CN115650454A - Preparation and application of slow-release fluorescent scale inhibition microspheres - Google Patents
Preparation and application of slow-release fluorescent scale inhibition microspheres Download PDFInfo
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Abstract
The invention provides a preparation method and application of a slow-release fluorescent scale inhibition microsphere, belonging to the technical field of slow-release materials. The invention provides a scale inhibition slow release microsphere which is prepared by utilizing an adsorption medium loaded curcumin to graft a fluorescent scale inhibitor obtained by modifying polyethyleneimine ethoxylate. The slow release microsphere is prepared by a solid phase/oil phase/water phase solvent volatilization method, the preparation conditions are explored, the slow release capability and the scale inhibition performance of the prepared slow release microsphere are explored by synthesizing the loaded fluorescent scale inhibitor, the result shows that the dynamic release characteristic and the static release characteristic of the prepared slow release microsphere are obviously different, the long-term (> 10 h) static scale inhibition effect of the slow release microsphere is higher than that of the slow release microsphere obtained by directly adding the scale inhibitor, the frequent medicine adding is avoided, and the slow release microsphere has the potential of large-scale use.
Description
Technical Field
The invention belongs to the technical field of slow-release materials, and particularly relates to preparation and application of a slow-release fluorescent scale inhibition microsphere.
Background
In high-temperature industrial circulating water such as geothermal exploitation and the like, the high temperature causes the silicon scale inhibitor to be easily dissolved and adsorbed by rock soil or deposited along with silicon dioxide scale, the effective action time and distance of the scale inhibitor are greatly reduced, and the system needs higher scale inhibitor concentration to maintain the scale inhibition effect. The slow-release scale inhibitor enables the medicament to be slowly released and uniformly distributed, prolongs the medicament adding time and saves the medicament dosage, and is one of hot spots of scale inhibitor research.
The slow release scale inhibitor prepared at present mainly comprises two types. One is slow-release scale inhibitor coated with polyvinyl alcohol and other gels, and the other is slow-release scale inhibitor formed by adsorbing medicaments with halloysite and other fine particles. When the temperature is higher than 90 ℃, the former is quickly dissolved and loses the slow release effect, and the latter causes the slow release effect to be poorer because of quick desorption. The microcapsule technology is a novel slow release technology, is widely applied in the medical field, and how to apply the microcapsule technology to slow release of the high-temperature scale inhibitor is still in the beginning stage.
The microcapsule has the advantages that the performance of the microcapsule cannot be separated from the performance of materials and the preparation method, the selection of wall materials directly determines the release characteristics and the temperature tolerance of the microspheres, and the preparation method influences the encapsulation efficiency and the particle size of the microspheres and indirectly influences the slow release effect of the microspheres. The design and use temperature of the common microcapsule is lower, and a proper high-temperature resistant wall material needs to be selected for high-temperature circulating water. Studies prove that the polystyrene has higher heat resistance and solubility resistance and is suitable to be used as a wall material of the sustained-release microsphere. The emulsion-solvent evaporation method is a common method for preparing microcapsules. The solid phase/oil phase/water phase method is carried by solid phase, and compared with the conventional oil phase/water phase method, the solid phase/oil phase/water phase method greatly improves the encapsulation efficiency and enhances the slow release effect. The preparation process of the solid phase/oil phase/water phase method is influenced by multiple factors, and the research on the influence of the emulsifier type, the emulsifier concentration, the stirring speed and the adsorption medium concentration on the size and the encapsulation efficiency of the microcapsule is necessary. Therefore, how to provide a high temperature resistant scale inhibition slow release microsphere capable of preventing the silica scale of high temperature circulating water is an important problem to be solved urgently.
Disclosure of Invention
The invention provides a preparation method and application of a slow-release fluorescent scale inhibition microsphere.
In order to achieve the purpose, the invention provides a fluorescent scale inhibitor which is obtained by grafting curcumin to polyethyleneimine ethoxylate for modification.
Preferably, the obtained fluorescent scale inhibitor presents the following functional groups on an infrared spectrogram:
ether group-O-: 1250-1100 cm -1 methylene-CH 2 -：2800cm -1 Unimodal of condensation of polyethyleneimine ethoxylate and curcumin: 3350cm -1 And a benzene ring structure: 1400cm -1 And 1600cm -1 。
Preferably, the preparation method comprises the following steps:
uniformly mixing the polyethyleneimine ethoxylate and curcumin according to a mass ratio of 20.
The invention also provides a scale inhibition slow release microsphere which is prepared by loading the fluorescent scale inhibitor in any technical scheme on an adsorption medium.
Preferably, the scale inhibition slow release microspheres are prepared by the following method:
dissolving polystyrene in dichloromethane to prepare an oil phase solution;
selecting an adsorption medium loaded with a fluorescent scale inhibitor as a solid phase, adding the solid phase into the oil phase solution, and shearing at a high speed by using a homogenizer to obtain a suspension;
adding emulsifier, stirring at 30 deg.C for 1.5-3 hr at 200-400r/min, filtering, and lyophilizing to obtain scale inhibiting slow release microsphere.
Preferably, the adsorption medium is selected from at least one of diatomaceous earth, halloysite, kaolin and sepiolite, preferably diatomaceous earth.
Preferably, the addition amount of the adsorption medium is less than or equal to 50mg/L.
Preferably, the emulsifier is selected from at least one of sodium hexadecyl sulfonate and tween 60, and the sodium hexadecyl sulfonate is preferred.
Preferably, the concentration of the emulsifier is 0.5% to 2%, preferably 1% to 2%.
The invention also provides an application of the scale inhibition slow release microspheres according to any one of the technical schemes in preventing the formation of silica scale in high-temperature circulating water.
Preferably, the prepared microspheres have the static release time of 120h at 25 ℃ and the stable release time of 100h at 95 ℃; and the dynamic release time of 2h frequency water change is as long as 30h.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention prepares the slow release microspheres by a solid phase/oil phase/water phase solvent volatilization method, researches the preparation conditions, and researches the slow release capability and scale inhibition performance of the prepared slow release microspheres by synthesizing the loaded fluorescent scale inhibitor. The research result shows that:
polystyrene, diatomite and sodium hexadecylsulfonate are respectively suitable to be used as a wall material, a solid phase material and an emulsifier in the preparation process; in addition, the stirring speed, the concentration of the emulsifier and the loading capacity of the adsorption medium all significantly influence the average particle size and the encapsulation efficiency of the prepared microspheres, wherein the influence of the stirring speed on the microspheres is more significant.
In addition, the dynamic release characteristic and the static release characteristic of the sustained-release microspheres prepared by the invention are obviously different. The release time of the prepared microsphere is 120h at static 25 ℃, and 100h at 95 ℃; and the dynamic release time of 2h frequency water change is as long as 30h. The sustained-release microspheres avoid frequent dosing and have the potential of large-scale use.
Drawings
FIG. 1 is an infrared spectrum of HP20-E100 and HP20 provided in accordance with an embodiment of the present invention;
FIG. 2 shows the release characteristics of HP20-E100 adsorbed by four adsorption media provided by an embodiment of the present invention;
FIG. 3 is a schematic diagram of a process for preparing silica scale-blocking fluorescent sustained-release microspheres by a solid phase/oil phase/water phase solvent evaporation method according to an embodiment of the present invention;
FIG. 4 is a graph showing the effect of emulsifier type (first row), emulsifier concentration (second row), agitation speed (third row) and adsorption media concentration (fourth row) on the morphology and particle size distribution of microspheres prepared according to an embodiment of the present invention;
FIG. 5 shows the sustained release characteristics of microspheres under static conditions (a) and dynamic conditions (b) provided by an example of the present invention;
FIG. 6 is a scale inhibition concentration-time variation graph and a scale inhibition rate-time variation graph using the slow release scale inhibitor and HP20-E100 provided by the embodiment of the invention;
FIG. 7 is an SEM image of scale formation under different treatment groups provided by the embodiment of the invention, without scale inhibitor (a), HP20-E100 (b), and slow release scale inhibitor (c).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Material
Polyethyleneimine ethoxylate (HP 20, unmodified scale inhibitor), sodium hexadecylsulfonate (emulsifier), and tween 60 (emulsifier) were purchased from shandong yousu chemical limited (chinese linyi). Curcumin (E100, fluorescent monomer), polystyrene (PS, wall material), polyvinyl alcohol (PVA, emulsifier), and dichloromethane (DCM, solvent) were purchased from wuxi city feng gao biotechnology limited (wuxi, china). Diatomaceous earth, halloysite, kaolin, sepiolite were purchased from the young island of the young island, lebocess technologies ltd (young island, china) and used as solid phase load materials. Sodium silicate (analytically pure) was purchased from remote chemical agents limited (tianjin, china).
Example 1 preparation of fluorescent Scale inhibitor
Uniformly mixing polyethyleneimine ethoxylate (HP 20) and curcumin (E100) according to a mass ratio of 20. And (4) determining the functional groups of the product by using a Fourier infrared spectrometer, and verifying whether the synthesis is successful.
At 500-3500cm -1 In the range of (1), FTIR analysis was performed on HP20-E100 and HP20, and the success of the synthesis of the fluorescent scale inhibitor was judged by determining their functional groups (FIG. 1). Both HP20-E100 and HP20 are 1250-1100 cm -1 A strong absorption peak was found, indicating the presence of ether groups (-O-), both at 2800cm -1 In the presence of methylene (-CH) 2 -) which indicates that HP20-E100 contains HP20.HP20 is 3300-3600cm -1 There is a doublet, which is characteristic of a typical primary amine, whereas HP20-E100 is at 3350cm -1 There is a single peak, which is characteristic of a typical secondary amine, indicating that polycondensation of HP20 and E100 has occurred. And HP20-E100 at 1400cm -1 And 1600cm -1 There is an absorption peak, which is a characteristic absorption peak of the benzene ring structure, indicating that HP20-E100 contains E100. In conclusion, the fluorescent monomer E100 successfully reacts with the scale inhibitor HP20 to generate the fluorescent scale inhibitor HP20-E100.
Example 2 adsorption and desorption of Scale inhibitors
Diatomite, halloysite, kaolin and sepiolite which are widely applied are respectively used as adsorption media for loading a fluorescent scale inhibitor, the adsorption and desorption rules are explored, and the adsorption media suitable for loading HP20-E100 are preferably selected.
The adsorption capacity was measured by a saturated adsorption method: weighing 5g of adsorption medium, adding enough HP20-E100, filtering, freeze-drying, weighing, and subtracting the adsorption medium to obtain the adsorption quantity.
And (3) measuring a desorption curve: weighing 1g of the freeze-dried adsorption medium after adsorption, adding 300mL of distilled water, sampling at 0.5, 1, 3, 6 and 12h respectively, and drawing a desorption curve.
The release ratios of the four common adsorbing materials are shown in fig. 2 (a), for example, the four adsorbing media have substantially the same release tendency after adsorbing HP20-E100, and the 12-hour release rate of diatomite is slightly higher than that of the other three adsorbing media. The unit adsorption amount, 12h release amount and 12h release rate of the four common adsorption materials are shown in fig. 2 (b), wherein the adsorption amount of the diatomite is the largest, which indicates that more scale inhibitor can be adsorbed by the diatomite per unit mass. Halloysite generally has a tubular structure, which may be the reason for its lowest release rate. Because the adsorption capacity and the release rate of the diatomite are higher than those of other three adsorption materials, the diatomite is more suitable to be used as a scale inhibitor carrier.
Example 3 preparation of Scale inhibition Slow Release microspheres
The preparation process of the scale inhibition sustained-release microspheres is shown in figure 3.
Dissolving polystyrene in dichloromethane to prepare an 'oil' phase solution, selecting an adsorption medium loaded with a fluorescent scale inhibitor as a 'solid' phase, adding the 'oil' phase solution into the 'solid' phase solution, and shearing the solution at a high speed (12000 r/min) by using a homogenizer to obtain a suspension; then adding emulsifiers (Tween 80 (R1), polyvinyl alcohol (R2) and sodium hexadecyl sulfonate (R3)) into the solution respectively, stirring at low speed for 3 hours at 30 ℃, filtering and freeze-drying to obtain the scale inhibition slow release microspheres.
And determining the proper emulsifier type according to the appearance and the particle size distribution of SEM analysis. After the optimal emulsifier type is determined, the influence of the emulsifier concentration, the stirring speed and the adsorption medium concentration on the loading rate is researched, and the detailed description is shown in table 1, wherein the emulsifiers used in the groups A-G are all sodium hexadecyl sulfonate.
TABLE 1 Experimental condition table for sustained-release microsphere preparation
3.1 influence of emulsifier type on microsphere morphology and encapsulation efficiency
The kind of the emulsifier has great influence on the appearance of the microsphere. The morphological characteristics of microspheres prepared under the same conditions using three emulsifiers are shown in fig. 4 (R1, R2, R3). The sustained-release microspheres prepared by using the sodium hexadecyl sulfonate as an emulsifier have the average particle size of 122.4 mu m and relatively uniform particle size distribution; when Tween 60 is used as an emulsifier to prepare the sustained-release microspheres, the average particle size of the microspheres is 82.4 mu m, and the particle size distribution is very uneven; when polyvinyl alcohol is used as an emulsifier, the average particle size of the microspheres is 75.9 μm, the particle size distribution is mainly concentrated below 80 μm, and a large amount of diatomite can be seen in the figure, which indicates that the encapsulation efficiency is low.
According to table 2, the encapsulation efficiency of tween 60 is lower than 80%, the encapsulation efficiency of polyvinyl alcohol is lower than 45%, and the encapsulation efficiency of sodium hexadecyl sulfonate is higher, more than 85%. This is probably because the scale inhibitor is itself a surface active substance, which is more compatible with anionic emulsifiers. Considering the influence of the particle size and the encapsulation efficiency on the sustained-release efficiency, sodium hexadecyl sulfonate was selected as the emulsifier for subsequent study.
TABLE 2 Change in encapsulation efficiency under different preparation conditions
3.2 influence of emulsifier concentration on microsphere morphology and encapsulation efficiency
The effect of the type concentration of the emulsifier on the morphology of the microspheres is shown in FIG. 4 (second rows A, B, C). When the concentration of the emulsifier is 2%, the average particle size of the microspheres is the largest, the distribution is uniform, and the encapsulation efficiency is the highest and reaches 87.9%; when 1% emulsifier concentration is used, the average particle size of the microspheres is 98.6 μm, and the encapsulation condition is better; at 0.5% emulsifier concentration, the microspheres had a smaller average particle size and were not completely encapsulated by the diatomaceous earth. This is substantially consistent with the effect of emulsifier concentration on microsphere morphology in the literature.
3.3 influence of stirring speed on microsphere morphology and encapsulation efficiency
The stirring speed has a large influence on the morphology of the microspheres, as shown in fig. 4 (third row D, B, E). The stirring speed is 200r/min, the particle size of the formed microspheres is larger, but the encapsulation efficiency is lower, mainly because the rotating speed is low, the shearing action of water on the microspheres is small, the microspheres are easy to aggregate into large microspheres, but the solvent is slowly volatilized, so that part of the microspheres break and the adsorption medium flows out. When the stirring speed is 400r/min, small microspheres are formed due to strong shearing action, most of the particle sizes are distributed in the range of 60-100 mu m, and a small amount of microsphere contents are broken. And when the stirring speed is 300r/min, the average grain diameter is about 100 mu m, and the method is more suitable for preparing microspheres.
3.4 influence of addition of adsorption Medium on morphology and encapsulation efficiency of microspheres
The influence of different adsorption medium addition rates on the particle size is not obvious, but the influence on the encapsulation efficiency is very large, as shown in fig. 4 (fourth rows B, F, G). When the addition amount of the adsorption medium is 25 mg/L and 50mg/L, the encapsulation efficiency is higher, and when the addition amount of the adsorption medium is 75mg/L, the outflow of the diatomite can be seen, and the encapsulation efficiency is lower than 70 percent. This may be due to the fact that the oil phase is too viscous and the emulsification effect is poor due to too high a concentration of the adsorption medium. In view of economy, it is preferable to increase the concentration of the adsorbent as much as possible while ensuring the encapsulation efficiency, and a concentration of 50mg/L is selected.
Example 4 sustained Release efficiency assay
The slow release efficiency was measured by a static method and a dynamic method, respectively.
Static method: a1 g sample of microspheres was weighed and added to 400mL of distilled water. And respectively controlling the temperature to be kept at 25 ℃, 65 ℃ and 95 ℃, standing the solution, and slowly releasing the scale inhibitor in the microspheres into water to obtain a slow-release sample solution. The absorbance was measured at 1, 2, 4, 8, 16, 24, 32, 40, 52, 64, 76, 88, 100 and 120h and the concentration of the scale inhibitor was determined according to the standard curve of HP20-E100.
Dynamic method: the centrifugal separation is carried out once every 2h, and then the water is replenished. And (3) measuring the absorbance at different times until the 30 th hour, simultaneously researching the influence of the temperature and the stirring speed on the dynamic release of the scale inhibitor, and setting the experimental conditions to be 25 ℃,95 ℃, 300r/min and 95 ℃ and 300r/min respectively.
The release condition of the microspheres under static conditions, namely under the condition of not changing water, is shown in fig. 5 (a), and under different temperatures, the release rate of the microspheres is higher at the early stage, then gradually slows down, and finally tends to be stable, the release rate of 60h exceeds 70%, and the release rate of 120h exceeds 90%. The temperature can influence the release rate of the microspheres, when the water temperature is 95 ℃, the release rate is obviously higher than that of 35 ℃, the release time of the prepared microspheres at a static temperature of 25 ℃ is 120h, and the microspheres at a static temperature of 95 ℃ are stably released for 100h. But compared with polyvinyl alcohol gel and the like, the microsphere has small influence of temperature and has the characteristic of keeping good slow release capacity at high temperature.
In addition, the release characteristics of the microspheres at different temperatures and under stirring were also examined, fig. 5 (b). Under the condition that water is replaced every 2h, the sustained release rate of the microspheres is high and basically constant, and the microspheres can be stably released for 30h. The release rate of the microspheres can be obviously improved by increasing the temperature and stirring, the early-stage release rate is accelerated, and the release time is shortened. The release rate is faster under high-temperature stirring, and the release time can be smoothly controlled for 20h.
Example 5 measurement of Scale inhibition efficiency
500mg/L of sodium silicate Solution (SiO) is prepared 2 Meter), respectively adding sustained-release microspheres (the concentration of the complete release solution HP20-E100 is 200 mg/L), 50mg/L HP20-E100 and 100mg/L HP20-E100, then maintaining a water bath at 40 ℃, respectively measuring the characteristic absorbance of the HP20-E100 in 1, 3, 6, 12, 18 and 24 hours, measuring the content of soluble silicon dioxide by using a silicon-molybdenum blue colorimetric method, and calculating the scale inhibition efficiency according to the formula (1).
E＝(c 2 -c 1 )/(c 0 -c 1 )×100％ (1)
In the formula: e is the scale inhibition efficiency,%; c. C 1 Is the active silicon dioxide content of the sample without adding the scale inhibitor after the experiment, mg/L; c. C 2 The content of active silicon dioxide of a sample added with the scale inhibitor after an experiment is mg/L; c. C 0 Is the active silicon dioxide content of the sample solution before the experiment, mg/L.
And (3) measuring the scale inhibition effect of the slow release microspheres by using a static scale inhibition method, and comparing by using a fluorescent scale inhibitor with a known concentration. The change of the scale inhibition rate with time is shown in fig. 6 (a), the scale formation rate is faster because only a small amount of scale inhibitor is released in the initial stage, but the scale formation phenomenon is inhibited and the rate is obviously slowed down when the concentration of the scale inhibitor reaches a higher level. Meanwhile, the concentration of the scale inhibitor is detected as shown in fig. 6 (b), and the phenomenon that the concentration of the scale inhibitor is reduced is found in an experimental group added with the scale inhibitor, which is probably because the concentration of the scale inhibitor added with the slow-release scale inhibitor is slowly increased along with scale coprecipitation.
SEM analysis is carried out on the scale components formed by adding 100mg/L HP20-E and slow-release scale inhibitor without adding scale inhibitor. Without addition of the fluorescent scale inhibitor, the scale appeared to be a dense block structure, as shown in FIG. 7 (a). And the scale formed by adding the fluorescent scale inhibitor HP20-E100 is obviously spherical, and is loose compared with the former, as shown in figure 7 (b). And the slow release scale inhibitor (the main component is HP 20-E100) is added, so that the scale is fluffy, but the scale is relatively uneven in size, and wall materials or diatomite can be mixed, as shown in figure 7 (c). The fluffiness and the unevenness make the dirt easily washed away by water flow, thereby improving the effect of inhibiting the dirt.
Claims (10)
1. The fluorescent scale inhibitor is characterized by being obtained by grafting curcumin to polyethyleneimine ethoxylate for modification.
2. The fluorescent scale inhibitor according to claim 1, wherein the obtained fluorescent scale inhibitor has the following functional groups on an infrared spectrogram:
ether group-O-: 1250-1100 cm -1 methylene-CH 2 -：2800cm -1 Unimodal of condensation of polyethyleneimine ethoxylate and curcumin: 3350cm -1 And a benzene ring structure: 1400cm -1 And 1600cm -1 。
3. The fluorescent scale inhibitor according to claim 1 or 2, which is prepared by the following method:
uniformly mixing polyethyleneimine ethoxylate and curcumin according to a mass ratio of 20 to 1, heating to 200 ℃ in a nitrogen atmosphere, reacting for 3 hours, ensuring full polycondensation of reactants, and grafting the curcumin to the polyethyleneimine ethoxylate to obtain the fluorescent scale inhibitor HP20-E100.
4. The scale inhibition slow release microsphere is characterized by being prepared by loading the fluorescent scale inhibitor of any one of claims 1 to 3 on an adsorption medium.
5. The scale inhibition sustained-release microsphere of claim 4, which is prepared by the following method:
dissolving polystyrene in dichloromethane to prepare an oil phase solution;
selecting an adsorption medium loaded with a fluorescent scale inhibitor as a solid phase, adding the solid phase into the oil phase solution, and shearing at a high speed by using a homogenizer to obtain a suspension;
adding emulsifier, stirring at 30 deg.C for 1.5-3 hr at 200-400r/min, filtering, and lyophilizing to obtain scale inhibiting slow release microsphere.
6. The scale inhibition slow release microsphere according to claim 4 or 5, wherein the adsorption medium is selected from at least one of diatomite, halloysite, kaolin and sepiolite, preferably diatomite;
the addition amount of the adsorption medium is less than or equal to 50mg/L.
7. The scale inhibition sustained-release microsphere of claim 5, wherein the emulsifier is at least one selected from sodium hexadecyl sulfonate and Tween 60, preferably sodium hexadecyl sulfonate.
8. The scale inhibition sustained-release microsphere of claim 4, wherein the concentration of the emulsifier is 0.5-2%, preferably 1-2%.
9. The use of the scale inhibiting slow release microspheres according to any one of claims 1-8 in preventing the formation of silica scale in high temperature circulating water.
10. The use according to claim 9, wherein the microspheres are prepared to have a static release time of 120h at 25 ℃ and a stable release time of 100h at 95 ℃; and the dynamic release time of 2h frequency water change is as long as 30h.
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