CN109181367A - A method of preparing transparent zinc oxide liquid dispersion - Google Patents
A method of preparing transparent zinc oxide liquid dispersion Download PDFInfo
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- CN109181367A CN109181367A CN201811148029.9A CN201811148029A CN109181367A CN 109181367 A CN109181367 A CN 109181367A CN 201811148029 A CN201811148029 A CN 201811148029A CN 109181367 A CN109181367 A CN 109181367A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/04—Compounds of zinc
- C09C1/043—Zinc oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of method for preparing transparent zinc oxide liquid dispersion, includes the following steps: that 1) salt is dissolved in liquid phase medium A, obtain salting liquid；By alkali soluble in liquid phase medium B, aqueous slkali is obtained；The salt is zinc salt or mixed zinc salts, and the mixed zinc salts are that the salt of the zinc salt that molar ratio is 10~100:1 and doped chemical mixes；2) salting liquid and lye are added in high gravity rotating packed bed reactor, obtain zinc oxide suspension after reacting under certain temperature；3) surface capping agents are added in zinc oxide suspension, modified cladding a period of time under certain temperature；4) by the modification liquid precipitate of standing, centrifugation, washing, redisperse obtains ZnO transparent liquid dispersion into liquid phase medium C.The present invention completes in high gravity rotating packed bed reactor, significantly reinforcing mass transfer, the microcosmic mixing of reinforcing, and product is transparent and dispersed fine；Stability is good, stands more than 12 months without sedimentation.
Description
Technical field
The invention belongs to chemical technology fields, are related to the preparation method of liquid dispersion, prepare more particularly, to a kind of
The method of bright zinc oxide liquid dispersion.
Background technique
Nano zine oxide is risen as a kind of important inorganic nano material, research the 1990s.Nowadays oxygen
The purposes for changing zinc is very extensive, except applying also for electronics in addition to rubber industry, petrochemical industry, coatings industry are widely used
Laser material, fluorescence flour additive agent, magnetic material, piezoelectric material, ceramics etc..In rubber industry, nano zine oxide is a kind of heavy
The inorganic active material wanted, can not only reduce the dosage of common zinc oxide, can also improve the wearability of rubber product and resist
Ageing properties prolong the service life；In coatings industry, nano zine oxide can greatly improve the covering power and coloring of coating products
Power, also can be improved all other indexs of coating, and can be applied to prepare functional nano coating；In addition in ceramic industry side
The addition in face, nano zine oxide makes ceramic have the self-cleaning action of decomposing organic matter and deodorization and sterilization, ensure that product
Quality.
The ultraviolet shielding performance of nano zine oxide depends primarily on the factors such as morphological feature, granular size and degree of scatter.
Wherein, the size distribution and degree of scatter of nano particle are a very important factors.Traditional preparation method is first to prepare
Solid nanometer Zinc oxide powder, then add modifying agent and carry out surface modification to it, and then be filled into conduct in high molecular material
Ultraviolet shielding function.But such method prepares Zinc oxide particles and part reunion just occurs before modification, so that modified partial size
It is big and be unevenly distributed, it is difficult to grain shape to be controlled, therefore its dispersion performance is bad after refilling resin base, with polymer
Compatibility is poor.
High-gravity technology (high gravity rotating packed bed) is to utilize the Elevated Gravity more much bigger than terrestrial gravitation acceleration
To the new technology that mass transfer and micro mixing are strengthened, obtained on earth by the Elevated Gravity that rotation generates simulation
?.It can increase substantially the conversion ratio and selectivity of reaction, reduce the volume of reactor significantly, simplify technique, process,
Realization process it is energy-efficient.Under Elevated Gravity, the intermolecular molecule diffusion of different size and interphase mass transfer process compare
Terrestrial gravitation off field much faster, solution-air, liquid-liquid, liquid-solid two-phase are at hundreds times to thousand times bigger than earth gravitational field
In porous media under Elevated Gravity generate flowing contact, huge shearing force make liquid crushing at nanoscale film, silk and
Drop generates phase interface that is huge and quickly updating, improves 1~3 order of magnitude in the tower for keeping interphase mass transfer speed ratio traditional,
It is greatly strengthened mass transport process.
It is existing to use Synthesis of Nanometer ZnO by High-Gravity using zinc chloride and sodium hydroxide for raw material, using hypergravity
Nanometer Zinc oxide powder is made using filter, washing, drying in the way of liquid--liquid reaction in (rotary packed bed) technology,
This method is disadvantageous in that zinc oxide partial size obtained is larger, minimum 68nm.
It is the obtained precursor of raw material that nanometer Zinc oxide powder is prepared in the prior art using zinc nitrate and ammonium hydroxide, then through high temperature
The shortcomings that ultrasound, drying and calcining obtain Zinc oxide powder, the technique is that zinc oxide partial size obtained is larger, is 20-200nm.
Therefore, the present invention provides a kind of methods for preparing transparent zinc oxide liquid dispersion, using hypergravity rotary filling
Bed is filled, mass transfer can be strengthened significantly, strengthen microcosmic mixing, the Zinc oxide particles morphology controllable and even particle size distribution prepared.
Summary of the invention
It is an object of the present invention to provide a kind of methods for preparing transparent zinc oxide liquid dispersion.This method uses
High gravity rotating packed bed can strengthen mass transfer significantly, strengthen microcosmic mixing, the Zinc oxide particles morphology controllable and grain prepared
Degree is evenly distributed, and the Zinc oxide particles that the method is prepared further are modified consolidating for transparent zinc oxide liquid dispersion obtained
For content up to 70wt%, zincite crystal partial size is small and is evenly distributed, one-dimensional having a size of 3~10nm；In addition, product dispersion effect
Good, stability is good, stands the several months without sedimentation, and using water and a variety of organic solvents as liquid phase dispersion medium, has wide range of applications；This
The problem of dispersion performance and poor compatibility that method very good solution nano zine oxide occurs in the application, to assign product
Higher application performance and added value.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
A method of transparent zinc oxide liquid dispersion is prepared, is included the following steps:
1) salt is dissolved in liquid phase medium A, obtains salting liquid；By alkali soluble in liquid phase medium B, aqueous slkali is obtained；
The salt is zinc salt or mixed zinc salts, and the mixed zinc salts are the zinc salt that molar ratio is 10~100:1 and doping member
The salt of element mixes；
2) salting liquid and lye are added in high gravity rotating packed bed reactor, it is suspended that zinc oxide is obtained after reaction
Liquid；
3) surface capping agents are added in zinc oxide suspension and are modified cladding, modified standing modification liquid；
4) by the modification liquid precipitate after standing, centrifugation, washing, redisperse obtains ZnO transparent liquid into liquid phase medium C
Phase dispersion；
In step 4), the liquid phase medium C is selected from the one or more of following substance: diesel oil, naphtha, heavy oil, positive heptan
Alkane, normal octane, JP-10 Aviation Fuel, C4 lighter hydrocarbons, C5 lighter hydrocarbons, vacuum distillate, wax tailings, reduced crude, decompression residuum.
Wherein heavy oil refers to that crude oil extracts the remaining mink cell focus after gasoline, diesel oil；Reduced crude and decompression residuum respectively refer to original
Oil is through air-distillation and is evaporated under reduced pressure resulting residual oil；Wax tailings refer to the tower for being used as fuel (ship) from coking plant output
Base oil.
Preferably, in step 1), the zinc salt is selected from one of following substance or a variety of: zinc chloride, zinc bromide, nitric acid
Zinc, zinc sulfate, zinc acetate；The salt of the doped chemical is selected from one of following substance or a variety of: aluminum sulfate, aluminum nitrate, vinegar
Sour aluminium, aluminium isopropoxide, aluminium chloride, gallium nitrate, gallium sulfate, indium acetate, indium nitrate, inidum chloride, stannic chloride, tin acetate；The alkali
Selected from one of following substance or a variety of: lithium hydroxide, sodium hydroxide, potassium hydroxide, a hydration ammonia.
Preferably, the concentration of zinc salt described in step 1) is 0.05mol/L~1mol/L, and preferably zinc salt concentration is
0.15mol/L~0.6mol/L；
Preferably, the concentration of lye described in step 1) is 0.1mol/L~2mol/L, and preferably concentration of lye is
0.3mol/L~1.2mol/L.
Preferably, liquid phase medium A described in step 1) is selected from one of following substance or a variety of: water, methanol, ethyl alcohol,
Ethylene glycol, isopropanol, butanol, benzyl alcohol, glycerol, ether, dimethyl ether, acetone, butanone, cyclohexanone；The liquid phase medium B is selected from
One or more of following substance: water, methanol, ethyl alcohol, ethylene glycol, isopropanol, glycerol, butanol, acetone, butanone, acetic acid second
Ester, butyl acetate, toluene, dimethylbenzene, dimethyl sulfoxide, tetrahydrofuran, n-hexane, hexamethylene.
Preferably, reaction temperature is 20~85 DEG C in step 2)；It is highly preferred that reaction temperature is 25~75 DEG C；Most preferably
Ground, reaction temperature are 40~70 DEG C.
Preferably, in step 2), the rotating packed bed reactor is selected from the high-gravity rotating bed reaction of rotary packed bed
Device, deflection type overgravity rotary bed reactor, helical duct rotating packed bed reactor, fixed-rotor are high-gravity rotating bed anti-
Answer device or rotating compact disc rotating packed bed reactor；Preferably, the rotor speed of revolving bed is 300~5000rpm；More preferably
Ground, the rotor speed of revolving bed are 600~2600rpm.
Preferably, in step 2), being passed through the volume flow ratio of salting liquid and lye in rotary packed bed to be is 0.2~3.5:
1；The salting liquid be passed through rotary packed bed feed rate be 50ml/min~1000ml/min, lye be 40ml/min~
800ml/min。
Preferably, in step 3), the surface capping agents be selected from following substance it is one or more: titanate esters, Aluminate,
Esters of silicon acis, stearic acid, odium stearate, oleic acid, polyvinylpyrrolidone, γ-methacryloxypropyl trimethoxy silane,
Polyethylene glycol, polyvinyl alcohol, octadecylamine, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy
Silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, n-octyl trimethoxy silane, dodecyltrimethoxysilane,
Octadecyl trimethoxysilane, 3- TSL 8330, phenyltrimethoxysila,e, dimethyl dichlorosilane (DMCS).This
The selection of invention discovery, covering depends on decentralized medium, and every kind of decentralized medium has required suitably to coat agent prescription therewith
Corresponding, the surface capping agents of use are improper or the covering proportion and amount of covering is improper will lead to final difficulty
It is unstable to form dispersion or dispersion.
Preferably, surface capping agents described in step 3) and zinc oxide mass ratio are 0.1~2:1.
Preferably, when surface capping agents described in step 3) are a variety of, adding manner is that mixed once is added or adds by several times
Enter different surfaces covering.
Preferably, it is 5min~2h that surface capping agents, which are time interval when being added by several times, in step 3), preferably 10min~
1h。
Preferably, surface capping agents are when being added by several times in step 3), and number is 2~3 times.
Preferably, surface capping agents are when being added by several times in step 3), and the surface capping agents being added every time are one kind or two
Kind；Preferably, when the surface capping agents being added every time are two kinds, two kinds of coverings are adjusted through test of many times according to actual needs
Ratio.
It is a discovery of the invention that different coverings form clad, the layer in particle surface simultaneously when being added using mixed once
The group that clad is exposed at surface is mixed group.Different groups has different polarity, by adjusting several not homopolarities
The ratio of property covering is smooth to adjust cover surface polarity, finally nano zine oxide is enabled to be scattered in opposed polarity
Solvent.
Being added in the present invention using multiple time segment is then to react to form multilayer coating structure layer in former covering
Another kind is added after completely, then new surface is more advantageous to cladding, is added after former covering reaction a part another
Kind, help to adjust the amount of different coverings claddings, thus the property of accuracy controlling nano grain surface, is suitable for it point
The solvent molecule system of dispersion media makes particle dispersion more stable；Another aspect multilayer coating structure has adjusted the activity of nano particle,
Be conducive to the practical application in later period.It has also been found that the property of particle surface depends on being coated on outermost group, i.e., most
The group for the covering being once added afterwards, repeatedly preceding covering several times is used to adjust work of the particle in later period application in addition
Property.
Preferably, in step 3), the modification time is 5min~6h, preferably 20min~3h；The modification temperature is 40
~90 DEG C, preferably 50~80 DEG C.
Preferably, in step 3), time of repose is 2h~48h, preferably 10h~for 24 hours after reaction.
Preferably, described to be separated into ultrasonic disperse in step 4).
Preferably, in step 4), in the transparent zinc oxide liquid dispersion, solid content is 1wt%~70wt%；Into one
Step ground, solid content be 40wt%~70wt%, 45wt%~70wt%, 50wt%~70wt%, 55wt%~70wt%,
60wt%~70wt% etc.；It is highly preferred that solid content is 70wt%.
Preferably, in step 4), in the transparent zinc oxide liquid dispersion, zincite crystal partial size is small and distribution is equal
It is even, it is one-dimensional having a size of 3~10nm；Further, one-dimensional having a size of 3~8nm, 3~7nm, 3~6nm, 3~5nm, 3~4nm etc..
Above-mentioned transparent zinc oxide liquid dispersion can be used as filling out for rubber, coating, plastics, fabric and other polymers
Agent is filled, in addition, also acting as the additive of cosmetics, oil product etc., can be used for photocatalysis Decomposition organic matter processing industry, life
Waste water living.
The present invention is based on basic principle be to rotate zinc solution or mixed zinc salts solution and lye in hypergravity to fill
It is reacted in bed reactor, nano zinc oxide suspension is made in reinforcing mass transfer, the microcosmic mixing of reinforcing significantly in turn, aoxidizes in suspension
Zinc particle surface reacts to form clad with surface capping agents, after filter, washing, dispersion, obtains transparent zinc oxide liquid phase
Dispersion, wherein decentralized medium is water or organic solvent.
Surface capping agents form clad in particle surface, advantageously form the monodispersed oxidation in water phase or organic phase
Zinc particle.Surface of nanometer zinc oxide is reacted there are a large amount of hydroxyl with surface capping agents, and the work of surface of nanometer zinc oxide cladding
There are biggish steric hindrance between larger organic group brought by property agent, make to be not susceptible to reunite between nano particle.But
It is the selection of suitable surface capping agents and decentralized medium is critically important.The present invention needs to carry out precipitation reaction, surface simultaneously
Therefore the more complicated technical process such as modified-reaction and redisperse process selects suitable surface capping agents and each raw material
Between proportion, reaction rate and the control of time etc. be all the technological difficulties for needing to solve.
In addition, unless otherwise specified, any range documented by the present invention includes any number between end value and end value
Any subrange that any number between value and end value or end value is constituted.
Beneficial effects of the present invention are as follows:
1) present invention prepares the process of particle and completes in high gravity rotating packed bed reactor, significantly reinforcing mass transfer, strong
Change microcosmic mixing, in addition, being dispersed in zinc oxide in liquid phase medium by suitable surface capping agents, forms point of stable transparent
Granular media.Dispersion can be appreciated that apparent Tyndall phenomenon, and nano zine oxide transparent dispersion of the invention is it is seen that obvious
Tyndall phenomenon, product it is transparent and it is dispersed very well；
2) the zincite crystal partial size in transparent zinc oxide liquid dispersion of the invention is small and is evenly distributed, one-dimensional size
Minimum 3nm.
3) transparent zinc oxide liquid dispersion of the invention is still able to maintain higher clarity and ultraviolet shielded in higher concentrations
Ability.
4) when the solid content of transparent zinc oxide liquid dispersion prepared by the present invention can be matched by feed change, be reacted
Between, the process conditions such as reaction temperature adjust.The solid content of the product of preparation is up to 70wt%.Product is transparent, and stability is good.This
The product stability for inventing synthesis is good, stands 12 months without sedimentation.Present invention process process is simple, easily operated, repeatability
Height, good product quality are easy to amplify.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the transmission electron microscope picture of gained transparent zinc oxide liquid dispersion in the embodiment of the present invention 1.
Fig. 2 shows the ultraviolet-visible spectrograms of gained transparent zinc oxide liquid dispersion in the embodiment of the present invention 1.
Fig. 3 shows the X-ray diffractogram of gained transparent zinc oxide liquid dispersion in the embodiment of the present invention 1.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
In the description of the present invention, unless otherwise indicated, the meaning of " plurality " is two or more；Term " on ",
The orientation or positional relationship of the instructions such as "lower", "left", "right", "inner", "outside", " front end ", " rear end ", " head ", " tail portion " is
It is based on the orientation or positional relationship shown in the drawings, is merely for convenience of description of the present invention and simplification of the description, rather than instruction or dark
Show that signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as pair
Limitation of the invention.
Embodiment 1
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) the zinc acetate methyl alcohol mixed liquor A 1000g that mass concentration is 11% is added in reactant storage tank A, stirring and dissolving
It is heated to 70 DEG C；The ethanolic potassium hydroxide mixed liquid B 1000g that mass concentration is 5.26% is added in reactant storage tank B, is stirred
It mixes dissolution and is heated to 55 DEG C；
2) 70 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1800rpm；Feed pump is opened, feed rate is 200ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A to be mixed and mixed liquid B charging finish, and all outflow hypergravity rotating device enters reaction gained suspension
After modified tank, hypergravity rotating device is closed, and ethyl orthosilicate covering 6g is gradually added into modified tank, 70 DEG C of claddings are anti-
Answer 0.5h, after be gradually added into covering 20g (γ-methacryloxypropyl trimethoxy silane and oleic acid, mass ratio 1:1
Mixing), the control of modified tank temperature is 70 DEG C, modification time 0.5h, and 100g deionization is added into modified gained mixed liquor
Stand 12h；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in flask plus appropriate diesel oil disperses, is passed through
45 DEG C of revolving modes remove remaining ethyl alcohol.Finally by transferred product into dispersion tank；The ultrasonic disperse device of redisperse tank is opened,
30g diesel oil is conveyed into dispersion tank again, obtains zinc oxide/transparent diesel oil dispersion after ultrasonic disperse.
As shown in Figures 1 to 3, product is light blue transparent, solid content 50%, stands December without sedimentation, through detection dispersion
Granular one dimension is still able to maintain higher clarity and ultraviolet shielded ability having a size of 5-8nm in higher concentrations.
Embodiment 2
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reactant storage is added for 8% zinc acetate and 0.4% gallium nitrate methyl alcohol mixed liquor A 1000g in mass concentration
In slot A, stirring and dissolving is heated to 50 DEG C；Reactant is added in the ethanolic potassium hydroxide mixed liquid B 1000g that mass concentration is 4%
In storage tank B, dissolution is stirred at room temperature；
2) 50 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1000rpm；Feed pump is opened, feed rate is 500ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) it is finished to zinc solution and lye charging, reaction gained suspension whole outflow hypergravity rotating device, which enters, to be changed
Property tank after, close hypergravity rotating device, and be gradually added into modified tank mixing covering 24g (ethyl orthosilicate, octadecylamine
And oleic acid, mass ratio 2:5:5) mixing), the control of modified tank temperature is 70 DEG C, modification time 0.5h, is mixed toward modified gained
95g deionization is added in liquid and stands 15h；
4) a large amount of n-hexanes are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, and it is heavy to take
Shallow lake is filtered under diminished pressure, and n-hexane washs to obtain filter cake, and filter cake is transferred in flask plus appropriate heavy oil disperses, passes through 30 DEG C of revolving sides
Formula removes remaining n-hexane.Finally by transferred product into dispersion tank；The ultrasonic disperse device for opening redisperse tank, to redisperse
40g heavy oil is conveyed in tank, obtains zinc oxide/heavy oil transparent dispersion after ultrasonic disperse.
Through detecting, product is light blue transparent, solid content 30%, stands December without sedimentation, the granular one dimension size of dispersion
For 8-9nm.
Embodiment 3
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reactant storage is added for 8% zinc acetate and 0.4% gallium nitrate methyl alcohol mixed liquor A 1000g in mass concentration
In slot A, stirring and dissolving is heated to 50 DEG C；Reactant is added in the ethanolic potassium hydroxide mixed liquid B 1000g that mass concentration is 4%
In storage tank B, dissolution is stirred at room temperature；
2) 50 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1600rpm；Feed pump is opened, feed rate is 400ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) it is finished to zinc solution and lye charging, reaction gained suspension whole outflow hypergravity rotating device, which enters, to be changed
Property tank after, close hypergravity rotating device, and be gradually added into butyl titanate covering 4g in modified tank, 70 DEG C of coating reactions
1h, after be gradually added into covering 15g (γ-glycidyl ether oxygen propyl trimethoxy silicane and polyvinylpyrrolidone, mass ratio
1:2 mixing), modified tank temperature control be 70 DEG C, modification time 0.5h, into modified gained mixed liquor addition 95g go from
Son stands 12h；
4) a large amount of n-hexanes are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, and it is heavy to take
Shallow lake is filtered under diminished pressure, and n-hexane washs to obtain filter cake, and filter cake is transferred in flask and adds appropriate reduced pressure distillate oil dispersed, passes through 30 DEG C
Revolving mode removes remaining n-hexane.Finally by transferred product into dispersion tank；The ultrasonic disperse device for opening redisperse tank, to
40g vacuum distillate is conveyed in redisperse tank, obtains zinc oxide/vacuum distillate transparent dispersion after ultrasonic disperse.
Through detecting, product is light blue transparent, solid content 30%, stands December without sedimentation, the granular one dimension size of dispersion
For 8-9nm.
Embodiment 4
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reactant is added for 10% zinc chloride and 0.7% inidum chloride alcohol mixeding liquid A 1000g in mass concentration
In storage tank A, stirring and dissolving is heated to 65 DEG C；Reaction is added in the sodium hydroxide methyl alcohol mixed liquor B 1000g that mass concentration is 5%
In object storage tank B, stirring and dissolving is heated to 50 DEG C；
2) 65 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1800rpm；Feed pump is opened, feed rate is 200ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A to be mixed and mixed liquid B charging finish, and all outflow hypergravity rotating device enters reaction gained suspension
After modified tank, hypergravity rotating device is closed, and ethyl orthosilicate covering 5g is gradually added into modified tank, 70 DEG C of claddings are anti-
Answer 50min, after be gradually added into covering 19g (dodecyltrimethoxysilane, mass ratio 3:2 mixing), modified tank temperature control
60 DEG C, modification time 1.5h are made as, 95g deionization is added into modified gained mixed liquor and stands 15h；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in flask and adds appropriate JP-10 Aviation Fuel
Dispersion, removes remaining ethyl alcohol by 35 DEG C of revolving modes.Finally by transferred product into dispersion tank；Open the ultrasound of redisperse tank
Dispersal device conveys 45gJP-10 Aviation Fuel into redisperse tank, obtains zinc oxide/JP-10 Aviation Fuel after ultrasonic disperse
Transparent dispersion.
Through detecting, product is light blue transparent, solid content 40%, stands December without sedimentation, the granular one dimension size of dispersion
For 6-8nm.
Embodiment 5
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reactant storage is added for 8% zinc nitrate and 0.7% tin acetate alcohol mixeding liquid A 1000g in mass concentration
In slot A, stirring and dissolving is heated to 60 DEG C；Reactant is added in the ethanolic potassium hydroxide mixed liquid B 1000g that mass concentration is 4%
In storage tank B, dissolution is stirred at room temperature；
2) 50 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1200rpm；Feed pump is opened, feed rate is 300ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A and B charging to be mixed finishes, and all outflow hypergravity rotating device enters modified tank to reaction gained suspension
Afterwards, hypergravity rotating device is closed, and is gradually added into aluminic acid methyl esters covering 4g, 60 DEG C of coating reaction 0.5h in modified tank,
After be gradually added into covering 16g n-octyl trimethoxy silane, the control of modified tank temperature is 60 DEG C, modification time 0.5h, past
The static 10h of 95g deionization is added in modified gained mixed liquor；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in flask plus appropriate normal heptane disperses, is led to
It crosses 35 DEG C of revolving modes and removes remaining ethyl alcohol.Finally by transferred product into dispersion tank；Open the ultrasonic disperse dress of redisperse tank
It sets, 20g normal heptane is conveyed into redisperse tank, obtains zinc oxide/normal heptane transparent dispersion after ultrasonic disperse.
Through detecting, product is light blue transparent, solid content 70%, stands December without sedimentation, the granular one dimension size of dispersion
For 3-5nm.
Embodiment 6
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reactant storage is added for 8% zinc acetate and 0.7% aluminum acetate methyl alcohol mixed liquor A 1000g in mass concentration
In slot A, stirring and dissolving is heated to 50 DEG C；Reactant is added in the ethanolic potassium hydroxide mixed liquid B 1000g that mass concentration is 4%
In storage tank B, dissolution is stirred at room temperature；
2) 50 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1800rpm；Feed pump is opened, feed rate is 300ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A and B charging to be mixed finishes, and all outflow hypergravity rotating device enters modified tank to reaction gained suspension
Afterwards, hypergravity rotating device is closed, and is gradually added into butyl borate and ethyl orthosilicate covering 4g (mass ratio in modified tank
1:1), 60 DEG C of coating reaction 0.5h, after be gradually added into covering 16g n-octyl trimethoxy silane, the control of modified tank temperature is
60 DEG C, modification time 50min, the static 15h of 95g deionization is added into modified gained mixed liquor；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in dispersion tank；Open the super of redisperse tank
Sound dispersal device conveys 50g reduced crude into redisperse tank, obtains the transparent dispersion of zinc oxide/reduced crude after ultrasonic disperse
Body.
Through detecting, product is light blue transparent, solid content 30%, stands December without sedimentation, the granular one dimension size of dispersion
For 6-10nm.
Embodiment 7
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) reaction is added for 10% zinc acetate and 0.1% aluminium isopropoxide methyl alcohol mixed liquor A 1000g in mass concentration
In object storage tank A, stirring and dissolving is heated to 60 DEG C；The sodium hydroxide alcohol mixeding liquid B 1000g that mass concentration is 5% is added anti-
It answers in object storage tank B, stirring and dissolving is heated to 45 DEG C；
2) 60 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 800rpm；Feed pump is opened, feed rate is 400ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A and B charging to be mixed finishes, and all outflow hypergravity rotating device enters modified tank to reaction gained suspension
Afterwards, hypergravity rotating device is closed, and is gradually added into ethyl orthosilicate covering 5g in modified tank, 70 DEG C of coating reactions
20min, after be gradually added into covering 19g (gamma-aminopropyl-triethoxy-silane and octadecyl trimethoxysilane mass ratio 1:
3 mixing), the control of modified tank temperature is 70 DEG C, modification time 2h, and it is quiet that 95g deionization is added into modified gained mixed liquor
Set 12h；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in flask plus appropriate decompression residuum disperses,
Remaining ethyl alcohol is removed by 35 DEG C of revolving modes.Finally by transferred product into dispersion tank；Open the ultrasonic disperse of redisperse tank
Device conveys 45g decompression residuum into redisperse tank, obtains zinc oxide/decompression residuum transparent dispersion after ultrasonic disperse.
Through detecting, product is light blue transparent, solid content 40%, stands December without sedimentation, the granular one dimension size of dispersion
For 6-8nm.
Embodiment 8
A kind of preparation of transparent zinc oxide liquid dispersion, includes the following steps:
1) the zinc acetate methyl alcohol mixed liquor A 1000g that mass concentration is 15% is added in reactant storage tank A, stirring and dissolving
It is heated to 70 DEG C；The sodium hydroxide alcohol mixeding liquid B 1000g that mass concentration is 8% is added in reactant storage tank B, is stirred molten
Solution is heated to 70 DEG C；
2) 70 DEG C of the recirculated water high-gravity rotating bed bed bodies of heating are opened, revolving bed is opened after temperature is stablized, adjusts revolving speed
For 1800rpm；Feed pump is opened, feed rate is 600ml/min, and two kinds of reactants are delivered in revolving bed simultaneously and are carried out
Reaction；
3) liquid A and B charging to be mixed finishes, and all outflow hypergravity rotating device enters modified tank to reaction gained suspension
Afterwards, hypergravity rotating device to be closed, and is gradually added into covering oleic acid 20g in modified tank, the control of modified tank temperature is 60 DEG C,
Modification time is 1h, and the static 15h of 95g deionization is added into modified gained mixed liquor；
4) a large amount of deionized waters are added into the modification liquid after standing keeps its Precipitation complete, and suspension is centrifuged, is taken
Precipitating is filtered under diminished pressure, and deionized water and ethanol washing obtain filter cake, and filter cake is transferred in flask plus appropriate petroleum ether disperses, is led to
It crosses 35 DEG C of revolving modes and removes remaining ethyl alcohol.Finally by transferred product into dispersion tank；Open the ultrasonic disperse dress of redisperse tank
It sets, 45g naphtha is conveyed into redisperse tank, obtains zinc oxide/naphtha transparent dispersion after ultrasonic disperse.
Through detecting, product is light blue transparent, solid content 40%, stands December without sedimentation, the granular one dimension size of dispersion
For 4-6nm.
Comparative example 1
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
Ethyl orthosilicate 6g is first added in middle use, and adds γ-methacryloxypropyl trimethoxy silane 20g, obtained knot
Fruit is shown in Table 1.
Comparative example 2
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
Aluminic acid methyl esters 6g is first added in middle use, and adds oleic acid 20g, what is obtained the results are shown in Table 1.
Comparative example 3
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
Butyl titanate 6g is first added in middle use, and adds octadecyl trimethoxysilane 20g, what is obtained the results are shown in Table 1.
Comparative example 4
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
Ethyl orthosilicate 6g is first added in middle use, and adds 3- aminopropyl triethoxysilane 20g, what is obtained the results are shown in Table 1.
Comparative example 5
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
Aluminic acid methyl esters 6g is first added in middle use, and adds covering 20g (3- aminopropyl triethoxysilane and octadecyl
Silane, mass ratio 1:1 mixing), what is obtained the results are shown in Table 1.
Comparative example 6
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
It is middle using first be added ethyl orthosilicate 6g, add covering 20g (γ-methacryloxypropyl trimethoxy silane and
Oleic acid, mass ratio 2:1 mixing), what is obtained the results are shown in Table 1.
Comparative example 7
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
It is middle using first be added ethyl orthosilicate 6g, add covering 20g (γ-methacryloxypropyl trimethoxy silane and
Oleic acid, mass ratio 1:1 mixing), what is obtained the results are shown in Table 1.
Comparative example 8
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that: step 3)
It is middle using first be added ethyl orthosilicate 6g, add covering 20g (γ-methacryloxypropyl trimethoxy silane and
Oleic acid, mass ratio 1:1 mixing), what is obtained the results are shown in Table 1.
The transparent zinc oxide liquid dispersion that 1 different surfaces covering of table is prepared
Embodiment 1 is dispersed in zinc oxide in liquid phase medium by suitable surface capping agents, forms point of stable transparent
Granular media.The selection of covering depends on decentralized medium, and every kind of decentralized medium has required specific covering and has been corresponding to it, and uses
Surface capping agents are improper or improper will lead to of amount of covering proportion and covering finally is difficult to form dispersion
Body or dispersion are unstable.
As known from Table 1, compared with Example 1, the covering of second of comparative example 1 addition only has γ-methacryloxypropyl
Base propyl trimethoxy silicane, so that particle surface properties do not meet diesel oil property, causes final modified particles to exist without oleic acid
Disperse poor in diesel oil, there is agglomeration；Compared with Example 1, second of comparative example 2 only with oleic acid as covering, directly
Connecing causes not disperse finally；Compared with Example 1, it is butyl titanate that comparative example 3, which only changes the covering added for the first time, finally
Dispersion of the particle in diesel oil is had no effect on, illustrates that the covering being added for the first time has no effect on particle exterior surface property, still
Influence the active size of final granule；Compared with Example 1, comparative example 4 covering will be added simultaneously twice, final dispersion effect
It is bad, because the related substances group so that particle outermost layer cladding ethyl orthosilicate is added simultaneously, change original surface
Property causes not disperse finally, therefore, needs to pay attention to the different respective amounts of covering to final covering surface when being once added
Property role weight, be added preferably can control and hold the amount and proportion of covering by several times, but encounter
Complicated decentralized medium system such as decentralized medium is a variety of mixtures, and primary be added can be such that surface group more enriches to meet
Complicated liquid phase medium environment；Compared with Example 1, the oleic acid of the covering of second of addition is substituted in comparative example 5, and final point
It is poor to dissipate property, is not able to satisfy dispersion requirement, when illustrating using a variety of coverings, it is reasonable to need to be carried out according to the property of dispersion
Collocation；Compared with Example 1, comparative example 6 changes the relative scale of two kinds of coverings of second of addition, and total amount is constant,
It can finally disperse, but dispersion effect is general, illustrate that the proportion of covering influences dispersion effect；Compared with Example 1, comparative example 7
The amount for reducing second of addition covering causes to disperse, and same comparative example 8 increases the addition of second of covering
Amount, final dispersion effect is general, illustrates that the amount of covering is also most important to scattered result is obtained.
Embodiment 9~13
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 1)
In concentration of lye be followed successively by 0.1mol/L, 0.3mol/L, 0.6mol/L, 1.2mol/L, 2mol/L.Test different concentration of lye
Influence to preparation result, the results are shown in Table 2.
Comparative example 9~10
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 1)
In concentration of lye be followed successively by 0.08mol/L, 2.5mol/L.It the results are shown in Table 2.
The transparent zinc oxide liquid dispersion that the different concentration of lye of table 2 are prepared
Therefore, it can be learnt from table 2, within the scope of 0.1~2mol/L of alkali concentration, dispersion average particle size particle size is with material
Concentration increases and presents and first reduce the trend increased afterwards, exceeds the range, causes finally form dispersion.
Embodiment 14~17
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In lye feed rate be followed successively by 40ml/min, 100ml/min, 500ml/min, 800ml/min.Test different concentration of lye
Influence (flow-rate ratio of salting liquid and lye is constant) to preparation result, the results are shown in Table 3.
Comparative example 11~12
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In lye feed rate be followed successively by 20ml/min, 1000ml/min.It the results are shown in Table 3.
The transparent zinc oxide liquid dispersion that the different lye feed rates of table 3 are prepared
Therefore, it can be learnt from table 3, be dispersion particle size within the scope of 40~800ml/min in aqueous slkali feed rate
Increase with the concentration of material and present and first reduce the trend increased afterwards, exceeds the range, cause finally form dispersion.
Embodiment 18~21
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In revolving bed revolving speed be followed successively by 300rpm, 600rpm, 1400rpm, 2600rpm.Different rotary bed revolving speed is tested to tie preparation
The influence of fruit, the results are shown in Table 4.
Comparative example 13~15
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In revolving bed revolving speed be followed successively by 100rpm, 3600rpm, 5000rpm.It the results are shown in Table 4.
The transparent zinc oxide liquid dispersion that 4 different rotary bed revolving speed of table is prepared
Therefore, it can be learnt from table 4, be within the scope of 300~5000rpm in revolving bed, dispersion particle size is with material
Concentration increases and is gradually reduced, and exceeds 2600rpm, and change in particle size is no longer obvious, and to save energy consumption, general control exists
Within 2600rpm, it is irregular to will lead to mixed effect less than 300rpm, leads to that stabilising dispersions cannot be formed.
Embodiment 22~24
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In reaction temperature be followed successively by 20 DEG C, 40 DEG C, 85 DEG C.Influence of the differential responses temperature to preparation result is tested, the results are shown in Table 4.
Comparative example 16~18
Transparent zinc oxide liquid dispersion is prepared using step as described in example 1 above, the difference is that, step 2)
In reaction temperature be followed successively by 10 DEG C, 90 DEG C, 110 DEG C.It the results are shown in Table 4.
The transparent zinc oxide liquid dispersion that 5 differential responses temperature of table is prepared
Therefore, it can be learnt from table 5, within the scope of 20~85 DEG C, dispersion particle size increases reaction temperature with reaction temperature
It presents greatly and first reduces the trend increased afterwards, exceed the range, cause finally form dispersion.
Conclusion: high-gravity technology is used to prepare transparent zinc oxide liquid dispersion by the present invention, and it is reachable to obtain solid content
70% dispersion.Additionally by enabling particle surface to form multilayer coating structure layer for the addition by several times of a variety of coverings, so that
Dispersion dispersion is more stable.Improvement, operating procedure and the parameter that the introducing of high-gravity technology, surface capping agents are added it is accurate
Mutual cooperation, synergistic effect between setting, not only solid content is high for finally obtained transparent zinc oxide liquid dispersion, stability
It is good, and 12 months are stood without sedimentation.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of method for preparing transparent zinc oxide liquid dispersion, which comprises the steps of:
1) salt is dissolved in liquid phase medium A, obtains salting liquid；By alkali soluble in liquid phase medium B, aqueous slkali is obtained；
The salt is zinc salt or mixed zinc salts, and the mixed zinc salts are the zinc salt and doped chemical that molar ratio is 10~100:1
Salt mixes；
2) salting liquid and lye are added in high gravity rotating packed bed reactor, zinc oxide suspension is obtained after reaction；
3) surface capping agents are added in zinc oxide suspension and are modified cladding, modified standing modification liquid；
4) by the modification liquid precipitate of standing, centrifugation, washing, redisperse obtains ZnO transparent solution dispersion into liquid phase medium C
Body；
In step 4), the liquid phase medium C is selected from the one or more of following substance: diesel oil, naphtha, heavy oil, normal heptane, just
Octane, JP-10 Aviation Fuel, C4 lighter hydrocarbons, C5 lighter hydrocarbons, vacuum distillate, wax tailings, reduced crude, decompression residuum.
2. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 1)
In, the zinc salt is selected from one of following substance or a variety of: zinc chloride, zinc bromide, zinc nitrate, zinc sulfate, zinc acetate；It is described
The salt of doped chemical is selected from one of following substance or a variety of: aluminum sulfate, aluminum nitrate, aluminum acetate, aluminium isopropoxide, aluminium chloride,
Gallium nitrate, gallium sulfate, indium acetate, indium nitrate, inidum chloride, stannic chloride, tin acetate；The alkali be selected from one of following substance or
It is a variety of: lithium hydroxide, sodium hydroxide, potassium hydroxide, a hydration ammonia.
3. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 1)
In, the concentration of the zinc salt is 0.05mol/L~2mol/L；The concentration of the lye is 0.1mol/L~4mol/L.
4. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 1)
In, the liquid phase medium A is selected from one of following substance or a variety of: water, methanol, ethyl alcohol, ethylene glycol, isopropanol, butanol, benzene
Methanol, glycerol, ether, dimethyl ether, acetone, butanone, cyclohexanone；The liquid phase medium B is selected from one of following substance or several
Kind: water, methanol, ethyl alcohol, ethylene glycol, isopropanol, glycerol, butanol, acetone, butanone, ethyl acetate, butyl acetate, toluene, diformazan
Benzene, dimethyl sulfoxide, tetrahydrofuran, n-hexane, hexamethylene.
5. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 2)
In, reaction temperature is 20~85 DEG C.
6. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 2)
In, the rotary drill reactor is rotary packed bed rotating packed bed reactor, deflection type overgravity rotary bed reactor, spiral shell
Revolve channel rotating packed bed reactor, fixed-rotor rotating packed bed reactor or the high-gravity rotating bed reaction of rotating compact disc
Device；The rotor speed of the revolving bed is 300~5000rpm.
7. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 2)
In, being passed through the molar flow rate ratio of salting liquid and lye in rotary packed bed is 0.2~3.5:1；The mixing salt solution is passed through rotation
The feed rate for turning packed bed is 50ml/min~1000ml/min, and lye is 40ml/min~800ml/min.
8. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step 3)
In, the surface capping agents are selected from the one or more of following substance: titanate esters, Aluminate, esters of silicon acis, stearic acid, stearic acid
Sodium, oleic acid, polyvinylpyrrolidone, γ-methacryloxypropyl trimethoxy silane, polyethylene glycol, polyvinyl alcohol, ten
Eight amine, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen
Propyl trimethoxy silicane, n-octyl trimethoxy silane, dodecyltrimethoxysilane, octadecyl silicon
Alkane, 3- TSL 8330, phenyltrimethoxysila,e, dimethyl dichlorosilane (DMCS)；The addition of the surface capping agents
Quality and zinc oxide mass ratio are 0.1~2:1；The modification time is 5min~6h；The reaction temperature is 40~90 DEG C；Instead
Time of repose is 2h~48h after answering.
9. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 8, which is characterized in that step 3)
In, when the surface capping agents are a variety of, adding manner is that mixed once is added or divides different time that different surfaces cladding is added
Agent；Time interval when being added by several times is 5min~2h, preferably 10min~1h.
10. a kind of method for preparing transparent zinc oxide liquid dispersion according to claim 1, which is characterized in that step
4) described to be separated into ultrasonic disperse in.
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| CN112777627A (en) * | 2021-01-13 | 2021-05-11 | 北京化工大学 | Preparation method of nano zinc oxide and nano zinc oxide |
| CN113952917A (en) * | 2021-10-18 | 2022-01-21 | 济源市鲁泰纳米材料有限公司 | Hypergravity reactor and preparation method of active nano zinc oxide prepared by same |
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| CN105621475A (en) * | 2014-12-01 | 2016-06-01 | 北京化工大学 | Metal-doped zinc oxide liquid-phase transparent dispersoid and preparation method therefor |
| CN107140676A (en) * | 2017-04-11 | 2017-09-08 | 南昌大学 | A kind of preparation method of metal doped zinc oxide even in liquid phase dispersion |
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| CN1513590A (en) * | 2003-05-30 | 2004-07-21 | 中国科学院金属研究所 | Nano-level iron oxide dispersion liquid and its preparation method |
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| CN113952917A (en) * | 2021-10-18 | 2022-01-21 | 济源市鲁泰纳米材料有限公司 | Hypergravity reactor and preparation method of active nano zinc oxide prepared by same |
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