CN100455345C - Composite heat exchange type micro reactor - Google Patents

Composite heat exchange type micro reactor Download PDF

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Publication number
CN100455345C
CN100455345C CNB2006100883984A CN200610088398A CN100455345C CN 100455345 C CN100455345 C CN 100455345C CN B2006100883984 A CNB2006100883984 A CN B2006100883984A CN 200610088398 A CN200610088398 A CN 200610088398A CN 100455345 C CN100455345 C CN 100455345C
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heat
substrate
reactor
import
outlet
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CN1907555A (en
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王豪杰
涂善东
张锴
巩建鸣
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention relates to a micro chemical mechanical system for heat transfer, mass transfer and chemical reaction among micro-fluid media, in particular to a heat exchange type micro-reactor integrating multiple temperature regions. The structure comprises a base plate and a sealing plate, wherein one or a plurality of base plates and the sealing plate are combined to form a single-layer structure or a multi-layer structure. The substrate is provided with a micro chemical reaction channel and a plurality of heat exchange channels, and a multi-section heat exchange area is formed along a group of micro chemical reaction channels, so that the isothermal operation or the variable temperature operation in the strong exothermic reaction process, the isothermal operation or the variable temperature operation in the endothermic reaction process and the instant termination of the endothermic reaction are integrally realized. In addition, the device can also be used as a measuring and analyzing tool for the heat absorption (release) of chemical reaction.

Description

Composite heat transfer micro reactor
Affiliated technical field
The present invention relates to conduct heat between a kind of microfluid medium, the very small chemical chemical mechanical system of mass transfer, generation chemical reaction, particularly a kind of composite heat transfer micro reactor of integrated many temperature provinces.
Background technology
The micro-system of accepting extensively according to chemical field (microsystem) defines, microreactor (microreactor) is meant the small-sized reaction system of making by little processing and precision processing technology, and the microchannel size of microreactor inner fluid arrives the submillimeter magnitude in sub-micron.For the reaction of molecular level, the volume of microreactor is very large, and therefore, it is very little to the influence of reaction mechanism and reacting dynamics characteristic.Compare with traditional consersion unit, its main advantage is to the reinforcement of quality and heat transfer process and the improvement of fluid-flow mode.In microreactor, thermograde causes the remarkable increase of driving force of heat transfer along with the very fast increase that reduces of linear content, thereby has enlarged the thermal diffusion flux of unit volume or unit are; In addition, owing to reduced fluid thickness, corresponding area-volume ratio is significantly improved.It is controlled easily with extraneous exchange heat that powerful driving force of heat transfer and enough big contact surface amass the reacting fluid that makes in the microchannel.
Aspect the microreactor heat exchange mode, early stage over-borrowing is with oil bath, water-bath, baking oven or ice chest that laboratory installation adopted.This mode influences the integrated of microreactor and system element, and is unfavorable for on-line monitoring.Therefore integrated heat exchange element becomes the development trend of microreactor.At present in the microreactor of integrated heat exchange element, generally resistance heater is put in employing provides reaction zone required heat in little reaction channel wall outside or in the mode that increases little heat tunnel plate, removes the heat of reaction zone by the mode that increases chilly but channel plate.But when course of reaction needed the alternating temperature operation, in same microreactor, above-mentioned heating and cooling mode was not easy to make up and encapsulate.
The U.S. mattress of Germany now the scientist of microtechnology research institute (IMM) by arranging little reaction channel and little heat exchanger channels at interval at the upper and lower plates face of same substrate, designed a kind of compact more integrated heat exchange type metal microreactors, and gone up work with open in the 2nd " little reaction technology " international conference (IMRET 2).But this two sides arranges alternately that the mode of microchannel is not easy to shape with the stack of board structure and amplifies, and, when course of reaction needs the alternating temperature operation, be not easy to arrange simultaneously heat tunnel and cooling duct in the reactor.
The scientist of Massachusetts Institute Technology (MIT) is at Angewandte Chemie Int.Ed.2005,44, a kind of integrated three kinds of temperature provinces are disclosed among the 2-6 in the silica-based microfabricated chemical reactor device of one, this reactor is by the mode of external heat aluminium block and external refrigeration aluminium block, make aluminium block and the silicon plate that contains little reaction channel carry out exchange heat, remove the silicon materials between each exchange heat district on the substrate by etching, warm area, localized hyperthermia district and local low-temperature space on same little reaction channel substrate, forming.But the aluminium block heat exchange unit of this microreactor obviously is unsuitable for further encapsulation and industrial applications.
Summary of the invention
The objective of the invention is in order to overcome prior art in the deficiency aspect manufacturing, combination, the integrated and encapsulation and a kind of composite heat transfer micro reactor that can have heat exchanger and reactor advantage simultaneously concurrently is provided.This reactor can in time discharge (supply) reaction unnecessary (required) heat for heat release (heat absorption) reaction in same device, realize the isothermal operation or the alternating temperature operation of strong exothermal reaction process, the isothermal operation of endothermic reaction process or alternating temperature operation, the instant termination of the endothermic reaction; Another object of the present invention is to carry out heat balance by the heat exchanging fluid, and the present invention also can be used as the Measurement and analysis instrument that chemical reaction is inhaled (putting) heat.
Technical scheme of the present invention is: to achieve these goals, the present invention is the little reaction channel of reasonable Arrangement, heat exchanger channels on same substrate, in a microreactor, form multistage exchange heat district along one group of microfabricated chemical reactor passage, its heat transfer efficiency height, reaction speed is fast, and the selectivity of course of reaction is good, material conversion ratio height, flow resistance is low, the structural strength height, high temperature resistant, low temperature, reactor volume is little, in light weight, the space arrangement convenience is easy to expand the reaction member number, and manufacturing process is simple, easily produce the cost performance height in batches.
Concrete technical scheme of the present invention is: a kind of composite heat transfer micro reactor, to form by shrouding 05 and at least one substrate 01, and the upper face of substrate 01 has little reaction channel 10 and heat exchanger channels simultaneously, and each passage has an import and an outlet at least; Shrouding 05 is provided with a series of import through holes and outlet through hole, and corresponds respectively to the import and the outlet of each passage on the described substrate 01; At least have one group of corresponding heat dam 16,56 in substrate 01 and the shrouding 05, this heat dam can constitute by removing solid material or filling with insulation material.
Upper face compact Layout at a substrate 01 has a little reaction channel and at least two heat exchanger channels; The number of heat exchanger channels is according to how many suitably increases of the required heat output of reaction, for example, when the caloric receptivity of endothermic reaction process is big, for guarantee to conduct heat fully or the reaction channel temperature even, should increase the heat exchanger channels number, but heat exchanger channels hop count order too much can influence the compact degree of reactor.Described heat exchanger channels is micro-meter scale or mm-scale, and described reaction channel is a micro-meter scale, and heat exchanger channels 11,12,13 is accompanied by described little reaction channel 10 with waveform or serpentine bend form segmentation compact Layout.The flow through hot fluid medium of described heat exchanger channels of segmentation can provide chemical reaction that needed heat takes place accurately and efficiently; The segmentation heat that the cold fluid medium of described heat exchanger channels can be in time produces chemical reaction of flowing through be taken away.In each heat exchanger channels section on the described substrate, the channel section of heat is provided and removes to have one between the channel section of heat at least by removing the heat dam that solid material or filling with insulation material constitute.Endothermic reaction process can provide heat by the parameter of controlling hot fluid medium in first section heat exchanger channels, the OnNow chemical reaction, keeping chemical reaction by the parameter of control interlude heat exchanger channels inner fluid medium carries out along the optimum temperature curve, remove heat by the parameter of controlling cold fluid medium in the latter end heat exchanger channels, stop chemical reaction immediately.
The shrouding and the substrate length and width that encapsulate described substrate are measure-alike, and thickness is micron dimension or millimeter magnitude.Be provided with in the described shrouding corresponding to the through hole of each channel entrance and outlet on the substrate and corresponding to the heat dam of substrate heat dam.
Shrouding 05 mode of back by bonding or Diffusion Welding of aliging with substrate 01 is closely linked it to form the composite heat transfer micro reactor of a single layer structure.The import of single layer structure composite heat transfer micro reactor is connecting the fluid chemistry material container respectively, and fluid media (medium) flows into corresponding passage along vertical panel face direction from import, and microreactor is flowed out in the outlet along vertical panel face direction from passage.
The invention still further relates to a kind of composite heat transfer micro reactor, described shrouding 05 is made the top shrouding, and described substrate 01 is made bottom substrate, also has an Intermediate substrate 03 to be contained between described top shrouding and the described bottom substrate at least.Wherein, the import of all passages and outlet are through hole on the Intermediate substrate 03, and all the other features are identical with substrate 01.Shrouding, Intermediate substrate and substrate alignment back are made the composite heat transfer micro reactor of its sandwich construction of formation that is closely linked by the mode of bonding or Diffusion Welding.The import of sandwich construction composite heat transfer micro reactor is connecting the fluid chemistry material container respectively, the fluid chemistry material distributes along vertical panel face direction from import and flows into corresponding each layer passage, and concentrates outflow along vertical panel face direction in the exit of each layer passage.The number of wherein said Intermediate substrate needs to require also comprehensive flow, each channel cross-section size, the passage length that participates in each flowing material of reaction and heat exchange to select according to output, should guarantee that per share flowing material is full of the place passage in reaction is carried out.If will guarantee that reaction time is even, Intermediate substrate is too much unsuitable.
Wherein said substrate, Intermediate substrate and shrouding are made up of silicon, silicon compound, pottery, metal or heat resistant glass, perhaps are made up of silicon or silicon compound and heat resistant glass.
Wherein said substrate, Intermediate substrate and shrouding are processed by milling, chemical etching, plasma etching, electric spark ablation, laser ablation or LIGA technology.
Wherein said substrate, Intermediate substrate and shrouding adopt the mode of bonding or Diffusion Welding to encapsulate.
For catalytic reaction, catalyst can adopt the mode of gas phase deposition technology or embedding porous material to arrange before encapsulation, also can adopt slurry attitude technology at the reaction channel wall coating after encapsulation is finished.
The present invention also provides the application of described reactor in the Measurement and analysis of chemical reaction suction (putting) heat.By measuring flow mass M, the inlet temperature T of heat exchanging fluid 1, outlet temperature T 2And the flow mass M of reacting fluid ', in conjunction with heat balance formula Q '=Q=Mc (T 2-T 1) can calculate absorption or liberated heat Q ' and unit mass reactant suction (putting) heat Q '/M ' in the interior chemical reaction process of unit interval.In the formula, Q is the heat output of heat exchanging fluid in the unit interval, and c is the thermal capacitance of heat exchanging fluid.
Beneficial effect:
1, the present invention's little reaction channel of reasonable Arrangement, heat exchanger channels on same substrate forms multistage exchange heat district, its heat transfer efficiency height along one group of microfabricated chemical reactor passage in a microreactor, reaction speed is fast, the selectivity of course of reaction is good, material conversion ratio height, and flow resistance is low.
2, rapidoprint and manufacturing means are flexible, can produce the structural strength height, the reactor of high temperature resistant, low temperature.
3, reactor volume is little, and is in light weight, the space arrangement convenience.
4, compared with prior art, the present invention has compact conformation, easy to process, and assembled package is simple, is easy to expand the reaction member number, easily produces in batches, is more suitable for the distinguishing feature of industrial applications.
Description of drawings
Fig. 1 is by a substrate and the composite heat transfer micro reactor principle schematic that shrouding is formed.
Fig. 2 illustrates the single layer structure embodiment exploded view of a composite heat transfer micro reactor.
Fig. 3 illustrates a single layer structure composite heat transfer micro reactor embodiment exploded view of looking from below.
Fig. 4 illustrates the substrate vertical view of a single layer structure composite heat transfer micro reactor embodiment.
Fig. 5 illustrates the sandwich construction embodiment exploded view of a composite heat transfer micro reactor.
Fig. 6 illustrates the Intermediate substrate structure chart of a sandwich construction composite heat transfer micro reactor embodiment.
Fig. 7 illustrates the Intermediate substrate structure chart of a sandwich construction composite heat transfer micro reactor embodiment who looks from below.
Wherein 01 is substrate, and 02,03 is Intermediate substrate, 10,30 is little reaction channel, 10a, 30a is little reaction channel import one, and 10b, 30b are little reaction channel import two, 10c, 30c are little reaction channel outlet, 11,31 is first group of heat exchanger channels, and 11a, 31a are first group of heat exchanger channels import, 11c, 31c is first group of heat exchanger channels outlet, and 12,32 is second group of heat exchanger channels, 12a, 32a is second group of heat exchanger channels import, and 12c, 32c are second group of heat exchanger channels outlet, 13,33 is the 3rd group of heat exchanger channels, and 13a, 33a are the 3rd group of heat exchanger channels import, 13c, 33c is the 3rd group of heat exchanger channels outlet, and 16,36 is the heat dam on the substrate, 17,37 is the pin mouth on the substrate, and 05 is shrouding, 50a, 50b is the reacting fluid import, 50c is the reacting fluid outlet, and 51a is first group of heat exchanging fluid import, and 51c is first group of heat exchanging fluid outlet, 52a is second group of heat exchanging fluid import, 52c is second group of heat exchanging fluid outlet, and 53a is the 3rd group of heat exchanging fluid import, and 53c is the 3rd group of heat exchanging fluid outlet, 56 is the heat dam on the shrouding, and 57 is the pin via hole on the shrouding.
The specific embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
Be illustrated in figure 1 as the principle of composite heat transfer micro reactor, this schematic construction comprises substrate 01 and shrouding 05 two parts.
The upper face of substrate 01 is provided with and is used for the reactant hybrid concurrency and gives birth to the microchannel 10 of reaction, follow first group of heat exchanger channels 11 that little reaction channel 10 arranges, follow second group of heat exchanger channels 12 that little reaction channel 10 arranges, follow the 3rd group of heat exchanger channels 13 that little reaction channel 10 arranges, the heat dam 16 that plays heat-blocking action.Wherein, little reaction channel 10 comprises import 10a, 10b and outlet 10c, and first group of heat exchanger channels 11 comprises import 11a and outlet 11c, and second group of heat exchanger channels 12 comprises import 12a and outlet 12c, and the 3rd group of heat exchanger channels 13 comprises import 13a and outlet 13c.
Shrouding 05 is provided with reacting fluid import 50a, 50b and outlet 50c, first group of heat exchanging fluid import 51a and outlet 51c, second group of heat exchanging fluid import 52a and outlet 52c, the 3rd group of heat exchanging fluid import 53a and exports the heat dam 56 of 53c, a heat-blocking action.
Described structurized substrate 01 and shrouding 05 adopt the mode of bonding or Diffusion Welding to encapsulate.
Import 50a, 50b, 51a, 52a, 53a are connecting the fluid chemistry material container respectively, the fluid chemistry material flows into corresponding passage along the direction of vertical shrouding 05 from import, and flows out through the outlet and the outlet of the correspondence on the shrouding 05 of passage along the direction of vertical shrouding 05.
The flow through hot fluid medium of described heat exchanger channels of segmentation can provide chemical reaction that needed heat takes place accurately and efficiently; The segmentation heat that the cold fluid medium of described heat exchanger channels can be in time produces chemical reaction of flowing through be taken away.Endothermic reaction process can provide heat by the parameter of controlling hot fluid medium in described first section heat exchanger channels 11, the OnNow chemical reaction, keeping chemical reaction by the parameter of hot fluid medium in the control interlude heat exchanger channels 12 carries out along the optimum temperature curve, remove heat by the parameter of controlling cold fluid media in the described latter end heat exchanger channels 13, stop chemical reaction immediately.By measuring flow mass M, the inlet temperature T of heat exchanging fluid 1, outlet temperature T 2And the flow mass M of reacting fluid ', in conjunction with heat balance formula Q '=Q=Mc (T 2-T 1) can calculate absorption or liberated heat Q ' and unit mass reactant suction (putting) heat Q '/M ' in the interior chemical reaction process of unit interval.In the formula, Q is the heat output of heat exchanging fluid in the unit interval, and c is the thermal capacitance of heat exchanging fluid.
Embodiment 2
With heat absorption uncatalyzed reaction process is example, introduces shaping and the application of a single layer structure composite heat transfer micro reactor embodiment.
Be illustrated in figure 2 as the single layer structure embodiment exploded view of a composite heat transfer micro reactor, it is made up of silicon material substrate 01 and heat resistant glass shrouding 05.
Shown in Fig. 3 and figure, the exploded view of a single layer structure composite heat transfer micro reactor embodiment is shown with the angle of looking from below.
Be illustrated in figure 4 as the vertical view of silicon material substrate 01 among the single layer structure composite heat transfer micro reactor embodiment.
By adopting plasma etching technology to remove silicon materials, the second section heat exchanger channels 12 that cut out the reactant hybrid concurrency is given birth to the snakelike microchannel 10 of reaction, being used to of following that little reaction channel 10 arranges provides heat to start reaction first section heat exchanger channels 11 at the upper face of substrate 01, being used to of following that little reaction channel 10 arranges provides heat to keep reaction, follow the 3rd section heat exchanger channels 13 that is used to remove the instant cessation reaction of heat, the slit 16 of playing heat-blocking action that little reaction channel 10 arranges, play the pin mouth 17 that centering acts on.Wherein, little reaction channel 10 comprises import 10a, 10b and outlet 10c, and first section heat exchanger channels 11 comprises import 11a and outlet 11c, and second section heat exchanger channels 12 comprises import 12a and outlet 12c, and the 3rd section heat exchanger channels 13 comprises import 13a and outlet 13c.
By the wet chemical etch process on heat resistant glass shrouding 05, etch reacting fluid import 50a, 50b and outlet 50c, first group of heat exchanging fluid import 51a and outlet 51c, second group of heat exchanging fluid import 52a and outlet 52c, the 3rd group of heat exchanging fluid import 53a and outlet 53c, play heat-blocking action slit 56, play the pin via hole 57 that centering acts on.
Silicon material substrate 01 and heat resistant glass shrouding 05 adopt the anode linkage technology to encapsulate by after the pin centering.
Import 50a, 50b, 51a, 52a, 53a are connecting the fluid chemistry material container respectively, the fluid chemistry material flows into corresponding passage along the direction of vertical shrouding 05 from import, and flows out through the outlet and the outlet of the correspondence on the shrouding 05 of passage along the direction of vertical shrouding 05.
Embodiment 3
With heat absorption uncatalyzed reaction process is example, introduces shaping and the application of a sandwich construction composite heat transfer micro reactor embodiment.
Be illustrated in figure 5 as the three-decker embodiment exploded view of the composite heat transfer micro reactor that one 304 stainless steel material makes.It is made up of a substrate 01, a shrouding 05 and two identical Intermediate substrates 02 and 03 of feature.
By adopting the chemical etching technology to remove stainless steel material, the upper face in 304 stainless steel substrates, 01,304 stainless steel Intermediate substrate 02 and 03 etches identic channel design.Adopt the electric spark ablation technology on substrate 01, Intermediate substrate 02 and 03, to discharge to ablate out then and play the slit of heat-blocking action at the laminar brass electrode of employing on the spark-erosion sinking lathe.Adopt the electric spark ablation technology that import, outlet and the pin mouth brill of all passages on Intermediate substrate 02 and 03 are through hole at last.
Be that example is introduced forming process with 304 stainless steel Intermediate substrates 03 below.
Be illustrated in figure 6 as the structure chart of the Intermediate substrate 03 of the three-decker composite heat transfer micro reactor embodiment that one 304 stainless steel material makes.
Adopt metal isotropism wet chemical etch technology to etch and be used for the snakelike microchannel 30 that the reactant hybrid concurrency is given birth to reaction, follow the first section heat exchanger channels 31 that is used to provide heat that little reaction channel 30 arranges, follow the second section heat exchanger channels 32 that is used to provide heat that little reaction channel 30 arranges, follow the 3rd section heat exchanger channels 33 that is used to remove the instant cessation reaction of heat that little reaction channel 30 arranges, play the pin mouth 37 that centering acts at the upper face of 304 stainless steel Intermediate substrates 03.Wherein, little reaction channel 30 comprises import through hole 30a, 30b and outlet through hole 30c, first group of heat exchanger channels 31 comprises import through hole 31a and outlet through hole 31c, second group of heat exchanger channels 32 comprises import through hole 32a and outlet through hole 32c, and the 3rd group of heat exchanger channels 33 comprises import through hole 33a and outlet through hole 33c.Above-mentioned through hole is to be shaped by the electric-spark drilling technology after etching process.Aiming at each passway and pin mouth on the 304 stainless steel Intermediate substrates 03 with the brass electrode that is slightly less than passway or pin mouth diameter on the electric spark drill hole machine tool, the discharge boring of ablating successively.In the slit 36 of adopting laminar brass electrode on 304 stainless steel Intermediate substrates 03, discharge to ablate out a heat-blocking action on the spark-erosion sinking lathe.
Fig. 7 and 6 figure are similar, and the structure chart of the three-decker composite heat transfer micro reactor Intermediate substrate 03 that one 304 stainless steel material makes is shown with the angle of looking from below.
Adopt the electric spark ablation technology on 304 stainless steel shroudings 05, to form through hole and heat insulation slit.On 304 stainless steel shroudings 05, getting out reacting fluid import through hole 50a, 50b and outlet through hole 50c, first group of heat exchanging fluid import through hole 51a and outlet through hole 51c, second group of heat exchanging fluid import through hole 52a and outlet through hole 52c, the 3rd group of heat exchanging fluid import through hole 53a and outlet through hole 53c successively, playing the pin via hole 57 that centering acts on cylindric brass electrode on the electric spark drill hole machine tool.In the slit 56 of adopting laminar brass electrode on 304 stainless steel shroudings 05, discharge to ablate out a heat-blocking action on the spark-erosion sinking lathe.
304 stainless steel substrates, 01,304 stainless steel Intermediate substrates, 02,304 stainless steel Intermediate substrates, 03,304 stainless steel shroudings 05 adopt the vacuum diffusion welding connection technology to encapsulate by after the pin centering.
Import 50a, 50b, 51a, 52a, 53a are connecting the fluid chemistry material container respectively, the fluid chemistry material flows into corresponding passage along the direction of vertical shrouding 05 from import, and flows out through the outlet and the outlet of the correspondence on the shrouding 05 of passage along the direction of vertical shrouding 05.

Claims (9)

1. a composite heat transfer micro reactor is made up of shrouding (05) and at least one substrate, and the upper face of substrate has little reaction channel (10) and heat exchanger channels simultaneously, and each passage has an import and an outlet at least; Shrouding (05) is provided with a series of import through holes and outlet through hole, and corresponds respectively to the import and the outlet of each passage on the described substrate; At least have one group of corresponding heat dam (16), (56) in substrate and the shrouding (05), this heat dam can constitute by removing solid material or filling with insulation material.
2. reactor as claimed in claim 1 is characterized in that having on the substrate a little reaction channel of micro-meter scale, has two micro-meter scales or mm-scale heat exchanger channels at least.
3. reactor as claimed in claim 1 is characterized in that described heat exchanger channels is accompanied by described little reaction channel (10) with waveform or serpentine bend form segmentation compact Layout.
4. reactor as claimed in claim 1, when it is characterized in that the substrate number surpasses one, the import of all passages and outlet are through hole on the middle substrate.
5. reactor as claimed in claim 1 is characterized in that described fluid media (medium) flows into microreactor along vertical panel face direction along import, flows out microreactor along vertical panel face direction along outlet.
6. reactor as claimed in claim 1 is characterized in that described substrate and shrouding (05) by silicon, silicon compound, pottery, metal, heat resistant glass, silicon and heat resistant glass, or silicon compound and heat resistant glass composition.
7. reactor as claimed in claim 1 is characterized in that described substrate and shrouding (05) process by milling, chemical etching, plasma etching, electric spark ablation, laser ablation or LIGA technology.
8. reactor as claimed in claim 1 is characterized in that described substrate and shrouding (05) adopt the mode of bonding or Diffusion Welding to encapsulate.
9. the application of reactor as claimed in claim 1 in the Measurement and analysis of chemical reaction caloric receptivity or thermal discharge.
CNB2006100883984A 2006-07-17 2006-07-17 Composite heat exchange type micro reactor Expired - Fee Related CN100455345C (en)

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