CN113578286B - Adsorption material and preparation method and application thereof - Google Patents
Adsorption material and preparation method and application thereof Download PDFInfo
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- CN113578286B CN113578286B CN202110969466.2A CN202110969466A CN113578286B CN 113578286 B CN113578286 B CN 113578286B CN 202110969466 A CN202110969466 A CN 202110969466A CN 113578286 B CN113578286 B CN 113578286B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002121 nanofiber Substances 0.000 claims abstract description 71
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 61
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920002678 cellulose Polymers 0.000 claims abstract description 36
- 239000001913 cellulose Substances 0.000 claims abstract description 36
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 40
- 239000000839 emulsion Substances 0.000 claims description 34
- 239000004964 aerogel Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 239000003463 adsorbent Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 150000001350 alkyl halides Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 229920002201 Oxidized cellulose Polymers 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229940107304 oxidized cellulose Drugs 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- CPPKAGUPTKIMNP-UHFFFAOYSA-N cyanogen fluoride Chemical compound FC#N CPPKAGUPTKIMNP-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- -1 diatomite compound Chemical class 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorption material, a preparation method and application thereof, wherein the adsorption material comprises 0.16-0.18 weight part of nanofiber and 0.2-0.8 weight part of polyaryletherketone; wherein the nanofiber is selected from one of cellulose nanofiber, nanocellulose whisker or microfibrillated cellulose. The adsorption material can be used for removing aromatic hydrocarbon pollutants in water, and especially has higher adsorption efficiency on the diphenylamine.
Description
Technical Field
The invention relates to an adsorption material, a preparation method and application thereof.
Background
In recent years, with the intensive research on cellulose properties, cellulose aerogel, called "third generation aerogel material", has been developed. The nano cellulose aerogel is an organic aerogel, and is a product obtained by freeze drying emulsion. The cellulose aerogel has the characteristics of reproducibility, biodegradability, easiness in surface modification, high porosity, high specific surface area and low density, and is an environment-friendly multifunctional material.
CN111423553a discloses a bamboo nanocellulose and polyurethane composite foam, a preparation method and application thereof. The preparation method comprises the following steps: (1) preparing bamboo nanocellulose for adsorption by microwave liquefaction; (2) TEMPO oxidation grafted carboxyl; (3) And (3) preparing the bamboo nanocellulose/polyurethane foam adsorption material. The material can be used for adsorbing heavy metal pollutants.
CN107486160a discloses a nano-cellulose/diatomite composite adsorption material and a preparation method thereof. The preparation method comprises the steps of dripping diatomite into a nano cellulose suspension; stirring and then regulating the pH value to 5-9; stirring to obtain a nanocellulose/diatomite mixed solution; centrifugally washing to neutrality, and drying to obtain a nano cellulose/diatomite compound; fully dispersing the obtained nanocellulose/diatomite composite into suspension, adding ferric chloride hexahydrate and ferrous sulfate heptahydrate under the protection of nitrogen, heating and stirring for reaction, centrifugally washing, and drying in vacuum to obtain the magnetic nanocellulose/diatomite composite adsorption material. The adsorption material can remove heavy metal ions and organic dyes in water.
CN112742358A discloses a polyaniline/cellulose composite nanofiber aerogel, preparation and application thereof, nano cellulose is taken as an aerogel skeleton, and an oxidant and an aniline monomer are crosslinked in situ in the cellulose gel process, and the polyaniline/cellulose composite nanofiber aerogel is obtained by a post-in-situ polymerization method. The nanofiber composite aerogel can be used for carrying out adsorption treatment on high-concentration dye wastewater.
So far, no report is made on the adsorption material formed by the nanofiber and the polyaryletherketone.
Disclosure of Invention
Accordingly, an object of the present invention is to provide an adsorbent material that can remove aromatic hydrocarbon contaminants in water, especially para-diphenylamine, with high adsorption efficiency. For example, the adsorption efficiency may be 96.1% or more. Another object of the present invention is to provide a method for preparing an adsorbent material. It is a further object of the present invention to provide the use of an adsorbent material as described above. The invention achieves the above object by the following technical scheme.
In one aspect, the invention provides an adsorption material comprising 0.16 to 0.18 weight parts of nanofibers and 0.2 to 0.8 weight parts of polyaryletherketone; wherein the nanofiber is selected from one of cellulose nanofiber, nanocellulose whisker or microfibrillated cellulose.
According to the adsorption material of the present invention, preferably, the nanofiber is selected from one of cellulose nanofiber or nanocellulose whisker.
The adsorption material according to the present invention preferably comprises 0.16 to 0.18 parts by weight of nanofibers and 0.25 to 0.7 parts by weight of polyaryletherketone.
The adsorption material according to the present invention preferably comprises 0.16 to 0.18 parts by weight of nanofibers and 0.28 to 0.6 parts by weight of polyaryletherketone.
According to the adsorption material of the present invention, preferably, the chemical structure of the nanofiber is as shown in formula (I):
in the formula (I), x is a natural number of 50-1000.
According to the adsorption material of the present invention, preferably, the chemical structure of the polyaryletherketone is as shown in formula (II) or formula (III):
in the formula (II), R is selected from one of methyl, ethyl, cyano, nitro or halogen; r is R 1 One selected from hydrogen, methyl, ethyl, cyano, nitro or halogen; n and m are natural numbers of 1 to 1000;
in the formula (III), R' is selected from one of methyl, ethyl, cyano, nitro or halogen; r is R 2 One selected from hydrogen, methyl, ethyl, cyano, nitro or halogen; n and M are natural numbers of 1-1000.
According to the adsorption material of the present invention, preferably, the adsorption material is an aerogel adsorption material.
In another aspect, the present invention also provides a method for preparing the adsorption material as described above, comprising the steps of:
(1) Dissolving polyaryletherketone in halogenated alkane to obtain polyaryletherketone solution;
(2) Mixing the dispersion liquid of the nanofibers with a polyaryletherketone solution to obtain emulsion; and then freezing the emulsion into solid by adopting liquid nitrogen, and freeze-drying the obtained solid to obtain the adsorption material.
The preparation method according to the present invention preferably comprises:
in the step (1), the concentration of the polyaryletherketone solution is 0.9-10wt%; the halogenated alkane is selected from one or more of chloroform, dichloromethane and dichloroethane;
in the step (2), the concentration of the nano fibers in the dispersion liquid is 1 to 7 weight percent; the volume ratio of the dispersion liquid of the nano fiber to the polyaryletherketone solution is 1-5:1.
In a further aspect, the present invention also provides the use of an adsorbent material as described above for removing aromatic hydrocarbon contaminants, including diphenylamine, from water.
The adsorption material can be used for removing aromatic hydrocarbon pollutants in water, and especially has higher adsorption efficiency on diphenylamine of the aromatic hydrocarbon pollutants, which can reach more than 96.1%, preferably 98.1%. The method of the invention can be used for stably preparing the adsorption material.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
< adsorbent Material >
The adsorbent material of the present invention may be an aerogel adsorbent material. The adsorption material has high adsorption efficiency to diphenylamine up to 96.1%, preferably up to 98.1%.
The adsorption material of the invention comprises 0.16 to 0.18 weight part of nanofiber and 0.2 to 0.8 weight part of polyaryletherketone. Preferably, the adsorption material of the present invention comprises 0.16 to 0.18 parts by weight of nanofibers and 0.25 to 0.7 parts by weight of polyaryletherketone. More preferably, the adsorption material of the present invention comprises 0.16 to 0.18 parts by weight of nanofibers and 0.28 to 0.6 parts by weight of polyaryletherketone. The nanofiber is selected from one of cellulose nanofiber, nanocellulose whisker or microfibrillated cellulose. Preferably, the nanofibers are selected from one of cellulose nanofibers or nanocellulose whiskers. This is advantageous for forming an adsorbent material having better adsorption properties.
In certain embodiments, the adsorbent material of the present invention is comprised of 0.16 to 0.18 parts by weight nanofibers and 0.2 to 0.8 parts by weight polyaryletherketone. Preferably, the adsorption material of the present invention consists of 0.16 to 0.18 parts by weight of nanofibers and 0.25 to 0.7 parts by weight of polyaryletherketone. More preferably, the adsorption material of the present invention is composed of 0.16 to 0.18 parts by weight of nanofibers and 0.28 to 0.6 parts by weight of polyaryletherketone.
According to a specific embodiment of the present invention, the adsorbent material of the present invention consists of 0.165 to 0.17 parts by weight of nanofibers and 0.28 to 0.5 parts by weight of polyaryletherketone.
In the present invention, the structure of the nanofiber may be as shown in formula (I):
in the formula (I), x is a natural number of 50 to 1000, preferably, x is a natural number of 80 to 700, more preferably, x is a natural number of 80 to 300. Thus being beneficial to forming aerogel adsorbing materials with better adsorption performance.
In certain embodiments, the chemical structure of the polyaryletherketone is represented by formula (II):
in the formula (II), R is selected from one of methyl, ethyl, cyano, nitro or halogen. Halogen is fluorine, chlorine, bromine or iodine. Preferably, R is selected from one of methyl, ethyl, cyano or halogen. More preferably, R is selected from one of methyl, ethyl, cyano, fluoro or chloro.
R 1 Selected from one of hydrogen, methyl, ethyl, cyano, nitro or halogen. Halogen is fluorine, chlorine, bromine or iodine. Preferably, R 1 Selected from one of hydrogen, methyl, ethyl, cyano or halogen. More preferably, R 1 Selected from one of hydrogen, methyl, ethyl, cyano, fluorine or chlorine.
n and m are natural numbers of 1-1000; preferably, n and m are both natural numbers of 2 to 600, more preferably, n and m are both natural numbers of 2 to 300.
In other embodiments, the polyaryletherketone has the structure of formula (III):
in the formula (III), R' is selected from one of methyl, ethyl, cyano, nitro or halogen. Halogen is fluorine, chlorine, bromine or iodine. Preferably, R' is selected from one of methyl, ethyl, cyano or halogen. More preferably, R' is selected from one of methyl, ethyl, cyano, fluoro or chloro. R is R 2 Selected from one of hydrogen, methyl, ethyl, cyano, nitro or halogen. Halogen is fluorine, chlorine, bromine or iodine. Preferably, R 2 Selected from one of hydrogen, methyl, ethyl, cyano or halogen. More preferably, R 2 Selected from one of hydrogen, methyl, ethyl, cyano, fluorine or chlorine.
N and M are natural numbers of 1-1000. Preferably, N and M are both natural numbers of 2 to 600. More preferably, N and M are both natural numbers of 2 to 300.
The polyaryletherketone is favorable for being matched with the nanofiber to form the aerogel adsorption material with higher adsorption efficiency on the diphenylamine in aromatic hydrocarbon pollutants. The aromatic hydrocarbon pollutant in the invention can be in pesticide residues or formed by dyes.
< method for producing adsorbent >
The invention also provides a preparation method of the adsorption material, which comprises the following steps:
(1) Dissolving polyaryletherketone in halogenated alkane to obtain polyaryletherketone solution;
(2) Mixing the dispersion liquid of the nanofibers with a polyaryletherketone solution to obtain emulsion; and then freezing the emulsion into solid by adopting liquid nitrogen, and freeze-drying the obtained solid to obtain the adsorption material.
In step (1), the alkyl group of the haloalkane may be a C1-C6 alkyl group, preferably a C1-C5 alkyl group, more preferably a C1-C3 alkyl group. The number of substituted halogen atoms of the haloalkane may be 1 to 3. The halogen atom may be chlorine or bromine. In certain embodiments, the haloalkane is selected from one or more of chloroform, dichloromethane, and dichloroethane. Preferably, the haloalkane is selected from one of chloroform, dichloromethane and dichloroethane. According to one embodiment of the present invention, the haloalkane of the present invention is 1, 2-dichloroethane. Thus being beneficial to forming evenly dispersed emulsion and further being beneficial to forming the adsorption material with better adsorption performance.
The mass fraction of the polyaryletherketone may be 0.9 to 10wt%, preferably 1 to 7wt%, more preferably 1 to 5wt%.
In the step (2), the dispersion liquid of the nano fibers can be added into the polymer solution, and the polymer solution is stirred at a high speed for 2 to 5 minutes by using a refiner, wherein the stirring speed is 1000 to 1500rpm, so that emulsion is obtained, and no suspended particles exist after standing.
The dispersion of nanofibers of the present invention may be commercially available or may be self-made. The dispersion of nanofibers may be a dispersion of cellulose nanofibers, a dispersion of nanocellulose whiskers, or a dispersion of microfibrillated cellulose. The nanofiber dispersions were all available from Zhejiang Jin Jiahao green nanomaterials Inc. The mass concentration of the nanofibers in the nanofiber dispersion is 1-7wt%.
In certain specific embodiments, the dispersion of nanofibers is 1 to 2 weight percent of the dispersion of cellulose nanofibers, preferably 1.6 to 1.73 weight percent of the dispersion of cellulose nanofibers, more preferably 1.65 to 1.70 weight percent of the dispersion of cellulose nanofibers.
In other specific embodiments, the dispersion of nanofibers is 1 to 7wt% of a dispersion of nanocellulose whiskers, preferably 2 to 6wt% of a dispersion of nanocellulose whiskers, more preferably 4 to 6wt% of a dispersion of nanocellulose whiskers.
In still other specific embodiments, the dispersion of nanofibers is a dispersion of 1 to 7wt% microfibrillated cellulose, preferably a dispersion of 1.5 to 5wt% microfibrillated cellulose, more preferably a dispersion of 2 to 3wt% microfibrillated cellulose.
In the present invention, the volume ratio of the dispersion of nanofibers to the haloalkane may be 1 to 5:1, preferably 1 to 4.5:1, more preferably 1 to 4:1. This facilitates the formation of a Pickering emulsion.
In the present invention, the cellulose nanofibers may have a diameter of 10 to 50nm and a length of 1 to 10. Mu.m. The diameter of the nanocellulose whisker can be 1-10 nm, and the length can be 100-500 nm. The microfibrillated cellulose may have a diameter of 30 to 300nm and a length of 30 to 500. Mu.m. Thus being beneficial to forming aerogel adsorbing materials with better adsorption performance.
In step (2), according to one embodiment of the present invention, the dispersion of nanofibers is mixed with a polyaryletherketone solution to obtain an emulsion; placing the emulsion in a container, placing the container on a copper bar, placing the copper bar and the copper bar into a Dewar flask, adding liquid nitrogen into the Dewar flask, freezing the emulsion into solid, placing the solid in a freeze dryer, and drying the solid at-30 to-60 ℃ for 24-120 hours to obtain the adsorption material.
The temperature of freeze-drying may be-30 to-60 ℃, preferably-40 to-60 ℃, more preferably-45 to-60 ℃. The time for freeze-drying may be 24 to 120 hours, preferably 56 to 96 hours, more preferably 60 to 96 hours, and still more preferably 70 to 90 hours. Therefore, the space structure of the nano cellulose aerogel can be reserved, the adsorption material has a nano pore structure, and the adsorption performance of the obtained adsorption material is remarkably improved.
< analytical test method >
Diphenylamine adsorption efficiency: the prepared aqueous solution of diphenylamine (100. Mu.g/ml) was diluted to a series of concentration gradient solutions. The final dilutions were made into five groups of 20. Mu.g/ml, 15. Mu.g/ml, 10. Mu.g/ml, 50. Mu.g/ml, 1. Mu.g/ml aqueous diphenylamine solution. The absorbance of each group was measured separately in an ultraviolet spectrometer and plotted as a concentration-absorbance standard curve.
0.5g of the adsorbent material was weighed by a balance, and added to a sample bottle containing an aqueous solution of diphenylamine, followed by stirring.
Before the experiment, the absorbance of the unadsorbed aqueous diphenylamine solution is measured in an ultraviolet spectrometer, and then the absorbance of the aqueous diphenylamine solution is measured after stirring for 10min, 30min, 1h, 2h, 4h, 6h, 8h and 18h respectively. Substituting the absorbance of the diphenylamine aqueous solution at the moment into a concentration-absorbance standard curve to obtain the concentration of the diphenylamine at the moment. And obtaining the adsorption efficiency of the adsorption material to the diphenylamine through the change of the ratio of the concentration of the diphenylamine.
The raw materials used in the following examples and comparative examples are described below:
polyaryletherketone is purchased from Zhejiang Park New Material Co., ltd;
the dispersion of Cellulose Nanofibers (CNF), the dispersion of nanocellulose whiskers (CNC), the dispersion of microfibrillated cellulose (MFC) and the dispersion of oxidized cellulose nanofibers (TOCNF) were all purchased from Zhejiang Jin Jiahao green nanomaterials inc.
Example 1
0.4 parts by weight of polyaryletherketone was dissolved in 3.94 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 10.05 parts by weight of a dispersion containing 1.68wt% of Cellulose Nanofibers (CNF) was added to the above polyaryletherketone solution, and stirred at high speed for 3 minutes using a homogenizer to obtain an emulsion, which was left standing without suspended particles. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 98.1%.
Example 2
0.28 parts by weight of polyaryletherketone was dissolved in 3.94 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 10.01 parts by weight of a dispersion containing 1.68wt% of Cellulose Nanofibers (CNF) was added to the above polyaryletherketone solution, and stirred at a high speed for 3 minutes using a homogenizer to obtain an emulsion, which was left standing without suspended particles. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 96.1%.
Comparative example 1
0.12 parts by weight of polyaryletherketone was dissolved in 3.94 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 10.02 parts by weight of a dispersion containing 1.68wt% of Cellulose Nanofibers (CNF) was added to the above polyaryletherketone solution, and stirred at high speed for 3 minutes using a homogenizer to obtain an emulsion, which was left standing without suspended particles. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 92.4%.
Comparative example 2
0.04 parts by weight of polyaryletherketone was dissolved in 3.94 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 20.01 parts by weight of a dispersion containing 1.68wt% of Cellulose Nanofibers (CNF) was added to the above polyaryletherketone solution, and stirred at a high speed for 3 minutes using a homogenizer to obtain an emulsion, which was left standing without suspended particles. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 82.9%.
Comparative example 3
0.01 parts by weight of polyaryletherketone was dissolved in 1.18 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 3.03 parts by weight of a dispersion containing 5.6wt% of Cellulose Nanowhiskers (CNC) was added to the above polyaryletherketone solution, and stirred at a high speed for 3 minutes using a homogenizer to obtain an emulsion, and after standing, no suspended particles were present. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 90.5%.
Comparative example 4
0.03 parts by weight of polyaryletherketone was dissolved in 2.76 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 7.04 parts by weight of a dispersion containing 2.3% by weight of microfibrillated cellulose (MFC) was added to the above polyaryletherketone solution, and stirred at a high speed for 3 minutes using a homogenizer to obtain an emulsion, which was left standing without suspended particles. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 92.9%.
Comparative example 5
0.04 parts by weight of polyaryletherketone was dissolved in 3.94 parts by weight of 1, 2-dichloroethane to form a polyaryletherketone solution. 10.05 parts by weight of a dispersion containing 1.55% by weight of oxidized cellulose nanofibers (TOCNF) was added to the above polyaryletherketone solution, and stirred at a high speed for 3 minutes using a homogenizer to obtain an emulsion, which was free of suspended particles after standing. The emulsion was poured into a container. The vessel was placed on a copper bar and placed together in a dewar. Liquid nitrogen was added to the dewar and the emulsion frozen to a solid. And (3) placing the solid in a freeze dryer, and drying at the temperature of-50 ℃ for 72 hours to obtain the aerogel adsorption material. The adsorption efficiency of the obtained adsorption material to the diphenylamine is 89.8%.
As is clear from examples 1 to 2 and comparative examples 1 to 5, when the amount of nanocellulose is 0.168 parts by weight, the amount of polyaryletherketone is controlled to be 0.2 to 0.7 parts by weight, and the obtained aerogel adsorbing material has good adsorption performance, and the adsorption efficiency of the polyaniline can reach more than 96.1%. The dosage of the nanofiber (the nanofiber is cellulose nanofiber CNF) is controlled to be 0.169 weight part, the dosage of the polyaryletherketone is controlled to be 0.4 weight part, and the adsorption performance of the obtained aerogel adsorption material is better, and the adsorption efficiency of the obtained aerogel adsorption material on the diphenylamine can reach 98.1%. The use amount ratio of the polyaryletherketone in comparative examples 1 to 4 is too small, resulting in poor adsorption performance of the obtained aerogel adsorption material. The amount of polyaryletherketone used in comparative example 5 was relatively small, and the nanofiber used was oxidized cellulose nanofiber TOCNF, resulting in poor adsorption performance of the resulting aerogel adsorbent.
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the adsorption material is characterized in that the adsorption material comprises 0.16 to 0.18 weight part of nanofiber and 0.2 to 0.8 weight part of polyaryletherketone; wherein the nanofiber is selected from one of cellulose nanofiber, nanocellulose whisker or microfibrillated cellulose; the preparation method comprises the following steps:
(1) Dissolving polyaryletherketone in halogenated alkane to obtain polyaryletherketone solution;
(2) Mixing the dispersion liquid of the nanofibers with a polyaryletherketone solution to obtain emulsion; and then freezing the emulsion into solid by adopting liquid nitrogen, and freeze-drying the obtained solid to obtain the adsorption material.
2. The method of manufacturing according to claim 1, characterized in that:
in the step (1), the concentration of the polyaryletherketone solution is 0.9-10wt%; the halogenated alkane is selected from one or more of chloroform, dichloromethane and dichloroethane;
in the step (2), the concentration of the nano fibers in the dispersion liquid is 1 to 7 weight percent; the volume ratio of the dispersion liquid of the nano fiber to the polyaryletherketone solution is 1-5:1.
3. The method of claim 1, wherein the nanofibers are selected from one of cellulose nanofibers or nanocellulose whiskers.
4. The method of claim 1, wherein the adsorbent material comprises 0.16 to 0.18 parts by weight nanofibers and 0.25 to 0.7 parts by weight polyaryletherketone.
5. The method according to claim 4, wherein the adsorbent material comprises 0.16 to 0.18 parts by weight of the nanofiber and 0.28 to 0.6 parts by weight of the polyaryletherketone.
6. The method of claim 1, wherein the chemical structure of the nanofiber is represented by formula (I):
in the formula (I), x is a natural number of 50-1000.
7. The preparation method according to claim 1, wherein the chemical structure of the polyaryletherketone is represented by formula (II) or formula (III):
in the formula (II), R is selected from one of methyl, ethyl, cyano, nitro or halogen; r is R 1 One selected from hydrogen, methyl, ethyl, cyano, nitro or halogen; n and m are natural numbers of 1 to 1000;
in the formula (III), R' is selected from one of methyl, ethyl, cyano, nitro or halogen; r is R 2 One selected from hydrogen, methyl, ethyl, cyano, nitro or halogen; n and M are natural numbers of 1-1000.
8. The method of any one of claims 1 to 7, wherein the adsorbent material is an aerogel adsorbent material.
9. An adsorbent material prepared according to the preparation method of any one of claims 1 to 8.
10. Use of an adsorbent material according to claim 9 for removing aromatic hydrocarbon contaminants, including diphenylamine, from water.
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