CN113617326B - Preparation device and preparation method for high-stability O/W nano emulsion - Google Patents

Preparation device and preparation method for high-stability O/W nano emulsion Download PDF

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CN113617326B
CN113617326B CN202110929928.8A CN202110929928A CN113617326B CN 113617326 B CN113617326 B CN 113617326B CN 202110929928 A CN202110929928 A CN 202110929928A CN 113617326 B CN113617326 B CN 113617326B
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CN113617326A (en
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刘志伟
张硕
武婵
田庆森
刘有智
祁贵生
罗莹
张珺
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North University of China
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00Feed or outlet devices; Feed or outlet control devices
    • B01J4/001Feed or outlet devices as such, e.g. feeding tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00Feed or outlet devices; Feed or outlet control devices
    • B01J4/02Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents

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Abstract

A preparation device and a preparation method for high-stability O/W nano-emulsion belong to the technical field of chemical industry and can solve the problems of equipment limitation and high energy consumption, large emulsifier consumption, long preparation period, difficulty in adapting to the mixing and emulsification of non-equivalent two-phase fluids and the like in the existing nano-emulsion preparation technology, a compound emulsifier is uniformly mixed with deionized water and then divided into two equal parts which are respectively fed through a horizontally symmetrical feed inlet I and a horizontally symmetrical feed inlet II, and cyclohexane is fed through a feed inlet III; further heating the premixed emulsion to prepare O/W nano emulsion with semitransparent appearance and average droplet particle size less than 250 nm; the invention adopts a three-nozzle restricted impinging stream reactor to realize the rapid mixing of the dispersed phase and the continuous phase.

Description

Preparation device and preparation method for high-stability O/W nano emulsion
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation device and a preparation method for high-stability O/W nano emulsion.
Background
As a colloid dispersion system with stable dynamics, the nano emulsion has been widely applied to the fields of high-end daily chemicals, foods, pharmacy, petroleum and the like due to the advantages of small particle size, good stability and the like. The nano-emulsion comprises three types of oil-in-water (O/W), water-in-oil (W/O) and bicontinuous, the specific type is determined according to actual application, and the nano-emulsion is prepared by selecting a proper emulsifier through HLB (hydrophilic-lipophilic balance). Researches show that the HLB value of an emulsifier required for preparing the O/W type nano emulsion is generally 8 to 18, and the compound emulsifier can improve the proportion of an internal dispersed phase, so that the interfacial tension can reach an ultralow level more easily, and the strength of an oil-water interfacial film is increased; because the span 80 and the Tween 80 have similar structures, have the same hydrophobic tail group and good synergistic effect, and because the double bonds on the carbon chain are more favorable for forming micro liquid drops, the span 80 and Tween 80 compound emulsifier has very wide application in the field of nano emulsion preparation.
The preparation method of the nano emulsion can be divided into a high-energy emulsification method and a low-energy emulsification method according to different energy consumption in the process. Chinese patents CN112042928A, CN109122905A, CN111616366A, CN106072623A and the like adopt a high-pressure homogenization technology and a microjet technology to prepare nano emulsion, firstly, the nano emulsion is stirred and premixed at a rotating speed of 10000 to 15000 r/min to prepare coarse emulsion, then, the coarse emulsion is subjected to high-pressure treatment, the homogenization pressure is up to 80 to 120 MPa, the homogenization frequency is 1 to 5 times, and the two processes have higher requirements on equipment and high energy consumption; chinese patent CN105694117A, CN107189077A and the like adopt ultrasonic emulsification to prepare nano emulsion, and the nano emulsion is prepared by stirring and premixing at the rotating speed of 10000 to 14000 r/min and then at the ultrasonic power of 300 to 450W, and the method has high input energy and is only suitable for small-batch production; chinese patents CN109369927A, CN106963657A and the like adopt a phase transition temperature method to prepare the nano emulsion, the preparation of the nano emulsion is realized by utilizing the change characteristic of the nonionic surfactant along with the temperature, the preparation temperature is increased to be higher than the PIT temperature, and then the temperature is rapidly reduced to realize the preparation of the O/W nano emulsion, the method has higher requirements on the operation conditions, and the continuous production is not easy to realize; chinese patent CN103506021A and the like adopt a phase transition component method to prepare nano emulsion, an oil phase and an emulsifier are uniformly mixed, and then water is dropwise added into a system under the stirring condition, the preparation period of the method is long, and the dosage of the emulsifier is up to 30 wt%. Therefore, although the high-energy emulsification method has relatively wide application and large operation flexibility, the high-energy emulsification method has the problems of high equipment cost, large energy consumption, limited treatment capacity and the like; the low-energy emulsification method has the advantages of low energy consumption and simple operation, but still has the problems of long preparation period, high proportioning precision requirement, large emulsifier consumption and the like. Therefore, the development of a nano emulsion preparation process with low energy consumption and short preparation period is urgently needed.
Impinging stream technology has been proposed to date for over half a century history and its application in hybrid unit operation has developed relatively rapidly. Two flows moving in opposite directions in the impinging stream mixer form an impinging surface through high-speed impingement, so that the contact area between materials is increased, fluid particles pass through the impinging surface in a reciprocating manner under the action of inertia force, and violent turbulence and great interphase relative speed are generated in an impinging area, so that the micro-mixing of the fluids is effectively promoted. The impact flow can be divided into a restricted type and a free type, the free type impact flow is formed by impacting two flows in an open environment, and the impact process is not influenced by a receptor wall; however, in many applications, it is often necessary to achieve rapid molecular-scale mixing, which requires the use of a restricted impinging stream reactor, and the initial mixing dimension is reduced by reducing the reactor dimension, thereby greatly increasing the fluid contact area and facilitating rapid and uniform mixing. Studies have shown that the micromixing performance of free-form impinging streams is weaker than confined impinging streams, and that the impingement surfaces are susceptible to fluid turbulence. Chinese patents CN112210087A, CN101665727A, etc. all adopt a dual-nozzle impinging stream device to prepare emulsion, but this device is only suitable for the case where the volume fractions of two materials are the same, and when the volume fractions of the dispersed phase and the continuous phase are different greatly, the collision of the dispersed phase with small volume fraction in the intersection area is relatively weak, so that the two materials are mixed unevenly. At present, most impinging stream mixers are symmetrical with two nozzles or four nozzles, and generally adopt a feeding mode of equal momentum and opposite impact to ensure the mixing effect, are not suitable for mixing two materials with overlarge momentum difference, and limit the application of the impinging stream mixers in the aspect of emulsion preparation to a certain extent.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation device and a preparation method for high-stability O/W nano-emulsion, aiming at solving the problems of equipment limitation, high energy consumption, large emulsifier dosage, long preparation period, difficulty in adapting to mixing and emulsification of non-equivalent two-phase fluid by a conventional impinging stream reaction device and the like in the prior art for preparing nano-emulsion and realizing simple and continuous preparation of high-stability nano-emulsion.
The invention adopts the following technical scheme:
the utility model provides a preparation facilities for high stable O W nanoemulsion, includes continuous phase storage tank I, continuous phase storage tank II, the limited formula impinging stream reactor of three nozzles, disperse phase storage tank and emulsion storage tank, the bilateral symmetry of the limited formula impinging stream reactor of three nozzles is equipped with horizontal direction's feed inlet I and feed inlet II, and the top is equipped with feed inlet III, and the bottom is equipped with the discharge gate, and feed inlet I, feed inlet II, feed inlet III and discharge gate communicate with each other, and continuous phase storage tank I loops through the pump, and valve and flowmeter are connected with feed inlet II, and continuous phase storage tank II loops through the pump, and valve and flowmeter are connected with feed inlet I, and the disperse phase storage tank loops through the pump, and valve and flowmeter are connected with feed inlet III, and the discharge gate is connected with the emulsion storage tank.
Furthermore, the feed inlet I and the feed inlet II are respectively positioned in the middle of the side wall of the three-nozzle limited impinging stream reactor.
Furthermore, feed inlet III is located the centre of feed inlet I and II lines of feed inlet, and perpendicular to feed inlet I and feed inlet II.
Further, the discharge hole and the feed inlet III are located on the same vertical plane.
Further, the pipe diameters of a feeding hole I, a feeding hole II and a feeding hole III of the impinging stream reactor are 0.5-2mm, and the flow of the feeding hole III is 10-200 mL/min.
A preparation method of high-stability O/W nano emulsion comprises the following steps:
firstly, uniformly mixing a compound emulsifier and deionized water in proportion to serve as a continuous phase, uniformly dividing the continuous phase into two equal parts, and feeding the two equal parts through a feeding hole I and a feeding hole II of a three-nozzle limited impinging stream reactor;
secondly, weighing cyclohexane as a disperse phase, feeding the cyclohexane through a feed inlet III, and adjusting the flow of the three feed inlets according to the volume ratio of oil to water;
and thirdly, heating the emulsion discharged from the discharge port to obtain the semitransparent stable O/W nano emulsion.
Further, the compound emulsifier comprises span 80 and Tween 80 in a mass ratio of 1 to 9 to 1.
Further, the mass fraction of the compound emulsifier is 1-10%, the mass fraction of the deionized water is 70-90%, and the mass fraction of the cyclohexane is 5-20%.
Further, the mass ratio of the cyclohexane to the compound emulsifier is 7 to 15; the volume ratio of cyclohexane to deionized water is 1 to 2 to 1.
Further, heating the emulsion at the discharge port at the temperature of 60-80 ℃ and at the rotating speed of 400-600 r/min to obtain the semitransparent stable O/W nano emulsion.
The nano emulsion prepared by the invention has the advantages of average particle size of 100-250 nm, uniform particle size (PDI of 0.2-0.4), no layering phenomenon after centrifugation for 5 min at the rotating speed of 15000 r/min, and high stability.
The invention has the following beneficial effects:
the invention adopts a three-nozzle restricted impinging stream reactor to prepare nano emulsion, divides a continuous phase into two equal parts, enters a device through a coaxially symmetrical feed inlet I and a feed inlet II, a through hole is arranged in the middle of the two vertical feed inlets, wherein a dispersed phase enters through a feed inlet III, and three parts of materials are impinged and mixed in a channel at a certain initial speed. Three-nozzle impinging stream is adopted, so that the problem of large volume fraction difference between a dispersed phase and a continuous phase is effectively solved, and the mixing of two materials with unequal momentum is realized; the premixing is carried out in a limited space, the initial size of the two-phase mixing can be reduced through the limited reactor size, the contact area between two-phase fluids is greatly increased, and the efficient and rapid mixing is facilitated. In addition, as shown in table 1, as can be seen from the comparative analysis of energy consumption with other high-energy emulsification devices, the specific energy input of the impinging stream reaction device is lower by 6 to 8 orders of magnitude than that of the other three high-energy emulsification devices when 100 g of the same nano emulsion is prepared, so that the production cost can be greatly reduced; compared with the conventional low-energy method for preparing the nano emulsion, the method has the advantages that the using amount of the emulsifier can be reduced to 3 wt%, the preparation time is greatly shortened, and the large-scale and continuous production can be realized.
TABLE 1 specific energy input for preparation of nanoemulsion using high pressure homogenization, microfluidization, phacoemulsification, impinging stream device
Figure DEST_PATH_IMAGE001
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a schematic illustration of the front view configuration of a three nozzle restricted impinging stream reactor of the present invention;
FIG. 3 is a schematic left view of a three nozzle confined impinging stream reactor of the present invention;
FIG. 4 is a schematic diagram of a top view of a three nozzle confined impinging stream reactor of the present invention;
FIG. 5 is a distribution diagram of the particle size of the nano-emulsions of examples 1 to 6 of the present invention;
wherein: 1-continuous phase storage tank I; 2-a flow meter; 3-a valve; 4-a pump; 5-continuous phase storage tank II; 6-feeding port I; 7-feed inlet III; 8-a discharge hole; 9-an emulsion storage tank; 10-feed inlet II; 11-three nozzle confined impinging stream reactor; 12-dispersed phase reservoir.
Detailed Description
The invention is further illustrated by the following specific examples. The following description is only examples embodying the objects, effects and technical lines of the present invention, and does not limit the scope of the present invention.
Example 1
Weighing 10.84 g of compound emulsifier and 194.7 g of deionized water, stirring for 30 min at 25 ℃ and the rotating speed of 400-600 r/min, and dividing into two parts after the mixing is finished; the pipe diameters of the three feed inlets are all 1.0 mm, the flow rates of the feed inlet I and the feed inlet II are respectively adjusted to be 150 mL/min, 25.3 g of cyclohexane is weighed, and the flow rate of the feed inlet III is adjusted to be 50 mL/min; inputting the materials into equipment for impacting and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nanoemulsion with the average particle size of 239.2 nm and the PDI of 0.359, and centrifuging for 5 min at 15000 r/min to avoid layering.
Example 2
Weighing 8.57 g of compound emulsifier and 200 g of deionized water, stirring for 30 min at 25 ℃ and at the rotating speed of 400-600 r/min, and dividing into two parts after the mixing is finished; the pipe diameters of the three feed inlets are all 1.0 mm, the flow rates of the feed inlet I and the feed inlet II are respectively adjusted to be 200 mL/min, 20 g of cyclohexane is weighed, and the flow rate of the feed inlet III is adjusted to be 50 mL/min; inputting the materials into equipment for impact and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nanoemulsion with the average particle size of 215.8 nm and the PDI of 0.319, and centrifuging for 5 min at 15000 r/min without layering.
Example 3
Weighing 6.86 g of compound emulsifier and 204 g of deionized water, stirring for 30 min at 25 ℃ and at the rotating speed of 400-600 r/min, and dividing into two parts after mixing; the pipe diameters of the three feed inlets are all 1.0 mm, the flow rates of the feed inlet I and the feed inlet II are respectively regulated to be 250 mL/min, 16 g of cyclohexane is weighed, and the flow rate of the feed inlet III is regulated to be 50 mL/min; inputting the materials into equipment for impacting and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nano emulsion with the average particle size of 200 nm and the PDI of 0.303, and centrifuging for 5 min at 15000 r/min without layering.
Example 4
Weighing 3.75 g of compound emulsifier and 86.625 g of deionized water, stirring for 30 min at 25 ℃ and at the rotating speed of 400-600 r/min, and dividing into two parts after the mixing is finished; the pipe diameters of the three feed inlets are all 1.0 mm, the flow rates of the feed inlet I and the feed inlet II are respectively adjusted to be 175 mL/min, 9.625 g of cyclohexane is weighed, and the flow rate of the feed inlet III is adjusted to be 50 mL/min; inputting the materials into equipment for impacting and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nanoemulsion with the average particle size of 239.9 nm and the PDI of 0.343, and centrifuging for 5 min at 15000 r/min without layering.
Example 5
Weighing 8.57 g of compound emulsifier and 200 g of deionized water, stirring for 30 min at 25 ℃ and at the rotating speed of 400-600 r/min, and dividing into two parts after mixing; the pipe diameters of the three feed inlets are all 0.5 mm, the flow rates of the feed inlet I and the feed inlet II are respectively adjusted to be 40 mL/min, 20 g of cyclohexane is weighed, and the flow rate of the feed inlet III is adjusted to be 10 mL/min; inputting the materials into equipment for impacting and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nanoemulsion with the average particle size of 169.1 nm and the PDI of 0.229, and centrifuging for 5 min at 15000 r/min without layering.
Example 6
Weighing 8.57 g of compound emulsifier and 200 g of deionized water, stirring for 30 min at 25 ℃ and at the rotating speed of 400-600 r/min, and dividing into two parts after the mixing is finished; the pipe diameters of the three feed inlets are all 2.0 mm, the flow rates of the feed inlet I and the feed inlet II are respectively adjusted to be 800 mL/min, 20 g of cyclohexane is weighed, and the flow rate of the feed inlet III is adjusted to be 200 mL/min; inputting the materials into equipment for impacting and premixing, and collecting coarse emulsion from a discharge port; heating the crude emulsion to 60 ℃, stirring for 30 min at 400-600 r/min to obtain the semitransparent nano emulsion with the average particle size of 229 nm and PDI of 0.233, and centrifuging at 15000 r/min for 5 min without layering.

Claims (3)

1. A preparation method of high-stability O/W nano emulsion comprises a preparation device, wherein the preparation device comprises a continuous phase storage tank I, a continuous phase storage tank II, a three-nozzle limited impinging stream reactor, a dispersed phase storage tank and an emulsion storage tank, a horizontal feed inlet I and a horizontal feed inlet II are symmetrically arranged on two sides of the three-nozzle limited impinging stream reactor, a feed inlet III is arranged at the top end, a discharge outlet is arranged at the bottom end, the feed inlet I, the feed inlet II, the feed inlet III and the discharge outlet are communicated, the continuous phase storage tank I is connected with the feed inlet II sequentially through a pump, a valve and a flowmeter, the continuous phase storage tank II is connected with the feed inlet I sequentially through the pump, the valve and the flowmeter, the dispersed phase storage tank is connected with the feed inlet III sequentially through the pump, the valve and the flowmeter, and the discharge outlet is connected with the emulsion storage tank;
the feed inlet I and the feed inlet II are respectively positioned in the middle of the side wall of the three-nozzle restricted impinging stream reactor;
the feed inlet III is positioned in the middle of a connecting line of the feed inlet I and the feed inlet II and is vertical to the feed inlet I and the feed inlet II;
the discharge port and the feed port III are positioned on the same vertical plane;
the pipe diameters of a feeding hole I, a feeding hole II and a feeding hole III of the impinging stream reactor are 0.5 to 2mm, and the flow of the feeding hole III is 10 to 200 mL/min;
the method is characterized in that: the preparation method comprises the following steps:
firstly, uniformly mixing a compound emulsifier and deionized water in proportion to serve as a continuous phase, uniformly dividing the continuous phase into two equal parts, and feeding the two equal parts through a feeding hole I and a feeding hole II of a three-nozzle limited impinging stream reactor;
secondly, weighing cyclohexane as a disperse phase, feeding the cyclohexane through a feed inlet III, and adjusting the flow of the feed inlet I, the flow of the feed inlet II and the flow of the feed inlet III according to the volume ratio of oil to water;
thirdly, heating the emulsion discharged from the discharge port to obtain semitransparent stable O/W nano emulsion;
the mass ratio of the cyclohexane to the compound emulsifier is 7 to 15; the volume ratio of cyclohexane to deionized water is 1 to 2 to 1;
and heating the emulsion at the discharge port at the temperature of 60-80 ℃ and the rotating speed of 400-600 r/min to obtain the semitransparent stable O/W nano emulsion.
2. The method for preparing high-stability O/W nano-emulsion according to claim 1, wherein the method comprises the following steps: the compound emulsifier comprises span 80 and tween 80 in a mass ratio of 1 to 9 to 1.
3. The method for preparing high-stability O/W nano-emulsion according to claim 1, wherein the method comprises the following steps: the mass fraction of the compound emulsifier is 1-10%, the mass fraction of the deionized water is 70-90%, and the mass fraction of the cyclohexane is 5-20%.
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