CN103623746B - Overcritical-solvent heat combines and prepares the device and method of nano material - Google Patents
Overcritical-solvent heat combines and prepares the device and method of nano material Download PDFInfo
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Abstract
The invention discloses a kind of overcritical-solvent heat combine preparation nano material device and method; 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.This device is spliced by circuit and elements, condition or the parameter such as the combination of regulating valve door switch, raw material modes of emplacement, entrainer mode of entrance, can realize multiple overcritical-preparation method that combines of solvent heat, the preparation of nano material can be met, and the demand such as the control of the crystal growth behavior such as the crystal transfer of inorganic nano material, grain size, 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, have very wide industrialization prospect.
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
Between nearest decades, nano material receives the extensive concern of various countries scientific research personnel, this is because find in research after scantling reaches Nano grade, the surface-interface effect not available for traditional material, small-size effect, quantum size effect will be had, the nano effects such as macro quanta tunnel effect.Not only these nano materials shown be different from atom or molecule, but also be different from the unusual or unusual photoelectricity of macroscopic materials, physics, the chemistry even characteristic of biology aspect, thus there is high potential using value.
In technical field of nanometer material preparation, how to obtain dispersed high, size distribution is narrower, 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.Because although solid phase method can obtain the higher nano material of degree of crystallinity, the method is that material is at high temperature carried out calcination process, thus causes the reunion of particle and melting comparatively serious, the nano material that therefore more difficult acquisition dispersiveness is high, size is less.Solvent-thermal method is also known as hydrothermal method, and referring in the pressure vessel of sealing, take liquid as solvent, the chemical reaction carried out under the condition of HTHP.Solvent-thermal method reacts being furnished with in teflon-lined stainless steel autoclave usually.Solvent thermal reaction can be divided into solvent heat oxidation, solvothermal, solvent heat precipitation, solvent-thermal process, solvent heat hydrolysis, thermal crystallization etc. according to the difference of reaction type.Wherein thermal crystallization is with the most use.Thermal crystallization is dissolution-recrystallization mechanism mainly.First raw material dissolves in hydro-thermal medium, enters solution with the form of ion, micel.Utilize strong convection (in still top and the bottom temperature difference and in still solution produce) these ions, molecule or ion cluster be transported to the vitellarium (i.e. low-temperature space) being placed with seed crystal form supersaturated solution, crystallization then.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 material.
But, solvent-thermal method is prepared reaction in common liquid phase environment, be limited to the condition such as reaction pressure, Solvent Solubility, though technique is more ripe, but can use various organic solvent in some preparation process, and aftertreatment technology is comparatively loaded down with trivial details, reaction promoter (as surfactant etc.) more difficult removal is clean, be difficult to obtain pure product, so researchers are still for finding preparation method advantageously and effort.
Ostwald ripening mechanism (SantenR.A.V.TheOstwaldsteprule.J.Phys.Chem., 1984,88,5768-5769) think, in growth course, finally can cause more short grained solubility in the solution to the consumption of monomer, this is because material has strong solubility size-dependent within the scope of nanoscale.This means, little crystal fine particle due to curvature comparatively large, energy is higher, solubility is higher, so can be dissolved in the medium of surrounding gradually, then again separates out on the surface of larger crystal fine particle, this makes larger crystal fine particle increase further, and little crystal fine particle diminishes further.By this mechanism, we can find, not only less particle will preferentially dissolve, and for the system that multiple crystal formation coexists, the crystal formation solubility that energy is higher is higher, also can preferentially dissolve; And more stable crystal formation, because solubility is relatively low, be present in metastable in reaction medium.
For the growth of nanocrystal, the control of nucleation process is the key obtaining Monodisperse nanocrystals.Want the nano particle obtaining a large amount of size uniformity, must within the time short as far as possible the nucleation of explosion type, make two stages of coring and increment separately.The following two kinds scheme can be taked: control the material diffusion in reaction system and migration, reduce material diffusion and transport coefficient; Or the surface tension (TalapinD.V. reconciled between solution and nano particle, RogachA.L., HasseM., etal.Evolutionofanensembleofnanoparticlesinacolloidalsol ution:theoreticalstudy.J.Phys.Chem.B, 2001,105,12278-12285).Therefore surfactant is widely used in the synthesis of nano material.In addition, under a certain condition, pyroreaction is utilized also can greatly to improve nucleation rate to reach the object (RedlF.X. controlling nano material particle diameter, ChoK.S., MurryC.B., etal.Three-dimensionalbinarysuperlatticesofmagneticnanoc rystalsandsemiconductorquantumdots.Nature, 2003,423,968-971; PuntesV.F., KrishnanK.M., AlivisatosA.P.Colloidalnanocrystalshapeandsizecontrol:th ecaseofcobalt.Science, 2001,291,2115-2117).
Organic solvent that supercritical carbon dioxide is progressively replacing some routines as the cleaning solvent of " Green Chemistry ", that environment is had to harm; all be applied in extract and separate, analytical technology, food industry, Chinese medicine extraction, biomaterial, environmental protection etc. are many, there is prospect widely.
Overcritical equipment is except for except supercritical liquid extraction technique, also can be used for preparing ultrafine dust, the general principle of its technology is: under the condition that supercritical fluid is formed, solute is made fully to be dissolved into saturated solution, reduce pressure, cause supersaturation, make the even nucleation of solute particulate, the particulate prepared has the advantages such as narrow diameter distribution, degree of crystallinity are high, surperficial rounding.The chemical purity of medicine can also be improved simultaneously, fall solvent residual amount.Because supercritical fluid has huge compressibility, by regulating pressure, temperature, easily the degree of supersaturation of solution can be saved, to control grain size within the specific limits.In addition, by controlling different experiment conditions, the crystal form 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, is 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, the deficiency that monotechnics exists can be made up, both advantages are performed to maximum efficiency.Under the condition that this solvent-thermal method combines with supercritical methanol technology, can effectively eliminate the surface tension causing colloidal particle to reunite, make two stages of coring and increment of nano material separately, realize the equipotential homogeneous nucleation of explosion type in the short period of time, 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 is spliced by circuit and elements, condition or the parameter such as the combination of regulating valve door switch, raw material modes of emplacement, entrainer mode of entrance, can realize multiple overcritical-preparation method that combines of solvent heat.
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 with the first valve after carbon dioxide carrier pipe section converge; Pipeline after converging is connected with the top of secondary reacting kettle respectively by the second valve, is connected with the supervisor road junction, top of main reaction still by the 3rd valve; 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, is connected bottom described main reaction still by pipeline through the 5th valve with separator entrance point.
Preferably, between described carbon dioxide pump and the first valve, Pressure gauge is installed; Described secondary reacting kettle and main reactor are all provided with Pressure gauge and thermometer.
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 top and the bottom of described metal hand basket.
Preferably, the carbon dioxide exported from described carbon dioxide cooler pressurizes through carbon dioxide pump, reaches above-critical state.
Preferably, described separator is provided with that separator first exports, separator second exports 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 adjust 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, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket; Raw material put into entrainer container and be dissolved in entrainer, forming uniform solution;
B, close first, second, third and fourth, five valves, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, make carbon dioxide reach above-critical state; The entrainer mixed solution being 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 being 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 flowing into secondary reacting kettle promotes to be 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
Preferably, after the fluid-mixing inflow separator that reaction is remaining, carbon dioxide is wherein discharged by separator first outlet or is recycled, entrainer is discharged by separator second outlet or is reclaimed, 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, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket; Raw material is put into main reaction still or secondary reacting kettle;
B, close first, second, third and fourth, five valves, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, 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 supercritical carbon dioxide fluid promotion entrainer flowing into secondary reacting kettle or the entrainer mixed solution being dissolved with raw material enter 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; 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, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket;
B, close first, second, third and fourth, five valves and entrainer pump, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, make carbon dioxide reach above-critical state;
C, be dissolved in entrainer by raw material, form uniform solution, the entrainer mixed solution this being dissolved with raw material puts 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 flowing into secondary reacting kettle promotes the prepositioned entrainer mixed solution being 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; 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 is spliced by circuit and elements, regulating valve door switch combines, raw material modes of emplacement, condition or the parameters such as entrainer mode of entrance, can realize multiple overcritical-preparation method that combines of solvent heat, organic nano material can be met, 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 the 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, have very wide industrialization prospect.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, the other features, objects and advantages of patent of the present invention will become more obvious:
Fig. 1 be of the present invention overcritical-solvent heat combines the structural representation of device of preparation nano material;
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 that separator first exports, E2 is that separator second exports, 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.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
The present invention for solve the problem equipment de-sign scheme proposed by the description combined 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 providing CO 2 fluid; 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 carry out heating 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 carry out heating and temperature control, be overcritical-solvent heat combine preparation nano material for main reactor, main reaction still A2 top has one to be responsible for road junction and a looped pipeline road junction, 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, for compounding substances purification & isolation; 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, and wherein lead up to after the second valve K2 and be connected with reactor A1 top, the 3rd valve K3 of separately leading up to is connected with the supervisor road junction at reactor A2 top; Reactor A1 and A2 has installed Pressure gauge P and thermometer T; Be connected by the looped pipeline road junction of pipeline with reactor A2 top bottom reactor A1, pipeline controls by the 4th valve K4; Connected by the 5th valve K5 and separator S-phase bottom reactor A2; Separator has three outlets, is that separator first exports E1, separator second exports E2, separator the 3rd exports E3 respectively, for separating of carbon dioxide, and cosolvent and other material.
Overcritical-solvent heat combines and prepares the method for nano material: before operation starts, and is installed on by the sintering pan with microcellular structure bottom cylindrical metal hand basket, and main reaction still A2 put into by cylindrical metal hand basket; Raw material put into entrainer container C S and be dissolved in entrainer, forming uniform solution; Connect pipeline afterwards, test air-tightness, is prepared operation; First valve-off K1-K5, first high-purity carbon dioxide in carbon dioxide steel cylinder C is cooled by carbon dioxide cooler H, after reaching the temperature required scope of super critical condition, enter carbon dioxide pump B, pressurizeed by pump, make carbon dioxide reach above-critical state, then control via the first valve K1, enter subsequent reactions flow process; The entrainer mixed solution being dissolved with raw material in entrainer container C S pressurizes through entrainer pump U, produces high-pressure fluid, enters subsequent reactions flow process; Now, open the second valve K2, make the entrainer mixed solution being 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, supercritical carbon dioxide fluid flows into reactor A1 and A2 simultaneously; The entrainer mixed solution that the supercritical carbon dioxide fluid flowing into A1 promotes to be 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 that overcritical-solvent heat combines; In course of reaction, target substance is nucleation, crystallization separating out under certain pressure, temperature and specific solution environmental, obtains target product nano particle; After reaction terminates, open valve K5, fluid-mixing flows into separator S, be separated through separator S, carbon dioxide exports E1 by separator first and is discharged or recycles, entrainer exports E2 by separator second and is discharged or reclaims, and other component in raw material except target product exports E3 through separator the 3rd and is discharged; 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 is squeezed into overcritical device by the pressurization of entrainer pump and is participated in reaction, also can be placed in reactor A1 or A2 before operation in advance; No matter being use single entrainer or multiple entrainer, also can be the multiple combination of above-mentioned three kinds of modes.
In another preferred technical scheme of the present invention, described raw material is squeezed into overcritical device by the pressurization of entrainer pump and is participated in reaction, also can be placed in reactor A1 or A2 before operation in advance; No matter being use single raw material or plurality of raw materials, also can be the multiple combination of above-mentioned three kinds of modes.
In another preferred technical scheme another 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 fluid flow to mode, 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 prepares nano material.
(1), before operation starts, be installed on by the sintering pan with microcellular structure bottom cylindrical metal hand basket, reactor A2 put into by cylindrical metal hand basket; Raw material put into entrainer container C S and be dissolved in entrainer, forming uniform solution; Connect pipeline afterwards, test air-tightness, is prepared operation;
(2) valve-off K1-K5, first high-purity carbon dioxide in steel cylinder C is cooled by carbon dioxide cooler H, after reaching the temperature required scope of super critical condition, enter carbon dioxide pump B, pressurizeed by pump, make carbon dioxide reach above-critical state, then control via valve K1, enter subsequent reactions flow process;
(3) the entrainer mixed solution being dissolved with raw material in entrainer container C S pressurizes through entrainer pump U, produces high-pressure fluid, enters subsequent reactions flow process; Now, open valve K2, make the entrainer mixed solution being 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, supercritical carbon dioxide fluid flows into reactor A1 and A2 simultaneously; The entrainer mixed solution that the supercritical carbon dioxide fluid flowing into A1 promotes to be 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 that overcritical-solvent heat combines;
(5), in course of reaction, target substance is nucleation, crystallization separating out under certain pressure, temperature and specific solution environmental, obtains target product nano particle;
(6) after reaction terminates, open valve K5, fluid-mixing flows into separator S, be separated through separator S, carbon dioxide is discharged by outlet E1 or is recycled, entrainer is discharged by outlet E2 or is reclaimed, 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 the target substance components be soluble in raw material is when entrainer, the exemplary method that can combine according to overcritical as follows-solvent heat prepares nano material.
(1) before operation starts, raw material is put into cylindrical metal hand basket, the sintering pan with microcellular structure is installed bottom cylindrical metal hand basket, metal hand basket is put into reactor A1; Connect pipeline, test air-tightness, is prepared operation;
(2) valve-off K1-K5, first high-purity carbon dioxide in steel cylinder C is cooled by carbon dioxide cooler H, after reaching the temperature required scope of super critical condition, enter carbon dioxide pump B, pressurizeed by pump, make carbon dioxide reach above-critical state, then control via valve K1, enter subsequent reactions flow process;
(3) entrainer in entrainer container C S pressurizes through entrainer pump U, produces high-pressure fluid, enters subsequent reactions flow process; Now, open valve K2, make entrainer enter reactor A1, with contact raw in reactor A1, 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, supercritical carbon dioxide fluid flows into reactor A1 and A2 simultaneously; The entrainer mixed solution that the supercritical carbon dioxide fluid flowing into A1 promotes to be 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 that overcritical-solvent heat combines;
(5), in course of reaction, target substance is nucleation, crystallization separating out under certain pressure, temperature and specific solution environmental, obtains target product nano particle;
(6) after reaction terminates, open valve K5, fluid-mixing flows into separator S, is separated through separator S, and carbon dioxide is discharged by outlet E1 or is recycled, and entrainer is discharged by outlet E2 or is reclaimed;
(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
If when raw material can not be dissolved in entrainer, the exemplary method that can combine according to overcritical as follows-solvent heat prepares nano material.
(1) before operation starts, raw material is put into cylindrical metal hand basket, the sintering pan with microcellular structure is installed bottom cylindrical metal hand basket, metal hand basket is put into reactor A2; Connect pipeline, test air-tightness, is prepared operation;
(2) valve-off K1-K5, first high-purity carbon dioxide in steel cylinder C is cooled by carbon dioxide cooler H, after reaching the temperature required scope of super critical condition, enter carbon dioxide pump B, pressurizeed by pump, make carbon dioxide reach above-critical state, then control via valve K1, enter subsequent reactions flow process;
(3) entrainer in entrainer container C S pressurizes through entrainer pump U, 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, supercritical carbon dioxide fluid flows into reactor A1 and A2 simultaneously; The supercritical carbon dioxide fluid flowing 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 that overcritical-solvent heat combines;
(5), in course of reaction, there is the behaviors such as dissolving changes with recrystallization, crystal transfer, grain size, Morphology Evolution in target substance, obtain target product nano particle under certain pressure, temperature and specific solution environmental;
(6) after reaction terminates, open valve K5, fluid-mixing flows into separator S, is separated through separator S, and carbon dioxide is discharged by outlet E1 or is recycled, and entrainer is discharged by outlet E2 or is reclaimed;
(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 is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (4)
1. prepare the method for nano material for one kind, it is characterized in that, adopt overcritical-solvent heat to combine and prepare the device of nano material, 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 with the first valve after carbon dioxide carrier pipe section converge; Pipeline after converging is connected with the top of secondary reacting kettle respectively by the second valve, is connected with the supervisor road junction, top of main reaction still by the 3rd valve; 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, is connected bottom described main reaction still by pipeline through the 5th valve with separator entrance point; Cylindrical metal hand basket is placed in the inside of described secondary reacting kettle and/or main reaction still, and the sintering pan with microcellular structure is installed in the top of described metal hand basket and/or bottom;
Described method comprises the steps:
A, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket; Raw material put into entrainer container and be dissolved in entrainer, forming uniform solution;
B, close first, second, third and fourth, five valves, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, make carbon dioxide reach above-critical state; The entrainer mixed solution being 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 being 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 flowing into secondary reacting kettle promotes to be 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
2. prepare as claimed in claim 1 the method for nano material, it is characterized in that, described separator is provided with that separator first exports, separator second exports and separator the 3rd outlet; After the fluid-mixing inflow separator that reaction is remaining, carbon dioxide is wherein discharged by separator first outlet or is recycled, entrainer is discharged by separator second outlet or is reclaimed, and other component in raw material except target product is discharged through separator the 3rd outlet.
3. prepare the method for nano material for one kind, it is characterized in that, adopt overcritical-solvent heat to combine and prepare the device of nano material, 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 with the first valve after carbon dioxide carrier pipe section converge; Pipeline after converging is connected with the top of secondary reacting kettle respectively by the second valve, is connected with the supervisor road junction, top of main reaction still by the 3rd valve; 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, is connected bottom described main reaction still by pipeline through the 5th valve with separator entrance point; Cylindrical metal hand basket is placed in the inside of described secondary reacting kettle and/or main reaction still, and the sintering pan with microcellular structure is installed in the top of described metal hand basket and/or bottom;
Described method comprises the steps:
A, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket; Raw material is put into main reaction still or secondary reacting kettle;
B, close first, second, third and fourth, five valves, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, 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 supercritical carbon dioxide fluid promotion entrainer flowing into secondary reacting kettle or the entrainer mixed solution being partly dissolved raw material enter 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; Closing carbon dioxide pump, opens main reaction still upper cover, takes out the target product nano particle of precipitating in metal hand basket.
4. prepare the method for nano material for one kind, it is characterized in that, adopt overcritical-solvent heat to combine and prepare the device of nano material, 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 with the first valve after carbon dioxide carrier pipe section converge; Pipeline after converging is connected with the top of secondary reacting kettle respectively by the second valve, is connected with the supervisor road junction, top of main reaction still by the 3rd valve; 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, is connected bottom described main reaction still by pipeline through the 5th valve with separator entrance point; Cylindrical metal hand basket is placed in the inside of described secondary reacting kettle and/or main reaction still, and the sintering pan with microcellular structure is installed in the top of described metal hand basket and/or bottom;
Described method comprises the steps:
A, be installed on bottom cylindrical metal hand basket by the sintering pan with microcellular structure, main reaction still put into by cylindrical metal hand basket;
B, close first, second, third and fourth, five valves and entrainer pump, first high-purity carbon dioxide in carbon dioxide steel cylinder is cooled by carbon dioxide cooler, after reaching the temperature required scope of super critical condition, enters carbon dioxide pump, pressurizeed by pump, make carbon dioxide reach above-critical state;
C, be dissolved in entrainer by raw material, form uniform solution, the entrainer mixed solution this being dissolved with raw material puts 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 flowing into secondary reacting kettle promotes the prepositioned entrainer mixed solution being 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 that overcritical-solvent heat combines, reaction;
After E, reaction terminate, open the 5th valve, the fluid-mixing inflow separator that reaction is remaining, be separated; 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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| CN104707355A (en) * | 2015-03-20 | 2015-06-17 | 南通东泽数控机床有限公司 | 5 L supercritical carbon dioxide extraction nanocrystal device |
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| CN110478246A (en) * | 2019-08-09 | 2019-11-22 | 厦门大学 | A kind of pure medicine nano particle preparation facilities and method |
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