CN105727907B - A kind of magnetism persimmon tannin composite adsorbing material and preparation method thereof - Google Patents
A kind of magnetism persimmon tannin composite adsorbing material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 235000011511 Diospyros Nutrition 0.000 title claims abstract description 59
- 235000018553 tannin Nutrition 0.000 title claims abstract description 59
- 239000001648 tannin Substances 0.000 title claims abstract description 59
- 229920001864 tannin Polymers 0.000 title claims abstract description 59
- 244000236655 Diospyros kaki Species 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 7
- 230000005389 magnetism Effects 0.000 title claims abstract description 5
- 230000005291 magnetic effect Effects 0.000 claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 230000005298 paramagnetic effect Effects 0.000 claims abstract 2
- 239000012071 phase Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
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- 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
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims 1
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- 229910001868 water Inorganic materials 0.000 description 19
- 239000003463 adsorbent Substances 0.000 description 18
- 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 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052770 Uranium Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 6
- -1 graphite alkene Chemical class 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052776 Thorium Inorganic materials 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 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
- 238000000975 co-precipitation Methods 0.000 description 2
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- 235000019441 ethanol Nutrition 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
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002594 sorbent Substances 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
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241000723267 Diospyros Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001436 collagen Polymers 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
- 238000013461 design Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000008434 ginseng Nutrition 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 239000000320 mechanical mixture Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000010970 precious metal Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing 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
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011282 treatment Methods 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
A kind of magnetism persimmon tannin composite adsorbing material and preparation method thereof, the material is using persimmon tannin as absorption function of tonic chord constituent element, nanometer Fe3O4Particle is magnetic function constituent element, and the materials such as chitosan, graphene are optional to do the load for adsorbing constituent element and magnetic constituent element（Or crosslinking）Matrix.Substrate material surface carried magnetic nano particle is realized using inverse suspension method；Curing of the persimmon tannin on basis material is realized using cross-linking reaction.The materials such as graphene, which have its absorption property with the use of persimmon tannin Material cladding, significantly cooperates with enhancement effect；The material has good adsorption capacity to heavy metal ion, and possessed paramagnetic properties can be applied to the removal of the heavy metal ion under the specific conditions such as the delay of fluid line dead angle, complicated shape container.The material has the characteristics that stability is strong, resistance to environment capacity is strong, yield is high, at low cost, adsorption capacity is high, is easily isolated and recycled, non-secondary pollution.
Description
Technical field
The present invention relates to sorbing material field, the magnetic persimmon tannin adsorption material of specially a kind of green high-efficient and its preparation
Method.
Background technology
Persimmon tannin, which has, derives from a wealth of sources easy acquisition, and tannin relative amount is high, contained tannin phenolic hydroxyl group large percentage, for gold
The recycling of category ion has and its apparent effect.Sakaguchi etc. is using persimmon tannin absorption, recycling uranium (U) and thorium (Th)
Result of study finds that curing persimmon tannin is very high to the adsorption efficiency of thorium (Th), and 18.4 mg adsorbents can adsorb 100 in 1 h
The thorium (Th) of 9.3 mg/L of mL, and the uranium (U) and thorium (Th) adsorbed is easily desorbed by dilute hydrochloric acid and dilute sulfuric acid.Akira
Nakajima etc. using the uranium (U) cured in persimmon tannin absorption, recycling uranium refining wastewater, find the mass concentration of uranium (U) 1~
It can be by 100% absorption in the range of 50 mg/L；The hydrochloric acid of 0.1mol/L can more fully desorb the uranium of absorption (U), and solve
Suction will not cause the adsorption capacity of adsorbent to decline.Indium in indium extraction process/iron separation is carried out using persimmon tannin material is cured
Technical research, Selective Separation is with obvious effects, carries out absorption precious metal ion also with persimmon tannin material and grinds
Study carefully, wherein the adsorbance of silver reaches 320 mg/g, golden adsorbance reaches 2374mg/g, and the adsorbance of lead is 186mg/g, chromium
Adsorbance is 49.01mg/g, and the adsorbance of cadmium is 143mg/g.But research before this is only limitted to for the simple of tannic material
Extraction test, without targetedly deep processing, rests on original discovery test phase, it is necessary to carry out deeper research.
Further investigations have shown that persimmon tannin sorbing material heavy metal containing wastewater treatment, heavy-metal contaminated soil administer, it is valuable dilute expensive
The fields such as metal recovery have a extensive future.
Biomass absorbent material have many advantages, such as abundance, processing cost be low, nontoxic, non-secondary pollution and receive pass
Note, but its separation and recovery hardly possible restricts its application always.Magnetic guidance separation is a kind of effective solid-liquid separating method, in externally-applied magnetic field
Under effect, the separation of solid liquid phase is simple and practicable, saves centrifugal filtration process links when consumption energy consumptions, therefore the magnetic with magnetic effect
Property adsorbent can overcome the problems, such as separation of solid and liquid.Meanwhile in actual industrial production there are some shapes it is special, be difficult to what is touched
Some workpiece areas, such as fluid line bent angle, special shape reactor（Container）, nuclear reaction storehouse etc., it tends to be difficult to using conventional
Method is cleaned and is disposed, and can realize these under the traction control of external magnetic field with magnetic high-efficiency adsorbent
Cleaning and polluted heavy metals ion removal.Therefore, exploitation has the adsorbent of magnetic effect, high adsorption capacity, high stability
Material has wide application field and market popularization value.
Invention content
The technical problems to be solved by the invention be to provide a kind of green high-efficient magnetic persimmon tannin composite adsorbing material and
Preparation method, the material have good adsorption capacity to heavy metal ion, and the magnetic effect that material has can ensure adsorption material
Material is efficiently separated with the aqueous solution of disposition, the delay of characteristic fluid pipe road dead angle, complicated shape container, the nuclear reaction storehouse etc.
The removal of heavy metal ion under particular surroundings（Or enrichment）Provide effective means.
The 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 uses reverse phase（W/O）Suspension method prepares magnetic persimmon tannin adsorption material.
The sorbent preparation method includes the following steps：
（1）A certain amount of basis material is dissolved in corresponding solvent by the concentration of 10~15g/L, solution A is made, by tannin
Deionized water is dissolved in by the concentration of 30~50g/L, solution B is made, then mix solution A and solution B, basis material solution
Solution is mixed with persimmon tannin solution, and adds in magnetic nano-particle ultrasonic disperse and aqueous phase system is uniformly made；
（2）Hexamethylene and n-hexyl alcohol are 11 by volume:5~11:7 ratio is directly made into oil phase using paraffin oil
System；
（3）Oil-based system and aqueous phase system are pressed 11:4~17:4 ratio mixing, while add in aldehydes or amides friendship
Join agent solution and a certain amount of dispersant polyacrylic acid, be vigorously stirred and reverse phase is made（W/O）Suspension/dispersion.At a certain temperature
Crosslinked 3~8h of curing reaction up to persimmon tannin magnetic adsorptive material suspension；
（4）The links such as suspension obtained is detached through Soxhlet lifting, washing, filtering, drying, and detach removal by magnetic separation
Do not have magnetic reaction product, magnetic persimmon tannin absorbent resin particle is made and saves backup.
According to above-mentioned preparation scheme.Basis material（Load constituent element）With persimmon tannin（Adsorption function constituent element）Mass ratio model
Enclose is 10:1~1:10, magnetic nanoparticle（Magnetic effect constituent element）Mass ratio range with persimmon tannin is 1:5~1:8.
According to above-mentioned preparation scheme.Described matrix material can from collagenous fibres, chitosan, graphene oxide optionally its
One；The mass ratio of the collagenous fibres and persimmon tannin is 2:1~3:2, the mass ratio of chitosan and persimmon tannin is 1:3~2:3rd, oxygen
The mass ratio of graphite alkene and persimmon tannin is 10:1~15:1；The excellent sorbing material of characterization of adsorption can be made.
Persimmon tannin used is with blueness（It is puckery）Persimmon is raw material, using persimmon powder made from freeze-drying method, process
In persimmon tannin solution also can be used directly.
Ferroferric oxide magnetic nano-particles used can be synthesized with the methods of coprecipitation, hydro-thermal method, collosol and gel, also may be used
To use the ferroso-ferric oxide powder of 50~100nm of commercialization.
According to above-mentioned preparation scheme.Preparation process（2）In hexamethylene and n-hexyl alcohol can be used paraffin oil replace or other
Organic solvent replaces, and organic solvent can recycle, and so as to reduce cost, while reduce the pollution of organic solution.
Preparation process（3）In reasonable temperature for 25 DEG C~40 DEG C namely reaction can carry out at normal temperatures.
Preparation process（3）The crosslinking agent used is glyoxal, glutaraldehyde, formalin aldehyde crosslinking agent or N, N- are sub-
Bisacrylamide amides crosslinking agent.
Preparation process（3）In the rational range of speeds 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 solution to be treated
In, sorbing material is made to be sufficiently mixed with solution using modes such as stirrings, it will by the way of externally-applied magnetic field after it reaches balance
It is separated from solution, then desorption, washing, regeneration is used to dispose to recycle.
The advantages and features of the present invention
1st, the present invention proposes the innovation method of multifunctional material, realizes the integration of more material systems and provides new material
System researches and develops method.
2nd, by the larger puckery persimmon of China's yield and persimmon, green persimmon etc. are fallen without larger economic value and be easily decomposed by the microorganisms can not
The biomaterial processing directly used synthesizes multi-functional adsorbent, is purified by modern biotechnology extraction process and utilizes hydrogen
The chemical methodes such as conjunction, crosslinking curing, functional modification are bonded, its reprocessing is modified by the tannin of extraction, and functionalization utilizes same
Shi Shixian waste treatments, kill two birds with one stone.
The 3rd, resin in modern chemical industry is granulated to the anti-phase suspension method used for fabricating tannin adsorptive material,
Realize that product is granulated while innovatively tannic material is cured and is modified.
4th, magnetic imparting causes persimmon tannin adsorbent to be easily isolated disposition in real life production process, and can adopt
Used in container bottom the spies such as the delay of fluid line dead angle, complicated shape container, nuclear reaction storehouse are used in a manner that magnetism is drawn
The removal of heavy metal ion under different environment（Or enrichment）, it is widely used.
Description of the drawings
Fig. 1 synthesizes schematic diagram for material system；
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 curves of magnetic tannin adsorbent；
Fig. 5 is the design sketch of magnetic persimmon tannin adsorbent Magnetic Isolation in aqueous solution；
Fig. 6 is adsorbance of the magnetic persimmon tannin adsorbent to heavy metal ions in sewage.
Specific embodiment
Further description is unfolded to the present invention below in conjunction with specific embodiment and attached drawing.
Embodiment 1：
(1) magnetic nano-particle is prepared using chemical coprecipitation.Fig. 1 synthesizes schematic diagram for material system.By FeC13·
6H2O and FeC12·4H2O （Molar ratio is 2:1）It is added in three-necked bottle after being dissolved in water, it is 0.3 mol/ to make total iron concentration
L.Nitrogen protection is lower to add in NH3·H2O forms precipitation, is vigorously stirred simultaneously, maintains pH=10.0,30 min are reacted at 80 DEG C,
Separation solid phase is washed after being washed to neutrality with ethyl alcohol again, and 24 h are dried in vacuo at 70 DEG C, is ground up to Fe3O4Nano particle.
(2) preparation of water phase：1.0g chitosans are dissolved in the acetic acid that 100mL mass fractions are 1%, stirring forms it into
Uniform solution；3.0g persimmon tannin powder is dissolved in 100mL water, filters insoluble impurity, while adds in 1.0g Fe3O4Nanometer
Particle and ultrasonic disperse it is uniform, while prepare 2.5mL mass fractions be 25% glutaraldehyde water solution as crosslinking agent.
(3) preparation of oil phase：According to the volume of above-mentioned water phase by grease mutually with volume ratio 11:The body of oil phase needed for 4 calculating
Product, by hexamethylene and n-hexyl alcohol by volume 11:5, which are made oil phase, adds in reactor.
(4) turn on agitator is vigorously stirred, while adds in several water-phase components of step (2), adds 2.5mL polypropylene
Reverse phase (W/O) suspension/dispersion is made as dispersant in acid.The crosslinked curing of microballoon for 24 hours, is separated by filtration, with toluene and isopropyl
Alcohol washes away polyacrylic acid, then is washed with deionized water to neutrality, and vacuum drying magnetic separation separation saves backup.
Fig. 2 shows that the embodiment successfully synthesizes persimmon tannin adsorbent, which has the higher hole of density
Structure, material microstructure surface imperfection cover for near-spherical, are easy to trap heavy metals ion.Material specific surface area is larger,
Higher to the rate of adsorption of ion, qualified products must have the requirement that this microstructure gets to high adsorption capacity, technique ginseng
Number will be controlled strictly.
Embodiment 2：
(1) 2.0g collagens are placed in 200mL water, stirring forms uniform emulsion；3.0g persimmon tannin powder is molten
In 100mL water（Filter insoluble impurity）, while add in 1.0g Fe3O4Simultaneously ultrasonic disperse is uniform for nano particle, prepares simultaneously
Water phase is made as crosslinking agent in the glutaraldehyde water solution that 10mL mass fractions are 25%；
(2) grease is pressed mutually with volume ratio 11 according to the volume of above-mentioned water phase:The volume of oil phase needed for 4 calculating, by hexamethylene
With n-hexyl alcohol by volume 11:5, which are made oil phase, adds in reactor.Then it by oil phase and water phase by mixing, while adds in certain
Dispersant polyacrylic acid is measured, is vigorously stirred and reverse phase is made（W/O）Suspension/dispersion.Crosslinked curing reaction at a certain temperature
For 24 hours up to persimmon tannin magnetic adsorbent, be separated by filtration, polyacrylic acid washed away with toluene and isopropanol, then be washed with deionized water to
Neutrality, vacuum drying magnetic separation separation save backup.
Fig. 3 infrared spectrums show that product remains the active phenolic hydroxyl group functional group of raw material, at the same by chemical reaction with
Basis material is combined so that material is more stablized while having higher adsorption activity.It is stringent that production technology is controlled to reach
Certain reaction efficiency avoids mechanical mixture and reacts incomplete by-product.
Fig. 4 and Fig. 5 illustrates to modify magnetic-particle on the biological adsorption agent material of preparation by chemical method, is obtained with this
The performance of Magnetic Isolation is obtained, Magnetic Isolation is with obvious effects in actual application.
Embodiment 3：
(1) magnetic oxygenated graphene is prepared using hydro-thermal method.6 mmol FeCl3·6H2O and 12 mmol NaOH are in magnetic force
It is dissolved in the ethylene glycol of 60ml under stirring, while adds in 1.0g graphene oxide ultrasounds and be dispersed in solution, this is molten
The interior 12h filtration dryings that reacted at a temperature of 200 DEG C of autoclave that liquid adds in the polytetrafluoro liner of 100 ml can obtain.
(2) preparation of water phase：Step (1) the graphene oxide ultrasound is dispersed in 100mL water, 10.0g persimmons
Chinese tannin powder is dissolved in 100mL water（Filter insoluble impurity）, while prepare the glutaraldehyde water solution that 5.0mL mass fractions are 50%
As crosslinking agent.
(3) preparation of oil phase：According to the volume of above-mentioned water phase by grease mutually with volume ratio 17:The body of oil phase needed for 4 calculating
Product, by hexamethylene and n-hexyl alcohol by volume 11:7, which are made oil phase, adds in reactor.
(4) turn on agitator is vigorously stirred, while adds in several water-phase components of step (2), adds 2.5mL polypropylene
Reverse phase (W/O) suspension/dispersion is made as dispersant in acid.The crosslinked curing of microballoon for 24 hours, is separated by filtration, with toluene and isopropyl
Alcohol washes away polyacrylic acid, then is washed with deionized water to neutrality, and vacuum drying magnetic separation separation saves backup.
Embodiment 4：
(1) 1.0g chitosans are dissolved in the acetic acid that 100mL mass fractions are 1%, stirring forms it into uniform solution；
3.0g persimmon tannin powder is dissolved in 100mL water（Filter insoluble impurity）, while add in 1.0g Fe3O4Nano particle and ultrasound
Be uniformly dispersed, at the same prepare 2.5mL mass fractions be 25% glutaraldehyde water solution as crosslinking agent, water phase is made；
(2) grease is pressed mutually with volume ratio 11 according to the volume of above-mentioned water phase:The volume of oil phase needed for 4 calculating, adds in certain
The paraffin of volume is made oil phase and adds in reactor.Then by oil phase and water phase by mixing, while 1.5mL polyacrylic acid work is added in
For dispersant, it is vigorously stirred and reverse phase is made（W/O）Suspension/dispersion.Crosslinked curing reaction is for 24 hours at a certain temperature to obtain the final product
Persimmon tannin magnetic adsorbent, is separated by filtration, and polyacrylic acid is washed away with toluene and isopropanol, then is washed with deionized water to neutrality, very
Empty drying magnetic-separation separation saves backup.
Embodiment 5：
(1) 1.0g chitosans are dissolved in the acetic acid that 100mL mass fractions are 1%, stirring forms it into uniform solution；
3.0g persimmon tannin powder is dissolved in 100mL water（Filter insoluble impurity）, while add in 1.0g Fe3O4Nano particle and ultrasound
It is uniformly dispersed, by 1.0g N, N- methylene-bisacrylamides, which are dissolved in 50ml alcohol, is used as crosslinking agent.
(2) preparation of oil phase：According to the volume of above-mentioned water phase by grease mutually with volume ratio 11:The body of oil phase needed for 5 calculating
Product, by hexamethylene and n-hexyl alcohol by volume 11:7, which are made oil phase, adds in reactor.
(3) turn on agitator is vigorously stirred, while adds in several water-phase components of step (1), adds 2.5mL polypropylene
Acid adds in appropriate ammonium persulfate and sodium hydrogensulfite as dispersant and reverse phase (W/O) suspended dispersion is made as initiator simultaneously
System.The crosslinked curing 8h of microballoon, is separated by filtration, and washes away polyacrylic acid with toluene and isopropanol, then be washed with deionized water to neutrality,
Vacuum drying saves backup.
Embodiment 6：
Prepare a series of leaded a concentration of 100mg/L difference, cadmium, chromium ion solution, while with the NaOH of 0.5mol/L
And HNO3Adjusting pH is 1.0-5.5, adds in sorbent material prepared by the above method, and every part of addition 100mg adsorbent is placed in perseverance
(30,40,50 DEG C) concussion absorption, rotating speed are controlled at 140 revs/min warm shaking table at different temperature, use Atomic absorption afterwards for 24 hours
Spectrum test surplus solution concentration of metal ions, calculates its degree of absorption.
Fig. 6 shows that prepared magnetic tannin adsorbent has high adsorbance to heavy metal ion, to lead ion
Adsorbance reaches 136mg/g, reaches 75mg/g to the adsorbance of cadmium ion, reaches 102mg/g to the adsorbance of chromium ion, adsorbance is much
Better than previously reported tannic material and other low-cost bio adsorbents.
Claims (5)
1. a kind of magnetism persimmon tannin composite adsorbing material, it is characterised in that：The material is the material bodies of a multicomponent organic composite
System, including：The persimmon tannin constituent element of adsorption function is undertaken, paramagnetic performance is providedFerroso-ferric oxideNano-particle constituent element, for bearing
Carry the matrix constituent element of magnetic nano-particle and crosslinking curing persimmon tannin；The mass ratio model of magnetic nanoparticle and persimmon tannin
Enclose is 1:5~1:8；The basis material is collagenous fibres, one kind in chitosan, graphene oxide, collagenous fibres and persimmon
The mass ratio range of tannin is2:1~3:2,The mass ratio range of chitosan and persimmon tannin is1:3~2:3,Graphite oxide
The mass ratio range of alkene and persimmon tannin is10:1~15:1；Persimmon tannin used is using green persimmon or puckery persimmon as raw material；It can be direct
Using persimmon tannin solution, persimmon powder made from freeze-drying method can also be used；Ferroferric oxide magnetic nano-particles can be used altogether
The precipitation method or hydro-thermal method or sol-gel method synthesis；The commercial ferroso-ferric oxide powder of 50~100nm can also be used
Body.
2. according to the preparation method of sorbing material described in claim 1, it is characterised in that：Include the following steps：
（1）A certain amount of basis material is dissolved in corresponding solvent by the concentration of 10~15g/L, solution or homodisperse is made
Yu Shuizhong forms dispersion A, persimmon tannin is dissolved in deionized water by the concentration of 30~50g/L, solution B is made, then by solution
A and solution B mixing, and add in magnetic nano-particle ultrasonic disperse and aqueous phase system is uniformly made；
（2）It is 11 by volume by hexamethylene and n-hexyl alcohol:5~11:7 ratio is made into oil-based system；Or directly use stone
Wax oil is made into oil-based system；
（3）Oil-based system and aqueous phase system are pressed 11:4~17:4 ratio mixing, while add in aldehydes or amides crosslinking agent
Anti-phase suspension dispersion is made for 500~1000 revs/min in agitation revolution in solution and a certain amount of dispersant polyacrylic acid；
Crosslinked 3~8h of curing reaction, obtains the suspension of persimmon tannin magnetic adsorptive material at 25 DEG C~40 DEG C；
（4）Magnetic persimmon tannin absorption is made in the links such as suspension separating, washing obtained, filtering, drying, magnetic separation separation
Grain, saves backup.
3. sorbing material according to claim 1, it is characterised in that：During the materials'use, directly by the absorption of preparation
Material is put into aqueous solution to be treated, sorbing material is made to be sufficiently mixed with solution using agitating mode, is treated that it reaches flat
It from aqueous solution is separated by the way of externally-applied magnetic field after weighing apparatus, then desorption, washing, regeneration is used to dispose to recycle
It uses.
4. sorbing material according to claim 1, it is characterised in that：The material can be used as cleaning agent to add in common cleaning
It is used in conjunction in agent, for cleaning the accumulation of the heavy metal ion in nuclear reaction storehouse, special reaction vessel etc.；Application method is by material
Material adds in together with other cleaning agents, and the magnetic mode iterative cycles drawn is then used to rinse to reach effective in container periphery
The purpose of removing.
5. the preparation method of sorbing material according to claim 2, it is characterised in that：Preparation process（3）The crosslinking used
One kind in the aldehyde crosslinking agents such as glyoxal, glutaraldehyde, formalin can be used in agent；Or N,N methylene bis acrylamide is handed over
Join agent.
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| CN106442667B (en) * | 2016-09-23 | 2018-12-21 | 桂林电子科技大学 | A kind of method of the persimmon tannin@graphene@Pt-Pd without enzyme sensor detection blood glucose |
| CN107607597B (en) * | 2017-09-12 | 2019-11-26 | 桂林电子科技大学 | A kind of method of persimmon tannin-graphene-Pt composite material modification screen printing electrode detection hydrogen peroxide |
| CN109078623A (en) * | 2018-10-16 | 2018-12-25 | 齐鲁工业大学 | A kind of magnetic response type both sexes nano adsorption material and preparation method thereof |
| CN109329277B (en) * | 2018-12-03 | 2022-06-17 | 山东碧奥生物科技有限公司 | Adsorption carrier for herbicide |
| CN109575144B (en) * | 2018-12-03 | 2021-07-02 | 济南天邦化工有限公司 | Quaternary ammonium-sulfonated microcrystalline cellulose stabilizer and application thereof in cytometaherbicide |
| CN114196666B (en) * | 2020-09-18 | 2022-10-28 | 深圳市帝迈生物技术有限公司 | Reticulocyte simulant, preparation method thereof and reticulocyte quality control substance |
| CN113244896A (en) * | 2021-05-12 | 2021-08-13 | 中国矿业大学 | Persimmon peel imprinting composite material and preparation method thereof |
| CN114522672B (en) * | 2022-02-21 | 2023-10-24 | 广西科学院 | Biomass functional material for antibiotic adsorption and preparation method thereof |
| CN115646470B (en) * | 2022-12-27 | 2023-04-07 | 杭州德海艾科能源科技有限公司 | Magnetic composite material for treating vanadium-containing wastewater and preparation method and application thereof |
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