CN105833813A - Room temperature droplet micro-reactor and method of producing zirconium dioxide gel microspheres - Google Patents
Room temperature droplet micro-reactor and method of producing zirconium dioxide gel microspheres Download PDFInfo
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- CN105833813A CN105833813A CN201610174094.3A CN201610174094A CN105833813A CN 105833813 A CN105833813 A CN 105833813A CN 201610174094 A CN201610174094 A CN 201610174094A CN 105833813 A CN105833813 A CN 105833813A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
- B01J2219/00792—One or more tube-shaped elements
- B01J2219/00797—Concentric tubes
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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
- C01P2004/30—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
Abstract
The invention provides a room temperature droplet micro-reactor and a method of producing zirconium dioxide gel microspheres. The room temperature droplet micro-reactor comprises an internal phase fluid inject pipe, an external phase fluid inject pipe, a collection pipe, and a continuous phase fluid inlet pipe. The internal phase fluid inject pipe is provided with a first inlet, a first outlet and an internal phase fluid channel. The external phase fluid inject pipe sleeves outside the internal phase fluid inject pipe. An inlet end of the collection pipe sleeves the external side of an outlet end of the external phase fluid inject pipe. A third outlet is formed by the inner periphery of the collection pipe and the outer periphery of the external phase fluid inject pipe. The continuous phase fluid inlet pipe sleeves the external sides of the external phase fluid inject pipe and the collection pipe. A continuous fluid channel is formed by the inner periphery of the continuous phase fluid inlet pipe and the outer periphery of the external phase fluid inject pipe. The continuous phase fluid inlet pipe is provided with a third inlet and the third outlet. The room temperature droplet micro-reactor can be used for preparing the gel microspheres having excellent sphericity degree and uniformity.
Description
Technical field
The invention belongs to materials synthesis and forming technique field, specifically, the present invention relates to room temperature drop microreactor
With the method utilizing this room temperature drop microreactor to prepare zirconium dioxide gel micro-ball.
Background technology
Gel micro-ball is a new research field in macromolecule and material science, owing to its structure and physico-chemical property can
The feature of design, is widely used in the ambits such as the energy, environment, biology as new type functional material.With microfluid side
Gel micro-ball prepared by method has good monodispersity simultaneously so that it is can preferably meet standard metering, drug delivery, urge
Change the requirement of the concrete application such as carrier.
Utilize microreactor to cause the reaction between two liquid phases, be that microfluidic methods synthesizes and prepares of gel micro-ball
Important technology route.In traditional micro-reaction method, it it is the breast that the two phase liquid of question response is scattered in drops third phase
Change in drop, form the form of double emulsion, two drops are close to each other, merge after react.In this approach, two drops with
The form mixing of point cantact, easily causes the situation that reaction is uneven, and in continuous preparation process, easily blocking two reaction
The passage mouth of pipe of liquid phase.Therefore, in quantity-produced application scenario, need a kind of microreactor that can overcome problem above badly,
Prepare reaction gel micro-ball uniform, monodispersed.
Summary of the invention
It is contemplated that one of technical problem solved the most to a certain extent in correlation technique.To this end, the present invention
One purpose is a kind of method proposing room temperature drop microreactor He utilizing this reactor to prepare zirconium dioxide gel micro-ball,
Utilize this room temperature drop microreactor can be using the two phase liquid of question response as shell phase and nuclear core phase, at continuous phase stream
Body mutually merges initiation reaction with cladding form.The mixed form of this contact can make the uniformity of reaction significantly carry
Height, after solidification, can obtain the gel micro-ball that sphericity, uniformity are good.
According to an aspect of the present invention, the present invention proposes a kind of room temperature drop microreactor, including:
Internal phase fluid incidence pipe, described internal phase fluid incidence pipe has the first entrance, the first outlet and internal phase fluid passage；
External fluid phase incidence pipe, described external fluid phase incidence pipe box is located at the outside of described internal phase fluid incidence pipe, described
The inner peripheral surface of external fluid phase incidence pipe forms external fluid phase passage with the outer peripheral face of described internal phase fluid incidence pipe, and described foreign minister flows
Body passage has the second entrance and the second outlet,
Collecting pipe, the arrival end of described collecting pipe is set in outside the port of export of described external fluid phase incidence pipe, and described
The inner peripheral surface of collecting pipe forms the 3rd outlet with the outer peripheral face of described external fluid phase incidence pipe,
Continuous phase fluid incidence pipe, described continuous phase fluid incidence pipe box is located at described external fluid phase incidence pipe and described receipts
The outside of collector, and the outer peripheral face of the inner peripheral surface of described continuous phase fluid incidence pipe and described external fluid phase incidence pipe formed continuously
Phase fluid passage, described continuous phase fluid passage has the 3rd entrance and described 3rd outlet.
The room temperature drop reactor of the above embodiment of the present invention can be using the two phase liquid of question response as shell phase
With nuclear core phase, in continuous phase fluid, mutually merge initiation reaction with cladding form.The mixed form of this contact can make
The uniformity of reaction is greatly improved, and after solidification, can obtain the gel micro-ball that sphericity, uniformity are good.
It addition, room temperature drop microreactor according to the above embodiment of the present invention can also have following additional technology spy
Levy:
In some embodiments of the invention, described internal phase fluid incidence pipe, external fluid phase incidence pipe, collecting pipe and continuously
It is between phase fluid incidence pipe and is coaxially disposed.Internal phase fluid thus can be wrapped well with external fluid phase, and can be smooth
Ground is cut by continuous phase fluid, forms the microsphere of regular shape, and then so that internal phase fluid is occurred by external fluid phase parcel
Reaction, and then improve reaction efficiency.
In some embodiments of the invention, the port of export of described external fluid phase incidence pipe enters without departing from described internal phase fluid
Penetrate the port of export of pipe.Thus can successfully make external fluid phase wrap internal phase fluid, form microsphere.
In some embodiments of the invention, the port of export of described external fluid phase incidence pipe and the arrival end of described collecting pipe
Being throat structure, the inner peripheral surface of described throat structure is 13 degree with the angle of the central axis of above-mentioned external fluid phase incidence pipe.
Thus can be so that the formation of microsphere.
In some embodiments of the invention, the internal diameter d1 of described internal phase fluid incidence pipe is 40-70 micron,
Described external fluid phase incidence pipe is identical with the internal diameter d2 of described collecting pipe, and is 600 microns；
The minimum diameter d3 of the port of export of described external fluid phase incidence pipe is 90-110 micron,
The minimum diameter d4 of the port of export of the arrival end of described collecting pipe is 220-250 micron.Thus can prepare
The microsphere of predetermined dimension.
In some embodiments of the invention, described internal phase fluid incidence pipe, described external fluid phase incidence pipe and described company
Continuous phase fluid incidence pipe is connected with the syringe equipped with internal phase fluid, external fluid phase and continuous phase fluid respectively successively, Mei Gesuo
State syringe to be connected with a flow pump respectively.Thus can be by controlling internal phase fluid, external fluid phase and continuous phase fluid
Flow velocity, by the flow velocity of external fluid phase in controlling, reaches two phase liquid and is mixed to form the optimal proportion of colloidal sol microsphere, then by adjusting
The flow velocity of whole continuous phase fluid, formation size uniformity is stable, the colloidal sol microsphere of good sphericity.
According to the second aspect of the invention, the invention allows for one and utilize foregoing room temperature drop microreactor
The method preparing zirconium dioxide gel micro-ball, including:
In the internal phase fluid passage of described internal phase fluid incidence pipe, inject internal phase fluid respectively, lead to described external fluid phase
Inject external fluid phase in road, and in described continuous phase fluid passage, inject continuous phase fluid；
Described internal phase fluid contacts with described external fluid phase in the first exit of described internal phase fluid incidence pipe, and
Under the shear action of continuous phase fluid, form external fluid phase parcel internal phase fluid and carry out single emulsion droplet of gel reaction, institute
State single emulsion droplet along with the described continuous phase fluid described collecting pipe of entrance；
Collect described single emulsion droplet, and described single emulsion droplet is heated and stands, in order to make described internal phase stream
Body and external fluid phase react completely, obtain the gel micro-ball of solidification；
The gel micro-ball of described solidification is carried out, in order to remove continuous phase fluid；
Gel micro-ball after cleaning carries out drying and sintering processes, in order to obtain zirconium dioxide gel micro-ball,
Wherein, described internal phase fluid is zirconium dioxide precursor solution, and described external fluid phase is hexamethylenetetramine solution,
Described continuous phase fluid is silicon oil solution.
Thus, by utilizing the room temperature drop reactor that utilizes of the above embodiment of the present invention to prepare zirconium dioxide gel micro-ball
Method can be using the two phase liquid of question response as shell phase and nuclear core phase, to be coated with form phase in continuous phase fluid
Merge initiation reaction mutually.The mixed form of this contact can make the uniformity of reaction be greatly improved, and after solidification, can obtain
The gel micro-ball that sphericity, uniformity are good.
It addition, the method preparing zirconium dioxide gel micro-ball according to the above embodiment of the present invention can also have the most attached
The technical characteristic added:
In some embodiments of the invention, the above-mentioned method preparing zirconium dioxide gel micro-ball may further include:
Preparation zirconium dioxide precursor solution, hexamethylenetetramine solution and the silicone oil containing DOW CORNING 749 in advance,
Wherein,
Preparation zirconium dioxide precursor solution: weigh zirconyl nitrate and Yttrium trinitrate respectively, be dissolved in water, makes mixing molten
Liquid, and by mixed solution heating in water bath 30min under 70 degrees Celsius of environment；
Preparation hexamethylenetetramine solution: weigh hexamethylenetetramine and carbamide respectively, be dissolved in water, makes mixing molten
Liquid, and be sufficiently mixed with eccentric agitator；
Preparation silicon oil solution: DOW CORNING 749 is added viscosity in 20cst silicone oil with the ratio of 0.2-2wt%, and with inclined
Heart agitator is sufficiently mixed.
In some embodiments of the invention, with the flow velocity of 1-10 μ l/min to the internal phase stream of described internal phase fluid incidence pipe
Internal phase fluid is injected in body passage；
In described external fluid phase passage, external fluid phase is injected with the flow velocity of 0.8-8 μ l/min；
In described continuous phase fluid passage, continuous phase fluid is injected with the flow velocity of 3-30ml/h,
Preferably, described external fluid phase is 0.8:1 with the flow-rate ratio of described internal phase fluid.
In some embodiments of the invention, described heating and standing are the temperature of 90 degrees Celsius by described single emulsion droplet
Spend lower heating 30, and ambient temperatare puts 48 hours.
In some embodiments of the invention, described sintering is carried out according to the following step:
With the heating rate of 0.5 degree Celsius per minute, dried gel micro-ball is warming up to 600 degrees Celsius；
It is warming up to 1250 degrees Celsius with the heating rate of 1 degree Celsius per minute from 600 degrees Celsius, and is incubated 2.5 hours；With
And
It is cooled to 900 degrees Celsius, and furnace cooling from 1250 degrees Celsius with the rate of temperature fall of 4 degrees Celsius per minute.
In some embodiments of the invention, described cleaning is carried out according to the following step:
Using trichloro ethylene that gel micro-ball carries out the first cleaning, regulation shaking table speed is 140r/min, cleans 4 times altogether,
Clean 15 minutes every time；
Using ammonia to carry out the second cleaning, regulation shaking table speed is 140r/min, cleans 2 times altogether, cleans 30 minutes every time；
Using deionized water to carry out the 3rd cleaning, regulation shaking table speed is 140r/min, cleans 8 times altogether, cleans 30 every time
Minute, until measuring deionization electrical conductivity of water is 0；
Using propylene glycol monomethyl ether to carry out the 4th cleaning, regulation shaking table speed is 140r/min, cleans 2 times altogether, cleans every time
30 minutes.
In some embodiments of the invention, the mean diameter of described zirconium dioxide gel micro-ball is 80-160 micron.
Accompanying drawing explanation
Fig. 1 (a) is the structural representation of room temperature drop microreactor according to an embodiment of the invention.
Fig. 1 (b) is the partial enlarged drawing of the structure of room temperature drop microreactor according to an embodiment of the invention.
Fig. 2 is to utilize room temperature drop microreactor to prepare zirconium dioxide gel micro-ball according to an embodiment of the invention
The schematic flow sheet of method.
Fig. 3 is to utilize room temperature drop microreactor to prepare zirconium dioxide gel micro-ball according to an embodiment of the invention
The gel micro-ball microgram that method prepares.
Fig. 4 (a) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
Microsphere figure after the sintering that the method for ball prepares.
Fig. 4 (b) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
Microsphere sectional view after the sintering that ball method prepares.
Fig. 5 (a1) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconia sol microsphere microgram that ball method prepares.
Fig. 5 (b1) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconia sol microsphere microgram that ball method prepares.
Fig. 5 (c1) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconia sol microsphere microgram that ball method prepares.
Fig. 5 (a2) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconium dioxide gel micro-ball microgram that ball method prepares.
Fig. 5 (b2) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconium dioxide gel micro-ball microgram that ball method prepares.
Fig. 5 (c2) is that to utilize room temperature drop microreactor to prepare zirconium dioxide gel according to an embodiment of the invention micro-
The zirconium dioxide gel micro-ball microgram that ball method prepares.
Fig. 6 is the structural representation of tradition double-core microreactor in comparative example.
Fig. 7 is to prepare the stream of the method for zirconium dioxide gel micro-ball according to utilization tradition double-core microreactor in this comparative example
Journey schematic diagram.
Fig. 8 is the zirconium dioxide gelled pill microgram utilizing the tradition micro-reaction method of double-core to manufacture according to comparative example.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most from start to finish
Same or similar label represents same or similar element or has the element of same or like function.Below with reference to attached
The embodiment that figure describes is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In traditional micro-reaction method, it it is the emulsion that the two phase liquid of question response is scattered in drops third phase
In Diing, form the form of double emulsion, two drops are close to each other, merge after react.In the method, question response is biphase with point
The form mixing of contact reacts, and the reaction of this form is easy to occur reacting uneven or incomplete situation, and then
Affect microspheres product quality, and be also easy to block pipeline in continuous preparation process.
To this end, according to an aspect of the present invention, the present invention proposes a kind of room temperature drop microreactor.According to the present invention
The room temperature drop microreactor of specific embodiment, including:
Internal phase fluid incidence pipe, internal phase fluid incidence pipe has the first entrance, the first outlet and internal phase fluid passage；
External fluid phase incidence pipe, external fluid phase incidence pipe box is located at the outside of internal phase fluid incidence pipe, and external fluid phase is incident
The outer peripheral face of the inner peripheral surface of pipe and internal phase fluid incidence pipe forms external fluid phase passage, external fluid phase passage have the second entrance and
Second outlet,
Collecting pipe, the arrival end of collecting pipe is set in outside the port of export of external fluid phase incidence pipe, and the inner circumferential of collecting pipe
Face forms the 3rd outlet with the outer peripheral face of external fluid phase incidence pipe,
Continuous phase fluid incidence pipe, continuous phase fluid incidence pipe box is located at external fluid phase incidence pipe and the outside of collecting pipe,
And the outer peripheral face of the inner peripheral surface of continuous phase fluid incidence pipe and external fluid phase incidence pipe forms continuous phase fluid passage, continuous phase stream
Body passage has the 3rd entrance and the 3rd outlet.
The room temperature drop reactor of the above embodiment of the present invention can be using the two phase liquid of question response as shell phase
With nuclear core phase, in continuous phase fluid, mutually merge initiation reaction with cladding form.The mixed form of this contact can make
The uniformity of reaction is greatly improved, and after solidification, can obtain the gel micro-ball that sphericity, uniformity are good.
Below with reference to Fig. 1, room temperature drop microreactor according to embodiments of the present invention is described.It is embodied as according to the present invention
The room temperature drop microreactor of example, including: internal phase fluid incidence pipe 10, external fluid phase incidence pipe 20, collecting pipe 30 and continuous phase
Fluid incidence pipe 40, wherein, internal phase fluid incidence pipe 10 has first entrance the 11, first outlet 12 and internal phase fluid passage 13；
External fluid phase incidence pipe 20 is set in the outside of internal phase fluid incidence pipe 10, the inner peripheral surface of external fluid phase incidence pipe 20 and internal phase stream
The outer peripheral face of body incidence pipe 10 forms external fluid phase passage 21, and external fluid phase passage has the second entrance 22 and the second outlet 23,
The arrival end 31 of collecting pipe 30 is set in outside the port of export 24 of external fluid phase incidence pipe 20, and the inner peripheral surface of collecting pipe 30 is with outer
The outer peripheral face of phase fluid incidence pipe 20 forms the 3rd outlet 32, and continuous phase fluid incidence pipe 40 is set in external fluid phase incidence pipe 20
With the outside of collecting pipe 30, and the outer peripheral face of the inner peripheral surface of continuous phase fluid incidence pipe 40 and external fluid phase incidence pipe 20 formed even
Continuous phase fluid passage 41, continuous phase fluid passage 41 has the 3rd entrance 42 and the 3rd outlet 32.
Using the room temperature drop microreactor of above-described embodiment, in the two of question response, reactant liquor is respectively internal phase fluid with outer
Phase fluid, internal phase fluid the first entrance 11 is passed through in the internal phase fluid passage 13 of internal phase fluid incidence pipe 10, and external fluid phase is from
Two entrances 22 are passed through in the external fluid phase passage 21 formed by external fluid phase incidence pipe 20 and internal phase fluid incidence pipe 10.Continuous phase
Fluid, as medium, does not dissolve each other with internal phase fluid and external fluid phase and reacts, and continuous phase fluid is passed through from the 3rd entrance 42
In continuous phase fluid passage 41.Internal phase fluid contacts with external fluid phase at the first outlet 12, and external fluid phase parcel internal phase
Fluid, under the dissection of continuous phase fluid, forms external fluid phase parcel internal phase fluid microsphere, and further, microsphere is being collected
Collection it is discharged successively in pipe 30, while external fluid phase parcel internal phase fluid forms microsphere simultaneously, anti-between two-phase fluid
Answering liquid to occur therewith, due to the sphere that contact area is whole internal phase fluid of biphase liquid, therefore contact area is relatively big, and
Reaction can uniformly be carried out, and then can significantly improve the quality of microsphere.By using the room temperature drop of the above embodiments of the present application
The gel micro-ball that microreactor can prepare single dispersing, reaction is uniform and sphericity is good.
It addition, compare traditional micro-reaction method, the two phase liquid of question response third phase will be scattered in drops
Emulsion droplet in, form the form of double emulsion, two drops are close to each other, merge after react.Use the above-mentioned reality of the application
Execute the gel micro-ball that room temperature drop microreactor can prepare single dispersing, reaction is uniform and sphericity is good of example.
According to a particular embodiment of the invention, internal phase fluid incidence pipe 10, external fluid phase incidence pipe 20, collecting pipe 30 and company
It is between continuous phase fluid incidence pipe 40 and is coaxially disposed.Thus, it is possible to make the external fluid phase formed be wrapped in internal phase equably
Outside fluid, obtain homocentric sphere, and then the higher microsphere of quality can be obtained so that follow-up biphase liquid reactions is uniform.
According to a particular embodiment of the invention, the port of export 24 of external fluid phase incidence pipe 20 is without departing from internal phase fluid incidence pipe
The port of export 14 of 10.Arranged cleverly by this, so that external fluid phase wraps internal phase fluid easily, and continuously
Under the dissection of phase fluid, and then form the microsphere of external fluid phase parcel internal phase fluid.
According to a particular embodiment of the invention, the port of export 24 of external fluid phase incidence pipe 20 and the arrival end 31 of collecting pipe 30
Being throat structure, the inner peripheral surface of throat structure is 13 degree with the angle of the central axis of above-mentioned external fluid phase incidence pipe.Invention
People finds, by the port of export 24 of external fluid phase incidence pipe 20 and the arrival end 31 of collecting pipe 30 are arranged to throat structure, and can
So that microsphere is formed, and it is more beneficial for external fluid phase and wraps internal phase fluid.More specifically, screened by regulation, send out
When the inner peripheral surface of existing throat structure is 13 degree with the angle of the central axis of above-mentioned external fluid phase incidence pipe, best results.Reducing
Structure significantly improves the flow velocity of interior external fluid phase incidence pipe near exit continuous phase fluid, and then improves cutting of continuous phase fluid
Cut efficiency, be the most also effectively increased the mixing efficiency of interior external fluid phase.
According to the specific embodiment of the present invention, in the room temperature drop microreactor of above-described embodiment, described internal phase fluid is incident
The internal diameter d1 of pipe is 40-70 micron, and external fluid phase incidence pipe is identical with the internal diameter d2 of described collecting pipe, and is 600 microns；Outward
The minimum diameter d3 of the port of export of phase fluid incidence pipe is 90-110 micron, the minimum diameter of the port of export of the arrival end of collecting pipe
D4 is 220-250 micron.Thus can prepare the microsphere of predetermined dimension.D1 is internal phase fluid incidence pipe 10 internal diameter, intercepts
Wherein the part of 40-70 micron uses, it is ensured that remain unimpeded state when being passed through fluid, and d3 is that external fluid phase enters
Penetrate pipe 20 internal diameter, be wrapped in around internal phase fluid incidence pipe 10, so its internal diameter should be greater than the external diameter of internal phase fluid incidence pipe 10,
But in order to keep preferable mixed effect, its internal diameter should be slightly larger than the external diameter of internal phase fluid incidence pipe 10, and collecting pipe 30 is nested in
External fluid phase incidence pipe 20 port of export 24, so its internal diameter should be greater than the external diameter of the port of export 24, in order to keep good shearing to imitate
Rate, its internal diameter is unsuitable excessive again.
According to a particular embodiment of the invention, in the room temperature drop microreactor of above-described embodiment, it is preferable that internal phase fluid
The internal diameter d1 of incident pipe 10 is 50 microns, and external fluid phase incidence pipe 20 is identical with the internal diameter d2 of collecting pipe 30, and it is micro-to be 600
Rice；The minimum diameter d3 of the port of export 24 of external fluid phase incidence pipe 20 is 100 microns, the port of export of the arrival end 31 of collecting pipe 30
Minimum diameter d4 be 230 microns.Thus can prepare the microsphere of predetermined dimension.Further, internal phase fluid incidence pipe 10
Internal diameter d1 is 50 microns, it is possible to better ensure that the state remaining unimpeded when being passed through fluid；External fluid phase incidence pipe 20
Internal diameter d3 is 100 microns, and then keeps preferable mixed effect；The port of export minimum diameter d4 of the arrival end 31 of collecting pipe 30 is
230 microns, and then good shear efficiency can be kept.
According to a particular embodiment of the invention, internal phase fluid incidence pipe 10, external fluid phase incidence pipe 20 and continuous phase fluid
Incident pipe 40 is connected with the syringe equipped with internal phase fluid, external fluid phase and continuous phase fluid respectively successively, and each syringe divides
It is not connected with a flow pump.Thus, during using above-mentioned room temperature drop microreactor to prepare microsphere, can be by stream
Amount pump controls the flow velocity of three-phase fluid respectively, prepares size to fit and individual uniform microsphere.
According to the second aspect of the invention, the invention allows for one and utilize foregoing room temperature drop microreactor
The method preparing zirconium dioxide gel micro-ball, the method includes:
In the internal phase fluid passage of described internal phase fluid incidence pipe, inject internal phase fluid respectively, lead to described external fluid phase
Inject external fluid phase in road, and in described continuous phase fluid passage, inject continuous phase fluid；
Described internal phase fluid contacts with described external fluid phase in the first exit of described internal phase fluid incidence pipe, and
Under the shear action of continuous phase fluid, form external fluid phase parcel internal phase fluid and carry out single emulsion droplet of gel reaction, institute
State single emulsion droplet along with the described continuous phase fluid described collecting pipe of entrance；
Collect described single emulsion droplet, and described single emulsion droplet is heated and stands, in order to make described internal phase stream
Body and external fluid phase react completely, obtain the gel micro-ball of solidification；
The gel micro-ball of described solidification is carried out, in order to remove continuous phase fluid；
Gel micro-ball after cleaning carries out drying and sintering processes, in order to obtain zirconium dioxide gel micro-ball,
Wherein, described internal phase fluid is zirconium dioxide precursor solution, and described external fluid phase is hexamethylenetetramine solution,
Described continuous phase fluid is silicon oil solution.
Thus, by utilizing the room temperature drop reactor that utilizes of the above embodiment of the present invention to prepare zirconium dioxide gel micro-ball
Method can be using the two phase liquid of question response as shell phase and nuclear core phase, to be coated with form phase in continuous phase fluid
Merge initiation reaction mutually.The mixed form of this contact can make the uniformity of reaction be greatly improved, and after solidification, can obtain
The zirconium dioxide gel micro-ball that sphericity, uniformity are good.Compare traditional micro-reaction method, will the two phase liquid of question response
Be scattered in the emulsion droplet of third phase with drops, form the form of double emulsion, two drops are close to each other, merge after occur
Reaction.The room temperature drop microreactor using the above embodiments of the present application can be prepared single dispersing, react uniformly and sphericity
Good zirconium dioxide gel micro-ball.
According to a particular embodiment of the invention, the method preparing zirconium dioxide gel micro-ball of above-described embodiment can also be entered
One step includes: preparation zirconium dioxide precursor solution, hexamethylenetetramine solution and the silicone oil containing DOW CORNING 749 in advance.
According to the concrete example of the present invention, prepare zirconium dioxide precursor solution: weigh zirconyl nitrate and Yttrium trinitrate respectively,
It is dissolved in water, makes mixed solution, and by mixed solution heating in water bath 30min under 70 degrees Celsius of environment.
According to the concrete example of the present invention, prepare hexamethylenetetramine solution: weigh hexamethylenetetramine and carbamide respectively,
It is dissolved in water, makes mixed solution, and be sufficiently mixed with eccentric agitator.
According to the concrete example of the present invention, prepare silicon oil solution: add viscous by DOW CORNING 749 with the ratio of 0.2-2wt%
Degree is in 20cst silicone oil, and is sufficiently mixed with eccentric agitator.
According to a particular embodiment of the invention, the zirconium dioxide precursor solution for preparing above-mentioned, hexamethylenetetramine
Solution and the silicone oil containing DOW CORNING 749 are respectively as internal phase fluid, external fluid phase and continuous phase fluid.Further, respectively
The above-mentioned three-phase fluid prepared is carried out loading, i.e. can be respectively charged in three syringes, and by three syringe configurations
One flow pump.
According to a particular embodiment of the invention, further, the flow velocity of three-phase fluid is set by flow pump.Specifically,
In the internal phase fluid passage of described internal phase fluid incidence pipe, internal phase fluid is injected with the flow velocity of 1-10 μ l/min；With 0.8-8 μ l/
The flow velocity of min injects external fluid phase in described external fluid phase passage；Lead to described continuous phase fluid with the flow velocity of 3-30ml/h
Continuous phase fluid is injected in road.Internal phase fluid incidence bore is less, and therefore flow is unsuitable too high, and interior foreign minister's two-phase fluid needs
Carry out mixing according to a certain percentage and could obtain uniform gel micro-ball.If flow selects improper may generation to mix inequality
The incomplete phenomenon of even or gel process, it is impossible to obtain qualified gel micro-ball.To this end, inventor is sent out by great many of experiments
Existing, three-phase fluid is respectively adopted above-mentioned flow velocity, it is possible to obtain uniform gel micro-ball, and then improves the quality of gel micro-ball.
Being embodied as according to the present invention, it is preferable that above-mentioned external fluid phase is 0.8:1 with the flow-rate ratio of internal phase fluid.By
Gelled pill after colloidal sol drop mix homogeneously before this solidification obtained and size uniformity, and solidification, keeps mixing equally
The feature (see Fig. 5) that uniform-dimension is homogeneous.Thus can improve microsphere quality further.
According to a particular embodiment of the invention, described heating and standing are the temperature of 90 degrees Celsius by described single emulsion droplet
Spend lower heating 30, and ambient temperatare puts 48 hours.Thus, make hexamethylenetetramine decompose release ammonia by heating and trigger zirconium
The gel reaction of liquid, and be further advanced by stand and make gel micro-ball gradually solidify the unnecessary water of running off, and then easily facilitate
Follow-up sintering processes.
According to a particular embodiment of the invention, the gel micro-ball after cleaning carries out drying and sintering processes, in order to obtain
Zirconium dioxide gel micro-ball.Wherein, sintering can be carried out according to the following step: will with the heating rate of 0.5 degree Celsius per minute
Dried gel micro-ball is warming up to 600 degrees Celsius；It is warming up to from 600 degrees Celsius with the heating rate of 1 degree Celsius per minute
1250 degrees Celsius, and it is incubated 2.5 hours；And be cooled to 900 with the rate of temperature fall of 4 degrees Celsius per minute from 1250 degrees Celsius and take the photograph
Family name's degree, and furnace cooling.Thus, by using above-mentioned sintering process, the compactness of ceramic microsphere can be significantly improved, prevent two
The change of zirconium oxide crystal formation produces cracking, and then obtains the zirconia ceramic microsphere that hardness is higher.
According to a particular embodiment of the invention, the gel micro-ball of described solidification is carried out, in order to remove continuous phase stream
Body.Specifically, clean and carry out according to the following step: use trichloro ethylene that gel micro-ball carries out the first cleaning, regulation shaking table speed
Rate is 140r/min, cleans 4 times altogether, cleans 15 minutes every time；Using ammonia to carry out the second cleaning, regulation shaking table speed is
140r/min, cleans 2 times altogether, cleans 30 minutes every time；Using deionized water to carry out the 3rd cleaning, regulation shaking table speed is
140r/min, cleans 8 times altogether, cleans 30 minutes every time, until measuring deionization electrical conductivity of water is 0；Use propylene glycol monomethyl ether
Carrying out the 4th cleaning, regulation shaking table speed is 140r/min, cleans 2 times altogether, cleans 30 minutes every time.Thus can effectively remove
Remove the oil reservoir of microsphere surface.Step by step in cleaning process, trichloro ethylene is used can effectively to remove the silicone oil on gel micro-ball surface,
Use ammonia then can gel micro-ball be fully cured, use deionized water to remove ammonia, use propylene glycol monomethyl ether to remove
Deionized water, finally uses propylene glycol monomethyl ether readily volatilized, and then obtains the gel micro-ball being completely dried.Therefore, use above-mentioned
Cleaning method can improve cleaning performance further, and can directly obtain dry gel micro-ball.
According to a particular embodiment of the invention, by use the above embodiments of the present application utilize room temperature drop reactor system
It is 80-160 micron that the method for standby zirconium dioxide gel micro-ball can prepare the mean diameter of zirconium dioxide gel micro-ball, and
Sphericity, uniformity are the best.
Embodiment 1: conventional method
Use room temperature drop microreactor device, by molten to internal phase zirconium dioxide precursor colloidal sol and foreign minister's hexamethylenetetramine
Liquid mixes in device, is sheared by continuous phase silicone oil afterwards.Bag by zirconium colloidal sol Yu hexamethylenetetramine solution
Covering the fusion of form, initiated gel reacts, once purged, it is thus achieved that clear gel microsphere.Clear gel microsphere is at high temperature entered
Row sintering, can obtain zirconia ceramic microsphere.Concrete preparation method comprises the following steps:
1) micro-channel device is prepared: using microscope slide as substrate, by circular cone incidence pipe and circular cone collecting pipe respectively from square tube
Two ends are inserted confronting coaxial and are arranged, and assemble with nested type, and thin cylindrical tube is the most coaxially arranged with circular cone incidence pipe and stretches out circle
Cone incidence pipe, square tube two ends bonded needle respectively, syringe needle is bonded on substrate, and each syringe needle is connected with the flexible pipe injecting fluid
Connect.
2) preparation zirconium dioxide precursor solution, weighs 34.06g zirconyl nitrate and 4.28g Yttrium trinitrate respectively, adds water-soluble
Solve, make the mixed solution of 120ml, and by mixed solution heating in water bath 30min under 70 degrees Celsius of environment, transfer to after terminating
In drug bottle standby.Wherein the molar concentration of zirconium ion is 1.063mol/L, and the molar concentration of ruthenium ion is 0.093mol/L, nitre
The molar concentration of acid is 0.144mol/L.
3) hexamethylenetetramine solution processed, weighs 23.38g hexamethylenetetramine and 10.02g carbamide respectively, is dissolved in water,
Make the mixed solution of 52.2ml, and be sufficiently mixed with eccentric agitator.
4) preparation silicon oil solution, adds viscosity as 20cst by surfactant DOW CORNING 749 with the ratio of 0.2-2wt%
In silicone oil, and it is sufficiently mixed, as foreign minister's continuous phase fluid with eccentric agitator.
5) the zirconium dioxide precursor solution prepared is injected as internal phase fluid from thin cylindrical tube, six will prepared
Methine four amine aqueous solution flows into from one end of square tube along the gap between thin cylindrical tube and circular cone incidence pipe as external fluid phase,
Silicone oil using DOW CORNING 749 as surfactant as continuous phase fluid along circular cone incidence pipe one end from circular cone incidence pipe and square tube
Between gap flow into；By internal phase fluid Flow-rate adjustment to 1-10 μ l/min, external fluid phase Flow-rate adjustment to 0.8-8 μ l/min,
Continuous phase fluid Flow-rate adjustment, to 3-30ml/h, after internal phase fluid mixes at the circular cone incidence pipe mouth of pipe with external fluid phase, is connected
Continuous phase fluid is sheared and is entered circular cone collecting pipe.
6) will be heating and curing containing the fluid of single emulsion droplet, heating-up temperature is 90 DEG C, after heating 30 minutes, by it in room
Temperature is lower places more than 48 hours.
7) the clear gel microsphere after solidification is transferred in vial, successively uses trichloro ethylene, ammonia, deionized water
Repeatedly rinse with propylene glycol monomethyl ether, until clear gel microsphere surface oil reservoir is rinsed removing.
8) gel micro-ball after removing oil reservoir puts into calorstat dries, and oxygen transferred to by the white gels microsphere after drying
Change in the crucible of aluminium material, put in the sintering furnace that model is KSL1800X that Zhengzhou Ke Jing electric furnace company limited manufactures and burn
Knot, the first step is warming up to 600 DEG C with 0.5 DEG C per minute, and second step is warming up to 1250 DEG C with 1 DEG C per minute, and it is little to be incubated 2.5
Time, then cool to 900 DEG C with the rate of temperature fall of 4 DEG C per minute, after carry out cold going with stove, final obtain that sphericity is high, size is equal
One, the zirconia ceramic microsphere of compact structure.
Embodiment 2: utilize room temperature drop microreactor to prepare zirconium dioxide gelled pill
According to the method for embodiment 1 prepare zirconium dioxide precursor colloidal sol, hexamethylenetetramine solution, containing 2% road health
The silicone oil of peaceful 749, and respectively as internal phase fluid, external fluid phase and continuous phase fluid.Wherein, in zirconium dioxide precursor solution
Containing zirconyl nitrate and Yttrium trinitrate, their molar concentration is 1.063mol/L and 0.093mol/L respectively；Hexamethylenetetramine
Containing hexamethylenetetramine and carbamide in solution, their molar concentration is 3.2mol/L；Silicone oil adds according to volume ratio
DOW CORNING 749 surfactant of 2%.
By zirconium dioxide precursor solution, hexamethylenetetramine solution and the silicone oil containing 2%749 surfactants respectively
Load the syringe of 1ml, 1ml and 10ml and be connected to the internal phase fluid of room temperature drop microreactor device (Fig. 1-2), Wai Xiangliu
Body and continuous phase fluid inlet, then three syringe cylinders are loaded on digital control flow pump, flow pump model is Baoding
The OEMLSP012A-01 that Lange constant flow pump company limited produces.
By continuous phase fluid Flow-rate adjustment to 3ml/h, external fluid phase regulates to 1 μ l/min, internal phase fluid Flow-rate adjustment to 1
μl/min.Collecting pipe outlet connects PE-5 flexible pipe, after waiting that droplet formation is stablized and mixed, uses the training filling continuous phase fluid
Support ware and collect drop.After have collected sufficient amount of drop, culture dish is transferred to hot plate, and heats 30 points at 90 DEG C
Clock.After heating terminates, culture dish is at room temperature placed 48 hours, obtain the gel micro-ball of good sphericity.
With pipettor, zirconium dioxide gel micro-ball is transferred in vial, and exhaust the silicone oil in bottle as far as possible.The most right
Gelled pill is carried out: gelled pill is carried out by first step trichloro ethylene, is placed on shaking table by vial, regulates it
Speed is 140r/min, cleans 4 times altogether, changes liquid every time and cleans 15 minutes, and then natural air drying is until trichloro ethylene volatilizees completely；
Second step ammonia (after the dilution that deionized water carries out 1:10, add the Triton X-100 activating agent of 1%) is carried out clearly
Washing, regulation shaking table speed is 140r/min, cleans 2 times altogether, changes liquid every time and cleans 30 minutes；3rd step deionized water is carried out clearly
Washing, regulation shaking table speed is 140r/min, cleans 8 times altogether, changes liquid every time and cleans 30 minutes, until measuring the conductance of deionized water
Rate is 0；4th step propylene glycol monomethyl ether is carried out, and regulation shaking table speed is 140r/min, cleans 2 times altogether, changes liquid clear every time
Wash 30 minutes.Bead is placed in hot plate after cleaning by four steps, it is dried completely with 60 DEG C, obtains the gel micro-ball of 160 μm
(Fig. 3).
Embodiment 3: zirconium dioxide gelled pill sinter molding prepared by room temperature drop microreactor
The gel micro-ball that embodiment 2 utilizes 160 μm that room temperature drop microreactor prepares is transferred to, in crucible, put
Putting in sintering furnace and be sintered, sintering process is below 600 DEG C, heats up with the change of 0.5 DEG C per minute, and respectively
It is incubated 1 hour, between 600 DEG C to 1250 DEG C, with the change of 1 DEG C per minute at 90 DEG C, 240 DEG C, 320 DEG C, 470 DEG C, 600 DEG C
Heat up, and be incubated 1 hour at 1100 DEG C, at 1250 DEG C of maximum temperatures, be incubated 2 hours, afterwards with 8 DEG C of speed per minute
Rate is down to 850 DEG C from 1250 DEG C, naturally cools to room temperature afterwards, and sintering terminates, and obtains the zirconia ceramic of a size of 70 μm
Microsphere (Fig. 4).
Embodiment 4: regulation flow-rate ratio prepares zirconium dioxide gelled pill
Utilize the proportioning of room temperature microreactor method regulation and control two phase liquid during preparing zirconium dioxide gelled pill.
According to the method for embodiment 1 prepare zirconium dioxide precursor colloidal sol, hexamethylenetetramine solution, containing 2% road health
The silicone oil of peaceful 749, and respectively as internal phase fluid, external fluid phase and continuous phase fluid.Zirconium dioxide precursor solution contains
Zirconyl nitrate and Yttrium trinitrate, their molar concentration is 1.063mol/L and 0.093mol/L respectively；Hexamethylenetetramine solution
In containing hexamethylenetetramine and carbamide, their molar concentration is 3.2mol/L；Silicone oil adds 2% according to volume ratio
DOW CORNING 749 surfactant.
By zirconium dioxide precursor solution, hexamethylenetetramine solution and the silicone oil containing 2%749 surfactants respectively
The syringe loading 1ml, 1ml and 10ml the internal phase fluid foreign minister being connected to room temperature drop microreactor device (Fig. 1-Fig. 2) stream
Body and continuous phase fluid inlet, then three syringe cylinders are loaded on digital control flow pump, flow pump model is Baoding
The OEMLSP012A-01 that Lange constant flow pump company limited produces.
Experiment for the first time, by continuous phase fluid Flow-rate adjustment to 3ml/h, external fluid phase regulates to 0.5 μ l/min, internal phase stream
Body Flow-rate adjustment is to 1 μ l/min.Collecting pipe outlet connects PE-5 flexible pipe, and after waiting that droplet formation is stablized and mixed, use fills
The culture dish of continuous phase fluid collects drop, the zirconia sol microsphere such as Fig. 5 (a1) of collection.Wait to have collected sufficient amount of
After drop, culture dish is transferred to hot plate, and heats 30 minutes at 90 DEG C.After heating terminates, culture dish is at room temperature put
Put 48 hours, obtain completely crued gel micro-ball such as Fig. 5 (a2).The colloidal sol drop mix homogeneously size uniformity wherein obtained,
And solidify after gelled pill, due to the proportioning of urea liquid cause not uncured completely.
Second time experiment, by continuous phase fluid Flow-rate adjustment to 3ml/h, external fluid phase regulates to 0.8 μ l/min, internal phase stream
Body Flow-rate adjustment is to 1 μ l/min.Collecting pipe outlet connects PE-5 flexible pipe, and after waiting that droplet formation is stablized and mixed, use fills
The culture dish of continuous phase fluid collects drop, the zirconia sol microsphere such as Fig. 5 (b1) of collection.Wait to have collected sufficient amount of
After drop, culture dish is transferred to hot plate, and heats 30 minutes at 90 DEG C.After heating terminates, culture dish is at room temperature put
Put 48 hours, obtain completely crued gel micro-ball such as Fig. 5 (b2).The colloidal sol drop mix homogeneously wherein obtained and size are equal
Gelled pill after one, and solidification, the same feature keeping mix homogeneously size uniformity.
Third time experiment, by continuous phase fluid Flow-rate adjustment to 3ml/h, external fluid phase regulates to 1.5 μ l/min, internal phase stream
Body Flow-rate adjustment is to 1 μ l/min.Collecting pipe outlet connects PE-5 flexible pipe, and after waiting that droplet formation is stablized and mixed, use fills
The culture dish of continuous phase fluid collects drop, the zirconia sol microsphere such as Fig. 5 (c1) of collection.Wait to have collected sufficient amount of
After drop, culture dish is transferred to hot plate, and heats 30 minutes at 90 DEG C.After heating terminates, culture dish is at room temperature put
Put 48 hours, obtain completely crued gel micro-ball such as Fig. 5 (c2).The colloidal sol droplets mixing wherein obtained is uneven, Er Qiegu
Gelled pill after change presents aspheric state.
This example demonstrates that and utilize room temperature microreactor method can regulate and control the ratio of biphase aqueous phase solution to explore manufacture two
The optimal proportion of zirconium oxide gelled pill, thus obtain the product of size uniformity, mix homogeneously.The method can be additionally used in explores it
The optimal proportion of his reaction.
Comparative example: the tradition micro-reaction method of double-core manufactures zirconium dioxide gelled pill
Prepare zirconium dioxide precursor colloidal sol, hexamethylenetetramine solution, silicone oil containing 2% DOW CORNING 749 and
10wt% poly-vinyl alcohol solution is respectively as internal phase 1, internal phase 2, foreign minister and continuous phase.Containing nitre in zirconium dioxide precursor solution
Acid oxygen zirconium and Yttrium trinitrate, their molar concentration is 1.063mol/L and 0.093mol/L respectively；In hexamethylenetetramine solution
Containing hexamethylenetetramine and carbamide, their molar concentration is 3.2mol/L；Silicone oil adds the road of 2% according to volume ratio
Healthy and free from worry 749 surfactants；Poly-vinyl alcohol solution configures with deionized water according to mass ratio 10%, and heating in water bath is until complete
CL, is positioned over room temperature standby.By zirconium dioxide precursor solution, hexamethylenetetramine solution, containing 2%749 surface activitys
Silicone oil and the 10wt% poly-vinyl alcohol solution of agent are respectively charged into the syringe of 1ml, 1ml, 10ml and 10ml and are connected to traditional double
First internal phase fluid entrance the 1, second internal phase fluid entrance 2 of core micro-reaction device (Fig. 6-7), external fluid phase entrance 3 and continuously
Phase fluid inlet 4, then four syringe cylinders are loaded on digital control flow pump.
By continuous phase fluid Flow-rate adjustment to 2ml/h, external fluid phase regulates to 0.7ml/h, and two kinds of internal phase fluid flows are adjusted
Save to 1 μ l/min.Collecting pipe outlet connects PE-5 flexible pipe, after waiting that droplet formation is stablized and mixed, uses and fills continuous phase stream
Drop collected by the culture dish of body.After have collected sufficient amount of drop, culture dish is transferred to hot plate, and heats at 90 DEG C
30 minutes.After heating terminates, culture dish is at room temperature placed 48 hours, obtain being shaped as aspheric gel particle (Fig. 8).
As can be seen here, use the tradition micro-reaction method of double-core to prepare zirconium dioxide gel micro-ball and can cause the inequality of gel reaction
Even, therefore obtain aspheric gel particle.
In describing the invention, it is to be understood that term " " center ", " longitudinally ", " laterally ", " length ", " width ",
" thickness ", " on ", D score, "front", "rear", "left", "right", " vertically ", " level ", " top ", " end " " interior ", " outward ", " up time
Pin ", " counterclockwise ", " axially ", " radially ", the orientation of the instruction such as " circumferential " or position relationship be based on orientation shown in the drawings or
Position relationship, is for only for ease of the description present invention and simplifies description rather than instruction or imply that the device of indication or element must
Must have specific orientation, with specific azimuth configuration and operation, be therefore not considered as limiting the invention.
Additionally, term " first ", " second " are only used for describing purpose, and it is not intended that instruction or hint relative importance
Or the implicit quantity indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can express or
Implicitly include one or more this feature.In describing the invention, " multiple " are meant that two or more,
Unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, term " install ", " being connected ", " connection ", " fixing " etc.
Term should be interpreted broadly, and connects for example, it may be fixing, it is also possible to be to removably connect, or integral；Can be that machinery connects
Connect, it is also possible to be electrical connection；Can be to be joined directly together, it is also possible to be indirectly connected to by intermediary, in can being two elements
The connection in portion or the interaction relationship of two elements.For the ordinary skill in the art, can be according to concrete feelings
Condition understands above-mentioned term concrete meaning in the present invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature " on " or D score permissible
It is that the first and second features directly contact, or the first and second features are by intermediary mediate contact.And, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature directly over second feature or oblique upper, or be merely representative of
Fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " can be
One feature is immediately below second feature or obliquely downward, or is merely representative of fisrt feature level height less than second feature.
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ", " specifically show
Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or spy
Point is contained at least one embodiment or the example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be arbitrary
Individual or multiple embodiment or example combine in an appropriate manner.Additionally, in the case of the most conflicting, the technology of this area
The feature of the different embodiments described in this specification or example and different embodiment or example can be combined by personnel
And combination.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is example
Property, it is impossible to being interpreted as limitation of the present invention, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, revises, replaces and modification.
Claims (13)
1. a room temperature drop microreactor, it is characterised in that including:
Internal phase fluid incidence pipe, described internal phase fluid incidence pipe has the first entrance, the first outlet and internal phase fluid passage；
External fluid phase incidence pipe, described external fluid phase incidence pipe box is located at the outside of described internal phase fluid incidence pipe, described foreign minister
The inner peripheral surface of fluid incidence pipe forms external fluid phase passage with the outer peripheral face of described internal phase fluid incidence pipe, and described external fluid phase leads to
Road has the second entrance and the second outlet,
Collecting pipe, the arrival end of described collecting pipe is set in outside the port of export of described external fluid phase incidence pipe, and described collection
The inner peripheral surface of pipe forms the 3rd outlet with the outer peripheral face of described external fluid phase incidence pipe,
Continuous phase fluid incidence pipe, described continuous phase fluid incidence pipe box is located at described external fluid phase incidence pipe and described collecting pipe
Outside, and the outer peripheral face of the inner peripheral surface of described continuous phase fluid incidence pipe and described external fluid phase incidence pipe forms continuous phase stream
Body passage, described continuous phase fluid passage has the 3rd entrance and described 3rd outlet.
Room temperature drop microreactor the most according to claim 1, it is characterised in that described internal phase fluid incidence pipe, foreign minister
It is between fluid incidence pipe, collecting pipe and continuous phase fluid incidence pipe and is coaxially disposed.
Room temperature drop microreactor the most according to claim 1, it is characterised in that the outlet of described external fluid phase incidence pipe
Hold the port of export without departing from described internal phase fluid incidence pipe.
Room temperature drop microreactor the most according to claim 2, it is characterised in that the outlet of described external fluid phase incidence pipe
The arrival end of end and described collecting pipe is throat structure, the inner peripheral surface of described throat structure and above-mentioned external fluid phase incidence pipe
The angle of central axis is 13 degree.
Room temperature drop microreactor the most according to claim 4, it is characterised in that
The internal diameter d1 of described internal phase fluid incidence pipe is 40-70 micron,
Described external fluid phase incidence pipe is identical with the internal diameter d2 of described collecting pipe, and is 600 microns；
The minimum diameter d3 of the port of export of described external fluid phase incidence pipe is 90-110 micron,
The minimum diameter d4 of the port of export of the arrival end of described collecting pipe is 220-250 micron.
Room temperature drop microreactor the most according to claim 1, it is characterised in that described internal phase fluid incidence pipe, described
External fluid phase incidence pipe and described continuous phase fluid incidence pipe the most successively with equipped with internal phase fluid, external fluid phase and continuous phase stream
The syringe of body is connected, and each described syringe is connected with a flow pump respectively.
7. the room temperature drop microreactor utilized described in any one of claim 1～6 prepares zirconium dioxide gel micro-ball
Method, it is characterised in that including:
Internal phase fluid is injected respectively, in described external fluid phase passage in the internal phase fluid passage of described internal phase fluid incidence pipe
Inject external fluid phase, and in described continuous phase fluid passage, inject continuous phase fluid；
Described internal phase fluid contacts with described external fluid phase in the first exit of described internal phase fluid incidence pipe, and continuously
Under the shear action of phase fluid, form external fluid phase parcel internal phase fluid and carry out single emulsion droplet of gel reaction, described list
Emulsion droplet enters described collecting pipe along with described continuous phase fluid；
Collect described single emulsion droplet, and described single emulsion droplet heated and stands, in order to make described internal phase fluid with
External fluid phase reaction completely, obtains the gel micro-ball of solidification；
The gel micro-ball of described solidification is carried out, in order to remove continuous phase fluid；
Gel micro-ball after cleaning carries out drying and sintering processes, in order to obtain zirconium dioxide gel micro-ball,
Wherein, described internal phase fluid is zirconium dioxide precursor solution, and described external fluid phase is hexamethylenetetramine solution, described
Continuous phase fluid is silicon oil solution.
Method the most according to claim 7, it is characterised in that farther include: preparation zirconium dioxide presoma is molten in advance
Liquid, hexamethylenetetramine solution and the silicone oil containing DOW CORNING 749,
Wherein,
Preparation zirconium dioxide precursor solution: weigh zirconyl nitrate and Yttrium trinitrate respectively, be dissolved in water, make mixed solution, and
By mixed solution heating in water bath 30min under 70 degrees Celsius of environment；
Preparation hexamethylenetetramine solution: weigh hexamethylenetetramine and carbamide respectively, be dissolved in water, make mixed solution, and
It is sufficiently mixed with eccentric agitator；
Preparation silicon oil solution: DOW CORNING 749 is added viscosity in 20cst silicone oil with the ratio of 0.2-2wt%, and stirs by bias
Mix device to be sufficiently mixed.
Method the most according to claim 7, it is characterised in that
In the internal phase fluid passage of described internal phase fluid incidence pipe, internal phase fluid is injected with the flow velocity of 1-10 μ l/min；
In described external fluid phase passage, external fluid phase is injected with the flow velocity of 0.8-8 μ l/min；
In described continuous phase fluid passage, continuous phase fluid is injected with the flow velocity of 3-30ml/h,
Preferably, described external fluid phase is 0.8:1 with the flow-rate ratio of described internal phase fluid.
Method the most according to claim 7, it is characterised in that described heating and standing are to be existed by described single emulsion droplet
Heat 30 at a temperature of 90 degrees Celsius, and ambient temperatare puts 48 hours.
11. methods according to claim 7, it is characterised in that described sintering is carried out according to the following step:
With the heating rate of 0.5 degree Celsius per minute, dried gel micro-ball is warming up to 600 degrees Celsius；
It is warming up to 1250 degrees Celsius with the heating rate of 1 degree Celsius per minute from 600 degrees Celsius, and is incubated 2.5 hours；And
It is cooled to 900 degrees Celsius, and furnace cooling from 1250 degrees Celsius with the rate of temperature fall of 4 degrees Celsius per minute.
12. methods according to claim 7, it is characterised in that described cleaning is carried out according to the following step:
Using trichloro ethylene that gel micro-ball carries out the first cleaning, regulation shaking table speed is 140r/min, altogether cleaning 4 times, every time
Clean 15 minutes；
Using ammonia to carry out the second cleaning, regulation shaking table speed is 140r/min, cleans 2 times altogether, cleans 30 minutes every time；
Using deionized water to carry out the 3rd cleaning, regulation shaking table speed is 140r/min, cleans 8 times altogether, cleans 30 minutes every time,
Until measuring deionization electrical conductivity of water is 0；
Using propylene glycol monomethyl ether to carry out the 4th cleaning, regulation shaking table speed is 140r/min, cleans 2 times altogether, cleans 30 points every time
Clock.
13. methods according to claim 7, it is characterised in that the mean diameter of described zirconium dioxide gel micro-ball is 80-
160 microns.
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