CN103623746A - Supercritical-solvent heat combined device and method for preparing nanometer material - Google Patents
Supercritical-solvent heat combined device and method for preparing nanometer material Download PDFInfo
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Abstract
The invention discloses a supercritical-solvent heat combined device and a method for preparing a nanometer material. The device comprises a carbon dioxide steel bottle, a carbon dioxide cooler, a carbon dioxide pump, an entrainer accommodator, an entrainer pump, a first valve, a second valve, a third valve, a secondary reactor, a fourth valve, a main reactor, a fifth valve and a separator. The device can realize a plurality of supercritical-solvent heat combined preparation methods, and can satisfy the preparation of the nanometer material and the demands of controlling such crystal growth behaviors as crystal transfer, grain size and morphology evolution of an inorganic nanometer material through splicing pipelines and modules and adjusting such conditions or parameters as valve switch combinations, raw material placing mode and entrainer entering mode. The device has such advantages as simplicity and convenience for operation, wide adjusting range of experimental parameters, strong stability and high productivity, has huge application potential in the research, preparation and application fields of the nanometer material, and has wider industrialization foreground.
Description
Technical field
General plotting of the present invention and design relate to a kind of overcritical device and technology, more particularly, relate to a kind of overcritical-solvent heat combine preparation nano material device and method.
Background technology
Recently between decades, nano material has been subject to various countries scientific research personnel's extensive concern, this is because find in research after scantling reaches Nano grade, will there is the not available surface-interface effect of traditional material, small-size effect, quantum size effect, the nano effects such as macro quanta tunnel effect.These nano materials are shown be different from the even characteristic of biology aspect of atom or molecule, the unusual or unusual photoelectricity that is different from again macro-size material, physics, chemistry, thereby there is high potential using value.
In nano material preparing technical field, how to obtain dispersiveness high, size distribution is narrower, and the nano material that degree of crystallinity is high is key prepared by material.At present, the preparation method of nano material is mainly divided into two large classes: solvent-thermal method and solid phase method.Although because solid phase method can obtain the nano material that degree of crystallinity is higher, the method is that material is at high temperature carried out to calcination process, thus cause the reunion of particle and melting comparatively serious, therefore more difficultly obtain dispersed high, nano material that size is less.Solvent-thermal method claims again hydrothermal method, refers in the pressure vessel of sealing, take liquid as solvent, the chemical reaction carrying out under the condition of HTHP.Solvent-thermal method reacts conventionally in being furnished with teflon-lined stainless steel autoclave.Solvent thermal reaction according to the difference of reaction type can be divided into that solvent heat oxidation, solvothermal, solvent heat precipitation, solvent heat are synthetic, solvent heat hydrolysis, solvent heat crystallization etc.Wherein solvent heat crystallization is with the most use.Solvent heat crystallization is mainly dissolution-recrystallization mechanism.First raw material dissolves in hydro-thermal medium, with the form of ion, micel, enters solution.Utilize strong convection current (in still the temperature difference of top and the bottom and in still solution produce) these ions, molecule or ion cluster be transported to the vitellarium (being low-temperature space) that is placed with seed crystal form supersaturated solution, then crystallization.Solvent thermal reaction has that reactivity is high, solution is easy to control, and the advantages such as air pollution is little, low energy consumption, have been widely used in the preparation of various materials.
Yet, solvent-thermal method is to be prepared reaction in common liquid phase environment, be limited to the conditions such as reaction pressure, dissolution with solvents degree, though technique is more ripe, but can use various organic solvents in some preparation process, and aftertreatment technology is comparatively loaded down with trivial details, the more difficult removal of reaction promoter (as surfactant etc.) is clean, be difficult to obtain pure product, so researchers are still being the more favourable preparation method's effort of searching.
Ostwald ripening mechanism (Santen R.A.V.The Ostwald step rule.J.Phys.Chem., 1984,88,5768-5769) think, in growth course, to the consumption of monomer, finally can cause more short grained solubility in solution, this is because material has strong solubility size-dependent within the scope of nanoscale.This means, little crystal fine particle is because curvature is larger, and energy is higher, solubility is higher, so can be dissolved into gradually in medium around, then on the surface of larger crystal fine particle, again separates out, this further increases larger crystal fine particle, and little crystal fine particle further diminishes.By this mechanism, we can find, not only less particle will preferentially dissolve, the system coexisting for multiple crystal formation, and the crystal formation solubility that energy is higher is higher, also can preferentially dissolve; And more stable crystal formation, because solubility is relatively low, is present in reaction medium metastable.
For the growth of nanocrystal, the control of nucleation process is the key that obtains Monodisperse nanocrystals.Want to obtain the nano particle of homogeneous of taking measurements greatly, must be within the short as far as possible time nucleation of explosion type, make two stages of nucleation and growth separately.Can take following two schemes: control material diffusion and migration in reaction system, reduce material diffusion and transport coefficient; Or reconcile surface tension (the Talapin D.V. between solution and nano particle, Rogach A.L., Hasse M., et al.Evolution of an ensemble of nanoparticles in a colloidal solution:theoretical study.J.Phys.Chem.B, 2001,105,12278-12285).Therefore surfactant was widely used in synthesizing of nano material.In addition, under a certain condition, utilize pyroreaction also can greatly improve nucleation rate and reach object (the Redl F.X. that controls nano material particle diameter, Cho K.S., Murry C.B., et al.Three-dimensional binary superlattices of magnetic nanocrystals and semiconductor quantum dots.Nature, 2003,423,968-971; Puntes V.F., Krishnan K.M., Alivisatos A.P.Colloidal nanocrystal shape and size control:the case of cobalt.Science, 2001,291,2115-2117).
Supercritical carbon dioxide is progressively replacing organic solvent some routines, that environment is had to harm as the cleaning solvent of " Green Chemistry "; in extract and separate, analytical technology, food industry, Chinese medicine extraction, biomaterial, environmental protection etc., be all applied aspect many, there is prospect widely.
Overcritical equipment is except for supercritical liquid extraction technique, also can be used for preparing ultrafine dust, the basic principle of its technology is: under the condition forming at supercritical fluid, make solute fully be dissolved into saturated solution, reduce pressure, cause supersaturation, make the even nucleation of solute particulate, the particulate of preparing has the advantages such as narrow diameter distribution, degree of crystallinity are high, surperficial rounding.Solvent residual amount, falls in the chemical purity that can also improve medicine simultaneously.Because supercritical fluid has huge compressibility, can, by regulating pressure, temperature, easily the degree of supersaturation of solution be saved, to control grain size within the specific limits.In addition, by controlling different experiment conditions, the crystal formation purity of particulate also can reach high level.
Supercritical carbon dioxide easily reaches critical condition, and supercritical carbon dioxide fluid has that diffusion is high, viscosity is low, dissolving power is strong, be easy to realize the excellent characteristics such as product is separated with reaction medium, environmental friendliness.Therefore, if solvent-thermal method can be combined with supercritical methanol technology, can make up the deficiency that monotechnics exists, both advantages are performed to maximum efficiency.Under the condition combining with supercritical methanol technology at this solvent-thermal method, can effectively eliminate the surface tension that causes that colloidal particle is reunited, nucleation and two stages of growth of nano material are separated, realize in the short period of time the equipotential homogeneous nucleation of explosion type, final acquisition is dispersed high, size distribution is narrower, the nano material that degree of crystallinity is high.
Summary of the invention
The object of the present invention is to provide a kind of overcritical-solvent heat combine preparation nano material device and method; This device splices by circuit and elements, adjusts condition or the parameters such as valve switch combination, raw material modes of emplacement, entrainer mode of entrance, can realize multiple overcritical-preparation method that solvent heat combines.
The object of the invention is to be achieved through the following technical solutions:
First aspect, the present invention relates to a kind of overcritical-solvent heat combine preparation nano material device, described device comprises carbon dioxide steel cylinder, carbon dioxide cooler, carbon dioxide pump, entrainer container, entrainer pump, the first valve, the second valve, the 3rd valve, auxiliary reactor, the 4th valve, main reactor, the 5th valve and separator; Described carbon dioxide steel cylinder, carbon dioxide cooler, carbon dioxide pump, the first valve are connected by carbon dioxide transfer pipeline successively, after described entrainer container, entrainer pump are connected by pipeline, converge with the first valve carbon dioxide carrier pipe section afterwards; Pipeline after converging is connected with the top of secondary reacting kettle by the second valve respectively, by the 3rd valve, is connected with the supervisor road junction, top of main reaction still; The bottom of described secondary reacting kettle is connected with the looped pipeline road junction, top of main reaction still through the 4th valve by pipeline, and described main reaction still bottom is connected with separator entrance point through the 5th valve by pipeline.
Preferably, between described carbon dioxide pump and the first valve, Pressure gauge is installed; Pressure gauge and thermometer are all installed on described secondary reacting kettle and main reactor.
Preferably, cylindrical metal hand basket all can be placed in the inside of described secondary reacting kettle and main reaction still, and the sintering pan with microcellular structure can be installed in the top of described metal hand basket and bottom.
Preferably, from the carbon dioxide of described carbon dioxide cooler output, through carbon dioxide pump, pressurize, reach above-critical state.
Preferably, described separator is provided with separator the first outlet, separator the second outlet and separator the 3rd outlet.
In device of the present invention, the switch combination mode of valve K1-K5 and the mode that flows to of fluid can be adjusted according to concrete needs.
Second aspect, the present invention relates to a kind of adopt above-mentioned overcritical-the combine device of preparation nano material of solvent heat prepares the method for nano material, comprises the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still; Raw material is put into entrainer container and is dissolved in entrainer, form uniform solution;
B, close first, second, third and fourth, five valves, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state; The entrainer mixed solution that is dissolved with raw material in entrainer container, through the pressurization of entrainer pump, produces high-pressure fluid;
C, open the second valve, make the entrainer mixed solution that is dissolved with raw material enter secondary reacting kettle, in secondary reacting kettle, adjust to target temperature and pressure; Open first and third, four valves, close entrainer pump simultaneously, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The entrainer mixed solution that the supercritical carbon dioxide fluid promotion of inflow secondary reacting kettle is dissolved with raw material enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
Preferably, the fluid-mixing that reacts remaining flows into after separator, carbon dioxide is wherein discharged or is recycled by separator the first outlet, entrainer is discharged or is reclaimed by separator the second outlet, and other component in raw material except target product is discharged through separator the 3rd outlet.
The third aspect, the present invention relates to a kind of adopt above-mentioned overcritical-the combine device of preparation nano material of solvent heat prepares the method for nano material, comprises the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still; Raw material is put into main reaction still or secondary reacting kettle;
B, close first, second, third and fourth, five valves, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state; Entrainer in entrainer container, through the pressurization of entrainer pump, produces high-pressure fluid;
C, open the second valve, make entrainer enter secondary reacting kettle, in secondary reacting kettle, adjust to target temperature and pressure; Open first and third, four valves, close entrainer pump simultaneously, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The entrainer mixed solution that the supercritical carbon dioxide fluid that flows into secondary reacting kettle promotes entrainer or is dissolved with raw material enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
Fourth aspect, the present invention relates to a kind of adopt above-mentioned overcritical-the combine device of preparation nano material of solvent heat prepares the method for nano material, comprises the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still;
B, close first, second, third and fourth, five valves and entrainer pump, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state;
C, raw material is dissolved in entrainer, forms uniform solution, the entrainer mixed solution that this is dissolved with to raw material is put into secondary reacting kettle or main reaction still; Open first and third, four valves, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The supercritical carbon dioxide fluid that flows into secondary reacting kettle promotes the prepositioned entrainer mixed solution that is dissolved with raw material and enters main reaction still, or directly enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
The beneficial effect that the present invention has is: the invention provides a kind of overcritical-solvent heat combine preparation nano material device and method, this device splices by circuit and elements, the combination of adjustment valve switch, raw material modes of emplacement, condition or the parameters such as entrainer mode of entrance, can realize multiple overcritical-preparation method that solvent heat combines, can meet organic nano material, the preparation of inorganic nano material and organic/inorganic composite nano materials, and the crystal transfer of inorganic nano material, grain size, the demands such as control of the crystal growth behaviors such as Morphology Evolution.This device has easy and simple to handle, and equipment experiment parameter adjustable extent is wide, and stability is strong, and production efficiency advantages of higher has huge application potential in nano materials research, preparation and application field, has very wide industrialization prospect.
Accompanying drawing explanation
By reading the detailed description of non-limiting example being done with reference to the following drawings, it is more obvious that the other features, objects and advantages of patent of the present invention will become:
Fig. 1 be of the present invention overcritical-the combine structural representation of device of preparation nano material of solvent heat;
Wherein, A1 is secondary reacting kettle, and A2 is main reaction still, and B is carbon dioxide pump, C is carbon dioxide steel cylinder, and CS is entrainer container, and E1 is separator the first outlet, E2 is separator the second outlet, and E3 is separator the 3rd outlet, and H is carbon dioxide cooler, K1 is the first valve, and K2 is the second valve, and K3 is the 3rd valve, K4 is the 4th valve, and K5 is the 5th valve, and P is Pressure gauge, S is separator, and T is thermometer, and U is entrainer pump.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
The present invention be address the above problem proposed equipment design in connection with description below, embodiment and schematically accompanying drawing be achieved or obtain.
As shown in Figure 1, overcritical-solvent heat combine preparation nano material device comprise following assembly: high-purity carbon dioxide steel cylinder C, for CO 2 fluid is provided; Carbon dioxide cooler H, for cooled carbon dioxide fluid; Carbon dioxide pump B, pressurizes for CO 2 fluid; Entrainer container C S, for providing entrainer; Entrainer pump U, for entrainer pressurized with fluid; Secondary reacting kettle A1, can heat and temperature control, for the pretreatment of material or fluid, reach required goal pressure and temperature, secondary reacting kettle A1 can place inside cylindrical metal hand basket band, and the sintering pan with microcellular structure can be installed in metal hand basket top and bottom; Main reaction still A2, can heat and temperature control, be overcritical-solvent heat combine preparation nano material for main reactor, a supervisor road junction and a looped pipeline road junction are arranged at main reaction still A2 top, main reaction still A2 can place cylindrical metal hand basket in inside, and the sintering pan with microcellular structure can be installed in metal hand basket top and bottom; Separator S, purifies for compounding substances separated; And some pipelines etc.
The combine said modules connected mode of preparation nano material device of overcritical-solvent heat is as follows: carbon dioxide steel cylinder C is connected with carbon dioxide cooler H, carbon dioxide pump B by pipeline; Entrainer container C S is connected with entrainer pump U; After two-way pipeline meets at the first valve K1, between carbon dioxide pump B and the first valve K1, Pressure gauge P is installed; The pipeline of joining is divided into two-way again, wherein leads up to after the second valve K2 and is connected with reactor A1 top, and the 3rd valve K3 of separately leading up to is connected with the supervisor road junction at reactor A2 top; Reactor A1 and A2 have installed Pressure gauge P and thermometer T; Reactor A1 bottom is connected with the looped pipeline road junction at reactor A2 top by pipeline, and pipeline is controlled by the 4th valve K4; Reactor A2 bottom is connected with separator S by the 5th valve K5; Separator has three outlets, is respectively separator the first outlet E1, separator the second outlet E2, separator the 3rd outlet E3, for separating of carbon dioxide, and cosolvent and other material.
Overcritical-solvent heat combines and prepares the method for nano material: before operation starts, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still A2; Raw material is put into entrainer container C S and is dissolved in entrainer, form uniform solution; Connect afterwards pipeline, test air-tightness, is prepared operation; First valve-off K1-K5, high-purity carbon dioxide in carbon dioxide steel cylinder C is first cooling by carbon dioxide cooler H, reach after the temperature required scope of super critical condition, enter carbon dioxide pump B, by pump, pressurize, make carbon dioxide reach above-critical state, then via the first valve K1, control, enter subsequent reactions flow process; The entrainer mixed solution that is dissolved with raw material in entrainer container C S, through entrainer pump U pressurization, produces high-pressure fluid, enters subsequent reactions flow process; Now, open the second valve K2, make the entrainer mixed solution that is dissolved with raw material enter secondary reacting kettle A1, in secondary reacting kettle A1, adjust to target temperature and pressure; Then open valve K1, K3 and K4, close entrainer pump U simultaneously, supercritical carbon dioxide fluid flows into reactor A1 and A2; The entrainer mixed solution that the supercritical carbon dioxide fluid promotion of inflow A1 is dissolved with raw material enters reactor A2; In reactor A2, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat; In course of reaction, target substance nucleation, crystallization separate out under certain pressure, temperature and specific solution environmental, obtain target product nano particle; After reaction finishes, open valve K5, fluid-mixing flows into separator S, through separator S, carry out separation, carbon dioxide is discharged or is recycled by separator the first outlet E1, entrainer is discharged or is reclaimed by separator the second outlet E2, and other component in raw material except target product is discharged through separator the 3rd outlet E3; After operation completes, closing carbon dioxide pump B, opens the upper cover of reactor A2, takes out the target product nano particle of precipitating in metal hand basket.
In a preferred technical scheme of the present invention, described entrainer can be squeezed into overcritical device by the pressurization of entrainer pump and participate in reaction, also can before operation, be placed in advance in reactor A1 or A2; No matter being to use single entrainer or multiple entrainer, can be also the multiple combination of above-mentioned three kinds of modes.
In another preferred technical scheme of the present invention, described raw material can be squeezed into overcritical device by the pressurization of entrainer pump and participate in reaction, also can before operation, be placed in advance in reactor A1 or A2; No matter being to use single raw material or plurality of raw materials, can be also the multiple combination of above-mentioned three kinds of modes.
In another another preferred technical scheme of the present invention, described overcritical-solvent heat combines in the device of preparation nano material, the switch combination mode of valve K1-K5 and the mode that flows to of fluid, can adjust according to concrete needs.Specifically see following embodiment:
embodiment 1
When raw material can be dissolved in entrainer completely.The exemplary method that can combine according to overcritical as follows-solvent heat is prepared nano material.
(1) before operation starts, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into reactor A2; Raw material is put into entrainer container C S and is dissolved in entrainer, form uniform solution; Connect afterwards pipeline, test air-tightness, is prepared operation;
(2) valve-off K1-K5, high-purity carbon dioxide in steel cylinder C is first cooling by carbon dioxide cooler H, reach after the temperature required scope of super critical condition, enter carbon dioxide pump B, by pump, pressurize, make carbon dioxide reach above-critical state, then via valve K1, control, enter subsequent reactions flow process;
(3) the entrainer mixed solution that is dissolved with raw material in entrainer container C S, through entrainer pump U pressurization, produces high-pressure fluid, enters subsequent reactions flow process; Now, open valve K2, make the entrainer mixed solution that is dissolved with raw material enter reactor A1, in reactor A1, adjust to target temperature and pressure;
(4) open valve K1, K3 and K4, close entrainer pump U simultaneously, supercritical carbon dioxide fluid flows into reactor A1 and A2; The entrainer mixed solution that the supercritical carbon dioxide fluid promotion of inflow A1 is dissolved with raw material enters reactor A2; In reactor A2, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat;
(5), in course of reaction, target substance nucleation, crystallization separate out under certain pressure, temperature and specific solution environmental, obtain target product nano particle;
(6) after reaction finishes, open valve K5, fluid-mixing flows into separator S, through separator S, carry out separation, carbon dioxide is discharged or is recycled by outlet E1, and entrainer is discharged or is reclaimed by outlet E2, and other component in raw material except target product is discharged through outlet E3;
(7) after operation completes, closing carbon dioxide pump B, opens the upper cover of reactor A2, takes out the target product nano particle of precipitating in metal hand basket.
embodiment 2
If raw material can not be dissolved in entrainer completely, and target substance component in raw material is while dissolving in entrainer, and the exemplary method that can combine according to overcritical as follows-solvent heat is prepared nano material.
(1) before operation starts, raw material is put into cylindrical metal hand basket, the sintering pan with microcellular structure is installed in cylindrical metal hand basket bottom, and metal hand basket is put into reactor A1; Connect pipeline, test air-tightness, is prepared operation;
(2) valve-off K1-K5, high-purity carbon dioxide in steel cylinder C is first cooling by carbon dioxide cooler H, reach after the temperature required scope of super critical condition, enter carbon dioxide pump B, by pump, pressurize, make carbon dioxide reach above-critical state, then via valve K1, control, enter subsequent reactions flow process;
(3) entrainer in entrainer container C S, through entrainer pump U pressurization, produces high-pressure fluid, enters subsequent reactions flow process; Now, open valve K2, make entrainer enter reactor A1, in reactor A1, contact with raw material, under certain temperature and pressure, target substance is extracted in entrainer from raw material;
(4) open valve K1, K3 and K4, close entrainer pump U simultaneously, supercritical carbon dioxide fluid flows into reactor A1 and A2; The entrainer mixed solution that the supercritical carbon dioxide fluid promotion of inflow A1 is dissolved with target substance enters reactor A2; In reactor A2, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat;
(5), in course of reaction, target substance nucleation, crystallization separate out under certain pressure, temperature and specific solution environmental, obtain target product nano particle;
(6) after reaction finishes, open valve K5, fluid-mixing flows into separator S, through separator S, carries out separation, and carbon dioxide is discharged or is recycled by outlet E1, and entrainer is discharged or is reclaimed by outlet E2;
(7) after operation completes, closing carbon dioxide pump B, opens the upper cover of reactor A1, other impurity composition in cleaning raw material except target substance; Open the upper cover of reactor A2, take out the target product nano particle of precipitating in metal hand basket.
embodiment 3
When if raw material can not be dissolved in entrainer, the exemplary method that can combine according to overcritical as follows-solvent heat is prepared nano material.
(1) before operation starts, raw material is put into cylindrical metal hand basket, the sintering pan with microcellular structure is installed in cylindrical metal hand basket bottom, and metal hand basket is put into reactor A2; Connect pipeline, test air-tightness, is prepared operation;
(2) valve-off K1-K5, high-purity carbon dioxide in steel cylinder C is first cooling by carbon dioxide cooler H, reach after the temperature required scope of super critical condition, enter carbon dioxide pump B, by pump, pressurize, make carbon dioxide reach above-critical state, then via valve K1, control, enter subsequent reactions flow process;
(3) entrainer in entrainer container C S, through entrainer pump U pressurization, produces high-pressure fluid, enters subsequent reactions flow process; Now, open valve K2, make entrainer enter reactor A1, in reactor A1, adjust to required target temperature and pressure;
(4) open valve K1, K3 and K4, close entrainer pump U simultaneously, supercritical carbon dioxide fluid flows into reactor A1 and A2; The supercritical carbon dioxide fluid that flows into A1 promotes entrainer mixed solution and enters reactor A2; In reactor A2, entrainer, supercritical carbon dioxide fluid and raw material are had an effect, and adjust to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat;
(5), in course of reaction, there is the behaviors such as dissolving and recrystallization, crystal transfer, grain size change, Morphology Evolution in target substance, obtain target product nano particle under certain pressure, temperature and specific solution environmental;
(6) after reaction finishes, open valve K5, fluid-mixing flows into separator S, through separator S, carries out separation, and carbon dioxide is discharged or is recycled by outlet E1, and entrainer is discharged or is reclaimed by outlet E2;
(7) after operation completes, closing carbon dioxide pump B, opens the upper cover of reactor A2, takes out the target product nano particle of precipitating in metal hand basket.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (9)
1. overcritical-solvent heat combines and prepares the device of nano material, it is characterized in that, described device comprises carbon dioxide steel cylinder, carbon dioxide cooler, carbon dioxide pump, entrainer container, entrainer pump, the first valve, the second valve, the 3rd valve, auxiliary reactor, the 4th valve, main reactor, the 5th valve and separator; Described carbon dioxide steel cylinder, carbon dioxide cooler, carbon dioxide pump, the first valve are connected by carbon dioxide transfer pipeline successively, after described entrainer container, entrainer pump are connected by pipeline, converge with the first valve carbon dioxide carrier pipe section afterwards; Pipeline after converging is connected with the top of secondary reacting kettle by the second valve respectively, by the 3rd valve, is connected with the supervisor road junction, top of main reaction still; The bottom of described secondary reacting kettle is connected with the looped pipeline road junction, top of main reaction still through the 4th valve by pipeline, and described main reaction still bottom is connected with separator entrance point through the 5th valve by pipeline.
As claimed in claim 1 overcritical-solvent heat combine preparation nano material device, it is characterized in that, between described carbon dioxide pump and the first valve, Pressure gauge is installed; Pressure gauge and thermometer are all installed on described secondary reacting kettle and main reactor.
As claimed in claim 1 overcritical-solvent heat combine preparation nano material device, it is characterized in that, cylindrical metal hand basket all can be placed in the inside of described secondary reacting kettle and main reaction still, and the sintering pan with microcellular structure can be installed in the top of described metal hand basket and bottom.
As claimed in claim 1 overcritical-the combine device of preparation nano material of solvent heat, it is characterized in that, from the carbon dioxide of described carbon dioxide cooler output, through carbon dioxide pump, pressurize, reach above-critical state.
As claimed in claim 1 overcritical-the combine device of preparation nano material of solvent heat, it is characterized in that, described separator is provided with separator first outlet, separator the second outlet and separator the 3rd outlet.
6. adopt device as claimed in claim 1 to prepare a method for nano material, it is characterized in that, comprise the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still; Raw material is put into entrainer container and is dissolved in entrainer, form uniform solution;
B, close first, second, third and fourth, five valves, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state; The entrainer mixed solution that is dissolved with raw material in entrainer container, through the pressurization of entrainer pump, produces high-pressure fluid;
C, open the second valve, make the entrainer mixed solution that is dissolved with raw material enter secondary reacting kettle, in secondary reacting kettle, adjust to target temperature and pressure; Open first and third, four valves, close entrainer pump simultaneously, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The entrainer mixed solution that the supercritical carbon dioxide fluid promotion of inflow secondary reacting kettle is dissolved with raw material enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
7. the method for preparing nano material as claimed in claim 6, it is characterized in that, the fluid-mixing that reacts remaining flows into after separator, carbon dioxide is wherein discharged or is recycled by separator the first outlet, entrainer is discharged or is reclaimed by separator the second outlet, and other component in raw material except target product is discharged through separator the 3rd outlet.
8. adopt device as claimed in claim 1 to prepare a method for nano material, it is characterized in that, comprise the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still; Raw material is put into main reaction still or secondary reacting kettle;
B, close first, second, third and fourth, five valves, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state; Entrainer in entrainer container, through the pressurization of entrainer pump, produces high-pressure fluid;
C, open the second valve, make entrainer enter secondary reacting kettle, in secondary reacting kettle, adjust to target temperature and pressure; Open first and third, four valves, close entrainer pump simultaneously, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The entrainer mixed solution that the supercritical carbon dioxide fluid that flows into secondary reacting kettle promotes entrainer or is partly dissolved raw material enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
9. adopt device as claimed in claim 1 to prepare a method for nano material, it is characterized in that, comprise the steps:
A, the sintering pan with microcellular structure is installed on to cylindrical metal hand basket bottom, cylindrical metal hand basket is put into main reaction still;
B, close first, second, third and fourth, five valves and entrainer pump, high-purity carbon dioxide in carbon dioxide steel cylinder is first cooling by carbon dioxide cooler, reaches after the temperature required scope of super critical condition, enters carbon dioxide pump, by pump, pressurize, make carbon dioxide reach above-critical state;
C, raw material is dissolved in entrainer, forms uniform solution, the entrainer mixed solution that this is dissolved with to raw material is put into secondary reacting kettle or main reaction still; Open first and third, four valves, supercritical carbon dioxide fluid flows into secondary reacting kettle and main reaction still; The supercritical carbon dioxide fluid that flows into secondary reacting kettle promotes the prepositioned entrainer mixed solution that is dissolved with raw material and enters main reaction still, or directly enters main reaction still;
D, in main reaction still, mixed solution mixes with supercritical carbon dioxide, and adjusts to target temperature and pressure, heat-insulation pressure keeping under the condition combining at overcritical-solvent heat, reaction;
After E, reaction finish, open the 5th valve, the fluid-mixing that reacts remaining flows into separator, carries out separation; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
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