US20200289956A1 - Preparation of nanoparticles by flash evaporation - Google Patents
Preparation of nanoparticles by flash evaporation Download PDFInfo
- Publication number
- US20200289956A1 US20200289956A1 US16/892,122 US202016892122A US2020289956A1 US 20200289956 A1 US20200289956 A1 US 20200289956A1 US 202016892122 A US202016892122 A US 202016892122A US 2020289956 A1 US2020289956 A1 US 2020289956A1
- Authority
- US
- United States
- Prior art keywords
- solution
- solvent
- nanoparticles
- compound
- spray drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 47
- 238000001704 evaporation Methods 0.000 title claims abstract description 16
- 230000008020 evaporation Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000590 phytopharmaceutical Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000001694 spray drying Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 40
- 239000004480 active ingredient Substances 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000000889 atomisation Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000015 trinitrotoluene Substances 0.000 description 5
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 4
- 239000012717 electrostatic precipitator Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 3
- 238000000586 desensitisation Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- -1 lipid compounds Chemical class 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000001046 rapid expansion of supercritical solution Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093495 ethanethiol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
- B01D9/0027—Evaporation of components of the mixture to be separated by means of conveying fluid, e.g. spray-crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/16—Evaporating by spraying
- B01D1/18—Evaporating by spraying to obtain dry solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0018—Evaporation of components of the mixture to be separated
- B01D9/0022—Evaporation of components of the mixture to be separated by reducing pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C9/00—Combinations with other devices, e.g. fans, expansion chambers, diffusors, water locks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D2009/0086—Processes or apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C9/00—Combinations with other devices, e.g. fans, expansion chambers, diffusors, water locks
- B04C2009/001—Combinations with other devices, e.g. fans, expansion chambers, diffusors, water locks with means for electrostatic separation
Abstract
Description
- The invention relates to the field of nanoparticle preparation. In particular the invention provides a method for preparing organic or inorganic nanoparticles by instantaneous evaporation or flash evaporation, for example to produce nanoparticles of fertilizers, pharmaceutical or phytopharmaceutical active ingredients or insensitive energetic materials.
- The method of the invention comprises the heating of a solution of an organic or inorganic compound at a temperature higher than the boiling point of the solvent at standard pressure, whilst avoiding evaporation of this solvent through the action of strong pressure on the solution. Atomization of the solution after it has passed through a nozzle causes expansion and evaporation of the solvent in an extremely short time, generally in the order of a fraction of a second. Evaporation of the solvent causes extreme supersaturation of the droplets and the compound crystallizes to form nanoparticles. The nanoparticles can then be separated e.g. in an electrostatic precipitation device or using an axial flow cyclone, these devices possibly being associated. Separation is generally conducted at reduced pressure.
- One of the advantages of the method of the invention is that it allows control over the size of the nanoparticles, in particular by acting on pressure, temperature, solvent, concentration or type of nozzle used.
- There are existing methods to prepare nanoparticles of compounds.
- Nonetheless these known methods do not always allow particle sizes to be reached which are truly of submicron size.
- Other known methods do not allow the preparation of large quantities of nanoparticles within reasonable time. The known methods often have reduced production capacities, in particular on account of the difficulties encountered when recovering the particles.
- Therefore, different methods are known to prepare nanoparticles in a supercritical fluid, applied for example to derivatives of carotenoids (DE-2943267) and to protein derivatives (WO-2006/101352) or for the depositing of nanometric film (U.S. Pat. Nos. 4,734,451, 4,970,093). These documents describe RESS technology (Rapid Expansion of Supercritical Solutions) which is only efficient on a reduced scale and cannot therefore be transferred onto industrial level.
- Another method describes the preparation of nano- and microparticles, applied to lipid compounds through the successive use of two supercritical fluids (WO-2007/028421).
- The first fluid is used to prepare a solution containing these lipid derivatives and the second fluid allows the dispersing of this solution. This method describes the obtaining of nano- and microparticles by modifying the solubility of the lipid composition in the two supercritical fluids.
- One of the disadvantages of the methods using supercritical fluids is that they are limited by the solubility of the composition in these supercritical fluids.
- In addition, these prior art methods do not allow the preparation of composite nanoparticles with a determined ratio of the composite elements. In fact, the ratio of the composite elements in the initial solution does not correspond to the ratio of the elements of the targeted composite. This difference between the initial ratio and the final ratio of the composite elements results from the respective solubility of the composite elements in the initial solution used and treated with the supercritical fluid.
- Also, these methods cannot be universally applied irrespective of the nature of the composition.
- The preparation of nanoparticles by misting is also known with the use of transducers (FR-2897281).
- Finally, a semi-continuous nanoparticle trapping method is known to purify water and integrates an evaporation step (U.S. Pat. No. 7628893).
- There is therefore a need for a method to prepare nanoparticles which provides solutions to the problems of known methods. The invention concerns a method for preparing nanoparticles which brings a solution to all or part of the problems of known methods.
- In particular, the method of the invention is easier to implement since it uses a solution and not a compressed gas and the pressures to be reached are lower than for methods in a supercritical medium.
- In addition, the method of the invention allows the preparation of nanoparticles of very small size in large quantities, these being dispersed and do not aggregate.
- In a particularly advantageous manner, the method of the invention can be carried out on industrial scale.
- The invention therefore provides a method for preparing nanoparticles of at least one compound, at least one dimension of the nanoparticles being smaller than 100 nm, comprising the successive steps of:
-
- preparing a solution comprising at least one organic or mineral compound and at least one solvent;
- heating the solution under pressure ranging from 3 to 300 bars, at a temperature higher than the boiling point of the solvent or at a temperature higher than the boiling point of the solvent mixture;
- atomizing the solution in an spray drying chamber using at least one dispersing device and at an angle ranging from 30 to 150° at a pressure ranging from 0.0001 to 2 bars;
- separating the solvent in gaseous form.
-
FIG. 1 . A device for preparing nanoparticles. -
FIG. 2 . BNCP (bis-5-nitrotetrazolato tetra-amine cobalt perchlorate) particles produced have a spherical shape. The mean size evaluated by image analysis under Scanning Electron Microscope (SEM) is 300±200 nm. - The size of the compound nanoparticles prepared according to the invention is submicron for at least one of the dimensions of these particles, preferably the size of the prepared nanoparticles ranges from 2 to 100 nm, more preferably from 5 to 90 nm or 10 to 80 nm.
- The method of the invention is suitable for preparing nanoparticles of numerous organic or inorganic compounds. In particular, the method of the invention is particularly efficient and advantageous for preparing nanoparticles of energetic compounds, pharmaceutical compounds, phytopharmaceutical compounds, dye compounds, pigments, inks, paints and metal oxides.
- Numerous solutions comprising at least one organic or mineral compound are suitable for the method of the invention.
- In a particularly advantageous manner, the organic or mineral compound is selected from among compounds soluble in solvents whose boiling point is lower than 80° C.
- The method of the invention can be applied for continuous or semi-continuous preparation of nanoparticles.
- Advantageously, the method of the invention comprises a final step to recover the nanoparticles of compounds. This recovery can be performed using one or more devices selected from among an electrostatic separator, a cyclone separator, a cyclone separator comprising an electrostatic device.
- To increase the rate of evaporation and hence the degree of saturation, the heating of the solution is performed before atomization.
- In the method of the invention, heating is conducted above the boiling point of the solvent and allows a strong increase in the solubility of the compound in the chosen solvent. Within the superheated solution, the vaporisation heat is stored in the form of thermal energy.
- With the method of the invention, it is possible to cause the level of vaporized solvent to vary according to the degree of superheating applied to the solution.
- Numerous solvents are suitable for the method of the invention. They can be used alone or in a mixture.
- The preferred solvents have the following properties:
-
- low boiling point;
- low enthalpy of vaporization;
- high specific heat.
- Among the solvents used for the method of the invention, preference is given to solvents whose boiling point is lower than 80° C., even lower than 60° C.
- As examples of solvents suitable for the method of the invention, alkanes can be cited e.g. pentane (bp=36° C.) or hexane (bp=68° C.); alcohols e.g. methanol (bp=65° C.) or ethanol (bp=78-79° C.); thiols e.g. ethane-thiol (bp=35° C.); aldehydes e.g. ethanal (bp=20° C.) or propionic aldehyde (bp=48° C.); ketones e.g. acetone (bp=56° C.); ethers e.g. methyl-tert-butyl ether (bp=55° C.) or tetrahydrofuran (bp=66° C.); acid esters, in particular the esters of formic acid e.g. methyl formiate (bp=32° C.), the esters of acetic acid e.g. methyl acetate (bp=57-58° C.); amines e.g. trimethylamine (bp=2-3° C.).
- To prevent the solvent from evaporating too rapidly when heating the solution, strong overpressure in relation to atmospheric pressure is applied to the solution. The heating of the solution is thus advantageously conducted at a pressure ranging from 5 to 150 bars, preferably at a pressure ranging from 10 to 60 bars.
- Advantageously, the pressure applied to the solution when heating is applied under the pressure of an inert gas, in particular an inert gas selected from among nitrogen, argon, helium, neon, xenon. Nitrogen is preferred
- The reducing of overpressure causes instantaneous evaporation of the solvent at a flash evaporation step in a fraction of a second. This flash evaporation leads to such supersaturation that the compound dissolved in the solvent crystallizes immediately.
- This crystallization is therefore initiated at the time the solution is atomized in the spray drying chamber. This atomization of the solution is advantageously performed at a pressure ranging from 0.001 to 2 bars.
- Preferably, atomization is conducted using a dispersion device selected from among a hollow cone nozzle, solid cone nozzle, flat jet nozzle, rectilinear jet nozzle, a pneumatic atomizer and the associations thereof. The preferred device is a hollow cone nozzle.
- The method of the invention is suitable for atomizing the solution in a spray drying chamber using a dispersion device. Atomization is performed using a number of dispersion devices totaling between 1 and 100, advantageously between 1 and 50, more advantageously between 3 and 5.
- In particularly advantageous manner, notably on an industrial scale, the method of the invention can be implemented by atomizing the solution in a spray drying chamber using a number of dispersion devices totaling 100 or more.
- Also preferably, atomization is implemented at an angle of 60 to 80°.
- After atomizing the solution, the separating of the nanoparticles from the gas phase is advantageously carried out in an electrostatic precipitator, in an axial cyclone separator or in a combination of an electrostatic precipitator and an axial cyclone separator.
- The electrostatic precipitator is operated at atmospheric pressure whilst the axial cyclone is operated at a pressure lower than atmospheric pressure.
- In particularly advantageous manner, the combination of two axial cyclone separators in parallel allows the semi-continuous production of nanoparticles.
- One example of an electrostatic precipitator suitable for the method of the invention is described in FR-2897281 (page 4) and comprises a cylindrical device having a central electrode and a peripheral metal electrode. The central electrode is a wire of small diameter and the peripheral electrode is a copper electrode. The difference in potential between the two electrodes is between 5 and 20 kV for a distance of about 4 to 5 cm.
- One example of an axial cyclone separator suitable for the method of the invention is described in U.S. Pat. No. 6,969,420, in particular in
embodiments - Said device allows the separation of nanoparticles as a function of their dynamic diameter further to the circular movement imparted to the particles inside the cyclone. The particles are finally collected in a vessel or filter-holder cassette.
- The solvent in gaseous state is removed for example by means of a vacuum pump. It can then be collected or recycled.
- In addition to a method for preparing nanoparticles, the invention concerns a device allowing the implementation of this method. The invention therefore provides a device for crystallizing the nanoparticles of at least one compound, comprising:
-
- a reactor comprising:
- a feed of a solution of the compound and at least one solvent;
- a pressurizing device up to 3 to 300 bars;
- a heating device;
- a spray drying chamber comprising:
- at least one device for dispersing the solution at an angle ranging from 30 to 150° and at a pressure ranging from 0.0001 to 2 bars;
- a solvent separating device;
- one or more devices to recover the compound nanoparticles selected from among an electrostatic separator, a cyclone, a cyclone comprising an electrostatic device.
- a reactor comprising:
- One embodiment of the device of the invention is illustrated in
FIG. 1 . - The device is composed of four main parts: a vessel (1) for storing the solution of solvent and precursor under high pressure, a spray drying chamber comprising an integrated heated nozzle (3), two axial cyclones (5) mounted in parallel and allowing semi-continuous production, a vacuum pump (6).
- In the vessel (1) containing the solvent with the solute an overpressure of compressed nitrogen is applied. Initially this overpressure allows displacement of the oxygen and prevents evaporation of the solvent. The volume flow rate in this system is induced by the overpressure of compressed nitrogen.
- A 15 μm filter (2) repels all the solid impurities in the initial solution.
- A nozzle (3) with hollow cone and electric heating is installed in the spray drying chamber. The parameters of pressure, temperature and particle size distribution are controlled. The type of connection allows rapid changing of nozzles. The electric heating temperature is chosen by the user.
- A solvent reservoir or vessel (4) is filled with the same solvent as the vessel (1) and is used to rinse the line and nozzle after use.
- The axial flow cyclones (5) are installed in parallel. When in service only one cyclone is operative; the second cyclone is in idle mode. By means of centrifugal force the solid particles are deposited inside the cyclone, the gaseous components leave the cyclone via a suction tube. To drain the cyclone first the circuit leading to the second cyclone is opened and the first circuit leading to the first cyclone is then closed.
- The vacuum pump (6) ensures permanent flow in the installation and allows the extraction of solvent vapours from the system.
- The preparation of nanoparticles according to the invention is described below in particular embodiments using the following examples.
- The device in
FIG. 1 was used. - 4.3 g of BNCP (bis-5-nitrotetrazolato tetra-amine cobalt perchlorate) were dissolved in 2300 mL of acetone. The solution was heated to 160° C. under a pressure of 20 to 25 bars. Using a nozzle with hollow cone the solution was dispersed in a spray drying chamber at an atomizing angle of 60°. The pressure in the spray drying chamber was 5 mbar. Particle separation was performed using an axial flow cyclone. The spray drying chamber and axial flow cyclone were heated externally to 100° C.
- 2.3 g of BNCP nanoparticles were obtained.
- The BNCP particles produced have a spherical shape. The mean size evaluated by image analysis under Scanning Electron Microscope (SEM) is 300±200 nm (
FIG. 2 ). - In addition, nanocrystallization results in BNCP desensitization. Compared with the initial product the nanocrystallization of BNCP allows 400% desensitization to friction and 65% desensitization to electrostatic discharge (ESD) (see Table 1). The sensitivity to friction was measured using the BAM method (Bundesanstalt für Materialprüfung) and friction testing apparatus of “Julius Peters” type. Sensitivity to electrostatic discharge was measured using a spark sensitivity tester; model ESD 2008, OZM Research s.r.o.
-
TABLE 1 Impact (J) Friction (N) ESD (mJ) BNCP yellow 1.56 20 120.74 BNCP yellow & <1.56 84 199.59 nanocrystallized - The device in
FIG. 1 was used. - 1.2 g of RDX (cyclotrimethylenetrinitramine) and 0.8 g of TNT (trinitrotoluene) were dissolved in 500 mL of acetone. The solution was heated to 150° C. under a pressure of 25 bars. Using a nozzle with hollow cone the solution was dispersed in a spray drying chamber at an atomization angle of 60°. The pressure in the spray drying chamber was 5 mbar. Particle separation was performed using two axial flow cyclones in parallel.
- After one hour, 0.75 g of composite RDX-TNT nanoparticles were obtained. The mean size evaluated by image analysis was between 200 nm and 500 nm.
Claims (25)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/892,122 US20200289956A1 (en) | 2012-02-07 | 2020-06-03 | Preparation of nanoparticles by flash evaporation |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1251143 | 2012-02-07 | ||
FR1251143 | 2012-02-07 | ||
PCT/EP2013/052478 WO2013117671A1 (en) | 2012-02-07 | 2013-02-07 | Preparation of nanoparticles by flash evaporation |
US201414377161A | 2014-08-06 | 2014-08-06 | |
US16/892,122 US20200289956A1 (en) | 2012-02-07 | 2020-06-03 | Preparation of nanoparticles by flash evaporation |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/377,161 Division US10722813B2 (en) | 2012-02-07 | 2013-02-07 | Preparation of nanoparticles by flash evaporation |
PCT/EP2013/052478 Division WO2013117671A1 (en) | 2012-02-07 | 2013-02-07 | Preparation of nanoparticles by flash evaporation |
Publications (1)
Publication Number | Publication Date |
---|---|
US20200289956A1 true US20200289956A1 (en) | 2020-09-17 |
Family
ID=47664309
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/377,161 Active 2033-10-28 US10722813B2 (en) | 2012-02-07 | 2013-02-07 | Preparation of nanoparticles by flash evaporation |
US16/892,122 Abandoned US20200289956A1 (en) | 2012-02-07 | 2020-06-03 | Preparation of nanoparticles by flash evaporation |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/377,161 Active 2033-10-28 US10722813B2 (en) | 2012-02-07 | 2013-02-07 | Preparation of nanoparticles by flash evaporation |
Country Status (4)
Country | Link |
---|---|
US (2) | US10722813B2 (en) |
EP (1) | EP2812104B1 (en) |
ES (1) | ES2751337T3 (en) |
WO (1) | WO2013117671A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2987279A1 (en) | 2012-02-29 | 2013-08-30 | Saint Louis Inst | PROCESS FOR THE PREPARATION OF NANOPARTICLES OF ULTIMATE SIZES BY DETONATION OF NANO-AND / OR SUBMICROSTRUCTURED EXPLOSIVE LOADS |
FR3023177B1 (en) * | 2014-07-04 | 2016-08-12 | Centre Nat De La Rech Scient (C N R S) | PROCESS FOR THE PREPARATION OF CO-CRYSTALS BY FLASH EVAPORATION |
WO2019179598A1 (en) | 2018-03-19 | 2019-09-26 | Centre National De La Recherche Scientifique | Core-shell particles |
FR3087351B1 (en) * | 2018-10-22 | 2021-07-16 | Centre Nat Rech Scient | HIGH AND LOW TEMPERATURE OUT OF BALANCE SYNTHESIS BY SPRAY FLASH SYNTHESIS |
FR3112341B1 (en) | 2020-07-09 | 2023-01-20 | Davey Bickford | DETONATING COMBINATION, RELAY FOR DETONATOR COMPRISING SUCH DETONATING COMBINATION AND DETONATOR COMPRISING SUCH RELAY |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008030028A (en) * | 2006-07-31 | 2008-02-14 | Ind Technol Res Inst | Multi-stage type cyclone apparatus and method for classifying and collecting particulate |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2943267A1 (en) | 1979-10-26 | 1981-05-07 | Basf Ag, 6700 Ludwigshafen | Finely dispersed carotenoid pigments prodn. - by dissolving carotenoid in a supercritical gas, pref. carbon di:oxide, and dispersing the soln. in an aq. colloidal matrix |
US4734451A (en) | 1983-09-01 | 1988-03-29 | Battelle Memorial Institute | Supercritical fluid molecular spray thin films and fine powders |
US4970093A (en) | 1990-04-12 | 1990-11-13 | University Of Colorado Foundation | Chemical deposition methods using supercritical fluid solutions |
DK0901786T3 (en) * | 1997-08-11 | 2007-10-08 | Pfizer Prod Inc | Solid pharmaceutical dispersions with increased bioavailability |
US8771740B2 (en) * | 1999-12-20 | 2014-07-08 | Nicholas J. Kerkhof | Process for producing nanoparticles by spray drying |
US6969420B2 (en) | 2003-12-04 | 2005-11-29 | Industrial Technology Research Institute | Method of collecting nanoparticles by using a cyclone and method of designing the cyclone |
EP1855652B1 (en) * | 2005-01-28 | 2015-12-02 | Bend Research, Inc | Drying of drug-containing particles |
EP1866407A4 (en) | 2005-03-22 | 2010-07-14 | Regeron Inc | Apparatus and method for submicroni zation of proteins using supercritical fluids |
US7628893B1 (en) * | 2005-08-01 | 2009-12-08 | Pure Energy Technology Co | Apparatus and method for separation |
WO2007028421A1 (en) | 2005-09-09 | 2007-03-15 | Universita' Degli Studi Di Padova | Process for the production of nano-particles |
FR2897281B1 (en) | 2006-02-14 | 2009-01-23 | Saint Louis Inst | PROCESS FOR THE MANUFACTURE BY NANOCRYSTALLIZATION OF ENERGETIC OR INERT COMPOUNDS |
US20090197085A1 (en) * | 2006-08-07 | 2009-08-06 | Coppa Nicholas V | Organic nanoparticles and method of preparation thereof |
EP1920765A1 (en) * | 2006-11-07 | 2008-05-14 | Medigene AG | Liposome preparation by single-pass process |
WO2009105792A1 (en) * | 2008-02-18 | 2009-08-27 | Csir | Nanoparticle carriers for drug administration and process for producing same |
CN103037946B (en) * | 2010-07-29 | 2015-07-22 | 田边工业株式会社 | Reduced-pressure spray-drying method and reduced-pressure spray-drying device |
PT2611529T (en) * | 2010-09-03 | 2019-05-09 | Bend Res Inc | Spray-drying method |
-
2013
- 2013-02-07 US US14/377,161 patent/US10722813B2/en active Active
- 2013-02-07 EP EP13702660.5A patent/EP2812104B1/en active Active
- 2013-02-07 WO PCT/EP2013/052478 patent/WO2013117671A1/en active Application Filing
- 2013-02-07 ES ES13702660T patent/ES2751337T3/en active Active
-
2020
- 2020-06-03 US US16/892,122 patent/US20200289956A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008030028A (en) * | 2006-07-31 | 2008-02-14 | Ind Technol Res Inst | Multi-stage type cyclone apparatus and method for classifying and collecting particulate |
Non-Patent Citations (1)
Title |
---|
JP2008030028A English Translation obtained from Espacenet (Year: 2023) * |
Also Published As
Publication number | Publication date |
---|---|
US20150000846A1 (en) | 2015-01-01 |
ES2751337T3 (en) | 2020-03-31 |
EP2812104B1 (en) | 2019-08-14 |
WO2013117671A1 (en) | 2013-08-15 |
EP2812104A1 (en) | 2014-12-17 |
US10722813B2 (en) | 2020-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20200289956A1 (en) | Preparation of nanoparticles by flash evaporation | |
Risse et al. | Continuous formation of submicron energetic particles by the flash-evaporation technique | |
JP3839042B2 (en) | Salmeterol xinafoate with sized particles | |
JP2020108890A (en) | Method for producing cocrystals by means of flash evaporation | |
Kröber et al. | Materials processing with supercritical antisolvent precipitation: process parameters and morphology of tartaric acid | |
JP2001502350A (en) | Novel polymorphic crystalline form of fluticasone propionate, process for its preparation, and pharmaceutical composition thereof | |
US20040119179A1 (en) | Method for making very fine particles consisting of a principle inserted in a host molecule | |
JPH08511987A (en) | Method and apparatus for forming particles | |
DE60118983T3 (en) | Process for the preparation of nano and micro particles | |
Peng et al. | Enhanced the oral bioavailability of salvianolic acid B by phospholipid complex loaded nanoparticles | |
Xu et al. | Preparation of high-performance ultrafine budesonide particles for pulmonary drug delivery | |
CN106892952A (en) | A kind of Loteprednol etabonate novel crystal forms and preparation method thereof | |
Kwon et al. | Preparation of micro particles of functional pigments by gas-saturated solution process using supercritical carbon dioxide and polyethylene glycol | |
US20020189454A1 (en) | Method for capturing fine particles by percolation in a bed of granules | |
Wenli et al. | Production of submicroparticles of β-sitosterol using an aerosol solvent extraction system | |
CN108159001B (en) | A kind of method that the overcritical compression fluid precipitation method prepare tripterine nanometer particle | |
CN106892953A (en) | Loteprednol etabonate monohydrate and its crystal formation and preparation method | |
Tian et al. | Investigation of Physical Effects on Nanoparticle Size in Aerosol Solvent Extraction System | |
JPH05317690A (en) | Method for generating solid particle aerosol | |
CN115400103B (en) | Porous respiratory particle and preparation method thereof | |
CN106883283B (en) | Ciclesonide monohydrate, crystal form and preparation method thereof | |
RU2481362C2 (en) | Method of producing porous microparticles of especially pure polystyrene as carriers of biologically active forms of prolonged action | |
CN106860426A (en) | A kind of core shell nanoparticles and preparation method with medicine two-stage control-release function | |
CN106692164A (en) | Ciclesonide azelastine compound composition | |
CN101264059A (en) | Super-critical rapid expansion preparation for water-soluble nano artemisinin powder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ISL - INSTITUT FRANCO-ALLEMAND DE RECHERCHES DE SAINT-LOUIS, FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RISSE, BENEDIKT;HASSLER, DOMINIQUE;SPITZER, DENIS;SIGNING DATES FROM 20150720 TO 20150721;REEL/FRAME:052842/0672 Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.R.S), FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:RISSE, BENEDIKT;HASSLER, DOMINIQUE;SPITZER, DENIS;SIGNING DATES FROM 20150720 TO 20150721;REEL/FRAME:052842/0672 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: FINAL REJECTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |