are mixed within the microreactor and a reaction takes place, producing the desired chemical product. That product exits microreactor 52 through a product fluid line 36e.
- the fluid paths for heat transfer media, reactants and the product through microreactor 52 are quite simplified as illustrated in FIGURE 9.
- the fluid paths of the heat transfer media within the microreactor are arranged so as to define at least one heat exchanger, and often, a plurality of heat exchangers, so that different portions of the microreactor can be controlled with regard to temperature. A plurality of different mixing and reaction volumes are readily provided within microreactor 52.
- microreactor As noted earlier, a preferred microreactor is described in detail in the commonly assigned, co- pending U.S. patent application. Yet, a wide variety of different microreactor designs are possible, and, while it is preferred that the reactor be of the microreactor type, it is possible that reactors not incorporating microscale fluidic channels could alternatively be used as well.
- FIGURES 10 and 11 provide details of one preferred embodiment of mounting bracket 76.
- the mounting bracket in these Figures includes a plate 84, a plate 85, and a plate 86.
- the microreactor is sandwiched between plates 84 and 85. The positions of plates 84 and 86 are fixed, while plate 85 is movable relative to the other two plates. In a closed position, plate 85 is adjacent to the outlet side of microreactor 52.
- Plate 82 includes temperature sensor 54, a port 96c and a port 96d, both for heat transfer media fluid, and a port96e for removing product from the microreactor.
- Mounting bracket 76 also includes a release lever 88, which is used to move and lock plate 85 against the microreactor to secure the microreactor between plates 84 and 85. In FIGURE 10, a release lever 88 is in the closed and locked position, and plate 85 is firmly abutted against microreactor 52.
- release lever 88 is in its open or unlocked position, and plate 85 has been moved away from the microreactor, enabling a reactor frame 90 to be rotated outwardly away from plates 84 and 85 through an angle of 90 degrees.
- Microreactor 52 can now be readily inserted into or removed from reactor frame 90.
- a plurality of fluid ports can be seen in plate 85, including fluid ports 96c and 96d, which are provided for the heat transfer media, and a Reactant 1 fluid port 96a and a Reactant 2 fluid port 96b.
- FIGURE 12 shows further details of the interior of one preferred embodiment of residence time module 20a.
- this module includes bayonet connections 72 at opposite sides, each including one power/data port 64, two heat transfer media ports 66, and two reactant/product ports 68.
- Within housing 50 of residence time module 20a are inner cylindrical core 60, capillary passage 56 (which is wound around inner cylindrical core 60), and outer shell 58.
- Product from reaction module 18 enters residence time module 28 via one of two fluid ports 68b. It is not critical which fluid port 68b is selected, so long as the fluid port 68b that is selected is properly mated to that fluid port 68b which is used to remove the product from reaction module 18.
- the length of capillary passage 56 is preferably selected to provide a desired residence time. As noted above, the length of capillary passage 56 in the exemplary preferred embodiment enables a residence time of approximately 45 minutes, which is generally sufficient time for a product to be thoroughly reacted before being transferred to collection vessel 22.
- Heat transfer media enters residence time module 20a from one of heat transfer fluid ports 66 and flows through fluid line 36c into the region between inner cylindrical core 60 and outer shell 58.
- the physical arrangement of the inner cylindrical core, the outer shell, and capillary passage 56 provides a heat exchanger, which maintains the product at the desired temperature.
- the heat transfer media exits the region between the inner cylindrical core and the outer shell via fluid line 36c, which leads to one of the heat transfer fluid ports 66 at the opposite end of module 20a. From there, the heat transfer fluid is directed either to an additional processing module, or to a flow reverser (generally a U-shaped tube) if the heat transfer fluid is to be returned to upstream modules. Spent heat transfer (from the flow reverser or additional process modules), enters residence time module 20a via heat transfer fluid port 66 (i.e., the one that is not used by heat transfer media exiting the module) and moves through the module via fluid line 36d.
- a flow reverser generally a U-shaped tube
- fluid line 36d is not involved in the moderation of temperature within residence time module, and merely enables spent heat transfer fluid to move upstream of the system to preceding modules, and eventually be deposited in spent heat transfer recovery vessel 16f
- Arrows have been used in FIGURE 12 to indicate the relative flow directions of each fluid. Bi-directional arrows have been used in the Figure with power/data bus 48, indicating that electrical signals are able to move both to and from control module 12 and residence time module 20a.
- FIGURE 13 illustrates a serial fluidic system.
- Temperature conditioned heat transfer fluid (indicated by as " ⁇ T Fluid”) flows from heat transfer media supply 16b through fluid lines 36c to pump module 14, then to reaction module 18, and finally to any additional process modules 20. It is understood that after passing through each successive module, the temperature of the heat transfer fluid is normally changed as a result of the transfer of heat either to or from the fluid as the fluid passes through the module. After exiting additional process module 20, the temperature conditioned fluid enters a U-shaped flow reverser 92.
- Spent heat transfer media is then routed back through processing module 20, reaction module 18 and pump module 14 via fluid lines 36d, and finally collected in spent heat transfer media recovery vessel 16f.
- Other shaped flow reversers can be used, and it is also envisioned that spent heat transfer media recovery vessel 16f could be disposed at the end of the system, rather than at the beginning of the system, thus eliminating the need for the flow reverser and fluid lines 36d in processing module 20, reaction module 18, and pump module 14.
- An advantage of locating spent heat transfer media recovery vessel 16f adjacent to heat transfer media supply 16b is that the spent fluid can be thermally reconditioned and used to replenish the supply of heat transfer fluid, providing a closed loop system.
- FIGURE 14 illustrates a parallel fluidic system.
- this parallel system once the temperature conditioned heat transfer fluid has entered a heat exchanger in a module, the spent heat transfer fluid from that heat exchanger is immediately returned through flow reversers 92 and through a spent heat transfer media fluid line to the spent heat transfer fluid recovery vessel, rather than being passed to successive heat exchangers in succeeding modules.
- This system allows better control of temperature, especially in heat exchangers in modules farther away from the temperature conditioned heat transfer media fluid supply.
- flow reverser 92a which is located in the last module of the system, is considered optional.
- Flow reverser 92a could be replaced by a fluid line (not shown) in fluid communication with spent heat transfer media recovery vessel 16f, or with an additional spent heat transfer media recovery vessel (not separately shown) located adjacent to additional process module 20.
- the use of flow reverser 92a provides for better fluidic equilibrium, and is therefore preferred.
- these flow reversers can be incorporated into the modules, or into components within the modules (such as within the microreactor of the reaction module, or within the heat exchanger of the residence time module defined by inner cylindrical core 60 and outer shell 58).
- FIGURE 15 illustrates an embodiment of the invention the includes a serial heat transfer media fluidic system, and further includes control module 12, pump module 14, reaction module 18, and residence time module 20a.
- control module 12 Prior to producing any product, a user must first select the desired product with the user interface of the control module. Furthermore, it is possible that more than one reaction is capable of producing the same product, so the user may also need to choose a preferred reaction.
- Optional reaction database 26 within control module 12 can be useful in selecting the desired product and method. Once the proper reaction conditions have been determined, the appropriate reactants, solvent and heat transfer media that are required must be provided.
- the selection of the reactants is based upon the specific product that is desired.
- a solvent is selected based on its compatibility with the reagents that will be used. The solvent will be used to flush the system.
- the selection of the heat transfer media is determined based upon the required reaction temperature. A heat transfer media that is useful at one reaction temperature may not be useful at a significantly different reaction temperature. Specific pump modules, reaction modules and/or additional processing modules may be required, as a function of the desired product. Because the system of the present invention is designed to facilitate the interchangeability of modules, the user must ensure that the appropriate modules are provided for a desired reaction.
- the pump module used will depend upon required flow rates of the reactants and heat transfer fluid, while reaction modules used will typically depend upon reactor throughput and/or the specific design of the reactor required to implement a particular reaction. Finally, many products may necessitate the use of a residence time chamber, while others will not.
- the desired amount of product required is also a parameter that will effect the configuration of the system, as system capacity can be modified by increasing the flow rate provided by the pump module, and by using a reactor that can accommodate that flow rate. As noted above, if the reactants are pressurized gases, a separate pump module may not be required.
- Step 3 Thermal Conditioning of the System
- the control module will begin pumping heat transfer media into the heat exchangers of the system.
- Heat exchangers will typically be included in the reaction module, and can also be included in any additional process modules.
- the system will include sufficient temperature sensors so that the control module can determine when the desired thermal conditions have been achieved, and so that no reactants are input to the system until that time. Thermal equilibrium is considered to have been obtained in this embodiment, when the temperature sensor data indicate no more than a 2 degrees Kelvin difference separates the system temperature from the desired temperature.
- the control module can be programmed to wait a predefined amount of time before introducing reactants into the system after the start command was actuated to enable the heat transfer media to bring the system to the desired temperatures.
- the control module will use the solvent to flush the reactant fluid passages and lines of the system.
- the flow rate for the solvent flush may be increased significantly over the flow rate employed for the reactants, to reduce the time required for the flushing step.
- Reactors designed to perform different operations can be installed in the reaction module. Reactor operations typically will include thermally preconditioning the reactants prior to mixing them, and precise temperature control of the mixing area and the product produced by the reaction. In addition, reactor operations may include the use of a catalyst, or the application of various types of energy or radiation as described above. The product of the reaction then exits the reactor and moves to either an additional processing module or a collection vessel. In most reactions, any additional module employed will be a residence time module, although if the reaction requires multiple reaction steps, the additional processing module will then likely include another reaction module.
- Step 5 Cleaning Cycle
- the system is once again flushed with solvent. This flush can be performed manually or under the direction of the control module. If the system is continually performing the same reaction for an extended period of time, it may be beneficial to interrupt the production of product and perform a system flush as a maintenance procedure at regularly scheduled intervals.
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Abstract
L'invention concerne un système de production chimique modulaire comprenant un microréacteur, destiné à la production d'un produit par mise en réaction d'au moins deux réactifs. La modularisation permet d'ajouter et d'enlever des composants, tels que des contrôleurs, des pompes, des soupapes, des microréacteurs, et des modules de traitement, selon les besoins, pour obtenir un produit désiré. Ce système comprend un module de commande et un module de réaction renfermant un volume de mélange et un volume de réaction. Plusieurs modules de pompage et de séjour peuvent également être inclus dans le système. Des raccords à engagement/dégagement rapide permettent un changement rapide des modules en cas de dysfonctionnement ou pour produire un produit ou une quantité différent. Une base de données comprend les paramètres optimaux pour une pluralité de réactions différentes permettant de produire différents produits chimiques. L'utilisateur sélectionne un produit et une quantité désirés, fournit les réactifs, les solvants et les agents caloporteurs, et le module de commande gère le système pour produire automatiquement le produit, jusqu'à obtention de la quantité désirée.
Priority Applications (2)
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JP2001585914A JP2004508919A (ja) | 2000-05-24 | 2001-05-15 | マイクロリアクタを組み入れたモジュラ式化学生産システム |
EP01935559A EP1286761A2 (fr) | 2000-05-24 | 2001-05-15 | Systeme de production chimique modulaire utilisant un microreacteur |
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US09/578,224 US7056477B1 (en) | 2000-02-03 | 2000-05-24 | Modular chemical production system incorporating a microreactor |
US09/578,224 | 2000-05-24 |
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WO2001089681A2 true WO2001089681A2 (fr) | 2001-11-29 |
WO2001089681A3 WO2001089681A3 (fr) | 2003-01-03 |
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PCT/US2001/015738 WO2001089681A2 (fr) | 2000-05-24 | 2001-05-15 | Systeme de production chimique modulaire utilisant un microreacteur |
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JP4904374B2 (ja) * | 2009-03-30 | 2012-03-28 | 東レエンジニアリング株式会社 | マイクロリアクタ |
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WO2001089681A3 (fr) | 2003-01-03 |
JP2004508919A (ja) | 2004-03-25 |
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