EP3870351A1 - Synthesis outside high and low temperature equilibrium by spray flash synthesis - Google Patents
Synthesis outside high and low temperature equilibrium by spray flash synthesisInfo
- Publication number
- EP3870351A1 EP3870351A1 EP19787305.2A EP19787305A EP3870351A1 EP 3870351 A1 EP3870351 A1 EP 3870351A1 EP 19787305 A EP19787305 A EP 19787305A EP 3870351 A1 EP3870351 A1 EP 3870351A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- compounds
- liquid
- pressure
- heating
- 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.)
- Pending
Links
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- 238000001704 evaporation Methods 0.000 claims abstract description 13
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- 239000012530 fluid Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
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- 229910052754 neon Inorganic materials 0.000 claims description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000002344 surface layer Substances 0.000 description 12
- 238000002663 nebulization Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229910002115 bismuth titanate Inorganic materials 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000006396 nitration reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
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- 239000004408 titanium dioxide Substances 0.000 description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-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
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- 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
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 238000007146 photocatalysis Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical class OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- MQRWPMGRGIILKQ-UHFFFAOYSA-N sodium telluride Chemical compound [Na][Te][Na] MQRWPMGRGIILKQ-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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Classifications
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
-
- 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
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/14—Production of inert gas mixtures; Use of inert gases in general
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
-
- 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
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
Definitions
- the invention relates to a device and a method for the chemical synthesis of organic, inorganic, metallic products and any one of their mixtures, by an instant evaporation or flash evaporation technique or also called Synthesis Spray Flash (or "SFS" for the English expression “Spray Flash Synthesis”).
- the invention relates to compounds or particles thus obtained by SFS.
- sol-gel type techniques are used.
- the sol-gel techniques have limited performance in terms of the quantity of products produced and the quality of the products obtained, in particular as regards their morphology and purity.
- the aim of the invention is to solve the technical problem of providing a device and a process for the continuous or discontinuous preparation of compounds, in particular in the form of particles, and in particular particles of micrometric, submicrometric or nanometric size.
- the object of the invention is in particular to solve the technical problem of facilitating or making possible the preparation of crystallized particles.
- the present invention aims to solve the technical problem of providing compounds, in particular in the form of particles, having properties for applications in the various fields of application of chemical compounds.
- the invention also aims to solve the technical problem of making possible the preparation of compounds, in particular in the form of particles, which are not accessible by conventional techniques, in particular of the sol-gel type.
- Another object of the invention is to solve the technical problem of manufacturing compounds, in particular in the form of particles, by improving the yields of the reactions.
- the invention makes it possible to solve at least one, and preferably all of the technical problems raised according to the invention.
- the invention relates to a technological invention, called “SFS” for Synthesis by Spray Flash (in English “Spray Flash Synthesis”).
- the invention relates to a chemical synthesis process, said process comprising flash evaporation misting, also known by the acronym SFE for the English acronym “Spray Flash Evaporation”, comprising the chemical reaction of at least one first compound with at least a second compound, under conditions in which the first compound and the second compound react to form at least a third compound.
- the invention also relates to a chemical synthesis device, said device comprising: ⁇ at least one first tank comprising:
- At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars;
- ⁇ at least a second tank comprising:
- At least one pressurizing device P1 ’, P1’ being preferably chosen in a pressure range from 3 to 300 bars and equal to or different from P1;
- an atomization chamber comprising:
- At least one device for dispersing the liquid compositions of each reservoir preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1 and P1 ′, P2 preferably being chosen from a pressure range ranging from 0.0001 to 2 bars, the dispersing devices being positioned so that the first compound and the second compound react together in the droplets formed in the atomization chamber, said dispersing device being preferably heated by a heating device at a temperature chosen in a range of 200 to 2000 ° C;
- ⁇ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
- the invention also relates to a chemical synthesis device, said device
- ⁇ at least one tank comprising:
- At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars;
- an atomization chamber comprising:
- At least one device for dispersing the fluid in each reservoir preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1, P2 preferably being chosen from a pressure range ranging from 0.0001 to 2 bars, said device being preferably heated by a heating device to a temperature chosen in a range from 200 to 2000 ° C;
- ⁇ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
- the SFS technique according to the invention is a new technique derived from SFE, but which incorporates a conceptual break in the approach of synthesis and a technical break. These ruptures constitute a real revolution in chemical synthesis in general (organic and inorganic synthesis).
- the conceptual break consists in carrying out a synthesis of one or more chemical compounds by passing from the pressurized medium upstream of a nebulization nozzle (spray), to a primary vacuum downstream of the latter.
- the synthesis is thus integrated into a vacuum atomization process, represented by the SFE.
- the synthesis according to the invention can be carried out both through a single nebulization nozzle or by intermingling jets of several nebulization nozzles. It is thus possible to carry out an almost infinite number of different types of syntheses and of products to be synthesized.
- the invention is described with reference to the first, second and third compounds in a generic manner.
- the invention covers any embodiment of chemical synthesis including the reaction between two or more reactive compounds (here called purely arbitrarily always first and second compounds) to form at least one or more third compounds (here called purely for purely always third arbitrary).
- the terms first compound and second compound are therefore arbitrary to designate at least two reactive compounds with one another.
- the terms third compound are therefore arbitrary to denote at least one reaction product of at least two reagents.
- the invention covers for example the reaction between at least two reactive compounds, to form one or more third compounds, products of the reaction.
- the first compound and the second compound are in liquid form until their reaction and that the third compound is in solid form.
- the conditions, in particular of temperature and pressure of the process and device according to the invention are therefore advantageously chosen accordingly.
- the reaction is carried out between two compounds of different state (liquid, solid, gas), as for example between a solid and a liquid, as for example for the synthesis of nitrocellulose, the cellulose is solid and the nitrating agent (HN0 3 ) is liquid.
- the invention advantageously allows a very localized synthesis, in very limited spaces (concept of micro or even nano-reactors, or even metastable reactors ”) constituted by the drops much finer still than those of the SFE of previous patents, in particular due to the higher heating, and which form nanoreactors or microreactors or intersections of different nanoreactors or micro-reactors (case of multiple nozzles) in which the synthetic chemical reaction takes place.
- This makes it possible to advantageously make a targeted, very localized synthesis, avoiding any runaway due to the mass effects (accumulation of heat) resulting from the use of too large quantities of reagents.
- this chemical reaction implemented according to the invention makes it possible to shift the thermodynamic equilibrium of the reaction carried out under "standard” reaction conditions without an SFE device or process. This is called out-of-balance synthesis. This displacement explains at least in part the improvement in the yields observed according to the present invention.
- the compounds in particular in the form of particles, obtained are crystalline, preferably the crystalline phase being controlled during the passage through the dispersing device.
- the invention allows continuous synthesis (up to several kilograms per hour), much more controlled than most of the techniques that exist.
- the invention makes it possible to synthesize molecules and the crystallization of the synthesized molecules.
- this synthesis is carried out very locally in a device according to the invention, to facilitate chemical reactions by promoting contact between the reagents (first and second compounds), in particular to increase the yields and / or to increase the safety of synthesis. .
- the invention constitutes a much more efficient technique than many, even all of the existing chemical synthesis techniques.
- Different (third) compounds can thus be synthesized such as oxides, ceramics or organic products, for example energetic materials, drugs, esters or organic compounds in general, conductive or non-conductive polymers, catalysts or transition metal complexes.
- the synthesis can take place using a nebulization device (or “spray”) of a single nozzle or the products can be synthesized in the intersection of the jets of several nozzles, each bringing the different (first (s ) and second (s)) compounds to be brought into contact to synthesize the different products (third compound).
- the nozzles spray jets which come into contact with each other.
- the jets are positioned opposite each other.
- the invention also relates to a device and method comprising a heating device or a step of heating the nebulization nozzle (s) allowing a rise in high temperature, generally greater than 200 ° C.
- the device and method comprises a means or device for regulating the flow or flows of the first compound and of the second compound.
- the flow rate was regulated by the pressure through the nozzle.
- the flow rates of one nozzle can be regulated independently of the flow rates of other nozzles.
- the dispersing device When it is indicated that the dispersing device is heated, it is in particular the spray nozzle or nozzles which are heated.
- the nebulization nozzle or nozzles are heated over a very wide temperature range which typically ranges from 20 ° C. to 2000 ° C.
- the temperature of the nozzle (s) is between 20 ° C and 2000 ° C.
- the temperature of the nozzle (s) is between 40 ° C and 2000 ° C.
- the temperature of the nozzle (s) is between 40 ° C and 200 ° C.
- the device and method according to the invention comprise a means or device for thermal treatment (heating) of the aerosol formed.
- the heat treatment means or device is arranged so as to heat the nozzle itself or downstream of the nozzle and for example in the upper part of the atomization chamber, that is to say near nebulized jets in the atomization chamber. This advantageously makes it possible to calcine or crystallize more completely certain desired products, formed by the reaction of the reactants.
- the device comprises a device or means for heat treatment is chosen from heating by microwaves, by pulsed light (flashes), laser, infrared light (radiation) or another suitable heating means.
- the heat treatment means or device can be a source of radiation, for example by microwave, preferably positioned so that the radiation reaches at least the outlet of the nozzle or nozzles and thus allow sufficient heating.
- the nebulization nozzle or nozzles are heated in a very wide temperature range which typically goes from 200 ° C to 2000 ° C, and for example from 250 ° C to 2000 ° C or even for example from 300 ° C at 1500 ° C.
- the dispersion device is heated by electrical resistance and / or induction and / or by vibrations (ultrasound or other).
- nozzles made of ceramic material are used.
- the heating of the dispersing device makes it possible to reduce even more than for the SFE, the size of the liquid droplets formed due to faster and more controlled evaporation of the solvents or of the dispersion products.
- the SFS technique according to the invention also reduces subsequent costs due to the efficiency of the products which it makes it possible to synthesize.
- the drugs obtained, because of their greater effectiveness, will be used in dosages (and therefore tonnages) involving lower quantities, which will lower their ecological footprint, and thereby promote sustainable development.
- This technical device or heating stage has a technical advantage by achieving two very important functions, which are to allow evaporation of the solvents or dispersion fluids much faster even than in the case of SFE, and also to ensure by the same occasion a heat treatment, such as for example the calcination of the products obtained, which often allows their optimal crystallization.
- This heat treatment for example in the sol-gel type techniques according to the prior art, is often carried out too long after the synthesis of the materials, which makes it difficult to obtain optimal products, from which it is often difficult to separate the impurities. .
- the present invention therefore advantageously makes it possible to carry out continuous "one pot" syntheses of crystallized or non-crystallized materials.
- the synthesis process according to the invention can advantageously be implemented on a large scale and can, for example, reach or even exceed production capacities of several kilograms per hour.
- the invention relates to a preparation process comprising atomization, and in particular by instant evaporation or flash evaporation, which makes it possible to provide a solution to all or part of the problems of the processes of the state of the art.
- the invention relates to compounds, in particular in the form of particles, and to their methods of preparation, in particular to a method of preparing compounds in particular in the form of particles, said method comprising the simultaneous atomization of at least one first compound and of at least a second compound, under reaction conditions at least the first compound and the second compound to form at least a third compound.
- the device according to the invention operates under reaction conditions of at least the first compound and the second compound to form at least a third compound.
- first compound denotes a compound different from the “second compound”.
- the compounds designated by “first compounds” can be multiple. Reference is made to this or these “first compounds” essentially to distinguish them from the “second compounds”.
- the SFS technique according to the invention therefore relates to chemical synthesis, that is to say the formation of new molecules, crystallized or not in the form of particles, and in particular of nanoparticles (preferably of which at least one dimension or the largest dimension is less than 100 nm (nanometer)), of particles of which at least one dimension or the largest dimension is submicrometric (preferably less than 1 ⁇ m) or micrometric (preferably less than 1 mm).
- the first compound (s) and the second compound (s) are dissolved and / or dispersed in one or more solvents, and are sent through one or more nozzles at room temperature or heated in a chamber maintained under primary vacuum (typically from 100 to 0.1 Pa).
- the third compound (s) are synthesized in the crystallized or non-crystallized state in the form of nanometric, submicrometric or micrometric particles.
- the particles of the invention are particles advantageously comprising all of their dimensions less than 1000 nm.
- the particles are nanoparticles, that is to say advantageously comprising at least one and preferably all of their dimensions, less than 100 nm.
- the invention relates in particular to solid particles, and more particularly to particles of which the smallest dimension and preferably all of the dimensions ranges from 30 to 100 nm.
- the particles synthesized comprise or consist of one or more metallic elements. According to a variant, the particles synthesized comprise or consist of one or more organic compounds.
- the compounds which can be synthesized according to the process of the invention are chosen from metal oxides, for example Ti0 2 , titanates, for example bismuth titanate, and MOFs, for example MOF called "HKUST-1" .
- the compounds that can be synthesized according to the method of the invention are Ti0 2 nanoparticles having, for example, an average diameter between 100 and 250 nm.
- the Ti0 2 nanoparticles obtained according to the process of the invention have, for example, an anatase type structure, an average diameter between 100 and 250 nm, and for example a BET specific area between 5 and 20 m 2 / g.
- the compounds which can be synthesized according to the method of the invention are nanoparticles of bismuth titanate.
- the bismuth titanate nanoparticles mainly comprise a Bi 2 Ti 2 0 7 crystalline phase.
- Energy storage in particular hydrogen storage.
- the process according to the invention relates to the preparation of particles, and in particular nanoparticles, of compounds chosen from energetic compounds, pharmaceutical compounds, phytopharmaceutical compounds, medical contrast compounds, fluorescent compounds, optical compounds, compounds dyes, aromas, fragrances (perfume), pigments, inks, paints, metals, metal oxides, semiconductor compounds, optical compounds, optoelectronic compounds, ferroelectric compounds, non-response compounds linear or bio-electronic compounds.
- the process according to the invention is particularly advantageous for the preparation of particles, and in particular nanoparticles, of crystallized compounds chosen from metal compounds, their oxides, and any one of their mixtures.
- the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is micrometric or which have at least one dimension less than 500 ⁇ m, preferably which have at least one dimension less than 100 pm.
- the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is submicrometric or which have at least one dimension of between 100 and 1000 nm.
- size of particles is meant the diameter or the smallest dimension for particles that are not substantially spherical, and advantageously all of the dimensions of the particles. Particle size can be measured by scanning electron microscopy and by transmission.
- the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is nanometric or which have at least one dimension less than 100 nm.
- the particles, and in particular the nanoparticles, prepared according to the invention have a size ranging from 2 to 100 nm; or ranging from 5 to 90 nm; or ranging from 10 to 80 nm; or ranging from 50 to 300 nm; or ranging from 50 to 200 nm; or ranging from 50 to 120 nm; or ranging from 10 to 100 nm; or ranging from 60 to 100 nm.
- the third compound is obtained in the form of particles, for example at least one dimension of which is less than 100 nm, preferably the largest dimension ranging from 5 to 100 nm, more preferably ranging from 10 to 30 nm.
- the particles of the invention can comprise, for example, semiconductor compounds, and / or co-crystals or composites, advantageously doped.
- the compounds of the invention may also comprise fluorescent materials, in particular for medical, therapeutic or diagnostic applications, such as for example in radiology, without any limitation.
- the compounds of the invention may also comprise compounds which are active from a pharmaceutical point of view, in particular for the preparation of medicaments or pharmaceutical or therapeutic applications.
- Such compounds in particular in the form of particles, make it possible in particular to improve biocompatibility, bioavailability and bodily assimilation.
- the invention makes it possible to increase the tracing power for diagnosis, in particular in radiology and medical imaging in general.
- the compounds of the invention in particular in the form of particles, can also comprise catalysis materials, such as, for example, materials for heterogeneous catalysis, in particular for applications in petrochemistry by way of example, without being limiting.
- catalysis materials such as, for example, materials for heterogeneous catalysis, in particular for applications in petrochemistry by way of example, without being limiting.
- the invention is also particularly suitable in the field of the production of forbidden band semiconductors adapted and adjusted to increase the efficiency of photocatalytic or photoconversion systems.
- the invention allows the development of materials having improved biocompatibility, and for example the coating of toxic substances or whose toxicity is to be reduced by at least one bark or biocompatible surface layer.
- the present invention is particularly advantageous in chemotherapy in order to limit the toxicity of the compounds used.
- the present invention also allows the preparation of multilayer particles.
- multilayer particles means a particle comprising a core (also called a “core”) and at least one layer on the surface of the core.
- the surface of the heart is preferably completely covered with a layer.
- the particles of the invention relate to particles comprising a core and a surface layer covering, preferably completely, the surface of the core.
- the present invention also relates to particles, in particular nanoparticles, comprising a core and several surface layers arranged concentrically.
- One or both of the core and one or more surface layers can be obtained by reacting at least a first compound and a second compound.
- the third compound synthesized can be coated with one or more surface layers.
- one or more compounds can be coated with one or more surface layers comprising one or more third synthesized compounds.
- each layer can be constituted independently of the other layers of one or more compounds, the compound (s) of a layer possibly being different from that or those of another layer.
- the invention also relates to particles of the organic / inorganic or organic / metallic hybrid type.
- the invention also relates specifically to particles capable of being obtained by a process as described according to the invention, said particles comprising at least a third compound synthesized.
- the method comprises the formation of particles comprising said third compound, said particles being in liquid, solid or gaseous form.
- the invention relates more specifically to a process comprising:
- the method comprises:
- the first compound and / or the second compound are independently liquid or solid or gaseous.
- the first and the second liquid phase comprise or consist respectively of the first compound in liquid form, optionally after dissolution in a solvent, or in solid form dispersed in a solvent, and / or of the second compound in form liquid, optionally after dissolving in a solvent, or in solid form dispersed in a solvent, the solvents of the first and second liquid phases possibly being identical or different.
- the method includes dispersing or dissolving the first solid compound in a first liquid.
- the method includes dispersing or dissolving the second solid compound in a second liquid.
- the first and second liquids are different or identical.
- the first compound in liquid form constitutes the first fluid composition.
- the second compound in liquid form constitutes the second fluid composition.
- reaction is carried out under pressure and temperature conditions for obtaining the third compound in solid form.
- the device or method of the invention uses a multiphase fluid comprising particles dispersed in a liquid phase so as to forming the third or more synthesized compounds, preferably in the form of micrometric, submicrometric or nanometric particles.
- the method of the invention uses a monophasic fluid comprising particles dispersed in a liquid phase so as to form the third compound (s) synthesized, preferably in the form of micrometric, submicrometric or nanometric particles.
- the first composition comprising the first solid compound forms a monophasic fluid.
- the first composition contains a solution of titanium isopropanolate (TTIP) in isopropanol, and advantageously makes it possible to obtain titanium dioxide or titanates, for example bismuth titanate.
- TTIP titanium isopropanolate
- the first composition comprising the first solid compound forms a multiphase fluid.
- the second composition comprising the second solid compound forms a monophasic fluid.
- the second composition comprising the second solid compound forms a multiphase fluid.
- liquid in particular means a liquid optionally comprising one or more solid dispersions and / or one or more gases.
- fluid in particular a liquid optionally comprising a solid dispersion.
- this term “fluid” does not cover a gas in which solid particles are dispersed.
- multiphase fluid denotes a fluid comprising one or more immiscible phases such as for example a liquid phase and a solid phase or two immiscible liquid phases.
- the multiphase fluid consists of a liquid phase and at least one solid phase preferably dispersed in the form of particles and typically in the form of nanoparticles.
- the multiphase fluid consists of a liquid phase and of several solids preferably dispersed in the form of particles and typically in the form of nanoparticles.
- the multiphase fluid consists of two liquid phases.
- the multiphase fluid consists of several liquid phases and of several solid phases, preferably dispersed in one or more liquid phases in the form of particles, and typically in the form of nanoparticles, said solid phases possibly being dispersed in different liquid phases.
- liquid phase is meant a liquid phase comprising one or more liquid compounds.
- a compound is defined as “liquid compound” especially when it is liquid at temperature and pressure under the conditions after obtaining the multiphase fluid. According to a variant, the compound is liquid at ambient temperature and pressure, that is to say at 25 ° C. and 101325 Pa.
- the process of the invention comprises heating the first and second compositions
- the heating of the first and second compositions can be simultaneous or independent.
- the method of the invention comprises the following steps:
- the dissolution of at least one organic or inorganic compound in a liquid the liquids comprising the dispersed compound or the dissolved compound possibly being identical or different,
- the process according to the invention is advantageously carried out continuously or semi-continuously. Preferably, it is implemented continuously.
- the method according to the invention comprises the preparation of at least two phases, a first liquid phase comprising at least one liquid compound, called the first liquid compound, and at least one solid, organic, mineral or organometallic compound, called first solid compound, and a second liquid phase comprising at least one liquid compound, called second liquid compound, and at least one compound, organic, inorganic or organometallic, called second solid compound, dissolved in the liquid phase.
- first liquid phase comprising at least one liquid compound, called the first liquid compound, and at least one solid, organic, mineral or organometallic compound, called first solid compound
- second liquid phase comprising at least one liquid compound, called second liquid compound, and at least one compound, organic, inorganic or organometallic, called second solid compound, dissolved in the liquid phase.
- these liquid phases can each independently comprise several of these compounds.
- the method comprises the preparation of particles comprising one or more layers surrounding a heart.
- the particles dispersed in step a) can themselves be particles to be coated with one or more layers.
- one or more additional surface layers are deposited on the particles.
- the method comprises the preparation of particles comprising several layers surrounding the core of the particles by using compounds having different solubilities in the liquids in which they are dissolved. For example, when the solubilities are sufficiently different, the least soluble compound is deposited first on the surface of the particles and then the most soluble compound is deposited on the surface of the layer of the compound (the least soluble) already deposited on the surface of the particles. .
- the method comprises dispersing a compound intended to form the core of the particles in a first liquid comprising a compound intended to form a first surface layer and dissolving in a second liquid a compound intended to form a second surface layer.
- the solubility in the second liquid of the compound intended to form the second surface layer is higher than the solubility in the first liquid the compound intended to form the first surface layer.
- the method comprises the preparation of crystalline particles comprising several crystals, called co-crystals.
- liquid (s) can in particular be adapted according to the compound to be dispersed or the compound to be dissolved.
- the heating of the composition or of the fluid compositions is, independently, carried out under a pressure ranging from 5 to 150 bars, preferably ranging from 10 to 60 bars.
- composition comprising the solid dispersed compound also comprises at least one dispersing agent.
- the method according to the invention comprises a final step of recovery of the synthesized compounds, in particular in the form of particles.
- the recovery of the particles is carried out by means of one or more particle retention devices chosen from an electrostatic separator, a cyclone, a cyclone comprising an electrostatic device and the filters (metal mesh, foams, sintered, etc.). ).
- the method comprises the final recovery of particles comprising the third compound synthesized, for example by means of one or more particle retention devices chosen from a filter, an electrostatic separator, a cyclone, a cyclone comprising a electrostatic device and a filter.
- the conditions for implementing the process according to the invention can vary quite widely, in particular as a function of the compounds synthesized, for example forming the particles or else as a function of the liquids used.
- the present invention relates in particular to a method of out-of-equilibrium synthesis of a third compound from a first compound and a second compound by reaction of the first compound and the second compound with one another using a device or method from SFE.
- the heating of the compositions is carried out under a pressure ranging from 5 to 150 bars or ranging from 10 to 60 bars.
- the respective heating of each solution can be carried out under a pressure ranging from 5 to 150 bars or ranging from 10 to 60 bars which can be identical or different for each composition.
- the reaction is carried out with heating of the composition or fluid compositions, independently or depending, preferably under pressure of an inert gas.
- the heating of compositions is carried out under pressure of an inert gas chosen from nitrogen, argon, helium, neon, xenon, SF 6 , CFC, etc.
- the heating of the compositions is carried out under pressure of one or more reactive gases.
- the reactive gas can constitute the first and / or the second compound and participate in the synthesis reaction of the third compound.
- the atomization of the composition or compositions is, independently, carried out at a pressure ranging from 0.001 to less than 1 bar, preferably from 0.02 to 0.2 bar, and / or at an angle of 60 to 80 °.
- the pressure of the atomization chamber (P2) is 10 times, preferably 100 times, preferably still 1000 times, or even 10,000 times, lower than the overpressure applied during heating (P1).
- the dispersing device used during the atomization of the compositions is advantageously chosen from a hollow cone nozzle, a solid cone nozzle, a flat jet nozzle, a rectilinear jet nozzle, a pneumatic atomizer and their combinations.
- a hollow cone nozzle is particularly advantageous.
- the atomization can be carried out at an angle which can vary very widely, and preferably at an angle ranging from 30 to 150 °. We can also cite a range of atomization angles from 60 to 80 °.
- the invention also relates to a device allowing the implementation of the method.
- nitrocellulose cellulose nitration
- the device and the method according to the invention make it possible to obtain a nitrocellulose molecule which is more stable over time, unlike existing techniques which often mix solid and liquid phases.
- the device and method according to the invention improve the problems instability of nitrocelluloses which are weakly nitrated (varnish) or highly nitrated (propellant powders) and no longer requires the use of stabilizers to avoid degradation of the latter, for example hazardous decompositions which can lead to dangerous explosions in the case of more highly nitrated nitrocelluloses.
- Nitration reactions of molecules where the targeted sites are relatively sterically congested are carried out on large quantities. These reactions carried out on large quantities, often experience delays in nitration, and can then get carried away very quickly when large quantities are present and when the nitration reaction then takes place instantaneously.
- the nitration reaction allowed by the device and the method according to the invention in particular continuously, and locally on very small quantities, avoids delays, and very greatly increases the safety of nitrations.
- MOF Metal Organic Frameworks
- the invention also relates to a compound or particles capable of being obtained by a process according to the invention.
- the present invention makes it possible to produce, for example, structures of synthesized compounds, in particular in the form of particles, in a continuous and reproducible manner, and is in a sense more efficient than batch type processes (batch) such as the sol-gel method.
- batch such as the sol-gel method.
- the present invention is much more efficient in terms of the quantity of products produced and the quality of the products obtained, in particular with regard to morphology, purity, etc.
- the process according to the present invention is more efficient than conventional continuous or discontinuous techniques in the various fields of targeted applications which are in particular:
- the technique according to the present invention has the advantage of only treating a minimal quantity of material at any time, unlike the discontinuous technique which involves the entire sample.
- the invention also makes it possible to provide recycling of the liquids used.
- FIG. 1 represents a diagram of the device of the invention for the preparation of the synthesized compounds, in particular in the form of particles.
- FIG. 1 An embodiment of a device according to the invention is shown in Figure 1.
- the device is composed of four main parts: a set of two tanks 1 and 1 'for the storage under high pressure of fluids containing the or the substances to be atomized, an atomization chamber comprising two integrated heated ceramic nozzles 3, two axial cyclones 5 mounted in parallel and allowing semi-continuous production, a vacuum pump 6.
- tanks 1 and 1 ’of 5 L containing the fluid with the first compound or the second compound an overpressure of compressed nitrogen is applied. At first, this overpressure displaces oxygen and prevents the evaporation of the fluid. The volume flow in this system is induced by the overpressure of compressed nitrogen.
- Filters 2 and 2 ’ retain all the solid impurities, having a dimension which does not allow the passage of the filters, in the initial fluid.
- the filters allow the passage of the first solid compound, generally in the form of nanoparticles.
- Two ceramic cone nozzles 3, each fitted with an electric heating system, are installed side by side in the atomization chamber.
- the parameters of pressure, temperature and distribution of the particle size are controlled.
- the type of connection allows quick change of the nozzles.
- the temperature of the electric heating is chosen by the user and automatically regulated, in particular to control the crystalline phase formed.
- the nozzles are oriented relative to each other so that their jets interpenetrate.
- a tank or liquid tank 4 is filled with the same liquid as the tank 1 and is used to rinse the pipe and the nozzle after use.
- the tank or liquid tank 4 ' is filled with the same liquid as the tank 1'.
- the axial cyclones 5 are installed in parallel. During the operation, only one cyclone is in service; the second cyclone is on standby. Thanks to the centrifugal force, the solid particles are deposited inside the cyclone, the gaseous components leave the cyclone by a plunger pipe. To empty the cyclone, the circuit leading to the second cyclone is first opened, and then the first circuit leading to the first cyclone is closed.
- the vacuum pump 6 ensures a permanent flow in the installation and makes it possible to extract the vapors of liquids from the system.
- FIG. 1 is a diagram of the device of the invention for the preparation of the synthesized compounds, in particular in the form of particles.
- FIG. 2 represents images of scanning electron microscopy of Ti0 2 particles formed by the method according to the invention before calcination (A, B and C) and after calcination (D, E and F).
- FIG. 3 represents images of an electron microscope in transmission of bismuth titanate particles obtained by the method according to the invention before calcination (A and B) and after calcination (C and D).
- FIG. 4 is an X-ray difractogram produced on a bismuth titanate powder prepared by the process according to the invention and after calcination.
- MOFs have a great interest in energy storage.
- the synthesis is carried out on an installation according to the invention comprising two nozzles, which spray towards one another
- a nozzle sprays a solution of Cu (N0 3 ) 2 with a concentration of 3.3 grams per liter of acetone .
- the second nozzle sprays a solution of BTC (1, 3.5-BenzeneTriCarboxylic acid) of 1.85 grams per liter of acetone.
- Pressure in the atomization chamber 7 mbar.
- the reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
- Fine particles of MOF "HKUST1" of chemical formula are obtained by the SFS process:
- the conventional techniques which use for example atomization (“spray-drying” in English) or an autoclave technique give particles of micrometric size while the invention allows particles of smaller size to be obtained, typically including unitary particles. have a larger dimension less than 200 nm. They can form larger agglomerates.
- the particles can be continuously prepared by a system or process according to the invention.
- Example 2 The synthesis of Titanium dioxide (Ti0 2 ).
- Ti0 2 is widely used in photocatalysis and in the energy field in general. In this example, the synthesis of particles of titanium dioxide is illustrated.
- the synthesis is carried out on an installation according to the invention comprising two nozzles, which spray towards one another.
- a nozzle sprays a 1% mass solution of Titanium Tetra Isopropoxide (TTIP) in isopropanol.
- the second nozzle sprays water.
- Temperatures of the two nozzles 160 ° C.
- Pressure in the atomization chamber 20 mbar.
- the reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
- Fine particles of Ti0 2 are obtained by the SFS process according to the invention.
- the invention makes it possible to limit impurities, in particular with regard to conventional sol-gel processes.
- Example 3 The synthesis of Titanium dioxide GPO2) by hydrolysis of an alcoholate.
- TIP titanium isopropanolate
- a first solution composed of TTIP dissolved in isopropanol of HPLC grade is introduced into one of the tanks at a concentration of one percent by mass; a second solution, consisting of isopropanol and water, is placed in the other tank.
- the quantity of water introduced is fixed so as to have TTIP / H2O molar ratios equal to 1: 1, 1: 2 and 1: 4.
- the two solutions are mixed in a device placed upstream from the nebulization nozzle, the temperature of which is maintained at 160 ° C.
- the reaction medium is then injected into the atomization chamber.
- Pressure in the atomization chamber 5 to 20 mbar.
- the reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
- the powders recovered are all three amorphous, composed of elementary particles, the average diameters of which, measured on scanning electron microscopy images (FIG. 2, A, B and C), are typically submicrometric.
- the posterior calcination in air, at a temperature of 400 ° C, for 4 hours, provides anatase powders (Ti0 2 ), formed of particles of submicrometric diameters ( Figure 2, D, E and F).
- Another example is the synthesis of bismuth titanates by the process according to the invention.
- a solution of titanium isopropanolate (TTIP) in isopropanol is placed in a second tank.
- the two solutions are mixed in a device placed upstream from the nebulization nozzle, the temperature of which is maintained at 160 ° C.
- the reaction medium is then injected into the atomization chamber. Pressure in the nozzle: 40 bar.
- Pressure in the atomization chamber 5 to 20 mbar.
- the reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
- EDX analyzes carried out in a transmission electron microscope on a titanate sample produced by the process according to the invention, show that the two metallic elements (Ti and Bi) are mixed with very intimate matter, on an atomic scale ( Figure 3 , B). Calcination in air at 650 ° C, for 4 hours, causes the formation of a titanate, possibly with phase segregation ( Figure 3, D), when the titanium or bismuth are excess relative to the stoichiometry of the titanate.
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Abstract
The invention relates to a chemical synthesis method, the method comprising Spray Flash Evaporation, also referred to as SFE, comprising the chemical reaction of at least one first compound with at least one second compound, in conditions in which the first compound and the second compound react to form at least one third compound. The invention relates to a device for implementing this method and the compounds obtained by this method.
Description
Synthèse hors équilibre haute et basse température par synthèse spray flash Synthesis out of equilibrium high and low temperature by synthesis flash spray
L’invention concerne un dispositif et un procédé de synthèse chimique de produits organiques, inorganiques, métalliques et l’un quelconque de leurs mélanges, par une technique d’évaporation instantanée ou évaporation flash ou encore dénommée Synthèse Spray Flash (ou « SFS » pour l’expression anglaise "Spray Flash Synthesis"). The invention relates to a device and a method for the chemical synthesis of organic, inorganic, metallic products and any one of their mixtures, by an instant evaporation or flash evaporation technique or also called Synthesis Spray Flash (or "SFS" for the English expression "Spray Flash Synthesis").
L’invention concerne des composés ou particules ainsi obtenues par SFS. The invention relates to compounds or particles thus obtained by SFS.
ETAT DE LA TECHNIQUE STATE OF THE ART
Des procédés de préparation de particules, en particulier de nanoparticules, sont connus dans l’art antérieur. Cependant les procédés de l’état de la technique sont essentiellement de type discontinus ou « batch ». En général, on utilise des techniques de type sol-gel. Cependant les techniques sol-gel ont des performances limitées en termes de quantité de produits élaborés et de qualité des produits obtenus notamment en ce qui concerne leur morphologie et leur pureté. Jusqu’ici les besoins industriels, notamment en nanoparticules, sont satisfaits par des techniques d’élaboration discontinue de type sol- gel. Methods for preparing particles, in particular nanoparticles, are known in the prior art. However, the prior art processes are essentially of the batch or "batch" type. In general, sol-gel type techniques are used. However, the sol-gel techniques have limited performance in terms of the quantity of products produced and the quality of the products obtained, in particular as regards their morphology and purity. Up to now, industrial needs, in particular in nanoparticles, have been met by discontinuous processing techniques of the sol-gel type.
Plus largement, pour la synthèse de composés chimiques, les besoins industriels sont satisfaits jusqu'à présent par l'utilisation de réactions chimiques à rendements parfois relativement faibles comme par exemple, mais pas uniquement, les réactions d'estérifications utilisant les techniques discontinue (« batch ») classiques avec des rendements qui plafonnent à 60%. L'augmentation de ces rendements, ne serait-ce que de quelques pourcents, représenterait un gain très conséquent du fait des forts tonnages des produits synthétisés. More generally, for the synthesis of chemical compounds, industrial needs have so far been met by the use of chemical reactions with sometimes relatively low yields, for example, but not only, esterification reactions using discontinuous techniques (“ batch ") classics with yields capping at 60%. The increase in these yields, if only by a few percent, would represent a very significant gain due to the heavy tonnages of the synthesized products.
Le besoin industriel est aussi satisfait par l'utilisation de divers produits qui sont tout simplement moins bons du point de vue de leurs qualités intrinsèques, à l'exemple des oxydes obtenus par les techniques sol-gel dont la séparation des impuretés reste ainsi toujours un problème, de même que la nécessité de faire un traitement thermique post-synthèse pour les cristalliser de manière satisfaisante, ce qui a pour effet de faire grossir les particules et de les agglomérer fortement (frittage). The industrial need is also satisfied by the use of various products which are simply less good from the point of view of their intrinsic qualities, for example the oxides obtained by sol-gel techniques whose separation of impurities thus always remains a problem, as well as the need to do a post-synthesis heat treatment to crystallize them satisfactorily, which has the effect of making the particles magnify and agglomerate them strongly (sintering).
Les limites des techniques de synthèses actuelles sont l'obtention de produits de moins bonnes qualités (du point de vue de leur cristallinité, taille des particules obtenus, et/ou présence d'impuretés, etc.) et avec a fortiori des rendements qui demandent à être améliorés. Ces techniques demandent en plus dans certains cas des étapes de purifications additionnelles longues et donc coûteuses.
En outre, la plupart des techniques existantes, du fait de leurs limitations (notamment avec l’impossibilité de contrôler localement finement la réaction) ne permettent pas de fabriquer de bons produits ou les produits voulus, en particulier lors d'une synthèse "one pot". The limits of current synthesis techniques are obtaining products of poorer quality (from the point of view of their crystallinity, size of the particles obtained, and / or presence of impurities, etc.) and a fortiori yields which require to be improved. These techniques also require, in some cases, additional long and therefore costly purification steps. In addition, most of the existing techniques, due to their limitations (in particular with the impossibility of locally finely controlling the reaction) do not make it possible to manufacture good products or the desired products, in particular during a "one pot" synthesis. ".
BUTS DE L’INVENTION GOALS OF THE INVENTION
L’invention a pour but de résoudre le problème technique consistant à fournir un dispositif et un procédé de préparation continue ou discontinue de composés notamment sous forme de particules, et en particulier de particules de taille micrométrique, submicrométrique ou nanométrique. The aim of the invention is to solve the technical problem of providing a device and a process for the continuous or discontinuous preparation of compounds, in particular in the form of particles, and in particular particles of micrometric, submicrometric or nanometric size.
L’invention a notamment pour but de résoudre le problème technique consistant à faciliter ou rendre possible la préparation de particules cristallisées. The object of the invention is in particular to solve the technical problem of facilitating or making possible the preparation of crystallized particles.
En particulier la présente invention a pour but de résoudre le problème technique consistant à fournir des composés, notamment sous forme de particules, présentant des propriétés pour des applications dans les domaines variés d’application des composés chimiques. In particular, the present invention aims to solve the technical problem of providing compounds, in particular in the form of particles, having properties for applications in the various fields of application of chemical compounds.
L’invention a encore pour but de résoudre le problème technique consistant à rendre possible la préparation de composés, notamment sous forme de particules, qui ne sont pas accessibles par les techniques classiques, notamment de type sol-gel. The invention also aims to solve the technical problem of making possible the preparation of compounds, in particular in the form of particles, which are not accessible by conventional techniques, in particular of the sol-gel type.
L’invention a encore pour but de résoudre le problème technique consistant à fabriquer des composés, notamment sous forme de particules, en améliorant les rendements des réactions. Another object of the invention is to solve the technical problem of manufacturing compounds, in particular in the form of particles, by improving the yields of the reactions.
DESCRIPTION DE L’INVENTION DESCRIPTION OF THE INVENTION
L’invention permet de résoudre au moins l’un, et de préférence l’ensemble des problèmes techniques posés selon l’invention. The invention makes it possible to solve at least one, and preferably all of the technical problems raised according to the invention.
L’invention concerne une invention de rupture, appelée « SFS » pour Synthèse par Spray Flash (en anglais « Spray Flash Synthesis »). The invention relates to a groundbreaking invention, called "SFS" for Synthesis by Spray Flash (in English "Spray Flash Synthesis").
L’invention concerne un procédé de synthèse chimique, ledit procédé comprenant une brumisation par évaporation flash, également connue sous le sigle SFE pour l’acronyme anglais « Spray Flash Evaporation », comprenant la réaction chimique d’au moins un premier composé avec au moins un deuxième composé, dans des conditions dans lesquelles le premier composé et le deuxième composé réagissent pour former au moins un troisième composé. The invention relates to a chemical synthesis process, said process comprising flash evaporation misting, also known by the acronym SFE for the English acronym "Spray Flash Evaporation", comprising the chemical reaction of at least one first compound with at least a second compound, under conditions in which the first compound and the second compound react to form at least a third compound.
L’invention concerne également un dispositif de synthèse chimique, ledit dispositif comprenant :
■ au moins un premier réservoir comprenant : The invention also relates to a chemical synthesis device, said device comprising: ■ at least one first tank comprising:
- une alimentation d’une composition liquide comprenant ou constituée d’un premier composé ; - a supply of a liquid composition comprising or consisting of a first compound;
- au moins un dispositif de mise sous une pression P1 , P1 étant de préférence choisi dans une plage de pression de 3 à 300 bars ; - At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars;
- au moins un dispositif de chauffage ; - at least one heating device;
■ au moins un deuxième réservoir comprenant : ■ at least a second tank comprising:
- une alimentation d’une composition liquide comprenant ou constituée d’un deuxième composé ; - a supply of a liquid composition comprising or consisting of a second compound;
- au moins un dispositif de mise sous une pression P1’, P1’ étant de préférence choisi dans une plage de pression de 3 à 300 bars et égale à ou différente de P1 ; - At least one pressurizing device P1 ’, P1’ being preferably chosen in a pressure range from 3 to 300 bars and equal to or different from P1;
- au moins un dispositif de chauffage ; - at least one heating device;
lesdits premier composé et deuxième composé étant réactifs ensemble, said first compound and second compound being reactive together,
■ une chambre d’atomisation comprenant : ■ an atomization chamber comprising:
- au moins un dispositif de dispersion des compositions liquide de chaque réservoir, de préférence sous un angle allant de 30 à 150°, et à une pression P2 inférieure à P1 et P1’, P2 étant de préférence choisi dans une plage de pression allant de 0,0001 à 2 bars, les dispositifs de dispersion étant positionnés de sorte que le premier composé et le deuxième composé réagissent ensemble dans les gouttelettes formée dans la chambre d’atomisation, ledit dispositif de dispersion étant de préférence chauffé par un dispositif de chauffage à une température choisie dans une plage de 200 à 2000°C ; at least one device for dispersing the liquid compositions of each reservoir, preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1 and P1 ′, P2 preferably being chosen from a pressure range ranging from 0.0001 to 2 bars, the dispersing devices being positioned so that the first compound and the second compound react together in the droplets formed in the atomization chamber, said dispersing device being preferably heated by a heating device at a temperature chosen in a range of 200 to 2000 ° C;
- au moins un dispositif de séparation de liquides ; et - at least one device for separating liquids; and
■ éventuellement un ou plusieurs dispositifs de récupération du troisième composé formé par réaction du premier composé et du deuxième composé. ■ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
L’invention concerne aussi un dispositif de synthèse chimique, ledit dispositif The invention also relates to a chemical synthesis device, said device
comprenant : including:
■ au moins un réservoir comprenant : ■ at least one tank comprising:
- une alimentation d'une ou plusieurs compositions liquides comprenant le premier composé et/ou le deuxième composé ; - a supply of one or more liquid compositions comprising the first compound and / or the second compound;
- au moins un dispositif de mise sous une pression P1 , P1 étant de préférence choisi dans une plage de pression de 3 à 300 bars ; - At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars;
- au moins un dispositif de chauffage ; - at least one heating device;
lesdits premier composé et deuxième composé étant réactifs ensemble,
■ une chambre d’atomisation comprenant : said first compound and second compound being reactive together, ■ an atomization chamber comprising:
- au moins un dispositif de dispersion du fluide de chaque réservoir, de préférence sous un angle allant de 30 à 150°, et à une pression P2 inférieure à P1 , P2 étant de préférence choisi dans une plage de pression allant de 0,0001 à 2 bars, ledit dispositif étant de préférence chauffé par un dispositif de chauffage à une température choisie dans une plage de 200 à 2000°C ; - at least one device for dispersing the fluid in each reservoir, preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1, P2 preferably being chosen from a pressure range ranging from 0.0001 to 2 bars, said device being preferably heated by a heating device to a temperature chosen in a range from 200 to 2000 ° C;
- au moins un dispositif de séparation de liquides ; et - at least one device for separating liquids; and
■ éventuellement un ou plusieurs dispositifs de récupération du troisième composé formé par réaction du premier composé et du deuxième composé. ■ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
La technique SFS selon l’invention est une nouvelle technique dérivée du SFE, mais qui intègre une rupture conceptuelle dans l’approche de la synthèse et une rupture technique. Ces ruptures constituent une véritable révolution dans la synthèse chimique en général (synthèse organique et inorganique). The SFS technique according to the invention is a new technique derived from SFE, but which incorporates a conceptual break in the approach of synthesis and a technical break. These ruptures constitute a real revolution in chemical synthesis in general (organic and inorganic synthesis).
La rupture conceptuelle consiste à réaliser une synthèse d’un ou plusieurs composés chimiques en passant du milieu en surpression en amont d'une buse de nébulisation (spray), à un vide primaire en aval de cette dernière. La synthèse est ainsi intégrée dans un procédé d'atomisation sous vide, représenté par la SFE. La synthèse selon l’invention peut se faire à la fois à travers une seule buse de nébulisation ou en faisant s’interpénétrer des jets de plusieurs buses de nébulisation. On peut ainsi réaliser un nombre quasi infini de différents types de synthèses et de produits à synthétiser. The conceptual break consists in carrying out a synthesis of one or more chemical compounds by passing from the pressurized medium upstream of a nebulization nozzle (spray), to a primary vacuum downstream of the latter. The synthesis is thus integrated into a vacuum atomization process, represented by the SFE. The synthesis according to the invention can be carried out both through a single nebulization nozzle or by intermingling jets of several nebulization nozzles. It is thus possible to carry out an almost infinite number of different types of syntheses and of products to be synthesized.
L’invention est décrite en référence au premier, deuxième et troisième composés de manière générique. Ainsi, l’invention couvre tout mode de réalisation de synthèse chimique incluant la réaction entre deux ou plus composés réactifs (dénommés ici à titre purement arbitraire toujours premier et deuxième composés) pour former au moins un ou plusieurs troisième composés (dénommés ici à titre purement arbitraire toujours troisième composé). Les termes de premier composé et deuxième composé sont donc arbitraires pour désigner au moins deux composés réactifs entre eux. Les termes de troisième composé sont donc arbitraires pour désigner au moins un produit de réaction d’au moins deux réactifs. Ainsi, l'invention couvre par exemple la réaction entre au moins deux composés, réactifs, pour former un ou plusieurs troisièmes composés, produits de la réaction. The invention is described with reference to the first, second and third compounds in a generic manner. Thus, the invention covers any embodiment of chemical synthesis including the reaction between two or more reactive compounds (here called purely arbitrarily always first and second compounds) to form at least one or more third compounds (here called purely for purely always third arbitrary). The terms first compound and second compound are therefore arbitrary to designate at least two reactive compounds with one another. The terms third compound are therefore arbitrary to denote at least one reaction product of at least two reagents. Thus, the invention covers for example the reaction between at least two reactive compounds, to form one or more third compounds, products of the reaction.
Selon une variante, il est intéressant selon l'invention que le premier composé et le deuxième composé soient sous forme liquide jusqu'à leur réaction et que le troisième composé soit sous forme solide. Les conditions, notamment de température et pression du procédé et dispositif selon l'invention sont donc avantageusement choisies en conséquence.
Selon une variante, la réaction est mise en oeuvre entre deux composés d’état différent (liquide, solide, gaz), comme par exemple entre un solide et un liquide, comme par exemple pour la synthèse de la nitrocellulose, la cellulose est solide et l’agent de nitration (HN03) est liquide. According to a variant, it is advantageous according to the invention that the first compound and the second compound are in liquid form until their reaction and that the third compound is in solid form. The conditions, in particular of temperature and pressure of the process and device according to the invention are therefore advantageously chosen accordingly. According to a variant, the reaction is carried out between two compounds of different state (liquid, solid, gas), as for example between a solid and a liquid, as for example for the synthesis of nitrocellulose, the cellulose is solid and the nitrating agent (HN0 3 ) is liquid.
L’invention permet avantageusement une synthèse très localisée, dans des espaces très restreints (notion de micro voire nano-réacteurs, ou encore de réacteurs métastables...) constitués par les gouttes largement plus fines encore que celles du SFE des brevets antérieurs, notamment du fait du chauffage plus élevé, et qui forment des nanoréacteurs ou microréacteurs ou des intersections de nanoréacteurs ou micro réacteurs différents (cas des multiples buses) dans lesquelles a lieu la réaction chimique de synthèse. Ceci permet de faire avantageusement une synthèse ciblée, très localisée, en évitant tout emballement dû aux effets de masse (accumulation de la chaleur) découlant de l’usage de quantités trop grandes de réactifs. De manière particulièrement avantageuse, cette réaction chimique mise en oeuvre selon l’invention permet de déplacer l’équilibre thermodynamique de la réaction opérée dans des conditions de réaction « standard » sans dispositif ou procédé SFE. On parle ainsi de synthèse hors-équilibre. Ce déplacement explique au moins en partie l’amélioration des rendements constatés selon la présente invention. The invention advantageously allows a very localized synthesis, in very limited spaces (concept of micro or even nano-reactors, or even metastable reactors ...) constituted by the drops much finer still than those of the SFE of previous patents, in particular due to the higher heating, and which form nanoreactors or microreactors or intersections of different nanoreactors or micro-reactors (case of multiple nozzles) in which the synthetic chemical reaction takes place. This makes it possible to advantageously make a targeted, very localized synthesis, avoiding any runaway due to the mass effects (accumulation of heat) resulting from the use of too large quantities of reagents. In a particularly advantageous manner, this chemical reaction implemented according to the invention makes it possible to shift the thermodynamic equilibrium of the reaction carried out under "standard" reaction conditions without an SFE device or process. This is called out-of-balance synthesis. This displacement explains at least in part the improvement in the yields observed according to the present invention.
De plus, du fait de la possibilité de chauffer la buse, on peut dans certains cas directement obtenir la phase cristalline souhaitée du produit en évitant une phase de traitement thermique ultérieur, pour obtenir le produit voulu. Dans certains cas, lorsque cela s’avère nécessaire, il faut également prévoir des post-traitements dans l’aérosol de composés, notamment sous forme de particules, par exemple sous forme cristallisée. Ainsi, selon une variante, les composés notamment sous forme de particules, obtenus sont cristallins, de préférence la phase cristalline étant contrôlée lors du passage au travers du dispositif de dispersion. In addition, due to the possibility of heating the nozzle, it is possible in certain cases to directly obtain the desired crystalline phase of the product while avoiding a subsequent heat treatment phase, in order to obtain the desired product. In certain cases, when this proves necessary, it is also necessary to provide post-treatments in the aerosol of compounds, in particular in the form of particles, for example in crystallized form. Thus, according to a variant, the compounds in particular in the form of particles, obtained are crystalline, preferably the crystalline phase being controlled during the passage through the dispersing device.
Avantageusement, l’invention permet la synthèse en continu (allant jusqu'à plusieurs kilogrammes par heure), bien plus contrôlée que la plupart des techniques qui existent. Selon un mode de réalisation, l’invention permet de synthétiser des molécules et la cristallisation des molécules synthétisées. Avantageusement, cette synthèse est réalisée très localement dans un dispositif selon l’invention, pour faciliter les réactions chimiques en favorisant le contact entre les réactifs (premier et deuxième composés), en particulier pour augmenter les rendements et/ou pour augmenter la sécurité de synthèse. Ainsi, l’invention constitue une technique beaucoup plus performante que bon nombre, voire l'ensemble des techniques de synthèse chimique existantes.
Différents (troisièmes) composés peuvent être ainsi synthétisés comme des oxydes, des céramiques ou des produits organiques à l'exemple de matériaux énergétiques, de médicaments, d'esters ou de composés organiques en général, de polymères conducteurs ou non, de catalyseurs ou des complexes de métaux de transition. La synthèse peut avoir lieu à l'aide d'un dispositif de nébulisation (ou « spray ») d'une seule buse ou les produits peuvent être synthétisés dans l'intersection des jets de plusieurs buses, apportant chacune les différents (premier(s) et deuxième(s)) composés à mettre en contact pour synthétiser les différents produits (troisième composé). Advantageously, the invention allows continuous synthesis (up to several kilograms per hour), much more controlled than most of the techniques that exist. According to one embodiment, the invention makes it possible to synthesize molecules and the crystallization of the synthesized molecules. Advantageously, this synthesis is carried out very locally in a device according to the invention, to facilitate chemical reactions by promoting contact between the reagents (first and second compounds), in particular to increase the yields and / or to increase the safety of synthesis. . Thus, the invention constitutes a much more efficient technique than many, even all of the existing chemical synthesis techniques. Different (third) compounds can thus be synthesized such as oxides, ceramics or organic products, for example energetic materials, drugs, esters or organic compounds in general, conductive or non-conductive polymers, catalysts or transition metal complexes. The synthesis can take place using a nebulization device (or “spray”) of a single nozzle or the products can be synthesized in the intersection of the jets of several nozzles, each bringing the different (first (s ) and second (s)) compounds to be brought into contact to synthesize the different products (third compound).
Selon un mode de réalisation, les buses pulvérisent des jets qui rentrent en contact les uns les autres. Par exemple, avec deux buses, les jets sont positionnés en regard l’un de l’autre. According to one embodiment, the nozzles spray jets which come into contact with each other. For example, with two nozzles, the jets are positioned opposite each other.
L’invention concerne également un dispositif et procédé comprenant un dispositif de chauffage ou une étape de chauffage de la ou des buses de nébulisation permettant une montée à température élevée, en général supérieure à 200°C. Avantageusement, le dispositif et procédé comprend un moyen ou dispositif de régulation du ou des débits du premier composé et du deuxième composé. Selon l’art antérieur, le débit était régulé par la pression au travers de la buse. Selon l’invention, on peut utiliser un débit mètre positionné sur les conduites d’approvisionnement des buses de manière à réguler finement le débit pour mieux contrôler les réactions mises en oeuvre selon‘invention. Les débit d’une buse peut être régulé indépendamment du débits des autres buses. The invention also relates to a device and method comprising a heating device or a step of heating the nebulization nozzle (s) allowing a rise in high temperature, generally greater than 200 ° C. Advantageously, the device and method comprises a means or device for regulating the flow or flows of the first compound and of the second compound. According to the prior art, the flow rate was regulated by the pressure through the nozzle. According to the invention, one can use a flow meter positioned on the supply lines of the nozzles so as to finely regulate the flow to better control the reactions implemented according to the invention. The flow rates of one nozzle can be regulated independently of the flow rates of other nozzles.
Lorsque l’on indique que le dispositif de dispersion est chauffé, il s’agit notamment de la ou des buses de nébulisation qui sont chauffées. La ou des buses de nébulisation sont chauffées dans une gamme de température très large qui va typiquement de 20°C à 2000°C. Typiquement, la température de la ou des buses est comprise entre 20°C et 2000°C. Selon une variante, la température de la ou des buses est comprise entre 40°C et 2000°C. Selon une variante, la température de la ou des buses est comprise entre 40°C et 200°C. Avantageusement, le dispositif et procédé selon l’invention comprennent un moyen ou dispositif de traitement thermique (de chauffage) de l’aérosol formé. Typiquement, le moyen ou dispositif de traitement thermique est disposé de manière à chauffer la buse elle-même ou en aval de la buse et par exemple dans la partie haute de la chambre d’atomisation, c’est-à-dire à proximité de jets nébulisés dans la chambre d’atomisation. Cela permet avantageusement de calciner ou cristalliser de manière plus complète certains produits désirés, formés par la réaction des réactifs. When it is indicated that the dispersing device is heated, it is in particular the spray nozzle or nozzles which are heated. The nebulization nozzle or nozzles are heated over a very wide temperature range which typically ranges from 20 ° C. to 2000 ° C. Typically, the temperature of the nozzle (s) is between 20 ° C and 2000 ° C. According to a variant, the temperature of the nozzle (s) is between 40 ° C and 2000 ° C. According to a variant, the temperature of the nozzle (s) is between 40 ° C and 200 ° C. Advantageously, the device and method according to the invention comprise a means or device for thermal treatment (heating) of the aerosol formed. Typically, the heat treatment means or device is arranged so as to heat the nozzle itself or downstream of the nozzle and for example in the upper part of the atomization chamber, that is to say near nebulized jets in the atomization chamber. This advantageously makes it possible to calcine or crystallize more completely certain desired products, formed by the reaction of the reactants.
Selon une variante, le dispositif comprend un dispositif ou moyen de traitement thermique est choisi parmi un chauffage par micro-ondes, par lumière pulsée (flashs), laser, lumière infrarouge (rayonnement) ou un autre moyen de chauffage adapté. Le
moyen ou dispositif de traitement thermique peut être une source de radiation, par exemple par micro-onde, de préférence positionnée de manière à ce que les radiations atteignent au moins la sortie de la buse ou des buses et ainsi permettre un chauffage suffisant. According to a variant, the device comprises a device or means for heat treatment is chosen from heating by microwaves, by pulsed light (flashes), laser, infrared light (radiation) or another suitable heating means. The heat treatment means or device can be a source of radiation, for example by microwave, preferably positioned so that the radiation reaches at least the outlet of the nozzle or nozzles and thus allow sufficient heating.
Selon une variante, la ou des buses de nébulisation sont chauffées dans une gamme de température très large qui va typiquement de 200°C à 2000°C, et par exemple de 250°C à 2000°C ou encore par exemple de 300°C à 1500°C. According to a variant, the nebulization nozzle or nozzles are heated in a very wide temperature range which typically goes from 200 ° C to 2000 ° C, and for example from 250 ° C to 2000 ° C or even for example from 300 ° C at 1500 ° C.
Selon un mode de réalisation, le dispositif de dispersion est chauffé par résistance électrique et/ou induction et/ou par vibrations (ultrasons ou autres). According to one embodiment, the dispersion device is heated by electrical resistance and / or induction and / or by vibrations (ultrasound or other).
Selon une variante, on utilise avantageusement des buses en matériau céramique. According to a variant, advantageously nozzles made of ceramic material are used.
Avantageusement, le chauffage du dispositif de dispersion, permet de diminuer encore davantage que pour le SFE, la taille des gouttelettes de liquide formées du fait d'une évaporation plus rapide et plus contrôlée des solvants ou des produits de dispersion. La technique SFS selon l’invention réduit aussi les coûts ultérieurs du fait de l'efficacité des produits qu’elle permet de synthétiser. On aura ainsi des médicaments, des engrais, des produits organiques en général et de manière plus générale des matériaux plus efficaces, à l'exemple de semi-conducteurs à bande interdite ajustée. Les médicaments obtenus, du fait de leur plus grande efficacité, seront utilisés dans des posologies (et par conséquent des tonnages) impliquant des quantités inférieures, ce qui abaissera leur empreinte écologique, et favorisera de ce fait le développement durable. Advantageously, the heating of the dispersing device makes it possible to reduce even more than for the SFE, the size of the liquid droplets formed due to faster and more controlled evaporation of the solvents or of the dispersion products. The SFS technique according to the invention also reduces subsequent costs due to the efficiency of the products which it makes it possible to synthesize. There will thus be drugs, fertilizers, organic products in general and more generally more effective materials, for example of adjusted band gap semiconductors. The drugs obtained, because of their greater effectiveness, will be used in dosages (and therefore tonnages) involving lower quantities, which will lower their ecological footprint, and thereby promote sustainable development.
Ce dispositif technique ou étape de chauffage présente un avantage technique en réalisant deux fonctions très importantes, qui sont de permettre une évaporation des solvants ou des fluides de dispersion bien plus rapide encore que dans le cas du SFE, et d’assurer également par la même occasion un traitement thermique, comme par exemple la calcination des produits obtenus, ce qui permet souvent leur cristallisation optimale. Ce traitement thermique, par exemple dans les techniques de types sol-gel selon l’art antérieur, est souvent réalisé trop longtemps après la synthèse des matériaux, ce qui rend difficile une obtention des produits optimaux, dont il est souvent difficile de séparer les impuretés. La présente invention permet donc avantageusement de réaliser des synthèses "one pot" en continu de matériaux cristallisés ou non. This technical device or heating stage has a technical advantage by achieving two very important functions, which are to allow evaporation of the solvents or dispersion fluids much faster even than in the case of SFE, and also to ensure by the same occasion a heat treatment, such as for example the calcination of the products obtained, which often allows their optimal crystallization. This heat treatment, for example in the sol-gel type techniques according to the prior art, is often carried out too long after the synthesis of the materials, which makes it difficult to obtain optimal products, from which it is often difficult to separate the impurities. . The present invention therefore advantageously makes it possible to carry out continuous "one pot" syntheses of crystallized or non-crystallized materials.
Le procédé de synthèse selon l’invention peut être avantageusement mis en oeuvre à grande échelle et peut par exemple atteindre, voire dépasser des capacités de production de plusieurs kilogrammes par heure. The synthesis process according to the invention can advantageously be implemented on a large scale and can, for example, reach or even exceed production capacities of several kilograms per hour.
L'invention concerne un procédé de préparation comprenant une atomisation, et en particulier par évaporation instantanée ou évaporation flash, qui permet d'apporter une solution à tout ou partie des problèmes des procédés de l'état de la technique.
L’invention concerne les composés, notamment sous forme de particules, et leurs procédés de préparation, en particulier un procédé de préparation de composés notamment sous forme de particules, ledit procédé comprenant l’atomisation simultanée d’au moins un premier composé et d’au moins un deuxième composé, dans des conditions de réaction au moins du premier composé et du deuxième composé pour former au moins un troisième composé. Le dispositif selon l’invention d’opérer dans des conditions de réaction au moins du premier composé et du deuxième composé pour former au moins un troisième composé. The invention relates to a preparation process comprising atomization, and in particular by instant evaporation or flash evaporation, which makes it possible to provide a solution to all or part of the problems of the processes of the state of the art. The invention relates to compounds, in particular in the form of particles, and to their methods of preparation, in particular to a method of preparing compounds in particular in the form of particles, said method comprising the simultaneous atomization of at least one first compound and of at least a second compound, under reaction conditions at least the first compound and the second compound to form at least a third compound. The device according to the invention operates under reaction conditions of at least the first compound and the second compound to form at least a third compound.
Comme cela a été indiqué précédemment, on désigne par « premier composé» un composé différent du « deuxième composé ». Les composés désignés par « premier composés » peuvent être multiples. Il est fait référence à ce ou ces « premiers composés » essentiellement pour les distinguer du ou des « deuxièmes composés ». As indicated above, the term “first compound” denotes a compound different from the “second compound”. The compounds designated by “first compounds” can be multiple. Reference is made to this or these “first compounds” essentially to distinguish them from the “second compounds”.
La technique SFS selon l’invention concerne donc la synthèse chimique, c'est-à- dire la formation de nouvelles molécules cristallisées ou non sous forme de particules, et en particulier de nanoparticules (de préférence dont au moins une dimension ou la plus grande dimension est inférieure à 100 nm (nanomètre)), de particules dont au moins une dimension ou la plus grande dimension est submicrométrique (de préférence inférieure à 1 pm) ou micrométrique (de préférence inférieure à 1 mm). The SFS technique according to the invention therefore relates to chemical synthesis, that is to say the formation of new molecules, crystallized or not in the form of particles, and in particular of nanoparticles (preferably of which at least one dimension or the largest dimension is less than 100 nm (nanometer)), of particles of which at least one dimension or the largest dimension is submicrometric (preferably less than 1 μm) or micrometric (preferably less than 1 mm).
Selon un mode de réalisation, le ou les premiers composés et le ou les deuxièmes composés sont dissous et/ou dispersés dans un ou plusieurs solvants, et sont envoyés à travers une ou plusieurs buses à température ambiante ou chauffés dans une chambre maintenue sous vide primaire (typiquement de 100 à 0,1 Pa). According to one embodiment, the first compound (s) and the second compound (s) are dissolved and / or dispersed in one or more solvents, and are sent through one or more nozzles at room temperature or heated in a chamber maintained under primary vacuum (typically from 100 to 0.1 Pa).
Dans cette chambre le ou les troisièmes composés sont synthétisés à l‘état cristallisé ou non cristallisé sous forme de particules nanométriques, submicrométriques ou micrométriques. In this chamber, the third compound (s) are synthesized in the crystallized or non-crystallized state in the form of nanometric, submicrometric or micrometric particles.
Selon une variante particulière, les particules de l’invention sont des particules comprenant avantageusement l’ensemble de leurs dimensions inférieures à 1000 nm. According to a particular variant, the particles of the invention are particles advantageously comprising all of their dimensions less than 1000 nm.
Selon une variante, les particules sont des nanoparticules, c’est-à-dire comprenant avantageusement au moins une et de préférence l’ensemble de leurs dimensions, inférieures à 100 nm. According to a variant, the particles are nanoparticles, that is to say advantageously comprising at least one and preferably all of their dimensions, less than 100 nm.
L’invention concerne en particulier des particules solides, et plus particulièrement des particules dont la plus petite dimension et de préférence l’ensemble des dimensions va de 30 à 100 nm. The invention relates in particular to solid particles, and more particularly to particles of which the smallest dimension and preferably all of the dimensions ranges from 30 to 100 nm.
Selon une variante, les particules synthétisées comprennent ou sont constituées d’un ou plusieurs éléments métalliques.
Selon une variante, les particules synthétisées comprennent ou sont constituées d’un ou plusieurs composés organiques. According to a variant, the particles synthesized comprise or consist of one or more metallic elements. According to a variant, the particles synthesized comprise or consist of one or more organic compounds.
Comme exemples non exhaustifs on cite la synthèse d'esters par des réactions d'estérification en mélangeant des alcools et des acides, la synthèse de la nitrocellulose par la réaction de nitration de la cellulose ou la nitration de molécules à sites encombrés stériquement, la synthèse de polymères conducteurs comme par exemple la polyaniline, la synthèse d'oxydes, notamment d’oxydes métalliques comme par exemple Ti02, ZnO, Fe203 ou leurs mélanges, la synthèse de titanate comme par exemple de titanate de bismuth, la synthèse de sulfures (chalocogénures (comme par exemple Tellurure de cadmium, Séléniure d'hydrogène, Disulfure de molybdène, Oxyde d'indium-étain (ITO), Tellurure de sodium, Séléniure de zinc)) ou de non oxydes, de terres rares, de matériaux carbonés comme C3N4 ou d'autres céramiques et composés carbonés, et de catalyseurs, en partant de leur précurseurs respectifs ou encore la synthèse de MOF (« Métal Organic Frameworks ») par une ou plusieurs buses. As non-exhaustive examples, we cite the synthesis of esters by esterification reactions by mixing alcohols and acids, the synthesis of nitrocellulose by the nitration reaction of cellulose or the nitration of molecules with sterically hindered sites, the synthesis conductive polymers such as, for example, polyaniline, the synthesis of oxides, in particular metal oxides such as, for example, Ti0 2 , ZnO, Fe 2 0 3 or mixtures thereof, the synthesis of titanate such as, for example, bismuth titanate, the synthesis sulfides (chalocogenides (such as cadmium telluride, hydrogen selenide, molybdenum disulfide, indium tin oxide (ITO), sodium telluride, zinc selenide)) or non-oxides, rare earths, carbonaceous materials such as C 3 N 4 or other ceramics and carbonaceous compounds, and catalysts, starting from their respective precursors or even the synthesis of MOF (“Metal Organic Frameworks”) by a or more nozzles.
De préférence, les composés synthétisables selon le procédé de l’invention sont choisis parmi les oxydes métalliques, par exemple Ti02, les titanates, par exemple le titanate de bismuth, et les MOF, par exemple le MOF nommé le « HKUST-1 ». Preferably, the compounds which can be synthesized according to the process of the invention are chosen from metal oxides, for example Ti0 2 , titanates, for example bismuth titanate, and MOFs, for example MOF called "HKUST-1" .
Selon un mode de réalisation de l’invention, les composés synthétisables selon le procédé de l’invention sont des nanoparticules de Ti02 présentant par exemple un diamètre moyen compris entre 100 et 250 nm. De préférence, les nanoparticules de Ti02 obtenues selon le procédé de l'invention présentent par exemple une structure de type anatase, un diamètre moyen compris entre 100 et 250 nm, et par exemple une aire spécifique BET comprise entre 5 et 20 m2/g. According to one embodiment of the invention, the compounds that can be synthesized according to the method of the invention are Ti0 2 nanoparticles having, for example, an average diameter between 100 and 250 nm. Preferably, the Ti0 2 nanoparticles obtained according to the process of the invention have, for example, an anatase type structure, an average diameter between 100 and 250 nm, and for example a BET specific area between 5 and 20 m 2 / g.
Selon un autre mode de réalisation de l’invention, les composés synthétisables selon le procédé de l’invention sont des nanoparticules de titanate de bismuth. De préférence, les nanoparticules de titanate de bismuth comprennent majoritairement une phase cristalline Bi2Ti207. According to another embodiment of the invention, the compounds which can be synthesized according to the method of the invention are nanoparticles of bismuth titanate. Preferably, the bismuth titanate nanoparticles mainly comprise a Bi 2 Ti 2 0 7 crystalline phase.
Parmi les composés synthétisables selon la présente invention, on peut citer à titre d’exemple les composés suivants ou les composés des domaines techniques suivants : Among the compounds which can be synthesized according to the present invention, there may be mentioned by way of example the following compounds or the compounds of the following technical fields:
Les médicaments, la galénique, la pharmacie, la parfumerie, Medicines, galenics, pharmacy, perfumery,
Les matériaux énergétiques : explosifs (primaires et secondaires) et les poudres propulsives, Energy materials: explosives (primary and secondary) and propellant powders,
La cosmétique, Cosmetics,
Les oxydes et les céramiques, Oxides and ceramics,
Les phytosanitaires. Phytosanitary products.
L'agroalimentaire,
Les pigments et les peintures, Food, Pigments and paints,
La chimie organique, Organic chemistry,
Les semi-conducteurs, Semiconductors,
La catalyse, Catalysis,
Le stockage de l'énergie, en particulier le stockage de l'hydrogène. Energy storage, in particular hydrogen storage.
Le procédé selon l'invention concerne la préparation de particules, et en particulier des nanoparticules, de composés choisis parmi les composés énergétiques, les composés pharmaceutiques, les composés phytopharmaceutiques, les composés de contraste médicaux, les composés fluorescents, les composés optiques, les composés colorants, les arômes, fragrances (parfum), les pigments, les encres, les peintures, les métaux, les oxydes métalliques, les composés semi-conducteurs, les composés optiques, les composés optoélectroniques, les composés ferroélectriques, les composés à réponse non-linéaire ou les composés bio-électroniques. The process according to the invention relates to the preparation of particles, and in particular nanoparticles, of compounds chosen from energetic compounds, pharmaceutical compounds, phytopharmaceutical compounds, medical contrast compounds, fluorescent compounds, optical compounds, compounds dyes, aromas, fragrances (perfume), pigments, inks, paints, metals, metal oxides, semiconductor compounds, optical compounds, optoelectronic compounds, ferroelectric compounds, non-response compounds linear or bio-electronic compounds.
Le procédé selon l'invention est particulièrement avantageux pour la préparation de particules, et en particulier des nanoparticules, de composés cristallisés choisis parmi les composés métalliques, leurs oxydes, et l’un quelconque de leurs mélanges. The process according to the invention is particularly advantageous for the preparation of particles, and in particular nanoparticles, of crystallized compounds chosen from metal compounds, their oxides, and any one of their mixtures.
De manière également avantageuse, le procédé selon l'invention permet de préparer des particules, et en particulier des nanoparticules, dont la taille est micrométrique ou qui possèdent au moins une dimension inférieure à 500 pm, de préférence qui possèdent au moins une dimension inférieure à 100 pm. Also advantageously, the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is micrometric or which have at least one dimension less than 500 μm, preferably which have at least one dimension less than 100 pm.
De manière également avantageuse, le procédé selon l'invention permet de préparer des particules, et en particulier des nanoparticules, dont la taille est submicrométrique ou qui possèdent au moins une dimension comprise entre 100 et 1 000 nm. Also advantageously, the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is submicrometric or which have at least one dimension of between 100 and 1000 nm.
Par « taille » de particules, on désigne le diamètre ou la plus petite dimension pour des particules non sensiblement sphériques, et avantageusement l’ensemble des dimensions des particules. La taille des particules peut être mesurée par microscopie électronique à balayage et par transmission. By “size” of particles is meant the diameter or the smallest dimension for particles that are not substantially spherical, and advantageously all of the dimensions of the particles. Particle size can be measured by scanning electron microscopy and by transmission.
De manière préférée, le procédé selon l'invention permet de préparer des particules, et en particulier des nanoparticules, dont la taille est nanométrique ou qui possèdent au moins une dimension inférieure à 100 nm. Preferably, the method according to the invention makes it possible to prepare particles, and in particular nanoparticles, the size of which is nanometric or which have at least one dimension less than 100 nm.
De manière plus préférée, les particules, et en particulier les nanoparticules, préparées selon l'invention ont une taille allant de 2 à 100 nm ; ou allant de 5 à 90 nm ; ou allant de 10 à 80 nm ; ou allant de 50 à 300 nm ; ou allant de 50 à 200 nm ; ou allant de 50 à 120 nm ; ou allant de 10 à 100 nm ; ou allant de 60 à 100 nm.
Selon une autre variante, le troisième composé est obtenu sous forme de particules, par exemple dont au moins une dimension est inférieure à 100 nm, de préférence la plus grande dimension allant de 5 à 100 nm, plus préférentiellement allant de 10 à 30 nm. More preferably, the particles, and in particular the nanoparticles, prepared according to the invention have a size ranging from 2 to 100 nm; or ranging from 5 to 90 nm; or ranging from 10 to 80 nm; or ranging from 50 to 300 nm; or ranging from 50 to 200 nm; or ranging from 50 to 120 nm; or ranging from 10 to 100 nm; or ranging from 60 to 100 nm. According to another variant, the third compound is obtained in the form of particles, for example at least one dimension of which is less than 100 nm, preferably the largest dimension ranging from 5 to 100 nm, more preferably ranging from 10 to 30 nm.
Les particules de l’invention peuvent comprendre à titre d’exemple des composés semi-conducteurs, et/ou des co-cristaux ou composites, avantageusement dopés. The particles of the invention can comprise, for example, semiconductor compounds, and / or co-crystals or composites, advantageously doped.
Les composés de l’invention peuvent également comprendre des matériaux fluorescents, en particulier pour des applications médicales, thérapeutiques ou de diagnostic, comme par exemple en radiologie, sans aucune limitation. The compounds of the invention may also comprise fluorescent materials, in particular for medical, therapeutic or diagnostic applications, such as for example in radiology, without any limitation.
Les composés de l’invention peuvent également comprendre des composés actifs d’un point de vue pharmaceutique, notamment pour la préparation de médicaments ou des applications pharmaceutiques ou thérapeutiques. De tels composés, notamment sous forme de particules, permettent notamment d’améliorer la biocompatibilité, la biodisponibilité et l’assimilation corporelle. The compounds of the invention may also comprise compounds which are active from a pharmaceutical point of view, in particular for the preparation of medicaments or pharmaceutical or therapeutic applications. Such compounds, in particular in the form of particles, make it possible in particular to improve biocompatibility, bioavailability and bodily assimilation.
Dans le domaine médical, l’invention permet d’augmenter le pouvoir traçant pour le diagnostic, en particulier en radiologie et en imagerie médicale en général. In the medical field, the invention makes it possible to increase the tracing power for diagnosis, in particular in radiology and medical imaging in general.
Les composés de l’invention, notamment sous forme de particules, peuvent également comprendre des matériaux de catalyse, comme par exemple des matériaux pour la catalyse hétérogène, notamment pour des applications dans la pétrochimie à titre d’exemple, sans être limitatif. The compounds of the invention, in particular in the form of particles, can also comprise catalysis materials, such as, for example, materials for heterogeneous catalysis, in particular for applications in petrochemistry by way of example, without being limiting.
L’invention est encore particulièrement adaptée dans le domaine de l’élaboration de semi-conducteurs à bande interdite adaptée et ajustée pour augmenter le rendement des systèmes photocatalytiques ou de photoconversion. The invention is also particularly suitable in the field of the production of forbidden band semiconductors adapted and adjusted to increase the efficiency of photocatalytic or photoconversion systems.
Dans le domaine pharmaceutique, l’invention permet l’élaboration de matériaux possédant une biocompatibilité améliorée, et par exemple l’enrobage de substances toxiques ou dont la toxicité est à diminuer par au moins une écorce ou couche superficielle biocompatible. Ainsi la présente invention est particulièrement avantageuse en chimiothérapie afin de limiter la toxicité des composés utilisés. In the pharmaceutical field, the invention allows the development of materials having improved biocompatibility, and for example the coating of toxic substances or whose toxicity is to be reduced by at least one bark or biocompatible surface layer. Thus the present invention is particularly advantageous in chemotherapy in order to limit the toxicity of the compounds used.
La présente invention permet également la préparation de particules multicouches. The present invention also allows the preparation of multilayer particles.
Par « particules multicouches », on entend une particule comprenant un cœur (appelé aussi « noyau ») et au moins une couche en surface du cœur. La surface du cœur est de préférence totalement recouverte d’une couche. Ainsi les particules de l’invention concernent des particules comprenant un cœur et une couche superficielle recouvrant, de préférence totalement, la surface du cœur. La présente invention concerne également des particules, en particulier des nanoparticules, comprenant un cœur et plusieurs couches superficielles disposées de manière concentrique.
L’un ou les deux parmi le cœur et une ou plusieurs couches superficielles peuvent être obtenus par réaction d’au moins un premier composé et deuxième composé. Ainsi, selon un mode de réalisation, on peut enrober le troisième composé synthétisé par une ou plusieurs couches superficielles. Selon un mode de réalisation, on peut enrober un ou plusieurs composés par une ou plusieurs couches superficielles comprenant un ou plusieurs troisièmes composés synthétisés. Dans l’ensemble des variantes, modes de réalisation, préférés ou avantageux, chaque couche peut être constituée indépendamment des autres couches d’un ou plusieurs composés, le ou les composés d’une couche pouvant être différents de celui ou ceux d’une autre couche. The term “multilayer particles” means a particle comprising a core (also called a “core”) and at least one layer on the surface of the core. The surface of the heart is preferably completely covered with a layer. Thus, the particles of the invention relate to particles comprising a core and a surface layer covering, preferably completely, the surface of the core. The present invention also relates to particles, in particular nanoparticles, comprising a core and several surface layers arranged concentrically. One or both of the core and one or more surface layers can be obtained by reacting at least a first compound and a second compound. Thus, according to one embodiment, the third compound synthesized can be coated with one or more surface layers. According to one embodiment, one or more compounds can be coated with one or more surface layers comprising one or more third synthesized compounds. In all of the variants, embodiments, preferred or advantageous, each layer can be constituted independently of the other layers of one or more compounds, the compound (s) of a layer possibly being different from that or those of another layer.
L’invention concerne également des particules de type hybride organique/inorganique ou organique/métallique. The invention also relates to particles of the organic / inorganic or organic / metallic hybrid type.
L’invention concerne en outre spécifiquement des particules susceptibles d’être obtenues par un procédé tel que décrit selon l’invention, lesdites particules comprenant au moins un troisième composé synthétisé. The invention also relates specifically to particles capable of being obtained by a process as described according to the invention, said particles comprising at least a third compound synthesized.
Selon une variante, le procédé comprend la formation de particules comprenant ledit troisième composé, lesdites particules étant sous forme liquide, solide ou gazeuse. According to a variant, the method comprises the formation of particles comprising said third compound, said particles being in liquid, solid or gaseous form.
L’invention concerne plus spécifiquement un procédé comprenant : The invention relates more specifically to a process comprising:
(a) la préparation d’une phase liquide comprenant le premier composé et le deuxième composé pour former une composition liquide atomisable ; (a) the preparation of a liquid phase comprising the first compound and the second compound to form a liquid atomizable composition;
(b) le chauffage de la composition liquide à une pression P1 supérieure à la pression atmosphérique, de préférence P1 allant de 3 à 300 bars, le chauffage étant réalisé à une température supérieure au point d’ébullition de la phase liquide ; (b) heating the liquid composition at a pressure P1 higher than atmospheric pressure, preferably P1 ranging from 3 to 300 bars, the heating being carried out at a temperature above the boiling point of the liquid phase;
(c) l’atomisation de la composition liquide comprenant le premier composé et le deuxième composé, l’atomisation étant de préférence réalisée dans une chambre d’atomisation au moyen d’un dispositif de dispersion à une pression P2 inférieure à P1 , de préférence P2 allant de 0,0001 à 2 bars ; (c) atomizing the liquid composition comprising the first compound and the second compound, the atomization preferably being carried out in an atomization chamber by means of a dispersing device at a pressure P2 lower than P1, preferably P2 ranging from 0.0001 to 2 bars;
(d) l’obtention dudit troisième composé par réaction du premier composé et du deuxième composé, et (d) obtaining said third compound by reaction of the first compound and the second compound, and
(e) éventuellement, la séparation du troisième composé de la phase liquide. (e) optionally, the separation of the third compound from the liquid phase.
La séparation des liquides des composés synthétisés, notamment sous forme de particules, se produit avantageusement lors de l’atomisation. The separation of liquids from the synthesized compounds, in particular in the form of particles, advantageously occurs during atomization.
Selon une variante, le procédé comprend : According to a variant, the method comprises:
(a) la préparation d’une première phase liquide comprenant le premier composé pour former une première composition liquide disposée dans un premier réservoir, et la préparation d’une deuxième phase liquide comprenant le deuxième composé formant une deuxième composition liquide disposée dans un deuxième réservoir ;
(b) le chauffage de la première composition, sous une pression P1 , à une température supérieure au point d’ébullition du liquide, et le chauffage de la deuxième composition sous une pression P1’, de préférence P1 et P1’, égales ou différentes, sont supérieures à la pression atmosphérique, de préférence encore, P1 et P1’ vont, indépendamment l’une de l’autre, de 3 à 300 bars, le chauffage de chaque composition liquide étant réalisé à une température supérieure au point d’ébullition respectivement de la phase liquide considérée; et (a) the preparation of a first liquid phase comprising the first compound to form a first liquid composition placed in a first tank, and the preparation of a second liquid phase comprising the second compound forming a second liquid composition placed in a second tank ; (b) heating the first composition, under a pressure P1, to a temperature higher than the boiling point of the liquid, and heating the second composition under a pressure P1 ', preferably P1 and P1', equal or different , are greater than atmospheric pressure, more preferably, P1 and P1 'range, independently of one another, from 3 to 300 bars, the heating of each liquid composition being carried out at a temperature above the boiling point respectively of the liquid phase considered; and
(c) l'atomisation simultanée des première et deuxième compositions chauffées sous pression, dans une chambre d’atomisation au moyen d’au moins un dispositif de dispersion sous une pression P2 inférieure à P1 , de préférence allant de 0,0001 à 2 bars, ladite dispersion étant réalisée de préférence sous chauffage, de préférence à une température comprise entre 20°C et 2000°C ; (c) the simultaneous atomization of the first and second compositions heated under pressure, in an atomization chamber by means of at least one dispersion device under a pressure P2 less than P1, preferably ranging from 0.0001 to 2 bars said dispersion preferably being carried out under heating, preferably at a temperature between 20 ° C and 2000 ° C;
(d) l’obtention dudit troisième composé par réaction du premier composé et du deuxième composé, et (d) obtaining said third compound by reaction of the first compound and the second compound, and
(e) éventuellement, la séparation dudit troisième composé des phases liquides. (e) optionally, the separation of said third compound from the liquid phases.
Selon une autre variante, le premier composé et/ou le deuxième composé sont indépendamment liquides ou solides ou gazeux. According to another variant, the first compound and / or the second compound are independently liquid or solid or gaseous.
Selon une autre variante, indépendamment, la première et la deuxième phase liquide comprennent ou sont constituées respectivement du premier composé sous forme liquide, éventuellement après dissolution dans un solvant, ou sous forme solide dispersée dans un solvant, et/ou du deuxième composé sous forme liquide, éventuellement après dissolution dans un solvant, ou sous forme solide dispersée dans un solvant, les solvants des première et deuxième phases liquides pouvant être identiques ou différents. According to another variant, independently, the first and the second liquid phase comprise or consist respectively of the first compound in liquid form, optionally after dissolution in a solvent, or in solid form dispersed in a solvent, and / or of the second compound in form liquid, optionally after dissolving in a solvent, or in solid form dispersed in a solvent, the solvents of the first and second liquid phases possibly being identical or different.
Selon une variante, le procédé comprend la dispersion ou dissolution du premier composé solide dans un premier liquide. Alternatively, the method includes dispersing or dissolving the first solid compound in a first liquid.
Selon une variante, le procédé comprend la dispersion ou dissolution du deuxième composé solide dans un deuxième liquide. Alternatively, the method includes dispersing or dissolving the second solid compound in a second liquid.
Selon une variante, les premier et deuxième liquides sont différents ou identiques. Selon une variante, le premier composé sous forme liquide constitue la première composition fluide. According to a variant, the first and second liquids are different or identical. According to a variant, the first compound in liquid form constitutes the first fluid composition.
Selon une variante, le deuxième composé sous forme liquide constitue la deuxième composition fluide. According to a variant, the second compound in liquid form constitutes the second fluid composition.
Avantageusement, la réaction est mise en œuvre dans des conditions de pression et température d’obtention du troisième composé sous forme solide. Advantageously, the reaction is carried out under pressure and temperature conditions for obtaining the third compound in solid form.
Selon une variante, le dispositif ou procédé de l’invention met en œuvre un fluide polyphasique comprenant des particules dispersées dans une phase liquide de manière à
former le ou les troisièmes composés synthétisés, de préférence sous forme de particules micrométriques, submicrométriques ou nanométriques. According to a variant, the device or method of the invention uses a multiphase fluid comprising particles dispersed in a liquid phase so as to forming the third or more synthesized compounds, preferably in the form of micrometric, submicrometric or nanometric particles.
Selon une variante, le procédé de l’invention met en oeuvre un fluide monophasique comprenant des particules dispersées dans une phase liquide de manière à former le ou les troisièmes composés synthétisés, de préférence sous forme de particules micrométriques, submicrométriques ou nanométriques. According to a variant, the method of the invention uses a monophasic fluid comprising particles dispersed in a liquid phase so as to form the third compound (s) synthesized, preferably in the form of micrometric, submicrometric or nanometric particles.
Selon une variante, la première composition comprenant le premier composé solide forme un fluide monophasique. According to a variant, the first composition comprising the first solid compound forms a monophasic fluid.
Selon une variante, la première composition contient une solution d’isopropanolate de titane (TTIP) dans l’isopropanol, et permet avantageusement l’obtention de dioxyde de titane ou de titanates, par exemple de titanate de bismuth. According to a variant, the first composition contains a solution of titanium isopropanolate (TTIP) in isopropanol, and advantageously makes it possible to obtain titanium dioxide or titanates, for example bismuth titanate.
Selon une variante, la première composition comprenant le premier composé solide forme un fluide polyphasique. According to a variant, the first composition comprising the first solid compound forms a multiphase fluid.
Selon une variante, la deuxième composition comprenant le deuxième composé solide forme un fluide monophasique. According to a variant, the second composition comprising the second solid compound forms a monophasic fluid.
Selon une variante, la deuxième composition comprenant le deuxième composé solide forme un fluide polyphasique. According to a variant, the second composition comprising the second solid compound forms a multiphase fluid.
Au sens de l’invention, on entend par « liquide » en particulier un liquide comprenant éventuellement une ou plusieurs dispersions solides et/ou un ou plusieurs gaz. Within the meaning of the invention, the term “liquid” in particular means a liquid optionally comprising one or more solid dispersions and / or one or more gases.
Au sens de l’invention, on entend par « fluide » en particulier un liquide comprenant éventuellement une dispersion solide. Dans l’invention ce terme « fluide » ne couvre pas un gaz dans lequel seraient dispersées des particules solides. Within the meaning of the invention, the term "fluid" in particular a liquid optionally comprising a solid dispersion. In the invention, this term "fluid" does not cover a gas in which solid particles are dispersed.
Par la présente invention, on désigne par fluide polyphasique un fluide comprenant une ou plusieurs phases non miscibles telles que par exemple une phase liquide et une phase solide ou deux phases liquides non miscibles. By the present invention, the term “multiphase fluid” denotes a fluid comprising one or more immiscible phases such as for example a liquid phase and a solid phase or two immiscible liquid phases.
Selon une variante, le fluide polyphasique est constitué d’une phase liquide et d’au moins une phase solide de préférence dispersée sous la forme de particules et typiquement sous la forme de nano-particules. Alternatively, the multiphase fluid consists of a liquid phase and at least one solid phase preferably dispersed in the form of particles and typically in the form of nanoparticles.
Selon une variante, le fluide polyphasique est constitué d’une phase liquide et de plusieurs solides de préférence dispersés sous la forme de particules et typiquement sous la forme de nano-particules. According to a variant, the multiphase fluid consists of a liquid phase and of several solids preferably dispersed in the form of particles and typically in the form of nanoparticles.
Selon une variante, le fluide polyphasique est constitué de deux phases liquides. According to a variant, the multiphase fluid consists of two liquid phases.
Selon une variante, le fluide polyphasique est constitué de plusieurs phases liquides et de plusieurs phases solides, de préférence dispersées dans une ou plusieurs phases liquides sous la forme de particules, et typiquement sous la forme de
nanoparticules, lesdites phases solides pouvant être dispersées dans des phases liquides différentes. According to a variant, the multiphase fluid consists of several liquid phases and of several solid phases, preferably dispersed in one or more liquid phases in the form of particles, and typically in the form of nanoparticles, said solid phases possibly being dispersed in different liquid phases.
Par « phase liquide », on désigne une phase liquide comprenant un ou plusieurs composés liquides. Un composé est défini comme « composé liquide » notamment lorsqu’il est liquide à température et pression dans les conditions après obtention du fluide polyphasique. Selon une variante, le composé est liquide à température et pression ambiantes, c’est-à-dire à 25°C et 101325 Pa. By "liquid phase" is meant a liquid phase comprising one or more liquid compounds. A compound is defined as "liquid compound" especially when it is liquid at temperature and pressure under the conditions after obtaining the multiphase fluid. According to a variant, the compound is liquid at ambient temperature and pressure, that is to say at 25 ° C. and 101325 Pa.
Parmi les composés liquides, on peut citer notamment les agents solvants ou dispersants des premier et/ou deuxième composés utilisés dans le cadre de la présente invention. Lorsque le procédé de l’invention comprend le chauffage des première et deuxième compositions, le chauffage des première et deuxième compositions peut être simultané ou indépendant. Among the liquid compounds, mention may in particular be made of the solvent or dispersing agents of the first and / or second compounds used in the context of the present invention. When the process of the invention comprises heating the first and second compositions, the heating of the first and second compositions can be simultaneous or independent.
Selon une variante spécifique, le procédé de l’invention comprend les étapes suivantes : According to a specific variant, the method of the invention comprises the following steps:
- la dispersion d’au moins un composé solide organique ou minéral dans un liquide, - the dispersion of at least one solid organic or mineral compound in a liquid,
- la dissolution d’au moins un composé organique ou minéral dans un liquide, les liquides comprenant le composé dispersé ou le composé dissous pouvant être identiques ou différents, - the dissolution of at least one organic or inorganic compound in a liquid, the liquids comprising the dispersed compound or the dissolved compound possibly being identical or different,
- le chauffage simultané ou indépendant, sous pression, des liquides comprenant le composé dispersé et le composé dissous, - simultaneous or independent heating, under pressure, of liquids comprising the dispersed compound and the dissolved compound,
- l’atomisation des liquides comprenant le composé dispersé et le composé dissous, - atomization of liquids comprising the dispersed compound and the dissolved compound,
- l’obtention de particules, et notamment de nanoparticules, et - obtaining particles, and in particular nanoparticles, and
- la séparation des nanoparticules obtenues des liquides. - separation of the nanoparticles obtained from liquids.
Le procédé selon l'invention est avantageusement mis en oeuvre de manière continue ou de manière semi-continue. De préférence, il est mis en oeuvre de manière continue. The process according to the invention is advantageously carried out continuously or semi-continuously. Preferably, it is implemented continuously.
De manière également préférée, le procédé selon l'invention comprend la préparation d’au moins deux phases, une première phase liquide comprenant au moins un composé liquide, appelé premier composé liquide, et au moins un composé solide, organique, minéral ou organométallique, appelé premier composé solide, et une deuxième phase liquide comprenant au moins un composé liquide, appelé deuxième composé liquide, et au moins un composé, organique, minéral ou organométallique, appelé deuxième composé solide, dissous dans la phase liquide. Ces phases liquides peuvent chacune indépendamment comprendre plusieurs de ces composés.
Selon une variante, le procédé comprend la préparation de particules comprenant une ou plusieurs couches entourant un cœur. On peut par exemple préparer de telles particules par itération du procédé selon l’invention en réutilisant les particules formées par le procédé, c’est-à-dire que les particules formées par le procédé de l’invention subissent une nouvelle fois le procédé de l’invention pour déposer en surface au moins une nouvelle couche superficielle avec ou sans réaction de synthèse d’un nouveau troisième composé. Ainsi les particules dispersées dans l’étape a) peuvent être elles- mêmes des particules à enrober par une ou plusieurs couches. Selon cette variante à chaque mise en œuvre du procédé de l’invention, une ou plusieurs couches superficielles additionnelles sont déposées sur les particules. Also preferably, the method according to the invention comprises the preparation of at least two phases, a first liquid phase comprising at least one liquid compound, called the first liquid compound, and at least one solid, organic, mineral or organometallic compound, called first solid compound, and a second liquid phase comprising at least one liquid compound, called second liquid compound, and at least one compound, organic, inorganic or organometallic, called second solid compound, dissolved in the liquid phase. These liquid phases can each independently comprise several of these compounds. According to a variant, the method comprises the preparation of particles comprising one or more layers surrounding a heart. One can for example prepare such particles by iteration of the process according to the invention by reusing the particles formed by the process, that is to say that the particles formed by the process of the invention again undergo the process of the invention for depositing on the surface at least one new surface layer with or without synthesis reaction of a new third compound. Thus, the particles dispersed in step a) can themselves be particles to be coated with one or more layers. According to this variant at each implementation of the method of the invention, one or more additional surface layers are deposited on the particles.
Selon une variante, le procédé comprend la préparation de particules comprenant plusieurs couches entourant le cœur des particules en mettant en œuvre des composés présentant des solubilités différentes dans les liquides dans lesquels ils sont dissous. Par exemple, lorsque les solubilités sont suffisamment différentes, le composé le moins soluble est déposé en premier sur la surface des particules puis le composé le plus soluble est déposé en surface de la couche du composé (le moins soluble) déjà déposé en surface des particules. According to a variant, the method comprises the preparation of particles comprising several layers surrounding the core of the particles by using compounds having different solubilities in the liquids in which they are dissolved. For example, when the solubilities are sufficiently different, the least soluble compound is deposited first on the surface of the particles and then the most soluble compound is deposited on the surface of the layer of the compound (the least soluble) already deposited on the surface of the particles. .
Selon une variante, le procédé comprend la dispersion d’un composé destiné à former le cœur des particules dans un premier liquide comprenant un composé destiné à former une première couche de surface et la dissolution dans un seconde liquide d’un composé destiné à former une deuxième couche de surface. De préférence, la solubilité dans le second liquide du composé destiné à former la deuxième couche de surface est plus élevée que la solubilité dans le premier liquide le composé destiné à former la première couche de surface. Alternatively, the method comprises dispersing a compound intended to form the core of the particles in a first liquid comprising a compound intended to form a first surface layer and dissolving in a second liquid a compound intended to form a second surface layer. Preferably, the solubility in the second liquid of the compound intended to form the second surface layer is higher than the solubility in the first liquid the compound intended to form the first surface layer.
Selon une variante, le procédé comprend la préparation de particules cristallines comprenant plusieurs cristaux, appelés co-cristaux. According to a variant, the method comprises the preparation of crystalline particles comprising several crystals, called co-crystals.
Le choix du ou des liquides peut notamment être adapté en fonction du composé à disperser ou du composé à dissoudre. The choice of liquid (s) can in particular be adapted according to the compound to be dispersed or the compound to be dissolved.
De manière préférée, le chauffage de la composition ou des compositions fluides est, indépendamment, effectué sous une pression allant de 5 à 150 bars, de préférence allant de 10 à 60 bars. Preferably, the heating of the composition or of the fluid compositions is, independently, carried out under a pressure ranging from 5 to 150 bars, preferably ranging from 10 to 60 bars.
Comme solvant, on peut citer les alcanes, par exemple le pentane (PE= 36°C) le cyclopentane (PE= 49°C) ou l’hexane (PE= 68°C) rajouter aussi le cyclohexane (PE= 81 °C) ; les acides organiques (comme par exemple l’acide formique, l’acide oxalique, ou l’acide trifluoroacétique) ; l’eau (PE= 100°C)les alcools, par exemple le méthanol (PE= 65°C) ou l’éthanol (PE= 78-79°C) ; les thiols, par exemple l’éthane-thiol (PE= 35°C) ; les
aldéhydes, par exemple l’éthanal (PE= 20°C) ou l’aldéhyde propionique (PE= 48°C) ; les cétones, par exemple l’acétone (PE= 56°C) ; les éthers, le méthylal (Diméthoxyméthane, PE= 42°C), par exemple le méthyl-tert-butyl éther (PE= 55°C) ou le tetrahydrofurane (PE= 66°C) ; les esters d’acides, notamment les esters d’acide formique, par exemple le formiate de méthyle (PE= 32°C), les esters d’acide acétique, par exemple l’acétate de méthyle (PE= 57-58°C) ; les amines, par exemple la triméthylamine (PE= 2-3°C), les hydrocarbures halogénés ; et de manière plus générale les liquides et mélanges azéotropiques. As solvent, mention may be made of alkanes, for example pentane (PE = 36 ° C) cyclopentane (PE = 49 ° C) or hexane (PE = 68 ° C) also add cyclohexane (PE = 81 ° C ); organic acids (such as, for example, formic acid, oxalic acid, or trifluoroacetic acid); water (PE = 100 ° C) alcohols, for example methanol (PE = 65 ° C) or ethanol (PE = 78-79 ° C); thiols, for example ethane-thiol (PE = 35 ° C); the aldehydes, for example ethanal (PE = 20 ° C) or propionic aldehyde (PE = 48 ° C); ketones, for example acetone (PE = 56 ° C); ethers, methylal (Dimethoxymethane, PE = 42 ° C), for example methyl-tert-butyl ether (PE = 55 ° C) or tetrahydrofuran (PE = 66 ° C); acid esters, especially formic acid esters, for example methyl formate (PE = 32 ° C), acetic acid esters, for example methyl acetate (PE = 57-58 ° C ); amines, for example trimethylamine (PE = 2-3 ° C), halogenated hydrocarbons; and more generally azeotropic liquids and mixtures.
Avantageusement, la composition comprenant le composé solide dispersé comprend également au moins un agent dispersant. Advantageously, the composition comprising the solid dispersed compound also comprises at least one dispersing agent.
De manière préférée, le procédé selon l’invention comprend une étape finale de récupération des composés synthétisés, notamment sous forme de particules. Avantageusement, la récupération des particules est réalisée au moyen d’un ou plusieurs dispositifs de rétention des particules choisis parmi un séparateur électrostatique, un cyclone, un cyclone comprenant un dispositif électrostatique et les filtres (treillis métalliques, mousses, frittés, etc...). Ainsi, selon une variante, le procédé comprend la récupération finale de particules comprenant le troisième composé synthétisé, par exemple au moyen d’un ou plusieurs dispositifs de rétention des particules choisi parmi un filtre, un séparateur électrostatique, un cyclone, un cyclone comprenant un dispositif électrostatique et un filtre. Preferably, the method according to the invention comprises a final step of recovery of the synthesized compounds, in particular in the form of particles. Advantageously, the recovery of the particles is carried out by means of one or more particle retention devices chosen from an electrostatic separator, a cyclone, a cyclone comprising an electrostatic device and the filters (metal mesh, foams, sintered, etc.). ). Thus, according to a variant, the method comprises the final recovery of particles comprising the third compound synthesized, for example by means of one or more particle retention devices chosen from a filter, an electrostatic separator, a cyclone, a cyclone comprising a electrostatic device and a filter.
Les conditions de mise en oeuvre du procédé selon l'invention peuvent varier assez largement, notamment en fonction des composés synthétisés, par exemple formant les particules ou bien en fonction des liquides utilisés. The conditions for implementing the process according to the invention can vary quite widely, in particular as a function of the compounds synthesized, for example forming the particles or else as a function of the liquids used.
La présente invention concerne en particulier un procédé de synthèse hors- équilibre d’un troisième composé à partir d’un premier composé et d’un deuxième composé par réaction du premier composé et du deuxième composé entre eux en mettant en oeuvre un dispositif ou procédé de SFE. The present invention relates in particular to a method of out-of-equilibrium synthesis of a third compound from a first compound and a second compound by reaction of the first compound and the second compound with one another using a device or method from SFE.
De manière avantageuse, le chauffage des compositions est effectué sous une pression allant de 5 à 150 bars ou allant de 10 à 60 bars. Lors de la mise en oeuvre de plusieurs solutions, le chauffage respectif de chaque solution peut être effectué sous une pression allant de 5 à 150 bars ou allant de 10 à 60 bars qui peut être identique ou différente pour chaque composition. Advantageously, the heating of the compositions is carried out under a pressure ranging from 5 to 150 bars or ranging from 10 to 60 bars. During the implementation of several solutions, the respective heating of each solution can be carried out under a pressure ranging from 5 to 150 bars or ranging from 10 to 60 bars which can be identical or different for each composition.
De manière également avantageuse, la réaction est réalisée avec un chauffage de la composition ou des compositions fluides, indépendamment ou dépendamment, de préférence sous pression d’un gaz inerte. Selon une variante, le chauffage des
compositions est effectué sous pression d’un gaz inerte choisi parmi l’azote, l’argon, l’hélium, le néon, le xénon, SF6, CFC, etc. Also advantageously, the reaction is carried out with heating of the composition or fluid compositions, independently or depending, preferably under pressure of an inert gas. Alternatively, the heating of compositions is carried out under pressure of an inert gas chosen from nitrogen, argon, helium, neon, xenon, SF 6 , CFC, etc.
Selon une variante, le chauffage des compositions est effectué sous pression d’un ou plusieurs gaz réactifs. Par exemple le gaz réactif peut constituer le premier et/ou le deuxième composé et participer à la réaction de synthèse du troisième composé. According to a variant, the heating of the compositions is carried out under pressure of one or more reactive gases. For example, the reactive gas can constitute the first and / or the second compound and participate in the synthesis reaction of the third compound.
Typiquement, l’atomisation de la composition ou des compositions est, indépendamment, réalisée à une pression allant de 0,001 à moins de 1 bars, de préférence de 0,02 à 0,2 bars, et/ou sous un angle de 60 à 80°. Typically, the atomization of the composition or compositions is, independently, carried out at a pressure ranging from 0.001 to less than 1 bar, preferably from 0.02 to 0.2 bar, and / or at an angle of 60 to 80 °.
Selon une variante, la pression de la chambre d’atomisation (P2) est 10 fois, de préférence 100 fois, de préférence encore 1000 fois, voire 10000 fois, inférieure à la surpression appliquée lors du chauffage (P1 ). According to a variant, the pressure of the atomization chamber (P2) is 10 times, preferably 100 times, preferably still 1000 times, or even 10,000 times, lower than the overpressure applied during heating (P1).
Le dispositif de dispersion mis en œuvre lors de l’atomisation des compositions est avantageusement choisi parmi une buse à cône creux, une buse à cône plein, une buse à jet plat, une buse à jet rectiligne, un atomiseur pneumatique et leurs associations. Une buse à cône creux est particulièrement avantageuse. The dispersing device used during the atomization of the compositions is advantageously chosen from a hollow cone nozzle, a solid cone nozzle, a flat jet nozzle, a rectilinear jet nozzle, a pneumatic atomizer and their combinations. A hollow cone nozzle is particularly advantageous.
De manière générale, l'atomisation peut être effectuée sous un angle pouvant varier très largement, et de préférence sous un angle allant de 30 à 150°. On peut également citer une gamme d'angle d'atomisation allant de 60 à 80°. In general, the atomization can be carried out at an angle which can vary very widely, and preferably at an angle ranging from 30 to 150 °. We can also cite a range of atomization angles from 60 to 80 °.
Ces conditions s'appliquent également lors de l'atomisation d'au moins deux compositions. These conditions also apply when atomizing at least two compositions.
L'invention concerne également un dispositif permettant la mise en œuvre du procédé. The invention also relates to a device allowing the implementation of the method.
A titre d'information quelques exemples de points d'amélioration que permet le dispositif et le procédé selon l’invention : For information, some examples of improvement points that allow the device and the method according to the invention:
1 ) Une augmentation des rendements des réactions de synthèse telles gue les estérifications. Ces réactions, qui consistent à faire réagir des alcools avec des acides, sont souvent limitées à des rendements de 60%, voire moins selon notamment la nature de l’alcool. Le dispositif et le procédé selon l’invention augmentent fortement le rendement réactionnel. 1) An increase in the yields of synthesis reactions such as esterifications. These reactions, which consist in reacting alcohols with acids, are often limited to yields of 60%, or even less depending in particular on the nature of the alcohol. The device and method according to the invention greatly increase the reaction yield.
2) La synthèse de polymères conducteurs comme la polyaniline, pure ou dans des nanocomposites. 2) The synthesis of conductive polymers such as polyaniline, pure or in nanocomposites.
3) La synthèse de nitrocellulose (nitration de cellulose). Le dispositif et le procédé selon l’invention permettent l'obtention d'une molécule de nitrocellulose plus stable dans le temps contrairement à des techniques existantes qui mélangent souvent des phases solides et liquides. Le dispositif et le procédé selon l’invention améliorent les problèmes
d'instabilité des nitrocelluloses bassement nitrées (vernis) ou fortement nitrées (poudres propulsives) et ne nécessite plus l'utilisation de stabilisants pour éviter la dégradation de ces dernières comme par exemple les décompositions hasardeuses qui peuvent conduire à des explosions dangereuses dans le cas des nitrocelluloses plus fortement nitrées.3) The synthesis of nitrocellulose (cellulose nitration). The device and the method according to the invention make it possible to obtain a nitrocellulose molecule which is more stable over time, unlike existing techniques which often mix solid and liquid phases. The device and method according to the invention improve the problems instability of nitrocelluloses which are weakly nitrated (varnish) or highly nitrated (propellant powders) and no longer requires the use of stabilizers to avoid degradation of the latter, for example hazardous decompositions which can lead to dangerous explosions in the case of more highly nitrated nitrocelluloses.
4) Les réactions de nitration de molécules où les sites visés sont relativement stériquement encombrés. Ces réactions menées sur de grandes quantités, connaissent souvent des retards à la nitration, et peuvent s'emballer ensuite très vite lorsque de grandes quantités sont présentes et lorsque la réaction de nitration se fait alors instantanément. La réaction de nitration permise par le dispositif et le procédé selon l’invention, notamment en continu, et localement sur de très petites quantités, évite les retards, et augmente très fortement la sécurité des nitrations. 4) Nitration reactions of molecules where the targeted sites are relatively sterically congested. These reactions carried out on large quantities, often experience delays in nitration, and can then get carried away very quickly when large quantities are present and when the nitration reaction then takes place instantaneously. The nitration reaction allowed by the device and the method according to the invention, in particular continuously, and locally on very small quantities, avoids delays, and very greatly increases the safety of nitrations.
5) La synthèse de MOF (« Métal Organic Frameworks ») en utilisant une ou plusieurs buses de nébulisation. 5) The synthesis of MOF (“Metal Organic Frameworks”) using one or more nebulization nozzles.
6) Les réactions de synthèse de différents oxydes ou de mélanges d'oxydes par l'utilisation d'une ou de plusieurs buses de nébulisation. Ici on donne les exemples comme Ti02, ZnO, Fe203, W03, Bi203, etc, y compris des oxydes complexes. L'avantage d’un dispositif et du procédé selon l’invention est ici à la fois de produire en continu de très petites tailles de particules, souvent jamais atteintes auparavant, mais également d'être en mesure de les obtenir à l'état cristallin ciblé après leur calcination par passage au travers d'une buse chauffée (chauffage des particules formées par l’évaporation flash (micro-ondes, flash lumineux, etc....) à la température adaptée au type de composé.6) Synthesis reactions of different oxides or mixtures of oxides by the use of one or more nebulization nozzles. Here we give examples like Ti0 2 , ZnO, Fe 2 0 3 , W0 3 , Bi 2 0 3 , etc, including complex oxides. The advantage of a device and method according to the invention is here both to continuously produce very small particle sizes, often never reached before, but also to be able to obtain them in the crystalline state. targeted after their calcination by passage through a heated nozzle (heating of the particles formed by flash evaporation (microwave, light flash, etc.) at the temperature suitable for the type of compound.
7) La synthèse d'autres céramiques ou matériaux carbonés comme C3N4 ou de mélanges notamment au travers de la décomposition thermique de différents précurseurs, ceci par l'utilisation d'une seule buse ou de plusieurs buses. 7) The synthesis of other ceramics or carbonaceous materials such as C 3 N 4 or of mixtures in particular through the thermal decomposition of different precursors, this by the use of a single nozzle or of several nozzles.
8) Les réactions acides base (formation d’eau qui s’évapore)) 8) Basic acid reactions (formation of water that evaporates))
9) les réactions de complexation (ligands/centre métallique) 9) complexation reactions (ligands / metal center)
L’invention concerne aussi un composé ou des particules susceptibles d’être obtenues par un procédé selon l’invention. The invention also relates to a compound or particles capable of being obtained by a process according to the invention.
La présente invention permet de produire par exemple des structures de composés synthétisés, notamment sous forme de particules, de manière continue et reproductible, et est dans un sens plus performante que les procédés de type discontinus (Batch) comme la méthode sol-gel. Notamment, la présente invention est beaucoup plus performante en termes de quantité des produits élaborés et de qualité des produits obtenus, notamment en regard de la morphologie, de la pureté, etc.
Le procédé selon la présente invention est plus performant que les techniques continues ou discontinues classiques dans les différents domaines d’applications visés qui sont notamment : The present invention makes it possible to produce, for example, structures of synthesized compounds, in particular in the form of particles, in a continuous and reproducible manner, and is in a sense more efficient than batch type processes (batch) such as the sol-gel method. In particular, the present invention is much more efficient in terms of the quantity of products produced and the quality of the products obtained, in particular with regard to morphology, purity, etc. The process according to the present invention is more efficient than conventional continuous or discontinuous techniques in the various fields of targeted applications which are in particular:
La technique selon la présente invention présente l’avantage de ne traiter qu’une quantité de matière minime à chaque instant, contrairement à la technique discontinue qui implique la totalité de l’échantillon. The technique according to the present invention has the advantage of only treating a minimal quantity of material at any time, unlike the discontinuous technique which involves the entire sample.
Avantageusement, l’invention permet également de fournir un recyclage des liquides utilisés. Advantageously, the invention also makes it possible to provide recycling of the liquids used.
Sur les figures : In the figures:
La figure 1 représente un schéma du dispositif de l’invention pour l’élaboration des composés synthétisés, notamment sous forme de particules. FIG. 1 represents a diagram of the device of the invention for the preparation of the synthesized compounds, in particular in the form of particles.
Un mode de mise en oeuvre d’un dispositif selon l’invention est représenté par la figure 1. Le dispositif est composé de quatre parties principales : un ensemble de deux réservoirs 1 et 1’ pour le stockage sous forte pression des fluides contenant la ou les substances à atomiser, une chambre d’atomisation comprenant deux buses en céramique chauffées 3 intégrées, deux cyclones axiaux 5 montés en parallèle et permettant une production semi-continue, une pompe à vide 6. An embodiment of a device according to the invention is shown in Figure 1. The device is composed of four main parts: a set of two tanks 1 and 1 'for the storage under high pressure of fluids containing the or the substances to be atomized, an atomization chamber comprising two integrated heated ceramic nozzles 3, two axial cyclones 5 mounted in parallel and allowing semi-continuous production, a vacuum pump 6.
Dans les réservoirs 1 et 1’ de 5 L contenant le fluide avec le premier composé ou le deuxième composé, on applique une surpression d’azote comprimé. Dans un premier temps, cette surpression permet de déplacer l’oxygène et empêche l’évaporation du fluide. Le débit volumique dans ce système est induit par la surpression d’azote comprimé. In tanks 1 and 1 ’of 5 L containing the fluid with the first compound or the second compound, an overpressure of compressed nitrogen is applied. At first, this overpressure displaces oxygen and prevents the evaporation of the fluid. The volume flow in this system is induced by the overpressure of compressed nitrogen.
Des filtres 2 et 2’ par exemple de 15 pm retiennent toutes les impuretés solides, ayant une dimension ne permettant pas le passage des filtres, dans le fluide initial. Les filtres permettent le passage du premier composé solide, en général sous la forme de nanoparticules. Filters 2 and 2 ’, for example of 15 pm, retain all the solid impurities, having a dimension which does not allow the passage of the filters, in the initial fluid. The filters allow the passage of the first solid compound, generally in the form of nanoparticles.
Deux buses en céramique à cône creux 3, chacune équipée d'un système de chauffage électrique, sont installées côte à côte dans la chambre d’atomisation. On contrôle les paramètres de pression, de température et de distribution de la taille des particules. Le type de branchement permet un changement rapide des buses. La température du chauffage électrique est choisie par l’utilisateur et régulée automatiquement, notamment pour contrôler la phase cristalline formée. Les buses sont orientées l’une par rapport à l’autre de manière à ce que leurs jets s’interpénétrent. Two ceramic cone nozzles 3, each fitted with an electric heating system, are installed side by side in the atomization chamber. The parameters of pressure, temperature and distribution of the particle size are controlled. The type of connection allows quick change of the nozzles. The temperature of the electric heating is chosen by the user and automatically regulated, in particular to control the crystalline phase formed. The nozzles are oriented relative to each other so that their jets interpenetrate.
Un réservoir ou bac de liquide 4 est rempli avec le même liquide que le réservoir 1 et sert à rincer la conduite et la buse après utilisation. De même, le réservoir ou bac de liquide 4’ est rempli avec le même liquide que le réservoir 1’.
Les cyclones axiaux 5 sont installés en parallèle. Pendant l’opération, seul un cyclone est en service ; le deuxième cyclone est en veille. Grâce à la force centrifuge, les particules solides se déposent à l’intérieur du cyclone, les composants gazeux quittent le cyclone par un tuyau plongeur. Pour vider le cyclone, on ouvre d’abord le circuit conduisant vers le second cyclone, pour ensuite fermer le premier circuit conduisant vers le premier cyclone. A tank or liquid tank 4 is filled with the same liquid as the tank 1 and is used to rinse the pipe and the nozzle after use. Likewise, the tank or liquid tank 4 'is filled with the same liquid as the tank 1'. The axial cyclones 5 are installed in parallel. During the operation, only one cyclone is in service; the second cyclone is on standby. Thanks to the centrifugal force, the solid particles are deposited inside the cyclone, the gaseous components leave the cyclone by a plunger pipe. To empty the cyclone, the circuit leading to the second cyclone is first opened, and then the first circuit leading to the first cyclone is closed.
La pompe à vide 6 assure un écoulement permanent dans l’installation et permet d’extraire les vapeurs de liquides du système. The vacuum pump 6 ensures a permanent flow in the installation and makes it possible to extract the vapors of liquids from the system.
Différents aspects de l'invention sont illustrés par les exemples qui suivent. Different aspects of the invention are illustrated by the following examples.
Figures Figures
La figure 1 est un schéma du dispositif de l’invention pour l’élaboration des composés synthétisés, notamment sous forme de particules. FIG. 1 is a diagram of the device of the invention for the preparation of the synthesized compounds, in particular in the form of particles.
La figure 2 représente des clichés de microscopie électronique à balayage de particules de Ti02 formés par le procédé selon l’invention avant calcination (A, B et C) et après calcination (D, E et F). FIG. 2 represents images of scanning electron microscopy of Ti0 2 particles formed by the method according to the invention before calcination (A, B and C) and after calcination (D, E and F).
La figure 3 représente des clichés de microscope électronique en transmission de particules de titanate de bismuth obtenues par le procédé selon l’invention avant calcination (A et B) et après calcination (C et D). FIG. 3 represents images of an electron microscope in transmission of bismuth titanate particles obtained by the method according to the invention before calcination (A and B) and after calcination (C and D).
La figure 4 est un difractogramme de rayons X réalisé sur une poudre de titanate de bismuth préparée par le procédé selon l’invention et après calcination. FIG. 4 is an X-ray difractogram produced on a bismuth titanate powder prepared by the process according to the invention and after calcination.
Exemples Examples
Exemple 1 : La synthèse de MOFs (Métal Oraanic Frameworks) Example 1: Synthesis of MOFs (Metal Oraanic Frameworks)
Les MOFs ont un grand intérêt dans le stockage d’énergie. MOFs have a great interest in energy storage.
Dans cet exemple, on illustre la synthèse du polymère de coordination (MOF) nommé le « HKUST-1 ». In this example, the synthesis of the coordination polymer (MOF) called "HKUST-1" is illustrated.
La synthèse est réalisée sur une installation selon l’invention comprenant deux buses, qui pulvérisent l’une vers l’autre Une buse pulvérise une solution de Cu(N03)2 d’une concentration de 3,3 grammes par litre d’acétone. La seconde buse pulvérise une solution de BTC (1 ,3,5-BenzeneTriCarboxylic acid) de 1 ,85 grammes par litre d’acétone. The synthesis is carried out on an installation according to the invention comprising two nozzles, which spray towards one another A nozzle sprays a solution of Cu (N0 3 ) 2 with a concentration of 3.3 grams per liter of acetone . The second nozzle sprays a solution of BTC (1, 3.5-BenzeneTriCarboxylic acid) of 1.85 grams per liter of acetone.
Températures des deux buses : 160 °C.
Pressions dans les deux buses : 40 bar. Temperatures of the two nozzles: 160 ° C. Pressures in the two nozzles: 40 bar.
Pression dans la chambre d’atomisation : 7 mbar. La pression réduite est obtenue par une pompe à vide en communication avec la chambre d’atomisation. Pressure in the atomization chamber: 7 mbar. The reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
On obtient par le procédé SFS des fines particules du MOF « HKUST1 » de formule chimique : Fine particles of MOF "HKUST1" of chemical formula are obtained by the SFS process:
Les techniques classiques qui utilisent par exemple l’atomisation (« spray-drying » en anglais) ou une technique en autoclave donnent des particules de taille micrométriques alors que l’invention permet l’obtention de particules de taille inférieure, typiquement dont les particules unitaires ont une plus grande dimension inférieure à 200 nm. Elles peuvent former des agglomérats de plus grande dimension. The conventional techniques which use for example atomization (“spray-drying” in English) or an autoclave technique give particles of micrometric size while the invention allows particles of smaller size to be obtained, typically including unitary particles. have a larger dimension less than 200 nm. They can form larger agglomerates.
Les particules peuvent être préparées en continu par un système ou procédé selon l’invention. The particles can be continuously prepared by a system or process according to the invention.
Exemple 2 : La synthèse de dioxyde de Titane (Ti02). Example 2: The synthesis of Titanium dioxide (Ti0 2 ).
Le Ti02 est très employé en photocatalyse et dans le domaine de l’énergie en général. Dans cet exemple, on illustre synthèse de particules de dioxyde de Titane. Ti0 2 is widely used in photocatalysis and in the energy field in general. In this example, the synthesis of particles of titanium dioxide is illustrated.
La synthèse est réalisée sur une installation selon l’invention comprenant deux buses, qui pulvérisent l’une vers l’autre. Une buse pulvérise une solution à 1 % massique de Tétra Isopropoxyde de Titane (TTIP) dans l’isopropanol. La seconde buse pulvérise de l’eau. Températures des deux buses : 160 °C. The synthesis is carried out on an installation according to the invention comprising two nozzles, which spray towards one another. A nozzle sprays a 1% mass solution of Titanium Tetra Isopropoxide (TTIP) in isopropanol. The second nozzle sprays water. Temperatures of the two nozzles: 160 ° C.
Pressions dans les deux buses : 40 bar. Pressures in the two nozzles: 40 bar.
Pression dans la chambre d’atomisation : 20 mbar. La pression réduite est obtenue par une pompe à vide en communication avec la chambre d’atomisation. Pressure in the atomization chamber: 20 mbar. The reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
On obtient par le procédé SFS selon l’invention de fines particules de Ti02. Fine particles of Ti0 2 are obtained by the SFS process according to the invention.
Les techniques classiques donnent des particules nanométriques. Une installation ou procédé selon l’invention d’obtenir des particules encore plus fines. Il est en général nécessaire de prévoir un précipitateur électrostatique pour récolter ces particules de faible
taille nanométrique (inférieur typiquement à 20nm mesuré par microscopies AFM par exemple). Conventional techniques give nanometric particles. An installation or process according to the invention for obtaining even finer particles. It is generally necessary to provide an electrostatic precipitator to collect these particles of weak nanometric size (typically less than 20nm measured by AFM microscopy for example).
L’invention permet de limiter les impuretés, notamment au regard des procédés de sol-gel classiques. The invention makes it possible to limit impurities, in particular with regard to conventional sol-gel processes.
Exemple 3 : La synthèse de dioxyde de Titane GPO2) par hydrolyse d’un alcoolate. Example 3: The synthesis of Titanium dioxide GPO2) by hydrolysis of an alcoholate.
Un autre exemple est l’hydrolyse de l’isopropanolate de titane (TTIP) pour produire du dioxyde de titane. Another example is the hydrolysis of titanium isopropanolate (TTIP) to produce titanium dioxide.
Pour cela, une première solution composée de TTIP dissous dans de l’isopropanol de grade HPLC est introduite dans l’un des réservoirs à une concentration d’un pourcent en masse; une seconde solution, composée d’isopropanol et d’eau, est placée dans l’autre réservoir. La quantité d’eau introduite est fixée de manière à avoir des ratios molaires TTIP/H2O égaux 1 :1 , 1 :2 et 1 :4. For this, a first solution composed of TTIP dissolved in isopropanol of HPLC grade is introduced into one of the tanks at a concentration of one percent by mass; a second solution, consisting of isopropanol and water, is placed in the other tank. The quantity of water introduced is fixed so as to have TTIP / H2O molar ratios equal to 1: 1, 1: 2 and 1: 4.
Les deux solutions se mélangent dans un dispositif placé en amont de la buse de nébulisation, dont la température est maintenue à 160°C. Le milieu réactionnel est alors injecté dans la chambre d’atomisation. The two solutions are mixed in a device placed upstream from the nebulization nozzle, the temperature of which is maintained at 160 ° C. The reaction medium is then injected into the atomization chamber.
Pressions dans la buse : 40 bar. Pressure in the nozzle: 40 bar.
Pression dans la chambre d’atomisation : 5 à 20 mbar. La pression réduite est obtenue par une pompe à vide en communication avec la chambre d’atomisation. Pressure in the atomization chamber: 5 to 20 mbar. The reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
Les poudres récupérées, sont toutes trois amorphes, composées de particules élémentaires, dont les diamètres moyens, mesurés sur des clichés de microscopie électronique à balayage (Figure 2, A, B et C), sont typiquement submicrométriques. The powders recovered are all three amorphous, composed of elementary particles, the average diameters of which, measured on scanning electron microscopy images (FIG. 2, A, B and C), are typically submicrometric.
La calcination postérieure sous air, à une température de 400°C, durant 4h, fournit des poudres d’anatase (Ti02), formées de particules de diamètres submicrométriques (Figure 2, D, E et F). The posterior calcination in air, at a temperature of 400 ° C, for 4 hours, provides anatase powders (Ti0 2 ), formed of particles of submicrometric diameters (Figure 2, D, E and F).
Les caractéristiques morphologiques et structurales des poudres submicrométriques obtenues par le procédé selon l’invention avant et après calcination sont reprises dans le tableau ci-dessous.
The morphological and structural characteristics of the submicrometric powders obtained by the process according to the invention before and after calcination are listed in the table below.
Exemple 4 : Synthèse de titanates de bismuth Example 4 Synthesis of Bismuth Titanates
Un autre exemple est la synthèse de titanates de bismuth par le procédé selon l’invention. Another example is the synthesis of bismuth titanates by the process according to the invention.
Dans ce cas, une solution de nitrate de bismuth (NB) dans l’acétone, contenant également de l’acide acétique et de l’eau, est placée dans un premier réservoir. Une solution d’isopropanolate de titane (TTIP) dans l’isopropanol est placée dans un second réservoir. Les deux solutions se mélangent dans un dispositif placé en amont de la buse de nébulisation, dont la température est maintenue à 160°C. Le milieu réactionnel est alors injecté dans la chambre d’atomisation. Pressions dans la buse : 40 bar. In this case, a solution of bismuth nitrate (NB) in acetone, also containing acetic acid and water, is placed in a first tank. A solution of titanium isopropanolate (TTIP) in isopropanol is placed in a second tank. The two solutions are mixed in a device placed upstream from the nebulization nozzle, the temperature of which is maintained at 160 ° C. The reaction medium is then injected into the atomization chamber. Pressure in the nozzle: 40 bar.
Pression dans la chambre d’atomisation : 5 à 20 mbar. La pression réduite est obtenue par une pompe à vide en communication avec la chambre d’atomisation. Pressure in the atomization chamber: 5 to 20 mbar. The reduced pressure is obtained by a vacuum pump in communication with the atomization chamber.
Selon le ratio molaire NB/TTIP, différents titanates de bismuth peuvent être produits. Depending on the NB / TTIP molar ratio, different bismuth titanates can be produced.
Les analyses EDX, réalisées dans un microscope électronique en transmission sur un échantillon de titanate produit par le procédé selon l’invention, montrent que les deux éléments métalliques (Ti et Bi) sont mélangés de matière très intime, à une échelle atomique (Figure 3, B). La calcination sous air à 650°C, durant 4h, provoque la formation d’un titanate, avec éventuellement une ségrégation de phases (Figure 3, D), lorsque le titane ou le bismuth sont excès par rapport à la stœchiométrie du titanate. EDX analyzes, carried out in a transmission electron microscope on a titanate sample produced by the process according to the invention, show that the two metallic elements (Ti and Bi) are mixed with very intimate matter, on an atomic scale (Figure 3 , B). Calcination in air at 650 ° C, for 4 hours, causes the formation of a titanate, possibly with phase segregation (Figure 3, D), when the titanium or bismuth are excess relative to the stoichiometry of the titanate.
La diffraction des rayons X, réalisées sur les échantillons calcinés (sous air, à 650 °C, pendant 4 h) montre clairement la cristallisation de titanate, ici B^T^O? (Figure 4). The X-ray diffraction carried out on the calcined samples (in air, at 650 ° C., for 4 h) clearly shows the crystallization of titanate, here B ^ T ^ O ? (Figure 4).
Autres exemples de mise en œuvre de l’invention : Other examples of implementation of the invention:
1 ) Les réactions d’estérification, La synthèse de la nitrocellulose ;
2) Les réactions de nitration, 1) Esterification reactions, Synthesis of nitrocellulose; 2) Nitration reactions,
3) L’hydrolyse d’alkoxydes pour la synthèse des oxydes (ex. les alkoxydes de Ti) 3) Hydrolysis of alkoxides for the synthesis of oxides (eg Ti alkoxides)
4) Les réactions de précipitation (réaction acide/base), ex. des picrates 4) Precipitation reactions (acid / base reaction), ex. picrates
5) Les réactions de complexation (métal/ligands) ; 5) Complexation reactions (metal / ligands);
6) La synthèse de polymères conducteurs ; 6) The synthesis of conductive polymers;
7) La synthèse d’oxydes ; 7) The synthesis of oxides;
8) La synthèse de céramiques.
8) The synthesis of ceramics.
Claims
1. Procédé de synthèse chimique, ledit procédé comprenant une brumisation par évaporation flash, également connue sous le sigle SFE pour l’acronyme anglais « Spray Flash Evaporation », comprenant la réaction chimique d’au moins un premier composé avec au moins un deuxième composé, dans des conditions dans lesquelles le premier composé et le deuxième composé réagissent pour former au moins un troisième composé. 1. A method of chemical synthesis, said method comprising misting by flash evaporation, also known by the acronym SFE for the English acronym "Spray Flash Evaporation", comprising the chemical reaction of at least one first compound with at least one second compound , under conditions in which the first compound and the second compound react to form at least a third compound.
2. Procédé de préparation selon la revendication 1 , caractérisé en ce que le procédé comprend la formation de particules comprenant ledit troisième composé. 2. Preparation process according to claim 1, characterized in that the process comprises the formation of particles comprising said third compound.
3. Procédé de préparation selon la revendication 1 , caractérisé en ce que le procédé comprend : 3. Preparation process according to claim 1, characterized in that the process comprises:
(a) la préparation d’une phase liquide comprenant le premier composé et le deuxième composé pour former une composition liquide atomisable ; (a) the preparation of a liquid phase comprising the first compound and the second compound to form a liquid atomizable composition;
(b) le chauffage de la composition liquide à une pression P1 supérieure à la pression atmosphérique, de préférence P1 allant de 3 à 300 bars, le chauffage étant réalisé à une température supérieure au point d’ébullition de la phase liquide ; (b) heating the liquid composition at a pressure P1 higher than atmospheric pressure, preferably P1 ranging from 3 to 300 bars, the heating being carried out at a temperature above the boiling point of the liquid phase;
(c) l’atomisation de la composition liquide comprenant le premier composé et le deuxième composé, l’atomisation étant de préférence réalisée dans une chambre d’atomisation au moyen d’un dispositif de dispersion à une pression P2 inférieure à P1 , de préférence P2 allant de 0,0001 à 2 bars ; (c) atomizing the liquid composition comprising the first compound and the second compound, the atomization preferably being carried out in an atomization chamber by means of a dispersing device at a pressure P2 lower than P1, preferably P2 ranging from 0.0001 to 2 bars;
(d) l’obtention dudit troisième composé par réaction du premier composé et du deuxième composé, et (d) obtaining said third compound by reaction of the first compound and the second compound, and
(e) éventuellement, la séparation du troisième composé de la phase liquide. (e) optionally, the separation of the third compound from the liquid phase.
4. Procédé de préparation selon la revendication 1 , caractérisé en ce que le procédé comprend : 4. Preparation process according to claim 1, characterized in that the process comprises:
(a) la préparation d’une première phase liquide comprenant le premier composé pour former une première composition liquide disposée dans un premier réservoir, et la préparation d’une deuxième phase liquide comprenant le deuxième composé formant une deuxième composition liquide disposée dans un deuxième réservoir ; (a) the preparation of a first liquid phase comprising the first compound to form a first liquid composition placed in a first tank, and the preparation of a second liquid phase comprising the second compound forming a second liquid composition placed in a second tank ;
(b) le chauffage de la première composition, sous une pression P1 , à une température supérieure au point d’ébullition du liquide, et le chauffage de la deuxième composition sous une pression PT, de préférence P1 et PT, égales ou différentes, allant de 3 à 300
bars, le chauffage de chaque composition liquide étant réalisé à une température supérieure au point d’ébullition respectivement de la phase liquide considérée; et (b) heating the first composition, under a pressure P1, to a temperature above the boiling point of the liquid, and heating the second composition under a pressure PT, preferably P1 and PT, equal or different, ranging from 3 to 300 bars, the heating of each liquid composition being carried out at a temperature above the boiling point respectively of the liquid phase considered; and
(c) l'atomisation simultanée des première et deuxième compositions chauffées sous pression, dans une chambre d’atomisation au moyen d’au moins un dispositif de dispersion sous une pression P2 inférieure à P1 et P1’, de préférence allant de 0,0001 à 2 bars, ladite dispersion étant réalisée de préférence sous chauffage, de préférence à une température comprise entre 20°C et 2000°C ; (c) the simultaneous atomization of the first and second compositions heated under pressure, in an atomization chamber by means of at least one device for dispersing under a pressure P2 lower than P1 and P1 ', preferably ranging from 0.0001 at 2 bars, said dispersion being preferably carried out under heating, preferably at a temperature between 20 ° C and 2000 ° C;
(d) l’obtention dudit troisième composé par réaction du premier composé et du deuxième composé, et (d) obtaining said third compound by reaction of the first compound and the second compound, and
(e) éventuellement, la séparation dudit troisième composé des phases liquides. (e) optionally, the separation of said third compound from the liquid phases.
5. Procédé de préparation selon la revendication 1 , caractérisé en ce que le premier composé et/ou le deuxième composé sont indépendamment liquides ou solides ou gazeux. 5. Preparation process according to claim 1, characterized in that the first compound and / or the second compound are independently liquid or solid or gaseous.
6. Procédé selon l’une quelconque des revendications 3 à 5, caractérisé en ce que, indépendamment, la première et la deuxième phase liquide comprennent ou sont constituées respectivement du premier composé sous forme liquide, éventuellement après dissolution dans un solvant, ou sous forme solide dispersée dans un solvant, et/ou du deuxième composé sous forme liquide, éventuellement après dissolution dans un solvant, ou sous forme solide dispersée dans un solvant, les solvants des première et deuxième phases liquides pouvant être identiques ou différents. 6. Method according to any one of claims 3 to 5, characterized in that, independently, the first and the second liquid phase comprise or consist respectively of the first compound in liquid form, optionally after dissolution in a solvent, or in the form solid dispersed in a solvent, and / or the second compound in liquid form, optionally after dissolution in a solvent, or in solid form dispersed in a solvent, the solvents of the first and second liquid phases possibly being identical or different.
7. Procédé selon l’une quelconque des revendications 1 à 6 caractérisé en ce que le troisième composé est obtenu sous forme de particules, par exemple dont au moins une dimension est inférieure à 100 nm, de préférence la plus grande dimension allant de 5 à 100 nm, plus préférentiellement allant de 10 à 30 nm. 7. Method according to any one of claims 1 to 6 characterized in that the third compound is obtained in the form of particles, for example of which at least one dimension is less than 100 nm, preferably the largest dimension ranging from 5 to 100 nm, more preferably ranging from 10 to 30 nm.
8. Procédé selon la revendication 7, caractérisé en ce que le procédé comprend la récupération finale de particules comprenant le troisième composé synthétisé, par exemple au moyen d’un ou plusieurs dispositifs de rétention des particules choisi parmi un filtre, un séparateur électrostatique, un cyclone, un cyclone comprenant un dispositif électrostatique et un filtre. 8. Method according to claim 7, characterized in that the method comprises the final recovery of particles comprising the third compound synthesized, for example by means of one or more particle retention devices chosen from a filter, an electrostatic separator, a cyclone, a cyclone comprising an electrostatic device and a filter.
9. Procédé selon l’une quelconque des revendications 1 à 8, caractérisé en ce que la réaction est réalisée par chauffage, indépendamment ou non l’un de l’autre, du premier
composé et du deuxième composé et en ce que le chauffage est effectué sous une pression allant de 5 à 150 bars, de préférence allant de 10 à 60 bars. 9. Method according to any one of claims 1 to 8, characterized in that the reaction is carried out by heating, independently or not of one another, of the first compound and the second compound and in that the heating is carried out under a pressure ranging from 5 to 150 bars, preferably ranging from 10 to 60 bars.
10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que la réaction est réalisée par chauffage, indépendamment ou non l’un de l’autre, du premier composé et du deuxième composé , de préférence sous pression d’un gaz inerte par exemple choisi parmi l’azote, l’argon, l’hélium, le néon, le xénon, SF6, CFC. 10. Method according to one of claims 1 to 9, characterized in that the reaction is carried out by heating, independently or not of one another, the first compound and the second compound, preferably under pressure of a inert gas for example chosen from nitrogen, argon, helium, neon, xenon, SF 6 , CFC.
1 1 . Procédé selon l'une des revendications 3 à 10, caractérisé en ce que l’atomisation de la composition ou des compositions est, indépendamment, réalisée 1 1. Method according to one of claims 3 to 10, characterized in that the atomization of the composition or compositions is, independently, carried out
■ à une pression allant de 0,001 à moins de 1 bars, de préférence de 0,02 à 0,2 bars ; et/ou ■ at a pressure ranging from 0.001 to less than 1 bar, preferably from 0.02 to 0.2 bar; and or
■ sous un angle de 60 à 80°. ■ at an angle of 60 to 80 °.
12. Procédé selon l'une des revendications 1 à 1 1 , caractérisé en ce que les composés sont choisis parmi les composés énergétiques, les composés pharmaceutiques, les composés phytopharmaceutiques, les composés de contraste médicaux, les composés fluorescents, les composés optiques, les composés colorants, les arômes, fragrances (parfum), les pigments, les encres, les peintures, les métaux, les oxydes métalliques, les composés semi-conducteurs, les composés optiques, les composés optoélectroniques, les composés ferroélectriques, les composés à réponse non-linéaire ou les composés bio électroniques. 12. Method according to one of claims 1 to 1 1, characterized in that the compounds are chosen from energetic compounds, pharmaceutical compounds, phytopharmaceutical compounds, medical contrast compounds, fluorescent compounds, optical compounds, coloring compounds, aromas, fragrances (perfume), pigments, inks, paints, metals, metal oxides, semiconductor compounds, optical compounds, optoelectronic compounds, ferroelectric compounds, non response compounds -linear or bio electronic compounds.
13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce que la réaction est mise en œuvre dans des conditions de pression et température d’obtention du troisième composé sous forme solide. 13. Method according to one of claims 1 to 12, characterized in that the reaction is carried out under conditions of pressure and temperature to obtain the third compound in solid form.
14. Composé ou Particules susceptibles d’être obtenues par un procédé tel que décrit selon l’une quelconque des revendications 1 à 13. 14. Compound or Particles capable of being obtained by a process as described according to any one of claims 1 to 13.
15. Dispositif de synthèse chimique, ledit dispositif comprenant : 15. Device for chemical synthesis, said device comprising:
■ au moins un premier réservoir comprenant : ■ at least one first tank comprising:
- une alimentation d’une composition liquide comprenant ou constituée d’un premier composé ; - a supply of a liquid composition comprising or consisting of a first compound;
- au moins un dispositif de mise sous une pression P1 , P1 étant de préférence choisi dans une plage de pression de 3 à 300 bars ;
- au moins un dispositif de chauffage ; - At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars; - at least one heating device;
■ au moins un deuxième réservoir comprenant : ■ at least a second tank comprising:
- une alimentation d’une composition liquide comprenant ou constituée d’un deuxième composé ; - a supply of a liquid composition comprising or consisting of a second compound;
- au moins un dispositif de mise sous une pression P1’, P1’ étant de préférence choisi dans une plage de pression de 3 à 300 bars et égale à ou différente de P1 ; - At least one pressurizing device P1 ’, P1’ being preferably chosen in a pressure range from 3 to 300 bars and equal to or different from P1;
- au moins un dispositif de chauffage ; - at least one heating device;
lesdits premier composé et deuxième composé étant réactifs ensemble, said first compound and second compound being reactive together,
■ une chambre d’atomisation comprenant : ■ an atomization chamber comprising:
- au moins un dispositif de dispersion des compositions liquide de chaque réservoir, de préférence sous un angle allant de 30 à 150°, et à une pression P2 inférieure à P1 et P1’, P2 étant de préférence choisi dans une plage de pression allant de 0,0001 à 2 bars, ledit dispositif de dispersion étant positionné de sorte que le premier composé et le deuxième composé réagissent ensemble dans les gouttelettes formée dans la chambre d’atomisation, ledit dispositif de dispersion étant de préférence chauffé par un dispositif de chauffage à une température choisie dans une plage de 200 à 2000°C ; at least one device for dispersing the liquid compositions of each reservoir, preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1 and P1 ′, P2 being preferably chosen from a pressure range ranging from 0.0001 to 2 bars, said dispersing device being positioned so that the first compound and the second compound react together in the droplets formed in the atomization chamber, said dispersing device being preferably heated by a heating device to a temperature chosen in a range of 200 to 2000 ° C;
- au moins un dispositif de séparation de liquides ; et - at least one device for separating liquids; and
■ éventuellement un ou plusieurs dispositifs de récupération du troisième composé formé par réaction du premier composé et du deuxième composé. ■ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
16. Dispositif de synthèse chimique, ledit dispositif comprenant : 16. Device for chemical synthesis, said device comprising:
■ au moins un réservoir comprenant : ■ at least one tank comprising:
- une alimentation d'une ou plusieurs compositions liquides comprenant le premier composé et/ou le deuxième composé ; - a supply of one or more liquid compositions comprising the first compound and / or the second compound;
- au moins un dispositif de mise sous une pression P1 , P1 étant de préférence choisi dans une plage de pression de 3 à 300 bars ; - At least one pressurizing device P1, P1 preferably being chosen from a pressure range of 3 to 300 bars;
- au moins un dispositif de chauffage ; - at least one heating device;
lesdits premier composé et deuxième composé étant réactifs ensemble, said first compound and second compound being reactive together,
■ une chambre d’atomisation comprenant : ■ an atomization chamber comprising:
- au moins un dispositif de dispersion du fluide de chaque réservoir, de préférence sous un angle allant de 30 à 150°, et à une pression P2 inférieure à P1 , P2 étant de préférence choisi dans une plage de pression allant de 0,0001 à 2 bars, ledit dispositif étant de préférence chauffé par un dispositif de chauffage à une température choisie dans une plage de 200 à 2000°C ;
- au moins un dispositif de séparation de liquides ; et - at least one device for dispersing the fluid in each reservoir, preferably at an angle ranging from 30 to 150 °, and at a pressure P2 less than P1, P2 preferably being chosen from a pressure range ranging from 0.0001 to 2 bars, said device being preferably heated by a heating device to a temperature chosen in a range from 200 to 2000 ° C; - at least one device for separating liquids; and
■ éventuellement un ou plusieurs dispositifs de récupération du troisième composé formé par réaction du premier composé et du deuxième composé. ■ optionally one or more devices for recovering the third compound formed by reaction of the first compound and the second compound.
17. Dispositif selon la revendication 15 ou 16, ledit dispositif comprenant un dispositif ou moyen de traitement thermique du troisième composé.
17. Device according to claim 15 or 16, said device comprising a device or means for heat treatment of the third compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1859736A FR3087351B1 (en) | 2018-10-22 | 2018-10-22 | HIGH AND LOW TEMPERATURE OUT OF BALANCE SYNTHESIS BY SPRAY FLASH SYNTHESIS |
| PCT/EP2019/078770 WO2020083942A1 (en) | 2018-10-22 | 2019-10-22 | Synthesis outside high and low temperature equilibrium by spray flash synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3870351A1 true EP3870351A1 (en) | 2021-09-01 |
Family
ID=66530080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19787305.2A Pending EP3870351A1 (en) | 2018-10-22 | 2019-10-22 | Synthesis outside high and low temperature equilibrium by spray flash synthesis |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20210354103A1 (en) |
| EP (1) | EP3870351A1 (en) |
| JP (1) | JP2022508902A (en) |
| FR (1) | FR3087351B1 (en) |
| WO (1) | WO2020083942A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013117671A1 (en) * | 2012-02-07 | 2013-08-15 | Centre National De La Recherche Scientifique (C.N.R.S) | Preparation of nanoparticles by flash evaporation |
| 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 |
| FR3061439A1 (en) * | 2016-09-20 | 2018-07-06 | Centre National De La Recherche Scientifique | PARTICLES OF THE HEART-ECORCE TYPE |
-
2018
- 2018-10-22 FR FR1859736A patent/FR3087351B1/en active Active
-
2019
- 2019-10-22 EP EP19787305.2A patent/EP3870351A1/en active Pending
- 2019-10-22 JP JP2021546476A patent/JP2022508902A/en active Pending
- 2019-10-22 US US17/286,932 patent/US20210354103A1/en active Pending
- 2019-10-22 WO PCT/EP2019/078770 patent/WO2020083942A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US20210354103A1 (en) | 2021-11-18 |
| WO2020083942A1 (en) | 2020-04-30 |
| JP2022508902A (en) | 2022-01-19 |
| FR3087351B1 (en) | 2021-07-16 |
| FR3087351A1 (en) | 2020-04-24 |
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