CN105727907A - Magnetic persimmon tannin composite adsorption material and preparing method thereof - Google Patents
Magnetic persimmon tannin composite adsorption material and preparing method thereof Download PDFInfo
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- CN105727907A CN105727907A CN201610223056.2A CN201610223056A CN105727907A CN 105727907 A CN105727907 A CN 105727907A CN 201610223056 A CN201610223056 A CN 201610223056A CN 105727907 A CN105727907 A CN 105727907A
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- 235000018553 tannin Nutrition 0.000 title claims abstract description 60
- 239000001648 tannin Substances 0.000 title claims abstract description 60
- 229920001864 tannin Polymers 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 58
- 235000011511 Diospyros Nutrition 0.000 title claims abstract description 54
- 244000236655 Diospyros kaki Species 0.000 title claims abstract description 54
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 9
- 229920001661 Chitosan Polymers 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract 3
- 230000005298 paramagnetic effect Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 15
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 229920002125 Sokalan® Polymers 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000004584 polyacrylic acid Substances 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 102000008186 Collagen Human genes 0.000 claims description 5
- 108010035532 Collagen Proteins 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229920001436 collagen Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 238000003980 solgel method Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052770 Uranium Inorganic materials 0.000 description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 4
- 229910052776 Thorium Inorganic materials 0.000 description 4
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- -1 formalin aldehyde Chemical class 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a magnetic persimmon tannin composite adsorption material and a preparing method thereof.According to the material, persimmon tannin serves as a main adsorption functional component, nanometer Fe3O4 particles serve as a magnetic functional component, and materials suck as chitosan and graphene can be selected as a loading (or cross linking) matrix of the adsorption component and the magnetic component.Magnetic nanometer particles are loaded on the surface of the matrix material with a reversed phase suspension method; solidification of persimmon tannin on the matrix material is achieved through a cross-linking reaction.The materials such as graphene, and the persimmon tannin material are used in combination, and thus a remarkable synergistic promoting effect is achieved on the adsorption performance of the magnetic persimmon tannin composite adsorption material; the material has very good adsorption capability on heavy metal ions, and can be applied to removal of heavy metal ions under the special conditions such as fluid pipeline dead corner retention and containers with complex shapes due to the paramagnetic property of the material.The material has the advantages of being high in stability and environment withstanding capability, high in yield, low in cost, extremely high in adsorption capacity, easy to separate and recycle, free of secondary pollution and the like.
Description
Technical field
The present invention relates to adsorbing material field, magnetic persimmon tannin adsorption material being specially a kind of green high-efficient and preparation method thereof.
Background technology
Persimmon tannin has wide material sources and easily gathers, and tannin relative amount is high, contained tannin phenolic hydroxyl group large percentage, and the recovery for metal ion has and obvious effect.Sakaguchi etc. adopt persimmon tannin absorption, reclaim the result of study of uranium (U) and thorium (Th), find to solidify persimmon tannin the adsorption efficiency of thorium (Th) is significantly high, 18.4mg adsorbent can at the thorium (Th) of 1h internal adsorption 100mL9.3mg/L, and absorption uranium (U) and thorium (Th) all easily by dilute hydrochloric acid and dilute sulfuric acid desorbing.AkiraNakajima etc. utilize the uranium (U) solidifying persimmon tannin absorption, reclaiming in uranium refining wastewater, it has been found that the mass concentration of uranium (U) all can be adsorbed by 100% within the scope of 1～50mg/L；The hydrochloric acid of 0.1mol/L can more fully will absorption uranium (U) desorbing, and desorbing do not result in adsorbent absorbability decline.Solidification persimmon tannin material is utilized to carry out the technical research that indium in indium extraction process/ferrum separates, its Selective Separation effect is obvious, the research of absorption precious metal ion is carried out also with persimmon tannin material, wherein the adsorbance of silver reaches 320mg/g, the adsorbance of gold reaches 2374mg/g, plumbous adsorbance is 186mg/g, and the adsorbance of chromium is 49.01mg/g, and the adsorbance of cadmium is 143mg/g.But research before this is only limitted to simply extract test for tannic material, it does not have deep processing targetedly, rests on original discovery test phase, it is necessary to carry out deeper research.Further investigations have shown that, persimmon tannin adsorbing material is administered at heavy metal containing wastewater treatment, heavy-metal contaminated soil, is had the fields such as valency precious and rare metals recovery to have a extensive future.
Biomass absorbent material has the advantage such as abundance, low, nontoxic, the non-secondary pollution of processing cost and receives much concern, but its separation and recovery difficulty restricts its application always.It is a kind of effective solid-liquid separating method that Magnetic guidance separates, and under additional the action of a magnetic field, the separation of solid liquid phase is simple, saves process links during the consumption energy consumptions such as centrifugal filtration, and the magnetic adsorbent therefore with magnetic effect can overcome a difficult problem for solid-liquid separation.Simultaneously, actual industrial production exists some shapes are special, is difficult to some workpiece area of touching, such as fluid line bent angle, special shape reactor (container), nuclear reaction storehouse etc., often it is difficult to adopt conventional method be carried out and dispose, and the cleaning in these places and the removal of polluted heavy metals ion can be realized with magnetic high-efficiency adsorbent under the traction control of external magnetic field.Therefore, exploitation has the sorbent material of magnetic effect, high adsorption capacity, high stability, has wide application and market popularization value.
Summary of the invention
The technical problem to be solved magnetic persimmon tannin composite adsorbing material being to provide a kind of green high-efficient and preparation method thereof, this material heavy metal ion has good absorbability, the magnetic effect that material has can ensure efficiently separating of the aqueous solution of adsorbing material and disposal, and the removal (or enrichment) of the heavy metal ion under the special environment such as this delays of characteristic convection cell pipeline dead angle, complicated shape container, nuclear reaction storehouse provides effective means.
This material is the material system of a multicomponent organic composite, including adsorption function constituent element, magnetic effect constituent element and load matrix constituent element.The present invention adopts anti-phase (W/O) suspension method to prepare magnetic persimmon tannin adsorption material.
This sorbent preparation method comprises the steps:
(1) a certain amount of matrix material is dissolved in corresponding solvent by the concentration of 10～15g/L and makes solution A, tannin is dissolved in deionized water by the concentration of 30～50g/L and makes solution B, then solution A and solution B are mixed, matrix material Solutions Solution mixes with persimmon tannin solution, and adds magnetic nano-particle ultrasonic disperse and uniformly make aqueous phase system；
(2) hexamethylene and hexanol are made into oil-based system for the ratio of 11:5～11:7 or direct use paraffin oil by volume；
(3) oil-based system and aqueous phase system are mixed in the ratio of 11:4～17:4, be simultaneously introduced aldehydes or amide-type cross-linking agent solution and a certain amount of dispersant polyacrylic acid, be stirred vigorously and make anti-phase (W/O) suspension/dispersion.Namely crosslinked curing reaction 3～8h obtains the suspension of persimmon tannin magnetic adsorptive material at a certain temperature；
(4) suspension prepared separate through Soxhlet lift, washing, filter, the link such as dry, and do not have magnetic product through magnetic separation separation removal, make magnetic persimmon tannin absorbent resin granule and save backup.
According to above-mentioned preparation scheme.The mass ratio range of matrix material (load constituent element) and persimmon tannin (adsorption function constituent element) is 10:1～1:10, and the mass ratio range of magnetic nanoparticle (magnetic effect constituent element) and persimmon tannin is 1:5～1:8.
According to above-mentioned preparation scheme.Described matrix material can from collagen fiber, chitosan, graphene oxide optional one；The mass ratio of described collagen fiber and persimmon tannin is the mass ratio that mass ratio is 1:3～2:3, graphene oxide and persimmon tannin of 2:1～3:2, chitosan and persimmon tannin is 10:1～15:1；All can prepare the adsorbing material that characterization of adsorption is excellent.
Persimmon tannin used is with blue or green (puckery) Fructus Kaki for raw material, adopts the persimmon powder that freeze-drying method prepares, and the persimmon tannin solution in its course of processing also can directly use.
Ferroferric oxide magnetic nano-particles used can use the method synthesis such as coprecipitation, hydro-thermal method, collosol and gel, it is possible to use the ferroso-ferric oxide powder body of commercial 50～100nm.
According to above-mentioned preparation scheme.Hexamethylene and hexanol in preparation process (2) can adopt paraffin oil replacement or other organic solvents to replace, and organic solvent can recycle, thus reducing cost, reduces the pollution of organic solution simultaneously.
Reasonable temperature in preparation process (3) is 25 DEG C～40 DEG C, namely reaction can carry out at normal temperatures.
The cross-linking agent that preparation process (3) uses is Biformyl, glutaraldehyde, formalin aldehyde crosslinking agent, or N,N methylene bis acrylamide amide-type cross-linking agent.
In preparation process (3), the rational range of speeds is between 500～1000 revs/min.
The magnetic persimmon tannin adsorption material of green high-efficient prepared in accordance with the present invention, can direct plunge into and need in solution to be processed, the modes such as stirring are adopted to make adsorbing material and solution be sufficiently mixed, reach to adopt the mode of externally-applied magnetic field it to be separated from solution after balance until it, then adopt desorption, washing, regeneration to dispose to recycle.
Advantages of the present invention and feature
1, the present invention proposes the innovation method of multifunctional material, it is achieved the integration of many material systems also provides new material system research and development method.
2, puckery Fructus Kaki bigger for China's yield and the Fructus Kaki that falls, blue or green Fructus Kaki etc. without bigger economic worth and are easily decomposed by the microorganisms the biomaterial processing that cannot directly use synthesize multi-functional adsorbent, the chemical methodes such as hydrogen bonded, crosslinking curing, functional modification are purified and are utilized by modern biotechnology extraction process, its reprocessing of the tannin extracted is modifiied, functionalization realizes waste treatment while utilizing, and kills two birds with one stone.
3, the anti-phase suspension method that resin pelletize in modern chemical industry adopts is used for processing and manufacturing tannin adsorptive material, while being undertaken solidifying and modifiying by tannic material innovatively, realizes product pelletize.
4, the imparting of magnetic makes persimmon tannin adsorbent be easily isolated disposal in real life production process, and it can be deployed in adopt the mode removal (or enrichment) for the heavy metal ion under the special environments such as the delay of fluid line dead angle, complicated shape container, nuclear reaction storehouse of magnetic traction at container bottom, of many uses.
Accompanying drawing explanation
Fig. 1 is material system synthesis schematic diagram；
Fig. 2 is the stereoscan photograph of magnetic persimmon tannin high-performance bio adsorbent；
Fig. 3 is the infrared spectrogram of tannin raw material and synthesizing magnetic adsorbent；
Fig. 4 is the XRD scanning curve of magnetic tannin adsorbent；
Fig. 5 is the design sketch of magnetic persimmon tannin adsorbent Magnetic Isolation in aqueous；
Fig. 6 is the magnetic persimmon tannin adsorbent adsorbance to heavy metal ions in sewage.
Specific embodiment
Below in conjunction with detailed description of the invention and accompanying drawing, the present invention is launched further description.
Embodiment 1:
(1) chemical coprecipitation is adopted to prepare magnetic nano-particle.Fig. 1 is material system synthesis schematic diagram.By FeC13·6H2O and FeC12·4H2O(mol ratio is 2:1) it is dissolved in after water and adds in three-necked bottle, making total iron concentration is 0.3mol/L.NH is added under nitrogen protection3·H2O forms precipitation, is stirred vigorously simultaneously, maintains pH=10.0, reacts 30min at 80 DEG C, separates solid phase after being washed to neutrality again with washing with alcohol, vacuum drying 24h at 70 DEG C, grinds and obtain Fe3O4Nano-particle.
(2) preparation of aqueous phase: be dissolved in by 1.0g chitosan in the acetic acid that 100mL mass fraction is 1%, stirring forms it into uniform solution；3.0g persimmon tannin powder is dissolved in 100mL water, filters insoluble impurity, be simultaneously introduced 1.0gFe3O4Nano-particle ultrasonic disperse are uniform, and prepare 2.5mL mass fraction is that the glutaraldehyde water solution of 25% is as cross-linking agent simultaneously.
(3) preparation of oil phase: press profit according to the volume of above-mentioned aqueous phase and calculate the volume of required oil phase with volume ratio 11:4, hexamethylene and hexanol 11:5 by volume are made oil phase and adds in reactor.
(4) turn on agitator is stirred vigorously, and is simultaneously introduced several water-phase components of step (2), adds 2.5mL polyacrylic acid and makes anti-phase (W/O) suspension/dispersion as dispersant.Microsphere crosslinked solidification 24h, isolated by filtration, wash away polyacrylic acid with toluene and isopropanol, then be washed till neutrality with deionized water, vacuum drying magnetic separation separates and saves backup.
Fig. 2 shows that this embodiment successfully synthesizes persimmon tannin adsorbent, and this sorbent material has the pore structure that density is higher, material microstructure surface imperfection, covers for near-spherical, it is easy to trap heavy metals ion.Material specific surface area is relatively big, and the rate of adsorption of ion is higher, and qualified products must possess this microstructure and get to the requirement of high adsorption capacity, and technological parameter strictly to control.
Embodiment 2:
(1) being placed in 200mL water by 2.0g collagen protein, stirring forms uniform emulsion；3.0g persimmon tannin powder is dissolved in 100mL water (filtering insoluble impurity), is simultaneously introduced 1.0gFe3O4Nano-particle ultrasonic disperse are uniform, prepare simultaneously 10mL mass fraction be the glutaraldehyde water solution of 25% as cross-linking agent, make aqueous phase；
(2) press profit according to the volume of above-mentioned aqueous phase and calculate the volume of required oil phase with volume ratio 11:4, hexamethylene and hexanol 11:5 by volume are made oil phase and adds in reactor.Then oil phase and aqueous phase are pressed mixing, be simultaneously introduced a certain amount of dispersant polyacrylic acid, be stirred vigorously and make anti-phase (W/O) suspension/dispersion.Namely crosslinked curing reaction 24h obtains persimmon tannin magnetic adsorbent, isolated by filtration at a certain temperature, washes away polyacrylic acid with toluene and isopropanol, then is washed till neutrality with deionized water, and vacuum drying magnetic separation separates and saves backup.
Fig. 3 infrared spectrum shows that product remains raw-material activity phenolic hydroxyl group functional group, is combined with matrix material by chemical reaction so that material is more stable while possessing higher adsorption activity simultaneously.The strict production technology that controls is to reach certain reaction efficiency, it is to avoid mechanical mixture and the incomplete by-product of reaction.
Fig. 4 and Fig. 5 illustrates to modify by chemical method on the biological adsorption agent material of preparation by magnetic-particle, obtains the performance of Magnetic Isolation with this, and in actual application, Magnetic Isolation effect is obvious.
Embodiment 3:
(1) hydro-thermal method is adopted to prepare magnetic oxygenated Graphene.6mmolFeCl3·6H2O and 12mmolNaOH is dissolved in the ethylene glycol of 60ml under magnetic stirring, be simultaneously introduced that 1.0g graphene oxide is ultrasonic to be dispersed in solution, this solution is added 100ml polytetrafluoro liner autoclave at 200 DEG C of temperature, react 12h filtration drying can obtain.
(2) preparation of aqueous phase: be dispersed in 100mL water by ultrasonic for step (1) described graphene oxide, 10.0g persimmon tannin powder is dissolved in 100mL water (filtering insoluble impurity), prepare 5.0mL mass fraction is that the glutaraldehyde water solution of 50% is as cross-linking agent simultaneously.
(3) preparation of oil phase: press profit according to the volume of above-mentioned aqueous phase and calculate the volume of required oil phase with volume ratio 17:4, hexamethylene and hexanol 11:7 by volume are made oil phase and adds in reactor.
(4) turn on agitator is stirred vigorously, and is simultaneously introduced several water-phase components of step (2), adds 2.5mL polyacrylic acid and makes anti-phase (W/O) suspension/dispersion as dispersant.Microsphere crosslinked solidification 24h, isolated by filtration, wash away polyacrylic acid with toluene and isopropanol, then be washed till neutrality with deionized water, vacuum drying magnetic separation separates and saves backup.
Embodiment 4:
(1) being dissolved in by 1.0g chitosan in the acetic acid that 100mL mass fraction is 1%, stirring forms it into uniform solution；3.0g persimmon tannin powder is dissolved in 100mL water (filtering insoluble impurity), is simultaneously introduced 1.0gFe3O4Nano-particle ultrasonic disperse are uniform, prepare simultaneously 2.5mL mass fraction be the glutaraldehyde water solution of 25% as cross-linking agent, make aqueous phase；
(2) pressing profit according to the volume of above-mentioned aqueous phase and calculate the volume of required oil phase with volume ratio 11:4, the paraffin adding certain volume is made in oil phase addition reactor.Then oil phase and aqueous phase are pressed mixing, be simultaneously introduced 1.5mL polyacrylic acid as dispersant, be stirred vigorously and make anti-phase (W/O) suspension/dispersion.Namely crosslinked curing reaction 24h obtains persimmon tannin magnetic adsorbent, isolated by filtration at a certain temperature, washes away polyacrylic acid with toluene and isopropanol, then is washed till neutrality with deionized water, and vacuum drying magnetic separation separates and saves backup.
Embodiment 5:
(1) being dissolved in by 1.0g chitosan in the acetic acid that 100mL mass fraction is 1%, stirring forms it into uniform solution；3.0g persimmon tannin powder is dissolved in 100mL water (filtering insoluble impurity), is simultaneously introduced 1.0gFe3O4Nano-particle ultrasonic disperse are uniform, are dissolved in 50ml ethanol 1.0gN, N-methylene-bisacrylamide as cross-linking agent.
(2) preparation of oil phase: press profit according to the volume of above-mentioned aqueous phase and calculate the volume of required oil phase with volume ratio 11:5, hexamethylene and hexanol 11:7 by volume are made oil phase and adds in reactor.
(3) turn on agitator is stirred vigorously, it is simultaneously introduced several water-phase components of step (1), adds 2.5mL polyacrylic acid and be simultaneously introduced suitable Ammonium persulfate. and sodium sulfite as dispersant and make anti-phase (W/O) suspension/dispersion as initiator.Microsphere crosslinked solidification 8h, isolated by filtration, wash away polyacrylic acid with toluene and isopropanol, then be washed till neutrality with deionized water, vacuum drying saves backup.
Embodiment 6:
Preparing a series of concentration is that 100mg/L distinguishes solution leaded, cadmium, chromium ion, simultaneously with NaOH and the HNO of 0.5mol/L3Adjustment pH is 1.0-5.5, add sorbent material prepared by said method, every part adds 100mg adsorbent, it is placed in constant-temperature table at different temperature (30,40,50 DEG C) concussion absorption, rotating speed controls at 140 revs/min, test surplus solution concentration of metal ions with atomic absorption spectrum after 24h, calculate its degree of absorption.
Fig. 6 shows that prepared magnetic tannin adsorbent heavy metal ion has high adsorbance, the adsorbance of lead ion is reached 136mg/g, the adsorbance of cadmium ion is reached 75mg/g, the adsorbance of chromium ion is reached 102mg/g, and adsorbance is far superior to previously reported tannic material and other low-cost bio adsorbents.
Claims (9)
1. a magnetic persimmon tannin composite adsorbing material, it is characterized in that: this material is the material system of a multicomponent organic composite, including: undertake the persimmon tannin constituent element of adsorption function, there is provided the ferric oxide nano particles constituent element of paramagnetic performance, for the matrix constituent element of carried magnetic nano particle and crosslinking curing persimmon tannin；The mass ratio range of magnetic nanoparticle and persimmon tannin is 1:5～1:8；Described matrix material is the one in collagen fiber, chitosan, graphene oxide, the mass ratio range of collagen fiber and persimmon tannin is (2:1～3:2), the mass ratio range of chitosan and persimmon tannin is (1:3～2:3), and the mass ratio range of graphene oxide and persimmon tannin is (10:1～15:1).
2. adsorbing material according to claim 1, it is characterised in that: persimmon tannin used is with blue or green Fructus Kaki or puckery Fructus Kaki for raw material；Can directly use persimmon tannin solution, it is possible to adopt the persimmon powder that freeze-drying method prepares.
3. adsorbing material according to claim 1, it is characterised in that: described ferroferric oxide magnetic nano-particles can use coprecipitation or hydro-thermal method or sol-gel method synthesis；The commercial ferroso-ferric oxide powder body of 50～100nm can also be used.
4. the preparation method of adsorbing material described in claim 1, it is characterised in that: comprise the steps:
(1) a certain amount of matrix material is dissolved in corresponding solvent by the concentration of 10～15g/L and makes solution, or it is dispersed in water and forms dispersion A, persimmon tannin is dissolved in deionized water by the concentration of 30～50g/L and makes solution B, then solution A and solution B are mixed, and add magnetic nano-particle ultrasonic disperse and uniformly make aqueous phase system；
(2) ratio that hexamethylene and hexanol are 11:5～11:7 by volume is made into oil-based system；Or directly use paraffin oil to be made into oil-based system；
(3) oil-based system and aqueous phase system are mixed in the ratio of 11:4～17:4, be simultaneously introduced aldehydes or amide-type cross-linking agent solution and a certain amount of dispersant polyacrylic acid, be stirred vigorously and make anti-phase suspension dispersion；Crosslinked curing reaction 3～8h, obtains the suspension of persimmon tannin magnetic adsorptive material at a certain temperature；
(4) links such as the suspension separating, washing for preparing, filtration, dry, magnetic separation separation, make magnetic persimmon tannin adsorption particle, save backup.
5. the preparation method of adsorbing material according to claim 4, it is characterised in that: the preferable temperature in preparation process (3) is 25 DEG C～40 DEG C.
6. the preparation method of adsorbing material according to claim 4, it is characterised in that: the cross-linking agent that preparation process (3) uses can adopt the one in the aldehyde crosslinking agent such as Biformyl, glutaraldehyde, formalin；Or N,N methylene bis acrylamide cross-linking agent.
7. the preparation method of adsorbing material according to claim 4, it is characterised in that: in preparation process (3), speed of agitator scope is between 500～1000 revs/min.
8. adsorbing material according to claim 1, it is characterized in that: during described materials'use, directly being put into by the adsorbing material of preparation needs in aqueous solution to be processed, alr mode is adopted to make adsorbing material and solution be sufficiently mixed, reach to adopt the mode of externally-applied magnetic field it to be separated from aqueous solution after balance until it, then adopt desorption, washing, regeneration to dispose to recycle.
9. adsorbing material according to claim 1, it is characterised in that: described material can be used in conjunction with as in the conventional abluent of abluent addition, and the heavy metal ion for cleaning nuclear reaction storehouse, specific response vessel etc. is gathered；Using method is to be added together with other abluents by material, then adopts the mode iterative cycles of magnetic traction to rinse to reach the purpose of effectively removing in container periphery.
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| CN106442667A (en) * | 2016-09-23 | 2017-02-22 | 桂林电子科技大学 | Method for detecting blood glucose by virtue of persimmon tannin@graphene@Pt-Pd non-enzymatic sensor |
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