CN116212832A - Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof - Google Patents
Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof Download PDFInfo
- Publication number
- CN116212832A CN116212832A CN202310351564.9A CN202310351564A CN116212832A CN 116212832 A CN116212832 A CN 116212832A CN 202310351564 A CN202310351564 A CN 202310351564A CN 116212832 A CN116212832 A CN 116212832A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- reaction
- liquid
- adsorption
- alkenyl
- 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.)
- Pending
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 57
- 239000001913 cellulose Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 title abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 halogen anion Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract 6
- 239000003999 initiator Substances 0.000 claims abstract 3
- 238000005349 anion exchange Methods 0.000 claims abstract 2
- 230000000977 initiatory effect Effects 0.000 claims abstract 2
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract 2
- 238000002444 silanisation Methods 0.000 claims abstract 2
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- 238000001291 vacuum drying Methods 0.000 claims abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 4
- 229910021641 deionized water Inorganic materials 0.000 claims 4
- 238000000034 method Methods 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims 1
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 claims 1
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 claims 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 claims 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims 1
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 claims 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a polyion liquid-cellulose composite double-absorption purification material and a preparation method thereof. The preparation method mainly comprises the following steps: firstly, adding cellulose powder into methanol solution of an alkenyl silane coupling agent, performing hydrothermal reaction for 24-48 hours, performing suction filtration on the reaction solution, washing filter residues, and performing vacuum drying to obtain silanized cellulose; mixing the cellulose after silanization treatment with halogen anion liquid monomer containing alkenyl according to different mass percentagesMixing, namely initiating free radical polymerization reaction by taking water as a solvent and ammonium persulfate as an initiator; after the polymerization reaction is finished, adding hexafluorophosphate into the reaction solution to carry out anion exchange reaction, and replacing halogen anions with hydrophobic PF 6 － And washing and drying to obtain the polyion liquid-cellulose composite adsorption material. The composite adsorption material enhances the hydrophobicity of cellulose, and has unsaturated C=C double bond, imidazole cation and PF in the structure 6 － The adsorption material not only can enhance the hydrophobicity of the adsorption material, but also can improve the adsorption performance of the adsorption material, can be used for removing oil and heavy metal ions in wastewater, can solve the problems that the traditional cellulose adsorbent is easy to absorb water, low in adsorption capacity and difficult to recover, can realize the simultaneous adsorption of heavy metal ions and greasy dirt, and has huge social and economic benefits.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to a polyion liquid-cellulose composite double-adsorption purification material capable of absorbing oil and heavy metal ions and a preparation method thereof.
Background
The oily wastewater and the heavy metal wastewater are used as two common pollution sources of water resources, and cause great harm to human health, water environment and ecological environment balance. The direct discharge of oily wastewater can seriously pollute the surrounding environment, greatly destroy ecological balance and simultaneously cause great harm to human health. In mechanical equipment of industrial media, a small amount of engine oil, lubricating oil and the like enter a production system due to sealing and other problems, and a large amount of heavy metal ions exist in a reaction system, so that the content of organic carbon and heavy metal in the system exceeds the standard. The production of materials in certain mechanical devices requires strict control of the organic carbon and heavy metal content, and when the content is higher than the corresponding index, the requirements of downstream processes cannot be met. The physicochemical properties of heavy metal and oil pollution are greatly different, and the simultaneous removal of various pollutants is difficult to realize by the existing adsorbent. Therefore, suitable purification materials and efficient purification processes must be used to remove organic carbon and heavy metal ions to reduce or remove the organic carbon and heavy metal ion content of the material production system. Cellulose is a renewable biomass resource, and is widely used as an inexpensive adsorbent in recent years due to wide sources and large reserves, and the adsorption capacity of the cellulose to pollutants is remarkably improved after a series of chemical modification treatment, but the cellulose serving as the adsorbent has the greatest defect of hydrophilicity, and can adsorb less pollutants at the same time, so that the adsorption capacity of the adsorbent to the pollutants is reduced, the difficulty of recycling the adsorbent is increased, and secondary pollution to the environment is extremely easy to cause.
Polyionic liquids (PILs) are special high molecular compounds, have excellent properties of ionic liquids and polymers, can change functional groups of the PILs through monomer structure design, have various interactions with organic matters and heavy metal ions, including electrostatic force, van der Waals force, hydrogen bond force, hydrophobic force, pi-pi force, dispersion force and the like, and can change the hydrophilicity of the PILs by adjusting the types of anions in the PILs. Therefore, the functionalized PILs and cellulose are compounded by the silane coupling agent to prepare the novel sponge structure polyion liquid-cellulose composite double-absorption purification material, so that the hydrophobicity of the adsorption material can be enhanced, the adsorption performance of the adsorption material can be improved, the adsorption material can be used for removing oil and heavy metal ions in wastewater, the problems that the cellulose adsorbent is easy to absorb water, low in adsorption capacity and difficult to recover can be solved, and the adsorption of heavy metal ions and greasy dirt can be realized simultaneously, so that the adsorption material has huge social and economic benefits.
Disclosure of Invention
The invention aims to provide a novel polyion liquid-cellulose composite double-suction purifying material which can be used for removing oil and heavy metal ions in wastewater.
The invention further aims at providing a preparation method of the polyionic liquid-cellulose composite double-absorption purification material.
The technical scheme adopted by the invention is as follows:
the invention provides a novel sponge structure polyion liquid-cellulose composite double-absorption purification material, which takes a silane coupling agent as a cross-linking agent and loads polyion liquid on cellulose through an ionic liquid polymerization reaction in a water system.
The invention relates to a preparation method of a novel sponge structure polyion liquid-cellulose composite double-absorption purification material, which comprises the following steps:
(1) Adding cellulose powder into a methanol solution of a silane coupling agent (the volume ratio of the cellulose to the solution of the coupling agent is 1 (15-20)), wherein the dosage of the methanol solution of the silane coupling agent is 8-15 mL/g (cellulose), carrying out hydrothermal reaction for 24-48 h at 40-60 ℃, and carrying out post-treatment to obtain the silanized cellulose;
(2) Adding 10-25 wt% (of cellulose) of alkenyl imidazole biscationic ionic liquid monomer into the silanized cellulose obtained in the step (1), taking water as a reaction solvent, taking 30-50 mL/g (of cellulose) of ammonium persulfate as a polymerization initiator, and carrying out reflux reaction for 24 hours at 80-90 ℃ in a nitrogen atmosphere to obtain a halogen anion polyionic liquid-cellulose suspension;
(3) Adding hexafluorophosphate (the molar ratio of hexafluorophosphate to ionic liquid monomer is 2.2:1) into the halogen anion polyion liquid-cellulose suspension obtained in the step (2), and carrying out reflux reaction for 12-24 hours at 50-60 ℃ in nitrogen atmosphere to obtain the hydrophobic polyion liquid-cellulose composite adsorption material;
(4) The ammonium persulfate in the step (2) is prepared into 0.01g/mL of aqueous solution, and the dosage is 5% of the mass of the monomer.
Drawings
Fig. 1 shows an SEM of a polyionic liquid-cellulose composite adsorbent material.
FIG. 2 shows FT-IR of a polyionic liquid-cellulose composite adsorbent material.
FIG. 3 shows the X-ray photoelectron spectrum of a polyionic liquid-cellulose composite adsorbent material
FIG. 4 shows the pair Pb of polyionic liquid-cellulose adsorbent 2+ 、Cu 2+ 、Ni 2+ Adsorption performance of (3)
FIG. 5 adsorption properties of polyionic liquid-cellulose adsorbent materials on silane oils
Detailed Description
The present invention will be further described with reference to examples, but the present invention is not limited to the following examples, and modifications are intended to be included within the scope of the present invention.
Example 1:
1.0g of cellulose powder is added into 10mL of methanol solution (volume ratio is 1:20) of vinyltrimethoxysilane, the reaction solution is filtered after hydrothermal reaction at 50 ℃ for 24 hours, and filter residues are sequentially washed by acetone, methanol and water and then are placed in a vacuum constant temperature drying oven at 50 ℃ for drying for 24 hours. 1g of silane-treated cellulose and [ VC ] were sequentially added to a three-necked flask 4 (Vim) 2 ]Cl 2 (with cellulose)Mass ratio 1:10), 40mL of water was added as solvent, 1mL of an aqueous solution of APS (APS) was added dropwise at 80℃at 0.01g/mL, and then the mixture was refluxed at 80℃for 24 hours, then cooled to 50℃and 0.114g of NH was added 4 PF 6 Reflux-reacting at 50deg.C for 12 hr, filtering, washing the residue with water and ethanol, and drying in a vacuum constant temperature oven at 100deg.C for 24 hr to obtain Poly- [ VC 4 (Vim) 2 ][PF 6 ] 2 (10%) -cellulose composite adsorbent material.
Wherein [ VC ] 4 (Vim) 2 ]Cl 2 The molecular structure of (2) is as follows:
example 2:
1.0g of cellulose powder is added into 10mL of methanol solution (volume ratio is 1:20) of vinyltrimethoxysilane, the reaction solution is filtered after hydrothermal reaction at 50 ℃ for 24 hours, and filter residues are sequentially washed by acetone, methanol and water and then are placed in a vacuum constant temperature drying oven at 50 ℃ for drying for 24 hours. 1g of silane-treated cellulose and [ VC ] were sequentially added to a three-necked flask 4 (Vim) 2 ]Cl 2 (mass ratio to cellulose is 1:5), 50mL of water is taken as solvent, 2mL of APS aqueous solution of 0.01g/mL is dropwise added at 80 ℃, reflux reaction is carried out for 24h at 80 ℃, then the temperature is reduced to 50 ℃, and 0.228g of NH is added 4 PF 6 Reflux-reacting at 50deg.C for 12 hr, filtering, washing the residue with water and ethanol, and drying in a vacuum constant temperature oven at 100deg.C for 24 hr to obtain Poly- [ VC 4 (Vim) 2 ][PF 6 ] 2 (20%) -cellulose composite adsorbent material.
Example 3:
1.0g of cellulose powder is added into 15mL of methanol solution (volume ratio is 1:20) of vinyltrimethoxysilane, the reaction solution is filtered after hydrothermal reaction at 50 ℃ for 24 hours, and filter residues are sequentially washed by acetone, methanol and water and then are placed in a vacuum constant temperature drying oven at 50 ℃ for drying for 24 hours. 1g of silane-treated cellulose and [ C ] were sequentially charged into a three-necked flask 4 (Vim) 2 ]Br 2 (mass ratio to cellulose 1:5), 50mL of water was addedAs a solvent, 2mL of an aqueous APS solution of 0.01g/mL was added dropwise at 80℃and reacted under reflux at 85℃for 36 hours, followed by cooling to 50℃and addition of 0.177g of NH 4 PF 6 Reflux-reacting at 50deg.C for 12 hr, filtering, washing the residue with water and ethanol, and drying in vacuum constant temperature oven at 100deg.C for 24 hr to obtain Poly- [ C 4 (Vim) 2 ][PF 6 ] 2 (20%) -cellulose composite adsorbent material.
Wherein [ C ] 4 (Vim) 2 ]Br 2 The structural schematic diagram of (a) is as follows:
example 4:
0.1g of the polyionic liquid-cellulose adsorbent material obtained in example 3 was placed in 100mL of Pb with a concentration of 100mg/L 2+ 、Cu 2+ 、Ni 2+ In the aqueous solution, the initial pH is the original pH, a water bath constant temperature oscillator is used for setting the oscillation frequency to 150r/min and the temperature to 30 ℃, the supernatant fluid before and after adsorption is diluted to about 20-50 mg/L, the concentration of metal ions in the sample solution at different adsorption time is measured by utilizing an inductive coupling plasma emission spectrometry, and the removal rate of the polyion liquid-cellulose adsorption material to cadmium and nickel ions is calculated, so that the adsorption performance of the adsorption material is evaluated. The results are shown in FIG. 4.
Example 5:
placing 0.1g of the polyion liquid-cellulose adsorption material prepared in example 2 in 100mL of an oil-water mixture with a concentration of 100mL (oil)/L (water), standing at 25deg.C for 15min for oil absorption, taking out and standing for 5 mm until no oil drop is dropped, weighing (w 1 ) Then the adsorbed material is placed in a vacuum constant temperature drying oven at 50 ℃ for drying for 0.5h to remove the adsorbed water, and the material is taken out and weighed (w 2 ). Oil absorption multiplying power of adsorption material
w 0 =0.1 g, oil absorption test was performed in triplicate, averaged +.>
The results are shown in FIG. 5. />
Claims (8)
1. A novel polyion liquid-cellulose composite double-suction purifying material is characterized in that: taking cellulose powder as a base material, and loading polyimidazole biscationic ionic liquid on the base material by taking a silane coupling agent as a cross-linking agent.
2. The polyimidazole biscationic ionic liquid according to claim 1, wherein the main chain of the polyionic liquid has a bisimidazole cation repeating structural unit, and the main chain contains unsaturated alkenyl-C n H 2n-1 The anion is PF 6 － 。
3. The method for preparing the novel polyionic liquid-cellulose composite double-suction purifying material as claimed in claim 1, which is characterized by comprising the following steps:
step one: using alkenyl silane coupling agent as cross-linking agent and methanol as solvent, and silanizing cellulose by hydrothermal reaction;
step two: adding an alkenyl-containing bisimidazole cationic liquid monomer into the cellulose after silanization treatment, and initiating free radical polymerization reaction by taking deionized water as a solvent and ammonium persulfate as an initiator under the condition of constant temperature reflux;
step three: after the polymerization reaction is finished, a polyion liquid-cellulose suspension of halogen anions is obtained, the temperature is reduced to a certain temperature, hexafluorophosphate is added into a polymerization system, and anion exchange reaction is carried out, so that the hydrophobic polyion liquid-cellulose composite adsorption material is obtained.
4. The method of claim 3, wherein the alkenylsilane coupling agent in step one comprises alkenyloxy silanes (e.g., vinyltrimethoxysilane, triethoxyvinylsilane, diethoxymethylvinylsilane, allyltriethoxysilane, allyltrimethoxysilane, trimethoxy (7-octen-1-yl) silane, triisopropoxy (vinyl) silane, dimethylethoxyvinylsilane, dimethoxymethylvinylsilane, vinyltris (2-methoxyethoxy) silane, etc.), and alkenylchloro silanes (e.g., allyl chlorodimethylsilane, dimethylvinylchlorosilane, trichlorovinylsilane, etc.).
5. The preparation method of claim 3, wherein the dosage of the methanol solution of the silane coupling agent in the first step is 8-15 mL/g (cellulose), the volume ratio of the silane coupling agent to the methanol is 1 (15-20), the hydrothermal reaction temperature is 40-60 ℃, the reaction time is 24 hours, the filter residue is sequentially washed by acetone, methanol and deionized water after the reaction liquid is subjected to suction filtration, and the silanized cellulose is obtained by vacuum drying at 50 ℃ for 24 hours.
6. The preparation method of claim 3, wherein the mass ratio of the alkenyl-containing bisimidazole cationic liquid monomer to the silanized cellulose in the second step is 1:10-1:4, the dosage of the solvent deionized water is 30-50 mL/g (cellulose), the dosage of the initiator ammonium persulfate is 5wt% of the dosage of the alkenyl-containing bisimidazole cationic liquid monomer, the polymerization reaction temperature is 80-90 ℃, the reaction is carried out under the protection of nitrogen, and the reaction mode is magnetic stirring, condensing and refluxing, and the reaction time is 24-48 h.
7. The preparation method of claim 3, wherein in the third step, hexafluorophosphate comprises ammonium hexafluorophosphate, potassium hexafluorophosphate, sodium hexafluorophosphate and the like, the molar ratio of hexafluorophosphate to ionic liquid monomer is 2.2:1, the ion exchange reaction temperature is 50-60 ℃, the reaction time is 12-24 hours, after the reaction liquid is pumped and filtered, filter residues are washed with deionized water and absolute ethyl alcohol for several times in sequence, and the filter residues are dried in vacuum at 100 ℃ for 24 hours to obtain the polyionic liquid-cellulose composite adsorption material.
8. The method according to claim 3, wherein the structural formula of the alkenyl imidazole-containing biscationic ionic liquid monomer in the second step is shown as follows:
wherein r=c m H 2m Or C m H 2m-2 X=cl, br, I, etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310351564.9A CN116212832A (en) | 2023-04-04 | 2023-04-04 | Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310351564.9A CN116212832A (en) | 2023-04-04 | 2023-04-04 | Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116212832A true CN116212832A (en) | 2023-06-06 |
Family
ID=86575196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310351564.9A Pending CN116212832A (en) | 2023-04-04 | 2023-04-04 | Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116212832A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007308616A (en) * | 2006-05-19 | 2007-11-29 | Kagoshima Univ | Method for producing cellulose-polymer ion liquid hybrid |
| CN101928249A (en) * | 2009-12-30 | 2010-12-29 | 湖南大学 | Azobenzene-structured photosensitive ion liquid and preparation method thereof |
| US20110236295A1 (en) * | 2008-08-08 | 2011-09-29 | University Of Toledo | Polymeric Ionic Liquids, Methods of Making and Methods of Use Thereof |
| CN103007896A (en) * | 2012-12-24 | 2013-04-03 | 漳州师范学院 | Preparation method of cellulose adsorbent for adsorbing heavy metal cations |
| CN106890628A (en) * | 2017-02-07 | 2017-06-27 | 江南大学 | A kind of organic polymer adsorbent for removing precious metal ion in pharmaceutical synthesis system and preparation method thereof |
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
| CN111944195A (en) * | 2020-08-13 | 2020-11-17 | 西京学院 | Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof |
| CN112892501A (en) * | 2021-01-28 | 2021-06-04 | 辽宁大学 | Double-imidazole polyionic liquid and metal organic framework composite material as well as preparation method and application thereof |
| CN114870818A (en) * | 2022-05-13 | 2022-08-09 | 长春黄金研究院有限公司 | Method for adsorbing and separating gold, platinum and palladium by utilizing polyion liquid gel adsorbent |
-
2023
- 2023-04-04 CN CN202310351564.9A patent/CN116212832A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007308616A (en) * | 2006-05-19 | 2007-11-29 | Kagoshima Univ | Method for producing cellulose-polymer ion liquid hybrid |
| US20110236295A1 (en) * | 2008-08-08 | 2011-09-29 | University Of Toledo | Polymeric Ionic Liquids, Methods of Making and Methods of Use Thereof |
| CN101928249A (en) * | 2009-12-30 | 2010-12-29 | 湖南大学 | Azobenzene-structured photosensitive ion liquid and preparation method thereof |
| CN103007896A (en) * | 2012-12-24 | 2013-04-03 | 漳州师范学院 | Preparation method of cellulose adsorbent for adsorbing heavy metal cations |
| CN106890628A (en) * | 2017-02-07 | 2017-06-27 | 江南大学 | A kind of organic polymer adsorbent for removing precious metal ion in pharmaceutical synthesis system and preparation method thereof |
| CN109092265A (en) * | 2018-09-10 | 2018-12-28 | 陕西科技大学 | A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified |
| CN111944195A (en) * | 2020-08-13 | 2020-11-17 | 西京学院 | Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof |
| CN112892501A (en) * | 2021-01-28 | 2021-06-04 | 辽宁大学 | Double-imidazole polyionic liquid and metal organic framework composite material as well as preparation method and application thereof |
| CN114870818A (en) * | 2022-05-13 | 2022-08-09 | 长春黄金研究院有限公司 | Method for adsorbing and separating gold, platinum and palladium by utilizing polyion liquid gel adsorbent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110813251B (en) | Modified nano material and application thereof in antimony-containing wastewater treatment | |
| CN103025654B (en) | The preparation method and application of the Graphene that coordinating group is modified | |
| CN109092265B (en) | Cellulose-based adsorbent modified by polyimidazole ionic liquid and preparation method and application thereof | |
| CN106861658A (en) | A kind of preparation method and application of the imine modified porous adsorbing material of high-efficiency polyethylene | |
| CN109761331B (en) | Magnetic sewage treatment agent and preparation method thereof | |
| CN104226238A (en) | Preparation method and adsorption method of Ni<2+> adsorbent | |
| CN113214480B (en) | Synthesis method and adsorption application of cationic framework material | |
| CN110115984B (en) | Magnetic cyclodextrin-based cross-linked polymer adsorption material and preparation method thereof | |
| CN109608655A (en) | A kind of bifunctional group MOFs material and the preparation method and application thereof | |
| CN112646095A (en) | Dopamine-modified diatomite-adsorbed heavy metal hydrogel and preparation method and application thereof | |
| CN113042011A (en) | Fluorine-containing conjugated microporous polymer and preparation method and application thereof | |
| CN109759021B (en) | Cyclodextrin-Cu for treating ppcps in reclaimed water2Preparation method of O blend membrane | |
| CN116212832A (en) | Polyion liquid-cellulose composite double-absorption purifying material and preparation thereof | |
| CN110639481A (en) | Method for preparing polypyrrole and mesoporous molecular sieve composite material | |
| Lu et al. | Polyphosphonate-segmented macroporous organosilicon frameworks for efficient dynamic enrichment of uranium with in-situ regeneration | |
| Lu et al. | A promising absorbent of acrylic acid/poly (ethylene glycol) hydrogel prepared by glow-discharge electrolysis plasma | |
| CN113402632A (en) | Novel chitosan-based pyridine quaternary ammonium salt adsorption biological material and preparation method and application thereof | |
| Sun et al. | Hypophosphorous acid functionalized nanoporous silicon for selective adsorption of Hg (II) in industrial waste water | |
| CN115197382B (en) | Preparation method of cation covalent organic framework and application of cation covalent organic framework in gold adsorption | |
| CN115318241B (en) | Sludge-based hexavalent chromium composite adsorbent and preparation method thereof | |
| CN110215894A (en) | A kind of amino polymer modification layered double-hydroxide and its preparation method and application | |
| CN115254059B (en) | Chitosan/EDTA/polypyrrole adsorption material for efficiently removing hexavalent chromium ions in wastewater and preparation method thereof | |
| CN115672253A (en) | High-stability molybdenum disulfide coating composite adsorbent and preparation method and application thereof | |
| CN108126678B (en) | Renewable carbon nanomaterial coated fiber adsorbent and preparation method thereof | |
| CN113145083B (en) | Janus bifunctional blotting membrane and preparation method and application thereof |
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 |