KR20160121131A - Multi-layered hydrogel capsule and preparation method thereof - Google Patents
Multi-layered hydrogel capsule and preparation method thereof Download PDFInfo
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- KR20160121131A KR20160121131A KR1020150050689A KR20150050689A KR20160121131A KR 20160121131 A KR20160121131 A KR 20160121131A KR 1020150050689 A KR1020150050689 A KR 1020150050689A KR 20150050689 A KR20150050689 A KR 20150050689A KR 20160121131 A KR20160121131 A KR 20160121131A
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Abstract
Description
The present invention relates to a multi-layered chitosan-mineral hydrogel capsule and a method for producing the same, and more particularly, to a process for producing a chitosan multi-layered membrane hydrogel capsule to which high-tite mineral particles are bound using an anionic surfactant, The present invention relates to a water-treatment chitosan adsorbent comprising a mineral multilayer film hydrogel capsule and the capsule.
In recent years, environmental pollution problems have caused widespread problems both domestically and abroad. With the rapid industrial development and interest in environmental pollution in Korea, the development of new technologies for industrial wastewater treatment is actively under way. In general, industrial wastewater is treated physically, chemically or biologically. In order to remove the chromaticity, adsorbents such as activated carbon and ion exchange resins, oxidizing agents such as chlorine, hydrogen peroxide and bleaching agents are being developed. Recently, advanced oxidation methods such as electrolysis, ozone oxidation, Fenton oxidation, UV / TiO 2 and E-beam, and a new adsorption process using a natural adsorbent have been developed.
Most industrial wastewaters are based on physical deagglomeration processes and biological treatments, and chemical oxidation and adsorption processes are not widely used due to cost concerns. In particular, the adsorption technique has an advantage of being excellent in treatment efficiency, easy in designing and operation, and not producing harmful by-products. However, most of the conventional adsorption techniques have a problem in that economical efficiency is lowered by using expensive activated carbon. In particular, since the dye material contains various functional groups and is anionic or cationic, there is a problem in that the adsorbability by activated carbon is lowered. Therefore, development of an environmentally friendly adsorbent at low cost is required.
Chitosan is a biological resource estimated to produce over 100 billion tons per year on the earth. Chitosan, which is already commercially available, has alkaline saponification of N-acetyl group using N-acetylaminoglucose composed of aminogluco tm unit as a basic unit Rough chitin is used as the starting material.
When the acetyl group is removed from the chitin by chemical or biological treatment, it is converted to a free amino group (-NH 2), and the thus formed pyranose unit of the glucosamine is a natural polymer which is linked to the β-1,4 bond. Commercially available chitosan mainly has a degree of deacetylation of 60 to 90% and a mean degree of polymerization of 500 to 10,000.
Chitosan ((1-4) -2-amino-deoxy-β-D-glucan) is a functional polymer containing a large number of amine groups and is a bioabsorbable suture, Korean Journal of Polymer, Immunosuppressive agents, anticholesterolemic agents, tumor metastasis inhibitors, drug delivery media) (Journal of Polymer Science, Vol.14, No.4, p385 ~ 391 Vol.36, No.3, p484 ~ 490 (1998), Carbohydrate polymer, < RTI ID = 0.0 > (Korean Journal of Food Science and Technology, Vol. 24, No. 6, p. 574 to 580 (1992)), etc., (Eds., Vol. 53, No. 1, p. 70, No. 3, p. 36 (1998)), 76 (1996), The Chemical Society of Japan, p48 ~ 53 (1996), Polymer Bulletin, 38, p387 ~ 3 93 (1997)), and coagulant (water treatment technology (Sun), Vol.38, No.11 (1997), Bioindusty (1996)).
In particular, chitosan is an environmentally friendly natural polysaccharide and has been known to have the ability to adsorb the greatest number of anions per unit mass in a low-cost natural adsorbent due to its amino-functional group abundant on the surface (Prog. Polym. Sci. , pp. 38-70, 2005). In addition, raw materials can be supplied in large quantities from crustacean waste and can be produced at low cost. However, since chitosan is in the form of an insoluble powder, the structure of the chitosan polymer fiber is excessively adhered and the adsorption performance is low and it is difficult to apply to the adsorption process because it is a powder form. To overcome this problem, It is true.
However, the conventional chitosan beads were produced by neutralization-assisted gelation by adding chitosan solution, which is generally dissolved in an acid, to an alkaline solution. This is because, in the form of a hydrogel having a very high porosity, And had the same disadvantages.
First, the adsorption amount per unit dry mass was very large, while the amount of adsorption per volume was small. Second, the strength was weak. Third, the acid resistance was weak. Accordingly, research has been conducted to overcome the above limitations.
Korean Patent Laid-Open Publication No. 1998-055159 discloses that chitin or chitosan is converted into N- (carboxymethyl) to be water-soluble and then adjusted to a low molecular weight chitin or chitosan having a molecular weight in the range of 12,000-25,000. To thereby produce an organic coagulant for treating wastewater. The organic coagulant for treating wastewater according to the above literature has various ionic pollutants adsorbed and has an effect of improving the adsorption amount per volume but can not solve the improvement of acid resistance and strength and does not adsorb pollutants in acidic wastewater There is a problem that the function as a coagulant is not exhibited.
Korean Patent Laid-Open Publication No. 2014-0070727 discloses an adsorbent in which a carrier, chitosan and magnetite are mixed and beaded. The pollutant adsorbent according to the above prior art has a solid bead shape in which a chitosan-magnetite mixture solution is stabilized by using a tripolyphosphate (TPP) crosslinking agent containing a phosphate group, and an acid resistance improving effect However, since the strength improvement can not be solved yet, there is still a limit to obtain a strength that can be commercialized.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a chitosan-mineral multilayered membrane using chitosan and an anionic surfactant combined with high- A method for producing a chitosan-mineral multi-layered membrane hydrogel capsule having remarkably improved adsorption capacity per dry weight using the same, and a chitosan-mineral multi-layered membrane hydrogel capsule prepared according to the method.
Another object of the present invention is to provide a chitosan adsorbent for water treatment comprising the prepared chitosan-mineral multilayer film hydrogel capsules.
(1) preparing a chitosan-mineral mixture by adding a goethite mineral solution to a chitosan solution; And (2) dropping the prepared chitosan-mineral mixture solution into a gelling solution to which an anionic surfactant has been added to prepare a multilayered chitosan-mineral hydrogel capsule; The present invention relates to a method for producing a hydrogel capsule of chitosan-mineral multilayered membrane.
In the present invention, the step (1) comprises the steps of: a) preparing a chitosan solution by adding chitosan powder to an aqueous acid solution; b) agitating the mineral solution to produce a hard mineral solution; And c) adding the ghtite mineral solution to the chitosan solution to prepare a chitosan-mineral mixture.
In the present invention, the aging in the step b) may include a step of keeping at a high temperature for 5 to 60 hours.
In the present invention, the method may further comprise adding at least one additive selected from the group consisting of an ionic emulsifier, an anionic improver, a cationic improver and a chelating agent to the mineral solution of step b).
In the present invention, the additive may be added in an amount of 0.01 to 30 parts by volume relative to the mineral solution.
In the present invention, after the step b), it may further include a step of ultrasonifying the prepared high-tide mineral solution.
In the present invention, the hot mineral solution of step c) may be added to the chitosan solution at a ratio of 1 to 90 by volume.
In the present invention, the anionic surfactant in the step (2) may be at least one selected from the group consisting of an alkylbenzenesulfonate, an alkylsulfate, an alkylether sulfate, an alkanesulfonate, Sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium sulfoxyl sulfosuccinate, and sodium dodecyl sulfate.
In the present invention, the anionic surfactant may be added in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the gelled solution.
The present invention relates to chitosan-mineral multi-layered hydrogel capsules comprising 10 to 300 parts by weight of hard mineral particles and 0.2 to 5.0 parts by weight of an anionic surfactant with respect to 100 parts by weight of chitosan.
The present invention also relates to a chitosan adsorbent for water treatment comprising the above-mentioned chitosan-mineral multilayer film hydrogel capsules.
In the present invention, the chitosan adsorbent may be added to the polluted water in which ionic pollutants or organic pollutants exist in order to adsorb one or more selected from anionic pollutants, cationic pollutants, and organic pollutants .
In addition to improving the strength and acid resistance of the chitosan-mineral multi-layered membrane hydrogel capsules prepared by the process for producing the chitosan-mineral multilayer membrane hydrogel capsules of the present invention, the capsule can be chemically modified, and the alkali gelated chitosan beads It is possible to manufacture a multi-layered membrane-type capsule having a high density, thereby improving the amount of adsorption per unit volume. In addition, the hydrogel capsules of chitosan-mineral multilayer membrane gelled with the anionic surfactant according to the present invention can significantly reduce the pollutant removal efficiency in comparison with the conventional pollutant adsorbent, It is possible to obtain a chitosan adsorbent for water treatment comprising the multi-layered hydrogel capsules which can be used in a pollutant removal and separation process of polluted water generated in various industrial fields because of excellent adsorption ability against various kinds of pollutants.
Brief Description of the Drawings Figure 1 is a graph showing the shape of a capsule membrane of a chitosan-mineral multi-layered membrane according to Example 1 of the present invention and Comparative Example 1. Fig. C: cross section of the capsule film according to Comparative Example 1, d: cross section of the capsule film according to Example 1)
FIG. 2 shows the particle distribution of the chitosan-mineral multilayer film hydrogel capsules according to Example 1 of the present invention and the shape of the chitosan-hardite mineral particle composite.
The present invention provides a method for producing a chitosan-mineral multilayer film hydrogel capsule, comprising the steps of: (1) preparing a chitosan-mineral mixture by adding a high-tide mineral solution to a chitosan solution; And (2) dropping the prepared chitosan-mineral mixture solution into a gelling solution to which an anionic surfactant has been added to prepare a multi-layered chitosan-mineral hydrogel capsule.
More specifically, the present invention provides a method for preparing a chitosan-mineral mixture by adding a high-strength mineral solution to a chitosan solution, comprising the steps of: a) preparing a chitosan solution by adding chitosan powder to an aqueous acid solution; b) agitating the mineral solution to produce a hard mineral solution; And c) adding the ghtite mineral solution to the chitosan solution to prepare a chitosan-mineral mixture; . ≪ / RTI >
In the present invention, the chitosan can be obtained abundantly from the natural world and is widely available as a commodity. Chitosan is a kind of aminopolysaccharide present in nature and is a natural substance obtained by deacetylation of chitin contained in the cell wall of microorganism such as crab, shrimp bark, squid bone, mold, mushroom and bacteria. And contains many hydroxyl groups and amino groups on the surface. Chitosan has no toxicity, biodegradable, biocompatibility, and high applicability.
In the present invention, the Goethite mineral refers to a hydroxide mineral of iron, and includes Fe (OH) 3 , Fe (OH) 2 , Fe 5 HO 8 .4H 2 O, Fe 3 O 4 , FeO, FeOOHs, Fe 3 O 4 and HFeO 2 and Fe 2 O 3 ㅇ H 2 O among 16 pure phase iron oxides.
The chitosan powder prepared by adding the chitosan powder to the a) aqueous acid solution according to the present invention is prepared by dissolving chitin prepared by decalcifying and deproteinizing the shell of crustaceans such as crab, shrimp and the like with sodium hydroxide Chitosan powder treated by deacetylation with a sodium hydroxide (NaOH) solution may be used, but there is no particular limitation, and commercially available chitosan powder may be used. Also, the acid aqueous solution of step a) may include, but is not limited to, acetic acid, lactic acid, formic acid, glycolic acid, acrylic acid, propinic acid, succinic acid, , An organic acid such as toluenesulfonic acid, or an acid solution such as hydrochloric acid, phosphoric acid, and the like, and the acid solution may contain 5 to 50% by volume of the total acid aqueous solution. The volume of the acid solution and the acid solution contained is not particularly limited as long as it can dissolve the chitosan powder, but within the above range, the dissolution of the chitosan for the purpose of using the aqueous acid solution in the step a) It is good to get up.
In addition, the mineral solution in the step b) of producing the high-tide mineral solution through aging of the b) mineral solution according to the present invention is preferably a solution containing oxidation, preferably a sodium hydroxide solution and a ferric chloride solution But it is not limited thereto.
In the present invention, the aging in the step b) is carried out by keeping the mineral solution at 30 to 100 ° C, preferably 45 to 80 ° C for 5 to 60 hours, preferably 12 to 48 hours, more preferably 20 to 30 hours Process. In the present invention, it is possible to produce a high-tide mineral solution capable of improving the adsorption ability of contaminants by binding with chitosan through aging of the mineral solution.
In the present invention, by using the ghtite mineral solution, unlike the surface charge of most minerals, it has a positive surface charge, thereby improving the adsorption ability to anions. Unlike iron ions, The membrane is separated to form a multi-layered film. Unlike other minerals, the nanoparticles have a rod-like shape and form a lot of space in the agglomerate, thereby providing an adsorption space for the material.
The mineral solution of step b) according to the present invention may further comprise adding at least one additive selected from the group consisting of an ionic emulsifier, an anionic improver, a cationic improver and a chelating agent to the mineral solution.
The additive of the present invention may be prepared by adding the additive at a ratio of 0.01 to 30 parts by volume to the mineral solution. As the ionic emulsifier in the additive, any one selected from a cationic surfactant, an anionic surfactant and a nonionic surfactant And preferably anionic surfactants are used for anionic contaminants, anionic surfactants are used for cationic contaminants, cationic, anionic and nonionic interfaces for organic contaminants Activators are used. This increases the electrostatic attraction between the opposite charges, and in the case of organic materials, it increases the hydrophobic attraction, thereby improving the adsorption ability.
Among the above additives, the anionic improver may be at least one selected from inorganic minerals including bentonite, zeolite, montmorillonite, kaolinite, ilite, clay, loess and the like or powders thereof, preferably bentonite But is not limited thereto. By using such an anionic improver, it is possible to improve the adsorption performance against the cationic contaminants, and at the same time, the effect of increasing the strength of the material can be obtained.
The cationic modifier in the additive is selected from, but not limited to, ferric nitrate, ferric sulfate, ferrous sulfate, ammonium sulfate, sodium sulfate, zwitterion, nano-zirconium iron, potassium hydrogen sulfate and sodium hydrogen sulphate Any one or more can be used. The use of such a cationic improving agent can improve the adsorption performance against anionic contaminants, and in the case of zero valence iron and nano-zirconium iron, it can effectively improve the adsorption of ionic substances by electron migration while being present as oxides.
The chelating agent may be any one selected from the group consisting of ethylenediamine, oxine, o-phenanthroline, ethylene glycol tetraacetic acid (EGTA), and ethylenediamine tetraacetic acid (EDTA) And EDTA is preferably used, but not limited thereto. By using the chelating agent, the adsorption performance against the heavy metals in the wastewater can be effectively improved.
In addition, the ghtite mineral solution prepared through the step b) according to the present invention may further comprise a step of ultrasonication after the step b), so that the ghtite mineral solution in the form of the ghtite mineral fine particles is dispersed. The apparatus used for the ultrasonic wave treatment is not limited as long as it is an apparatus capable of generating an ultrasonic wave, and a probe type ultrasonic wave generator can be used. In the process of preparing the chitosan-mineral multi-layered hydrogel capsules, the high-tight mineral microparticles produced by the ultrasonic treatment exhibit a high binding force with the chitosan to form a high-density uniform chitosan-mineral multilayer film, Can be effectively improved.
In the present invention, the chitosan-mineral mixture solution is prepared by adding the gutite mineral solution to the chitosan solution in an amount of 1 to 90 parts by volume relative to the chitosan solution to prepare a chitosan-mineral mixture solution . The added amount of the high-sodium mineral solution is not particularly limited as long as it can bond the high-hardness mineral particles and the chitosan. However, within the above range, in the process of preparing the chitosan-mineral multilayer hydrogel capsule of the present invention It is more preferable that the synergistic effect is most effectively improved by the adsorption performance by the formation of a uniform layer of the chitosan-mineral bonding film.
In the present invention, (2) a step of preparing a chitosan-mineral hydrogel capsule in the form of a multilayer membrane by dropping the prepared chitosan-mineral mixture solution into a gelling solution to which an anionic surfactant has been added; , A mixture of chitosan and mineral having a cationic charge is neutralized with a solution containing an anionic surfactant to form capsules. At this time, a gel having a high density is formed on the capsule surface formed by the long hydrophobic part of the anionic surfactant do. In addition, a high-density chitosan-mineral multilayer membrane is formed on the surface in the process of moving the chitosan polymer bound to the hard mineral particles to the capsule surface and the anionic surfactant moving continuously into the capsule, thereby forming a multilayered chitosan- . The multi-layered chitosan-mineral capsules produced by this process have higher density, higher strength, and improved acid resistance than single-membrane chitosan capsules, and have high adsorption performance by chitosan-mineral bonding There is an advantage. Therefore, when the chitosan-mineral capsule in the form of a multilayer film is used as a chitosan adsorbent for water treatment, it can exhibit remarkably improved pollutant adsorption performance as compared with a conventional chitosan adsorbent.
The anionic surfactant of the step (2) of the present invention may be an alkylbenzenesulfonate, an alkylsulfate, an alkylether sulfate, an alkanesulfonate, Sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium sulfoxyl sulfosuccinate, sodium dodecyl sulfate, and the like. Preferably, sodium dodecyl sulfate is used, but the present invention is not limited thereto.
The anionic surfactant may be added in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the gelling solution. The above-mentioned range of the added weight is not particularly limited as long as the object of the present invention is attained. However, within the above range, the reaction between the chitosan-mineral binding and the anionic surfactant of the present invention in step (2) It is possible to produce a chitosan-mineral hydrogel capsule having a multilayered chitosan-mineral multilayer, thereby making it possible to manufacture a water-treatment chitosan adsorbent having improved high-strength adsorption performance.
The present invention provides a chitosan-mineral multi-layered membrane hydrogel capsule prepared from the above-mentioned process for producing a chitosan-mineral multilayer film hydrogel capsule.
In the present invention, the chitosan-mineral multilayer film hydrogel capsules may contain 10 to 300 parts by weight, preferably 50 to 250 parts by weight, more preferably 100 to 200 parts by weight of hard mineral particles per 100 parts by weight of chitosan. , And 0.2 to 5.0 parts by weight of an anionic surfactant. In addition, in the present invention, it is preferable that the high-sodium mineral solution is added in an amount of 25 to 65 parts by volume of the high-sodium mineral solution to 100 parts by volume of the chitosan solution.
In the present invention, the high-sodium mineral particles may include at least one selected from HFeO 2 and Fe 2 O 3 O H 2 O, and the anionic surfactant may be at least one selected from the group consisting of alkylbenzenesulfonic acids containing an alkyl group having 12 to 18 carbon atoms A salt selected from a salt, an olefin sulfonate, an alkyl sulfate ester salt, an alkyl ether sulfate ester salt, an alkanesulfonate salt, a vanillic acid, sodium decyl sulfate, sodium dodecylbenzenesulfate, dioxylsulfosuccinate sodium and sodium dodecyl sulfate It can be more than one.
In addition, the above-mentioned chitosan-mineral multilayer film hydrogel capsules may further contain an additive, and the additive may be selected from cationic surfactants, anionic surfactants, nonionic surfactants, bentonites, zeolites, montmorillonites, kaolinites, , Inorganic minerals including clay, loess and the like, powders of inorganic minerals, such as ferric nitrate, ferric sulfate, perus sulfate, ammonium sulfate, sodium sulfate, zircon iron, nano-zirconium iron, potassium hydrogensulfate, (EGTA), and ethylenediamine tetraacetic acid (EDTA) may be used as the organic solvent.
In addition, the present invention provides a chitosan adsorbent for water treatment comprising the above-mentioned chitosan-mineral multilayer film hydrogel capsules.
The chitosan adsorbent according to the present invention may be added to the polluted water in which ionic pollutants or organic pollutants exist in order to adsorb any one or more selected from anionic pollutants, cationic pollutants and organic pollutants have.
The chitosan adsorbent for water treatment according to the present invention is capable of removing various contaminants and more specifically about 10 times or more anionic contaminants (for example, about 10 times as much as the chitosan adsorbent containing chitosan multilayer film hydrogel capsules containing no chitosan mineral particles (Cadmium, arsenic mercury, etc.) and anionic dyes (Congoled, reactive black 5, etc.). In addition, the conventional chitosan adsorbent can be applied to organic pollutants (naphthalene etc.) and cationic dyes (methylene blue, etc.), which have poor adsorption efficiency, And the like.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, it should be understood that the following examples are provided for the purpose of further understanding the present invention, and the present invention is not limited by the examples, and various other modifications and changes may be possible.
First, the experimental method performed in the present invention is presented.
[Experiment 1] Comparison of membrane shape of chitosan hydrogel capsules according to whether or not high-tite mineral particles were introduced
The morphology of the chitosan hydrogel capsule membrane prepared by Scanning Electron Microscope (SEM) and the morphology of the capsule membrane was observed.
[Experiment 2] Particle distribution and complex shape observation of chitosan-mineral multi-layered hydrogel capsules
Particle distribution and complex shape of chitosan - mineral multilayer hydrogel capsules prepared by Scanning Electron Microscope (SEM) were observed.
[Experiment 3] Congo red adsorption efficiency and capsule dry weight of chitosan-mineral multilayer hydrogel capsules according to addition amount of high-tight mineral particles
(1-naphthalene sulfonic acid, 3,3 '- (4,4'-biphenylene bis (azo) bis (4-amino) disodium salt, Sigma Aldrich, USA) / L concentration to prepare two Congo red aqueous solutions. 20 g of the prepared chitosan-mineral multi-layered membrane hydrogel capsules were placed in two 20 ml glass vials, 10 ml of each of the above two Congo red aqueous solutions was added to the glass vials, And the mixture was stirred at 150 rpm for 24 to 240 hours to proceed the adsorption reaction. The concentration of Congo red was analyzed at 497 nm using DR 5000 Spectrophotometer, and the adsorption efficiency (mg / g) of Congo red was measured. The dry weight (mg / capsule) of the chitosan-mineral multi-layered hydrogel capsules according to the addition amount of high-tight mineral particles was measured using a dryer (Vision Science, Korea, kk-141209).
[Experiment 4] Congo red adsorption efficiency of chitosan-mineral multilayer hydrogel capsules according to anionic surfactant concentration in gelling solution
A chitosan-mineral mixture prepared by adding 10% and 20% by volume of a high-sodium mineral solution to the chitosan solution was mixed with 0.5% sodium dodecyl sulfate (SDS), an anionic surfactant, , 1 and 2 wt% of the anionic surfactant were added to the other gelation solution to prepare a chitosan-mineral multi-layered hydrogel capsule. The Congo red adsorption experiments were carried out in 20 ml glass vials each containing 20 g of each of the prepared chitosan-mineral multilayer hydrogel capsules prepared in different conditions, 10 ml of Congo red aqueous solution having a concentration of 1000 mg / l in the glass vial, After the addition, the mixture was stirred at 30 DEG C and 150 rpm for 24 hours to carry out the adsorption reaction. Thereafter, the adsorption efficiency (mg / g) of Congo red was measured in the same manner as in Experiment 3.
[Experiment 5] Congo red adsorption efficiency measurement of chitosan-mineral multilayer hydrogel capsules prepared by adding additives or ultrasonic treatment
A chitosan-mineral mixture solution prepared by adding a chelating agent or a non-ionic surfactant in an amount of 20% by volume to a chitosan solution containing a 10% by volume of a high-sodium mineral solution or an ultrasonic treatment was mixed with an anionic surfactant Sodium dodecyl sulfate (SDS) was added to the gelled solution containing 0.5 and 2 wt% based on the total weight of the gelled solution to prepare a chitosan-mineral multi-layered hydrogel capsule. The Congo red adsorption experiments were carried out in 20 ml glass vials each containing 20 g of each of the prepared chitosan-mineral multilayer hydrogel capsules prepared in different conditions, 10 ml of Congo red aqueous solution having a concentration of 1000 mg / l in the glass vial, After the addition, the mixture was stirred at 30 ° C and 150 rpm for 120 hours and 240 hours, and the adsorption reaction was allowed to proceed. Thereafter, the adsorption efficiency (mg / g) of Congo red was measured in the same manner as in Experiment 3.
[Example 1] 10% by volume of goitite mineral solution + 0.2% by mass of SDS -Preparation of chitosan-mineral multilayered membrane hydrogel capsules
10 g of chitosan powder was added to 1 L of an aqueous acid solution containing 300 mL of a 5% acetic acid solution, and the mixture was stirred at 25 DEG C and 150 rpm for 24 hours using a shaking incubator to prepare a chitosan solution. 20 ml of a 2.5 M sodium hydroxide (NaOH) solution was added to 80 ml of a 0.2 M ferric chloride (FeCl 3 ) solution to prepare a mineral solution containing iron hydroxide particles. The mineral solution was aged in a dryer at 60 ° C for 24 hours (aging) to prepare 100 ml of a hard mineral solution containing high-tite mineral particles. To the prepared chitosan solution, 10% by volume of the prepared high-tight mineral solution was added to the chitosan solution to prepare a chitosan-mineral mixture. The chitosan-mineral mixture was added to the prepared sodium chitosan solution using an injection syringe Sodium dodecyl sulfate (SDS) was added to the gelled solution containing 0.2 wt% to prepare a hydrogel capsule of chitosan-mineral multilayer film. The prepared capsules were filtered through filter paper and washed several times with distilled water to remove residual sodium dodecyl sulfate.
The shape of the chitosan-mineral multi-layered hydrogel capsule membrane, the shape of the capsule membrane cross-section, the particle size distribution of the capsule and the complex shape of the chitosan-mineral multi-layered membrane hydrogel capsules prepared by the above method were observed by the methods of Experiments 1 to 2, The Congo red adsorption efficiency (mg / g) of the chitosan-mineral multi-layer membrane hydrogel capsules was measured by the method of Fig.
[Example 2] 20% by volume of goitite mineral solution + 0.2% by weight of SDS
A chitosan-mineral multi-layered hydrogel capsule was prepared in the same manner as in Example 1, except that 20% by volume of the hard mineral solution was added to the chitosan solution. The adsorption efficiency of Congol Red mg / g) was measured.
[Example 3] 30% by volume of goitite mineral solution + 0.2% by weight of SDS
In the same manner as in Example 1, except that 30% by volume of the hard mineral solution was added to the chitosan solution, the hydrogel capsules of chitosan-mineral multilayer film were prepared in the same manner as above. mg / g) was measured.
[Example 4] 40 volume% of hot mineral solution + 0.2 mass% of SDS,
A chitosan-mineral multi-layered hydrogel capsule was prepared in the same manner as in Example 1, except that 40% by volume of the hard mineral solution was added to the chitosan solution. The adsorption efficiency of Congol Red mg / g) was measured.
[Example 5] 50% by volume of goitite mineral solution + 0.2% by weight of SDS
A chitosan-mineral multi-layered hydrogel capsule was prepared in the same manner as in Example 1, except that 50% by volume of the hard mineral solution was added to the chitosan solution. The adsorption efficiency of Congol Red mg / g) was measured.
[Example 6] 60% by volume of hot mineral solution + SDS 0.2%
A chitosan-mineral multi-layered hydrogel capsule was prepared in the same manner as in Example 1, except that 60% by volume of the hard mineral solution was added to the chitosan solution. The adsorption efficiency of Congol Red mg / g) was measured.
[Example 7] 70% by volume of goitite mineral solution + 0.2% by weight of SDS
In the same manner as in Example 1, except that 70% by volume of the hard mineral solution was added to the chitosan solution, the hydrogel capsules of chitosan-mineral multilayer film were prepared in the same manner as above. mg / g) was measured.
[Example 8] 10% by volume of a 2-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
The same procedure as in Example 1 was followed except that 10% by volume of a 2-fold concentrated concentrated maltitol solution having a concentration of 2 times that of the ghtite mineral solution added to the chitosan solution was added to the chitosan solution, and the chitosan-mineral multilayer membrane hydrogel capsules And the dry weight (mg / capsule) of the capsule was measured by the method of Experiment 3 above.
The 2-fold concentrated high-tide mineral solution contained twice the same amount of high-grade mineral as the high-grade mineral solution of Example 1. The high-sodium mineral solution prepared in Example 1 was centrifuged at 3500 centrifugation at rpm for 30 min and removal of the supernatant.
[Example 9] 20% by volume of a 2-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
In Example 8, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared by the same procedure as above except that 20% by volume of a 2-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 10] 50% by volume of a 2-fold concentrated high-strength mineral solution + 0.2% by weight of SDS
In Example 8, the chitosan-mineral multi-layered membrane hydrogel capsules were prepared by the same procedure except that 50% by volume of a 2-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 11] 70% by volume of 2-fold concentrated hot mineral solution + 0.2% by weight of SDS,
In Example 8, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared by the same procedure as above except that 70% by volume of a 2-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 12] 10% by volume of a 3-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
The same procedure as in Example 1 was followed except that 10% by volume of a 3-fold concentrated high-strength mineral solution was added to the chitosan solution, which had a concentration of 3 times that of the hot mineral solution added in Example 1, to form a chitosan-mineral multilayer hydrogel capsule And the dry weight (mg / capsule) of the capsule was measured by the method of Experiment 3 above.
The 3-fold concentrated high-maltitol mineral solution was three times as high as that of the high-maltitol mineral solution of Example 1. The high-maltitol mineral solution prepared in Example 1 was centrifuged at 3500 centrifugation at rpm for 30 min and removal of the supernatant.
[Example 13] 20% by volume of a 3-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
In Example 12, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared in the same manner as in Example 12, except that 20% by volume of a 3-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 14] 50% by volume of a 3-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
In Example 12, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared in the same manner as in Example 12, except that 50% by volume of a 3-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 15] 70% by volume of a 3-fold concentrated high-strength mineral solution + 0.2% by weight of SDS,
In Example 12, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared by the same procedure as above except that 70% by volume of a 3-fold concentrated high-strength mineral solution was added to the chitosan solution. Weight (mg / capsule) was measured.
[Example 16] 10% by volume of hot mineral solution + 0.5% by SDS
In the same manner as in Example 1 except that a gelled solution containing 0.5 wt% of sodium dodecyl sulfate as an anionic surfactant was used, the hydrogel capsules of chitosan-mineral multilayer membrane were prepared in the same manner as in Example 1, Red adsorption efficiency (mg / g) was measured.
[Example 17] 10% by volume of hot mineral solution + 1% by mass of SDS,
In the same manner as in Example 1 except that a gelled solution containing 1 wt% of sodium dodecyl sulfate as an anionic surfactant was used, the hydrogel capsules of chitosan-mineral multilayer membrane were prepared in the same manner as in Example 1, Red adsorption efficiency (mg / g) was measured.
[Example 18] 10% by volume of hot mineral solution + 2% by SDS%
A multilayered chitosan-mineral multilayer membrane capsule was prepared in the same manner as in Example 1, except that a gelling solution containing 2 wt% of sodium dodecyl sulfate as an anionic surfactant was used. Red adsorption efficiency (mg / g) was measured.
[Example 19] 20% by volume of hot mineral solution + 0.5% by weight of SDS,
In the same manner as in Example 2 except that a gelled solution containing 0.5 wt% of sodium dodecyl sulfate as an anionic surfactant was used, the chitosan-mineral multi-layered membrane hydrogel capsules were prepared. The adsorption efficiency (mg / g) of Congo red was measured.
[Example 20] 20% by volume of goitite mineral solution + 1% by weight of SDS,
In the same manner as in Example 2 except that a gelling solution containing 1 wt% of sodium dodecyl sulfate as an anionic surfactant was used, the hydrogel capsules of chitosan-mineral multilayer membrane were prepared in the same manner as in Example 2, Red adsorption efficiency (mg / g) was measured.
[Example 21] 20% by volume of goitite mineral solution + 2% by SDS%
In the same manner as in Example 2 except that a gelled solution containing 2 wt% of sodium dodecyl sulfate as an anionic surfactant was used, a chitosan-mineral multi-layered membrane hydrogel capsule was prepared. The adsorption efficiency (mg / g) of Congo red was measured.
[Example 22] 20 vol% of chelate-containing gutite mineral solution containing 10 vol% + SDS 0.5 wt%
In the same manner as in Example 19, except for adding 10% by volume of ethylenediaminetetraacetic acid (EDTA) as a chelating agent to the mineral solution and then adding the hot mineral solution prepared by aging to the mineral solution, Mineral multilayer membrane hydrogel capsules were prepared and the adsorption efficiency (mg / g) of Congo red was measured by the method of Experiment 5 above.
[Example 23] 20% by volume of ghtite mineral solution containing 10% by volume of chelating agent + 2% by mass of SDS,
A multilayered chitosan-mineral multi-layered membrane capsule was prepared in the same manner as in Example 22, except that a gelled solution containing 2 wt% of sodium dodecyl sulfate as an anionic surfactant was used. Red adsorption efficiency (mg / g) was measured.
[Example 24] 20% by volume of high-sodium mineral solution treated with ultrasonic treatment + 0.5% by weight of SDS,
In the same manner as in Example 19, except for adding the gelatinized high-sodium mineral solution, the chitosan-mineral multi-layered hydrogel capsules were prepared in the same manner as above. The adsorption efficiency (mg / g) Were measured.
The sonicated mineral solution was prepared by adding the hot mineral solution prepared in Example 19 to a 750 W ultrasonic generator for 10 minutes at a strength of 21%.
[Example 25] 20% by volume of high-sodium mineral solution by ultrasonication + 2% by mass of SDS,
In the same manner as in Example 24 except that a gelled solution containing 2 wt% of sodium dodecyl sulfate as an anionic surfactant was used, the capsule of hydrogel of chitosan-mineral multilayer film was prepared in the same manner as in Example 24, Red adsorption efficiency (mg / g) was measured.
[Example 26] 20% by volume of hot mineral solution containing 10% by volume of nonionic surfactant + 0.5% by SDS of SDS,
In the same manner as in Example 22 except that 10% by volume of Triton X-100 as a non-ionic surfactant was added to the mineral solution and then aged to make a high-tide mineral solution. The multi-layered hydrogel capsules were prepared and the adsorption efficiency (mg / g) of Congo red was measured by the method of Experiment 5 above.
[Comparative Example 1] Preparation of 0.2 wt% SDS-chitosan hydrogel capsules
10 g of chitosan powder was added to 1 L of an aqueous acid solution containing 300 mL of a 5% acetic acid solution, and the mixture was stirred at 25 DEG C and 150 rpm for 24 hours using a shaking incubator to prepare a chitosan solution. The prepared chitosan solution was dropped into a gelled solution containing 0.2 wt% sodium dodecyl sulfate (SDS) as an anionic surfactant using a syringe to prepare a chitosan hydrogel capsule. The prepared capsules were filtered through filter paper and washed several times with distilled water to remove residual sodium dodecyl sulfate.
The shape of the chitosan hydrogel capsule membrane and the shape of the cross section of the capsule membrane were observed by the method of Experiment 1 and the dry weight (mg / capsule) of the capsule was measured by the method of Experiment 3.
[Comparative Example 2] 100 ml of goatite mineral solution
In the same manner as in Example 1 except that the chitosan solution and the chitosan-mineral mixture were prepared in the same manner as in the preparation of the chitosan-mineral multi-layered membrane hydrogel capsules, the hard mineral solution was prepared. The Congo red absorption efficiency (mg / g) of the hot mineral solution was measured by the same procedure except that 100 ml of the hot mineral solution was placed in a 20 ml glass vial.
[Comparative Example 3] 200 ml of goatite mineral solution
The Congo red absorption efficiency (mg / g) of the hot mineral solution was measured by the same procedure except that 200 ml of the hot mineral solution in Comparative Example 2 was put into each 20 ml glass vial.
[Comparative Example 4] 300 ml of hot mineral solution
The Congo red absorption efficiency (mg / g) of the hot mineral solution was measured by the same procedure except that the hot mineral solution (300 ml) was added to the 20 ml glass vial.
[Comparative Example 5] 400 ml of goatite mineral solution
The Congo red absorption efficiency (mg / g) of the high-sodium mineral solution was measured by the same procedure except that 400 ml of the high-sodium mineral solution was added to 20 ml of the glass vial in Comparative Example 2.
[Comparative Example 6] 500 ml of hot mineral solution
The Congo red absorption efficiency (mg / g) of the high-sodium mineral solution was measured by the same procedure except that 500 ml of hot mineral solution was added to 20 ml glass vial in Comparative Example 2.
[Comparative Example 7] Preparation of 0.5 wt% SDS-chitosan hydrogel capsules
Chitosan hydrogel capsules were prepared in the same manner as in Comparative Example 1, except that the chitosan solution was dropped into a gelled solution containing 0.5 wt% of sodium dodecyl sulfate (SDS) as an anionic surfactant. The Congo red absorption efficiency (mg / g) of the chitosan hydrogel capsules was measured by the same procedure except that 20 g of the chitosan hydrogel capsules were placed in a 20 ml glass vial.
[Comparative Example 8] Preparation of 1 wt% SDS-chitosan hydrogel capsules
In Comparative Example 1, chitosan hydrogel capsules were prepared by the same procedure except that the chitosan solution was dropped into a gelled solution containing 1 wt% of sodium dodecyl sulfate (SDS) as an anionic surfactant. In the experiment 4, The Congo red absorption efficiency (mg / g) of the chitosan hydrogel capsules was measured by the same procedure except that 20 g of the chitosan hydrogel capsules were placed in a 20 ml glass vial.
[Comparative Example 9] Preparation of 2 wt% SDS-chitosan hydrogel capsules
The chitosan hydrogel capsules were prepared in the same manner as in Comparative Example 1 except that the chitosan solution was dropped into a gelling solution containing 2 wt% of sodium dodecyl sulfate (SDS) as an anionic surfactant. The Congo red absorption efficiency (mg / g) of the chitosan hydrogel capsules was measured by the same procedure except that 20 g of the chitosan hydrogel capsules were placed in a 20 ml glass vial.
[Comparative Example 10] 20 vol% of non-aged mineral solution + SDS 0.5 wt%
In Example 19, a chitosan-mineral multi-layered hydrogel capsule was prepared by the same procedure except that the mineral solution not subjected to the aging process was added. The adsorption efficiency (mg / g) of Congo red was measured by the method of Experiment 5, Were measured.
[Comparative Example 11] 20 vol% non-aged mineral solution + SDS 2 wt%
In Example 21, a chitosan-mineral multi-layered hydrogel capsule was prepared by the same procedure except that the mineral solution not subjected to the aging process was added. The adsorption efficiency (mg / g) of Congo red was measured by the method of Experiment 5, Were measured.
In order to observe the multilayer formation phenomenon in the chitosan-mineral multi-layered membrane hydrogel capsule membrane according to the introduction of high-tight mineral particles, the capsule prepared in Comparative Example 1 and the capsule prepared in Example 1 were observed with a scanning electron microscope The results of Example 1 and Comparative Example 1 of Experiment 1 observed with a scanning electron microscope (SEM) are shown in Fig.
1, in the case of the chitosan-mineral hydrogel capsule of Example 1 to which the high-tite mineral particles were added, unlike the capsules prepared in Comparative Example 1, the multi-layered structure in which the thin film below the surface layer was formed And it was confirmed that the membrane of each layer constituting the multi-layered structure was much thinner than the membrane of the capsule prepared in Comparative Example 1 and thinner in thickness toward the inside of the capsule.
2 shows the results of Example 1 of Experiment 2 in which the particle distribution of the chitosan-mineral multi-layered membrane hydrogel capsules prepared in Example 1 and the shape of the chitosan-highite mineral particle composite were further observed.
From the results of FIG. 2, it was confirmed that the nano-sized gut-tite particles formed a mass and bonded to the chitosan polymer, and were uniformly distributed throughout the film. In addition, it was confirmed that the hard particles were not simply coated on the surface of the membrane, but existed in the membrane and strongly bound to the chitosan polymer. As a result of elemental analysis using the elemental analyzer attached to the scanning electron microscope, the nanorod particles were iron-containing high-tight mineral particles. Part of the high-hardness mineral particles were very thinly bonded to the chitosan polymer, The results are shown in Fig.
Examples 1 to 7 and Comparative Example 1 relating to Experiment 3, in which the contaminant adsorption performance of the chitosan-mineral multilayer film hydrogel capsules was observed according to the amount of the high-sodium mineral particles using Congo red dye, which is one of harmful substances, (Comparative Example 6) are shown in the following Table 1, and the results of Experiment 3 in which the dry weight (mg / capsule) of the chitosan-multilayer film hydrogel capsules according to the addition amounts of the high- The results of Examples 8 to 15 and Comparative Example 1 are shown in Table 2 below.
From the results shown in Table 1, it was confirmed that when the chitosan-mineral multilayer film was formed by adding the high-tite mineral particles, the adsorption amount of the congo red was significantly increased compared with the general capsule without the high-tite mineral particles. Specifically, in the case of Example 3 in which 30 wt% of high-tite mineral particles were added, the adsorption efficiency of Congo red was increased by 5 times or more as compared with the comparative example. As a result, the adsorption efficiency of chitosan-mineral multi-layered hydrogel capsules was remarkably increased, and the adsorption efficiency of chitosan- It was confirmed that the binding efficiency of the tight minerals and the adsorption efficiency by the multi-layer formation of the capsule membrane produced by the binding are synergistic effects. The synergistic effect was found to be 5.5 times higher than the predicted adsorption efficiency by the simple sum of the adsorption efficiencies of the individual chitosan capsules and the high-mined mineral particles.
Also, it was confirmed from the results of Table 2 that the dry weight of the prepared chitosan-mineral multi-layered membrane hydrogel capsules was increased by increasing the content of the high-tight mineral particles concentrated two or three times, The dry weight of hydrogel capsules was about three times higher than that of ordinary chitosan capsules. As shown in Table 1, the adsorption efficiency of the chitosan-mineral multi-layered hydrogel capsules, which are increased in weight, is further increased because the amount of Congo red adsorbed per the dry weight of the capsule is increased.
Examples 16 to 21 of Experiment 4 in which the pollutant adsorption performance of the chitosan-mineral multilayer film hydrogel capsules prepared according to the concentration of the anionic surfactant used in the gelation solution for encapsulating the chitosan-mineral mixture was observed The results of Comparative Examples 7 to 9 are shown in Table 3 below.
As shown in Table 3, as the concentration of sodium dodecyl sulfate as an anionic surfactant in the gelling solution increased, the general chitosan capsules prepared through Comparative Examples 7 to 9 showed the adsorption efficiency of Congo red, a contaminant, It was confirmed that the adsorption amount of the chitosan-mineral multilayer hydrogel capsules prepared in Examples 16 to 18 and Examples 19 to 21 was increased. In order to increase the strength and acid resistance of the chitosan capsule, it is possible to drastically improve the existing problems that the adsorption amount and the adsorption efficiency are lowered by increasing the concentration of the anionic surfactant, and at the same time, It was found that it is possible to prepare a hydrogel capsule of chitosan-mineral multilayer film having acid-resistant properties.
In addition, it was confirmed that the performance of adsorbing contaminants on the chitosan-mineral multilayer hydrogel capsules prepared by adding the additives in the mineral solution or the ultrasonic treatment of the high-tide mineral solution was observed in Example 19 and Example 21, Examples 22 to 26, and Comparative Examples 10 to 11 are shown in Table 4 below.
The results of Table 4 indicate that the chitosan-mineral multi-layered membrane hydrogel capsules prepared in Example 22 and Example 23 using the high-tide mineral solution prepared by incorporating ethylenediamine tetraacetic acid (EDTA) as a chelating agent into the mineral solution The adsorption efficiency was higher than that of the chitosan-mineral multilayer hydrogel capsules prepared in Example 19 and Example 21 using the basic hard mineral solution and the chitosan-mineral capsules prepared in Comparative Examples 10 to 11 I could confirm. It was found that the cationic charge of nitrogen contained in chelating agent EDTA increased the adsorption of Congo red which is anion. The results of Example 26 show that the chitosan-mineral multilayered membrane hydrogel capsules containing the nonionic surfactant Triton X-100 in the ionic emulsifier have significantly improved adsorption efficiency compared to the basic chitosan-mineral multilayered membrane hydrogel capsules of Example 19 . These results suggest that Triton X-100, a non-ionic surfactant, promotes adsorption of organic moieties constituting Congo red.
In Table 4, in the case of the chitosan-mineral multi-layered membrane hydrogel capsules prepared by further introducing the ultrasonic treatment of the hard mineral solution through Examples 24 and 25, Minerals multilayered membrane hydrogel capsules and the chitosan-mineral capsules prepared in Comparative Example 10 through Comparative Example 11, respectively. As a result of the above results, it was confirmed that the addition of the small size of the high-tite mineral particles results in more uniform bonding with the chitosan and the improvement of the adsorption efficiency by the uniform bonding.
The results shown in Tables 1 to 4 indicate that the efficiency of adsorbing contaminants can be effectively improved by preparing a capsule having structurally specificity through the formation of a multilayer film. Such chitosan-mineral multilayered membrane hydrogel capsules can be prepared by (1) maximizing the concentration of mineral particles through the addition of concentrated high-sodium mineral particles; (2) increasing the concentration of the anionic surfactant (SDS) as a gelling agent; (3) reducing the size of the hard minerals bound to chitosan using ultrasonic waves; (4) adding various functional additives; (5) a significantly improved pollutant adsorption efficiency can be achieved through a combination of the above methods.
Claims (12)
(2) preparing a multilayered chitosan-mineral hydrogel capsule by dropping the chitosan-mineral mixture prepared in the step (1) in a gelled solution containing an anionic surfactant;
Wherein the hydrogel encapsulates the chitosan-mineral multilayer membrane.
(A) preparing chitosan solution by adding chitosan powder to an aqueous acid solution;
b) preparing a high-tide mineral solution through aging of the mineral solution; And
c) adding the ghtite mineral solution to the chitosan solution to prepare a chitosan-mineral mixture;
Wherein the hydrogel encapsulates the chitosan-mineral multilayer membrane.
Wherein the aging in the step b) is carried out at 30 to 100 ° C for 5 to 60 hours.
The method according to claim 1, further comprising the step of adding at least one additive selected from an ionic emulsifier, an anionic improver, a cationic improving agent and a chelating agent to the mineral solution of step b) Way.
Wherein the additive is added in a ratio of 0.01 to 30 parts by volume to the mineral solution.
The method of manufacturing a hydrogel capsule of chitosan-mineral multi-layered membrane according to claim 1, further comprising the step of ultrasonically treating the prepared high-sodium mineral solution.
The method of producing a chitosan-mineral multi-layered film hydrogel capsule according to claim 1, wherein the hard mineral solution of step (c) is added to the chitosan solution in a volume ratio of 1 to 90.
The anionic surfactant in the step (2) may be at least one selected from the group consisting of an alkylbenzenesulfonic acid salt containing an alkyl group having 12 to 18 carbon atoms, an olefin sulfonic acid salt, an alkyl sulfuric acid ester salt, an alkyl ether sulfuric acid ester salt, an alkane sulfonic acid salt, , Sodium dodecylbenzenesulfate, sodium sulfoxyl sulfosuccinate, and sodium dodecylsulfate. The method for producing a chitosan-mineral multi-layered film hydrogel capsule according to claim 1,
Wherein the anionic surfactant is added in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the gelled solution.
The chitosan adsorbent may be added to contaminated water containing ionic contaminants or organic contaminants for adsorbing at least one selected from anionic contaminants, cationic contaminants, and organic contaminants. absorbent.
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| CN112399829A (en) * | 2018-06-07 | 2021-02-23 | 辛辛那提大学 | Hydrogel and aerogel based method and apparatus for sample pretreatment |
| KR20220108680A (en) * | 2021-01-27 | 2022-08-03 | 한밭대학교 산학협력단 | Chitosan hydrogel capsule for protein immobilization and preparing method thereof |
| CN115010344A (en) * | 2022-06-24 | 2022-09-06 | 昭仕（厦门）新材料有限公司 | Sludge dehydrating agent and application method thereof in sludge dehydrating |
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