CN107915788B - Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof - Google Patents
Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof Download PDFInfo
- Publication number
- CN107915788B CN107915788B CN201711417077.9A CN201711417077A CN107915788B CN 107915788 B CN107915788 B CN 107915788B CN 201711417077 A CN201711417077 A CN 201711417077A CN 107915788 B CN107915788 B CN 107915788B
- Authority
- CN
- China
- Prior art keywords
- cyclodextrin
- water
- molecular polymer
- organic acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 126
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 17
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 title abstract description 27
- 239000000463 material Substances 0.000 title description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 23
- 239000001116 FEMA 4028 Substances 0.000 claims description 19
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 19
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 19
- 229960004853 betadex Drugs 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 8
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 6
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 125000003636 chemical group Chemical group 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- 150000003384 small molecules Chemical class 0.000 description 14
- 239000011148 porous material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004676 glycans Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Cyclodextrin high molecular polymer, which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C. The preparation method of the cyclodextrin high-molecular polymer comprises the following steps: (1) adding cyclodextrin into a water-organic acid mixed system, wherein the water content in the water-organic acid mixed system is 0-50% by volume, and obtaining a ternary mixture system with the concentration of cyclodextrin being 0.05-1.0 g/ml; (2) heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours; (3) cooling, filtering, washing filter cakes with water, and drying to obtain the cyclodextrin high-molecular polymer with the yield of 50-70%. The cyclodextrin high molecular polymer has extremely high adsorption speed and extremely high selectivity on micromolecular pollutants. The adopted raw materials are simple, and the cost is lower; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical.
Description
Technical Field
The invention belongs to the field of water treatment, relates to a treatment material and a preparation method thereof, and particularly relates to a cyclodextrin-based micromolecular pollutant adsorption material and a preparation method thereof.
Background
The production wastewater and the domestic wastewater contain various toxic and harmful substances, and the pollution to water bodies is becoming serious day by day, so that the effective treatment of the wastewater is a social problem which is greatly concerned. In particular, in some waste water from pesticide and medicine industries, the waste water often contains a plurality of small molecule pollutants with high concentration, and the harm to the ecological environment and the human health is particularly serious. The common treatment method nowadays is to use porous material to adsorb these small molecules, so as to achieve the purpose of removal. The activated carbon has a high specific surface area and relatively low cost, so that the activated carbon becomes one of the most widely used small-molecule pollutant adsorbing materials. However, the disadvantages of activated carbon as a water treatment material are also quite obvious, mainly including the following points: (1) the material has strong hydrophobicity, which is not beneficial to the dispersion of the material in water; (2) the adsorption speed is relatively slow; (3) the material regeneration treatment needs to consume a large amount of energy, and the treatment efficiency is obviously reduced after regeneration.
In order to overcome the above-mentioned drawbacks of activated carbon, a large number of porous materials have been synthesized and applied to research in the field of wastewater treatment. One class of materials is inclusions (Inclusion complex) formed based on Host-guest chemistry (Host-guest chemistry) systems, which can form porous structures that effectively adsorb small molecule contaminants. Traditional host-guest chemical materials, such as calixarene and cyclodextrin, are representative systems that are widely used in wastewater treatment. Among them, the research on the water treatment porous material system using cyclodextrin as a raw material is more intensive.
Cyclodextrins are oligomeric polysaccharide structures formed by enzymatic conversion of starch, and are one of the most common materials in the field of water treatment. The method has the advantages that the method is used for treating the wastewater polluted by small molecules: (1) the numerous hydroxyl groups distributed around the molecules endow the hydrophilic polymer with good hydrophilicity, and meanwhile, the hydrophobic polymer has certain hydrophobicity in the cavity; therefore, the cyclodextrin molecule provides a cavity with a specific size, can contain organic small molecule pollutants and is a good carrier for removing the organic small molecule pollutants in the water body. (2) The chemical action of the host and the guest between the cyclodextrin and the micromolecular pollutants has stronger reversibility, so that the low-cost regeneration and use of the material become possible. (3) The cyclodextrin has low cost, can be completely biodegraded due to the rich polysaccharide structure, and is environment-friendly.
The university of northwest Dichtel group of the united states developed a very economical and efficient process for the preparation of beta cyclodextrin porous materials (alaeddin Alsbaiee, Brian j.smith, leileileilei Xiao, et al nature 2016,529, 190-. The method uses tetrafluoroterephthalonitrile as a monomer (shown in figure 1), tetrahydrofuran is used for forming a solvent, and the beta-cyclodextrin porous material P-CDP is obtained by copolymerization reaction for two days at the temperature of 80 ℃ and with the yield of-20%. Compared with activated carbon, the material can adsorb and remove various small molecular pollutants at a higher speed, and can be regenerated simply after being cleaned by methanol, and the small molecular adsorption performance of the regenerated material is not reduced basically.
However, this method still has certain disadvantages: (1) the tetrafluoroterephthalonitrile used in the method has large irritation and toxicity to human bodies; in addition, the material contains more fluorine elements, is not easy to biodegrade and is not environment-friendly; (2) the preparation steps are complex, alkali is required to be added into an organic solvent as a catalyst, and the preparation of the material can be completed only after 48 hours at 80 ℃, in addition, the whole process needs inert gas for protection, and the steps of drying and dewatering under the condition of vacuum liquid nitrogen are required after the preparation is completed, so that the preparation cost is greatly increased; (3) because the solubility of beta cyclodextrin in organic solvent is limited, and the efficiency of fluoro nucleophilic substitution reaction in the preparation process is relatively low, the yield is not high, and the method is not favorable for further industrial scale-up process.
Jaouadi et al prepared four types of activated carbon materials, including β cyclodextrin prepared porous material CCD (mount Jaouadi, Souhaira Hbaieb, Hanen Guedidi, et al, Journal of Saudi chemical Society2017,21, 822-829). The method was performed by dehydrating 3.26 g β cyclodextrin in a mixed solvent of toluene and sulfuric acid (30: 1 by volume) at a high temperature of 110 ℃ for 24 hours, then removing the solvent by vacuum rotary evaporation, thoroughly washing with water, performing Soxhlet extraction at a high temperature of 48 hours, and drying at a high temperature to obtain the target materialBET) Is one of the important indexes for representing the porosity of the porous material; the higher the specific surface area, the better the adsorption properties of the material tend to be. The specific surface area of the material is 90m2About/g, which is only one tenth of that of activated carbon (FIG. 2). However, the adsorption curve of the boron-containing wastewater demonstrates (fig. 3) that the adsorption efficiency of the material is significantly higher than that of activated carbon; this is because the surface of the material is rich in phenolic hydroxyl groups which interact with boron.
However, the drawbacks of this method are also quite evident: (1) a large amount of toluene is used as a main solvent, and the cyclodextrin is dehydrated under the condition of high-temperature reflux; after the material preparation is completed, the post-treatment of the waste liquid is very troublesome; (2) the purification after the material preparation is more complicated, the final product can be obtained only by vacuum rotary evaporation and long-time Soxhlet extraction, and the energy consumption is quite large; (3) toluene as a solvent and cyclodextrin as a raw material both have a possibility of undergoing a dehydration reaction with sulfuric acid, so that toluene and cyclodextrin have a competitive effect; and cyclodextrin has poor solubility in toluene, and thus, the yield is low.
Compared with other host-guest chemical systems, the technology in the above example treats small molecular pollutants in wastewater, the cyclodextrin raw material is cheaper, and the removal efficiency and the regeneration capacity are greatly improved compared with those of the traditional activated carbon material. However, the preparation steps of the method are complicated, and the preparation cost is greatly increased. Furthermore, neither is the selectivity of contaminant adsorption concerned.
Disclosure of Invention
Aiming at the problems existing in the treatment of small molecular pollutants in wastewater in the prior art, the invention provides the adsorbing material based on cyclodextrin, which has low toxicity, easy degradation and high selectivity, and has the advantages of simple preparation, high yield and greatly reduced production cost; in addition, the material also has the advantages of high hydrophilicity, fast adsorption and easy regeneration, and has wide market application prospect.
The technical scheme of the invention is as follows:
a cyclodextrin high molecular polymer has a structural general formula:
wherein n is 5,6 or 7. The high-molecular polymer is a cyclodextrin high-molecular polymer which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) adding cyclodextrin into a water-organic acid mixed system, wherein the water content in the water-organic acid mixed system is 0-50% by volume, and obtaining a ternary mixture system with the concentration of cyclodextrin being 0.05-1.0 g/ml; the organic acid is p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid or acetic acid; the cyclodextrin is alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin or any combination of the three.
(2) Heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black or brown powder, and the yield is 50-70%.
Preferably, the water content in the water-organic acid mixed system in the step (1) is 0-40% by volume; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.50 g/ml.
More preferably, the water content of the water-organic acid mixed system in the step (1) is 0-30% by volume; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.20 g/ml.
Preferably, the reaction temperature in the step (2) is 50 to 150 ℃ and the reaction time is 24 to 72 hours.
More preferably, the reaction temperature in the step (2) is 50 to 120 ℃ and the reaction time is 24 to 48 hours.
The application of cyclodextrin high molecular polymer in wastewater treatment, wherein the wastewater contains micromolecular pollutants.
The application of the cyclodextrin high molecular polymer is applied to the preparation of a wastewater treatment device, wherein the wastewater treatment device is a filter element or a chromatographic column.
The invention has the beneficial effects that: compared with the prior art, the invention has the following advantages:
(1) the cyclodextrin high molecular polymer provided by the invention has extremely high adsorption speed and extremely high selectivity on small molecular pollutants.
(2) The preparation method of the cyclodextrin high molecular polymer can generate the adsorbing material based on cyclodextrin only by one-step reaction, and has simple steps and no need of complex synthesis; the post-treatment only needs to be cleaned by water, and the post-treatment is easy, simple and quick; and the synthesis yield (50% -70%) is obviously improved compared with the existing method (20%).
(3) The preparation method adopts cyclodextrin and solvent as raw materials, and has simple raw materials and lower cost; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical.
Drawings
FIG. 1 is a reaction scheme of beta cyclodextrin with tetrafluoroterephthalonitrile to form copolymer P-CDP;
FIG. 2 shows the specific surface area of a quasi-activated carbon material (CCD) prepared from beta-cyclodextrin and Activated Carbon (AC);
FIG. 3 is an adsorption curve of four materials for boron-containing wastewater (activated carbon: ●, CCD:tangle-solidup);
FIG. 4 is an infrared spectrum of a material of the present invention;
FIG. 5 shows the adsorption effect of cyclodextrin adsorption material prepared by the present invention on dye molecules of different sizes.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
a cyclodextrin high molecular polymer has a structural general formula:
wherein n is 6. The high-molecular polymer is a cyclodextrin high-molecular polymer which is obtained by reacting cyclodextrin with organic acid and contains chemical groups such as C-O, C-C and C-O-C.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 5g of beta cyclodextrin, adding the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 10%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.05 g/ml; the organic acid is p-toluenesulfonic acid.
(2) Heating to the reaction temperature of 90 ℃ and the reaction time of 72 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 70%.
Example 2:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 5g of beta cyclodextrin, adding the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 20%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.1 g/ml; the organic acid is trifluoromethanesulfonic acid.
(2) Heating to the reaction temperature of 120 ℃ and the reaction time of 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 62%.
Example 3:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of gamma cyclodextrin, and adding the gamma cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 30%, so as to obtain a ternary mixture system with the concentration of cyclodextrin being 0.2 g/ml; the organic acid is methanesulfonic acid.
(2) Heating to the reaction temperature of 150 ℃ and the reaction time of 36 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 63%.
Example 4:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 5 or 6.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of alpha cyclodextrin and 3g of beta cyclodextrin, adding the alpha cyclodextrin and the beta cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 40%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.5 g/ml; the organic acid is trifluoroacetic acid.
(2) Heating to the reaction temperature of 180 ℃ and the reaction time of 48 hours;
(3) cooling, filtering, washing the filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 52%.
Example 5:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 6 or 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 3.5g of beta cyclodextrin and 0.5g of gamma cyclodextrin, adding the beta cyclodextrin and the gamma cyclodextrin into a water-organic acid mixed system, wherein the volume part of water in the water-organic acid mixed system is 50%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 1.0 g/ml; the organic acid is acetic acid.
(2) Heating to the reaction temperature of 50 ℃ and the reaction time of 60 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 50%.
Example 6:
different from the embodiment 1, the cyclodextrin high molecular polymer has the structural general formula:
wherein n is 5,6 or 7.
The preparation method of the cyclodextrin high-molecular polymer comprises the following steps:
(1) weighing 1g of alpha cyclodextrin, 2.5g of beta cyclodextrin and 0.5g of gamma cyclodextrin, adding the alpha cyclodextrin, the 2.5g of beta cyclodextrin and the 0.5g of gamma cyclodextrin into a water-organic acid mixed system, wherein the volume fraction of water in the water-organic acid mixed system is 30%, and obtaining a ternary mixture system with the concentration of the cyclodextrin being 0.5 g/ml; the organic acid is p-toluenesulfonic acid.
(2) Heating to the reaction temperature of 70 ℃ and the reaction time of 24 hours;
(3) cooling, filtering, washing filter cake with water, and drying to obtain the cyclodextrin high molecular polymer, wherein the appearance of the cyclodextrin high molecular polymer is black powder, and the yield is 65%.
Example 7: confirmation of structural aspects of materials
The cyclodextrin high molecular polymers prepared in examples 1-6 were insoluble in water and various organic solvents.
As can be seen from the IR spectrum of FIG. 5, several new peaks with higher intensity appeared in the cyclodextrin polymers prepared in examples 1-6, compared to the cyclodextrin used as the starting material. Wherein, the thickness is 3000cm-1The new peak is the stretching vibration of C-H in olefin; at 1714cm-1And 1650cm-1The new peak appeared at (A) can be attributed to the stretching vibration peak of the C ═ O bond and the C ═ C bond; furthermore, it is located at 1153cm-1The stretching vibration peak intensity of the ether bond is obviously increased, which indicates that a large amount of ether bonds are generated in the preparation process of the material.
According to the results of element analysis, no other new elements appear before and after the reaction, the content of the carbon element after the reaction is obviously increased, and the content of the hydrogen element and the oxygen element are obviously reduced.
TABLE 1 elemental analysis results of the materials obtained in examples 1 to 6
| Examples | Cyclodextrin | Cyclodextrin adsorption material |
| 1 | C:H:O＝44.45:6.22:49.33 | C:H:O＝65.52:4.71:28.77 |
| 2 | Same as above | C:H:O＝67.02:4.74:28.24 |
| 3 | Same as above | C:H:O＝68.14:4.52:27.34 |
| 4 | Same as above | C:H:O＝68.07:4.49:27.44 |
| 5 | Same as above | C:H:O＝63.22:4.90:31.88 |
| 6 | Same as above | C:H:O＝65.72:4.63:29.65 |
By combining the properties of the material and the characterization results, the material is a high molecular polymer obtained by losing part of water molecules from cyclodextrin, and the material contains more C ═ O bonds and C ═ C bonds. At the same time, the cyclic structure of the cyclodextrin is still maintained.
Example 8: treatment of wastewater containing small molecular pollutants
Dye molecules are commonly used to study and simulate small molecule contaminants in wastewater. The materials prepared in the embodiments 1 to 6 are added into a plurality of aqueous solutions containing dyes with higher concentration, and the absorption intensity of the residual dyes is tested by an ultraviolet-visible spectrometer at intervals, so that the adsorption balance removal efficiency of the cyclodextrin on the dye molecules can be calculated. The time at which the absorption intensity of the residual dye no longer changed was marked as the adsorption equilibrium time, and the specific results are detailed in tables 2 to 7.
Results similar to those in tables 2 to 7 can also be obtained if a mixed solution of two or more dyes is passed through a column or cartridge packed with the materials prepared in examples 1 to 6.
TABLE 2 comparison of the selective adsorption properties of the dyes prepared in example 1
TABLE 3 comparison of the selective adsorption properties of the dyes prepared in example 2
TABLE 4 comparison of the selective adsorption properties of the dyes prepared in example 3
TABLE 5 comparison of the selective adsorption properties of the dyes prepared in example 4
Table 6 comparison of selective adsorption properties of dyes prepared in example 5
TABLE 7 comparison of the selective adsorption properties of the dyes prepared in example 6
As shown in tables 2-7, firstly, the cyclodextrin adsorbing material prepared by the invention has extremely high adsorption speed on small molecule pollutants with specific sizes, and can completely adsorb high-content (0.1mM,32ppm) methylene blue dye in only 10 seconds under the condition of concentration of 1 mg/mL. Bisphenol a, a common industrial wastewater contaminant, can be completely adsorbed within 10 minutes.
Second, the material has very high selectivity for adsorption of small molecule contaminants. The cyclodextrin forms an inclusion compound with the small molecules with a certain volume, such as bisphenol A and methylene blue, because the cyclodextrin and the cyclodextrin can form an inclusion compound with stability. In contrast, dye molecules with larger sizes cannot enter the intramolecular cavity of the cyclodextrin, and the adsorption speed and efficiency of the dye molecules are greatly reduced.
In conclusion, according to the preparation method disclosed by the invention, the adsorbing material based on the cyclodextrin can be obtained by only one-step reaction, the steps are simple, and complex synthesis is not needed; the post-treatment only needs to be cleaned by water, and the post-treatment is easy, simple and quick; and the synthesis yield (50% -70%) is obviously improved compared with the existing method (20%). In addition, the method has the advantages of simple raw materials and low cost; the preparation process has low toxicity to the environment, and the cyclodextrin is easy to biodegrade, environment-friendly and economical. Therefore, the method has wide application prospect in the field of wastewater treatment and generates great economic benefit.
Claims (7)
1. The preparation method of the cyclodextrin high-molecular polymer is characterized by comprising the following steps: the method comprises the following steps: (1) adding cyclodextrin into a water-organic acid mixed system to obtain a ternary mixture system with a certain concentration; the organic acid is p-toluenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, trifluoroacetic acid or acetic acid, the water content in the water-organic acid mixed system is 10-50% by volume, and the concentration of cyclodextrin in the ternary mixed system is 0.05-1.0 g/ml; (2) heating to the reaction temperature of 50-180 ℃ and the reaction time of not less than 24 hours; (3) cooling, filtering, washing a filter cake with water, and drying to obtain the cyclodextrin high molecular polymer.
2. The method for producing a cyclodextrin high-molecular polymer according to claim 1, wherein: the cyclodextrin in the step (1) is alpha cyclodextrin, beta cyclodextrin, gamma cyclodextrin or any combination of the three.
3. The method for producing a cyclodextrin high-molecular polymer according to claim 2, wherein: the water content of the water-organic acid mixed system in the step (1) is 10-30% by volume ratio; the concentration of cyclodextrin in the ternary mixture system obtained in the step (1) is 0.05-0.20 g/ml.
4. The method for producing a cyclodextrin high-molecular polymer according to any one of claims 1 to 3, wherein: in the step (2), the reaction temperature is 50-150 ℃, and the reaction time is 24-72 hours.
5. The method for producing a cyclodextrin high-molecular polymer according to any one of claims 1 to 3, wherein: in the step (2), the reaction temperature is 50-120 ℃, and the reaction time is 24-48 hours.
6. The use of a cyclodextrin polymer obtained by the process according to claim 1, wherein: the method is applied to wastewater treatment, and the wastewater contains small molecular pollutants.
7. The use of a cyclodextrin polymer obtained by the process according to claim 1, wherein: the method is applied to the preparation of a wastewater treatment device which is a filter element or a chromatographic column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711417077.9A CN107915788B (en) | 2017-12-25 | 2017-12-25 | Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711417077.9A CN107915788B (en) | 2017-12-25 | 2017-12-25 | Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107915788A CN107915788A (en) | 2018-04-17 |
| CN107915788B true CN107915788B (en) | 2020-08-28 |
Family
ID=61894168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711417077.9A Active CN107915788B (en) | 2017-12-25 | 2017-12-25 | Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107915788B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4071181A1 (en) * | 2021-04-09 | 2022-10-12 | Qatar Foundation for Education, Science and Community Development | Cyclodextrin-derived polymer nanoparticles for adsorption and synthesis thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475079A (en) * | 2016-10-25 | 2017-03-08 | 昆明理工大学 | Polyurethane foam surface is coupled sorbing material of beta cyclodextrin and its preparation method and application |
-
2017
- 2017-12-25 CN CN201711417077.9A patent/CN107915788B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475079A (en) * | 2016-10-25 | 2017-03-08 | 昆明理工大学 | Polyurethane foam surface is coupled sorbing material of beta cyclodextrin and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| An Improved Synthesis of 6-O-Monotosyi-6-deoxy-β-cyclodextrin;Ning Zhong等;《Tetrahedron Letters》;19981231;第39卷;第2919-2920页 * |
| β-环糊精酯类衍生物的合成;肖璐;《中国优秀博硕士学位论文全文数据库 (硕士)工程科技Ⅰ辑》;20060115(第1期);第15-16，27-28页 * |
| 单取代β-环糊精对甲苯磺酸酯的合成(简报);徐伟亮;《浙江农业大学学报》;19920930;第18卷(第3期);第6页 * |
| 碱性水溶液中β-环糊精的选择性磺酰化;黄怡等;《西北大学学报（自然科学版）》;20030225;第33卷(第1期);第41-44页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107915788A (en) | 2018-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Modification of chitin with high adsorption capacity for methylene blue removal | |
| Godiya et al. | Amine functionalized sodium alginate hydrogel for efficient and rapid removal of methyl blue in water | |
| CN110922508B (en) | Novel cyclodextrin polymer for rapidly adsorbing dissolved organic pollutants in water | |
| Li et al. | Effect of pyrolytic temperature on the adsorptive removal of p-benzoquinone, tetracycline, and polyvinyl alcohol by the biochars from sugarcane bagasse | |
| Luo et al. | Preparation and characterization of amine-functionalized sugarcane bagasse for CO2 capture | |
| CN106279698B (en) | A kind of 2,4-dinitrophenol surface molecularly imprinted polymer and its preparation method and application | |
| Jian et al. | Preparation of polydopamine nanofibers mat as a recyclable and efficient adsorbent for simultaneous adsorption of multiple tetracyclines in water | |
| CN111748055B (en) | Molecularly imprinted polymer with eutectic solvent as functional monomer and application thereof | |
| Jabir et al. | Cellulose based pH-sensitive hydrogel for highly efficient dye removal in water treatment: kinetic, thermodynamic, theoretical and computational studies | |
| CN109806851B (en) | Cyclodextrin porous material and preparation method thereof | |
| CN113831512B (en) | Polynitrogen conjugated microporous polymer and preparation method and application thereof | |
| CN102489268B (en) | Amine-modified fibrous emergent absorbing material and preparation method thereof | |
| Zhao et al. | An azine-based polymer derived hierarchically porous N–doped carbon for hydrophilic dyes removal | |
| CN113083254A (en) | Preparation method and application of functionalized biomass carbon-based adsorbent | |
| CN109364880B (en) | Supramolecular organic framework material with cyclic analysis function and application of supramolecular organic framework material in removal of organic dye in water body | |
| CN115138341B (en) | Preparation method of cross-linked chitosan nanosponge adsorbent for efficiently removing anionic and cationic dyes | |
| Chen et al. | Spatial confinement and ion exchange synergetic strategy for highly selective removal of metal ions from the spinning solution containing ionic liquids | |
| Phillips et al. | Cyclodextrin-derived polymer networks for selective molecular adsorption | |
| Yong et al. | Biomass ferulic acid-derived hollow polymer particles as selective adsorbent for anionic dye | |
| Purwiandono et al. | Comparison of two biosorbent beads for methylene blue discoloration in water | |
| CN107915788B (en) | Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof | |
| CN110938184A (en) | Schiff base type bio-based porous material based on organic aldehyde and melamine and preparation method thereof | |
| CN111203197A (en) | Adsorbent material based on epoxy and amino cross-linking and preparation method thereof | |
| CN114409009A (en) | Method for adsorbing hydroquinone based on polymer PIM-1 | |
| CN112915808A (en) | Clustering rotaxane membrane, preparation method and application in separation of biodiesel wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |