CN101444709A - Method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide - Google Patents
Method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide Download PDFInfo
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- CN101444709A CN101444709A CNA2008100722977A CN200810072297A CN101444709A CN 101444709 A CN101444709 A CN 101444709A CN A2008100722977 A CNA2008100722977 A CN A2008100722977A CN 200810072297 A CN200810072297 A CN 200810072297A CN 101444709 A CN101444709 A CN 101444709A
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Abstract
A method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide relates to a method for obtaining solid particles and composite solid particles with release control effect from water solution. The invention provides a device and a method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide. A carbon dioxide conveying mechanism, a water solution conveying mechanism, a particle collecting and recycling mechanism and a control and display mechanism are arranged. Solution of a water-soluble material, an entrainer and water is arranged in a high pressure system and then enters a passage of a two-way nozzle; carbon dioxide is conveyed into the other passage of the coaxial two-way nozzle so as to achieve a supercritical fluid state; the solution of the water-soluble material, the entrainer and the water is atomized; solid particles are collected in a particle collecting chamber after the atomization; the entrainer and the water solution is taken away by the carbon dioxide; after cooling and separation, the entrainer and the carbon dioxide are recycled.
Description
Technical field
The present invention relates to a kind of method of from the aqueous solution, obtaining solid particle and having the complex solid particle of controlled-release effect, especially relating to a kind of is means with the supercritical carbon dioxide atomizing, with the entrainer is supplementary means, obtains the method and the device thereof of protein body, water-soluble inorganic or organic material particle and composite particles thereof from the aqueous solution.
Background technology
Obtain solid particle or prepare complex solid particle (comprising microcapsules) from water-soluble fluid drying is the key areas of industries such as chemical industry, pharmacy, food always.For biologically active, shock-sensitive, thermo-responsive, structural instability be easy to the material of chemical breakdown, need gentle drying condition, avoid using poisonous organic solvent etc.Therefore, the spray drying process of industrial extensive use has run into very big obstacle, and technology such as adoptable freeze drying are difficult to a large amount of employings because process consumes energy greatly, exists problems such as scale difficulty.For this reason, supercritical fluid technique can play a significant role.
The supercritical fluid drying technology has been applied to prepare the aeroge of inorganic material.The traditional concept of supercritical fluid drying is meant that generally the utilization organic solvent is replaced water or part is replaced, and then uses the supercritical fluid extraction organic solvent, thereby reaches dry purpose, so this is an indirect approach.On the other hand, through ten years development, supercritical fluid prepares the anti-solvent recrystallization process of gas (the The Supercritical Anti～solvent Process in the microparticle technology, SAS/GAS) derived many new processes: 1989 by [Gallagher P M such as Gallagher, Coffey M P, Krukonis V J, KlasutisN.Gas antisolvent recrystallization:New process to recrystallize compounds insoluble insupercritical fluids.Supercritical Fluid Science and Technology, American Chemical Society, Washington D.C., 1989,406:334～354] propose the gas anti-solvent technology (Gas Anti～Solvent, GAS); 1993 by [Bleich J such as Bleich, Muller BW, Wabmus W.Aerosol solventextraction system:a newmicroparticle production technique.International Journal of Pharmaceutics, 1993 (97): 111-117] the aeroge solvent extraction system of Ti Chuing (Aerosol Solvent Extraction System, ASES); 1994 by York and Hanna[Hanna M, York P.Method and apparatus for the formation of particles, WO95/01221, the SCF enhancing solution diffusion technique that 1994] proposes (Solution Enhanced Dispersion by Supercritical fluids, SEDS); Nineteen ninety-five is by [Bodmeier R such as Bodmeier, Wang H, Dixon DJ, Mawson S, Johnston KP.Polymericmicrospheres prepared by spraying into compressed carbon dioxide.Pharmaceutical Research, 1995,12:1211-1217] propose the anti-solvent precipitation of compressed fluid (Precipitation using compressed antisolvent, PCA).Wherein the SEDS process synthesis advantage of SAS and ASES, can realize from the aqueous solution, obtaining solid particle by the form of supercritical fluid～organic solvent～water three logistics contact.In addition, also have a class supercritical fluid to prepare microparticle technology [Li J, Gomes de Azevedo E.Particle formation techniques using supercritical fluids, Recent Patents onChemical Engineering, 2008,1 (2): 157～169], comprise CAN～BD ([Sievers of Carbon dioxide Nebulizationwith a Bubble～Dryer), R.E, Karst, U.:EP0677332 (1995)/US5639441 (1997)] and SAA (Supercritical～Assisted Atomization) [Reverchon, E.:EP1263412 (2002)/US20040178529 (2004)/DE 60118983T (2007)] technology, also can be used for handling moisture system and obtain solid particle.Obtain solid particle though above-mentioned these supercritical fluid techniques all can be used for handling Aquo System, and be in industrialization phase, these methods all require higher operating pressure (as SEDS) or operating temperature (as CAN～BD and SAA).Advantage for comprehensive SEDS and CAN～BD and SAA, seminar and external cooperation have proposed the anti-solvent of supercritical fluid assists～atomizing (Supercritical Anti～Solvent Atomization, the technology of SAS～A), from oxolane, obtained the particle [J.Li of different-shape, M.Rodrigues, A.Paiva, H.A.Matos, E.G.de Azevedo, Vapor～liquid equilibrium andvolume expansion of the tetrahydrogenfuran/CO
2System:Applications to a SAS～atomizationprocess, J.Supercrit.Fluids, 2007,41:343～351].
Summary of the invention
The object of the present invention is to provide a kind of device that from the aqueous solution, obtains solid particle with supercritical carbon dioxide.
Another object of the present invention is to provide a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide.
The technical solution adopted in the present invention is to be means with the supercritical fluid technique, obtains albumen, water-soluble inorganic or organic material particle and composite particles thereof from the aqueous solution.
The device that obtains solid particle from the aqueous solution with supercritical carbon dioxide of the present invention is provided with carbon dioxide conveying mechanism, aqueous solution conveying mechanism, particle collection and recovering mechanism and control indication mechanism.
The carbon dioxide conveying mechanism is provided with carbon dioxide storage tank, condensation of gas jar, counterbalance valve and high-pressure plunger pump or gas compressor (counterbalance valve and pump or compressor are installed on one), high-pressure buffering pot, extractor and valve, carbon dioxide storage tank links to each other with the gas drainer, and the outlet of condensation of gas jar links to each other with gas compressor or high-pressure plunger pump (containing counterbalance valve).Gas compressor or high-pressure plunger pump output terminal link to each other with high-pressure buffering pot.The outlet of high-pressure buffering pot connects extractor, and the effect of extractor is therefrom to extract adding entrainer or preparing another material that composite particles is used of adding.Extractor is provided with the reservation import, can be continuously pumped into the material (needing fusion or solution) that entrainer or composite particles are used when needing.Extractor outlet connects the passage that stop valve and check (non-return) valve are sent into coaxial bilateral nozzle.
Aqueous solution conveying mechanism is used for to nozzle transporting water solution (moisture and water-soluble substances also can be suspension or emulsion).Aqueous solution conveying mechanism is provided with NaOH solution tank NaOH, high-pressure pump, high-pressure buffering pot and valve.The NaOH solution tank NaOH outlet links to each other with the high-pressure pump inlet, and the high-pressure pump outlet links to each other with high-pressure buffering pot, and the high-pressure buffering pot outlet links to each other with check (non-return) valve, sends into another passage of coaxial bilateral nozzle then.
Particle is collected and the effect of recovering mechanism is with carbon dioxide the aqueous solution to be atomized, and collects solid particle and reclaims entrainer and carbon dioxide.Particle is collected and recovering mechanism is provided with coaxial bilateral nozzle, particle collecting cells, filter, condenser, flowmeter and compressor.The above-mentioned supercritical carbon dioxide and the aqueous solution meet at coaxial bilateral nozzle, enter collecting chamber after the aqueous solution is atomized, and particles settling is at the particle collecting cells top or bottom or side.Particle collecting cells top or bottom or sidepiece have gas vent, and gas vent is installed filter, and the filter back is installed condenser and carried out vapor-liquid separation, at last carbon dioxide and entrainer is reclaimed.
The demonstration and/or the control of the temperature that the control indication mechanism is used to operate, pressure, flow.The control indication mechanism is provided with air thermostat, material temperature controller, pressure indicator and temperature dial gauge.Particle collecting cells, surge tank, extractor, valve, pipeline etc. are located in the air thermostat or the pipeline insulation is handled.Pressure gauge one links to each other with surge tank and shows its pressure and with counterbalance valve control, Pressure gauge two links to each other with particle collecting cells.
The method of obtaining solid particle with supercritical carbon dioxide from the aqueous solution of the present invention may further comprise the steps:
1) solution with Water-solubility Material, entrainer and water adds high-pressure system, enters a passage of bilateral nozzle;
2) carbon dioxide is sent into another passage of coaxial bilateral nozzle, reach the supercritical fluid state, solution to Water-solubility Material, entrainer and water atomizes, solid particle is collected in particle collecting cells in the atomizing back, the entrainer and the aqueous solution are taken away by carbon dioxide, through refrigerated separation, entrainer and carbon dioxide recovery utilization.
In step 1), described Water-solubility Material is protein, water-soluble inorganic material, water-soluble organic material, can form the inorganic material of emulsion or suspension in water, can form a kind of in the organic material etc. of emulsion or suspension in water; Described entrainer be meant volatile and with water and the good organic solvent of supercritical carbon dioxide compatibility, be selected from least a in ethanol, methyl alcohol, oxolane, acetate, acetone, Ethyl formate, the ethyl acetate etc.; The adding mode of described entrainer can disposable and aqueous solution, also can measure separately to pump into or be extracted in the supercritical carbon dioxide fluid with another high-pressure pump; By mass percentage, Water-solubility Material is 0.1%～50%, and entrainer is 5%～85%, Yu Weishui, and the temperature of high-pressure system is preferably 35～60 ℃, and pressure is preferably 7.5～10MPa.
In step 2) in, operating temperature that described supercritical fluid state is a carbon dioxide and pressure are greater than the critical-temperature and the critical pressure of carbon dioxide; Described coaxial bilateral nozzle is to make with two pressure pipes that differ in size, and interior external diameter of pipe is littler than outer tube diameter.Interior pipe can link to each other with the supercritical carbon dioxide or the aqueous solution with outer tube in selection, and the outer tube bottom is provided with at least 1 laser opening, and the laser opening diameter is preferably 25～1000 μ m; The temperature of atomizing is preferably 32～100 ℃, and pressure is preferably 7.3～12MPa before the nozzle, and pressure is preferably 0.1～7MPa behind the nozzle, and the flow of the solution of Water-solubility Material, entrainer and water is 1ml/min～10L/min.
Maximum characteristics of the present invention be with supercritical carbon dioxide to the capable atomizing of the aqueous solution, and can quickly moisture content be removed in the acting in conjunction of supercritical carbon dioxide and entrainer, form solid particle; Its operating pressure and operating temperature are low to be the advantage (operating temperature is about 40 ℃, and the about 8MPa of pressure can achieve the goal) of giving prominence to.Second characteristic of the present invention are at the complex solid particle, the non-water-soluble material that solubility is big in the supercritical carbon dioxide is as core or wall material if desired, it directly can be joined extractor, take nozzle then to and form target complex solid grain products.
The prepared solid composite particles of the present invention 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 solid particle of preparation may be controlled to spherical, can be non-spherical, prepared product cut size can be controlled at nanoscale (＜200nm), certain section of submicron order (＜1 μ m) or micron order (1～50 μ m) distributes.
Description of drawings
Fig. 1 obtains structure and the process flow diagram thereof of the device embodiment of solid particle from the aqueous solution for supercritical carbon dioxide of the present invention.
The specific embodiment
Referring to Fig. 1, supercritical carbon dioxide of the present invention is provided with carbon dioxide steel cylinder a, counterbalance valve b, condenser c, surge tank d, air bath e, extractor f, bilateral nozzle system g, particle collecting cells h, solution tank i, solution buffer j, filter k, gas-liquid separator 1, flowmeter m, CO from the device that the aqueous solution obtains solid particle
2Pump or compressor P1, liquid pump P2, CO
2Reclaim compressor P3, valve V# and temperature control system TC.
Below provide supercritical carbon dioxide of the present invention obtains solid particle from the aqueous solution implementation method.
Preparation.Before the operation, check that supercritical carbon dioxide shows and the control situation from air-tightness, each road heat tracing situation and the instrument that the aqueous solution obtains the solid particle device, confirm no problem after, design and control well temperature T in the air thermostat.
Carbon dioxide is carried.In the time need in extractor f, adding the required material of entrainer or composite particles, need in advance it to be added extractor or pumps into extractor.Open the outlet valve of carbon dioxide storage tank a, carbon dioxide enters condensation of gas jar c and forms liquid, liquid CO 2 is sent into buffer d by high-pressure plunger pump or gas compressor P1 (not needing during gas compressor carbon dioxide is cooled to liquid in drainer), the pressure indicator indicated pressure is wherein arranged, and by counterbalance valve b steady pressure to operating pressure.Buffer and extractor can directly communicate, when opening stop valve V1, and carbon dioxide or have entrainer or the carbon dioxide of the material that composite particles is required is sent into a passage of bilateral nozzle.
Solution is carried.The aqueous solution (entrainer that can comprise certain proportioning) that the desire of packing in solution tank i is handled is opened liquid pump P2 solution is squeezed into solution surge tank j, and solution enters another passage of bilateral nozzle through check (non-return) valve V2.
Atomizing and particle are collected.Above-mentioned two fluid streams are intersected in bilateral nozzle system g, and CO 2 fluid atomizes in nozzle to aqueous topical fluids and enters particle collecting cells h.Droplet is through the effect of high-pressure carbon dioxide (nozzle exit is high pressure still) and entrainer, solid particle is sedimentation in particle collecting cells, moisture content and entrainer and carbon dioxide from the top or the gas vent of bottom or sidepiece discharge, gas vent is installed filter, gas-liquid separator 1 (the suitable condenser of separator is installed in the filter back, its top is an incoagulable gas, the bottom be a condensed fluid), the compressed machine P3 of carbon dioxide compression reclaim and by after the gas flowmeter m metering through the return condensed jar of check (non-return) valve V3 c.The entrainer aqueous solution of gas-liquid separator 1 bottom determines whether to need to concentrate by analysis, reuses then.
Embodiment 1: from SiO
2Obtain sub-micron SiO in the colloidal sol
2Particle.
Institute's with medicament has: positive tetraethyl orthosilicate TEOS (Chemical Reagent Co., Ltd., Sinopharm Group), absolute ethyl alcohol (Chemical Reagent Co., Ltd., Sinopharm Group), glacial acetic acid (Chemical Reagent Co., Ltd., Sinopharm Group), CO
2(Tongan City, Xiamen carbon dioxide fueling station provides, purity 〉=98%).
When preparing colloidal sol proportion of raw materials TEOS: water: ethanol: acid=1: 6.4: 8: 0.085 (mol ratio), colloidal sol digestion time 5h, liquid inventory are 2ml/min, and pre-expansion temperature T1 is 45 ℃, and nozzle diameter is 100 μ m, pressure P behind the nozzle
2Be 0.1MPa, and as pre-bulbs of pressure P
1Be the solid SiO that obtains under 8MPa and the 10MPa
2Average grain diameter is respectively 0.38 μ m and 0.58 μ m (particle aggregation is serious under the 17MPa).Can determine that by infrared analysis resulting solid particle is SiO
2
Embodiment 2: from SiO
2Obtain nanometer SiO in the colloidal sol
2Particle.
Institute's with medicament has: positive tetraethyl orthosilicate TEOS (Chemical Reagent Co., Ltd., Sinopharm Group), absolute ethyl alcohol (Chemical Reagent Co., Ltd., Sinopharm Group), ammoniacal liquor (Chemical Reagent Co., Ltd., Sinopharm Group), CO
2(Tongan City, Xiamen carbon dioxide fueling station provides, purity 〉=98%).
When preparing colloidal sol proportion of raw materials TEOS: water: ethanol: ammoniacal liquor=1: 5: 35.8: 1.25 (mol ratios), colloidal sol digestion time 5h, liquid inventory are 2ml/min, pre-expansion temperature T
1Be 45 ℃, nozzle diameter is 100 μ m, pressure P behind the nozzle
2Be 0.1MPa, and as pre-bulbs of pressure P
1Be the solid SiO that obtains under 8MPa and the 10MPa
2Particle diameter all＜100nm.
Embodiment 3: obtain the pure particle of ox blood from the aqueous solution.
Institute's with medicament has: and BSA (purchase Yu Xinglong and reach the bright bio tech ltd of medicine Co., Ltd and Fujian China, Sanland～Chem International Inc.and Huagene Biosciences, LTD.); Carbon dioxide (purity 〉=98%, the empty dtex gas in Xiamen Co., Ltd); Absolute ethyl alcohol (Chemical Reagent Co., Ltd., Sinopharm Group).
(1) at pre-expansion temperature T
1Be 50 ℃, the 100m nozzle, BSA concentration 20mg/g, concentration of alcohol 20% (mass percent of ethanol in water), liquid inventory is 1ml/min, P
2Be 0.1MPa, and as pre-bulbs of pressure P
1For the particle for preparing BSA under 8MPa and the 10MPa is sphere, solid BSA average grain diameter is respectively 0.82 μ m and 0.73 μ m.Other condition is the same, works as P
2Be 1MPa, P
1For the particle for preparing BSA under the 8MPa is sphere, solid BSA average grain diameter is respectively 0.90 μ m (some particle aggregation).
(2) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 50 ℃, nozzle diameter 100 μ m, BSA concentration 20mg/g, concentration of alcohol 20%, and when liquid inventory be 0.5 and 5ml/min under prepare BSA particle for spherical, solid BSA average grain diameter is respectively 0.71 μ m and 1.1 μ m.
(3) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 50 ℃, nozzle diameter 100 μ m, liquid inventory is 1ml/min, concentration of alcohol 20%, and the particle for preparing BSA under BSA concentration 10 and 50mg/g is for spherical, and solid BSA average grain diameter is respectively 0.50 μ m and 0.98 μ m.
(4) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 50 ℃, nozzle diameter 100 μ m, liquid inventory is 1ml/min, BSA concentration 20mg/g, and when concentration of alcohol 10% and the particle for preparing BSA for 25% time for spherical, solid BSA average grain diameter is respectively 0.81 μ m and 0.96 μ m.
Embodiment 4: polyethylene glycol and BSA composite particles
Institute's with medicament has: and polyethylene glycol (PEG 6000, chemical pure, Shanghai chemical reagent purchasing and supply station provides); BSA (purchase Yu Xinglong and reach the bright bio tech ltd of medicine Co., Ltd and Fujian China, Sanland～Chem International Inc.andHuagene Biosciences, LTD.); Carbon dioxide (purity 〉=98%, the empty dtex gas in Xiamen Co., Ltd); Absolute ethyl alcohol (Chemical Reagent Co., Ltd., Sinopharm Group).
Experiment condition: P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 50 ℃, nozzle diameter 100 μ m, liquid inventory is 1ml/min, concentration of alcohol 20%, the content of solute is 5g in the ethanol/water solution; Solute is BSA+PEG.And the particle for preparing BSA under BSA concentration 10 and 50mg/g is for spherical, and solid BSA average grain diameter is respectively 0.50 μ m and 0.98 μ m.(BSA: PEG=1: 4 and BSA: PEG=1: 2) Zhi Bei PEG/BSA composite particles major part was spherical, and average grain diameter is less than 1 μ m when BSA content was higher; (BSA: PEG=1: 9), the PEG/BSA composite particles of preparation is reunited, and average grain diameter is greater than 4 μ m when BSA content is lower.Above-mentioned composite particles all has tangible controlled-release effect.
Embodiment 5: obtain the insulin particle from the aqueous solution.
Institute's with medicament has: insulin is purchased the biochemical medical Co., Ltd (China Wanbang Biopharma Inc.) of ten thousand nations in Jiangsu; Absolute ethyl alcohol (purity〉99.7%) provide by Chemical Reagent Co., Ltd., Sinopharm Group; CO
2(purity〉98%), the empty subsidiary factory of the special gas in Xiamen provides.
(1) at pre-expansion temperature T
1Be 45 ℃, the 120m nozzle, insulin concentration 10mg/g, concentration of alcohol 40% (mass percent of ethanol in water) and small amount of acetic acid (regulating the pH value is 2.98), liquid inventory is 3ml/min, P
2Be 0.1MPa, and as pre-bulbs of pressure P
1For the particle for preparing insulin under 8MPa and the 10MPa is sphere, the particle average grain diameter of insulin is respectively 0.44 μ m and 0.50 μ m (under the 10MPa gathering being arranged).
(2) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 45 ℃, nozzle diameter 120 μ m, liquid inventory 3ml/min, concentration of alcohol 40%, and when insulin concentration be 2 and 8mg/g under prepare insulin particle for spherical, insulin particle average grain diameter is respectively 0.88 μ m and 0.49 μ m.
(3) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 45 ℃, nozzle diameter 120 μ m, insulin concentration is 10mg/g, concentration of alcohol 40%, and when liquid inventory be 1 and 5ml/min under prepare insulin particle for spherical, insulin particle average grain diameter is respectively 0.47 μ m and 0.79 μ m.
(4) work as P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, pre-expansion temperature T
1Be 50 ℃, nozzle diameter 120 μ m, liquid inventory is 3ml/min, insulin concentration 10mg/g, and when concentration of alcohol 20% and the particle for preparing insulin for 85% time for spherical, insulin particle average grain diameter is respectively 0.38 μ m and 0.57 μ m.
Embodiment 6: obtain insulin and tripalmitin composite particles from the aqueous solution.
Institute's with medicament has: insulin is purchased the biochemical medical Co., Ltd (China Wanbang Biopharma Inc.) of ten thousand nations in Jiangsu; Absolute ethyl alcohol (purity〉99.7%) provide by Chemical Reagent Co., Ltd., Sinopharm Group; CO
2(purity〉98%), the empty subsidiary factory of the special gas in Xiamen provides; Tripalmitin (purity〉95%) purchase in Chemical Reagent Co., Ltd., Sinopharm Group.
Operating condition is: jet size 100m, P
2Be 0.1MPa, pre-bulbs of pressure P
1Be 8MPa, the solution concentration stuck-at-0mg/ml of insulin, solution flow rate is fixed on 3ml/min, and the ethanol mass concentration is fixed as 40%, pre-expansion temperature T
1It is 50 ℃.When liquid inventory be changed to 2,3 and the particle that obtains during 4ml/min be the chrysanthemum shape, the median particle diameter of composite particles is respectively 3.9m, 3.9m and 3.8m.Prepared composite particles carries out the dissolution rate experiment of composite particles with RCA～1A dissolution test instrument (Shanghai Huanghai Sea medicine inspection instrument plant); the result shows that it is in phosphate-buffered salt (PBS; PH=7.2) under 37 ℃, do not dash forward fully in and release phenomenon; discharging the time of experiencing fully is 2700min, far above the pure product of insulin (discharging fully before and after 200min).
The present invention is based on SAS～A technology of from organic solvent, obtaining solid particle, at protein, water-soluble inorganic or organic material, with the supercritical carbon dioxide atomizing is means, with the entrainer is supplementary means, proposes a kind of method and equipment thereof for preparing solid particle and composite particles from the aqueous solution.Being compared to other supercritical fluid technique prepares the method for ultrafine solids particle (SAA), institute of the present invention extracting method has operating pressure low (getting final product about 8MPa) for SEDS, CAN～BD, the advantage of operating temperature gentleness (about 40 ℃ get final product) from the aqueous solution.Institute of the present invention extracting method adopts and the similar flow process of SEDS process, and difference is: SEDS only controls the expansion chamber pressure P
2, pre-bulbs of pressure P before the institute of the present invention extracting method control nozzle
1With expansion chamber pressure P behind the nozzle
2Work as P
2During for atmospheric pressure, institute of the present invention extracting method is similar with SAA or CAN～BD, but difference is: the back both all adopt hot nitrogen to evaporate moisture content, the mist of carbon dioxide, steam and nitrogen that flow process is last separates and reclaims very difficulty, and uses general T type nozzle or the single-pass nozzle of atomizing effect.Institute of the present invention extracting method is because the intervention of entrainer (as ethanol) need not to increase the hot gas source, and the last carbon dioxide of flow process is easy to realize separate under the normal pressure and recycle with solvent gas, and employing bilateral nozzle in the flow process, and mixing and atomizing effect are good.
Claims (10)
1. obtain the device of solid particle with supercritical carbon dioxide from the aqueous solution, it is characterized in that being provided with carbon dioxide conveying mechanism, aqueous solution conveying mechanism, particle collection and recovering mechanism and control indication mechanism;
The carbon dioxide conveying mechanism is provided with carbon dioxide storage tank, condensation of gas jar, counterbalance valve and high-pressure plunger pump or gas compressor, high-pressure buffering pot, extractor and valve, carbon dioxide storage tank links to each other with the condensation of gas jar, the outlet of condensation of gas jar links to each other with gas compressor or high-pressure plunger pump, gas compressor or high-pressure plunger pump output terminal link to each other with high-pressure buffering pot, the outlet of high-pressure buffering pot connects extractor, extractor is provided with the reservation import, and extractor outlet connects the passage that stop valve and check (non-return) valve are sent into coaxial bilateral nozzle;
Aqueous solution conveying mechanism is used for to nozzle transporting water solution, aqueous solution conveying mechanism is provided with NaOH solution tank NaOH, high-pressure pump, high-pressure buffering pot and valve, the NaOH solution tank NaOH outlet links to each other with the high-pressure pump inlet, the high-pressure pump outlet links to each other with high-pressure buffering pot, the high-pressure buffering pot outlet links to each other with check (non-return) valve, sends into another passage of coaxial bilateral nozzle then;
Particle collection and recovering mechanism are used for carbon dioxide the aqueous solution are atomized, collect solid particle and reclaim entrainer and carbon dioxide, particle is collected and recovering mechanism is provided with coaxial bilateral nozzle, particle collecting cells, filter, condenser, flowmeter and compressor, particle collecting cells top or bottom or sidepiece have gas vent, gas vent is installed filter, and the filter back is installed condenser and carried out vapor-liquid separation;
The demonstration and/or the control of the temperature that the control indication mechanism is used to operate, pressure, flow, the control indication mechanism is provided with air thermostat, material temperature controller, pressure indicator and temperature dial gauge, particle collecting cells, surge tank, extractor, valve, pipeline are located in the air thermostat, the 1st Pressure gauge links to each other with surge tank and shows its pressure and with counterbalance valve control, the 2nd Pressure gauge links to each other with particle collecting cells.
2. one kind is obtained the method for solid particle with supercritical carbon dioxide from the aqueous solution, it is characterized in that may further comprise the steps:
1) solution with Water-solubility Material, entrainer and water adds high-pressure system, enters a passage of bilateral nozzle;
2) carbon dioxide is sent into another passage of coaxial bilateral nozzle, reach the supercritical fluid state, solution to Water-solubility Material, entrainer and water atomizes, solid particle is collected in particle collecting cells in the atomizing back, the entrainer and the aqueous solution are taken away by carbon dioxide, through refrigerated separation, entrainer and carbon dioxide recovery utilization.
3. a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide as claimed in claim 2, it is characterized in that in step 1) described Water-solubility Material is protein, water-soluble inorganic material, water-soluble organic material, can form the inorganic material of emulsion or suspension in water, can form a kind of in the organic material of emulsion or suspension in water.
4. as claimed in claim 2ly a kind ofly from the aqueous solution, obtain the method for solid particle, it is characterized in that in step 1) with supercritical carbon dioxide, described entrainer be meant volatile and with water and the good organic solvent of supercritical carbon dioxide compatibility.
5. as claimed in claim 4ly a kind ofly from the aqueous solution, obtain the method for solid particle, it is characterized in that described organic solvent is selected from least a in ethanol, methyl alcohol, oxolane, acetate, acetone, Ethyl formate, the ethyl acetate with supercritical carbon dioxide.
6. a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide as claimed in claim 2, it is characterized in that in step 1), the adding mode of described entrainer is disposable and aqueous solution, or metering pumps into or is extracted in the supercritical carbon dioxide fluid with another high-pressure pump separately.
7. a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide as claimed in claim 2, it is characterized in that in step 1), by mass percentage, Water-solubility Material is 0.1%～50%, entrainer is 5%～85%, Yu Weishui, the temperature of high-pressure system is 35～60 ℃, pressure is 7.5～10MPa.
8. a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide as claimed in claim 2, it is characterized in that in step 2) in, operating temperature that described supercritical fluid state is a carbon dioxide and pressure are greater than the critical-temperature and the critical pressure of carbon dioxide.
9. as claimed in claim 2ly a kind ofly from the aqueous solution, obtain the method for solid particle, it is characterized in that in step 2 with supercritical carbon dioxide) in, described coaxial bilateral nozzle is to make with two pressure pipes that differ in size, interior external diameter of pipe is littler than outer tube diameter; Interior pipe links to each other with the supercritical carbon dioxide or the aqueous solution with outer tube, and the outer tube bottom is provided with at least 1 laser opening, and the laser opening diameter is 25～1000 μ m.
10. a kind of method of from the aqueous solution, obtaining solid particle with supercritical carbon dioxide as claimed in claim 2, it is characterized in that in step 2) in, the temperature of atomizing is 32～100 ℃, pressure is 7.3～12MPa before the nozzle, pressure is 0.1～7MPa behind the nozzle, and the flow of the solution of Water-solubility Material, entrainer and water is 1ml/min～10L/min.
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| CN2008100722977A CN101444709B (en) | 2008-12-05 | 2008-12-05 | Method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide |
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| CN2008100722977A CN101444709B (en) | 2008-12-05 | 2008-12-05 | Method for obtaining solid particles from water solution by utilizing supercritical carbon dioxide |
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| CN101444709A true CN101444709A (en) | 2009-06-03 |
| CN101444709B CN101444709B (en) | 2010-06-02 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327186A (en) * | 2011-09-30 | 2012-01-25 | 四川大学 | Method adopting supercritical CO2 fluid technology to produce water-soluble medicine controlled-release particles |
| CN103950998A (en) * | 2014-04-22 | 2014-07-30 | 山东玉皇新能源科技有限公司 | Method for synthesizing nano flaky nickel oxide by adopting supercritical ethanol |
| CN108295501A (en) * | 2018-04-04 | 2018-07-20 | 南通市华安超临界萃取有限公司 | A kind of overcritical nanometer drying preparation facilities |
| CN109157545A (en) * | 2018-10-09 | 2019-01-08 | 淮安安莱生物科技有限公司 | A method of extracting shellac acid and jalaric acid from shellac |
| 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 |
| TWI721599B (en) * | 2019-09-26 | 2021-03-11 | 大陸商上海複璐帝流體技術有限公司 | Supercritical carbon dioxide extraction device and method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9413202D0 (en) * | 1994-06-30 | 1994-08-24 | Univ Bradford | Method and apparatus for the formation of particles |
| SI1363726T1 (en) * | 2001-02-26 | 2005-02-28 | Dompe S.P.A. | Apparatus and method for micron and submicron particle formation |
| CN100478062C (en) * | 2006-07-20 | 2009-04-15 | 厦门大学 | Method for preparing microsphere with nitrogen aid and apparatus thereof |
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2008
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102327186A (en) * | 2011-09-30 | 2012-01-25 | 四川大学 | Method adopting supercritical CO2 fluid technology to produce water-soluble medicine controlled-release particles |
| CN103950998A (en) * | 2014-04-22 | 2014-07-30 | 山东玉皇新能源科技有限公司 | Method for synthesizing nano flaky nickel oxide by adopting supercritical ethanol |
| CN108295501A (en) * | 2018-04-04 | 2018-07-20 | 南通市华安超临界萃取有限公司 | A kind of overcritical nanometer drying preparation facilities |
| CN109157545A (en) * | 2018-10-09 | 2019-01-08 | 淮安安莱生物科技有限公司 | A method of extracting shellac acid and jalaric acid from shellac |
| CN109157545B (en) * | 2018-10-09 | 2021-10-01 | 海门茂发美术图案设计有限公司 | Method for extracting Lacca acid and Lacca alcohol acid from Lacca |
| 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 |
| TWI721599B (en) * | 2019-09-26 | 2021-03-11 | 大陸商上海複璐帝流體技術有限公司 | Supercritical carbon dioxide extraction device and method thereof |
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