CN101406818B - Method for acquiring ultrafine grains using supercritical carbon dioxide saturated solution - Google Patents
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Abstract
The invention discloses a method for obtaining superfine particles through supercritical saturated carbon dioxide solution, and relates to a superfine particle with fat, fat soluble substances or macromolecules. The invention provides a device for preparing the superfine particles by using the supercritical saturated carbon dioxide solution and the preparation method thereof. The device is provided with a carbon dioxide storage tank, a high pressure atomized fluid storage tank, a condensing tank, a buffer tank, a high pressure mixing tank, a collecting chamber, a filter, a normal pressure charging bucket, two pumps or compressors with pressure control, a high pressure circulating pump, a high pressure liquor pump, a compressor, a valve, a pressure gauge and a thermometer. The preparation method comprises the following steps: placing the material to be processed into the mixing tank after being melted, introducing carbon dioxide into the mixing tank, and heating up the mixing tank till the carbon dioxide reaches a supercritical state; and starting the circulating pump to pump materials in the mixing tank from the bottom of the mixing tank to the top of the mixing tank for circulation till the saturated carbon dioxide solution is formed in the mixing tank, then loading the saturated carbon dioxide solution into one passage of a coaxial bi-pass nozzle, adding atomized fluid into the other passages of the bi-pass nozzle, atomizing the saturated carbon dioxide solution, and collecting the particles in the particle collecting chamber.
Description
Technical field
The present invention relates to a kind of ultra-fine fat, fat-soluble thing or polymeric particles, especially relate to a kind of saturated solution of supercritical carbon dioxide is atomized and obtain preparation method and the device thereof of fat, fat-soluble thing or high molecular micro nanometer and composite particles thereof.
Background technology
The ultra-fine grain material is owing to there are special physicochemical properties, is a focus in the current new and high technology, and it has important using value at material, chemical industry, light industry, metallurgy, electronics, medical science and the field such as biological, and is used widely.The Manufacture of Superfine Powder by Fast Expending of Supercritical Liquid Flow technology is a new granulation technique of just actively researching and developing both at home and abroad in recent ten years, compare with grinding, solution crystallization and chemical reaction etc. with traditional method for forming particles such as mechanical disintegration, this method has product purity height, geometry homogeneous, narrow diameter distribution, manufacturing process is simple, operating temperature is low and avoid with an organic solvent waiting many obvious advantages, and especially responsive, thermo-responsive, the structural instability of impact and the processing that is easy to the system of chemical breakdown have clear superiority.
Development through more than 20 years, emerge in large numbers in the world multiple use supercritical fluid and prepared the technology of microparticle, wherein, relatively more outstanding has: supercritical solution fast expansion (Rapid Expansion of Supercritical Solutions, RESS), the anti-solvent recrystallization process of supercritical fluid (The Supercritical Anti-solvent Process, SAS/GAS) and the gas-saturated solutions particle form technology (Particles from Gas Saturated Solutions, PGSS) etc.These diverse ways and improvement technology thereof, a large amount of patent literatures is all arranged (referring to Li J, Gomes de Azevedo E.Particle formationtechniques using supercritical fluids, Recent Patents on Chemical Engineering, 2008,2:157-169).
The SAS method has comprised again a lot of Innovative methods in the above-mentioned technology, and SEDS (the Solution Enhanced Dispersion by Supercritical fluid) method of continued operation process is arranged near industrialized method at present.PGSS is newer a kind of in the preparation ultrafine powder technology relevant with supercritical fluid technique, the present inventor (referring to: Li J, Matos HA, Gomes deAzevedo E.Modeling of particle formation from a gas-saturated solution Process, Proceedings ofthe Sixth Intemational Symposium on Supercritical Fluids, Versailles (France), 2003) process of PGSS experimental study and simulation have been carried out, and the atomization process of PGSS process set up model, the droplet size that nozzle exit liquid atomizes mutually and produces is discussed.Thereafter (referring to: Li J, Matos H A, Gomes de Azevedo E.Two-PhaseHomogeneous Model for Particle Formation from Gas-Saturated Solution Process, J.ofSupercritical Fluids, 2004, (32): 275-286) considered again the fusion-crystallization mechanism of PGSS process, various operating conditions are inquired into the impact of microparticle size, yet analog result reflects the variation of granule-morphology, particularly experimental result spherical and irregular crystal shape are not arranged, the multimodal distribution of particles.So further (Li J, Rodrigues M A, Matos H A, Almeida A, Gomes de Azevedo E.Modeling of the PGSS Process by Crystallization andAtomization, AIChE J, 2005,51 (8), 2345-2357) fusion-crystallization and atomization mechanism combination are paid attention to, can produce simultaneously the particle of RESS mechanism, particle and the particle corresponding to atomized drop of fusion-crystallization; Its quantity, size and pattern change with operating condition, thereby can simulate the mechanism corresponding to particle of multimodal distribution of particles and sign different-shape: atomizing produces spheroidal particle, and crystallization produces irregular crystal.
Above-mentioned traditional PGSS technology, still there are the following problems: if the saturated solution of gas is carried out intermittently operated, its flow can not accurately be controlled (referring to Wang Xia, Guo Yanni, Chen Hui, Su Yuzhong, Wang Hongtao, Li Jun, supercritical fluid technique prepares the compound grain of brufen/fat, modern chemical industry, 2007,27 (increasing): 398-402); If continued operation, fused materials can not guarantee that by gas uniform saturated (not reaching thermodynamical equilibrium) Shekunov etc. has proposed to mix with the method for blender in its patent (WO2004071614) for this reason.
On the other hand, according to the description of mechanism model, the applicant proposes overcritical microsphere with nitrogen aid preparation method (Chinese patent CN1907553), the material of processing lipid material and polymer substance and dissolving in organic solvent.The particle of preparation is mainly used in fat-soluble or water soluble drug, medicinal compound type, but the control that especially is applied to inhalant discharges.Because the particle of preparation mainly occurs with the single shape of microballoon (containing bulky grain low bulk density microballoon), the other medicines granule-morphology is more suitable for sucking and entering lung relatively.And can control easily product at the particle size distribution range of 1～5 μ m.Yet, use the microsphere with nitrogen aid preparation method, more the particle of small particle diameter, particularly average grain diameter are difficult to reach nanoscale to be difficult to control microballoon.In addition, this preparation method still belongs to the intermittently operated process, and as the intermittently operated of PGSS, the flow of its solution can not accurately be controlled.
Summary of the invention
The object of the present invention is to provide a kind of device for preparing ultra-fine grain (espespecially submicron and nano particle and composite particles) with the supercritical carbon dioxide saturated solution and preparation method thereof.
The technical solution adopted in the present invention is to circulate with solution and supercritical carbon dioxide to be mixed to get the supercritical carbon dioxide saturated solution, and carries out fine atomizing (atomizing with high-pressure carbon dioxide or nitrogen) with this.
The device for preparing ultra-fine grain with the supercritical carbon dioxide saturated solution of the present invention is provided with carbon dioxide storage tank, high-pressure atomization fluid reservoir, drainer, surge tank, high pressure mixing tank, collecting chamber, filter, normal pressure batch can, the 1st and is with pressure controlled pump or compressor, the 2nd to be with pressure controlled pump or compressor, high-pressure circulation pump, pressure liquid pump, compressor, valve, pressure indicator and temperature indicating meter.The outlet of carbon dioxide storage tank connects drainer through valve, the outlet of drainer connects the 1st entrance with pressure controlled pump or compressor, the 1st outlet with pressure controlled pump or compressor connects surge tank through valve respectively, high pressure mixing tank and the 2nd is with pressure controlled pump or compressor, the outlet of high pressure mixing tank connects the entrance of high-pressure circulation pump, cycle of higher pressure delivery side of pump one tunnel connects the entrance of high pressure mixing tank through valve, another road of cycle of higher pressure delivery side of pump connects collecting chamber through valve, another entrance of high pressure mixing tank connects the highly pressurised liquid delivery side of pump through valve, the entrance of pressure liquid pump connects the normal pressure batch can, collecting chamber connects surge tank through valve, collecting chamber connects compressor through filter, compressor is connected to the entrance of drainer through valve, and the outlet of high-pressure atomization fluid reservoir connects the 2nd through valve and is with pressure controlled pump or compressor.
The method of obtaining ultra-fine grain with the supercritical carbon dioxide saturated solution of the present invention may further comprise the steps:
1) with pumping into or the disposable blending tank of directly putting into of solid material with pump after the pending material normal pressure melting, in blending tank, is filled with carbon dioxide, and blending tank is heated to carbon dioxide reaches overcritical;
2) start the circulating pump that links to each other with the blending tank outlet at bottom, material in the blending tank is got to the blending tank top be circulated to the saturated solution of formation carbon dioxide the blending tank from the bottom;
3) with step 2) in the saturated solution of carbon dioxide switch a passage sending into coaxial bilateral nozzle with circulating pump, another passage of coaxial bilateral nozzle adds atomizing fluids, the solution saturated to carbon dioxide atomizes, material enters particle collecting cells after the atomizing, collects the particle that solidifies.
In step 1) in, described pending material can be at least a in fat, liposoluble substance (espespecially fat-soluble medicine), the polymer substance etc., can be for the preparation of the microcapsules with controlled release or solubilizing effect or composite particles system, the espespecially microcapsules of medicine or composite particles system; Describedly overcritically refer to heat the temperature of carbon dioxide greater than the critical-temperature of carbon dioxide, the pressure of heating carbon dioxide is greater than the critical pressure of carbon dioxide, the temperature of heating carbon dioxide is preferably 32～100 ℃, and the pressure P 1 of heating carbon dioxide is preferably 7.3～50MPa.
In step 2) in, the time of described circulation is preferably 0.5～5h; The circular flow of the saturated solution of described circulating pump is preferably 1mL～10L/min; Circulating pump can be one or more.
In step 3) in, described atomizing fluids can be supercritical carbon dioxide itself, also can be nitrogen, helium or air etc.; When described atomizing fluids is supercritical carbon dioxide, the gas after the gas solid separation after the atomizing (filtering through the filter that is installed in particle collecting cells), compressed machine compression and back carbon dioxide storage tank has more recycling economy.When high-pressure fluid is not supercritical carbon dioxide (such as overcritical nitrogen), because the gas after the filter filtration of particle collecting cells is mist, can not directly reclaim.Described coaxial bilateral nozzle is to make with two pressure pipes that differ in size, and the inner tube external diameter is less than outer tube diameter.Inner and outer tubes can be selected to link to each other with supercritical carbon dioxide saturated solution or high-pressure atomization fluid, and the outer tube bottom is provided with the thin slice of at least 1 laser opening of band, and this laser opening diameter is 25～1000 μ m.The temperature of described atomizing fluids is preferably 32～100 ℃, and the pressure of atomizing fluids is preferably 7.3～50MPa; The pressure of described particle collecting cells is preferably 0.1～7MPa.
Maximum characteristics of the present invention are high-pressure circulation pump to be set realize dual function, supercritical carbon dioxide and fused materials are mixed form the saturated solution of carbon dioxide, quantitatively carry this saturated solution to nozzle to realize serialization or semicontinuous operation.In addition, the present invention atomizes to the carbon dioxide saturated solution with the high-pressure atomization fluid and forms fat, fat-soluble thing or high molecular micro nanometer grain.Simultaneously, the present invention can carry out low-temperature operation for heat sensitive material, and material is placed directly in the high pressure mixing tank, and after passing into supercritical carbon dioxide, its fusing point can reduce by 10～30 ℃ at suitable pressures; And to its can be continuously, quantitatively carry.
The handled material object of the present invention can be fat, fat-soluble thing or polymer substance, and their mixture (referring to prepare composite particles).Prepared micro-nano granules is mainly used in fat-soluble or water soluble drug, medicinal compound type (microcapsules), especially is applied to control discharge or the pharmaceutical dosage form of solubilizing effect.The particle of preparation may be controlled to spherical, can be non-spherical, and certain section distribution of the particle diameter that product cut size can be controlled at 0.05～50 μ m on a large scale.The present invention prepares the particle size range that particle especially can be controlled at nanometer and sub-micron (0.05～1 μ m), therefore has clear superiority.
Description of drawings
Fig. 1 is that the structure for preparing the device embodiment of ultra-fine grain with the supercritical carbon dioxide saturated solution of the present invention forms and process flow diagram.
The specific embodiment
Referring to Fig. 1, the device for preparing ultra-fine grain with the supercritical carbon dioxide saturated solution of the present invention is provided with carbon dioxide storage tank A, high-pressure atomization fluid reservoir A ', drainer B, surge tank C, high pressure mixing tank D, collecting chamber E, filter F, normal pressure batch can G, the 1st is with pressure controlled pump or compressor Pu1, the 2nd is with pressure controlled pump or compressor Pu2, high-pressure circulation pump Pu3, pressure liquid pump Pu4, compressor Pu5, valve (comprises V1, V1 ', V2, V3, V4, V5, V5 ', V6, V7, V8, V9), pressure indicator P1 and P2 and temperature indicating meter T1 and T2.The outlet of carbon dioxide storage tank A meets drainer B through valve V1, the outlet of drainer B connects the 1st entrance with pressure controlled pump or compressor Pu1, the 1st outlet with pressure controlled pump or compressor Pu1 meets surge tank C through valve V2 and V3 respectively, high pressure mixing tank D and the 2nd outlet with pressure controlled pump or compressor Pu2, the outlet of high pressure mixing tank D connects the entrance of high-pressure circulation pump Pu3, the outlet one tunnel of high-pressure circulation pump Pu3 connects the entrance of high pressure mixing tank D through valve V6, another road of the outlet of high-pressure circulation pump Pu3 meets collecting chamber E through valve V5 (stop valve) and valve V5 ' (check (non-return) valve), another entrance of high pressure mixing tank D connects the outlet of pressure liquid pump Pu4 through valve V7, the entrance of pressure liquid pump Pu4 meets normal pressure batch can G, collecting chamber E connects surge tank through valve V4, collecting chamber E meets compressor Pu5 through filter F, compressor Pu5 is connected to the entrance of drainer B through valve V9, and the outlet of high-pressure atomization fluid reservoir A ' connects the 2nd through valve V1 ' and is with pressure controlled pump or compressor Pu2.
The implementation method that fat, fat-soluble thing or high molecular micro nanometer particle are obtained in carbon dioxide saturated solution atomizing preparation is as follows:
Preparation.Before the operation, the air-tightness of testing fixture, each road heat tracing situation and instrument show and the control situation, confirm no problem after, design and control well temperature in the air thermostat.
The preparation of carbon dioxide saturated solution.Non-heat sensitive material can be placed on and pump into high pressure mixing tank D with pressure liquid pump Pu4 through valve V7 after normal pressure batch can G is heated to fusing or higher temperature, also can directly put into D (particularly can protect heat sensitive material).Open the outlet valve V1 of carbon dioxide storage tank A, carbon dioxide enters condensation of gas tank B and forms liquid, liquid CO 2 is with pressure controlled pump or compressor Pu1 (not needing during compressor carbon dioxide is cooled to liquid in drainer) to send into D through V2 by the 1st, and steady pressure is P1.Open high-pressure circulation pump Pu3 and stop valve V6, so that material circulates, form the saturated material solution of carbon dioxide after a period of time in D.
High-pressure fluid atomizing saturated solution forms particle and particle is collected.Open the outlet valve V1 ' of high-pressure fluid storage tank A ', with pressure controlled pump or compressor Pu2 high-pressure fluid is pumped into surge tank C constant temperature (temperature value that temperature indicating meter T1 shows) with the 2nd, and controlled pressure is P2.If high-pressure fluid is carbon dioxide, then need not to open Pu2.Open valve V4 is so that high-pressure fluid enters passage of coaxial bilateral nozzle.Close V6, regulate high-pressure circulation pump Pu3 to required flow, aforementioned carbon dioxide saturated solution is sent into another passage of coaxial bilateral nozzle through stop valve V5 and check (non-return) valve V5 '.Through the laser beam drilling of nozzle, then atomizing entered particle collecting cells E after the fluid of two passages fierceness was mixed in coaxial bilateral nozzle.Material cooling (throttling action of carbon dioxide) is solidified in particle collecting cells, and the promoting the circulation of qi of going forward side by side separates admittedly, and gas is from the upper shed process filter F emptying of E or through compressor Pu5 compression and back condenser B.Particle can be emitted packing from the E bottom.In Fig. 1, pressure indicator P3 shows the pressure of collecting chamber E.
Embodiment 1: myristic acid and Co-Q10 composite particles.
Institute's with medicament has: myristic acid, and chemical pure, purity 〉=98%, Chemical Reagent Co., Ltd., Sinopharm Group provides (bulk, the about 200 μ m of average diameter); Carbon dioxide, purity 〉=98%, the empty dtex gas in Xiamen Co., Ltd; Co-Q10 (Jin Dawei vitamin Co., Ltd (bulk, the about 20 μ m of average diameter).Below provide result's (particle is scattered in the water and uses the laser particle analyzer analysis, and the gained particle diameter is expressed as the surface area average grain diameter, i.e. the Sauter average grain diameter) of myristic acid and Co-Q10 composite particles under the different operating condition.
(1) myristic acid and Co-Q10 (latter contains 10%), nozzle diameter 80 μ m, pre-expansion temperature 323K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 20MPa, fluid flow 0.2mL/min.Prepared particle average grain diameter is 840nm.
(2) myristic acid and Co-Q10 (latter contains 40%), nozzle diameter 80 μ m, pre-expansion temperature 323K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 20MPa, fluid flow 0.2mL/min.Prepared particle average grain diameter is 650nm.
(3) myristic acid and Co-Q10 (latter contains 70%), nozzle diameter 80 μ mm, pre-expansion temperature 323K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 20MPa, fluid flow 0.2mL/min.Prepared particle average grain diameter is 560nm.
(4) myristic acid and Co-Q10 (latter contains 70%), nozzle diameter 80 μ m, pre-expansion temperature 338K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 20MPa, fluid flow 0.2mL/min.Prepared particle average grain diameter is 770nm.
(5) myristic acid and Co-Q10 (latter contains 70%), nozzle diameter 80 μ m, pre-expansion temperature 323K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 50MPa, fluid flow 0.2mL/min.Prepared particle average grain diameter is 650nm.
Embodiment 2: polyethylene glycol and Co-Q10 composite particles
Institute's with medicament has: Macrogol 6000 (PEG), chemical pure, Solution on Chemical Reagents in Shanghai purchasing and supply station provide (bulk, the about 2mm of average diameter); Carbon dioxide, purity 〉=98%, the empty dtex gas in Xiamen Co., Ltd; Co-Q10 (Xiamen Jin Dawei vitamin Co., Ltd, bulk, the about 20 μ m of average diameter).As follows with the composite particles that institute's description equipment obtains: PEG and Co-Q10 (latter contains 10%), nozzle diameter 80 μ m, pre-expansion temperature 333K, particle collecting cells control temperature 293K (room temperature), the pre-bulbs of pressure are 20MPa, fluid flow 0.5mL/min.Prepared particle average grain diameter is 170nm.)
Device and technique that the present invention obtains fat, fat-soluble thing or high molecular micro nanometer particle take the atomizing preparation of supercritical carbon dioxide saturated solution are summed up as three parts: first as the preparation of carbon dioxide saturated solution standby, second portion is that high-pressure fluid atomizing saturated solution forms particle and particle is collected, and third part is the control display part.
Supercritical carbon dioxide saturated solution preparation part is used for preparing the target saturated solution, is provided with carbon dioxide storage tank, drainer, the 1st and is with pressure controlled pump or compressor, high pressure mixing tank, normal pressure batch can, high-pressure circulation pump and stop valve, check (non-return) valve.Carbon dioxide storage tank links to each other with drainer, and the drainer outlet is with pressure controlled pump or compressor to link to each other with the 1st.The 1st with pressure controlled pump or compressor output end bifurcation road: one and stop valve also are with pressure controlled pump or compressor, surge tank to link to each other the input port that another links to each other and receive the high pressure mixing tank with stop valve with the 2nd of second portion.The bottom of high pressure mixing tank is through connecing the cycle of higher pressure pump intake, cycle of higher pressure pump discharge bifurcation road: one connects stop valve and takes back the top of high pressure mixing tank, and it two connects the passage that stop valve and check (non-return) valve are sent into coaxial bilateral nozzle.The high pressure mixing tank top is established in addition an entrance and is linked to each other with another highly pressurised liquid pump discharge, and this highly pressurised liquid pump intake then links to each other with normal pressure batch can outlet at bottom.The normal pressure batch can is provided with heating and heat insulation function.
High-pressure fluid atomizing saturated solution forms particle and particle is collected part, be used for to nozzle carry the carbon dioxide saturated solution of aforementioned arrangements to atomize and collect atomizing and solidify after solid particle.This part is provided with high-pressure fluid storage tank (if carbon dioxide then need not this storage tank as high-pressure fluid), the 2nd and is with pressure controlled pump or compressor, surge tank, stop valve, coaxial bilateral nozzle, filter, particle collecting cells, compressor.The outlet of high-pressure fluid storage tank links to each other with surge tank through stop valve, and the surge tank outlet links to each other through another passage of stop valve and coaxial bilateral nozzle.Coaxial bilateral nozzle and particle collecting cells top or bottom or side link to each other.Particle collecting cells top or bottom or sidepiece have a gas vent, and gas vent is installed filter, and filter outlet links to each other with the gas compressor entrance or passes through stop valve emptying.The gas compressor outlet links to each other with the drainer of first.
Control display partly is used for temperature, the pressure of material, demonstration and/or the control of flow.Control display partly is provided with air thermostat, material temperature controller, pressure indicator, temperature indicating meter.Surge tank, high pressure mixing tank, valve, pipeline etc. place in the air thermostat.The normal pressure batch can is connected to control the temperature of material by temperature controller and thermocouple in the tank.Pressure gauge one links to each other with the high pressure mixing tank and shows its pressure and be used for the 1st control with pressure controlled pump or compressor, and Pressure gauge two links to each other before nozzle with the branch road that the second portion surge tank is come, and is used for the 2nd control with pressure controlled pump or compressor.
Claims (8)
1. method of obtaining ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that adopting the device for preparing ultra-fine grain with the supercritical carbon dioxide saturated solution, the described device for preparing ultra-fine grain with the supercritical carbon dioxide saturated solution is provided with carbon dioxide storage tank, the high-pressure atomization fluid reservoir, drainer, surge tank, the high pressure mixing tank, collecting chamber, filter, the normal pressure batch can, the 1st is with pressure controlled pump or compressor, the 2nd is with pressure controlled pump or compressor, high-pressure circulation pump, pressure liquid pump, compressor, valve, pressure indicator and temperature indicating meter, the outlet of carbon dioxide storage tank connects drainer through valve, the outlet of drainer connects the 1st entrance with pressure controlled pump or compressor, the 1st outlet with pressure controlled pump or compressor connects the high pressure mixing tank through valve, the outlet of high-pressure atomization fluid storage pipe connects the 2nd entrance with pressure controlled pump or compressor through valve, the 2nd outlet with pressure controlled pump or compressor connects surge tank, the 1st has a passage to link to each other by valve with pressure controlled pump or compressor with the 2nd outlet with pressure controlled pump or compressor in addition, the outlet of high pressure mixing tank connects the entrance of high-pressure circulation pump, cycle of higher pressure delivery side of pump one tunnel connects the entrance of high pressure mixing tank through valve, another road of cycle of higher pressure delivery side of pump enters collecting chamber through the passage that valve connects coaxial bilateral nozzle, the outlet of surge tank enters collecting chamber through another passage that valve connects coaxial bilateral nozzle, another entrance of high pressure mixing tank connects the highly pressurised liquid delivery side of pump through valve, the entrance of pressure liquid pump connects the normal pressure batch can, collecting chamber connects surge tank through valve, collecting chamber connects compressor through filter, and compressor is connected to the entrance of drainer through valve.
2. obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that may further comprise the steps:
1) will pump into pump after the pending material normal pressure melting or solid material is disposable directly puts into a blending tank, in blending tank, be filled with carbon dioxide, and blending tank is heated to carbon dioxide reaches overcritical;
2) start the circulating pump that links to each other with the blending tank outlet at bottom, material in the blending tank is got to the blending tank top be circulated to the saturated solution of formation carbon dioxide the blending tank from the bottom;
3) with step 2) in the saturated solution of carbon dioxide switch a passage sending into coaxial bilateral nozzle with circulating pump, another passage of coaxial bilateral nozzle adds atomizing fluids, the solution saturated to carbon dioxide atomizes, material enters particle collecting cells after the atomizing, collects the particle that solidifies; Described coaxial bilateral nozzle is two pressure pipes that differ in size, and the inner tube external diameter is less than outer tube diameter;
Inner and outer tubes link to each other with supercritical carbon dioxide saturated solution or high-pressure atomization fluid, and the outer tube bottom is provided with the thin slice of at least 1 laser opening of band, and this laser opening diameter is 25～1000 μ m.
3. as claimed in claim 2ly obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that in step 1) in, described pending material is fat.
4. the method for obtaining ultra-fine grain with the supercritical carbon dioxide saturated solution as claimed in claim 2, it is characterized in that in step 1) in, the described overcritical temperature that refers to heat carbon dioxide is 32～100 ℃, and the pressure P 1 of heating carbon dioxide is 7.3～50MPa.
5. as claimed in claim 2ly obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that in step 2) in, the time of described circulation is 0.5～5h.
6. as claimed in claim 2ly obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that in step 2) in, the circular flow of the saturated solution of described circulating pump is 1mL～10L/min.
7. as claimed in claim 2ly obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that in step 3) in, described atomizing fluids is supercritical carbon dioxide itself, or nitrogen, or helium, or air.
8. as claimed in claim 2ly obtain the method for ultra-fine grain with the supercritical carbon dioxide saturated solution, it is characterized in that in step 3) in, the temperature of described atomizing fluids is 32～100 ℃, the pressure of atomizing fluids is 7.3～50MPa; The pressure of described particle collecting cells is 0.1～7MPa.
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| CN102041170B (en) * | 2009-10-15 | 2013-04-17 | 福建中烟工业有限责任公司 | Technology and equipment for integrating essence and spice extraction and micro-capsule preparation |
| CN103877051B (en) * | 2014-04-19 | 2015-09-30 | 青岛科技大学 | A kind of preparation method of Ezetimibe sheet |
| CN104826552B (en) | 2015-05-29 | 2017-06-23 | 厦门大学 | A kind of devices and methods therefor of scale pressure carbonization reaction |
| CN108850322A (en) * | 2018-06-29 | 2018-11-23 | 浙江茗皇天然食品开发股份有限公司 | The method of instant tea powder hollow granulation device and the hollow instant tea powder of production |
| CN110396396A (en) * | 2019-08-06 | 2019-11-01 | 西南石油大学 | A kind of includes the drying agent nanoscale ultramicro powder production method that ionic type metal carbide is applied to compact reservoir |
| CN114605368B (en) * | 2022-03-27 | 2023-05-26 | 中国药科大学 | Method for preparing luteolin ultrafine particles by using supercritical fluid enhanced solution dispersion technology |
| CN114832740A (en) * | 2022-04-28 | 2022-08-02 | 长安大学 | Carbon nanotube aerosol preparation device and preparation method |
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| E.Weidner, et.al.Multifunctional composites by high-pressure spray processes.《Current Opinion in Solid State and Materials Science》.2003,(第7期),385-390. * |
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