阅读说明：本技术 一种高分散纳米氢氧化镧的制备方法 (preparation method of high-dispersion nano lanthanum hydroxide ) 是由 王洁欣 谢瑜 陈博 曾晓飞 陈建峰 于 2018-06-05 设计创作，主要内容包括：本发明公开一种高分散纳米氢氧化镧的制备方法,包括如下步骤：将镧盐溶于水、有机溶剂或水和有机溶剂的混合液中,制得镧盐溶液；将碱溶于水、有机溶剂或水和有机溶剂的混合液中,制得碱液；将镧盐溶液与碱液加入到普通反应器或超重力旋转填充床中进行沉淀结晶反应,制得氢氧化镧悬浮液；将氢氧化镧悬浮液放入恒温箱陈化处理；在陈化处理后的浆液中加入改性剂进行改性；将改性后的浆液冷却至常温,经超滤或离心洗涤,得到滤饼；将滤饼分散到液相介质中,制得高分散纳米氢氧化镧分散液；或将滤饼烘干制得高分散纳米氢氧化镧粉体。该方法制得的氢氧化镧颗粒一维尺寸15～250nm,可实现≥6个月稳定的分散不团聚。(The invention discloses a preparation method of high-dispersion nano lanthanum hydroxide, which comprises the following steps: dissolving lanthanum salt in water, an organic solvent or a mixed solution of water and the organic solvent to prepare a lanthanum salt solution; dissolving alkali in water, organic solvent or the mixed solution of water and organic solvent to obtain alkali liquor; adding a lanthanum salt solution and alkali liquor into a common reactor or a supergravity rotating packed bed for precipitation and crystallization reaction to prepare a lanthanum hydroxide suspension; putting the lanthanum hydroxide suspension into a constant temperature box for aging treatment; adding a modifier into the aged slurry for modification; cooling the modified slurry to normal temperature, and performing ultrafiltration or centrifugal washing to obtain a filter cake; dispersing the filter cake into a liquid phase medium to prepare a high-dispersion nano lanthanum hydroxide dispersion liquid; or drying the filter cake to obtain the high-dispersion nano lanthanum hydroxide powder. The lanthanum hydroxide particles prepared by the method have the one-dimensional size of 15-250 nm, and can be stably dispersed and not agglomerated for more than 6 months.)

1. A preparation method of high-dispersion nano lanthanum hydroxide is characterized by comprising the following steps:

1) dissolving lanthanum salt in water, an organic solvent or a mixed solution of water and the organic solvent to prepare a lanthanum salt solution; dissolving alkali in water, organic solvent or the mixed solution of water and organic solvent to obtain alkali liquor;

2) adding a lanthanum salt solution and alkali liquor into a common reactor or a supergravity rotating packed bed for precipitation and crystallization reaction to prepare a lanthanum hydroxide suspension;

3) Putting the lanthanum hydroxide suspension into a constant temperature box for aging treatment;

4) Adding a modifier into the aged slurry for modification;

5) cooling the modified slurry to normal temperature, and performing ultrafiltration or centrifugal washing to obtain a filter cake;

6) dispersing the filter cake into a liquid phase medium to prepare a high-dispersion nano lanthanum hydroxide dispersion liquid; or drying the filter cake to obtain the high-dispersion nano lanthanum hydroxide powder.

2. The method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 1), the lanthanum salt in the lanthanum salt solution comprises one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, lanthanum fluoride, lanthanum acetate and lanthanum sulfate; the alkali in the alkali liquor is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water and hydrazine hydrate.

3. The method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 1), the concentration of lanthanum salt in the lanthanum salt solution is 0.01-2 mol/L; preferably, the concentration of the lanthanum salt is 0.02-1.6 mol/L; more preferably, the concentration of the lanthanum salt is 0.05-0.8 mol/L;

preferably, in the step 1), the concentration of the alkali liquor is 0.03-6 mol/L; more preferably, the concentration of the alkali liquor is 0.06-4.8 mol/L; most preferably, the concentration of the alkali liquor is 0.15-2.4 mol/L.

4. the method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: preferably, in step 1), the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, glycerol, n-butanol, isobutanol, diethyl ether, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran and dimethyl sulfoxide;

Preferably, in the step 1), the temperature of the prepared lanthanum salt solution and the temperature of the prepared alkali liquor are respectively maintained at 2-40 ℃.

5. the method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 2), the reaction temperature of the precipitation crystallization reaction is 2-40 ℃; more preferably, the reaction temperature is 5-35 ℃; most preferably, the reaction temperature is 7-30 ℃;

preferably, in step 2), the high-gravity rotating packed bed is selected from one of a baffled high-gravity rotating packed bed, a spiral channel high-gravity rotating packed bed, a stator-rotor high-gravity rotating packed bed or a rotating disc high-gravity rotating packed bed;

Preferably, in the step 2), the feeding flow rate of the peristaltic pump of the rotary bed during mixing of the super-gravity rotary packed bed is 50-800 mL/min, preferably, the feeding flow rate of the peristaltic pump of the rotary bed is 60-600 mL/min, and more preferably, the feeding flow rate of the peristaltic pump of the rotary bed is 70-550 mL/min;

preferably, in the step 2), the rotating speed of a rotor of the supergravity rotating packed bed is 100-3000 rpm; more preferably, the rotating speed of the rotor of the supergravity rotating packed bed is 300-2500 rpm;

preferably, in the step 2), the volume flow ratio of the lanthanum salt solution to the alkali liquor introduced into the supergravity rotating packed bed is 0.5-5: 1;

preferably, in the step 2), the linear speed of the nozzle for introducing the lanthanum salt solution into the hypergravity rotating packed bed is 2-10 m/s, and the linear speed of the nozzle for introducing the alkali liquor into the hypergravity rotating packed bed is 3-12 m/s.

6. the method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 3), the aging temperature is 2-70 ℃; preferably, the aging temperature is 5-50 ℃; more preferably, the aging temperature is 7-30 ℃;

preferably, in the step 3), the aging time is 0.1-8 h; preferably, the aging time is 0.2-7 h; more preferably, the aging time is 0.5-6 h.

7. The method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 4), the modifier is selected from one or more of the following substances: KH570, KH550, PVP, CTAB, TBAB, lauric acid, oleic acid, stearic acid, Tween;

preferably, in the step 4), the modification temperature is 10-100 ℃; preferably, the modification temperature is 20-90 ℃; more preferably, the modification temperature is 30-80 ℃;

Preferably, in the step 4), the modification time is 0.5-6 h; preferably, the modification time is 0.7-5 h; more preferably, the modification time is 1-4 h;

preferably, in the step 4), the modifier is used in an amount of 1 wt% to 30 wt%; preferably, the modifier is used in an amount of 2 to 25 wt%; more preferably, the modifier is used in an amount of 3 wt% to 20 wt%.

8. The method for preparing the highly dispersed nano lanthanum hydroxide according to claim 1, wherein: in the step 6), the liquid phase medium is selected from one or more of deionized water, methanol, ethanol, ethylene glycol, diethylene glycol, glycerol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, n-hexane and cyclohexane;

preferably, in the step 6), the adopted dispersion method is ultrasonic dispersion;

preferably, in the step 6), the solid content of the highly dispersed nano lanthanum hydroxide dispersion liquid is 2 wt% to 40 wt%.

Technical Field

The invention relates to the technical field of nano materials. More particularly, relates to a preparation method of high-dispersion nano lanthanum hydroxide.

background

lanthanum hydroxide La (OH)₃Has excellent optical, electric and magnetic properties, and can be widely used as a catalyst, an adsorbent, a fluorescent agent, a time-resolved fluorescence (TRF) biological label, an up-conversion luminescent material and the like. Nanostructured materials exhibit many properties that are superior to their corresponding bulk materials due to quantum size effects. The nano-structure lanthanum hydroxide has relatively large specific surface area, can be fully contacted with reaction materials, and greatly improves the catalytic activity of the nano-structure lanthanum hydroxide.

the preparation method of the high-dispersion nano lanthanum hydroxide comprises a precipitation method, a thermal decomposition method, a hydrothermal method, a solvothermal method and a sol-gel method, and different methods show different advantages and disadvantages. At present, a preparation method of a high-dispersion nano lanthanum hydroxide dispersion liquid is not disclosed, and a preparation method of nano lanthanum hydroxide powder is disclosed, for example, a patent with Chinese patent publication No. CN201210458171.X and named as a preparation method of rod-shaped lanthanum hydroxide nanocrystalline prepares a precursor liquid by a precipitation method, and then a microwave-ultraviolet-ultrasonic three-in-one synthesis reactor is used for preparing superfine lanthanum hydroxide powder. The method can prepare the lanthanum hydroxide crystal grains with high purity and smaller grain diameter, but has the defects that: the prepared lanthanum hydroxide particles have serious agglomeration, complex preparation process and high energy consumption.

in addition, chinese patent publication No. CN201310035909.6, entitled "controlled synthesis of lanthanum hydroxide nanoparticles", discloses a method for regulating the size of lanthanum hydroxide nanoparticles. The method adopts a liquid phase precipitation method, and regulates and controls the size of the nano lanthanum hydroxide particles by controlling the amount of ammonia water, and has the defects that: the nanometer lanthanum hydroxide particles obtained by the process are seriously agglomerated, the particle appearance is not very regular, and the range of regulation and control through the amount of ammonia water is narrow.

disclosure of Invention

The technical problem to be solved by the invention is to provide a method for preparing high-dispersion nano lanthanum hydroxide; the method adopts a supergravity rotating packed bed, greatly strengthens the mass transfer and micro mixing processes of the reaction, prepares a nanometer lanthanum hydroxide suspension with regular appearance and uniform particle size distribution, and prepares high-dispersion nanometer lanthanum hydroxide dispersion liquid or powder through the steps of constant-temperature aging treatment, washing, dispersion and the like; the method adopts the mixed solution of water and an organic solvent as a reaction medium, and can effectively realize the controllable preparation of the particle size of the lanthanum hydroxide particles by adjusting the content of water; the grain size of lanthanum hydroxide particles is also prepared by controlling the rotating speed of the supergravity rotating packed bed; through modification, the solid content of the obtained dispersion liquid is 2-40 wt%, the lanthanum hydroxide particles in the dispersion liquid are in a hexagonal-phase rod-shaped structure, the particle size distribution is uniform, controllable preparation of different particle sizes can be realized, the control range of one-dimensional size is 15-250 nm, and the dispersion liquid has higher Zeta potential and obvious Tyndall effect; the dispersion liquid can realize stable dispersion for more than or equal to 6 months after being modified, and the product has high purity and good dispersion effect; the liquid phase dispersion can use water and various organic solvents as dispersion media, and the application range of the product is wide; the raw materials adopted in the invention are cheap and easily available, the selected solvent is a common solvent in industry, and the designed preparation process is simple.

In order to achieve the purpose, the invention adopts the following technical scheme:

A preparation method of high-dispersion nano lanthanum hydroxide comprises the following steps:

1) Dissolving lanthanum salt in water, an organic solvent or a mixed solution of water and the organic solvent to prepare a lanthanum salt solution; dissolving alkali in water, organic solvent or the mixed solution of water and organic solvent to obtain alkali liquor;

2) Adding a lanthanum salt solution and alkali liquor into a common reactor or a supergravity rotating packed bed for precipitation and crystallization reaction to prepare a lanthanum hydroxide suspension;

3) Putting the lanthanum hydroxide suspension into a constant temperature box for aging treatment;

4) Adding a modifier into the aged slurry for modification;

5) Cooling the modified slurry to normal temperature, and performing ultrafiltration or centrifugal washing to obtain a filter cake;

6) Dispersing the filter cake into a liquid phase medium to prepare a high-dispersion nano lanthanum hydroxide dispersion liquid; or drying the filter cake to obtain the high-dispersion nano lanthanum hydroxide powder.

as a further improvement of the technical solution, in the step 1), the lanthanum salt in the lanthanum salt solution comprises one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, lanthanum fluoride, lanthanum acetate and lanthanum sulfate; the alkali in the alkali liquor is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water and hydrazine hydrate.

preferably, in the step 1), the concentration of lanthanum salt in the lanthanum salt solution is 0.01-2 mol/L; preferably, the concentration of the lanthanum salt is 0.02-1.6 mol/L; more preferably, the concentration of the lanthanum salt is 0.05-0.8 mol/L.

Preferably, in the step 1), the concentration of the alkali liquor is 0.03-6 mol/L; more preferably, the concentration of the alkali liquor is 0.06-4.8 mol/L; most preferably, the concentration of the alkali liquor is 0.15-2.4 mol/L.

preferably, in step 1), the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, glycerol, n-butanol, isobutanol, diethyl ether, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran and dimethyl sulfoxide.

Preferably, in the step 1), the temperature of the prepared lanthanum salt solution and the temperature of the prepared alkali liquor are respectively maintained at 2-40 ℃.

as a further improvement of the technical scheme, in the step 2), the reaction temperature of the precipitation crystallization reaction is 2-40 ℃; more preferably, the reaction temperature is 5-35 ℃; most preferably, the reaction temperature is 7-30 ℃.

Preferably, in step 2), the high-gravity rotating packed bed is selected from one of a baffled high-gravity rotating packed bed, a spiral channel high-gravity rotating packed bed, a stator-rotor high-gravity rotating packed bed or a rotating disc high-gravity rotating packed bed.

Preferably, in the step 2), the feeding flow rate of the rotary bed peristaltic pump during the mixing of the super-gravity rotary packed bed is 50-800 mL/min, preferably, the feeding flow rate of the rotary bed peristaltic pump is 60-600 mL/min, and more preferably, the feeding flow rate of the rotary bed peristaltic pump is 70-550 mL/min.

preferably, in the step 2), the rotating speed of a rotor of the supergravity rotating packed bed is 100-3000 rpm; more preferably, the rotating speed of the rotor of the super-gravity rotating packed bed is 300-2500 rpm.

preferably, in the step 2), the volume flow ratio of the lanthanum salt solution to the alkali liquor introduced into the supergravity rotating packed bed is 0.5-5: 1.

Preferably, in the step 2), the linear speed of the nozzle for introducing the lanthanum salt solution into the hypergravity rotating packed bed is 2-10 m/s, and the linear speed of the nozzle for introducing the alkali liquor into the hypergravity rotating packed bed is 3-12 m/s.

as a further improvement of the technical scheme, in the step 3), the aging temperature is 2-70 ℃; preferably, the aging temperature is 5-50 ℃; more preferably, the aging temperature is 7-30 ℃.

Preferably, in the step 3), the aging time is 0.1-8 h; preferably, the aging time is 0.2-7 h; more preferably, the aging time is 0.5-6 h.

As a further improvement of the technical scheme, in the step 4), the modifier is selected from one or more of the following substances: KH570, KH550, PVP, CTAB, TBAB, lauric acid, oleic acid, stearic acid and Tween.

Preferably, in the step 4), the modification temperature is 10-100 ℃; preferably, the modification temperature is 20-90 ℃; more preferably, the modification temperature is 30-80 ℃.

preferably, in the step 4), the modification time is 0.5-6 h; preferably, the modification time is 0.7-5 h; more preferably, the modification time is 1-4 h.

preferably, in the step 4), the modifier is used in an amount of 1 wt% to 30 wt%; preferably, the modifier is used in an amount of 2 to 25 wt%; more preferably, the modifier is used in an amount of 3 to 20 wt%;

As a further improvement of the technical solution, in step 6), the liquid-phase medium is selected from one or more of deionized water, methanol, ethanol, ethylene glycol, diethylene glycol, glycerol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, n-hexane, and cyclohexane.

preferably, in step 6), the dispersion method used is ultrasonic dispersion.

preferably, in the step 6), the solid content of the highly dispersed nano lanthanum hydroxide dispersion liquid is 2 wt% to 40 wt%.

The high-dispersion nano lanthanum hydroxide prepared by the invention can be well applied to inorganic material compounding, organic polymer material compounding, supercapacitors, catalysts, adsorbents and electrochemical catalysis, and can be applied to the industrial fields of biomedicine, water treatment, fuel cells, lithium ion batteries, electrocatalysis and the like.

it is further noted that any range recited herein includes the endpoints and any values therebetween and any subranges subsumed therein or any values therebetween unless otherwise specified.

the invention has the following beneficial effects:

1) the invention can greatly strengthen the mass transfer and micro mixing process of reaction by utilizing the supergravity technology, and can obtain the nano lanthanum hydroxide particles with small particle size and uniform particle size distribution after the lanthanum hydroxide suspension prepared by the supergravity rotating packed bed is aged at a proper constant temperature, and the one-dimensional size of the particles can be regulated and controlled between 15 nm and 250 nm.

2) Meanwhile, the method adopts a novel process strengthening reactor to strengthen the micromixing among reactants, thereby achieving the purpose of controlling the appearance and the particle size of the transparent lanthanum hydroxide liquid-phase dispersoid. Different from the conventional batch stirred tank reactor, the novel reactors are operated in a continuous mode, the stay time of reactants in the reactors is extremely short, the reaction products leave the reactors immediately after being formed, the continuous operation mode of the novel process strengthening reactor can greatly improve the production efficiency, shorten the production period and meet the requirement of large-scale production of transparent lanthanum hydroxide liquid-phase dispersoid. The required reactor has small volume, convenient operation, strong experimental repeatability and easy amplification;

3) the invention provides two methods for regulating and controlling the size of nano lanthanum hydroxide particles, one method adopts a mixed solution of water and an organic solvent as a reaction medium, effectively realizes the controllable preparation of the particle size of the lanthanum hydroxide particles by regulating the content of water, and the other method is to controllably prepare the nano lanthanum hydroxide by regulating and controlling the rotating speed of a rotor of a supergravity rotating packed bed;

4) The solid content of the high-dispersion nano lanthanum hydroxide dispersion liquid prepared by the invention can be regulated and controlled by changing the mass ratio of the filter cake to the dispersion medium, and can also be regulated by means of rotary evaporation and the like, the obtained product can be kept transparent and stable after standing for more than or equal to 6 months, and the solid content of the product is 2-40 wt%; the appearance is a regular hexagonal rod-shaped structure;

5) the method has the advantages of simple process flow, easy operation of the process and cheap and easily obtained raw materials; the product has high purity and good quality; the experiment has strong repeatability and is easy to amplify.

drawings

the following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

Figure 1 shows a process flow diagram for the production of a hypergravity rotating packed bed used in the solution of the invention.

Figure 2 shows a schematic diagram of a high gravity rotating packed bed used in the solution of the invention.

FIG. 3 is a schematic diagram showing the dispersions obtained in examples 1, 7 and 9 of the present invention.

FIG. 4 shows a transmission electron micrograph of a product obtained in example 1 of the present invention.

FIG. 5 shows a transmission electron micrograph of a product obtained in example 7 of the present invention.

FIG. 6 shows a transmission electron micrograph of a product obtained in example 9 of the present invention.

FIG. 7 shows a transmission electron micrograph of a product obtained in example 14 of the present invention.

FIG. 8 shows a transmission electron micrograph of a product obtained in example 15 of the present invention.

FIG. 9 shows the IR spectra of the products obtained in examples 9 and 16 of the present invention.

figure 10 shows XRD diffraction patterns of the products obtained in examples 1, 7 of the present invention.

The numbers referred to in the figures are numbered as follows:

1-lanthanum salt solution storage tank, 2-pump, 3-liquid flowmeter, 4-alkali liquor storage tank, 5-pump, 6-liquid flowmeter, 7-super gravity rotary packed bed, 8-low temperature constant temperature bath, 9-beaker, 10-water bath, 11-inert gas control valve, 12-washing liquid inlet, 13-ultrafiltration tank, 14-filtrate outlet, 15-liquid phase dispersion medium storage tank, 16-pump, 17-liquid flowmeter, 18-dispersion tank, 19-lanthanum salt solution inlet, 20-alkali liquor inlet, 21-filler, 22-motor, 23-liquid phase outlet

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

the technology of the super-gravity rotating packed bed used by the invention is the prior art, for example, the technology of the super-gravity rotating packed bed used by the invention is disclosed in the patent (the publication number is CN2221437A, the name of the invention is 'super-gravity field device of a rotating bed for strengthening transfer reaction'), the production process flow chart of the super-gravity rotating packed bed used by the invention is shown in figure 1, and figure 2 is a schematic diagram of the super-gravity rotating packed bed used by the invention, the concrete embodiment is as follows, the super-gravity rotating packed bed device 7 is opened, the rotating speed is adjusted to enable the rotating speed of a rotor in the super-gravity rotating packed bed device to reach the preset value, lanthanum salt solution in a lanthanum salt solution storage tank 1 is pumped into a lanthanum salt solution feed inlet 18 in the super-gravity rotating packed bed by a pump 2 after being measured by a flowmeter 3, alkali solution in an alkali solution storage tank 4 is pumped into an alkali solution feed inlet 19 in the super-gravity rotating packed bed after being measured by a pump 5 and a, thereby obtaining a hypergravity environment; the lanthanum salt solution and the alkali liquor are sprayed to the inner edge of the rotor filler of the super-gravity rotating packed bed through the liquid distributor on the feeding pipe, and then collide with the filler and enter the filler; the lanthanum salt solution and the alkali liquor entering the filler generate a large amount of rapidly updated liquid surface after being divided, crushed and torn by the silk screen filler, thereby greatly strengthening the intermolecular mass transfer process, shortening the crystal nucleus growth time after the reactant is reacted, precipitated and crystallized, and further effectively controlling the particle size and the morphology of the nucleated particles; the lanthanum hydroxide precursor suspension liquid after reaction and precipitation of the hypergravity rotating packed bed flows out from a liquid phase discharge port 22 at the lower part of the hypergravity rotating packed bed; then transferring the beaker into a beaker 9, placing the beaker into a low-temperature constant temperature box 8 with controllable temperature for constant temperature treatment, transferring the beaker into a three-neck flask after constant temperature treatment for a certain time, carrying out high-temperature modification in a water bath 10, cooling the modified suspension, and transferring the modified suspension into an ultrafiltration tank 13; when the suspension circularly flows in the ultrafiltration tank, inert gas is introduced into the ultrafiltration tank through a pressure reducing valve 11 to pressurize and filter the suspension, and filtrate is discharged from a filtrate outlet 14 at the bottom of the ultrafiltration tank; after the filtration is finished, the washing liquid is introduced from the washing liquid inlet 12 to fully and thoroughly wash the filter cake, and the washing liquid is discharged from the filtrate outlet 14; transferring the washed filter cake into a dispersion tank 18, and pumping the liquid-phase dispersion medium in a liquid-phase dispersion medium storage tank 15 into the dispersion tank after the liquid-phase dispersion medium is metered by a pump 16 through a flowmeter 17; the filter cake completes the dispersion process under the ultrasonic condition, the particles are rapidly and uniformly dispersed into the liquid phase medium, and finally the high-dispersion nano lanthanum hydroxide dispersion liquid is formed.

the invention relates to a preparation method of high-dispersion nano lanthanum hydroxide, which comprises the following steps:

1) Dissolving lanthanum salt in water, an organic solvent or a mixed solution of water and the organic solvent to prepare a lanthanum salt solution; dissolving alkali in water, organic solvent or the mixed solution of water and organic solvent to obtain alkali liquor;

2) Adding a lanthanum salt solution and alkali liquor into a common reactor or a supergravity rotating packed bed for precipitation and crystallization reaction to prepare a lanthanum hydroxide suspension;

3) Putting the lanthanum hydroxide suspension into a constant temperature box for aging treatment;

4) adding a modifier into the aged slurry for modification;

5) cooling the modified slurry to normal temperature, and performing ultrafiltration or centrifugal washing to obtain a filter cake;

6) dispersing the filter cake into liquid medium to obtain high-dispersion nano lanthanum hydroxide dispersion liquid or drying the filter cake to obtain high-dispersion nano lanthanum hydroxide powder.

The high-dispersion nano lanthanum hydroxide prepared by the method has controllable particle size and regular hexagonal rod-shaped structure.

In certain embodiments of the present invention, in step 1), the lanthanum salt in the lanthanum salt solution comprises one or more of lanthanum chloride heptahydrate, lanthanum nitrate hexahydrate, lanthanum fluoride, lanthanum acetate, lanthanum sulfate; the alkali in the alkali liquor is selected from one or more of sodium hydroxide, potassium hydroxide, ammonia water and hydrazine hydrate.

In some embodiments of the invention, in the step 1), the concentration of the lanthanum salt in the lanthanum salt solution is 0.01-2 mol/L; preferably, the concentration of the lanthanum salt is 0.02-1.6 mol/L; more preferably, the concentration of the lanthanum salt is 0.05-0.8 mol/L.

In some embodiments of the invention, in step 1), the concentration of the alkali liquor is 0.03-6 mol/L; more preferably, the concentration of the alkali liquor is 0.06-4.8 mol/L; most preferably, the concentration of the alkali liquor is 0.15-2.4 mol/L.

In certain embodiments of the present invention, the organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, glycerol, n-butanol, isobutanol, diethyl ether, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, n-hexane, cyclohexane, benzene, toluene, xylene, tetrahydrofuran, dimethyl sulfoxide.

in some embodiments of the present invention, in step 1), the temperature of the prepared lanthanum salt solution and the temperature of the prepared alkali liquor are respectively maintained at 2-40 ℃.

in certain embodiments of the invention, in the step 2), the reaction temperature of the precipitation crystallization reaction is 2-40 ℃; more preferably, the reaction temperature is 5-35 ℃; most preferably, the reaction temperature is 7-30 ℃.

in certain embodiments of the invention, in step 2), the high-gravity rotating packed bed is selected from one of a baffled high-gravity rotating packed bed, a spiral channel high-gravity rotating packed bed, a stator-rotor high-gravity rotating packed bed, or a rotating disc high-gravity rotating packed bed.

In certain embodiments of the invention, in step 2), the feeding flow rate of the rotary bed peristaltic pump during the mixing of the super-gravity rotary packed bed is 50-800 mL/min, preferably, the feeding flow rate of the rotary bed peristaltic pump is 60-600 mL/min, and more preferably, the feeding flow rate of the rotary bed peristaltic pump is 70-550 mL/min.

in some embodiments of the invention, in the step 2), the rotating speed of the rotor of the supergravity rotating packed bed is 100-3000 rpm; more preferably, the rotating speed of the rotor of the super-gravity rotating packed bed is 300-2500 rpm.

in some embodiments of the invention, in the step 2), the volume flow ratio of the lanthanum salt solution to the alkali liquor introduced into the supergravity rotating packed bed is 0.5-5: 1.

in some embodiments of the invention, in the step 2), the linear speed of the nozzle for introducing the lanthanum salt solution into the supergravity rotating packed bed is 2-10 m/s, and the linear speed of the nozzle for introducing the alkali liquor into the supergravity rotating packed bed is 3-12 m/s.

In certain embodiments of the present invention, in step 3), the aging temperature is 2 to 70 ℃; preferably, the aging temperature is 5-50 ℃; more preferably, the aging temperature is 7-30 ℃.

in some embodiments of the invention, in the step 3), the aging time is 0.1-8 h; preferably, the aging time is 0.2-7 h; more preferably, the aging time is 0.5-6 h.

In certain embodiments of the invention, in step 4), the modifying agent is selected from one or more of the following: KH570, KH550, PVP, CTAB, TBAB, lauric acid, oleic acid, stearic acid and Tween.

In certain embodiments of the invention, in the step 4), the temperature of the modification is 10 to 100 ℃; preferably, the modification temperature is 20-90 ℃; more preferably, the modification temperature is 30-80 ℃.

in certain embodiments of the invention, in the step 4), the modification time is 0.5-6 h; preferably, the modification time is 0.7-5 h; more preferably, the modification time is 1-4 h.

in certain embodiments of the present invention, in step 4), the modifier is used in an amount of 1 wt% to 30 wt%; preferably, the modifier is used in an amount of 2 to 25 wt%; more preferably, the modifier is used in an amount of 3 to 20 wt%;

in certain embodiments of the present invention, in step 5), the liquid medium is selected from one or more of deionized water, methanol, ethanol, ethylene glycol, diethylene glycol, glycerol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, butanone, methyl acetate, ethyl acetate, butyl acetate, benzene, toluene, xylene, tetrahydrofuran, carbon tetrachloride, n-hexane, cyclohexane.

in certain embodiments of the invention, in step 5), the dispersion method employed is ultrasonic dispersion.

In certain embodiments of the present invention, in step 5), the solid content of the highly dispersed nano lanthanum hydroxide dispersion is 2 wt% to 40 wt%.

In the high-dispersion nano lanthanum hydroxide prepared by the method, the lanthanum hydroxide particles are in a hexagonal-phase rod-shaped structure, the particle size distribution is uniform, controllable preparation of different particle sizes can be realized, and the regulation and control range of one-dimensional size is 15-250 nm. In the step 2), when a common reactor is used, such as a three-neck flask, the one-dimensional size is 15-250 nm; when the super-gravity rotating packed bed is used, the one-dimensional size is 15-120 nm.

compared with the prior art, the technical scheme of the invention has the characteristics that the shape, the size and the dispersity of the nano lanthanum hydroxide dispersoid particles are regulated and controlled by regulating and controlling the process parameters of each step, the conversion rate and the selectivity of the reaction are greatly improved by utilizing the supergravity technology, the volume of the reactor is obviously reduced, and the process and the flow are simplified. According to the invention, through an effective modification scheme, the modified lanthanum hydroxide particles can be stably dispersed in water or various organic solvents, and the technical scheme of the invention can solve the problems of the shape, size, dispersibility and the like of the nano lanthanum hydroxide particles, and endows the product with higher application performance and wider application range.

The invention mainly realizes the regulation and control of the process parameters as follows:

The preparation process of the high-dispersion nano lanthanum hydroxide liquid-phase dispersion comprises a series of technological processes of supergravity-enhanced micro mixing reaction, aging, washing, dispersion and the like, the control of the feeding flow of a peristaltic pump of the supergravity rotating packed bed, the rotating speed of a rotor of the supergravity rotating packed bed, lanthanum salt solution and reaction temperature is extremely important, a large number of researches show that the feeding flow and the rotating speed of the rotor of the supergravity rotating packed bed can adjust the size and the dispersibility of nano lanthanum hydroxide particles, and meanwhile, the reaction temperature can adjust the crystal form strength and the dispersibility. Therefore, in order to obtain highly dispersed nano lanthanum hydroxide, the above conditions need to be strictly controlled. Due to the regulation and the coordination of the process parameters, the particle length of the finally obtained nano lanthanum hydroxide product can be regulated and controlled between 15 nm and 250nm, and the product has good crystal form and high purity.