CN108246221A - Micropore is vortexed casing mixing reactor and its application - Google Patents

Abstract

The present invention provides a kind of micropore vortex casing mixing reactor and its application, and micropore vortex casing mixing reactor includes：The concentric tubes of outer tube and inner tube composition, form circular passage between inner and outer pipes；Wherein, outer tube is equipped with continuous phase inlet and outlet, inner tube one end is that the dispersed phase import other end is blind end, continuous one group of microwell array or the multi-group micropores array of interruption is distributed with along two dimensions of tube wall circumferential and axial between inner tube both ends, is formed and is vortexed in circular passage after dispersed phase enters continuous phase.The present invention is relative to current existing bushing type micro-channel mixer, ensure that stronger microcosmic mixing while high throughput or higher concentration of substrate is reached, also due to the formation of vortex and can effectively alleviate or avoid in technique that there may be the blockage problems of solid granule.

Description

Micropore is vortexed casing mixing reactor and its application

Technical field

The present invention relates to a kind of micropores to be vortexed casing mixing reactor, and the invention further relates to a kind of vortex casing mixing of micropore The application of reactor, belongs to chemical field.

Background technology

It is absorbed about gas-liquid mixed or gas and the mixing of liquid liquid, especially water phase and an oil phase mixing or liquid liquid mixes production The reaction of raw solid precipitate small particles, document or industrially in addition to designing fluid distributor, such as Chinese patent CN200810011995.6 is using fluid distributor and mixes the combination of microchannel, falling film reactor or is set using shell-tube type Meter, also there is the design of inner and outer pipes bushing type, and wherein two fluids is inputted by inner and outer tubes, and the annular formed in inner and outer pipes The process engineering that mass transfer heat exchange realizes that gas absorbs or liquid liquid mixes is carried out in channel.Bushing type it is compact to design it is simple for process, Easy to operate manufacture is easy, suitable for the various devices of large, medium and small type；Can be used alone can also integrate using combination shape Into tubulation, and the ratio of its specific surface area/volume and the coefficient of heat transfer are all higher.Chinese patent CN00239823.0 is reported A kind of spiral-flow type sleeve gas absorption device is mainly used for gas-liquid and is in direct contact absorption, and gas is flowed into from gas phase import, passes through gas-liquid Inducer flows into gas liquid reaction section, and liquid tangentially flows into gas phase inlet tube through fluid inlet pipe by fluid inlet, enters back into gas-liquid Conversion zone, and eddy flow is formed in gas liquid reaction section, it carries out being in direct contact absorbing reaction, absorption process institute with flowing into gas therein The heat of generation is quickly taken away by the cooling water for flowing through cooling collar.Wherein fluid inlet pipe and the angle of gas phase inlet tube oblique In 35 °~75 ° of range, it can specifically design best oblique angles according to the size of design flow rate of liquid and form eddy flow, liquid Body forms jet attached flow in pipe, increases the effective length of liquid absorption gas, and the disturbance for increasing liquid flowing is easily formed Turbulent flow, so enhancing mass-and heat-transfer.But the spiral-flow type sleeve gas absorption device still falls within the mixing of traditional routine or changes Thermal, with there is no small gap compared with the mass transfer exchange capability of heat of micro-channel mixer or reactor.

Since the 1990s, an important trend of natural science and engineering development is strided forward to micromation, The especially development of nano material causes great interest of the researcher to small scale and Fast Process.Microreactor is usually Refer to the small-sized reaction system manufactured by micro Process and precision processing technology, the microchannel size of fluid is in sub-micro in microreactor Rice arrives submillimeter magnitude.For liquid phase or gas phase mixed process, molecule diffusion is the final step of mixed process.By Fick Law is it is found that t~d2/D, wherein D are diffusion coefficient, and d is diffusion characteristic scale, and t is incorporation time.It follows that mixing with Diffusion coefficient D is related with diffusion length d, other than high molecular polymer, the diffusion coefficient phase of liquid or soluble solids It is poor little.Therefore, it in order to reduce incorporation time, can be realized by reducing diffusion length d.Micro passage reaction is based on this What one principle put forward.Microreactor has the geometrical property entirely different with big reactor：Narrow regular microchannel, very Small reaction compartment and very big specific surface area.Its geometrical property determines the transmission characteristic and macroscopic view of fluid in microreactor Flow behavior, and and then it is caused to have temperature is controlled, reactor volume is small, conversion ratio and high income and is had a safety feature A series of unique superiority of beyond tradition reactors, in fields such as chemical synthesis, chemical kinetics research and process exploitations It has broad application prospects.Casing micro-channel mixer/reactor generally forms set using by an outer tube and an inner tube Pipe, forms annular microchannel between inner and outer pipe, and outer tube is equipped with fluid inlet and outlet as mobile phase, one in inner tube End is equipped with the fluid inlet of dispersed phase and the other end is solid blind end；It is (such as porous using different materials between inner tube both ends Agglomerated material or polymer microporous material) formed perforated pipe wall can make dispersed phase be distributed in mobile phase realize mixing and change Heat.Document report or commercially available casing micro passage reaction have two major class substantially at present：1) a kind of dispersive film reactor uses Conventional sintering metal or woven wire micropore filtering film make fluid dispersion into small bubble or drop, so as to strengthen microcosmic mass transfer Heat transfer process, but the aperture of normal sintering material and distribution be it is unordered be randomly formed, generally can only be circumferentially certain in tube wall In the range of uniformly form injection stream, can be adapted for gas-liquid two-phase mixing or liquid liquid be mixed into lotion or liquid liquid and form solid precipitation React synthetizing micro-nano particle.But still have for the application of liquid liquid formation solid precipitation reaction synthetizing micro-nano particle no small Block risk, it is also not possible to which size and distribution and micropore for micropore carry out system design relative to the injection direction of tube wall And form vortex.2) it is another kind of to use Teflon poromerics (such asAF-2400 it is) good for multiple gases permeability But it is double tube reactor (" tube-in-tube for redesign after polymer inner tube made of the good characteristic of liquid-tight Reactor "), but it is constrained to characteristic (heat resisting and pressure resisting problem during large scale etc.) of the polymer material double tube reactor mesh Preceding only laboratory level equipment development success, is only applicable to gas-liquid two-phase mixed heat transfer.Due to the Teflon pipe calibers of use Small (such as outer diameter only has 1 millimeter) thus longer pipeline is needed to improve flux and promote mixed effect；This Type of Collective object set Pore size and micropore are distributed and can not equally realize that system designs and shape relative to the injection direction of tube wall in the inner tube of pipe Into vortex.

US20060073080(PCT：CN101084061b the multiphase mixing side using microchannel process technology) is discussed Method makes one of two-phase form discontinuous phase in microchannel and is scattered in continuous phase by the hole of microchannel, and big from hole emphatically Strengthen mixing in the length of small or hole extension and in terms of the transformation of microchannel surface characteristic.One of example mentions second fluid Stream is flowed through from second fluid circulation road has porose area to enter process microchannel, and process microchannel and fluid passage include concentric arrangement of Pipe.It is characterized in that, process microchannel is in annular space, and second fluid circulation road in central space or is adjoining In annular space or process microchannel is in central space, and second fluid circulation road is in the annular space adjoined.Although it carries It flows through after each aperture area enters continuous phase microchannel and can promote to disperse in mixed zone generation eddy current effect to dispersed phase fluid, But for pore size distribution in inner tube, have a combination of porose area and imperforate section how system design and to form vortex and strengthen grinding for mass transfer heat exchange Study carefully the actual geometric configuration feature being not directed to or at least without open similar microreactor inner wall pore arrangement combination.

Chinese patent CN101158556A (CN200710176046.9) realizes that liquid liquid is not mutual using micropore film disperse technology The method of molten system heat exchanging belongs to heat transfer, technical field of heat exchange in chemical.This method utilizes film dispersing apparatus, with micropore Film makes the phase in liquid liquid system pass through microporous barrier as dispersed phase, in another phase as continuous phase as decentralized medium The droplet of 50 to 900 micron ranges is formed under fluid cross-flow shear action, so as to prepare liquid liquid micro disperse system.By The excellent mixing of liquid liquid micro disperse system, hereditary property realize two alternate high efficient heat exchangings.Equipment is simple needed for this method, behaviour Facilitate, it being capable of efficient hardening diabatic process.Using this method, material only needs the residence time of 20-200ms, it is possible to reach To 83%~95% heat transfer efficiency, volumetric heat transfer coefficient can reach the 15~20 of traditional liquid liquid direct contact heat transfer method Times.In addition, Chinese patent CN102617757A (CN201210072217.4) discloses a kind of utilization micropore film preparation polymer The method of nano particle.This method is from the polymer monomer containing initiator and crosslinking agent and the aqueous solution containing surfactant It sets out, using microporous barrier (aperture is 0.2-5 μm) for decentralized medium, oil-in-water colostrum is prepared first with cross-flow cutting method Liquid, then colostric fluid is pressed through to film preparation miniemulsion repeatedly, heating miniemulsion complete thermal-initiated polymerization reaction, finally by demulsification, Washing obtains polymer nano granules.The system that this method is related to easily is built, and the scope of application is wide, and preparation time is short, gained production The average grain diameter of product is adjustable between 30-300nm, and particle diameter distribution is narrow, be conducive to polymer nano granules prepare with scale and Using.But the process channel and its geometrical construction of dispersed phase and continuous phase are not retouched in above-mentioned two patents It states, does not also refer to the concept of casing micro passage reaction.

Chinese patent 001057790 discloses a kind of dispersive film extractor, which is equipped in a pillar buoy Membrane tube or plate membrane have 0.01-60 microns of micropore on film, and liquid is dispersed into small drop, and increase mass transfer area improves Effect of extracting, but the extractor lacks the micro-dimension after being contacted to fluid and limits, be less suitable for applying fast for the purpose of extracting The process of speed reaction synthesis nano particle.If a kind of CN1318429A (CN01115332.6) membrane dispersion is for the side of ultra-fine grain Method that is, using with the type reactor, prepares barium sulfate particle, sulfuric acid-butanol solution is dispersed by microporous barrier small Drop, then reacted with barium chloride solution and prepare barium sulfate particle, the patent is merely with microporous barrier to the initial particle of drop It is limited, but the mixed characteristic (such as thickness of flow velocity, fluid layer) after fluid contact is not controlled preferably, because This grain diameter obtained is (average grain diameter is 1 micron) bigger than normal.

CN200710177291.1 reports a kind of membrane dispersion type micro-channel reactor, belongs to sleeve structure and includes outside one Pipe and an inner tube, outer tube are equipped with continuous phase inlet and outlet, and inner tube one end is dispersed phase import, and the other end is tube wall circumferential direction side Increase mass transfer area to the microporous membrane structure for being evenly equipped with micropore；The annular microchannel formed between inner and outer pipes there are annular space is not only protected The high throughput of single reactor is demonstrate,proved, and it is stronger microcosmic to realize the micro-dimension control guarantee after the cross-flow contact of reaction two-phase Mixing, so as to be satisfied with during the fast reaction of liquid liquid or gas-liquid as the precipitation method prepare nano particle. CN200910092354.2 reports the method for carrying out CO2 absorptions using above-mentioned same casing microreactor, and gas, which is used as, to be divided Dephasing is micron order minute bubbles from inner tube micropore dispersion, and cross-flow is carried out with the liquid film formed in outer tube and collides haptoreaction suction It receives, then cocurrent enters the annular entire micro- mass transfer absorption process of microchannel completion.But since the general multiselect of microporous barrier is with spherical Or irregular shape metal or alloy powder it is shaped and sintering made of sintered porous material or woven wire, the micropore with Machine or uniformly distributed preparation process can limit the controllability of membrane pore size and spacing, so as to influence the efficiency of two-phase mixtures mass transfer；This The limited length (generally 10~20mm) of outer microporous barrier section, does not have other means further strong after two-phase cross-flow contact early period Change mixing, the technique of nano particle is prepared in annular microchannel it is possible that leading to the problem of blocking particularly with the precipitation method.

To sum up, though at present in document report or commercially available bushing type micro-channel mixer/reactor using sintered gold Belong to or woven wire micropore filtering film still generally can only be in tube wall circumferential direction a certain range using particular polymer microporous pipe Cloth or random unordered formation injection stream, size and distribution and micropore for micropore are all difficult to relative to the injection direction of tube wall The design of carry out system and form vortex and turbulent flow.The blender that declines of casing made of polymer micro pipe is only applicable to gas-liquid mixed Technique and amplification be restricted；Although the blender that declines of casing made of sintering metal or woven wire can be used for liquid liquid shape Synthetizing micro-nano particle is precipitated into solid, but due to there is no additional mixed media still to have no small blocking wind in circular passage Danger.Therefore it needs to develop and can the new casing that vortex strengthen mass transfer heat exchange be formed by inner tubal wall micropore distribution design Formula high throughput micro-channel mixer/reactor, while can small of the solid that be likely to form in technical process be avoided by vortex Grain blocking pipeline or fouling.Wherein inner tubal wall micropore distribution can use for example sintered microporous film of traditional porous material or silk screen structure Into, can also use numerically-controlled precise machine-building, can also by the Design Processings such as such as femtosecond laser or 3D printing and It realizes.

Invention content

The purpose of the present invention is to provide a kind of micropore vortex casing mixing reactor and its application, to solve above-mentioned ask Topic.

Present invention employs following technical solutions：

A kind of micropore is vortexed casing mixing reactor, which is characterized in that including：The concentric tubes of outer tube and inner tube composition, Circular passage is formed between inner and outer pipes；Wherein, outer tube is equipped with continuous phase inlet and outlet, and inner tube one end is another for dispersed phase import It holds as blind end, continuous one group of microwell array or interruption is distributed with along two dimensions of tube wall circumferential and axial between inner tube both ends Multi-group micropores array, after dispersed phase enters continuous phase circular passage formed be vortexed.

The micropore vortex casing mixing reactor of the present invention, also has the feature that：The distribution of inner tubal wall micropore is not connect Continuous multi-group micropores array is formed by being parallel to cross section in multigroup camber line of tube wall, these camber lines prolong it is axial successively it is progressive Spiral clockwise or counterclockwise is circumferentially presented in tube wall；Or multigroup straightway by being parallel to axial direction forms, these straight lines Section is prolonged radial and axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall；Or by being both not parallel to cross section Also multigroup camber line composition of circumferential direction is not parallel to, these similary camber lines prolong axial progressive in tube wall circumferential direction presentation up time successively Needle or counter-clockwise helical or the clockwise and anticlockwise combination of spiral predetermined order；Or by different camber lines or straight line Section predetermined order and length ratio are composed.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Inner tubal wall micropore is distributed One group of microwell array is continuous, by being parallel to cross section in multigroup camber line of tube wall and by being parallel to the multigroup straight of axial direction Line segment connection composition, these camber lines and straightway combination are prolonged axial progressive is successively circumferentially presented spiral shell clockwise or counterclockwise in tube wall Rotation；Either group is connected with multigroup camber line of the cross section in tube wall is not parallel to by the multigroup straightway for being parallel to axial direction Prolong into, these straightways and camber line combination and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Either It is connected in multigroup camber line of tube wall by being parallel to cross section and formed with the multigroup arc segment for being not parallel to axial direction, these are different Arc segment combination is prolonged axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall；It is or transversal by being both not parallel to Face is also not parallel to multigroup camber line connection composition of axial direction, and the combination of these camber lines is prolonged axial progressive is successively in circumferentially in tube wall Now spiral or the clockwise and anticlockwise combination of spiral predetermined order clockwise or counterclockwise；Either by above Various difference camber lines and straightway predetermined order and length ratio combination are formed by connecting.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Micropore arc segment is mutual Between be not overlapped or overlap in the axial direction, the segment angle that adjacent arc segment is formed after being projected on cross section with the center of circle It is 5-320 °, preferably 10-240 ° to spend, more preferable 15-180 °, most preferably 30-120 °；

Micropore straightway is not overlapped or overlaps in crosscutting radial direction each other, adjacent straightway and center of circle institute The angle of the dihedral angle of formation be 5-180 °, preferably 10-120 °, more preferable 15-90 °, most preferably 30-75 °.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：The micropore of inner tubal wall point Cloth is continuous one group of microwell array and is formed by being both not parallel to cross section or being not parallel to multigroup camber line of axial direction,

Multigroup camber line is distributed along the circular helix of inner tube,

Multigroup camber line prolongs and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Either clockwise It is distributed with counter-clockwise helical predetermined order.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Inner tubal wall micropore is by more Porous materials are formed to be manufactured either by numerically-controlled precise machine-building or by the processing technology of such as femtosecond laser or 3D printing； It is preferred that laser boring and 3D processing technologies.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Micropore hole on inner tubal wall Ranging from 0.05 micron -2 millimeters, preferably 5-200 microns of diameter；Percent opening is 5-80%, preferably 30-60%；

Inner tube external diametrical extent is 0.5 millimeter -500 millimeters, preferably 5-300 millimeters；

Annular microchannel radial spacing is 100 microns -5 millimeters, preferably 200 microns -1 millimeter；

The angle of opening direction of the micropore on tube wall and tube wall tangent plane institute into dihedral angle is 5 ° -175 °, preferably 15 ° - 75 ° or 105 ° -160 °.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Form the inside and outside of casing Tube exterior be concentric straight tube, bend pipe or coil pipe,

Respectively by the dispersed phase of inner tube and by between the continuous phase of outer tube or inner and outer pipes circular passage be cocurrent or Then cross-flow exports mixed fluid mixture from the outlet of outer tube.

Further, micropore of the invention vortex casing mixing reactor, also has the feature that：Micropore vortex casing Annular microchannel can extend entirely without porose area,

There is porose area with being 10 entirely without the length ratio of porose area comprising microwell array：1~1：30, preferably 5：1~1：20, More preferable 4：1~1：10；

The length for having porose area comprising microwell array is 10 microns -1 meter, and preferably 50 microns -500 millimeters, more preferable 100 is micro- - 300 millimeters of rice.

The present invention also provides a kind of micropore vortex casing mixing reactor lotion or liquid are mixed into gas absorption, liquid liquid Liquid forms the application of solid precipitation reaction, it is characterised in that：It is produced using the technique including synthetizing micro-nano particle, using acid-binding agent The reaction process of lithium salts precipitation formed insoluble in system that the reaction process or butyl lithium of raw salt precipitation participate in.

Advantageous effect of the invention

The micropore vortex casing mixing reactor of the present invention, along two dimensions of tube wall circumferential and axial between inner tube both ends Design is distributed with or continuous one group of microwell array or the multi-group micropores array of interruption, and pore size, shape, position and spacing can Control, can also obtain higher porosity.And the size of micropore vortex casing mixer/reactor inner and outer pipes facilitate amplification from And technique amplification demand can be met, while form the biography of vortex reinforcement process fluid in annular microchannel between inner and outer pipe Matter and heat exchange, while is formationed being vortexed can effectively be alleviated or avoid blocking up for issuable solid granule in process conditions Plug problem.The design of micropore vortex casing mixer, the simple processing of the present invention, is suitble to high-volume industry manufacture；Particularly suitable for The technique that gas-liquid mixing process and liquid liquid are mixed into lotion or liquid liquid forms solid precipitation reaction synthetizing micro-nano particle.Relatively In current existing bushing type micro-channel mixer, ensure that while high throughput or higher concentration of substrate is reached stronger Microcosmic mixing, also due to the formation of vortex and can effectively alleviate or avoid in technique that there may be the blockings of solid granule Problem.

In addition, while vortex can be formed in annular microchannel by the design of microwell array, it can be by dispersed phase The mass transfer heat transfer process of (being continuously injected into continuous phase in batches) and continuous phase is effectively decomposed into several different fragments, so as into One step strengthens mass transfer heat exchange of the entire reaction process especially in technique amplification process.

Description of the drawings

Fig. 1 is the cocurrent form schematic diagram of the micropore vortex casing mixing reactor of the present invention,

Fig. 2 is the cross-current configuration schematic diagram of the micropore vortex casing mixing reactor of the present invention,

Fig. 3 is the dimensional structure diagram of inner and outer pipes；

Fig. 4 is the distribution schematic diagram of discontinuous multi-group micropores array；

Fig. 5 is continuous one group of microwell array, by being parallel to cross section in multigroup camber line of tube wall and by being parallel to axial direction The schematic diagram of multigroup straightway connection composition in direction；

Fig. 6 is continuous one group of microwell array, by being both not parallel to cross section or being not parallel to multigroup arc of axial direction The schematic diagram of line composition.

Specific embodiment

Illustrate the specific embodiment of the present invention below in conjunction with attached drawing.

Term defines：

It is circumferential：Prolong concentric tubes especially inner tubal wall circumference direction

It is axial：Prolong the axis direction of concentric tubes

Radially：Prolong the concentric tubes cross section center of circle to tube wall circumferencial direction

Vortex：The rotational angular velocity vector for referring to fluid is zero, and also referred to as vortex flow, i.e. fluid particle or fluid micellar exist It is rotated in motion process around its own axis.

Turbulent flow：Turbulent flow is a kind of flow regime of fluid.When flow velocity increases to it is very big when, streamline is no longer clearly apparent, stream Many of field small whirlpool, laminar flow are destroyed, and adjacent flow interlayer not only has slip, also mixes.At this moment fluid is made irregular Movement, there is the component velocity generation perpendicular to flow tube axis direction, and this movement is known as turbulent flow, also known as sinuous flow, flow-disturbing or turbulent flow.

Microwell array：Micropore center is no more than to the institute of (being less than or equal to) micro-pore diameter three times in outer wall of inner tube circumferential distance It is exactly microwell array to have micropore to be connected using dummy line, including micropore camber line mentioned in the present invention, micropore straight line Section etc..What as above painted dummy line did not had a breakpoint is just continuous microwell array, is otherwise just discontinuous microwell array.

Entirely without porose area：Along continuous phase flow direction, the last one does not have after having porose area in inner tubal wall traverse sections The region of any microwell array is exactly entirely without porose area.

Imperforate section：Along continuous phase flow direction, any traverse sections more than or equal to four times of distances of micro-pore diameter of inner tubal wall On without microwell array distribution be exactly imperforate section；Imperforate section does not include entirely without porose area.

There is porose area：It is exactly porose area that inner tubal wall, which removes imperforate section, and have microwell array in inner tubal wall traverse sections is exactly Porose area,

Dispersion：(disperse system) is that one or more of substances are highly dispersed at formed in certain medium System

Dispersed phase：The substance disperseed when being dispersed into tiny distribution of particles with substance in another substance, Referred to as dispersed phase, also known as disperse phase.

Continuous phase：Continuous phase continuous phase disperse the substance i.e. continuous media of other substances in dispersion Claim continuous phase.

Cocurrent：Continuous phase and dispersed phase respectively by being mixed at micropore after outer tube import and inner tube import when two-phase fluid Flow direction it is identical, after mixing then from the outlet of outer tube outflow be for cocurrent.

Cross-flow or convection current：Continuous phase and dispersed phase respectively by being mixed at micropore after outer tube import and inner tube import when The flow direction of two-phase fluid is opposite, and outflow is for cross-flow or convection current after mixing and then from the outlet of outer tube.

As shown in figure 3, outer tube 12 and inner tube 11 form concentric tubes, circular passage is formed between inner and outer pipes；Wherein, outer tube 12 are equipped with continuous phase inlet and outlet, and it is blind end that inner tube one end, which is the dispersed phase import other end, along tube wall between inner tube both ends Continuous one group of microwell array or the multi-group micropores array of interruption is distributed in two dimensions of circumferential and axial, when dispersed phase enters company It is formed and is vortexed in circular passage after continuous phase.

As shown in Figure 1, being the micropore vortex casing mixing reactor structure under cocurrent form, outer tube 11 is sleeved on inner tube 12 Outside.There is porose area 13 in inner tube 12.First fluid is flowed into from inner tube inlet 16, and second fluid is flowed into from continuous phase import 14, After being mixed in the circular passage that the two is formed between inner and outer pipes, from 15 outflow of continuous phase outlet.

As shown in Fig. 2, it is the micropore vortex casing mixing reactor structure under cross-current configuration, first fluid is from inner tube at this time Entrance 16 flows into, and second fluid is flowed into from continuous phase outlet 15, after being mixed in the circular passage that the two is formed between inner and outer pipes, It is flowed out from continuous phase import 14.In this structure, continuous phase outlet 15 originally actually becomes entering for second fluid of knowing clearly Mouthful, continuous phase import 14 originally becomes the outlet of fluid.

The distribution of inner tubal wall micropore is discontinuous multi-group micropores array, by being parallel to multigroup camber line group of the cross section in tube wall Prolong into, these camber lines and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Or by being parallel to axial side To multigroup straightway form, these straightways prolong it is radial and axial successively it is progressive tube wall circumferentially present clockwise or counterclockwise Spiral；Or formed by being both not parallel to cross section or being not parallel to multigroup camber line of circumferential direction, these similary camber lines prolong axis Spiral clockwise or counterclockwise or clockwise and anticlockwise spiral predetermined order is circumferentially presented in tube wall to progressive successively Combination；Or it is composed of different camber lines or straightway predetermined order and length ratio.

Inner tubal wall micropore distribution is continuous one group of microwell array, by be parallel to cross section multigroup camber line of tube wall and by Multigroup straightway connection composition of axial direction is parallel to, these camber lines and straightway combination are prolonged axial progressive in tube wall week successively To spiral clockwise or counterclockwise is presented；Or existed by being parallel to multigroup straightway of axial direction and being not parallel to cross section Multigroup camber line of tube wall connects composition, these straightways and camber line combination are prolonged axial progressive clockwise in tube wall circumferential direction presentation successively Or counter-clockwise helical；Either by being parallel to cross section in multigroup camber line of tube wall and being not parallel to multigroup camber line of axial direction Section connection composition, these different arc segments combinations are prolonged axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall； Or formed by being both not parallel to cross section or being not parallel to multigroup camber line connection of axial direction, axial direction is prolonged in the combination of these camber lines It is progressive successively that spiral clockwise or counterclockwise or clockwise and anticlockwise spiral predetermined order is circumferentially presented in tube wall Combination；Either combined and be formed by connecting by above various different camber lines and straightway predetermined order and length ratio.

Micropore arc segment is not overlapped or overlaps in the axial direction each other, and adjacent arc segment is in cross section upslide It is 5-320 ° to penetrate the fan angle that is formed afterwards with the center of circle, preferably 10-240 °, more preferable 15-180 °, most preferably 30-120 °；

Micropore straightway is not overlapped or overlaps in crosscutting radial direction each other, adjacent straightway and center of circle institute The angle of the dihedral angle of formation be 5-180 °, preferably 10-120 °, more preferable 15-90 °, most preferably 30-75 °.

The micropore distribution of inner tubal wall is continuous one group of microwell array by being both not parallel to cross section or being not parallel to axial direction Multigroup camber line composition in direction,

Multigroup camber line is distributed along the circular helix of inner tube,

Multigroup camber line prolongs and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Either clockwise It is distributed with counter-clockwise helical predetermined order.

Inner tubal wall micropore be made of porous material either by numerically-controlled precise machine-building or by such as femtosecond laser or The processing technology manufacture of person's 3D printing；It is preferred that laser boring and 3D processing technologies.

Ranging from 0.05 micron -2 millimeters of micropore size on inner tubal wall, preferably 5-200 microns；Percent opening is 5-80%, excellent Select 30-60%；Inner tube external diametrical extent is 0.5 millimeter -500 millimeters, preferably 5-300 millimeters；Annular microchannel radial spacing is 100 - 5 millimeters, preferably 200 microns -1 millimeter of micron；Opening direction of the micropore on tube wall and tube wall tangent plane into the angle of dihedral angle Spend is 5 ° -175 °, preferably 15 ° -75 ° or 105 ° -160 °.

The inside and outside tube exterior for forming casing is concentric straight tube, bend pipe or coil pipe.

Respectively by the dispersed phase of inner tube and by between the continuous phase of outer tube or inner and outer pipes circular passage be cocurrent or Then cross-flow exports mixed fluid mixture from the outlet of outer tube.

The annular microchannel of micropore vortex casing can extend entirely without porose area,

There is porose area with being 10 entirely without the length ratio of porose area comprising microwell array：1~1：30, preferably 5：1~1：20, More preferable 4：1~1：10；

The length for having porose area comprising microwell array is 10 microns -1 meter, and preferably 50 microns -500 millimeters, more preferable 100 is micro- - 300 millimeters of rice.

Microwell array cases of design on outer wall of inner tube:

As previously defined, all micropores for micropore distance on outer wall of inner tube being no more than to micro-pore diameter three times utilize dummy line It is exactly microwell array to connect, including discontinuous micropore arc segment mentioned in the present invention, micropore straightway and continuous Micropore camber line/straight line etc..These micropore permutations can be designed with various combination, this hair can be expanded on further in example below Bright practical operation method.

Embodiment one

As shown in figure 4, it is the structure diagram of discontinuous multi-group micropores array, by being parallel to cross section in the more of tube wall Group camber line composition, these camber lines prolong axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall；It can also be by putting down Row is formed in multigroup straightway of axial direction, these straightways prolong radial and axial progressive in tube wall circumferential direction presentation up time successively Needle or counter-clockwise helical；It can also be formed by being both not parallel to cross section or being not parallel to multigroup camber line of circumferential direction, together These camber lines of sample prolong axial progressive is successively circumferentially presented spiral clockwise or counterclockwise or clockwise and the inverse time in tube wall The combination of needle spiral in different order；Can also be in different order and long by above-described various different camber lines or straightway Degree ratio is composed.

In Fig. 4 microwell array be prolong it is axial it is progressive successively clock wise spirals are circumferentially presented in tube wall, in order to simplify inner tube The camber line or straightway at the wall back side are not shown in figure：

(a) microwell array that cross section is formed in multigroup camber line of tube wall is parallel to, above-mentioned micropore arc segment exists each other Axial direction is not overlapped, and the fan angle that arc segment is formed after being projected on cross section with the center of circle is 90 °, and adjacent arc segment exists Distance in axial direction is 6 times of length of micropore size；

(b) microwell array of multigroup straightway composition of axial direction is parallel to, the length of straightway is the 8 of micropore size Times length, above-mentioned micropore straightway overlap (30%) each other in crosscutting radial direction, adjacent straightway and center of circle institute The angle of the dihedral angle of formation is 60 °；

(c) micropore being composed of in different order with length ratio the various different camber lines or straightway of (a) and (b) Array such as presses (a) -->(b)-->(a) alternate succession equal length is combined as microwell array.

<Embodiment two>

As shown in figure 5, be continuous one group of microwell array, by be parallel to cross section tube wall multigroup camber line with by parallel Composition is connected in multigroup straightway of axial direction, these camber lines and straightway combination are prolonged axial progressive is successively in circumferentially in tube wall Now spiral clockwise or counterclockwise；Can also be by being parallel to multigroup straightway of axial direction and being not parallel to cross section in pipe Multigroup camber line connection composition of wall, these straightways and camber line combination prolong it is axial successively it is progressive tube wall circumferentially present clockwise or Counter-clockwise helical；Can also be by being parallel to cross section in multigroup camber line of tube wall and being not parallel to multigroup camber line of axial direction Section connection composition, these different arc segments combinations are prolonged axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall； It can also be formed by being both not parallel to cross section or being not parallel to multigroup camber line connection of axial direction, axis is prolonged in the combination of these camber lines To successively it is progressive tube wall circumferentially present spiral clockwise or counterclockwise or clockwise and anticlockwise spiral by not homogeneous The combination of sequence；Can also combine connection with length ratio in different order by above-described various different camber lines and straightway It forms.

In Fig. 5 the microwell array of (d) to (i) be prolong it is axial it is progressive successively counter-clockwise helical is circumferentially presented in tube wall, be The camber line or straightway at the simplified inner tubal wall back side are not shown in figure：

(d) it is parallel to cross section and is sequentially connected group in 1 camber line of tube wall and 1 straightway by being parallel to axial direction Into microwell array.

(e) it is parallel to cross section and is sequentially connected group in 2 camber lines of tube wall and 1 straightway by being parallel to axial direction Into microwell array.

(f) it is parallel to cross section and is sequentially connected group in 1 camber line of tube wall and 2 straightways by being parallel to axial direction Into microwell array.

(g) by being parallel to cross section in multigroup camber line of tube wall group is connected with the multigroup arc segment for being not parallel to axial direction Into microwell array

(h) by the multigroup straightway for being parallel to axial direction group is connected with multigroup camber line of the cross section in tube wall is not parallel to Into microwell array

(i) microwell array formed is connected by being both not parallel to cross section or being not parallel to multigroup camber line of axial direction.

<Embodiment three>

As shown in fig. 6, one group of microwell array is continuous, by being both not parallel to cross section or being not parallel to axial direction Multigroup camber line composition, these camber lines are similar to the mutual parallel distribution of coil for being wrapped in tube wall circumferential direction, the combination of these camber lines Prolong and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Can also be clockwise and anticlockwise spiral by not With the combination of order and length ratio.

In Fig. 6 microwell array be prolong it is axial it is progressive successively counter-clockwise helical or clock wise spirals are circumferentially presented in tube wall, The camber line or straightway at the inner tubal wall back side is shown in dotted portion：

(j) similar to the continuous multi-group micropores of counter-clockwise helical for the mutual parallel distribution of coil for being wrapped in tube wall circumferential direction Array.

(k) similar to the continuous multi-group micropores of clock wise spirals for the mutual parallel distribution of coil for being wrapped in tube wall circumferential direction Array.

(l) similar to the counter-clockwise helical and clock wise spirals of the mutual parallel distribution of coil for being wrapped in tube wall circumferential direction The continuous multi-group micropores array of combination.

The annular microchannel of micropore vortex casing, which can be extended for becoming entirely without porose area, realizes the anti-of more long residence time It answers device or integrates use with other micro passage reactions, convenient be combined with micro- heat exchanger mixes for micropore vortex casing The basic assembled unit of device/reactor meets various process requirements；And it is required according to actual process for the basic assembled unit Facilitated the change that the residence time that adjusting process needs is more complicated suitable for medication chemistry and fine chemistry industry in parallel or series Learn reaction process.

The detailed design of micropore casing mixer and reactor that application case and comparative example use and processing technology parameter It is as follows respectively：It is divided into description application case A-C and compares the configuration of case D-F.

A the micropore vortex casing mixer and reactor) made by Stainless steel 316 L of Laser Processing is basic by following 3 Assembled unit is formed in parallel：What inner tubal wall microwell array was formed to be parallel to cross section shown in Fig. 4 (a) in multigroup camber line of tube wall Discontinuous microwell array, above-mentioned micropore arc segment are not overlapped in the axial direction each other, and arc segment projects on cross section It it is afterwards 90 ° with the fan angle that the center of circle is formed, the distance of adjacent arc segment in the axial direction is 4 times of length of micropore size；Inner tube Micropore size is 10 microns on wall, and the angle of opening direction of the micropore on tube wall and tube wall dihedral angle is 60 °；Interior pipe outside diameter is 6 millimeters；Annular microchannel radial spacing is 500 microns, and inner and outer pipes are concentric 90 ° of bend pipes, and overall length is 200 millimeters, at 100 millimeters Place is at a right angle curved, wherein the length for having porose area comprising microwell array is 50 millimeters, then annular 150 millimeters of microchannel extension is Micropore vortex double tube reactor is formed entirely without porose area；Lead to respectively by the dispersed phase of inner tube and by outer tube or inner and outer pipes annular The continuous phase in road conveys material by the way of cross-flow.

B the micropore vortex casing mixer and reactor) made by Hastelloy of 3D printing technique is by following two Basic assembled unit is connected in series.

First basic unit：Inner tubal wall microwell array for be parallel to shown in Fig. 5 (d) cross section in 1 camber line of tube wall and The microwell array formed is sequentially connected by 1 straightway for being parallel to axial direction, arc segment projected on cross section after with circle The fan angle being formed centrally is 90 °, and the length of straightway is 6 times of length of micropore size；Micropore size is micro- for 50 on inner tubal wall The angle of rice, opening direction of the micropore on tube wall and tube wall dihedral angle is 60 °；Interior pipe outside diameter is 10 millimeters, annular microchannel Radial spacing is 1 millimeter；Inner and outer pipes are concentric straight tube, wherein the length for having porose area comprising microwell array is 100 millimeters, then It is to form micropore entirely without porose area to be vortexed double tube reactor that annular microchannel, which extends 100 millimeters,；Above-mentioned micropore vortex casing mixing Device and reactor are integrated with double pipe heat exchanger and are combined as micropore vortex casing mixer/basic assembled unit of reactor；Point Material is not conveyed using by way of cocurrent the dispersed phase of inner tube and by the continuous phase of outer tube or inner and outer pipes circular passage.

Second basic unit：Inner tubal wall microwell array for be parallel to shown in Fig. 5 (g) cross section in multigroup camber line of tube wall and Be not parallel to axial direction multigroup arc segment connection composition microwell array, arc segment projected on cross section after with center of circle shape Into fan angle for 90 °, arc segment lap project on cross section after with the fan angle that the center of circle is formed be 30 °, phase The distance of adjacent arc segment in the axial direction is 6 times of length of micropore size；Micropore size is 60 microns on inner tubal wall, and micropore is in tube wall On the angle of opening direction and tube wall dihedral angle be 90 °；Interior pipe outside diameter is 10 millimeters, and annular microchannel radial spacing is 1 milli Rice；Inner and outer pipes are concentric straight tube, wherein the length for having porose area comprising microwell array is 50 millimeters, then annular microchannel extends 50 millimeters are to form micropore entirely without porose area to be vortexed double tube reactor；Above-mentioned micropore vortex casing mixer and reactor are integrated There is double pipe heat exchanger to be combined as micropore vortex casing mixer/basic assembled unit of reactor；Pass through the dispersion of inner tube respectively Mutually and in a manner that the continuous phase of outer tube or inner and outer pipes circular passage uses cocurrent convey material.

Wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit, the first basic unit and The inner tube import of second basic unit can distinguish the input phase with material or different material according to technological requirement.

C the micropore vortex casing mixer and reactor) made by Stainless steel 316 L of Laser Processing is by following two Basic assembled unit is connected in series.

First basic unit：The coil that inner tubal wall microwell array is wrapped in tube wall circumferential direction to be similar to shown in Fig. 6 (j) is mutual Between parallel distribution the continuous multi-group micropores array of counter-clockwise helical, plane where arc segment and the dihedral angle of inner tube cross section are 45 °, the distance of coil arc segment in the axial direction is 8 times of length of micropore size；Micropore size is 75 microns on inner tubal wall, micropore The angle of opening direction and tube wall dihedral angle on tube wall is 45 °；Interior pipe outside diameter is 8 millimeters, annular microchannel radial spacing It is 250 microns；Inner and outer pipes are concentric straight tube, wherein the length for having porose area comprising microwell array is 150 millimeters, it is then annular micro- It is to form micropore entirely without porose area to be vortexed double tube reactor that channel, which extends 50 millimeters,；Above-mentioned micropore vortex casing mixer and reaction Device is integrated with double pipe heat exchanger and is combined as micropore vortex casing mixer/basic assembled unit of reactor；Respectively by interior The dispersed phase of pipe and material is conveyed using by way of cross-flow the continuous phase of outer tube or inner and outer pipes circular passage.

Second basic unit：The coil that inner tubal wall microwell array is wrapped in tube wall circumferential direction to be similar to shown in Fig. 6 (l) is mutual Between the counter-clockwise helical of parallel distribution and the continuous multi-group micropores array of clock wise spirals combination, plane where arc segment with it is interior The dihedral angle of pipe cross section is 45 °, and the distance of coil arc segment in the axial direction is 8 times of length of micropore size；It is micro- on inner tubal wall Hole aperture is 100 microns, and the angle of opening direction of the micropore on tube wall and tube wall dihedral angle is 45 °；Interior pipe outside diameter is 10 millis Rice, annular microchannel radial spacing are 1.5 millimeters；Inner and outer pipes are concentric straight tube, wherein the length for having porose area comprising microwell array It is 200 millimeters to spend, and it is to form micropore entirely without porose area to be vortexed double tube reactor that then annular microchannel, which extends 250 millimeters,；It is above-mentioned Micropore is vortexed casing mixer and reactor is integrated with double pipe heat exchanger and is combined as micropore vortex casing mixer/reactor Basic assembled unit；Respectively by the dispersed phase of inner tube and by the continuous phase of outer tube or inner and outer pipes circular passage using cocurrent Mode conveys material.

Wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit, the first basic unit and The inner tube import of second basic unit can distinguish the input phase with material or different material according to technological requirement.

Comparative example D-F is essentially identical with the combination of application case A-C retaining sleeve microreactors respectively, wherein internal and external casing Size is consistent, such as diameter and length.Micropore quantity and size are consistent, but the distribution of micropore is different or in random It is distributed or is evenly distributed, no systems array design cannot generate vortex.Specifically used micropore casing mixer and reaction The technical parameter of device is：

D it is) corresponding with application case (A), by the micropore casing mixer of Stainless steel 316 L sintered metal filtration film productions It is formed in parallel with reactor by following 3 basic assembled units：Interior pipe outside diameter is 6 millimeters, and annular microchannel radial spacing is micro- for 500 Meter, micropore size is 10 microns on inner tubal wall；Inner and outer pipes are concentric 90 ° of bend pipes, and overall length is 200 millimeters, into straight at 100 millimeters Angle is curved, wherein the length of porose area is constant for 50 millimeters for having comprising micropore random distribution, and application case (A) holding is identical opens Porosity, it is to form micropore double tube reactor entirely without porose area that then annular microchannel, which extends 150 millimeters,；Pass through point of inner tube respectively Dephasing and material is conveyed using by way of cross-flow the continuous phase of outer tube or inner and outer pipes circular passage.

E micropore casing mixer and reactor) corresponding with application case (B), being made by Hastelloy woven wire It is connected in series by following two basic units.

Wherein the first basic unit：Interior pipe outside diameter is 10 millimeters, and annular microchannel radial spacing is 1 millimeter, on inner tubal wall Micropore size is 50 microns；Inner and outer pipes are concentric straight tube, maintain porose area and imperforate section total length is constant, wherein including micropore edge The circumferentially equally distributed length for having porose area of inner tubal wall is constant for 100 millimeters, and the two has identical percent opening, then annular micro- It is to form micropore double tube reactor entirely without porose area that channel, which extends 100 millimeters,；Above-mentioned micropore casing mixer and reactor collect Basic assembled unit is combined as into there is double pipe heat exchanger；Respectively by the dispersed phase of inner tube and pass through outer tube or inner and outer pipes annular The continuous phase of channel conveys material by the way of cocurrent.Second basic unit：Interior pipe outside diameter is 10 millimeters, annular microchannel diameter It it is 1 millimeter to spacing, micropore size is 60 microns on inner tubal wall；Inner and outer pipes are concentric straight tube, maintain porose area and imperforate section is total Length is constant, wherein comprising micropore along the circumferentially equally distributed length for having a porose area of inner tubal wall for 5 millimeters but micropore total quantity with The second basic unit of application case (B) is consistent, and it is to form micropore entirely without porose area that then annular microchannel, which extends 95 millimeters, Double tube reactor；Above-mentioned micropore casing mixer and reactor are integrated with double pipe heat exchanger and are combined as basic assembled unit； Respectively material is conveyed using by way of cocurrent the dispersed phase of inner tube and by the continuous phase of outer tube or inner and outer pipes circular passage. Wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit, and the first basic unit and second is substantially The inner tube import of unit can distinguish the input phase with material or different material according to technological requirement.

F it is) corresponding with application case (C), the micropore casing mixer made by Stainless steel 316 L woven wires and reaction Device is connected in series by following two basic assembled units.Wherein the first basic unit：Interior pipe outside diameter is 8 millimeters, annular microchannel Radial spacing is 250 microns, and micropore size is 75 microns on inner tubal wall；Inner and outer pipes are concentric straight tube, maintain porose area and non-porous Area's total length is constant, wherein along the circumferentially equally distributed length for having a porose area of inner tubal wall being 18 millimeters but micropore sum comprising micropore Amount is consistent with the first basic unit of application case (C), and then annular microchannel extends 182 millimeters to be formed entirely without porose area Micropore double tube reactor；Above-mentioned micropore casing mixer and reactor are integrated with double pipe heat exchanger and are combined as combining list substantially Member；Respectively object is conveyed using by way of cross-flow the dispersed phase of inner tube and by the continuous phase of outer tube or inner and outer pipes circular passage Material.Second basic unit：Interior pipe outside diameter is 10 millimeters, and annular microchannel radial spacing is 1.5 millimeters, micropore size on inner tubal wall It is 100 microns；Inner and outer pipes are concentric straight tube, maintain porose area and imperforate section total length is constant, wherein comprising micropore along inner tubal wall The circumferential equally distributed length for having porose area is kept for 250 millimeters but micropore total quantity with the second basic unit of application case (C) Unanimously, it is to form micropore double tube reactor entirely without porose area that then annular microchannel, which extends 200 millimeters,；Above-mentioned micropore casing mixing Device and reactor are integrated with double pipe heat exchanger and are combined as basic assembled unit；Respectively by the dispersed phase of inner tube and by outer The continuous phase of pipe or inner and outer pipes circular passage conveys material by the way of cocurrent.

Wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit, the first basic unit and The inner tube import of second basic unit can distinguish the input phase with material or different material according to technological requirement.

<Example IV>

CaCO3 cium carbonate nanoparticles synthesis technologies are prepared using CaCl2 and Na2CO3 liquid-phase reaction systems.

It is as follows：1) by calcium chloride dissolving in deionized water, a concentration of 0.25mol/L, as dispersed phase.It will Sodium carbonate dissolves in deionized water, a concentration of 0.5mol/L, as continuous phase；Using use application case A) described in 3 The micropore vortex casing mixing reactor that basic assembled unit is formed in parallel.2) calcium chloride solution under the action of constant flow pump from into Mouth enters inner tube, and through the drop in micropore dispersion to continuous phase, forming micron dimension, the import volume flow of calcium chloride is 8L/min, sodium carbonate enter from outer tube, volume flow 4L/min.Calcium chloride in drop and the sodium carbonate entered from outer tube are anti- Should, calcium carbonate is generated, after the barium carbonate in water phase reaches saturation, the calcium carbonate of interface reaction generation is precipitated, and is formed small Calcium carbonate granule with continuous phase flow out equipment.3) particle in calcium carbonate saturated solution is diluted and terminates reaction.Ultrasound point It drips on slide after dissipating and is spontaneously dried under room temperature, it is 40-85 nanometers that measurement, which obtains particle size range, and average grain diameter is 50 nanometers of carbon Sour calcium particle.Using A) micropore vortex casing mixing reactor entire process conditions can be more than 72 hours with continuous production without stifled Plug, and use comparative example D) middle sleeve reactor is only capable of maintaining just to generate big pressure drop less than 6 hours or blocking needs are cleaned and set It is standby, although obtained particle size range and average grain diameter are essentially identical.

Embodiment five, the chemical reactive synthesis technique for generating salt precipitation for thering is acid-binding agent to participate in

Using application case B) described in following two basic assembled units be connected in series micropore vortex casing mixing Reactor, wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit.

It is as follows：1) substrate Cha Er alcohol is dissolved in anhydrous THF, a concentration of 0.25mol/L, then adds in and work as The triethylamine of amount is as continuous phase；Chloroacetic chloride is dissolved in anhydrous THF simultaneously, a concentration of 0.25mol/L is as dispersed phase.Two Kind reaction solution is maintained in for use in 0 DEG C of low temperature bath.2) using application case B) described in micropore vortex casing mixing it is anti- Device is answered, wherein continuous phase is pumped into from the outer tube import of the first basic unit, volume flow rate 2.0L/min, and dispersed phase is from the first base The inner tube import of this unit is pumped into, volume flow rate 1.0L/min, the first basic unit material outlet and the second basic unit Outer tube import is connected.3) dispersed phase solution and then from the inner tube import of the second basic unit is pumped into volume flow rate 1.0L/min. Entire micropore vortex casing mixing reactor keeps being reacted at 0 DEG C, and product after reaction is collected in the outlet of the second basic unit It is converted completely through analyzing substrate, it can be seen that the apparent solid salt for having precipitation.Use B) micropore vortex casing mixing reactor it is whole A process conditions can not be blocked with continuous production more than 60 hours, and use comparative example E) middle sleeve reactor be only capable of maintain not Just generating big pressure drop or blocking by 6 hours needs cleaning equipment.

The chemical reaction process for forming lithium salts precipitation that embodiment six, butyl lithium participate in

Using application case C) described in following two basic assembled units be connected in series micropore vortex casing mixing Reactor, wherein the material outlet of the first basic unit is connected with the outer tube import of the second basic unit.Wherein first basic group It closes two imports of unit and the inner tube import of the second basic unit is connected respectively with 3 coaxial heat exchangers, 3 during this is reacted A material is cooled to -20 DEG C before reaction system is entered.

It is as follows：1) substrate o-difluoro-benzene is dissolved in anhydrous THF, a concentration of 0.49mol/L, as dispersion Phase；Simultaneously using commercially available 1.0mol/L n-BuLis anhydrous THF solution as continuous phase.Two kinds of reaction solutions are respectively by same Axis heat exchanger enters micropore after being cooled to -20 DEG C and is vortexed casing mixing reactor system.2) using application case C) described in Micropore is vortexed casing mixing reactor, and wherein n-butyllithium solution is pumped into from the outer tube import of the first basic unit, volume flow rate For 0.5L/min, o-difluoro-benzene solution is pumped into from the inner tube import of the first basic unit, volume flow rate 1.0L/min, the first base The outlet of this supplies of unit is connected with the outer tube import of the second basic unit.3) and then third material dimethyl suflfate is a concentration of The THF solution of 0.50mol/L is after the cooling of third coaxial heat exchanger from the inner tube import of the second basic unit with volume flow rate 1.0L/min is pumped into the second basic unit.Entire micropore vortex casing mixing reactor keeps -20 DEG C or so and is reacted, the Product converts (post processing liquid chromatogram yield >=94%), low temperature through analyzing substrate completely after reaction is collected in the outlet of two basic units Lower product of collecting can see the apparent solid salt for having precipitation.Use C) the micropore vortex entire process conditions of casing mixing reactor Can not be blocked more than 48 hours with continuous production, and use comparative example F) middle sleeve reactor be only capable of maintain less than 4 hours just Generating big pressure drop or blocking needs cleaning equipment.

Claims (10)

1. a kind of micropore is vortexed casing mixing reactor, which is characterized in that including：

The concentric tubes of outer tube and inner tube composition, form circular passage between inner and outer pipes；

Wherein, outer tube is equipped with continuous phase inlet and outlet,

Inner tube one end is that the dispersed phase import other end is blind end, is divided between inner tube both ends along two dimensions of tube wall circumferential and axial Continuous one group of microwell array or the multi-group micropores array of interruption are furnished with, is formed after dispersed phase enters continuous phase in circular passage Vortex.

2. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

The distribution of inner tubal wall micropore is discontinuous multi-group micropores array, including being parallel to multigroup camber line of the cross section in tube wall, this A little camber lines prolong axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall；

Or multigroup straightway including being parallel to axial direction, these straightways prolong radial and axial progressive in tube wall week successively To spiral clockwise or counterclockwise is presented；

Or including being both not parallel to cross section or being not parallel to multigroup camber line of circumferential direction, these similary camber lines prolong it is axial according to It is secondary progressive spiral clockwise or counterclockwise or the group of spiral predetermined order clockwise and anticlockwise to be circumferentially presented in tube wall It closes；

Or it is combined including different camber lines or straightway predetermined order and length ratio.

3. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

The distribution of inner tubal wall micropore is continuous microwell array, including being parallel to cross section in multigroup camber line of tube wall and being parallel to axis To multigroup straightway in direction, these camber lines and straightway combination prolong it is axial successively it is progressive circumferentially presented in tube wall it is clockwise or inverse Hour hands spiral；

Or including being parallel to multigroup straightway of axial direction and being not parallel to multigroup camber line of the cross section in tube wall, these are straight Line segment and camber line prolong axial progressive is successively circumferentially presented spiral clockwise or counterclockwise in tube wall；

Or group is connected with the multigroup arc segment for being not parallel to axial direction including being parallel to cross section in multigroup camber line of tube wall Prolong into, these different arc segments combinations and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；

Or including being both not parallel to cross section or being not parallel to multigroup camber line of axial direction, the combination of these camber lines prolong it is axial according to It is secondary progressive spiral clockwise or counterclockwise or the group of spiral predetermined order clockwise and anticlockwise to be circumferentially presented in tube wall It closes；

Or including above-described various different camber lines and straightway predetermined order and length ratio combination connection.

4. micropore as claimed in claim 2 or claim 3 is vortexed casing mixing reactor, it is characterised in that：

The micropore arc segment is not overlapped or overlaps in the axial direction each other, and adjacent arc segment is in cross section upslide It is 5-320 ° to penetrate the fan angle that is formed afterwards with the center of circle, preferably 10-240 °, more preferable 15-180 °, most preferably 30-120 °；

The micropore straightway is not overlapped or overlaps in crosscutting radial direction each other, adjacent straightway and center of circle institute The angle of the dihedral angle of formation be 5-180 °, preferably 10-120 °, more preferable 15-90 °, most preferably 30-75 °.

5. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

The micropore distribution of inner tubal wall is continuous microwell array by being both not parallel to cross section or being not parallel to the more of axial direction Group camber line composition,

Multigroup camber line is distributed along the circular helix of inner tube,

Multigroup camber line prolongs and axial progressive successively spiral clockwise or counterclockwise is circumferentially presented in tube wall；Either clockwise It is distributed with counter-clockwise helical predetermined order.

6. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

Inner tubal wall micropore is made of either porous material by numerically-controlled precise machine-building or by such as femtosecond laser or 3D The processing technology manufacture of printing；It is preferred that laser boring and 3D processing technologies.

7. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

Ranging from 0.05 micron -2 millimeters of micropore size on said inner tube wall, preferably 5-200 microns；Percent opening is 5-80%, excellent Select 30-60%；

Said inner tube external diametrical extent is 0.5 millimeter -500 millimeters, preferably 5-300 millimeters；

Annular microchannel radial spacing is 100 microns -5 millimeters, preferably 200 microns -1 millimeter；

The angle of opening direction of the micropore on tube wall and tube wall tangent plane institute into dihedral angle be 5 ° -175 °, preferably 15 ° -75 ° or 105°-160°。

8. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

The inside and outside tube exterior of casing is formed as concentric straight tube, bend pipe or coil pipe,

Respectively by the dispersed phase of inner tube and by being cocurrent or cross-flow between the continuous phase of outer tube or inner and outer pipes circular passage, Then mixed fluid mixture is exported from the outlet of outer tube.

9. micropore as described in claim 1 is vortexed casing mixing reactor, it is characterised in that：

The annular microchannel of the micropore vortex casing can extend entirely without porose area,

There is porose area with being 10 entirely without the length ratio of porose area comprising microwell array：1~1：30, preferably 5：1~1：20, it is more excellent Select 4：1~1：10；

The length of porose area of having comprising microwell array is 10 microns -1 meter, preferably 50 microns -500 millimeters, more preferable 100 microns - 300 millimeters.

10. a kind of micropore vortex casing mixing reactor is mixed into lotion in gas absorption, liquid liquid or liquid liquid forms solid and sinks The application of shallow lake reaction, which is characterized in that the application includes：The technique of synthetizing micro-nano particle is sunk using acid-binding agent generation salt What the reaction process or butyl lithium in shallow lake participated in forms the reaction process of the lithium salts precipitation insoluble in system.