CN103182278A - Membrane dispersion type microchannel reactor - Google Patents
Membrane dispersion type microchannel reactor Download PDFInfo
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- CN103182278A CN103182278A CN2012100074133A CN201210007413A CN103182278A CN 103182278 A CN103182278 A CN 103182278A CN 2012100074133 A CN2012100074133 A CN 2012100074133A CN 201210007413 A CN201210007413 A CN 201210007413A CN 103182278 A CN103182278 A CN 103182278A
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Abstract
This invention provides a membrane component for preparing emulsion which has uniform and stable dimension and is applicable to industrialization. The membrane component comprises at least one membrane tube; two ends of the membrane tube respectively penetrate through a flowing phase liquid inlet baffle and a liquid outlet baffle; a housing is arranged outside the membrane tube; a liquid dividing column is arranged at the center in the membrane tube and is connected with the flowing phase liquid outlet baffle in a closed way. The membrane component is particularly applicable to the rapid industrialized preparation of nanoscale emulsion.
Description
Technical field
The present invention relates to a kind of membrane dispersion type micro-channel reactor, and the membrane module that is used for this membrane dispersion type micro-channel reactor.
Background technology
The particle of little, micro-nano structure such as metal and metal oxide nanoparticles, inorganic compound, organic compound and drug particles the modern life every field, as electronics, information, engineering, the energy, chemical industry, machinery and medical treatment etc., all have a wide range of applications, especially one of emerging point of economic increase.Preparation method and the technology little, the micro-nano structure material of various physics and chemistry are developed not broken hair exhibition, yet in technologies such as traditional chemical reaction and the precipitation method, need to utilize stir, ultrasonic and means such as injection and grinding mix and mass transfer, but these means are relatively poor on mass-transfer efficiency and effect, can't prepare emulsion droplet and the particle of size homogeneous, and particle diameter control difficulty height, the poor repeatability between batch.
Micro passage reaction based on micro-processing technology, can realize the accurate control of right micro liquid, the a series of unit operations of mixing, chemical reaction etc. is all carried out in accurate volume, can improve the homogeneity of micro emulsion and the particle of generation, but there is the shortcoming that processing cost is high and amplification is difficult in the microreactor that is based on micro-processing technology, can only be used for laboratory research at present, also can't be applied on a large scale in the actual generation.
Utilizing perforated membrane is a kind of novel reactor that grew up in recent years as the dispersive film reactor of decentralized medium, namely the fluid that makes a side by microporous barrier under the effect of pressure with all once the form of high size fine drop be distributed in the liquid of film opposite side, because fine drop has more bigger serface, mass transfer is faster more abundant with heat transfer when contacting with another, has improved efficient and the homogeneity of chemical reaction, extraction and unit operations such as emulsification and preparation of granules greatly.Strengthen the microcosmic mass transport process, some relevant researchs have been arranged both at home and abroad.Chinese patent CN1605359 discloses a kind of dispersive film extractor, and this extractor utilizes the aperture for film pipe or the Flat Membrane of 0.01-60 micron, and decentralized photo liquid is dispersed into small drop, increases mass transfer area, improves the effect of extraction.Chinese patent CN1318429 discloses the method that a kind of film dispersion method prepares ultra-fine grain, also adopt the reactor of the type, the preparation barium sulfate particle, sulfuric acid-butanol solution is crossed microporous barrier be dispersed into droplet, go out barium sulfate particle with the barium chloride solution prepared in reaction again, this patent only utilizes microporous barrier that the initial particle of drop is limited, but the mixed characteristic after the fluid contact (as the thickness of flow velocity, fluid layer etc.) is not controlled, therefore the particle diameter (average particulate diameter is 1 micron) bigger than normal of preparation.
Chinese patent CN101433815 discloses a kind of membrane dispersion type micro-channel reactor, manage forming sleeves by in an outer tube and one, between inner and outer pipes, form the microchannel of annular, outer tube is provided with continuous phase import and outlet, interior Guan Yiduan is provided with the import of decentralized photo, the other end is the uniform film tubular construction that porous is arranged of tube wall, this device has increased the sectional area of microchannel effectively and has increased the flow velocity of continuous phase, improved the treating capacity of single reactor and guaranteed that stronger microcosmic mixes, this reactor is more suitable in the fast reaction of liquid liquid or liquid gas, but the entrance of this device continuous phase is positioned at a side, can cause the annular inside microchannels difference of flow velocity everywhere, cause the difference to porous membrane tube surface shear power, finally have influence on the homogeneity of dispersant liquid drop, adopt this reactor to be difficult to obtain uniform emulsion droplet or particle.
The membrane emulsifier of CN201006421 and CN101683592 and the exploitation of Japanese SPG technology Co., Ltd, by emulsion under the effect of high pressure by the SPG fenestra, form the emulsion droplet of uniform particle diameter.CN101683592 discloses a kind of many film pipe component film assemblies side by side, the micropore of the decentralized photo filmed passing tube of film tube outside is distributed to the inside of pipe, in pipe under the shearing force effect of continuous phase liquid to the film pipe, realization is with the separation of film, in continuous phase, form tiny one by one drop or emulsion droplet, the use of membrane module realizes industrial high-throughout requirement, but because various business-like film bores are thicker, and the preparation internal diameter is subjected to cost and technology limitation less than the film pipe of 2mm, the film bore that uses is usually more than 4mm at present, therefore use the liquid flow transmission equipment of identical power to carry continuous phase, continuous phase is lower at the flow velocity in the film pipe, the shearing force that produces is less, reduced the efficient of mass transfer, the emulsion droplet of preparation is big (usually more than micron) also, can't satisfy the requirement of the littler nano-emulsion of preparation and nano particle and preparation high concentration product.To realize in this technology that continuous phase has higher shearing force at the film pipe internal surface, then need significantly improve the power of equipment, as using more powerful pump, increase equipment cost and energy consumption in the production.
Therefore, be necessary to develop a kind of raising emulsifying power, be easy to amplify the film emulsifier unit of energy-conservation suitable suitability for industrialized production.
Summary of the invention
In order to solve problems of the prior art, the purpose of this invention is to provide a kind of membrane module for microchannel film dispersion reaction unit, comprising:
At least one film pipe, described film pipe two ends are passed continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate respectively, and are tightly connected with continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate; Be provided with overcoat outside the film pipe, described overcoat and continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate are tightly connected; Described overcoat and continuous phase inlet baffle plate, continuous phase liquid outlet baffle plate form the decentralized photo cavity that is enclosed in the described film pipe outside; Described outer putting is provided with the decentralized photo inlet, passes inlet and liquid outlet that inlet baffle plate and liquid outlet baffle plate are respectively equipped with continuous phase;
It is characterized in that the inner center position of described film pipe is provided with a branch fluid column, divide fluid column to be conical near an end of inlet baffle plate, divide the other end of fluid column to fixedly connected with the liquid outlet baffle plate; Dividing fluid column and film pipe to form cross section is the microchannel of ring-type.
Film pipe of the present invention can be a film pipe, also can be many film pipes arranged side by side, for example 2-20 root, preferably 3-10 root.Described film pipe cross section can be circular, oval, rectangle.Circular.
Described film pipe is porous membrane tube, comprises film pipe, silicon dioxide film pipe, ceramic-film tube, metal film pipe of high-molecular organic material etc., selects the suitable film pipe for use according to different technological requirements; Hollow membrane pipe or silicon dioxide film pipe such as SPG film and stainless metal film to pharmaceutical industry preferably ceramic film, PTFE; To preferred organic material membrane or organic/inorganic composite films such as the reaction of carrying out inorganic system and preparation inorganic nanoparticles.
Decide according to the different and reaction requirement of material with percent opening in the aperture of described film pipe, and wherein the scope in aperture is 0.02-100 μ m, and percent opening is 3-60%; Preferred aperture 0.1-50 μ m.
The diameter of described minute fluid column is selected to change according to the diameter of film pipe, and dividing the external diameter of the annular cross section that forms between fluid column and the film pipe and the difference of internal diameter size is 100 microns-5 millimeters, preferred 100-2000 μ m, more preferably 100-1000 μ m.
Of the present invention minute fluid column will be rived from the centre from the continuous phase that inlet enters the film pipe, between film pipe and branch fluid column, form the liquid stream of annular interface, divide the cross section of fluid column and film pipe to form circular concentric, it is consistent with flow regime on the membrane tube wall in annular inside microchannels symmetric position guarantee to flow, inner each position continuous phase in circular passage has the flow velocity of homogeneous like this, and the drop that makes formation is homogeneous more.Add and divide the prior advantage of fluid column to show:
Under the certain situation of flow, add the formation microchannel of dividing fluid column with one heart, reduced the sectional area in the film pipe, increase pipe flow speed, under the situation that does not increase the plant capacity load, both can arrive turbulent flow, reduce requirement and energy consumption to equipment;
When improving the flow velocity of continuous phase in the film pipe on the other hand, turbulence state as shown in Figure 1, flow velocity is bigger, reynolds number Re is bigger, and the thickness of laminar flow internal layer is more thin, and continuous phase to the shear action of the drop crossing the film decentralized photo and form significantly, slowly compare with the drop for preparing tens microns usually with traditional SPG membrane emulsifier process, can reduce the size of dispersant liquid drop to a certain extent, strengthen the effect of mass transfer and be more conducive to prepare littler particle and emulsion droplet, accelerate the emulsification process simultaneously;
The present invention divides fluid column to reduce the volume of the non-mixed zone of tube hub (being non-boundary layer) by adding, significantly reduced the volume of the continuous phase that has neither part nor lot in mass transfer, increased the concentration of end-product, can reduce to concentrate even save concentrated operation to be particularly suitable for high-throughout suitability for industrialized production.
The applicant is by discovering in a large number, and especially when the difference of the external diameter that divides the annular cross section that forms between fluid column and the film pipe and internal diameter size during less than 2000 μ m, if the effect that can guarantee to mix mass transfer oversize, can cause microchannel film dispersion effect to reduce.On the other hand, the external diameter of the annular cross section that the present invention preferably forms between branch fluid column and film pipe and the difference of internal diameter size reduce the difficulty of processing of equipment greater than 100 μ m, general formula, guarantee the unimpeded of passage, be difficult for blockedly, and then guarantee that the homogeneity of particle improves.
Fluid column can be answered the demand difference in described minute, selected preparations such as metal, organic material or inorganic ceramic material, and according to those skilled in the art's general knowledge, the selection of material is complementary with the physicochemical property that flows mutually with decentralized photo.For example, pharmaceuticals industry field preferably polytetrafluoroethylene (PTFE) and stainless steel metal material; To the reaction of inorganic system or preparation inorganic nanoparticles etc., preferred organic material.
Further, several tiny fluid holes are established in the fixed connection place of described minute fluid column and liquid outlet baffle plate, as the outlet that mixes back continuous phase, shape and position are seen shown in the assembly 12 of Fig. 2, the quantity in hole can be 1-10, preferred 1-4, fluid hole is formed an anchor ring identical with the microchannel, gap between the fluid hole is in that to guarantee to fixedly secure under the situation of branch fluid column area occupied as far as possible little, the bottom of fluid hole and film pipe guarantees certain distance, and the length of distance is decided according to the size of film pipe and microchannel, for ceramic-film tube, preferred 5-40mm, more preferably 20mm.
Baffle plate of the present invention with divide being connected of fluid column and being connected of baffle plate and film pipe, can be by technological means well known in the art, the mode of for example welding or being threaded.
The invention provides a kind of enhancement mode bushing type membrane module microchannel film dispersion reactor, decentralized photo is dispersed into the drop of micron or nano-scale by the micropore on the film pipe in the assembly, this drop is in continuous phase or carry out chemical reaction, unit operations such as perhaps extract, perhaps form emulsion droplet, perhaps the drop internal solvent dissolves each other with continuous phase and causes solute to separate out nano particle with the form of solid.
Another object of the present invention provides a kind of microchannel film and disperses reaction unit, the detection of the membrane module, decentralized photo feed arrangement, continuous phase transmitting device that comprises the invention described above and relevant pressure, flow velocity and device such as the instrument of control and valve, and detection reaction is carried out devices such as instrument.
Described decentralized photo feed arrangement according to the general general knowledge of this area, can be the feed arrangement of the power of air pressure transmission, also can be voltage stabilizing transmitting devices such as constant-flux pump.The decentralized photo feed arrangement comprises equipment such as the material pipe that connects decentralized photo material cup and valve.
Described continuous phase transmitting device according to the general general knowledge of this area, comprises pipeline and the valve of charging, and various suitable liquid pump, the preferred peristaltic pump of pump, constant-flux pump, plunger displacement pump, circulating pump and membrane pump etc., more preferably four plunger membrance pumps of no pulse.
Microchannel of the present invention film disperses reaction unit to adopt this area routine techniques mode to connect, and for example adopts the assembling of CN101683592 disclosed method, in this citation as a reference.
Another object of the present invention provides membrane module of the present invention and is used for the purposes that assembling microchannel film disperses reaction unit.
Membrane module of the present invention and, can be used for chemical reaction, extraction, emulsification and get everything ready the microcosmic mixing of inorganic, organic or drug particles course of reaction of little, micro-nano structure or/and reaction unit based on liquid-liquid precipitate legal system.
Description of drawings
Fig. 1 is the schematic diagram of fluid flow boundary layer on flat board.
Fig. 2 is the structural representation that single microchannel of the present invention film disperses the membrane module of reaction unit.
Fig. 3 is the cross-sectional view at continuous phase inlet baffle plate place.
Fig. 4 is the structural representation of a kind of specific embodiment of the multiple microchannels reactor formed of 4 film pipes.
Fig. 5 utilizes membrane module of the present invention and does not adorn the efficient comparison diagram that the membrane module of branch fluid column extracts.
The specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing 2 and embodiment, but be not limited to the present invention.
The membrane module of embodiment 1 single micro passage reaction
Fig. 2 is the structural representation of a kind of specific embodiment of single film pipe micro passage reaction provided by the present invention, wherein 1 is the outlet of continuous phase, and 2 for connecing chuck soon, and 3 is sealing ring, 4 is the film pipe of porous, 5 is the inlet of decentralized photo, and 6 for dividing fluid column, and 7 is the baffle plate of inlet, 8 is the sealing ring of quick chuck, 9 is the continuous phase outlet damper, and 10 is the overcoat of membrane module, and 11 is the import of continuous phase.12 outlet openings for the mobile phase of sleeve channel among Fig. 3,13 expressions divide the position of fluid columns, 14 expression film pipes.
Be positioned between continuous phase inlet (11) and the continuous phase liquid outlet (1), form the microchannel by ceramic-film tube (4) and branch fluid column (6), continuous phase is from wherein passing through, ceramic-film tube (4) and divide fluid column (6) respectively with the inlet baffle plate (7) of continuous phase and liquid outlet baffle plate (9) welding of continuous phase.
Membrane module overcoat (10) is welded on continuous phase import baffle plate (7) and the continuous phase import baffle plate (9), and the outer wall of its inwall and ceramic-film tube (4) is formed the decentralized photo chamber, puts outward and is provided with opening (5) as the import of decentralized photo; The sealing ring (8) of applying mechanically quick chuck outward is airtight.
Above-mentioned all parts all seal by sealing ring (3).
Further, can connect pump installation near the continuous phase import, and at decentralized photo entrance connection feed arrangement, and can add other attachment devices, as devices such as the instrument of the detection of continuous phase transmitting device, flow velocity and control and valves, and detection reaction is carried out device such as instrument and is formed the microchannel film and disperse reaction unit.
When continuous phase pumps into component internal by import (11), be split into uniform ring section enters by film pipe (4) and separatory post and forms inside microchannels at the tip of a minute fluid column (6), at this moment, decentralized photo enters the dispersion sap cavity by inlet (5), under high pressure extruding meeting with continuous phase from the perforated membrane pore, both form cross-flow, the continuous phase that decentralized photo is crossed by high velocity stream cuts into droplet one by one, droplet or with around continuous phase carry out chemical reaction, perhaps extract, perhaps form micro emulsion one by one, precipitation perhaps takes place form microballoon or nano particle.
The parts that above-mentioned membrane module, liquid are flowed through, for example film pipe, branch fluid column, outer casing inner wall all need pass through polishing.
Single microchannel film disperses the membrane module of reaction to can be used as the laboratory use, perhaps do the small testing device before industry is amplified, the pressure of the condition decentralized photo of groping out on this device and the conditions such as flow velocity of continuous phase in the film pipe can directly be used in the multiple microchannels film dispersion reactor of technical grade.
The membrane module of embodiment 2 multiple microchannels film dispersion reactors
Fig. 4 is the structural representation of a kind of specific embodiment of the multiple microchannels reactor formed of 4 film pipes provided by the present invention.This design is similar with single micro passage reaction, forms the microchannel by minute fluid column and film inside pipe wall, how to form the decentralized photo chamber with the inwall of film pipe outer wall and continuous phase import and export baffle plate and assembly overcoat.
The fluid state of each channel interior of the membrane module of multiple microchannels film dispersion reaction is identical, therefore can amplify by the quantity that increases the film pipe, is fit to industrial big production requirement.
The HPMC (HPMC) of embodiment 3 preparation high concentrations disperses Itraconazole (ITA) to prepare its nanoparticle
At first the Itraconazole (ITA) with 0.5g is dissolved in methyl alcohol/oxolane (1:1) mixed solvent of 50ml, and about concussion 10min, making it to dissolve fully becomes decentralized photo;
And then compound concentration is the HPMC aqueous solution of 8.0mg/ml, stirs to make it to mix, and gets solution as continuous phase;
Under 40KPa, the flow of decentralized photo with 100ml/min injected the reactor of the embodiment of the invention 1 that the branch fluid column is housed respectively and the reactor that divides fluid column is not installed, wherein film is that average pore size is the tubulose SPG film of 100nm, the parameter of film is external diameter 10.0mm, internal diameter 8.0mm, length is 50.0mm, and dividing the diameter of fluid column is 6mm.Above-mentioned continuous phase is pressed into continuous phase cavity (for the device of the embodiment of the invention 1, the tip that refers to be pressed into branch fluid column (6) is split into uniform ring section and enters the inside microchannels that is formed by film pipe (4) and separatory post).
Generate white ultra-fine grain suspension after crossing film; And then use the particle of 1.0 μ m membrane filtration gained; Again the slurry that produces ultra-fine grain being carried out freeze drying respectively at last handles.The ITA/HPMC nanoparticle carries out being dispersed in the water after the freeze drying, uses DLS to detect particle diameter, and average grain diameter all is about 130nm, illustrates to divide fluid column that particle size is not had remarkable influence under this flow velocity.And reactor that measure to find to be equipped with the branch fluid column to produce the concentration of nanoparticle be 20.35mg/ml, can be without concentrated convection drying, and the concentration that the nanoparticle of the reactor generation that divides fluid column is installed is 2.43mg/ml, only be that 1/8 of back concentration is installed, as further reducing the size in gap, can obtain the higher nanometer suspension liquid of concentration.
The HPMC (HPMC) of embodiment 4 preparation different-grain diameters disperses Itraconazole (ITA) to prepare its nanoparticle
At first the Itraconazole (ITA) with 0.5g is dissolved in methyl alcohol/oxolane (1:1) mixed solvent of 50ml, and about concussion 10min, making it to dissolve fully becomes decentralized photo; And then compound concentration is the HPMC aqueous solution of 8.0mg/ml, stirs to make it to mix, and gets solution as continuous phase; Then, under 40KPa, with decentralized photo with the flow of 200ml/min the reactor of the embodiment of the invention 1 by the branch fluid column is housed and install in the reactor that divides fluid column respectively, film is that average pore size is the tubulose SPG film of 100nm, the parameter of film is external diameter 10.0mm, internal diameter 8.0mm, length is 50.0mm, dividing the diameter of fluid column is 6mm.
According to the method operation of embodiment 3, generate the ultra-fine grain suspension of white excessively behind the film; And then use the particle of 1.0 μ m membrane filtration gained; Again the slurry that produces ultra-fine grain being carried out freeze drying respectively at last handles.The ITA/HPMC nanoparticle carries out being dispersed in the water after the freeze drying, use DLS to detect particle diameter, it is about 100nm that adding divides the average grain diameter behind the fluid column, do not divide the device average grain diameter of fluid column to be still about 130nm and add, the big flow velocity that has improved continuous phase in the annular chamber of separatory post pole is described, the boundary layer of continuous phase enlarges, and the laminar flow internal layer reduces, the shearing force of disperseing the back to form drop increases, and has influenced the size that forms particle.
Experimental provision is as shown in Figure 2. and the tubular type aperture of testing used film and be oleophobic is the Al of 1.0 μ m
2O
3Micro-filtration ceramic membrane (being provided by Great Wall, Hefei Singapore dollar film science and technology limited Company).The parameter of film is external diameter 13.0mm, internal diameter 9.0mm, and length is 50.0mm, dividing the diameter of fluid column is 8mm.Experimental system is 25%TBP (kerosene)/nitric acid/water, and oil phase is as decentralized photo, and nitric acid passes to organic phase by water.Concentration of nitric acid is by determination of acid-basetitration.Respectively at the assembly of the embodiment of the invention 1 of loading onto the branch fluid column with do not adorn the comparison (according to the method operation of embodiment 4) of carrying out extraction efficiency in the assembly of branch fluid column, from the data of Fig. 5 as can be seen, the extraction efficiency of branch fluid column is housed under different pressure and the flow velocity about 99%, and the assembly extraction efficiency that is unkitted the branch fluid column only can reach about 90%.
Claims (9)
1. one kind is used for the membrane module that the microchannel film disperses reaction unit, comprising:
At least one film pipe, described film pipe two ends are passed continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate respectively, and are tightly connected with continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate; Be provided with overcoat outside the film pipe, described overcoat and continuous phase inlet baffle plate and continuous phase liquid outlet baffle plate are tightly connected; Described overcoat and continuous phase inlet baffle plate, continuous phase liquid outlet baffle plate form the decentralized photo cavity that is enclosed in the described film pipe outside; Described outer putting is provided with the decentralized photo inlet, passes inlet and liquid outlet that inlet baffle plate and liquid outlet baffle plate are respectively equipped with continuous phase;
It is characterized in that the inner center position of described film pipe is provided with a branch fluid column, divide fluid column to be conical near an end of inlet baffle plate, divide the other end of fluid column to fixedly connected with the liquid outlet baffle plate; Dividing fluid column and film pipe to form cross section is the microchannel of ring-type.
2. membrane module as claimed in claim 1 is characterized in that the external diameter of the ring shaped cross-section that described minute fluid column and film pipe form and the difference of internal diameter size are 100-2000 μ m.
3. membrane module as claimed in claim 2 is characterized in that, the size 100-1000 μ m between described annular gap.
4. membrane module as claimed in claim 1 is characterized in that, comprises many film pipes arranged side by side.
5. as each membrane module of claim 1-4, it is characterized in that the aperture of described film pipe is 0.02-100 μ m.
6. as each membrane module of claim 1-4, it is characterized in that the place of being tightly connected of described minute fluid column and continuous phase liquid outlet baffle plate is provided with aperture.
7. a microchannel film disperses reaction unit, comprises the membrane module as described in each as claim 1-6.
8. film dispersion reaction unit in microchannel as claimed in claim 7 also comprises the pump that is connected with the continuous phase inlet and the feed arrangement that is connected that is connected with the decentralized photo inlet.
9. as each described membrane module of claim 1-6, assembling is used for chemical reaction, extraction, emulsification and mix or/and the purposes of reaction unit based on the get everything ready microcosmic of inorganic, organic or drug particles course of reaction of little, micro-nano structure of liquid-liquid precipitate legal system.
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| CN103754919A (en) * | 2013-12-30 | 2014-04-30 | 广西大学 | Hollow fiber membrane reactor for producing nano calcium carbonate and equipment |
| CN104709921A (en) * | 2015-03-10 | 2015-06-17 | 中国天辰工程有限公司 | Micro-channel reactor and method applying micro-channel reactor to produce magnetic titanium silicalite |
| CN105664777A (en) * | 2016-03-24 | 2016-06-15 | 青岛科技大学 | Fluid mixing method and high-speed centrifugal fluid mixing apparatus |
| CN107261997A (en) * | 2017-07-03 | 2017-10-20 | 中国科学院过程工程研究所 | Liquid liquid heterogeneous reaction microreactor, system and liquid acid alkylation |
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| CN110404432A (en) * | 2018-04-28 | 2019-11-05 | 上海现代药物制剂工程研究中心有限公司 | Prepare film emulsification component and its application of micron grain size microballoon |
| CN111670068A (en) * | 2017-11-13 | 2020-09-15 | 微孔技术有限公司 | Cross-flow assembly and method for droplet generation for membrane emulsification control |
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| CN103754919B (en) * | 2013-12-30 | 2015-04-22 | 广西大学 | Hollow fiber membrane reactor for producing nano calcium carbonate and equipment |
| CN103754919A (en) * | 2013-12-30 | 2014-04-30 | 广西大学 | Hollow fiber membrane reactor for producing nano calcium carbonate and equipment |
| CN104709921A (en) * | 2015-03-10 | 2015-06-17 | 中国天辰工程有限公司 | Micro-channel reactor and method applying micro-channel reactor to produce magnetic titanium silicalite |
| CN104709921B (en) * | 2015-03-10 | 2016-08-24 | 中国天辰工程有限公司 | A kind of micro passage reaction and the method using its production Magnetic titanium silicon molecular sieve |
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