CN116764601A - Amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, and preparation method and application thereof - Google Patents
Amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, and preparation method and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 76
- 239000003463 adsorbent Substances 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 239000004005 microsphere Substances 0.000 title claims abstract description 52
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000005457 ice water Substances 0.000 claims abstract description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229960003330 pentetic acid Drugs 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical group Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- LGLMLRNXJDSTMP-UHFFFAOYSA-N Cc1ccc(cc1)S(O)(=O)=O.N=C=NC(CN1CCOCC1)C1CCCCC1 Chemical compound Cc1ccc(cc1)S(O)(=O)=O.N=C=NC(CN1CCOCC1)C1CCCCC1 LGLMLRNXJDSTMP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000005389 magnetism Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RAZLJUXJEOEYAM-UHFFFAOYSA-N 2-[bis[2-(2,6-dioxomorpholin-4-yl)ethyl]azaniumyl]acetate Chemical compound C1C(=O)OC(=O)CN1CCN(CC(=O)O)CCN1CC(=O)OC(=O)C1 RAZLJUXJEOEYAM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention belongs to the technical field of wastewater treatment, and discloses an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, a preparation method and application thereof. The preparation method comprises the following steps: mixing chitosan, an aminopolycarboxylic acid compound and water, regulating the pH value to obtain a mixed solution, and adding ferroferric oxide nano particles to mix to obtain a solution a; mixing liquid paraffin with span-80 to obtain a solution b; mixing the solution a and the solution b to obtain W/O emulsion; mixing the carbodiimide aqueous solution with the W/O emulsion in ice water bath to obtain a reactant, adding glutaraldehyde aqueous solution for crosslinking, separating solid matters by using a magnet, washing, and drying in vacuum to obtain the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent. The amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent can be used for removing heavy metal ions in water, and has the advantages of large adsorption capacity, high adsorption speed, stable treatment effect, magnetism, easy separation and recovery and repeated utilization.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and in particular relates to an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, a preparation method and application thereof.
Background
With the rapid development of industry, industries such as mining, metallurgy, chemical industry, electroplating, batteries and the like can generate a large amount of heavy metal wastewater. The wastewater is leaked into rivers and lakes, which can cause serious heavy metal pollution of water bodies. Heavy metals cannot be degraded by microorganisms, can be accumulated for a long time in a ecological environment, and can form a threat to human health through biological enrichment. Therefore, efficient removal of heavy metals from wastewater is imperative. At present, various technologies have been developed for removing heavy metal ions from wastewater, including adsorption, chemical precipitation, membrane separation, ion exchange, electrochemical methods, and the like. The adsorption method has the characteristics of low cost, simple operation and good effect, and is one of the most commonly used technologies. The key to the adsorption process is the choice of adsorbent. Chitosan is a natural high molecular polymer which has wide sources, high efficiency, no toxicity and easy biodegradation, has modifiable sites in the chemical structure, and is regarded as a potential heavy metal adsorption material. However, chitosan has low mechanical strength, is easily swelled, and is difficult to separate from an aqueous solution after adsorption. The chitosan and the magnetic material are compounded, so that the chitosan can be efficiently recovered through an externally applied magnetic field after being used, and the chitosan-magnetic material composite magnetic material is convenient to use, thereby avoiding secondary pollution to water. In order to further improve the adsorption performance, the magnetic chitosan needs to be modified.
The patent with publication number CN105921134A discloses a preparation method of a DTPA-chitosan modified magnetic adsorbent, which is prepared by mixing magnetic particles with chitosan, and then crosslinking and modifying the mixture by using DTPA anhydride. However, the preparation process of the method is complex, the cost is high, the product is in powder form, the specific surface area is low, and the adsorption efficiency is affected. Huang et al (Yaoyao Huang, et al, journal of Hazardous Materials,2022,126856) first prepared magnetic chitosan microspheres by emulsion crosslinking and then reacted with an amide to give a DTPA modified magnetic chitosan adsorbent. However, the amino group on the chitosan participates in the crosslinking reaction with glutaraldehyde, so that the grafting rate of the DTPA group in the next step is lower, and the adsorption efficiency is also influenced.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent and a preparation method thereof. The amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent is prepared by a reverse microemulsion crosslinking method, wherein the amino polycarboxylic acid compound not only is a functional group combined with heavy metal ions, but also has the crosslinking effect. The adsorbent has large adsorption capacity to heavy metal ions, good reusability, capability of being recovered by an external magnetic field and good industrial application prospect.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, the method comprising the steps of:
s1: mixing chitosan, amino polycarboxylic acid compound and water, stirring uniformly, and regulating pH to 5-6 with alkali to obtain a mixed solution; ultrasonically mixing the ferroferric oxide nano particles with the mixed solution to obtain a solution a;
s2: mixing and stirring liquid paraffin and span-80 uniformly to obtain a solution b; mixing and stirring the solution a and the solution b uniformly to obtain W/O emulsion;
s3: mixing and stirring carbodiimide and water uniformly to obtain a carbodiimide aqueous solution; mixing and reacting the carbodiimide aqueous solution and the W/O emulsion in an ice-water bath to obtain a reactant; and mixing the reactant with glutaraldehyde water solution, performing crosslinking reaction, separating solid matters by using a magnet, washing, and drying in vacuum to obtain the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent.
According to the present invention, preferably, in step S1, the aminopolycarboxylic acid compound is at least one of diethylenetriamine pentaacetic acid (DTPA), ethylenediamine tetraacetic acid (EDTA), and nitrilotriacetic acid (NTA).
According to the present invention, preferably, in step S1, the ratio of chitosan, aminopolycarboxylic acid compound and water is 1: (1-4): (45-55) g/g/mL; the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
According to the present invention, preferably, in step S1, the mass ratio of the chitosan and the ferroferric oxide nanoparticles is (3-55): 1, a step of; the ultrasonic mixing time is 25-35min.
According to the present invention, preferably, in step S2, the volume ratio of the liquid paraffin to span-80 is (20-15): 1.
preferably, in accordance with the present invention, in step S3,
the carbodiimide is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and/or 1-cyclohexyl-2-morpholinoethyl carbodiimide p-toluenesulfonate;
the ratio of carbodiimide to water is (1.5-3): 2g/mL;
the mass ratio of the carbodiimide to the chitosan in the step S1 is (0.7-6): 1.
according to the present invention, preferably, in step S3, the temperature of the ice water bath is 0 to 5 ℃ and the mixing time in the ice water bath is 10 to 15 hours.
Preferably, in accordance with the present invention, in step S3,
the concentration of the glutaraldehyde water solution is 20-30%;
the volume ratio of the W/O emulsion to the glutaraldehyde aqueous solution is (50-65): 1, a step of;
the temperature of the mixture of the reactant and glutaraldehyde water solution for crosslinking reaction is 20-30 ℃ and the time is 5-8h.
Preferably, in accordance with the present invention, in step S3,
the washing is to wash the solid matters separated by the magnet by at least one of ethanol, petroleum ether and deionized water;
the temperature of the vacuum drying is 35-45 ℃ and the time is 12-36h.
The invention also provides the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent prepared by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent.
The third aspect of the invention provides an application of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent in adsorbing heavy metal ions in water.
The technical scheme of the invention has the following beneficial effects:
the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent can be used for removing heavy metal ions in water. The adsorbent has the advantages of large adsorption capacity, high adsorption speed, stable treatment effect, magnetism, easiness in separation and recovery, repeated utilization and the like, and the preparation process is simple, easy to control and environment-friendly. The adsorbent of the invention is a novel practical adsorbent capable of replacing the traditional adsorbent. Specifically:
(1) The chitosan used in the invention is a biological high molecular polymer, has rich sources, is nontoxic and biodegradable, and does not cause secondary pollution.
(2) The amino polycarboxylic acid compound (such as DTPA, EDTA, NTA) used in the invention is a heavy metal chelating agent, and modification of the amino polycarboxylic acid compound enhances active groups, and grafting and crosslinking the amino polycarboxylic acid compound into the magnetic chitosan can obviously improve the adsorption performance of the adsorbent.
(3) The adsorbent provided by the invention has magnetism, can be quickly recycled by using the magnet, and has good repeated adsorptivity.
(4) The preparation process of the invention is simple, easy to control and environment-friendly.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 shows a preparation route diagram of a preparation method of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent.
Fig. 2 (a) - (B) show SEM images of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent obtained by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent provided in example 1 of the present invention.
FIG. 3 shows the effect of pH on Pb (II) removal by an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent in example 1 of the present invention. (wherein "Removal efficiency" is the removal efficiency and "Initial pH value" is the Initial pH value)
Fig. 4 shows adsorption isotherms of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent obtained by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent provided by the embodiment 1 of the invention on Pb (II) ions. (wherein, "Adsorption capacity" is the adsorption amount and "Equilibrium concentration" is the equilibrium concentration)
Fig. 5 shows a magnetic separation diagram of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent obtained by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent according to the embodiment 1 of the invention from an aqueous solution.
Fig. 6 shows a recycling performance diagram of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent obtained by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent provided by the embodiment 1 of the invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a preparation method of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, which comprises the following steps:
s1: dispersing 0.4g of chitosan and 1.5g of DTPA in 20mL of deionized water, and adjusting the pH to 5 by using sodium hydroxide to obtain a mixed solution; will be 0.08gFe 3 O 4 Dispersing nano particles in the 22g mixed solution, and carrying out ultrasonic vibration for 30 minutes to obtain a solution a;
s2: 3mLspan-80 and 57mL of liquid paraffin were mixed and stirred well to obtain a solution b. Slowly dripping 22g of solution a into solution b, and fully stirring to obtain W/O emulsion;
s3: 2.4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved in 2mL of cold water (0-5 ℃ C.) to give an aqueous carbodiimide solution; mixing the carbodiimide aqueous solution and the W/O emulsion in an ice water bath (0-5 ℃) and reacting for 12 hours to obtain a reactant; and (3) stirring the reactant and 1.5mL (the volume ratio of the W/O emulsion to the glutaraldehyde aqueous solution is 53.3:1) of 25% glutaraldehyde aqueous solution for 6 hours at 25 ℃, separating solid matters by using a magnet, washing by using ethanol, petroleum ether and deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the DTPA modified magnetic chitosan microsphere adsorbent.
Preparing Pb (II) ion solution with initial concentration of 15-1000mg/L, pouring 10ml Pb (II) ion solutions with different initial concentrations into a screw centrifuge tube, adding 10mg of the prepared DTPA modified magnetic chitosan microsphere adsorbent, sealing the centrifuge tube, placing the centrifuge tube in a constant-temperature water bath oscillating box, adjusting the temperature to 25 ℃, oscillating at 175rpm, and measuring the concentration of residual Pb (II) ions by an atomic absorption method after oscillating for 24 hours.
FIG. 2 is a scanning electron microscope image of an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent. As can be seen from FIG. 2, the adsorbent is spherical particles, the size is about 1.5-3 mu m, and the surface is smooth.
FIG. 3 shows the effect of different pH on Pb (II) removal by aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbents. As can be seen from fig. 3, the removal rate of Pb (II) by the aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent gradually increases with increasing pH, and still has a good removal effect under low pH conditions (ph=2-3), which means that the adsorbent can be used in a more acidic environment.
FIG. 4 is an adsorption isotherm of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent to Pb (II) ions. It can be seen that the maximum adsorption amount of Pb (II) ions by the adsorbent material was 214mg/g. In addition, the adsorption process accords with a Langmuir adsorption isothermal model, which shows that the adsorption process of the adsorbent disclosed by the invention on Pb (II) ions is mainly monolayer adsorption.
Fig. 5 is a magnetic separation picture of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, and as can be seen from fig. 5, the material can be adsorbed by a magnet, so that solid-liquid separation is realized.
FIG. 6 is a graph showing the recycling performance of the aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent. As can be seen from fig. 6, after 5 consecutive adsorption-desorption cycle experiments, the removal rate of the adsorbent was not significantly reduced, but was still 82% of the initial adsorption capacity, indicating that the adsorbent had good multiplexing performance.
Example 2
The embodiment provides a preparation method of an amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, which comprises the following steps:
s1: dispersing 2g of chitosan and 7.5g of DTPA in 100mL of deionized water, and adjusting the pH to 5 by using sodium hydroxide to obtain a mixed solution; will be 0.04g Fe 3 O 4 Dispersing nano particles in the 22g mixed solution, and carrying out ultrasonic vibration for 30 minutes to obtain a solution a;
s2: 3mLspan-80 and 57mL of liquid paraffin were mixed and stirred well to obtain a solution b. Slowly dripping 22g of solution a into solution b, and fully stirring to obtain W/O emulsion;
s3: 1.7g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved in 2mL of cold water (0-5 ℃ C.) to give an aqueous carbodiimide solution; mixing the carbodiimide aqueous solution and the W/O emulsion in an ice water bath (0-5 ℃) and reacting for 12 hours to obtain a reactant; and (3) stirring the reactant and 1.5mL (the volume ratio of the W/O emulsion to the glutaraldehyde aqueous solution is 53:1) of 25% glutaraldehyde aqueous solution for 6 hours at 25 ℃, separating solid matters by using a magnet, washing by using ethanol, petroleum ether and deionized water, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the DTPA modified magnetic chitosan microsphere adsorbent.
Preparing Pb (II) ion solution with initial concentration of 370mg/L, pouring 10ml Pb (II) ion solution with initial concentration into a screw centrifuge tube, adding 10mg of the prepared DTPA modified magnetic chitosan microsphere adsorbent, sealing the centrifuge tube, placing the centrifuge tube into a constant-temperature water bath oscillating box, adjusting the temperature to 25 ℃, oscillating at 175rpm for 24 hours, and measuring the concentration of the residual Pb (II) ion by an atomic absorption method to obtain the adsorption quantity of 120mg/g.
Example 3
The present embodiment provides a method for preparing an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, which is different from embodiment 2 only in that:
in S1, 0.08g of Fe 3 O 4 Dispersing nano particles in 22g of mixed solution, and carrying out ultrasonic vibration for 30 minutes to obtain solution a;
the static adsorption test was the same as in example 2, giving an adsorption amount of 130mg/g.
Example 4
The present embodiment provides a method for preparing an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, which is different from embodiment 2 only in that:
s1: 0.4g chitosan and 0.8g EDTA were dispersed in 20mL deionized water.
The static adsorption test differs from example 2 only in that: a Cu (II) ion solution with an initial concentration of 100mg/L was prepared, yielding an adsorption capacity of 85mg/g.
Example 5
The present embodiment provides a method for preparing an aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent, which is different from embodiment 2 only in that:
s1: 0.4g chitosan and 0.5g NTA were dispersed in 20mL deionized water.
The static adsorption test differs from example 2 only in that: a Cu (II) ion solution with an initial concentration of 100mg/L was prepared, yielding an adsorption capacity of 80mg/g.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. The preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent is characterized by comprising the following steps of:
s1: mixing chitosan, amino polycarboxylic acid compound and water, stirring uniformly, and regulating pH to 5-6 with alkali to obtain a mixed solution; ultrasonically mixing the ferroferric oxide nano particles with the mixed solution to obtain a solution a;
s2: mixing and stirring liquid paraffin and span-80 uniformly to obtain a solution b; mixing and stirring the solution a and the solution b uniformly to obtain W/O emulsion;
s3: mixing and stirring carbodiimide and water uniformly to obtain a carbodiimide aqueous solution; mixing and reacting the carbodiimide aqueous solution and the W/O emulsion in an ice-water bath to obtain a reactant; and mixing the reactant with glutaraldehyde water solution, performing crosslinking reaction, separating solid matters by using a magnet, washing, and drying in vacuum to obtain the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent.
2. The method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent according to claim 1, wherein in step S1, the aminopolycarboxylic acid compound is at least one of diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid and nitrilotriacetic acid;
the ratio of chitosan, amino polycarboxylic acid compound and water is 1: (1-4): (45-55) g/g/mL; the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
3. The preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent according to claim 1, wherein in the step S1, the mass ratio of the chitosan to the ferroferric oxide nanoparticle is (3-55): 1, a step of; the ultrasonic mixing time is 25-35min.
4. The method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent according to claim 1, wherein in the step S2, the volume ratio of the liquid paraffin to span-80 is (20-15): 1.
5. the method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent as claimed in claim 1, wherein, in the step S3,
the carbodiimide is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and/or 1-cyclohexyl-2-morpholinoethyl carbodiimide p-toluenesulfonate;
the ratio of carbodiimide to water is (1.5-3): 2g/mL;
the mass ratio of the carbodiimide to the chitosan in the step S1 is (0.7-6): 1.
6. the method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent according to claim 1, wherein in the step S3, the temperature of the ice water bath is 0-5 ℃ and the mixing time in the ice water bath is 10-15h.
7. The method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent as claimed in claim 1, wherein, in the step S3,
the concentration of the glutaraldehyde water solution is 20-30%;
the volume ratio of the W/O emulsion to the glutaraldehyde aqueous solution is (50-65): 1, a step of;
the temperature of the mixture of the reactant and glutaraldehyde water solution for crosslinking reaction is 20-30 ℃ and the time is 5-8h.
8. The method for preparing an aminopolycarboxylic acid compound-modified magnetic chitosan microsphere adsorbent as claimed in claim 1, wherein, in the step S3,
the washing is to wash the solid matters separated by the magnet by at least one of ethanol, petroleum ether and deionized water;
the temperature of the vacuum drying is 35-45 ℃ and the time is 12-36h.
9. The amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent prepared by the preparation method of the amino polycarboxylic acid compound modified magnetic chitosan microsphere adsorbent of any one of claims 1-8.
10. The use of the aminopolycarboxylic acid compound modified magnetic chitosan microsphere adsorbent of claim 9 for adsorbing heavy metal ions in water.
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