CN107282013A - The porous magnetic chitosan gel rubber microballoon and preparation method of a kind of size tunable - Google Patents
The porous magnetic chitosan gel rubber microballoon and preparation method of a kind of size tunable Download PDFInfo
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- CN107282013A CN107282013A CN201610198092.8A CN201610198092A CN107282013A CN 107282013 A CN107282013 A CN 107282013A CN 201610198092 A CN201610198092 A CN 201610198092A CN 107282013 A CN107282013 A CN 107282013A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 75
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 238000007747 plating Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 238000010952 in-situ formation Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 229910021642 ultra pure water Inorganic materials 0.000 claims 1
- 239000012498 ultrapure water Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002354 radioactive wastewater Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 35
- 239000011806 microball Substances 0.000 description 17
- 229910001385 heavy metal Inorganic materials 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 10
- 239000011805 ball Substances 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and substantially Substances 0.000 description 1
- 229940058573 b-d glucose Drugs 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/28014—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
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/28047—Gels
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
Abstract
The invention provides a kind of porous magnetic chitosan gel rubber microballoon of size tunable based on co-precipitation principle in situ and preparation method, including following key step：1、Fe2+、Fe3+Forerunner, which is prepared, with the complex reaction of chitosan mixed solution induces pre- colloidal sol；2nd, pre- colloidal sol is added drop-wise to co-precipitation generation nanometer Fe in the alkaline soak containing NaOH, sodium citrate etc. dropwise3O4；3rd, pre- colloidal sol, which is crosslinked, reacts and solidifies, and the chitosan gel rubber microballoon after crosslinking is in porous network structure, Fe3O4It is uniformly distributed wherein.Chitosan gel rubber microspherulite diameter size is controlled by adjusting wriggling revolution speed and solution concentration.Chitosan gel rubber microballoon hole made from this method is abundant, specific surface area is big, adsorptivity and acid resistance are strong, with preparation method is simple, material source is extensive, with low cost, easily separated recovery, non-secondary pollution the features such as.Enriching and recovering and pollution amelioration of the present invention available for metal in mine, smeltery, Electronics Factory, waste water from plating plant and radioactive wastewater.
Description
Technical field
The invention belongs to environment functional material field, be related to a kind of size tunable porous magnetic chitosan gel rubber microballoon and
Preparation method.
Background technology
The features such as heavy metal has big toxicity, difficult degradation and is easily enriched with vivo, to ecological environment and health
Cause greatly harm [1].At present, process for treating heavy-metal waste water mainly has chemical method, physical-chemical process, bioanalysis [2].
Wherein, chemical method and physical-chemical process treatment effeciency are higher, using relatively broad [3], but it has secondary pollution and to low dense
Spend the poor limitation of heavy metal containing wastewater treatment effect.By contrast, biosorption process is so that its treatment effeciency is high, reaction is thorough, nothing
The advantages such as secondary pollution are gradually paid close attention to [4] by researcher.Gone using the enrichment of the natural biomass materials such as chitosan in water removal
Low-concentration heavy metal research is increasingly active [5].
Chitosan (Chitosan) is the product that the chitin being widely present by nature passes through obtained by deacetylation,
Chemical name is Chitosan (1-4) -2- amino-B-D glucose, is the unique a kind of natural alkaline polysaccharide having now been found that,
It is also the second largest renewable resource [6] that cellulose is only second in nature.With wide material sources, environment-friendly, degradable etc.
Advantage [7], is widely used [8] in fields such as medicine, food, chemical industry, environment.It is used as typical natural biological high score
A large amount of amino in son, chitosan molecule（C2）, hydroxyl（C6）Isoreactivity group, can pass through chelating, ion exchange or formation
Heavy metal [9] in ion Peer adsorption and enrichment water.Because chitosan is easily protonated in an acidic solution, the trip of formation
Amorph amino can lose the coordination ability of heavy metal, directly affect the adsorption effect of chitosan heavy metal.Therefore, people is studied
Member attempts that chitosan is carried out into intramolecular under given conditions or intermolecular cross-linking is modified.Chitosan crosslinked product can not only be carried
The adsorption capacity of high heavy metal ion, also can obviously improve the mechanical performance of chitosan itself and acid-soluble [10], can also carry
High anti-degradability, enhancing stability of molecule [11].In order to reach the purpose of cycling and reutilization, adsorbent mechanical strength is improved, closely
Year chitosan magnetic micro-sphere has been widely applied to every field [12] as a kind of novel and multifunctional composite.
At present, chitosan magnetic micro-sphere preparation method mainly has simple investment, suspension polymerization, emulsion polymerization and divided
Dissipate copolyreaction method etc..The big multipair reaction preparation condition of these methods requires high [13], or need to be complete by complicated preparation flow
Into the preparation [14] of gel micro-ball, not only prepare that cost is high, and need in preparation process to use emulsifying agent, crosslinking agent,
The poisonous and hazardous chemical reagent such as initiator [15] has the potential hazard [16] of secondary pollution to environment.Actually should simultaneously
Limited with the form of middle sorbent suspension, the adsorbents of specific dimensions is only applicable to particular case processing, and due to acid resistance compared with
Difference, is unsuitable for the processing to acid waste water, there is certain limitation in the application.Therefore, select a kind of to environment potential hazard
Small, method with low cost prepares that a kind of performance is stable, acid resistance is stronger, applied widely, size tunable magnetic crust gathers
Sugared gel micro-ball is the emphasis and difficulties in natural biomass adsorbent preparation field urgent need to resolve.
Bibliography：
[1] Hu Man, Wang Xianglan modification of chitosan are to Study on adsorption properties [J] Agriculture of Anhui science of lead, 2012,07:
4208-4209+4212.
[2] Zhang Junli, Zhang Yan, Pan Qing ability synthesize chitosan/DNS hybrid materials and Adsorption of Heavy Metals Pb ~ (2+) performance is ground
Study carefully [J] and apply chemical industry, 2011,02: 225-228.
[3] Ministry of Chemical Industry's Environment Protection Design technique center station, environmental protection design manual [M], the .1998 of volume 6:
Beijing：Chemical Industry Press
[4] adsorbent for heavy metal new system progress [J], food research in Li Jianzhen, Hao's neck younger brother's efficient removal water
With exploitation, 2010,09: 215-218.
[5] Zang Yunbo, the influence [J] of the military of resistance to English Chitosan-phospholipid complex heavy metal ionic adsorption performance, Agriculture In Hubei Province
Science, 2013,01:5-8+18.
[6] [J] is studied in Li Wei, Wu Xiaomeng, absorption of the Anguo honor .N- carboxymethyl chitosans to chromium ion, Qinghai science and technology,
2011,03:68-70.
[7]MajetiN , R.K. V.A review of chitin and chitosan applications[J],
Reactive and Functional Polymers, 2000. 46,1: 1-27.
[8] research of Feng Lifan, Cheng Aihua, Liu Yan girl's cross-linked chitosan Adsorption of Heavy Metals ions is with applying [J], Chinese Resources
Comprehensive utilization, 2012,11:46-50.
[9]Nan, L. B. Renbi.A novel amine-shielded suiface cross-linking of
chitosan hydrogel beads for enhanced metal adsorption performance[J],
Reactive and Functional Polymers, 2005,44: 6692-6700.
[10] stone light, Yuan Yanchao, the old bright structure of cross-linked chitosans and its absorption property to different metal ions such as harvest
[J], applied chemistry, 2005,02:195-199.
[11] Xing Yun, Li Sujuan, Lee walk absorption property and Exploration of Mechanism [J] of the sea cross-linked chitosans to common metal ion,
Metallurgical analysis, 2014,09:58-65.
[12]Xiaowang Liu, Q.H., Zhen Fang,XiaojunZhang,andBeibei Zhang, Magnetic
chitosan nanocomposites a useful recyclable tool for heavy metal ion removal
[J]. Langmuir, 2009. 25(1):3-8.
[13]Zhou, L., et al., Adsorption of platinum(IV) and palladium(II) from
aqueous solution by magnetic cross-linking chitosan nanoparticles modified
with ethylenediamine[J]. J Hazard Mater,2010. 182(1-3):518-24.
[14]Vo, D.-T., C.G. Whiteley, and C.-K. Lee,Hydrophobically Modified
Chitosan-Grafted Magnetic Nanoparticles for Bacteria Removal[J]. Industrial &
Engineering Chemistry Research, 2015. 54(38): p. 9270-9277.
[15]Bagheri, M., et al., Application of chitosan-citric acid
nanoparticles for removal of chromium (VI)[J]. Int J BiolMacromol,2015. 80:
431-44.
[16]Mi, F.L., S.J. Wu, and Y.C. Chen, Combination of carboxymethyl
chitosan-coated magnetic nanoparticles and chitosan-citrate complex gel beads
as a novel magnetic adsorbent[J]. CarbohydrPolym,2015. 131: 255-63.。
The content of the invention
Technical problem solved by the invention is that providing a kind of size tunable porous magnetic chitosan gel rubber microballoon prepares
Method.The gel micro-ball can be as heavy metal ions in wastewater adsorbent, and substantially, acid resistance is strong for its inner porosity, system
Standby low with processing cost, regenerability is good, ideal treatment effect.
The present invention is achieved by the following technical programs：With Fe2+, Fe3+It is pre- that the chitosan solution that adulterates prepares forerunner's induction
Gel；Chelation by chitosan and metal ion makes Fe2+、Fe3+It is dispersed, the then chitosan after basification
Solidify, utilize original position co-precipitation principle formation nanoscale Fe3O4；Ionic crosslinker sodium citrate is sent out with chitosan simultaneously
Raw cross-linking reaction, forms loose structure.The porous magnetic chitosan gel rubber ball, nanoscale Fe3O4Chitosan is dispersed in coagulate
In the network structure of glue microballoon, the chitosan gel rubber ball acid resistance made it have after good magnetic induction intensity, and crosslinking is bright
It is aobvious to improve.The particle diameter of the porous magnetic chitosan gel rubber ball can be controlled in 100 ~ 5000 μ ms according to actual needs.
The preparation method of the porous magnetic chitosan gel rubber microballoon comprises the following steps.
1）Certain mass chitosan is dissolved in during 2% acetic acid is dissolved in, the chitosan that mass fraction is 1wt% ~ 5wt% is prepared
Colloidal sol.
2）Prepare Fe2+（0.005~0.02M）, Fe3+（0.0025~0.01M）Mixed solution, add chitosan colloidal sol in,
Above-mentioned mixed solution is sufficiently stirred for magnetic stirring apparatus and is changed into kermesinus from glassy yellow, after complex reaction is complete, forerunner's induction is pre-
Colloidal sol, which is prepared, to be completed.
3）Induce pre- colloidal sol to be instilled with peristaltic pump above-mentioned forerunner to be soaked in the alkaline solution prepared in advance, according to reality
Border demand, control drop speed is to control microspherulite diameter, and it is anti-with crosslinking that microballoon completes coprecipitation reaction in situ while balling-up is solidified
Should.
4）The porous magnetic chitosan gel rubber microballoon of gained is collected after separation by externally-applied magnetic field, deionized water rinsing is used
To after neutral, immersion in deionized water is stored for future use.
Step 1）Described in chitosan mass fraction be 3.0 × 105g/mol-1, deacetylation is 80% ~ 95%；
Step 1）Middle chitosan collosol concentration is 1wt% ~ 6wt%；
Step 2）In contain Fe2+Compound can be Fe (NO3)2、FeCl2·4H2O、FeSO4Deng containing at least one of ferrous salt；
It is described to contain Fe3+Compound can be Fe (NO3)3、FeCl3·6H2O、Fe2(SO4)3Deng containing at least one of molysite；
Step 2）Fe in the mixed solution prepared2+（0.1~0.5M）With Fe3+（0.2~1M）Mol ratio be 0.1 ~ 2.0；
Step 3）Described in alkaline soak main component be NaOH, sodium citrate and deionized water；
Step 3）NaOH concentration is 1 ~ 5M, 0.01 ~ 1M of sodium citrate concentration in neutral and alkali soak；
Step 3）Middle this drop of wriggling drop speed is controlled in 0.5 ~ 10ml/min. according to actual needs
Preparation method feature of the present invention is essentially consisted in
Preparation method is simple, prepares with low cost.
Use without poisonous and harmful reagent in environmental protection, preparation process, the generation of non-secondary pollution.
Obtained gel micro-ball can be reclaimed by externally-applied magnetic field, size tunable, and loose structure is obvious, with good
Adsorptivity and acid resistance.
Brief description of the drawings
Accompanying drawing 1 is porous magnetic chitosan gel rubber microballoon photo.
Accompanying drawing 2 is the FTIR spectrum comparison diagram of common chitosan microball and magnetic porous chitosan gel rubber microballoon.
Accompanying drawing 3 is common chitosan microball（A）With porous magnetic chitosan gel rubber microballoon（B）Outward appearance ESEM is contrasted
Figure.
The porous magnetic chitosan internal structure SEM of accompanying drawing 4（SEM）Photo.
Embodiment
The present invention is further illustrated with reference to specific embodiment 1, embodiment 2 and Figure of description.
Example 1：0.4g chitosans are added in beaker, 10 ~ 20ml 2% acetum is added, it is molten with magnetic stirring apparatus
Solution stirring 30min（3000r/min）, prepare and contain Fe simultaneously2+（0.5~1M）、Fe3+The mixed solution of (1 ~ 2M)（Mol ratio is
0.1~2.0）, add chitosan solution and continue to stir 30min（3000r/min）, solution is changed into kermesinus from glassy yellow.Spend from
Sub- water prepares alkaline soaking solution, weighs the sodium hydroxide and sodium citrate of certain mass, makes its concentration in the solution after dissolving
Respectively 1 ~ 5M and 0.01 ~ 1M.Chitosan solution is instilled in above-mentioned alkaline soaking solution dropwise with peristaltic pump, after immersion 24h,
Externally-applied magnetic field separates chitosan magnetic gel micro-ball, is repeatedly rinsed with deionized water until neutral, the magnetic crust obtained gathers
Sugared gel micro-ball immersion stores stand-by in deionized water.By Fourier infrared spectrum, SEM and light microscope are to adsorbent
Functional group and internal structure carry out phenetic analysis（Characterization result is shown in accompanying drawing 2, accompanying drawing 3, accompanying drawing 4）.
Example 2：Take 1mmol/L Pb2+Solution 3ml, adds 0.15g chitosan magnetics gel micro-ball as adsorbent, inhales
After attached 12h, by lead residual concentration in Flame Atomic Absorption Spectrometry Determination solution, its clearance is 1. calculated according to formula.It is logical
Overscanning Electronic Speculum is contrasted before and after being adsorbed to adsorbent（Characterization result is shown in accompanying drawing 4C, accompanying drawing 4D）.
Formula is 1.：Clearance=(Co-Ce)*V/Co*100%
Wherein CoFor initial concentration, CeFor adsorption equilibrium concentration, V is lead solution volume.
It is computed, Pb of the adsorbent to 1mmol/L2+The clearance of solution reaches more than 90%.
Each figure is reflection porous magnetic chitosan gel rubber microballoon optical photograph of different nature, accompanying drawing 1A figures in accompanying drawing 1
Middle gel micro-ball is scattered in beaker bottom, accompanying drawing 1B figures in the case where being acted on without externally-applied magnetic field and added after externally-applied magnetic field, gel micro-ball
The rapid side for being adsorbed to beaker, shows that the adsorbent has good magnetic induction intensity, therefore in actual application
Recovery purpose can be reached to bead by externally-applied magnetic field.Accompanying drawing 1C figures are common chitosan microball and chitosan magnetic gel ball
The deformation situation occurred after being extruded under identical active force.Common chitosan gel rubber ball is crushed completely, porous magnetic chitosan
Gel ball form keeps complete.Accompanying drawing 1D figures are the porous magnetic chitosan microball optical photograph of different-grain diameter, in practical application
In can change its grain size according to different demands regulation to adapt to actual treatment demand.Accompanying drawing 1E figures are chitosan magnetic gel
Internal pore structure figure under ball light microscope.Accompanying drawing 1F figures are particle diameter distribution post before and after chitosan magnetic gel micro-ball is dried
Shape figure and metamorphosis contrast photo.
Accompanying drawing 2 is FTIR spectrum comparison diagram, and infrared spectrum is in 574cm-1Locate for Fe-O shake peak, B, C is here
There is peak value and indicate Fe3O4Presence.1078cm-1Place is the vibrations peak of primary OH.1382cm-1Locate as primary alconol absworption peak,
A, B change less here, it was demonstrated that Fe3O4Introducing do not significantly affect the active function groups of chitosan herein, C is here
Change greatly, it was demonstrated that with active group chelation occurs for lead ion.1419cm-1Locate to shake peak for C-N, A, B becomes here
Change less, but C is changed greatly here, is due to Pb2+Absorption on amino causes displacement.1594cm in A-1Place is C=O
Vibrations peak, 1643cm-1For the vibrations peak of amino, 1598cm is moved to respectively in B-1And 1639cm-1, it is due to citrate
Play in displacement, and B caused by crosslinked action amino peak to weaken, carbonyl peak enhancing, it was demonstrated that crosslinking agent occurs at amino
Effect, reduces part amino, but citrate introduces more carboxylate radicals simultaneously, can also serve as adsorbing function
Group, the absworption peak of the two positions has decrease in C, it was demonstrated that the generation of absorption.2877cm-1And 2923cm-1Belong to-CH and-
CH2Absworption peak, 3430cm in A-1Locate to there occurs displacement here in the absworption peak for-OH and-NH, B, also demonstrate crosslinking anti-
The generation answered.
In accompanying drawing 3 A figures be using same procedure prepare without Fe3O4The common chitosan gel rubber microballoon existed, B figures are
Porous magnetic chitosan gel rubber microballoon, due to having the spy better than common chitosan gel rubber microballoon in chitosan magnetic gel micro-ball
Different loose structure, hence it is evident that it can be seen that A figure gel micro-balls surface is smooth, and B figures are more due to internal void, cause concave-convex surface
It is uneven.
A, B distinguish the gel micro-ball profile scanning electromicroscopic photograph under 45 times and 80 times amplifications in accompanying drawing 4, and C figures are 900 times and put
The netted structural scan electron microscope in inside of big lower porous magnetic chitosan gel rubber microballoon, D figures are to have adsorbed lead after amplifying 1200 times
Visible microsphere porous structure is substantially blocked in chitosan gel rubber microsphere optical microscope figure after ion, figure, and surface is attached
Substantial amounts of aggregate, is combined with Flame Atomic Absorption Spectrometry and results of IR, adsorption reaction is further determined
Generation.
Claims (10)
1. porous magnetic chitosan gel rubber microballoon of a kind of size tunable and preparation method thereof, it is characterised in that using chitosan as base
Material, using sodium citrate as ionic crosslinker, passes through coprecipitation in situ formation Fe3O4And uniformly it is distributed in chitosan network
In structure；The chitosan gel rubber microballoon has good magnetic induction intensity and obvious loose structure, and its particle diameter can basis
Control is needed at 100 ~ 5000 μm.
2. as described in right 1, the preparation method based on porous magnetic chitosan gel rubber microballoon, it is characterised in that including following step
Suddenly：
（1）Under room temperature normal pressure, chitosan is dissolved in 2wt% acetums, 30min is sufficiently stirred for；
（2）Prepare the Fe of certain mol proportion2+And Fe3+Mixed solution, is added in chitosan solution and persistently stirs before 30min preparations
Drive induction colloidal sol；
（3）By step（2）Middle mixed solution is instilled in alkaline soaking solution dropwise with peristaltic pump, co-precipitation generation Fe3O4, colloidal sol
Solidification occurs simultaneously with cross-linking reaction, generates chitosan gel rubber microballoon；
（4）Magnetic gel microballoon is separated by externally-applied magnetic field, with deionized water rinsing to pH6 ~ 7, is stored in standby in ultra-pure water.
3. as described in preparation method in claim 2, it is characterised in that step（1）Middle preferred mass fraction is more than 3.0 × 105g/
mol-1, deacetylation be chitosan more than 80%.
4. as described in preparation method in claim 2, it is characterised in that step（1）Middle chitosan solution concentration be 1wt% ~
6wt%。
5. as described in preparation method in claim 2, it is characterised in that step（2）Fe2+（0.005~0.02M）, Fe3+（0.0025
~0.01M）, Fe2+With Fe3+Mol ratio be 0.1 ~ 2.0.
6. as described in preparation method in claim 2, it is characterised in that step（3）Middle forerunner induces colloidal sol in alkaline solution
Soak time is 12 ~ 24h.
7. as described in preparation method in claim 2, it is characterised in that step（3）Contain NaOH and lemon in neutral and alkali soak
Lemon acid sodium.
8. as described in preparation method in claim 2, it is characterised in that step（3）In can by control peristaltic pump rotating speed and
Strength of fluid controls into porous magnetic chitosan gel rubber microspherulite diameter size, and particle size range is at 100 ~ 5000 μm.
9. as claimed in claim 7, it is characterised in that NaOH concentration is 1 ~ 5M, sodium citrate concentration is 0.01 ~ 1M.
10. having a large amount of natural spaces inside porous magnetic chitosan gel rubber microballoon as claimed in claim 1, it can be used for ore deposit
Metal ion enriching and recovering and pollution amelioration in the waste water such as mountain, smeltery, Electronics Factory, waste water from plating plant and radioactivity.
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