CN106145198A - Prepare the method and device of uranium oxide microsphere - Google Patents
Prepare the method and device of uranium oxide microsphere Download PDFInfo
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- CN106145198A CN106145198A CN201610502927.4A CN201610502927A CN106145198A CN 106145198 A CN106145198 A CN 106145198A CN 201610502927 A CN201610502927 A CN 201610502927A CN 106145198 A CN106145198 A CN 106145198A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G43/00—Compounds of uranium
- C01G43/01—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G43/00—Compounds of uranium
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- C01G43/025—Uranium dioxide
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The present invention provides one to prepare U3O8The method of microsphere, described method includes utilizing flow focusing effect to make uranium-bearing colloidal dispersion become uranium-bearing microlayer model, and and then gelling become uranium-bearing microsphere.Present invention provides one and prepare U3O8The device of microsphere, it is particularly well-suited to the U of the present invention3O8Microsphere manufacture method.Present invention also offers small particle single dispersing U3O8Microsphere and preparation UO2The method of microsphere.The inventive method achieves small particle single dispersing U3O8The preparation of microsphere.
Description
Technical field
The present invention relates to nuclear fuel preparation field, in particular it relates to prepare the method and device of uranium oxide microsphere.
Background technology
Dispersion type nuclear fuel is a kind of important kind of nuclear fuel.The preparation of dispersion type nuclear fuel is typically first to make
Standby nuclear fuel micro, then mixes with cold inertia dispersive medium and is pressed into raw fuel pellet, after high temperature sintering
Form final products.Wherein, the core procedure during the preparation of nuclear fuel micro is whole preparation process.The group of nuclear fuel micro
The factors such as the distribution of one-tenth, pattern, size, particle diameter, microstructure affect the performance of nuclear fuel strongly.
The oxide of uranium, such as U3O8And UO2, it is common nuclear fuel micro material.For a long time, by sol-gel work
Skill prepares uranium oxide microsphere.By making the colloidal sol of uranium-bearing be gelled, form uranium-bearing gel micro-ball, then gel micro-ball is forged
Burn, form uranium oxide microsphere.According to the gelling mode used, interior gelatinizing process, external gelatinizing process and other glue can be divided into
Solidifying technique.
No matter use which kind of gelling mode, be required for colloidal dispersion becomes colloidal sol drop be gelled again.Colloidal sol drop
Size and uniformity determine size and the uniformity of final uranium oxide microsphere.Owing to naturally disperseing the colloidal sol drop of formation
Size is in wider normal distribution, and the size range that dispersion type nuclear fuel requires uranium oxide microsphere is narrow, it is therefore desirable to right
Colloidal dispersion process is controlled, thus improves the size qualification rate of final uranium oxide microsphere.
Up to now, various spray nozzle device and relevant is concentrated on about the research controlling uranium-bearing colloidal dispersion process
In mode of vibration, can be divided mainly into double flowing nozzle dispersion, single-fluid nozzles vibration dispersion and double flowing nozzle vibration dispersion etc..At present,
The coarse grained Microsphere Size of centering controls to have had preferable effect, but particle diameter is less than small particle U of 150 μm3O8Microsphere
Size Control difficulty is the biggest.
Such as, U.S.'s Oak Ridge National Laboratory uses double flowing nozzle to utilize the turbulence effect driving stream to make Sol Jet
It is dispersed into drop (Hass P A, et al.Application of Drop Formation Procedures to Meet
Gel-Sphere-PAC Requirements.IAEA-161,1974,72-84, Vienna).Its result shows, when putting down of microsphere
During the most a diameter of 65 μm, diameter microsphere in 45 to 91 μ m has accounted for 60%.Although the method has prepared the uranium of small particle
Oxidate microspheres, but the size of microsphere is the most uneven, and monodispersity is poor.
King records congruent in order to control the distribution of sizes of little particulate microsphere, establishes a set of small-sized droplet jet stream vibration dispersion
Device, in order to the dispersive process of Sol Jet is directly observed and controlled, thus adjust in time and control parameter, but should
Apparatus structure is more complicated, and operation requires height, and (Wang Luquan, Ying Shihao, Ji Changhong, Sol Jet vibration dispersion and little granule are solidifying
The size Control research of glue microsphere, China's nuclear science echnology report, 00 phase in 2002).
Therefore, for the method and apparatus preparing high monodispersity small particle uranium oxide microsphere with simple device, deposit
At needs.
Summary of the invention
In order to achieve the above object, the present invention provides techniques below scheme.
A first aspect of the present invention provides one to prepare U3O8The method of microsphere, said method comprising the steps of: (1) will
The mixed aqueous solution of carbamide and hexamethylenetetramine joins in uranyl nitrtate aqueous solution, forms dispersion phase solution；(2) by described
Dispersion phase solution is passed through in continuous phase solution stream by capillary tube, and be provided with corresponding thereto in the downstream of described capillary tube is little
Hole, thus utilize flow focusing effect to make described dispersion phase solution be formed at the dispersed phase drop in described continuous phase solution；(3)
The gelling of described dispersed phase drop is made to form uranium-bearing gel micro-ball by heating；(4) collect, separate and wash described uranium-bearing gel
Microsphere；(5) calcine described uranium-bearing gel micro-ball, obtain U3O8Microsphere.
In one embodiment, in described dispersion phase solution, carbamide is 1: 1 with the mol ratio of hexamethylenetetramine, and
Uranyl nitrtate is 2: 1 to 3: 1 with the mol ratio of carbamide or hexamethylenetetramine.In a further embodiment, described
In dispersion phase solution, carbamide or hexamethylenetetramine are 2.3: 1 with the mol ratio of uranyl nitrtate, and uranyl nitrtate and water mole
Ratio is 1: 90 to 1: 100.
In one embodiment, by regulate the viscosity of described continuous phase solution and described continuous phase solution with described point
The velocity ratio of dephasing solution, adjusts described U3O8The particle diameter of microsphere.
In a further embodiment, described continuous phase solution is mixed to form with kerosene by low polar compound,
And by changing the viscosity of described low polar compound and continuous phase described in the proportion adjustment of described kerosene.
A second aspect of the present invention provides a kind of and prepares U for use according to the method described in first aspect3O8The dress of microsphere
Putting, described device includes: outer tube, and end is sealing surface downstream, and described sealing surface leaves opening, and described outer tube is for by institute
State the continuous phase solution stream described in method；First capillary tube, described first capillary tube has the outlet in described outer tube, uses
Make the capillary tube described in described method；Second capillary tube, described second capillary tube is positioned under described first capillary outlet
Trip, the opening on described sealing surface, one end in described outer tube of described second capillary tube is used as in described method
Described aperture.
In one embodiment, described first capillary tube is adjustable with the spacing of described second capillary tube.
A third aspect of the present invention provides by the U prepared according to the method described in first aspect3O8Microsphere, described U3O8
The particle size range of microsphere is 50 to 150 μm, and particle diameter breadth coefficient CV value is less than 5%.
A fourth aspect of the present invention provides one to prepare UO2The method of microsphere, said method comprising the steps of: by root
U is prepared according to the method described in first aspect3O8Microsphere, by prepared U3O8Microsphere reduces under reducing atmosphere, obtains UO2Microsphere.
The present invention, by utilizing flow focusing effect, is prepared for small particle (＜ 150 μm) single dispersing U3O8Microsphere.The present invention
Device based on the double capillary method that is applicable to the present invention.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the nuclear fuel micro preparation facilities according to one embodiment of the invention.
Fig. 2 is the schematic diagram of the nuclear fuel micro preparation facilities according to one embodiment of the invention.
Fig. 3 is the enlarged diagram of the T-shaped threeway in Fig. 2.
Fig. 4 is the photo of the focusing effect showing one embodiment of the invention.
Fig. 5 a-c is the light micrograph of the nuclear fuel micro prepared according to embodiments of the invention.
Detailed description of the invention
One aspect of the present invention provides one and prepares single dispersing small particle U3O8The method of microsphere.The method includes: (1) will
The mixed aqueous solution of carbamide and hexamethylenetetramine joins in uranyl nitrtate aqueous solution, forms dispersion phase solution；
(2) described dispersion phase solution is passed through in continuous phase solution stream by capillary tube, sets in the downstream of described capillary tube
It is equipped with aperture corresponding thereto, thus utilizes flow focusing effect to make described dispersion phase solution be formed in described continuous phase solution
Dispersed phase drop；(3) gelling of described dispersed phase drop is made to form uranium-bearing gel micro-ball by heating；(4) collect, separate also
Wash described uranium-bearing gel micro-ball；(5) calcine described uranium-bearing gel micro-ball, obtain U3O8Microsphere.
The present invention uses interior gelling mode to prepare U3O8Microsphere.Specifically, at low temperatures, to uranyl nitrtate (UO2(NO3)2)
Aqueous solution adds a certain amount of carbamide and hexamethylenetetramine (i.e. hexamethylenamine, HMTA) is configured to dispersion phase solution.Mixing
Slowly carry out with stirring at low temperatures, in case producing gel.For the not particularly requirement of the temperature residing for mixing, as long as point
Dephasing solution keeps relatively stable, is gelled the most rapidly.The temperature of mixing is preferably 0-5 DEG C.The dispersion phase solution prepared is
Solation, there is certain shelf-lifeing, it is possible to be dispersed in continuous phase organic media holding one with the form of microlayer model
The section time.In the present invention, the most also this dispersion phase solution is referred to as " colloidal sol ", and term is used interchangeably.When continuously
When colloidal sol microlayer model in phase organic media is heated, hexamethylenetetramine decomposes therein, and with water react release ammonia and
Formaldehyde, causes the pH value of colloidal sol drop to increase sharply and moisture reduces rapidly, thus is gelled.Droplet profile remains unchanged, and becomes
Smooth surface and there is the aqueous uranium-bearing gel micro-ball of some strength.Aqueous uranium-bearing gel micro-ball with after through collecting, separate, washing
Wash, calcine, form U3O8Microsphere.Wherein, carbamide has the effect of chelating agent and buffer agent concurrently.Carbamide and uranyl complexation, prevent uranium from sinking
Form sediment.Additionally, it can also react formation condensation product Lauxite with the formaldehyde released during hexamethylenetetramine decomposes, promote
Enter gelling.
For the disperse phase system of excellent, the formula of dispersion phase can be regulated.Usually, carbamide in dispersion phase
It is substantially 1: 1 with the mol ratio of hexamethylenetetramine.And carbamide or the hexamethylenetetramine mol ratio different from uranyl nitrtate
The time formed needed for gel can be directly affected.Owing in the present invention, the sol solution of preparation needs in microfluidic control device
It is dispersed into drop, therefore it is required that dispersion phase has time enough to be dispersed into drop before the dispersing.Experiment proves that carbamide/HTMA is too high
Time, dispersion phase solution is too fast formation gel in experimental situation, is unfavorable for being dispersed into drop.Inventor finds, by carbamide or six
The mol ratio of methine tetramine and uranyl nitrtate controls to be suitable between 2: 1 to 3: 1.
It is particularly preferred that in described dispersion phase solution, carbamide or hexamethylenetetramine with the mol ratio of uranyl nitrtate are
2.3: 1, and the mol ratio of uranyl nitrtate and water is 1: 90 to 1: 100.This formula is particularly suitable for interior gelatinization, has both had suitable
In stability, can obtain again the gel ball with good strength and hardness after gelling, and finally can obtaining property after calcining
The U that energy is good3O8Microsphere.
Gelling is carried out in continuous phase organic media.Continuous phase organic media is on the one hand as the company of dispersion gel microsphere
Continuous phase, on the other hand as the high-speed driving phase during following flow focusing.Continuous phase organic media can be by low polarity
Compound mixes with kerosene.Low polar compound can be such as silicone oil, soybean oil or salad oil.Employing mixture is continuous
One of advantage of phase can be by regulating component ratio to regulate its viscosity.
Flow focusing (Flow Focusing) phenomenon is a kind of capillary flow phenomenon, is described as the stream flowed out from capillary tube
Body is surrounded the fluid drives of its same-directional high-speed motion by another kind, forms stable taper, on the top of cone after aperture focuses on
End produces one microjet and passes aperture, and jet crushing becomes the microdroplet of monodispersity at a certain distance from aperture is outer.
In the method for the invention, uranium-bearing dispersion phase solution flows out from capillary tube, enters the continuous phase of same-directional high-speed flowing
In organic media stream.The downstream of capillary tube is provided with aperture corresponding thereto, so that uranium-bearing dispersion phase solution flows
Focusing, forms taper and converges, and produce the microjet through aperture.
Flow focusing phenomenon is affected by many factors, such as: the viscosity of dispersion phase and flow velocity, the viscosity of continuous phase and flow velocity,
The distance etc. of the outlet size of capillary tube, the diameter of aperture, capillary tube and aperture.When above-mentioned parameter meets certain relativeness
Time, stable flow focusing effect could be formed.
In the method for the invention, can be by utilizing the region between microscope amplifying observation capillary tube and aperture, really
Recognize flow focusing to be formed.And above-mentioned factor can be regulated, to form stable flow focusing while observing with microscope.
Additionally, change above-mentioned factor synergistically, thus it is possible to vary the size of the colloidal sol microlayer model of formation.
The viscosity of dispersion phase is determined by its composition.Because dispersion phase relates to solgel reaction, and changes its composition
Can be to the final U obtained3O8Microsphere performance produce impact, therefore general tree its carry out big adjustment, substantially take above-mentioned excellent
The formula of choosing.But, the flow velocity of dispersion phase is adjustable.
The size of microlayer model can be affected by changing the viscosity of continuous phase.Continuous phase viscosity is the biggest, cuts dispersion phase
Shear force is the biggest, and the drop that dispersion phase is dispersed into is the least, and the Microsphere Size finally obtained is the least.As it was noted above, even
The viscosity of continuous phase can be changed by its composition.Such as, when using the low polar compound mixture with kerosene as continuous phase
During solution, its viscosity can be regulated by the ratio of low polar compound Yu kerosene.
Additionally, continuous phase is the biggest with the velocity ratio of dispersion phase, drop is the least, and microsphere is the least；Velocity ratio diminishes, and microsphere is also
Strain is big mutually.It is to say, in the case of the geometric parameter of device is certain, can be by the viscosity of regulation continuous phase and company
The continuous velocity ratio with dispersion phase, the size of regulation product microsphere.The flow velocity of continuous phase and dispersion phase all can be filled by driving
Put syringe pump such as to regulate, such as, by changing the fltting speed of syringe pump.
In the method for the present invention, formed the heating after colloidal sol microlayer model, collect, separate, wash, the step such as calcining all may be used
To use sol-gel process to prepare the corresponding steps in the existing method of nuclear fuel microgranule.
Such as, in step (3), it is possible to use on-line heating device, heating temperature range is preferably 90-100 DEG C, such as
90℃.In step (4), gel microlayer model can be collected in weak ammonia.In step (5), will be containing solidifying by decantation
Glue microsphere separates with continuous phase.Wash for several times with other volatile compatible organic solvent, to remove the continuous phase of residual.It is placed in
Natural drying in ventilated chamber, obtains monodispersity uranium-bearing gel micro-ball, after obtain nuclear fuel micro through high-temperature calcination.At this
In the case of bright, the temperature range of calcining can be substantially at about 100 to 800 DEG C.As an example, the calcination condition of the present invention can
Be 100 DEG C carry out 1 hour, 200 DEG C carry out 2 hours, 300 DEG C carry out 2 hours, 500 DEG C carry out 2 hours and
800 DEG C carry out 3 hours.
The compatible organic solvent of washing is nonpolar and weakly polar organic solvent, the most volatile, more preferably
For hexane, petroleum ether, dichloromethane, chloroform, or hexane, petroleum ether, dichloromethane, chloroform are water-soluble with methanol, ethanol, acetone etc.
Property solvent composition mixed solvent.
The method of the present invention make use of flow focusing effect, has the following advantages.It is possible, firstly, to it is the least to obtain particle diameter
Microlayer model.The size of microlayer model, much smaller than the internal diameter of the capillary tube for delivering dispersion phase, is not limited by this capillary size
System.Such as, the capillary tube using internal diameter to be about 250 μm delivers dispersion phase, can prepare the U of a diameter of 50 μm3O8Microsphere.Secondly,
The monodispersity of the microlayer model of gained is the best.The method utilizing the present invention, particle diameter distribution variation coefficient CV can be less than 5%.
3rd, the method utilizing the present invention, by the velocity ratio of regulation continuous phase with dispersion phase, and continuous phase can be regulated if desired
Viscosity, simplicity regulates U neatly3O8The particle diameter of microsphere.
A second aspect of the present invention provides one and utilizes method of the present invention to prepare U3O8The device of microgranule, described
Device includes:
Outer tube, end is sealing surface downstream, and described sealing surface leaves opening, and described outer tube is for by described method
Described continuous phase solution stream；
First capillary tube, described first capillary tube has the outlet in described outer tube, described in described method
Capillary tube；
Second capillary tube, described second capillary tube is positioned at the downstream of described first capillary outlet, through described sealing surface
On opening, one end in described outer tube of described second capillary tube is used as the described aperture in described method.
The flow focusing process of the method for the present invention is to carry out in the stream of continuous phase, and therefore assembly of the invention is arranged
There is the outer tube for continuous phase flowing.
In outer tube, it is provided with the outlet of the first capillary tube, its described capillary tube being used as in the method for the present invention, it is used for
Dispersion phase solution stream is delivered in continuous phase.The Way out of the first capillary tube is towards the downstream of outer tube so that dispersion phase stream
Flowing equidirectional with continuous phase stream.Export relative place in the downstream of the first capillary outlet with it, the second capillary tube is set.Due to
The downstream of outer tube is closed and therefore the fluid in outer tube is only capable of going out outer tube by the second capillary flow, so the second capillary tube
Entrance play the effect of the described aperture in described method so that the microjet of the focusing of formation is injected in the second capillary tube,
And the colloidal sol microlayer model being dispersed in continuous phase.Colloidal sol microlayer model after dispersion flows out the outlet of the second capillary tube, after entrance
Continuous step.Second capillary tube is set and includes that it is easy to manufacture as the benefit of flow focusing aperture, it is easy to dismounting, and profit
In to the microexamination of focal zone and fine setting.
A kind of embodiment of the present invention is shown schematically in Fig. 1.In Fig. 1,1 is outer tube, continuous phase c in outer tube from a left side
Flow to the right.2 is the first capillary tube, and wherein dispersion phase d1 flows in capillary tube from left to right.3 is the second capillary tube, and it enters
Mouth is relative with the outlet of the first capillary tube 2, is positioned at downstream.4 is sealing surface.Owing to the velocity ratio dispersion phase of continuous phase is fast, and
Enter the second capillary tube 3 because of the existence of sealing surface 4 and further speed up suddenly, so the first capillary tube 2 and second mao
Between tubule 3, when the technological parameters such as flow velocity, viscosity, distance are suitable, fluid focus effect can be caused, form dispersion phase taper
d2.Dispersion phase solution is broken into uniform drop d3 in the second capillary tube 3, and moves on.Leaving the second capillary
After the outlet of pipe 3, microlayer model d4 is dispersed in continuous phase c.This microlayer model d4 is heated in subsequent step, becomes uranium-bearing
Gel micro-ball, and through subsequent treatment, finally after calcining, become U3O8Microsphere.
Assembly of the invention can be configured with follow-up output duct, (be such as attached on output duct is online for heater
Heater), catcher etc..These parts be those skilled in the art it is contemplated that, and can be with phase of the prior art
Answer parts identical.Output duct can be made up of politef, will not deform when being placed in long-time heating in 90 degree of water-baths,
Ensure that continuous phase flowing will not be impacted, and then the gel micro-ball formed after guarantee heating normally flows out.
In the apparatus of the present, with the simple stream of the aperture being formed directly on sheet material (Closed End of such as outer tube)
The dynamic structure that focuses on is compared, and arranges the second capillary tube and has following benefit as aperture.First, easily manufacture is described little
Hole, forming the capillary tube of hundreds of micron diameter, form the precision orifice of hundreds of microns than on slab much easier.Correspondingly, exist
Opening on the sealing surface of outer tube can be relatively big, if coupling capillary tube external diameter or the peripheral hardware attachment structure of capillary tube, this
Greatly reduce manufacture difficulty.In one embodiment, the size of opening even can be identical with outer tube diameter, and now second
Capillary tube can such as be arranged in the closed casing that external diameter and outer tube diameter match.Secondly, second capillary tube of the present invention
It is removably, the second capillary tube and adnexa thereof individually can be unloaded when needed.3rd, be conducive to implementing the present invention's
Flow focusing district is observed during method.In the method for the invention, generally require when forming focusing effect and focal zone is used
Microscopes etc. carry out observing and carrying out intense adjustment.Prominent second capillary inlet relative with the first capillary outlet is easy
Examine under a microscope, thus be beneficial to focal zone is finely adjusted.Fig. 4 shows the flow focusing district examined under a microscope,
Wherein it will be clear that dispersion phase focuses on the taper formed.
In the apparatus of the present, the diameter of the first capillary tube, the diameter of the second capillary tube and two are intercapillary
Flowing focusing effect is all had an impact by distance.These geometric parameters all have shadow to gel droplet size and final microsphere size
Ring.But, because in the method for the invention, the most substantially be enough to microsphere big by the viscosity and flow velocity adjusting continuous phase
Little make the adjustment wanted, the diameter of the first and second capillary tubies is fixed so general rather than be set to adjustable, with letter
Gasifying device.Two intercapillary distances can be adjusted, but the main purpose of regulation is to form flow focusing now
As.
A kind of specific embodiments of assembly of the invention is shown in Figure 2.This device includes a T-shaped threeway 5.At figure
In, the top port of T-shaped threeway is connected to continuous phase solution syringe 2-1 by pipeline 4, and it is transported at continuous phase syringe pump 1-1
Continuous phase solution is injected to T-shaped threeway 5 during row.Similarly, the left port of T-shaped threeway is connected to dispersion is mixed by pipeline 3
Liquid syringe 2-2, it injects dispersion phase solution when dispersion phase syringe pump 1-2 runs to T-shaped threeway 5.The right of T-shaped threeway 5
Port is downstream tube 6, and it is heated by water-bath 9.Outlet at pipe 6 obtains uranium-bearing gel micro-ball 11, they are collected in equipped with
In the collection container 8 of weak ammonia.
The enlarged drawing of T-shaped threeway 5 and part A about is as shown in Figure 3.T-shaped threeway 5 has two transverse port and
Individual longitudinal port.First capillary tube 3-1 is from the left end transverse port pass-out right-hand member transverse port of T-shaped threeway a bit.Horizontal at left end
To port, the first capillary tube is fixed in a closed casing 10.The outside of closed casing 10 is joined with T-shaped threeway internal diameter whorl
Close and seal.Herein referred closed casing is the sleeve pipe of middle other parts of closed conduct cross section through capillary tube, such as, and can
Be section be the sleeve pipe of the sealing surface with a through hole.Capillary tube can be positioned and easy by closed casing the most easily
In dismounting.And, closed casing prevents dispersion phase or continuous phase from will not overflow to around greatly because of pressure change in entering threeway.The
One capillary tube 3-1 is used for making dispersion phase solution flow into, and it extends through T-shaped threeway, from right-hand member transverse port pass-out, through one
Connect sleeve pipe and arrive focusing section (square portion in figure).Longitudinal port of T-shaped threeway is connected with continuous phase source.In focus cell
In with the relative downstream of outlet of the first capillary tube 3-1, be provided with the second capillary tube 3-2, it is positioned at another closed casing 10
In.This closed casing 10 i.e. defines the downstream sealing surface of the outer tube in apparatus of the present invention.Uranium-bearing colloidal sol microlayer model 7 is second
Capillary inlet is formed about, and along the second capillary flow downstream, enters output duct 6 from outlet.Can on output duct 6
To be provided with on-line heating device, uranium-bearing colloidal sol microlayer model is heated, form gel micro-ball 11.
As an example, described first capillary tube by threeway insert threaded closing pullover and be connected with threeway poly-
In tetrafluoroethene pipe, the first capillary tube port stretches out politef pipe port a bit, the second capillary tube be cased with internal diameter with it outside
The closed casing that footpath is identical；The polyfluortetraethylene pipe external diameter that this closed casing inserts with aforementioned first capillary tube is identical, incite somebody to action the two
Insert from two the connection conduit that another internal diameter is identical with its external diameter, focal zone will be formed at this connection conduit.By changing
Become the second capillary seal sleeve pipe and be inserted in the position connected in conduit, i.e. between scalable the first capillary tube and the second capillary tube
Away from.
In an instantiation of device, the catheter outer diameter that dispersion phase and continuous phase syringe are connected with T-shaped threeway is
1600um, internal diameter is 1000um；The first capillary tube external diameter that dispersion phase syringe is connected with T-shaped threeway is 160～750um, interior
Footpath is 20～540um.First capillary tube and the second intercapillary distance are about 350 μm.For preparing different size of system
Standby U3O8Microsphere, it is possible to use the first capillary tube that internal diameter is different.The internal diameter of the second capillary tube typically keeps constant.
The process specifically utilizing the method that assembly of the invention carries out the present invention is: the continuous phase solution that will prepare is passed through
Pump 1-1 drives, and injects longitudinal port of T-shaped threeway 5 from syringe 2-1 through conduit 4, and forms the company to the flowing of threeway right-hand member
The continuous liquid stream that mixes.The dispersion phase solution prepared is driven through pump 2-1, from syringe 2-2 through conduit 3, by through T-shaped three
First capillary tube 3-1 of two transverse port of logical 5 is passed through continuous phase solution stream.Dispersion phase solution stream and continuous phase solution stream exist
Region between first capillary tube 3-1 and the second capillary tube 3-2 produces flow focusing phenomenon.Dispersion phase solution forms taper and focuses on
With enter the microjet of the second capillary tube 3-2, and the uranium-bearing colloidal sol being dispersed in continuous phase subsequently breaking up uniformly size is micro-
Drop 7.Microlayer model flows out the second capillary tube 3-2 along with continuous phase, enters the output duct 6 in downstream, adds through online water-bath 9
Heat, forms gel micro-ball 11, and is collected in the returnable 8 being filled with weak ammonia.
The particle diameter of the microgel particle being achieved in that is much smaller than the size of the first capillary tube self, it is hereby achieved that small particle
Preparation U3O8Microsphere.
In a more particular embodiment, the step of the method it may also is that
I () adds appropriate analytical pure uranyl nitrtate (UO in beaker 12(NO3)2·6H2And appropriate amount of deionized water, magnetic force O)
Stirring makes it dissolve, and is configured to uranyl nitrate solution；Beaker 2 adds appropriate carbamide, hexamethylenetetramine (HMTA) and appropriate
Deionized water, magnetic agitation makes it dissolve completely；At low temperatures, the beaker 1 that the solution of beaker 2 is slowly added into limit stirring is molten
Liquid mixes, continues stirring, obtain dispersion phase solution；
(ii) low polar compound is mixed with kerosene control continuous phase viscosity, such as, can use low polar compound with
Kerosene weight ratio is the continuous phase solution of 6: 4；
(iii) dispersion phase and the flow velocity of continuous phase are adjusted: controlling dispersion phase flow rates is 80～900 μm min-1, even
Continuous phase flow rates is 390 μm min-1～1.96mm min-1；
(iv) the first capillary tube and the second intercapillary distance are the most manually regulated, until producing stable
Flow focusing；
V drop that () is formed can flow through online water-bath by polyfluortetraethylene pipe and heat, and forms gel micro-ball；
(vi) being collected in weak ammonia by gel micro-ball, after then passing through decantation, the continuous phase of residual is volatile with other
Compatible organic solvent washs for several times, is placed in natural drying in ventilated chamber, obtains monodispersity uranium-bearing gel micro-ball, after through height
Temperature calcining obtains U3O8Microsphere.
A third aspect of the present invention provides the small particle prepared by said method and controlled single dispersing U3O8Microsphere.
Described single dispersing U3O8The particle size range of microsphere is 50～150 μm, and configuration of surface is good, and particle diameter distribution variation coefficient CV value is less than
5%.
Wherein the surface distributed coefficient of variation is defined by the formula:
Wherein meansigma methodsStandard deviationRandomly select a number of micro-
Its diameter measured under the microscope by ball, respectively arithmetic average diameter and the standard deviation of diameter, finally presses formula and calculates CV.
A fourth aspect of the present invention provides preparation UO2The method of microsphere, said method comprising the steps of: according to first
Method described in aspect prepares U3O8Microsphere, by prepared U3O8Microsphere reduces under reducing atmosphere, obtains UO2Microsphere.
By U3O8It is reduced to UO2Actual conditions can use reaction condition well known in the art.Due to the raw material being reduced
Time the monodispersed U of small particle3O8Microsphere, so can obtain the monodispersed UO of small particle accordingly2Microsphere.
Further illustrate the present invention by the following examples, but the invention is not restricted to these embodiments.
Embodiment 1
Under low temperature (5 DEG C), 0.49g carbamide and 1.15g hexamethylenetetramine (HMTA) are joined containing 3mL deionization
In the beaker of water, magnetic agitation makes it dissolve；By 1.80g UO2(NO3)2·6H2O joins the burning containing 2.6mL deionized water
In Bei, magnetic agitation makes it dissolve, and then the mixed solution of carbamide and hexamethylenetetramine is poured slowly into uranyl nitrate solution,
And the stirring of limit bevelling, to prevent gel, after pouring into completely, continue agitating solution 10min, prepare dispersion phase solution.
In this dispersion phase solution, carbamide is 1: 1 with the mol ratio of HMTA；Carbamide (or HMTA) and uranyl nitrtate mole
Ratio is 2.3: 1；The total amount of water is 6mL, wherein comprises the water of crystallization from uranyl nitrtate.
Being mixed homogeneously with 40g kerosene by 60g silicone oil, it is thus achieved that continuous phase solution, its viscosity is 38.12mpa s.
60mL analytical pure ammonia is mixed with 60mL water, it is thus achieved that weak ammonia collects solution.
The device shown in Fig. 2 and Fig. 3 is used to carry out flow focusing.Dispersion phase solution and continuous phase solution are respectively charged into
In the syringe of 1mL and 20mL, it is built on two propelling pumps at hypothermia operation table, connects microfluidic controller, dispersion is set
Phase flow velocity is 80 μm min-1, continuous phase flow velocity is 1.96mm min-1.First capillary size is: external diameter/internal diameter is 360 μ
m/252μm.Second capillary size is: external diameter/internal diameter is 652 μm/500 μm.First capillary outlet and the second capillary tube enter
Spacing between Kou is about 350 μm.With this understanding, the dispersion phase solution flowed out from the first capillary outlet focuses on second mao
In tubule entrance, and disperse to form single dispersing uranium-bearing colloidal sol drop；It is collected in after the preliminary gel solidification of heating in water bath online
In culture dish equipped with above-mentioned ammonia spirit, obtain uranium-bearing gel microballon.After standing 10～12 hours after simple decantation,
The continuous phase of residual, with after petroleum ether 3 times, is placed in ventilated chamber natural drying 4 hours, then puts dried microsphere into height
In temperature stove, calcining can obtain U3O8Microsphere.Fig. 5 a is the optical microphotograph picture of thus obtained microsphere, it can be seen that microspherulite diameter is homogeneous, has
Monodispersity, particle diameter is 50 μm.
Embodiment 2
Under low temperature (5 DEG C), 0.49g carbamide and 1.15g hexamethylenetetramine (HMTA) are joined containing 3mL deionization
In the beaker of water, magnetic agitation makes it dissolve；By 1.80g UO2(NO3)2·6H2O joins the burning containing 2.6mL deionized water
In Bei, magnetic agitation makes it dissolve, and then the mixed solution of carbamide and hexamethylenetetramine is poured slowly into uranyl nitrate solution,
And the stirring of limit bevelling, to prevent gel, after pouring into completely, continue agitating solution 10min, prepare dispersion phase solution.
Being mixed homogeneously with 40g kerosene by 60g silicone oil, it is thus achieved that continuous phase solution, its viscosity is 38.12mpa s.
60mL analytical pure ammonia is mixed with 60mL water, it is thus achieved that weak ammonia collects solution.
The device shown in Fig. 2 and Fig. 3 is used to carry out flow focusing.Above-mentioned dispersion phase solution and continuous phase solution are filled respectively
Enter in the syringe of 1mL and 20mL, be placed at low ambient temperatures on two propelling pumps, connect microfluidic controller, dispersion is set
Phase flow velocity is 120 μm min-1, continuous phase flow velocity is 1.96mm min-1.First capillary size is: external diameter/internal diameter is 360
μm/252μm.Second capillary size is: external diameter/internal diameter is 652 μm/500 μm.First capillary outlet and the second capillary tube enter
Spacing between Kou is about 350 μm.With this understanding, the dispersion phase solution flowed out from the first capillary outlet focuses on second mao
In tubule entrance, and disperse to form single dispersing uranium-bearing colloidal sol drop；Online be collected in after heating in water bath primary solidification equipped with
In the culture dish of above-mentioned ammonia spirit, obtain uranium-bearing gel microballon.After standing 10～12 hours after simple decantation, residual
Continuous phase with after petroleum ether 3 times, be placed in ventilated chamber natural drying 4 hours, then put dried microsphere into high temperature furnace
Middle calcining can obtain U3O8Microsphere.Fig. 5 b is the optical microphotograph picture of thus obtained microsphere, it can be seen that microspherulite diameter is homogeneous, has single point
Dissipating property, particle diameter is 70 μm.
Embodiment 3
Under low temperature (5 DEG C), 0.49g carbamide and 1.15g hexamethylenetetramine (HMTA) are joined containing 3mL deionization
In the beaker of water, magnetic agitation makes it dissolve；By 1.80g UO2(NO3)2·6H2O joins the burning containing 2.6mL deionized water
In Bei, magnetic agitation makes it dissolve, and then the mixed solution of carbamide and hexamethylenetetramine is poured slowly into uranyl nitrate solution,
And the stirring of limit bevelling, to prevent gel, after pouring into completely, continue agitating solution 10min, prepare dispersion phase solution.
Being mixed homogeneously with 40g kerosene by 60g silicone oil, it is thus achieved that continuous phase solution, its viscosity is 38.12mpa s.
60mL analytical pure ammonia is mixed with 60mL water, it is thus achieved that weak ammonia collects solution.
The device shown in Fig. 2 and Fig. 3 is used to carry out flow focusing.Above-mentioned dispersion phase solution and continuous phase solution are filled respectively
Entering in the syringe of 1mL and 20mL, be placed on two propelling pumps, connect microfluidic controller, arranging dispersion phase flow velocity is 120 μ
m·min-1, continuous phase flow velocity is 780 μm min-1.First capillary size is: external diameter/internal diameter is 360 μm/252 μm.Second
Capillary size is: external diameter/internal diameter is 652 μm/500 μm.Spacing between first capillary outlet and the second capillary inlet
It is about 350 μm.With this understanding, the dispersion phase solution flowed out from the first capillary outlet focuses on the second capillary inlet,
And disperse to form single dispersing uranium-bearing colloidal sol drop；It is collected in equipped with above-mentioned ammonia spirit after heating in water bath primary solidification online
Culture dish in, obtain uranium-bearing gel microballon.After standing 10～12 hours after simple decantation, the continuous phase stone of residual
Oil ether washs after 3 times, is placed in ventilated chamber natural drying 4 hours, more dried microsphere is put into calcining in high temperature furnace can obtain U3O8
Microsphere.Fig. 5 c is the optical microphotograph picture of thus obtained microsphere, it can be seen that microspherulite diameter is homogeneous, has monodispersity, and particle diameter is 150
μm。
From embodiment 1-3 it will be seen that by methods and apparatus of the present invention, prepared the small particle that monodispersity is splendid
U3O8Microsphere.
In a word, the single dispersing U that prepared by the present invention3O8Microsphere surface form is preferable, and particle size range is 50～150 μm；This is prepared
Device assembly or disassembly is easy, the capillary size flowed through by dispersion phase in adjustment microfluidic controller, continuous phase and dispersion
Phase flow velocity and viscosity, can regulate and control the size of prepared microsphere easily, save production cost.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvements and modifications, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (9)
1. prepare U for one kind3O8The method of microsphere, said method comprising the steps of:
(1) mixed aqueous solution of carbamide and hexamethylenetetramine is joined in uranyl nitrtate aqueous solution, form dispersion phase solution；
(2) described dispersion phase solution is passed through in continuous phase solution stream by capillary tube, is provided with in the downstream of described capillary tube
Aperture corresponding thereto, thus utilizing flow focusing effect to make, described dispersion phase solution is formed in described continuous phase solution point
Dephasing drop；
(3) gelling of described dispersed phase drop is made to form uranium-bearing gel micro-ball by heating；
(4) collect, separate and wash described uranium-bearing gel micro-ball；
(5) calcine described uranium-bearing gel micro-ball, obtain U3O8Microsphere.
Method the most according to claim 1, it is characterised in that in described dispersion phase solution, carbamide and six methines four
The mol ratio of amine is 1: 1, and the mol ratio of carbamide or hexamethylenetetramine and uranyl nitrtate is 2: 1 to 3: 1.
Method the most according to claim 2, it is characterised in that in described dispersion phase solution, carbamide or six methines four
Amine is 2.3: 1 with the mol ratio of uranyl nitrtate, and the mol ratio of uranyl nitrtate and water is 1: 90 to 1: 100.
Method the most according to claim 1, it is characterised in that by regulating the viscosity of described continuous phase solution and described company
Continuous phase solution and the velocity ratio of described dispersion phase solution, adjust described U3O8The particle diameter of microsphere.
Method the most according to claim 4, it is characterised in that described continuous phase solution is mixed with kerosene by low polar compound
Close and formed, and by changing the viscosity of described low polar compound and continuous phase described in the proportion adjustment of described kerosene.
6. one kind is used for using method according to claim 1 to prepare U3O8The device of microsphere, described device includes:
Outer tube, end is sealing surface downstream, and described sealing surface leaves opening, and described outer tube is for by described in described method
Continuous phase solution stream；
First capillary tube, described first capillary tube has the outlet in described outer tube, as the capillary described in described method
Pipe；
Second capillary tube, described second capillary tube is positioned at the downstream of described first capillary outlet, on described sealing surface
Opening, described second capillary tube one end in described outer tube is used as the described aperture in described method.
Device the most according to claim 6, it is characterised in that described first capillary tube and the spacing of described second capillary tube
It is adjustable.
8. the U prepared by method according to claim 13O8Microsphere, described U3O8The particle size range of microsphere is 50 to 150
μm, particle diameter breadth coefficient CV value is less than 5%.
9. prepare UO for one kind2The method of microsphere, said method comprising the steps of:
U is prepared by method according to claim 13O8Microsphere,
By prepared U3O8Microsphere reduces under reducing atmosphere, obtains UO2Microsphere.
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