CN112774641A - Preparation method of carboxyl modified magnetic starch-based adsorption material - Google Patents
Preparation method of carboxyl modified magnetic starch-based adsorption material Download PDFInfo
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- CN112774641A CN112774641A CN202110038562.5A CN202110038562A CN112774641A CN 112774641 A CN112774641 A CN 112774641A CN 202110038562 A CN202110038562 A CN 202110038562A CN 112774641 A CN112774641 A CN 112774641A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 144
- 235000019698 starch Nutrition 0.000 title claims abstract description 144
- 239000008107 starch Substances 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 96
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 71
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003463 adsorbent Substances 0.000 claims abstract description 69
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- 240000003183 Manihot esculenta Species 0.000 claims description 9
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 244000017020 Ipomoea batatas Species 0.000 claims description 3
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940052223 basic fuchsin Drugs 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- -1 mercury ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
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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
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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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- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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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- Chemical & Material Sciences (AREA)
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- Hydrology & Water Resources (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a carboxyl modified magnetic starch-based adsorbing material, which specifically comprises the following steps: step 1, preparing ferroferric oxide magnetic starch particles; and 2, preparing the carboxyl modified magnetic starch-based adsorbent material according to the product obtained in the step 1. The invention takes starch as a main substrate material, and modifies magnetic starch particles through acrylic acid, so that the carboxyl modified magnetic starch-based adsorbent material has the properties of high adsorption efficiency, insolubility in water and recycling.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and relates to a preparation method of a carboxyl modified magnetic starch-based adsorbing material.
Background
With the continuous promotion of the industrialization process, a large amount of heavy metal ions and dye wastewater enter soil and water along with the discharge of industrial wastewater in the industries of mining and smelting, chemical fertilizer manufacturing, battery manufacturing, electroplating, printing and dyeing textile and the like, and the soil and the water are seriously polluted. The harm of the heavy metal ions is further amplified through the enrichment effect of a food chain, which is not only unfavorable to the health of human beings but also seriously threatens the balance of an ecological system. Chemical precipitation, ion exchange, membrane separation, photocatalysis, biological treatment, ion adsorption and other methods are commonly used for treating industrial wastewater, but the methods have limitations, for example, the chemical precipitation can generate a large amount of sludge which is difficult to treat, the biological treatment has harsh requirements on the environment, the membrane separation needs high operation cost, the photocatalysis treatment process is too slow, and the ion adsorption is widely applied to the treatment of heavy metal wastewater and dye wastewater due to the advantages of wide sources of used materials, simple preparation process, low cost and the like.
Materials commonly used for ion adsorption include: inorganic materials, natural polymer materials, biochar materials, magnetic materials and the like. The starch is a natural high polymer material which is low in cost, green, environment-friendly, renewable and degradable, contains a large amount of active hydroxyl groups and glycosidic bonds, and needs to be modified due to the limitations that the adsorption sites are limited, separation is not easy, and the like. The magnetic material has superparamagnetism, so that the adsorption material can be separated and recovered through an external magnetic field, and compared with the traditional separation methods such as filtration and centrifugation, the magnetic material is more convenient and efficient and has good reutilization performance. The magnetic starch-based adsorption material prepared by chemical modification has more research and application in wastewater treatment.
Chinese patent CN107486178A discloses a preparation method of aminated cross-linked MA/AA grafted xanthate esterified cassava starch magnetic imprinted microspheres and adsorption of lead ions, wherein the preparation method comprises the following steps: firstly, synthesizing aminated cross-linked methyl acrylate/acrylic acid grafted xanthate-esterified cassava starch, and wrapping ferroferric oxide into modified starch by using the composite modified starch derivative in a demulsifying phase solution to synthesize aminated cross-linked AA/MA grafted xanthate-esterified cassava starch magnetic microspheres; with Pb2+Reacting epichlorohydrin as a cross-linking agent under an alkaline condition for marking ions, and then oscillating and desorbing by using EDTA solution with the concentration of 0.1mol/L to prepare the aminated cross-linked MA/AA grafted xanthic acidEsterified cassava starch magnetic imprinted microspheres. The microsphere pair Pb2+The adsorption capacity of the adsorbent reaches 12.68mg/g, Pb2+The removal rate can reach 91.50 percent. The product has the characteristics of identification, specific selectivity, predetermination and the like, and can be used for metal ion adsorption, separation and enrichment.
Chinese patent CN110180517A discloses a preparation method of a starch/polyethyleneimine composite magnetic adsorption material, which comprises the following steps: firstly, carrying out ultrasonic dispersion on a nano carrier ferroferric oxide in 0.125mol/l HCl solution, washing the nano carrier ferroferric oxide for multiple times by using distilled water and absolute ethyl alcohol, and completely removing HCl; secondly, treating the acidified ferroferric oxide with ammonia water, ethyl orthosilicate and hexadecyl trimethyl ammonium bromide to obtain mesoporous ferroferric oxide; then in N2Under protection, pyridine, ammonia water and a silane coupling agent in a certain proportion are mixed and continuously stirred to obtain amino functionalized mesoporous ferroferric oxide; finally, dissolving starch in dimethyl sulfoxide, adding a silane coupling agent, and reacting for 12 hours at 90 ℃ in an argon atmosphere; adding a polyethyleneimine solution, amino functionalized mesoporous ferroferric oxide and glutaraldehyde, and reacting for 12 hours at 60 ℃ to obtain the adsorbent. The adsorbent has high specific surface area and rich functional groups such as hydroxyl, amino and the like, can quickly chelate mercury ions, and is suitable for a continuous flowing water treatment system.
However, in the prior art, starch is gelatinized at a temperature of above 53 ℃, so that a starch base and a composite material thereof are separated, and the adsorption effect is influenced. Meanwhile, in order to increase the active adsorption sites of the starch-based adsorption material and improve the firmness of combination with other base materials, the existing magnetic starch-based modified adsorption material usually uses a large amount of cross-linking agents in the modification process, so that the cost for preparing the magnetic starch-based modified adsorption material is greatly increased, the process is more complicated, and the large-scale application in the treatment of industrial wastewater is difficult to realize.
Therefore, it is an urgent need to solve the problem of developing a method for preparing a magnetic starch-based adsorbing material with low cost, simple process, good durability and high adsorption performance.
Disclosure of Invention
The invention aims to provide a preparation method of a carboxyl modified magnetic starch-based adsorbing material, and the adsorbing material prepared by the method has the properties of high adsorption efficiency, insolubility in water and recycling.
The technical scheme adopted by the invention is that the preparation method of the carboxyl modified magnetic starch-based adsorbing material specifically comprises the following steps:
and 2, preparing the carboxyl modified magnetic starch-based adsorbent material according to the product obtained in the step 1.
The present invention is also characterized in that,
the specific process of the step 1 is as follows: FeSO (ferric oxide) is added4·7H2O、FeCL3·6H2And mixing O, starch, NaOH and a solvent, and then reacting to obtain the ferroferric oxide magnetic starch granules.
In the step 1:
FeSO4·7H2o and FeCl3·6H2The molar ratio of O is 1: 0.5-3;
starch and FeSO4·7H2The molar ratio of O is 0.3-1: 1;
NaOH and FeSO4·7H2The molar ratio of O is 5-20: 1;
FeSO4·7H2the molar ratio of O to the solvent is 1: 150-200.
In the step 1, the starch is at least one of soluble starch, potato starch, sweet potato starch and cassava starch.
The reaction temperature in the step 1 is 80-100 ℃; the reaction time is 2-4 h; the solvent is deionized water.
The specific process of the step 2 is as follows:
and (2) mixing acrylic acid, a monomer, an initiator, a solvent and the ferroferric oxide magnetic starch particles prepared in the step (1) and then reacting to obtain the carboxyl modified magnetic starch-based adsorbent material.
In the step 2:
the initiator is at least one of azodiisobutyronitrile, sodium dodecyl sulfate and potassium persulfate;
the monomer is at least one of hydroxyethyl methacrylate, glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and styrene;
the solvent is tetrahydrofuran.
In the step 2:
the mass of the initiator is 0.1-3% of the mass of the monomer;
the molar ratio of the monomer to the solvent is 1: 5-10;
the molar ratio of the acrylic acid to the monomer is 1: 5-10;
the mass ratio of the ferroferric oxide magnetic starch particles obtained in the step 1 to acrylic acid is 1: 0.5-1.
In the step 2: the reaction temperature is 50-70 ℃; the reaction time is 2-4 h.
The invention has the beneficial effects that the adsorption material has wide use source, low cost and biodegradable starch as the main substrate material, and acrylic acid is used for modifying the magnetic starch particles to generate the water-insoluble recyclable Cu-like material2+、Cr3+、Pb2+、Cd2+The methylene blue, the methyl blue and the basic fuchsin have good adsorption effects on Cu2+The adsorption rate of the adsorbent is up to 96 percent, the maximum adsorption capacity is 130mg/g, the adsorbent can be recycled for 8 times, and the maximum adsorption capacity can still reach 93 percent of the first unit adsorption capacity. The adsorbent material has the advantages of simple preparation process, low cost, recycling and easy separation, and can be widely applied to the treatment of electroplating wastewater, dye wastewater, metal mining, smelting wastewater and the like.
Drawings
Fig. 1 is a graph showing the relationship between the number of recycling times and the regenerable effect of a carboxyl-modified magnetic starch-based adsorbent material according to example 1 of a method for preparing a carboxyl-modified magnetic starch-based adsorbent material according to the present invention;
FIG. 2 shows a preparation method of a carboxyl-modified magnetic starch-based adsorbent material according to example 1 of the present inventionAdsorption time of base adsorbent material and Cu2+Concentration dependence.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of a carboxyl modified magnetic starch-based adsorbent material, which specifically comprises the following steps:
FeSO (ferric oxide) is added4·7H2O、FeCL3·6H2Mixing O, starch, NaOH and a solvent, and then reacting to obtain ferroferric oxide magnetic starch particles, wherein the reaction temperature is 80-100 ℃; the reaction time is 2-4 h; the solvent is deionized water;
FeSO4·7H2o and FeCl3·6H2The molar ratio of O is 1: 0.5-3;
starch and FeSO4·7H2The molar ratio of O is 0.3-1: 1;
NaOH and FeSO4·7H2The molar ratio of O is 5-20: 1;
FeSO4·7H2the molar ratio of O to the solvent is 1: 150-200.
The starch is selected from any one or combination of at least two of soluble starch, potato starch, sweet potato starch and cassava starch;
and 2, preparing the carboxyl modified magnetic starch-based adsorbent material according to the product obtained in the step 1.
The specific process of the step 2 is as follows:
and (2) mixing acrylic acid, a monomer, an initiator, a solvent and the ferroferric oxide magnetic starch particles prepared in the step (1) and then reacting to obtain the carboxyl modified magnetic starch-based adsorbent material.
The monomer is any one or the combination of at least two of hydroxyethyl methacrylate, glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and styrene;
the molar ratio of the acrylic acid to the monomer is 1 (5-10);
the initiator is any one or the combination of at least two of azodiisobutyronitrile, sodium dodecyl sulfate and potassium persulfate;
the mass of the initiator is 0.1-3% of the mass of the monomer;
the solvent is Tetrahydrofuran (THF);
in the step 2, the reaction temperature is 50-70 ℃; the reaction time is 2-4 h; the molar ratio of the monomer to the solvent is 1 (5-10); the mass ratio of the ferroferric oxide magnetic starch particles to the acrylic acid in the step 2 is 1 (0.5-1);
drying and grinding the carboxyl modified magnetic starch-based adsorbent material prepared in the step 2 into powder, and adding the powder into waste liquid for adsorption; the adsorption temperature is 10-80 ℃; the pH value of the adsorption is 1-12; the concentration of the adsorbed waste liquid is 10-200 mg/L; the adsorption time is 5-400 min;
the waste liquid is Cu2+、Cr3+、Pb2+、Cd2+Any one or a combination of at least two of methylene blue, methyl blue and basic fuchsin;
the unit adsorption capacity of the carboxyl modified magnetic starch-based adsorbent material is 90-130 mg/g;
the adsorption rate of the carboxyl modified magnetic starch-based adsorbent material is 80-96%;
the reproducible effect of the carboxyl modified magnetic starch-based adsorbent material is 80-93%;
the carboxyl modified magnetic starch-based adsorbent material prepared by the invention is applied to electroplating wastewater treatment, dye wastewater treatment, chemical fertilizer and pesticide treatment, metal mine exploitation, smelting wastewater treatment and domestic wastewater treatment.
Performing Cu on the carboxyl modified magnetic starch-based adsorbent material obtained in the step 22+And (3) testing the adsorption performance, wherein the test method comprises the following steps: preparing Cu2+Putting 200mL of the solution in a beaker, adding a carboxyl modified magnetic starch-based adsorbent material, stirring, carrying out magnetic separation for 5min, taking the supernatant, and measuring Cu by using an ultraviolet-visible spectrophotometer2+Concentration;
the adsorption temperature is 10-80 ℃;
the pH value of the adsorption is 1-12; preferably, the adsorbed Cu2+The concentration is 10-200 mg/L;
the adsorption time is 5-400 min;
the unit adsorption amount and the removal rate were calculated according to the following formulas.
Unit adsorption amount:
wherein:
Qe: unit adsorption amount, unit mg/g;
c0：Cu2+initial concentration, in mg/L;
cv：Cu2+equilibrium concentration, in mg/L;
v: adsorption solution volume, unit L;
m: mass of adsorbent material in g;
the removal rate is as follows:
wherein:
eta: the removal rate;
c0：Cu2+initial concentration, in mg/L;
cv：Cu2+equilibrium concentration, in mg/L;
and (3) carrying out a regenerable effect test on the carboxyl modified magnetic starch-based adsorbent material obtained in the step (2), wherein the method comprises the following steps:
(1) standard Cu of 20mg/L is prepared2+Putting 200mL of the solution into a beaker, adding 15mg of carboxyl modified magnetic starch-based adsorbent material, stirring at room temperature for 3h, carrying out magnet separation for 5min, removing supernatant, and calculating unit adsorption amount and removal rate;
(2) 0.1mol/L of Na was used2Desorbing 200mL of EDTA solution, stirring for 3h, performing magnetic separation for 5min, and removing the supernatant;
(3) centrifugally washing the desorbed carboxyl modified magnetic starch-based adsorbent material for three times by using a centrifugal machine at 8000r/min, and drying;
the steps (1) - (3) are 1 cycle, 8 cycles are carried out in total, and the regenerable effect of the carboxyl modified magnetic starch-based adsorbent material is calculated according to the following formula;
wherein:
Qi: the unit adsorption amount of the adsorption material in the ith cycle test;
Q1: unit adsorption amount of adsorbent material at 1 st cycle test.
R: and (4) the effect can be regenerated.
Example 1
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO4 & 7H respectively2Dissolving O in 20mL of deionized water to prepare solution A, 1.08g of FeCl3 & 6H2Dissolving O in 20mL of deionized water to prepare a solution B, and dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C; adding 1 weight part of solution A, 2 weight parts of solution B, 3 weight parts of solution C and 0.25g of soluble starch into a flask, stirring, heating to 80 ℃, keeping the temperature for reaction for 2.5 hours, centrifuging, drying and grinding the reaction solution to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 2g of hydroxyethyl methacrylate, 4mL of tetrahydrofuran, 1g of acrylic acid, 0.032g of azobisisobutyronitrile and 0.5g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 65 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 20mg/LCu2+Putting 200mL of the solution in a beaker, adjusting the pH to 7 and the temperature to 60 ℃,adding 15mg of carboxyl modified magnetic starch-based adsorbent material, stirring for 3h, carrying out magnetic separation for 5min, measuring the unit adsorption capacity of 130mg/g, wherein the removal rate is 96%, and the regenerable effect is 86% after 8 cycles.
As shown in fig. 1, the test result is obtained by performing adsorption test on the copper ion solution by using the carboxyl modified magnetic starch-based adsorbent material in example 1. With the increase of the cycle times, the adsorption performance of the carboxyl modified magnetic starch-based adsorbent material is slowly reduced, and after 8 times of cyclic use, the adsorption capacity of the carboxyl modified magnetic starch-based adsorbent material is 86.3% of the adsorption capacity in the first adsorption.
As shown in fig. 2, the test result is obtained by performing an adsorption test on the copper ion solution by using the carboxyl group modified magnetic starch-based adsorbent material in example 1. With the increase of the adsorption time, the concentration of copper ions in the solution gradually decreases and finally tends to be constant. When the adsorption time exceeds 120min, the concentration of copper ions in the solution is almost kept at 2.3mg/L, and the unit adsorption amount of the carboxyl modified magnetic starch-based adsorbent material is 130 mg/g.
Example 2
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO are respectively added4·7H2O is dissolved in 20mL of deionized water to prepare solution A, 1.08g of FeCl3·6H2Dissolving O in 20mL of deionized water to prepare a solution B, and dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C; adding 1 weight part of solution A, 2 weight parts of solution B, 5 weight parts of solution C and 0.3g of soluble starch into a flask, stirring, heating to 80 ℃, keeping the temperature for reaction for 2 hours, centrifuging, drying and grinding the reaction solution to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 2.5g of glycidyl methacrylate, 4mL of tetrahydrofuran, 1g of acrylic acid, 0.032g of azobisisobutyronitrile and 0.25g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 65 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 20mg/LCu2+And (3) putting 200mL of the solution in a beaker, adjusting the pH to 8 and the temperature to 70 ℃, adding 20mg of carboxyl modified magnetic starch-based adsorbent material, stirring for 2 hours, and measuring the unit adsorption quantity of the solution to be 121mg/g, wherein the removal rate is 90 percent, and the regenerable effect is 90 percent after 8 cycles.
Example 3
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO are respectively added4·7H2O is dissolved in 20mL of deionized water to prepare solution A, 1.08g of FeCl3·6H2Dissolving O in 20mL of deionized water to prepare a solution B, dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C, and dissolving 0.7g of soluble starch; adding 1 part by weight of the solution A, 0.5 part by weight of the solution B and 3 parts by weight of the solution C into a flask, stirring and heating to 70 ℃, keeping the temperature for reaction for 2.5 hours, taking the reaction solution, centrifuging, drying and grinding to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 5g of glycidyl methacrylate, 4mL of tetrahydrofuran, 0.5g of acrylic acid, 0.032g of azobisisobutyronitrile and 0.2g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 65 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 30mg/LCu2+And (3) putting 200mL of the solution in a beaker, adjusting the pH to 6 and the temperature to 30 ℃, adding 15mg of the carboxyl modified magnetic starch-based adsorbent material, stirring for 3 hours, and measuring the unit adsorption quantity of 113mg/g, wherein the removal rate is 84 percent and the regenerable effect is 80 percent after 8 cycles.
Example 4
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO are respectively added4·7H2O is dissolved in 20mL of deionized water to prepare solution A, 1.08g of FeCl3·6H2Dissolving O in 20mL of deionized water to prepare a solution B, and dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C; adding 1 weight part of solution A, 3 weight parts of solution B, 3 weight parts of solution C and 0.2g of soluble starch into a flask, stirring, heating to 80 ℃, keeping the temperature for reaction for 3 hours, centrifuging, drying and grinding the reaction solution to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 1g of methyl methacrylate, 4mL of tetrahydrofuran, 0.8g of acrylic acid, 0.05g of sodium dodecyl sulfate and 0.5g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 65 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 20mg/LCu2+And (3) putting 200mL of the solution in a beaker, adjusting the pH to 5 and the temperature to 70 ℃, adding 30mg of carboxyl modified magnetic starch-based adsorbent material, stirring for 3 hours, and measuring that the unit adsorption amount is 117mg/g, the removal rate is 87%, and the regenerable effect is 82% after 8 cycles.
Example 5
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO are respectively added4·7H2O is dissolved in 20mL of deionized water to prepare solution A, 1.08g of FeCl3·6H2Dissolving O in 20mL of deionized water to prepare a solution B, and dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C; adding 1 part by weight of the solution A, 2 parts by weight of the solution B, 3 parts by weight of the solution C and 0.2g of cassava starch into a flask, stirring, heating to 80 ℃, keeping the temperature for reaction for 2.5 hours, centrifuging, drying and grinding the reaction solution to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 1g of hydroxyethyl methacrylate, 4mL of tetrahydrofuran, 1g of acrylic acid, 0.032g of azobisisobutyronitrile and 0.5g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 70 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 15mg/LCu2+And (3) putting 200mL of the solution in a beaker, adjusting the pH to 7 and the temperature to 50 ℃, adding 15mg of carboxyl modified magnetic starch-based adsorbent material, stirring for 2 hours, and measuring that the unit adsorption amount is 124mg/g, the removal rate is 92 percent, and the regenerable effect is 93 percent after 8 cycles.
Example 6
A carboxyl modified magnetic starch-based adsorbent material is prepared by the following steps:
1) preparing ferroferric oxide magnetic starch granules: 1.12g of FeSO are respectively added4·7H2O is dissolved in 20mL of deionized water to prepare solution A, 1.08g of FeCl3·6H2Dissolving O in 20mL of deionized water to prepare a solution B, and dissolving 4g of NaOH in 100mL of deionized water to prepare a solution C; adding 1 part by weight of the solution A, 2 parts by weight of the solution B, 3 parts by weight of the solution C and 1g of cassava starch into a flask, stirring and heating to 80 ℃, keeping the temperature for reaction for 2.5 hours, centrifuging, drying and grinding the reaction solution to obtain ferroferric oxide magnetic starch particles;
2) preparation of carboxyl modified magnetic starch-based adsorbent material: adding 2.5g of hydroxyethyl methacrylate, 4mL of tetrahydrofuran, 1g of acrylic acid, 0.032g of azobisisobutyronitrile and 0.5g of starch-based ferroferric oxide particle powder into a sealed flask with air exhausted, heating to 65 ℃, keeping the temperature for reaction for 2 hours, and drying the reaction solution to obtain a carboxyl modified magnetic starch-based adsorbent material;
3) cu of carboxyl modified magnetic starch-based adsorbent material2+And (3) testing the adsorption performance: preparing 50mg/LCu2+And (3) putting 200mL of the solution in a beaker, adjusting the pH to 6 and the temperature to 30 ℃, adding 15mg of carboxyl modified magnetic starch-based adsorbent material, stirring for 3 hours, measuring the unit adsorption capacity of 98mg/g, wherein the removal rate is 73 percent, and the regenerable effect is 86 percent after 8 cycles.
Cu was performed on the adsorbents in examples 1 to 62+Adsorption property ofThe regeneration effect was measured, and the results are shown in table 1.
TABLE 1
The data in table 1 show that the carboxyl modified magnetic starch-based adsorbent materials provided in examples 1 to 6 of the present invention can be used for adsorption of heavy metal ions, the unit adsorption amount reaches 90 to 130mg/g, the removal rate reaches 80 to 96%, the 8-cycle regenerable effect reaches 80 to 93%, and the materials can be applied to wastewater treatment of electroplating wastewater, dye wastewater, metal mine mining and smelting, and the like.
Claims (9)
1. A preparation method of a carboxyl modified magnetic starch-based adsorption material is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, preparing ferroferric oxide magnetic starch particles;
and 2, preparing the carboxyl modified magnetic starch-based adsorbent material according to the product obtained in the step 1.
2. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 1, characterized in that: the specific process of the step 1 is as follows: FeSO (ferric oxide) is added4·7H2O、FeCL3·6H2And mixing O, starch, NaOH and a solvent, and then reacting to obtain the ferroferric oxide magnetic starch granules.
3. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 2, characterized in that: in the step 1:
FeSO4·7H2o and FeCl3·6H2The molar ratio of O is 1: 0.5-3;
starch and FeSO4·7H2The molar ratio of O is 0.3-1: 1;
NaOH and FeSO4·7H2The molar ratio of O is 5-20: 1;
FeSO4·7H2the molar ratio of O to the solvent is 1: 150-200.
4. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 2, characterized in that: in the step 1, the starch is at least one of soluble starch, potato starch, sweet potato starch and cassava starch.
5. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 2, characterized in that: the reaction temperature in the step 1 is 80-100 ℃; the reaction time is 2-4 h; the solvent is deionized water.
6. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 1, characterized in that: the specific process of the step 2 is as follows:
and (2) mixing acrylic acid, a monomer, an initiator, a solvent and the ferroferric oxide magnetic starch particles prepared in the step (1) and then reacting to obtain the carboxyl modified magnetic starch-based adsorbent material.
7. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 6, characterized in that: in the step 2:
the initiator is at least one of azodiisobutyronitrile, sodium dodecyl sulfate and potassium persulfate;
the monomer is at least one of hydroxyethyl methacrylate, glycidyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate and styrene;
the solvent is tetrahydrofuran.
8. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 7, characterized in that: in the step 2:
the mass of the initiator is 0.1-3% of the mass of the monomer;
the molar ratio of the monomer to the solvent is 1: 5-10;
the molar ratio of the acrylic acid to the monomer is 1: 5-10;
the mass ratio of the ferroferric oxide magnetic starch particles obtained in the step 1 to acrylic acid is 1: 0.5-1.
9. The preparation method of the carboxyl modified magnetic starch-based adsorbing material according to claim 8, wherein the preparation method comprises the following steps: in the step 2: the reaction temperature is 50-70 ℃; the reaction time is 2-4 h.
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