CN117160421A - Preparation method and application of natural polymer magnetic gel microsphere - Google Patents
Preparation method and application of natural polymer magnetic gel microsphere Download PDFInfo
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- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 44
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- 238000010907 mechanical stirring Methods 0.000 claims abstract description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 33
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Abstract
The application discloses a preparation method and application of natural polymer magnetic gel microspheres. The natural polymer magnetic gel microsphere takes bamboo powder as a matrix, and the dried bamboo powder is placed into a sodium hydroxide solution for heating and dissolving; at the same time, heating and dissolving sodium alginate at room temperature, and synthesizing nano Fe by adopting a chemical coprecipitation method 3 O 4 Under the combined action of ultrasonic and mechanical stirring, uniform nano Fe is obtained 3 O 4 Mixing bamboo powder/sodium alginate solution; sucking the mixed solution by using a syringe, and slowly dripping the mixed solution into a positive magnetic stirring calcium chloride solutionA liquid for solidifying the gel microspheres; washing the gel microspheres for a plurality of times by using deionized water after finishing, and removing redundant sodium hydroxide, calcium chloride and unreacted monomers; and finally, placing the gel microspheres in an oven for drying to constant weight. The application uses nano Fe 3 O 4 The bamboo powder and the sodium alginate are used as the production raw materials of the gel microsphere, the synthesis cost of the gel microsphere is low, the gel microsphere has excellent adsorption capacity, and the material has good adsorption effect on heavy metals and dyes.
Description
Technical Field
The application relates to the technical field of waste recycling and adsorbent preparation, in particular to a preparation method and application of natural polymer magnetic gel microspheres.
Background
Scientists have been devoted to the study of various wastewater treatment methods such as coagulation, flocculation, chemical precipitation and the like in recent decades, and the traditional methods generally cannot meet the emission standard due to the difference of physical properties and chemical properties of pollutants, and have limited water recovery capability.
The existing method for treating the organic wastewater is more, and comprises an adsorption method, a membrane separation method, a chemical method, a biological method, an extraction method and the like, wherein the adsorption method has the advantages of high efficiency, wide raw material sources, convenient operation and the like, and particularly has unique advantages for treating the water body containing organic pollutants and heavy metal ions, so that the method not only makes up the defects of the prior art, but also can selectively adsorb and recover specific heavy metal ions and organic pollutants in the complex wastewater treatment process containing various organic pollutants and heavy metal ions. In recent years, biomass materials have been attracting attention because of their extremely strong selective adsorptivity to low-concentration heavy metals and organic pollutants, wide sources, easy degradation, low cost and the like, but the adsorbents produced in the prior art have low adsorption efficiency and are difficult to recover, although having certain adsorption performance.
Therefore, the technical problem to be solved by the technicians in the field is to provide the modified natural polymer raw material adsorbent so as to improve the adsorption performance and recovery rate of pollutants.
Disclosure of Invention
In order to solve the defects of poor mechanical stability, low adsorption efficiency, poor thermal stability and the like of the traditional hydrogel, the preparation method and the application of the natural polymer magnetic gel microsphere are provided, the gel microsphere material has magnetism, mechanical strength, thermal stability and chemical stability are improved, the adsorption performance is good, the environment is friendly, the recovery is easy, the gel microsphere material is used for treating pollutants in wastewater, the pollutants in the wastewater can be removed well, the gel material can be recycled, and the secondary pollution possibility is reduced.
In order to achieve the above object, the present application provides a method for preparing natural polymer gel microspheres, comprising the steps of:
(1) Heating and dissolving bamboo powder in NaOH solution with the concentration of 7-10wt%, heating and dissolving sodium alginate in deionized water solution, stirring the sodium alginate solution by using a magnetic stirrer to fully dissolve the sodium alginate solution, and then mixing the two solutions to obtain a bamboo powder/SA mixed solution; wherein, the mass ratio of the bamboo powder to the sodium alginate is 1:2 to 3; the mass ratio of the bamboo powder to the NaOH solution is 1: 50-100;
(2) FeCl is added 2 ·4H 2 O and FeCl 3 ·6H 2 O is prepared from the following components in percentage by mass: 1.5-2, and dissolving the prepared iron salt mixture in deionized water, using excess NH 3 ·H 2 O is stirred at a high speed under neutral pH value to carry out coprecipitation reaction, and the precipitate after the reaction is washed, filtered and dried to obtain Fe 3 O 4 Microparticle, finally Fe 3 O 4 Uniformly dispersing the particles in the bamboo powder/SA mixed solution prepared in the step (1) under the combined action of ultrasonic vibration and mechanical stirring to obtain nano Fe 3 O 4 Mixing bamboo powder/sodium alginate solution; the mixed solution of the bamboo powder and SA and Fe 3 O 4 The mass ratio of the particles is 100:3 to 7;
(3) Sucking the nano Fe in the step (2) by using a syringe under the action of magnetic stirring 3 O 4 Slowly dripping CaCl into the mixed solution of bamboo powder and sodium alginate 2 Solidifying the solution in room temperature environment to form gel microsphere;
(4) Filtering out gel microspheres formed by solidification, washing the gel microspheres with deionized water for a plurality of times, putting the gel microspheres into an oven, drying the gel microspheres until the gel microspheres are constant, obtaining natural polymer gel microspheres, and sealing and preserving the natural polymer gel microspheres for standby.
The application has the preferable technical scheme that: the bamboo powder in the step (1) is obtained by directly adopting bamboo or waste bamboo, cutting, grinding, sieving and drying.
The application has the preferable technical scheme that: in the step (1), the mass ratio of the sodium alginate to the deionized water is 1: 50-100, and the magnetic stirring time is 20-40 min; the temperature of the bamboo powder and the sodium alginate are respectively 60-80 ℃.
The application has the preferable technical scheme that: the deionized water in the step (2) is pure water for experiments, and 5-10 g of ferric salt mixture is added into every 100ml of deionized water.
The application has the preferable technical scheme that: NH in the step (2) 3 ·H 2 The concentration of O is 1-2 mol/L, the reaction pH is 8-11, and the temperature is controlled at 70-80 ℃.
The application has the preferable technical scheme that: the concentration of the CaCl2 solution in the step (3) is 5-10wt% and the curing time is 20-40min.
The application has the preferable technical scheme that: the washing times in the step (4) are 3-5 times, and the drying temperature is 60-80 ℃ until the quality of the gel microspheres is unchanged.
In order to achieve the technical aim, the application also provides application of the natural polymer gel microsphere prepared by the method, the pH of the wastewater is regulated to 6-10, then the natural polymer gel microsphere is directly added into the wastewater, the natural polymer gel microsphere is adsorbed for 1-1.5 h at the temperature of 20-35 ℃, and the addition amount of the polymer gel microsphere is 0.75-1g of polymer gel microsphere added into each liter of wastewater.
The application has the preferable technical scheme that: the wastewater contains methylene blue, lead ions, cadmium ions and copper ions.
The application has the preferable technical scheme that: the pH of the wastewater is adjusted by using sodium hydroxide solution or hydrochloric acid, and the pH of the wastewater has no influence on the adsorbent.
The application synthesizes and modifies natural bamboo powder fiber, and can increase the mechanical strength of hydrogel and the chemical stability in aqueous solution environment by crosslinking polymerization, and can increase the mechanical strength of the hydrogel by Ca 2+ Crosslinking increases functional groups (e.g., carboxyl and hydroxyl groups) in the hydrogel to enhance adsorption of heavy metal ions and organic contaminantsEffects. Application of the prepared hydrogel to pollutant removal in wastewater due to Ca 2+ The crosslinking increases the active adsorption point and functional group on the surface of the hydrogel, so that pollutants in the wastewater can be removed well, and meanwhile, because of Ca 2+ Cross-linking and nano Fe 3 O 4 The introduction of the gel material improves the mechanical strength, the thermal stability and the chemical stability of the material, and the gel material has magnetism, so that the recovery efficiency of the gel microsphere is improved, and the possibility of secondary pollution is reduced to a certain extent.
The greater the quality of the bamboo powder, the more cellulose content can be provided, and theoretically, the more cellulose is filled in the sodium alginate network along with the increase of the cellulose content, the greater the mechanical strength of the gel microsphere is. The concentration and the volume of the sodium hydroxide solution mainly influence the dissolution of the bamboo powder, and the greater the concentration of the sodium hydroxide is, the more fully the bamboo powder is dissolved. Experiments show that when the dosage of the bamboo powder is 1.0g, the optimal concentration of sodium hydroxide solution is 8wt%, the solution volume is 50mL, and the bamboo powder can be fully dissolved. However, the concentration and volume of the alkali liquor are specifically set according to the proportion of the bamboo powder to the sodium alginate.
The larger the mass of the sodium alginate is, the more hydroxyl groups and carboxyl groups can be provided, and the synthesized gel microsphere can obtain more reaction sites, but with the increase of the sodium alginate, the more viscous the solution is, and the more redundant sodium alginate is difficult to dissolve completely. The higher the temperature is, the more intense the molecular movement is, and the temperature of the solution is increased, so that the sodium alginate is more severely diffused in deionized water, the dissolution is sufficient, and the influence of incomplete dissolution and agglomeration of the sodium alginate on the subsequent crosslinking reaction is avoided. The stirring function is also to dissolve the two raw materials more sufficiently, and generally, the stirring time is more than 30min to dissolve the sodium alginate completely, but the specific stirring time is set according to the ratio of the raw materials to the solution, and the larger the ratio is, the longer the required time is. When the solution of sodium alginate is dropped into the solution of divalent cations, e.g. in Ca 2+ In the solution, na + Will quickly react with Ca 2+ Ion exchange occurs and stable hydrogel pellets are formed, with the degree of crosslinking of the resulting gel microspheres being greater as the calcium ion concentration increases. Is also fixedThe gel microsphere is formed by influencing the formation time, the mechanical strength of the gel microsphere is lower when the curing time is shorter, and the mechanical strength of the gel microsphere can be increased by increasing the curing time.
The application has the beneficial effects that:
(1) The method has simple steps and easy conditions, and the raw materials are widely available and greatly reduce the production cost due to the utilization of the bamboo powder and the sodium alginate, so that pollution control and solid waste recycling treatment are realized.
(2) The application takes bamboo powder and sodium alginate as the matrix, and uses Ca 2+ Crosslinking, improving the void structure and specific surface area inside the hydrogel, enriching the surface functional groups, and effectively improving the adsorption capacity of the finally obtained adsorbent. In addition, by introducing the nano magnetic particles, the mechanical strength, chemical stability and recovery rate of the adsorbent are further improved.
(3) The natural polymer gel microsphere of the application adsorbs methylene blue wastewater with the concentration content of organic matters of 160mg/L, the adsorption capacity reaches 98.17%, the application has better prospect for treating the methylene blue wastewater, and the prepared adsorbent provides basis for purifying the methylene blue wastewater.
Drawings
FIG. 1 is a scanning electron microscope image of natural polymer magnetic gel microspheres in example 1 of the present application;
FIG. 2 is a graph showing the effect of adding amount of the natural polymer gel microspheres in example 2 of the present application on removal of methylene blue;
FIG. 3 is a graph showing the comparative effect of the natural polymer gel microspheres of example 3 of the present application on methylene blue removal at different pH values;
FIG. 4 is a graph showing the comparative effect of the natural polymer gel microspheres of example 4 of the present application on methylene blue removal at different temperatures;
FIG. 5 is a graph showing the comparison of the recycling performance effect of the natural polymer gel microspheres in example 1 of the present application;
FIG. 6 is a scanning electron microscope image of a natural polymer gel without magnetic particles added in the application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1 provides a method for preparing natural polymer magnetic gel microspheres
(1) 1g of bamboo powder is heated and dissolved in 50mL of 8wt% NaOH solution, 2.0g of sodium alginate is heated and dissolved in 100mL of deionized water solution at 65 ℃, the sodium alginate solution is stirred for 30min by using a magnetic stirrer, and after the sodium alginate solution and the sodium alginate solution are fully dissolved, the two solutions are mixed to prepare a bamboo powder/SA mixed solution;
(2) FeCl is added 2 ·4H 2 O and FeCl 3 ·6H 2 O is prepared from the following components in percentage by mass: 1.25 in a ratio of 2mol/L NH in deionized water 3 ·H 2 O is stirred at a high speed at 80 ℃ and pH=10 to carry out coprecipitation reaction for 1h, and the precipitate is washed, filtered and dried to prepare Fe required by synthesis 3 O 4 Microparticle, finally 4.0g Fe 3 O 4 Uniformly dispersing the particles in 100g of the bamboo powder/SA mixed solution in the step (1) under the combined action of ultrasonic vibration and mechanical stirring to obtain nano Fe 3 O 4 Mixing bamboo powder/sodium alginate solution;
(3) Sucking the nano Fe in the step (2) by using a syringe under the action of magnetic stirring 3 O 4 Slowly dripping 7wt% CaCl into the mixed solution of bamboo powder and sodium alginate 2 Solidifying the solution for 30min at room temperature to form gel microspheres;
(4) Filtering out the gel microspheres formed by curing, and washing the gel microspheres with deionized water for 5 times to wash free monomers and salts and alkali which do not form hydrogel practically; and then placing the washed gel microspheres into an oven for drying until the gel microspheres are constant, obtaining the natural polymer magnetic gel microspheres, and sealing and preserving the natural polymer magnetic gel microspheres for standby.
The natural polymer magnetic gel microspheres prepared in the example 1 are subjected to electron microscope scanning, a scanning electron microscope image of the natural polymer magnetic gel microspheres is shown in fig. 1, the surface of the ground gel microspheres is rough, particles with different adhesion sizes are shown, the magnetic particles are successfully loaded on the gel microspheres, and the structure can increase the mechanical strength and the recovery rate of the gel microspheres to a certain extent.
Example 2 the inventors of the present application conducted the following study on the effect of the addition amount of the natural polymer magnetic gel microspheres prepared in example 1 on the methylene blue removal rate:
the methylene blue solution with the concentration of 160mg/L is taken, the pH value of the methylene blue solution is regulated to 7 by using hydrochloric acid solution or sodium hydroxide solution, then the methylene blue solution is divided into five groups, the natural polymer magnetic gel microspheres in the example 1 are respectively weighed and added into five groups of methylene blue solution (pH=7) with the addition amounts of 0.25g/L, 0.5g/L, 0.75g/L, 1g/L and 1.25g/L respectively, the methylene blue solution is subjected to shading oscillation for 30min (25 ℃ C., 200 r/min) in a water bath constant temperature box, sampling and filtering, and the methylene blue content in the five groups of test solutions is respectively measured by using an ultraviolet spectrophotometer, and the test results are shown in Table 1 and FIG. 2:
TABLE 1 adsorption efficiency of methylene blue by different gel microsphere addition amounts
As can be seen from the test results in example 2, when the addition amount of the natural polymer magnetic gel microspheres reaches 0.75g/L, the adsorption amount reaches more than 98%, the adsorption capacity reaches 200mg/g, and when the adsorption capacity is still increased when the adsorption capacity is increased to 1g/L, but when the adsorption capacity is reduced to about 157, the adsorption effect is optimal when the addition amount of the natural polymer magnetic gel microspheres is 0.75 g/L.
Example 3 the inventors of the present application have conducted the following specific experiments with respect to the effect of pH on methylene blue removal rate of natural polymer magnetic gel microspheres: weighing the natural polymer magnetic gel microspheres prepared in the example 1, and adding the natural polymer magnetic gel microspheres into a plurality of groups of methylene blue solutions with different pH values prepared in advance according to the addition amount of 0.75g/L, wherein the concentration of the methylene blue solution is 160mg/L; and placing the multiple groups of mixed solutions in a water bath constant temperature box, shading and oscillating for 30min (25 ℃ and 200 r/min), sampling, filtering, and measuring the content of methylene blue by using an ultraviolet spectrophotometer. As shown in table 2 and fig. 3:
table 2 shows the adsorption efficiency of methylene blue at different pH values
As can be seen from the test results in example 3, the adsorption amount reached 95% when the pH reached 6, the adsorption amount was highest when the pH reached 8, and the adsorption effect was best when the pH was 8 as seen from the gradual decrease of the adsorption amount when the pH was continuously increased.
Example 4 the inventors of the present application have conducted the following specific experiments with respect to the effect of temperature on the methylene blue removal efficiency of natural polymer magnetic gel microspheres: weighing the natural polymer magnetic gel microspheres prepared in the example 1, and adding a pre-prepared methylene blue solution (pH=7) according to the addition amount of 0.75g/L, wherein the concentration of the methylene blue solution is 160mg/L; the mixed solution is divided into a plurality of groups, the groups are respectively placed in a water bath constant temperature box with different temperatures to be shaded and oscillated for 30min (200 r/min), sampled and filtered, the content of methylene blue is measured by an ultraviolet spectrophotometer, and the test results are shown in table 3 and figure 4:
TABLE 3 adsorption efficiency of methylene blue at different temperatures
As can be seen from the test results in example 4, when the temperature reaches 25 ℃, the adsorption amount reaches more than 98%, when the temperature continues to rise to 35 ℃, the adsorption amount gradually decreases, and when the temperature is 30 ℃, the adsorption effect is optimal; in practical application, the cost of wastewater treatment is generally lowest at normal temperature, so that the optimal temperature is 25-30 ℃.
Example 5 the recycling property of the natural polymer magnetic gel microspheres prepared in the present application was studied, specifically as follows: resolving and regenerating the natural polymer magnetic gel microsphere prepared in the embodiment 1, wherein the resolving agent is prepared by mixing acetic acid and ethanol according to the volume ratio of 1:9, soaking and oscillating for 30min, washing the adsorbent to be neutral by deionized water, and drying; adding 0.75g/L of dried natural polymer magnetic gel microsphere adsorbent into a pre-prepared methylene blue solution (pH=7), wherein the concentration of the methylene blue solution is 160mg/L, shading and oscillating for 30min (25 ℃ and 200 r/min) in a water bath constant temperature box, sampling, filtering, and measuring the content of the methylene blue by an ultraviolet spectrophotometer. The effect of recycling is shown in Table 4 and FIG. 6, after 4 cycles according to the above method:
TABLE 4 Recycling Properties of bamboo powder/sodium alginate gel microspheres
Experiments show that: when the pH=7, the temperature is 25 ℃, the adding amount of the adsorbent is 0.75g/L, and when the initial concentration of the methylene blue is 160mg/L, the adsorption efficiency of the adsorbent on the methylene blue is as high as 98.17%; the adsorbent has a wider applicable pH range for methylene blue adsorption, and has very good effects in the pH range of 6-7; when nanometer Fe 3 O 4 After the bamboo powder/sodium alginate gel microsphere is reused for 4 times, the adsorption efficiency for methylene blue can still reach 79.45 percent.
Example 6 the inventors of the present application aimed at the application of natural polymer magnetic gel microspheres to the adsorption of heavy metal ion wastewater, and specifically tested as follows: the natural polymer magnetic gel microspheres prepared in example 1 were weighed and added with a pre-prepared lead ion solution (ph=5) in an amount of 0.75g/L, the lead ion concentration of the lead ion solution being 80-160mg/L. And (3) shading and oscillating for 45min (25 ℃ and 200 r/min) in a water bath constant temperature box, sampling and filtering, and measuring the content of lead ions by using a flame atomic absorption spectrophotometer. As shown in table 5.
The example 6 shows that the natural polymer magnetic gel microsphere prepared by the application has a strong adsorption effect on wastewater with heavy metal ions of different concentrations.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (10)
1. The preparation method of the natural polymer gel microsphere is characterized by comprising the following steps of:
(1) Heating and dissolving bamboo powder in NaOH solution with the concentration of 7-10wt%, heating and dissolving sodium alginate in deionized water solution, stirring the sodium alginate solution by using a magnetic stirrer to fully dissolve the sodium alginate solution, and then mixing the two solutions to obtain a bamboo powder/SA mixed solution; wherein, the mass ratio of the bamboo powder to the sodium alginate is 1:2 to 3; the mass ratio of the bamboo powder to the NaOH solution is 1: 50-100;
(2) FeCl is added 2 ·4H 2 O and FeCl 3 ·6H 2 O is prepared from the following components in percentage by mass: 1.5-2, and dissolving the prepared iron salt mixture in deionized water, using excess NH 3 ·H 2 O is stirred at a high speed under neutral pH value to carry out coprecipitation reaction, and the precipitate after the reaction is washed, filtered and dried to obtain Fe 3 O 4 Microparticle, finally Fe 3 O 4 Uniformly dispersing the particles in the bamboo powder/SA mixed solution prepared in the step (1) under the combined action of ultrasonic vibration and mechanical stirring to obtainTo nanometer Fe 3 O 4 Mixing bamboo powder/sodium alginate solution; the mixed solution of the bamboo powder and SA and Fe 3 O 4 The mass ratio of the particles is 100:3 to 7;
(3) Sucking the nano Fe in the step (2) by using a syringe under the action of magnetic stirring 3 O 4 Slowly dripping CaCl into the mixed solution of bamboo powder and sodium alginate 2 Solidifying the solution in room temperature environment to form gel microsphere;
(4) Filtering out gel microspheres formed by solidification, washing the gel microspheres with deionized water for a plurality of times, putting the gel microspheres into an oven, drying the gel microspheres until the gel microspheres are constant, obtaining natural polymer gel microspheres, and sealing and preserving the natural polymer gel microspheres for standby.
2. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: the bamboo powder in the step (1) is obtained by directly adopting bamboo or waste bamboo, cutting, grinding, sieving and drying.
3. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the sodium alginate to the deionized water is 1: 50-100, and the magnetic stirring time is 20-40 min; the temperature of the bamboo powder and the sodium alginate are respectively 60-80 ℃.
4. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: the deionized water in the step (2) is pure water for experiments, and 5-10 g of ferric salt mixture is added into every 100ml of deionized water.
5. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: NH in the step (2) 3 ·H 2 The concentration of O is 1-2 mol/L, the reaction pH is 8-11, and the temperature is controlled at 70-80 ℃.
6. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: the concentration of the CaCl2 solution in the step (3) is 5-10wt% and the curing time is 20-40min.
7. The method for preparing the natural polymer gel microsphere according to claim 1, wherein the method comprises the following steps: the washing times in the step (4) are 3-5 times, and the drying temperature is 60-80 ℃ until the quality of the gel microspheres is unchanged.
8. Use of natural polymer gel microspheres prepared by a method according to any one of claims 1 to 6, characterised in that: the pH value of the wastewater is regulated to 6-10, then the natural polymer gel microspheres are directly added into the wastewater, and are adsorbed for 1-1.5 hours at the temperature of 20-35 ℃, wherein the adding amount of the polymer gel microspheres is 0.75-1g of polymer gel microspheres added into each liter of wastewater.
9. The use of a natural polymer gel microsphere according to claim 8, wherein: the wastewater contains methylene blue, lead ions, cadmium ions and copper ions.
10. The use of a natural polymer gel microsphere according to claim 8, wherein: the pH of the wastewater is adjusted using sodium hydroxide solution or hydrochloric acid.
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