CN105536723A - Preparation method for beta-cyclodextrin grafted and modified attapulgite adsorption material - Google Patents
Preparation method for beta-cyclodextrin grafted and modified attapulgite adsorption material Download PDFInfo
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- CN105536723A CN105536723A CN201610028135.8A CN201610028135A CN105536723A CN 105536723 A CN105536723 A CN 105536723A CN 201610028135 A CN201610028135 A CN 201610028135A CN 105536723 A CN105536723 A CN 105536723A
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- attapulgite
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 80
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 80
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 24
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 24
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 24
- 229960004853 betadex Drugs 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 title abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 230000009257 reactivity Effects 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000013049 sediment Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method for a beta-cyclodextrin grafted and modified attapulgite adsorption material, and belongs to the technical field of new materials. The preparation method comprises the following steps: first, modifying attapulgite by adopting diisocyanate; then, grafting cyclodextrin onto the attapulgite by utilizing the reactivity of an isocyanate group and a hydroxyl group on the beta-cyclodextrin. According to the preparation method, the beta-cyclodextrin is bonded to the surface of the attapulgite through a covalent bond; the bonding strength of the beta-cyclodextrin and the attapulgite is greatly improved; the adsorption material prepared by the preparation method has the adsorption performance of the attapulgite and the inclusion of the beta-cyclodextrin, and has excellent adsorption performance on phenolic pollutants.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of organic surface modifying method of attapulgite, be specially the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin.
Background technology
Attapulgite is a kind of important inorganic non-metallic ore deposit, have 3 D stereo shape skeleton structure, crystal structure inside has a large amount of zeolite channels, and crystals zeolite cavity size is consistent, make it have the effect of molecular sieve, can be used for the absorption of various industrial wastewater.Natural attapulgite exists with the brilliant bundle form of rod, and excellent intergranular assembles formation aggregation, and normal containing some quartz in natural attapulgite clay, and silt etc., these all make its absorption property give full play to.
The cyclic oligomer that cyclodextrin is made up of D (+)-glucopyranose, its molecule is wide at the top and narrow at the bottom, both ends open, hollow tubular article, and inside, chamber is in relative hydrophobicity, and outside is hydrophily due to the gathering of hydroxyl.Cyclodextrin is combined by the hydrophobic organic pollutant envelope of hydrophobic binding sites in gas phase or aqueous phase of molecule inner chamber, thus reaches the object of the Adsorption to organic pollution.Select suitable method by cyclodextrin bonded on attapulgite, utilize attapulgite to the suction-operated of organic pollution and cyclodextrin to the clathration of organic pollution, the composite adsorbing material of absorption property excellence can be developed.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin, and the attapulgite modified absorption property to phenolic comp ' ds pollution obtained by this preparation method is significantly improved.
The present invention is to provide the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin for technical scheme that its technical problem of solution adopts, comprises the following steps:
(1) be scattered in anhydrous organic solvent by attapulgite powder, the mass volume ratio of attapulgite and anhydrous organic solvent counts 1:30-1:60 with g/mL, ultrasonic disperse 30-60min, makes attapulgite be dispersed in anhydrous organic solvent; Then under nitrogen protection, add appropriate vulcabond, after reacting 24-48h under normal temperature, poured into by reactant in carrene, the mass volume ratio of attapulgite and carrene counts 1:50-1:100 with g/mL, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 3-5 time, is dispersed in initial reaction in isopyknic anhydrous organic solvent by sediment again, obtains the attapulgite modified suspension of vulcabond;
(2) beta-schardinger dextrin-is dissolved in 100-200mL80-100 DEG C of anhydrous organic solvent; attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution; after dropping terminates, under nitrogen protection, 80-100 DEG C of reaction 8-12h; after reaction terminates; centrifugation, collecting precipitation, after sediment washs 3-5 time by dimethyl sulfoxide (DMSO), deionized water respectively; at 60-80 DEG C of vacuum drying 8-12h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
Wherein, the anhydrous organic solvent described in step (1) (2) is anhydrous DMF or anhydrous DMA.
Wherein, vulcabond described in step (1) is hexamethylene diisocyanate, PPDI, Toluene-2,4-diisocyanate, one in 4-vulcabond, '-diphenylmethane diisocyanate, wherein the mass ratio of vulcabond and attapulgite is 5:1-10:1.
Wherein, the beta-schardinger dextrin-described in step (2) and attapulgite mass ratio are 5:1-10:1.
As shown from the above technical solution: first the present invention introduces NCO in attapulgite's surface, the reactivity of recycling isocyanates and hydroxyl, by grafted by beta cyclodextrin to attapulgite's surface.
The invention has the beneficial effects as follows:
(1) natural compound sugar is adopted to carry out graft modification to attapulgite, environmental protection.
(2) by the mode of covalent bond, beta-schardinger dextrin-is bonded to recessed soil surface, utilizes the absorption property of attapulgite and the clathration of beta-schardinger dextrin-to improve its absorption property to phenolic comp ' ds pollution.
Detailed description of the invention
Below in conjunction with specific embodiment, in further detail the present invention is described.Should be understood that these embodiments just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1
(1) 1g attapulgite powder is dispersed in the anhydrous DMF of 30mL, ultrasonic disperse 30min, makes attapulgite be dispersed in anhydrous DMF; Then under nitrogen protection, add appropriate hexamethylene diisocyanate, the mass ratio of hexamethylene diisocyanate and attapulgite is 5:1, after reacting 24h, is poured into by reactant in 50mL carrene under normal temperature, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 3 times, is dispersed in the anhydrous N of 30mL by sediment again, in dinethylformamide, obtain the attapulgite modified suspension of vulcabond;
(2) 5g beta-schardinger dextrin-is dissolved in 100mL80 DEG C of anhydrous N; in dinethylformamide, attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 80 DEG C of reaction 12h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 3 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 60 DEG C of vacuum drying 12h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
Comparative example 1
1g attapulgite powder is dispersed in the anhydrous DMF of 30mL, ultrasonic disperse 30min; 5g beta-schardinger dextrin-is dissolved in 100mL80 DEG C of anhydrous N; in dinethylformamide, above-mentioned attapulgite suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 80 DEG C of reaction 12h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 3 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 60 DEG C of vacuum drying 12h.
Embodiment 2
(1) 1g attapulgite powder is dispersed in the anhydrous DMA of 60mL, ultrasonic disperse 60min, makes attapulgite be dispersed in anhydrous DMA; Then under nitrogen protection, add appropriate PPDI, the mass ratio of PPDI and attapulgite is 10:1, after reacting 48h, is poured into by reactant in 100mL carrene under normal temperature, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 5 times, is dispersed in the anhydrous N of 60mL by sediment again, in N-dimethylacetylamide, obtain the attapulgite modified suspension of vulcabond;
(2) 10g beta-schardinger dextrin-is dissolved in 200mL100 DEG C of anhydrous N; in N-dimethylacetylamide, attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 100 DEG C of reaction 8h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 5 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 80 DEG C of vacuum drying 8h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
Comparative example 2
1g attapulgite powder is dispersed in the anhydrous DMA of 60mL, ultrasonic disperse 60min; 10g beta-schardinger dextrin-is dissolved in 200mL100 DEG C of anhydrous N; in N-dimethylacetylamide, above-mentioned attapulgite suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 100 DEG C of reaction 8h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 5 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 80 DEG C of vacuum drying 8h.
Embodiment 3
(1) 1g attapulgite powder is dispersed in the anhydrous DMA of 40mL, ultrasonic disperse 40min, makes attapulgite be dispersed in anhydrous DMA; Then under nitrogen protection, appropriate Toluene-2,4-diisocyanate is added, 4-vulcabond, Toluene-2,4-diisocyanate, the mass ratio of 4-vulcabond and attapulgite is 6:1, after reacting 36h, is poured into by reactant in 80mL carrene under normal temperature, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 4 times, is dispersed in the anhydrous N of 40mL by sediment again, in N-dimethylacetylamide, obtain the attapulgite modified suspension of vulcabond;
(2) 8g beta-schardinger dextrin-is dissolved in 150mL90 DEG C of anhydrous N; in N-dimethylacetylamide, attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 90 DEG C of reaction 10h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 4 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 70 DEG C of vacuum drying 10h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
Embodiment 4
(1) 1g attapulgite powder is dispersed in the anhydrous DMF of 50mL, ultrasonic disperse 50min, makes attapulgite be dispersed in anhydrous DMF; Then under nitrogen protection, add appropriate '-diphenylmethane diisocyanate, the mass ratio of '-diphenylmethane diisocyanate and attapulgite is 8:1, after reacting 30h, is poured into by reactant in 70mL carrene under normal temperature, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 4 times, is dispersed in the anhydrous N of 50mL by sediment again, in dinethylformamide, obtain the attapulgite modified suspension of vulcabond;
(2) 6g beta-schardinger dextrin-is dissolved in 160mL85 DEG C of anhydrous N; in dinethylformamide, attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution, drips after terminating; under nitrogen protection; 85 DEG C of reaction 11h, after reaction terminates, centrifugation; collecting precipitation; after sediment washs 4 times by dimethyl sulfoxide (DMSO), deionized water respectively, at 75 DEG C of vacuum drying 11h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
Embodiment 5
Sorbing material and certain density phenols solution are joined in iodine flask with the weight ratio of 1:250,20 DEG C, after the 60min that vibrates under the condition of 200r/min, at 25 DEG C, centrifugal 30min under the condition of 3000r/min; Get a certain amount of supernatant liquor in colorimetric cylinder, measure its adsorbance with ultraviolet specrophotometer in maximum wavelength place.The computing formula of adsorbance is as follows:
In formula: q
efor equilibrium adsorption capacity (mg/g) C
0for the initial mass concentration (mgL of phenol
-1); C
emass concentration (the mgL of phenol when reaching balance for adsorbing
-1); V is the volume (L) of solution; M is the dosage (g) of adsorbent.Measurement result is as following table.
The attapulgite modified front and back of table 1 are to the adsorption capacity of phenolic compound
Experimental result shows: the attapulgite modified sorbing material of grafted by beta cyclodextrin of the present invention has the performance of attapulgite and beta-schardinger dextrin-concurrently, substantially increases the adsorption capacity of attapulgite to phenols.Comparative example 1, in 2, beta-schardinger dextrin-not with attapulgite covalent bond, materials adsorption performance is suitable with concave convex rod original soil.Gained sorbing material Environmental compatibility of the present invention is good, and high adsorption capacity, in treatment of Organic Wastewater field, has broad application prospects.
Claims (5)
1. the preparation method of the attapulgite modified sorbing material of grafted by beta cyclodextrin, it is characterized in that first adopting vulcabond to carry out modification to attapulgite, then the reactivity of hydroxyl on NCO and beta-schardinger dextrin-is utilized, by grafted by beta cyclodextrin on attapulgite.
2. the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin according to claim 1, is characterized in that: comprise the following steps:
(1) be scattered in anhydrous organic solvent by attapulgite powder, the mass volume ratio of attapulgite and anhydrous organic solvent counts 1:30-1:60 with g/mL, ultrasonic disperse 30-60min, makes attapulgite be dispersed in anhydrous organic solvent; Then under nitrogen protection, add appropriate vulcabond, after reacting 24-48h under normal temperature, poured into by reactant in carrene, the mass volume ratio of attapulgite and carrene counts 1:50-1:100 with g/mL, centrifugation, collecting precipitation, sediment, with after washed with dichloromethane 3-5 time, is dispersed in initial reaction in isopyknic anhydrous organic solvent by sediment again, obtains the attapulgite modified suspension of vulcabond;
(2) beta-schardinger dextrin-is dissolved in 100-200mL80-100 DEG C of anhydrous organic solvent; attapulgite modified for above-mentioned vulcabond suspension is slowly added drop-wise in beta-schardinger dextrin-solution; after dropping terminates, under nitrogen protection, 80-100 DEG C of reaction 8-12h; after reaction terminates; centrifugation, collecting precipitation, after sediment washs 3-5 time by dimethyl sulfoxide (DMSO), deionized water respectively; at 60-80 DEG C of vacuum drying 8-12h, obtain the attapulgite modified sorbing material of grafted by beta cyclodextrin.
3. the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin according to claim 2, it is characterized in that: the anhydrous organic solvent described in step (1) (2) is anhydrous N, dinethylformamide or anhydrous DMA.
4. the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin according to claim 2, it is characterized in that: the vulcabond described in step (1) is hexamethylene diisocyanate, PPDI, Toluene-2,4-diisocyanate, one in 4-vulcabond, '-diphenylmethane diisocyanate, wherein the mass ratio of vulcabond and attapulgite is 5:1-10:1.
5. the preparation method of the attapulgite modified sorbing material of a kind of grafted by beta cyclodextrin according to claim 2, is characterized in that: the beta-schardinger dextrin-described in step (2) and attapulgite mass ratio are 5:1-10:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786748A (en) * | 2018-06-25 | 2018-11-13 | 王秀玲 | A kind of hard shock resistance material for air purification and preparation method thereof |
| CN115350687A (en) * | 2022-08-16 | 2022-11-18 | 青海师范大学 | Attapulgite composite material and preparation method and application thereof |
| CN115350684A (en) * | 2022-08-16 | 2022-11-18 | 青海师范大学 | Modified attapulgite boron adsorbent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058682A (en) * | 2007-05-10 | 2007-10-24 | 复旦大学 | Method of preparing aromatic diamine modified nano concavo-convex stick |
| CN101306344A (en) * | 2008-01-25 | 2008-11-19 | 西北师范大学 | Modified lassalite supported belta-cyclodextrin compound absorbent and preparation method and use thereof |
| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN103585975A (en) * | 2013-10-29 | 2014-02-19 | 江苏大学 | Preparation method of beta-cyclodextrin/mesoporous attapulgite composite adsorbent |
-
2016
- 2016-01-16 CN CN201610028135.8A patent/CN105536723B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058682A (en) * | 2007-05-10 | 2007-10-24 | 复旦大学 | Method of preparing aromatic diamine modified nano concavo-convex stick |
| CN101306344A (en) * | 2008-01-25 | 2008-11-19 | 西北师范大学 | Modified lassalite supported belta-cyclodextrin compound absorbent and preparation method and use thereof |
| CN102443129A (en) * | 2011-10-24 | 2012-05-09 | 常州奥特纳新材料科技有限公司 | Method for preparing attapulgite/polyurethane composite material |
| CN103585975A (en) * | 2013-10-29 | 2014-02-19 | 江苏大学 | Preparation method of beta-cyclodextrin/mesoporous attapulgite composite adsorbent |
Non-Patent Citations (3)
| Title |
|---|
| 冯辉霞等: "甲苯二异氰酸酯改性凹凸棒石的研究及结构表征", 《化学与生物工程》 * |
| 李少光: "壳聚糖固载β-环糊精的制备及应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 闫洁等: "石墨烯／二异氰酸酯／环糊精复合材料的制备及对铜(Ⅱ)测定的应用", 《理化检验-化学分册》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786748A (en) * | 2018-06-25 | 2018-11-13 | 王秀玲 | A kind of hard shock resistance material for air purification and preparation method thereof |
| CN115350687A (en) * | 2022-08-16 | 2022-11-18 | 青海师范大学 | Attapulgite composite material and preparation method and application thereof |
| CN115350684A (en) * | 2022-08-16 | 2022-11-18 | 青海师范大学 | Modified attapulgite boron adsorbent and preparation method and application thereof |
| CN115350684B (en) * | 2022-08-16 | 2023-09-22 | 青海师范大学 | Modified attapulgite boron adsorbent and preparation method and application thereof |
| CN115350687B (en) * | 2022-08-16 | 2023-10-24 | 青海师范大学 | Attapulgite composite material and preparation method and application thereof |
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