CN113083248A - Preparation process of environment-friendly adsorption material - Google Patents
Preparation process of environment-friendly adsorption material Download PDFInfo
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- CN113083248A CN113083248A CN202110431106.7A CN202110431106A CN113083248A CN 113083248 A CN113083248 A CN 113083248A CN 202110431106 A CN202110431106 A CN 202110431106A CN 113083248 A CN113083248 A CN 113083248A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- 239000013067 intermediate product Substances 0.000 claims description 16
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004475 Arginine Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 9
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GQFCLJZQECVTDO-UHFFFAOYSA-N 2-(2-chloroethoxy)acetonitrile Chemical compound ClCCOCC#N GQFCLJZQECVTDO-UHFFFAOYSA-N 0.000 claims description 4
- ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 4-chlorobutanenitrile Chemical compound ClCCCC#N ZFCFBWSVQWGOJJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 6
- 239000012153 distilled water Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 Hydroxyl Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation process of an environment-friendly adsorption material, belonging to the technical field of adsorption material preparation, and comprising the following specific steps: adding modified chitosan, deionized water and absolute ethyl alcohol into a reactor, magnetically stirring for 2-4h, and adding modified Fe3O4Continuously stirring for reaction for 2 hours, adding a glutaraldehyde solution with the mass fraction of 25%, stirring for reaction for 8 hours at 40-45 ℃, filtering after the reaction is finished, drying a filter cake in a 60 ℃ oven for 12 hours, washing a dried product with an acetic acid solution with the mass fraction of 2% and distilled water for one time in sequence, and finally drying at 50 ℃ to constant weight to obtain the environment-friendly adsorbing material; by modifying chitosan and Fe3O4The adsorbing material prepared by the invention has excellent adsorption effect, antibacterial property and regeneration property, and has high utilization value in the remediation of water body pollution.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption materials, and particularly relates to a preparation process of an environment-friendly adsorption material.
Background
Along with the rapid development of social economy, the contradiction between economic construction and ecological environment becomes more and more prominent, the pollution conditions of copper, mercury, arsenic and chemical oxygen demand in river pollutants are increasing year by year, and water pollution treatment becomes a problem of close attention of the masses.
The industrial water body pollutants mainly relate to dyes, aromatic compounds (polycyclic aromatic hydrocarbons and the like), heavy metals, radioactive substances and the like, the discharge of the pollutants into the environment greatly threatens the health and ecological balance of human beings, the existing wastewater treatment method mainly comprises a chemical precipitation method, a chemical oxidation method, an ion exchange method, a membrane separation technology, an adsorption method and the like, wherein the adsorption method is to utilize adsorbents with high specific surface area or special groups and different functions to enrich and remove the pollutants such as heavy metal ions and organic dyes in the wastewater, and has the characteristics of simple operation, thorough pollutant treatment, small investment and the like, the adsorption method is divided into material adsorption and chemical adsorption according to different acting forces between the adsorbents and adsorption media, the physical adsorption is generated by intermolecular acting force between the adsorbents and the adsorbents, namely Van der Waals force, and has the characteristics of small adsorption heat, weak binding force, no selectivity and high adsorption and desorption rates, generally, the adsorbent is multi-layer adsorption, stable in chemical adsorption combination and selective, is monomolecular adsorption, and in the prior art, the adsorption effect of the adsorbent is poor, the adsorbent cannot be recycled, and some of the adsorbent has high N, P content, is used for water pollution treatment, and is easy to cause water eutrophication and secondary pollution, so that the improvement of the high-efficiency, environment-friendly and renewable adsorbent is the technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a preparation process of an environment-friendly adsorption material.
The technical problems to be solved by the invention are as follows:
in the prior art, the adsorption effect of the adsorption material is poor, the adsorption material cannot be recycled, and the adsorption material is easily corroded by microorganisms or molds in the storage and use processes, so that the adsorption performance of the adsorption material is reduced.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of an environment-friendly adsorption material comprises the following specific steps:
adding modified chitosan, deionized water and absolute ethyl alcohol into a reactor, magnetically stirring for 2-4h, and adding modified Fe3O4And continuously stirring for reaction for 2 hours, adding a glutaraldehyde solution with the mass fraction of 25%, stirring for reaction for 8 hours at 40-45 ℃, filtering after the reaction is finished, drying a filter cake in a 60 ℃ oven for 12 hours, washing a dried product with an acetic acid solution with the mass fraction of 2% and distilled water for one time in sequence, and finally drying at 50 ℃ to constant weight to obtain the environment-friendly adsorbing material.
Further, the modified chitosan, deionized water, absolute ethyl alcohol and modified Fe3O4And glutaraldehyde solutionThe dosage ratio of the components is 1 g: 5mL of: 5mL of: 0.25-0.35 g: 0.15-0.25 mL.
Further, the modified chitosan is prepared by the following steps:
step A1, adding chitosan and acetic acid solution with the mass fraction of 1% into a round-bottom flask, stirring for 4-6h at room temperature, then adding sodium hydroxide solution with the mass fraction of 35% to adjust the pH value to 7-8, then transferring into an ice bath, controlling the reaction temperature to be 0-5 ℃, dropwise adding 2-chloroethoxy acetonitrile into the round-bottom flask by using a constant-pressure dropping funnel, heating to 60 ℃ after dropwise adding, continuing stirring for reaction for 4-6h, adding sodium hydroxide solution with the mass fraction of 35% into the round-bottom flask to adjust the pH value to 7-8 after the reaction is finished, purifying and washing for three times by using methanol and acetone, and finally drying in an oven at 60 ℃ to constant weight to obtain an intermediate 1; dissolving chitosan in acetic acid solution, controlling reaction temperature to make-NH on chitosan molecule2Carrying out substitution reaction with chlorine atoms of 2-chloroethoxy acetonitrile to graft chitosan molecules with acetonitrile structures to obtain an intermediate 1;
step A2, adding the intermediate 1 and a methanol aqueous solution of hydroxylamine hydrochloride with the mass fraction of 3% into a three-neck flask, controlling the reaction temperature to be 85 ℃, carrying out reflux reaction for 2 hours, then adding a sodium hydroxide solution into the three-neck flask to adjust the pH value to be 7, carrying out rotary evaporation, repeatedly washing with ethanol, and finally drying to obtain an intermediate 2; converting a cyano group in the structure of the intermediate 1 into an amidoxime group through amidoxime reaction, namely an intermediate 2;
step A3, adding the intermediate 2 and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the pH value of 9, stirring and reacting for 10-12h at 80 ℃, adding acetone with the volume of 3 times after the reaction is finished, separating out floccules, carrying out suction filtration, washing a filter cake for 3-5 times by using ethanol with the volume fraction of 80%, and finally carrying out vacuum drying at 30 ℃ to constant weight to obtain modified chitosan; and (3) carrying out substitution reaction on alcoholic hydroxyl groups on original chitosan molecules of the intermediate 2 and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and grafting a quaternary ammonium salt structure on the intermediate 2 molecules to obtain the modified chitosan.
Further, in step A1, the amount ratio of chitosan, acetic acid solution and 2-chloroethoxy acetonitrile is 0.1 mol: 160-220 mL: 0.1mol, the methanol aqueous solution in the step A2 is prepared from methanol and deionized water according to the volume ratio of 1: 1, and the dosage ratio of the intermediate 1 to a methanol aqueous solution of hydroxylamine hydrochloride with the mass fraction of 3% is 1 g: 28-35mL, the ratio of the amounts of intermediate 2, 3-chloro-2-hydroxypropyltrimethylammonium chloride and sodium hydroxide solution in step A3 was 1 g: 3.8-4.2 g: 100 mL.
Further, the modified Fe3O4The preparation method comprises the following steps:
step B1, mixing Fe3O4Adding powder, absolute ethyl alcohol and deionized water into a three-neck flask, carrying out ultrasonic dispersion for 30min under the condition of frequency of 20-40kHz, adding a coupling agent KH-560 into the three-neck flask under the condition of rotating speed of 60-100r/min, heating to 45-48 ℃, and carrying out stirring reaction for 24h to obtain an intermediate product a; using Fe3O4Hydroxyl on the surface of the powder and a silane coupling agent kH-560 undergo a chemical reaction to obtain an intermediate product a containing an epoxy group;
the reaction process is as follows:
step B2, adding arginine into deionized water, stirring for 10min at the temperature of 50 ℃ and the rotation speed of 60-80r/min to obtain a solvent B, adding the solvent B into the intermediate product a by using a constant-pressure dropping funnel, stirring while dropping, controlling the rotation speed to be 40r/min, stirring and reacting for 24h at room temperature after dropping, washing and centrifuging by using deionized water after the reaction is finished, and drying the obtained solid in vacuum at the temperature of 60 ℃ to obtain modified Fe3O4(ii) a The intermediate product a and arginine are subjected to ring-opening reaction by utilizing the characteristic that the amino and the epoxy group can perform ring-opening reaction to obtain the modified Fe grafted with alcoholic hydroxyl, carboxyl, primary amino and secondary amino3O4And (3) granules.
The reaction process is as follows:
further, Fe in step B13O4The dosage ratio of the powder, the absolute ethyl alcohol, the deionized water and the coupling agent KH-560 is 0.1 mol: 180-200 mL: 200mL of: 0.1 mol; the dosage ratio of arginine to deionized water in the step B2 is 0.1 mol: 100-110mL, the volume ratio of the intermediate product a to the solvent b is 4-4.1: 1.
the invention has the beneficial effects that:
the invention uses modified chitosan and modified Fe3O4Is prepared from the main raw material through cross-linking glutaraldehyde to obtain the active functional carbonyl group of glutaraldehyde, modified chitosan and modified Fe3O4The amino groups react to form a cross-linked network, and the cross-linked network is filtered, washed and dried to prepare the chitosan magnetic composite adsorption material, the composite adsorption material can effectively adsorb heavy metal ions in a water body, is rich in more active groups, has good adsorption effect, repeated regeneration capacity, environmental protection, energy conservation and sustainable development performance, and chitosan is modified to graft a quaternary ammonium salt structure and an amidoxime group on a chitosan molecule, so that the adsorption material has excellent antibacterial performance, and is prevented from being damaged and decomposed by microorganisms during storage or use, the amidoxime group consists of amino and oxime, wherein the oxime (-RC-NOH) is two composite groups containing alkalescent nitrogen atoms and moderate acid hydroxyl, the adsorption performance on the metal ions is excellent, and Fe is used3O4The hydroxyl on the surface of the powder and a silane coupling agent kH-560 undergo a chemical reaction to obtain an intermediate product a containing an epoxy group, and then the intermediate product a and arginine undergo a ring-opening reaction by utilizing the characteristic that an amino group and the epoxy group can undergo a ring-opening reaction to obtain modified Fe grafted with alcoholic hydroxyl, carboxyl, primary amino and secondary amino3O4Particles of modified Fe3O4While having magnetism, graft multiple active chemical group, wherein primary amino, secondary amino are cationic group, carboxyl is anionic group, can show ion exchange and chelate adsorption effect simultaneously, realize the adsorption together of anion, cationic type pollutant, compare with the adsorption material of single groupThe adsorption efficiency and the capacity are obviously improved, so that the adsorption material prepared by the method has excellent adsorption effect, antibacterial property and regeneration property, and has higher utilization value in the remediation of water body pollution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The modified chitosan is prepared by the following steps:
step A1, adding 0.1mol of chitosan and 160mL of acetic acid solution with the mass fraction of 1% into a round-bottom flask, stirring for 4 hours at room temperature, then adding sodium hydroxide solution with the mass fraction of 35% to adjust the pH value to 7, then transferring into an ice bath, controlling the reaction temperature to be 0 ℃, dropwise adding 0.1mol of 2-chloroethyl acetonitrile into the round-bottom flask by using a constant-pressure dropping funnel, heating to 60 ℃ after dropwise adding, continuing stirring for reaction for 4 hours, adding sodium hydroxide solution with the mass fraction of 35% into the round-bottom flask after the reaction is finished, adjusting the pH value to 7, purifying and washing with methanol and acetone for three times, and finally drying in an oven at 60 ℃ to constant weight to obtain an intermediate 1;
step A2, adding 1g of intermediate 1 and 28mL of methanol aqueous solution of 3% hydroxylamine hydrochloride by mass fraction into a three-neck flask, controlling the reaction temperature to be 85 ℃, carrying out reflux reaction for 2 hours, then adding a sodium hydroxide solution into the three-neck flask to adjust the pH value to be 7, carrying out rotary evaporation, repeatedly washing with ethanol, and finally drying to obtain an intermediate 2;
step A3, adding 1g of intermediate 2 and 3.8g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into 100mL of sodium hydroxide solution with pH value of 9, stirring and reacting at 80 ℃ for 10h, adding 3 times of acetone after the reaction is finished, separating out floccules, carrying out suction filtration, washing a filter cake for 3 times by using ethanol with volume fraction of 80%, and finally carrying out vacuum drying at 30 ℃ to constant weight to obtain the modified chitosan.
Example 2
The modified chitosan is prepared by the following steps:
step A1, adding 0.1mol of chitosan and 185mL of acetic acid solution with the mass fraction of 1% into a round-bottom flask, stirring for 5 hours at room temperature, then adding sodium hydroxide solution with the mass fraction of 35% to adjust the pH value to 7, then transferring into an ice bath, controlling the reaction temperature to be 3 ℃, dropwise adding 0.1mol of 2-chloroethyl acetonitrile into the round-bottom flask by using a constant-pressure dropping funnel, heating to 60 ℃ after dropwise adding, continuing stirring for reaction for 5 hours, adding sodium hydroxide solution with the mass fraction of 35% into the round-bottom flask after the reaction is finished, adjusting the pH value to 7, purifying and washing the mixture for three times by using methanol and acetone, and finally drying the mixture in a 60 ℃ oven to constant weight to obtain an intermediate 1;
step A2, adding 1g of intermediate 1 and 33mL of methanol aqueous solution of hydroxylamine hydrochloride with the mass fraction of 3% into a three-neck flask, controlling the reaction temperature to be 85 ℃, carrying out reflux reaction for 2 hours, then adding a sodium hydroxide solution into the three-neck flask to adjust the pH value to be 7, carrying out rotary evaporation, repeatedly washing with ethanol, and finally drying to obtain an intermediate 2;
step A3, adding 1g of intermediate 2 and 4.0g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into 100mL of sodium hydroxide solution with pH value of 9, stirring and reacting at 80 ℃ for 11h, adding 3 times of acetone after the reaction is finished, separating out floccules, carrying out suction filtration, washing a filter cake for 4 times by using ethanol with volume fraction of 80%, and finally carrying out vacuum drying at 30 ℃ to constant weight to obtain the modified chitosan.
Example 3
The modified chitosan is prepared by the following steps:
step A1, adding 0.1mol of chitosan and 220mL of acetic acid solution with the mass fraction of 1% into a round-bottom flask, stirring for 6 hours at room temperature, then adding sodium hydroxide solution with the mass fraction of 35% to adjust the pH value to 8, then transferring into an ice bath, controlling the reaction temperature to be 5 ℃, dropwise adding 0.1mol of 2-chloroethyl acetonitrile into the round-bottom flask by using a constant-pressure dropping funnel, heating to 60 ℃ after dropwise adding, continuing stirring for reaction for 6 hours, adding sodium hydroxide solution with the mass fraction of 35% into the round-bottom flask after the reaction is finished, adjusting the pH value to 8, purifying and washing with methanol and acetone for three times, and finally drying in an oven at 60 ℃ to constant weight to obtain an intermediate 1;
step A2, adding 1g of intermediate 1 and 35mL of methanol aqueous solution of 3% hydroxylamine hydrochloride by mass fraction into a three-neck flask, controlling the reaction temperature to be 85 ℃, carrying out reflux reaction for 2 hours, then adding a sodium hydroxide solution into the three-neck flask to adjust the pH value to be 7, carrying out rotary evaporation, repeatedly washing with ethanol, and finally drying to obtain an intermediate 2;
step A3, adding 1g of intermediate 2 and 4.2g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into 100mL of sodium hydroxide solution with pH value of 9, stirring and reacting at 80 ℃ for 12h, adding 3 times of acetone after the reaction is finished, separating out floccules, carrying out suction filtration, washing a filter cake for 5 times by using ethanol with volume fraction of 80%, and finally carrying out vacuum drying at 30 ℃ to constant weight to obtain the modified chitosan.
Comparative example 1
This comparative example was chitosan purchased from Shanghai Michelin Biotechnology Ltd.
Example 4
Modified Fe3O4The preparation method comprises the following steps:
step B1, adding 0.1mol of Fe3O4Adding the powder, 180mL of absolute ethyl alcohol and 200mL of deionized water into a three-neck flask, ultrasonically dispersing for 30min under the condition of frequency of 20kHz, adding 0.1mol of coupling agent KH-560 into the three-neck flask under the condition of rotating speed of 60r/min, heating to 45 ℃, and stirring for reacting for 24h to obtain an intermediate product a;
step B2, adding 0.1mol of arginine into 100mL of deionized water, stirring at 50 ℃ and 60r/min for 10min to obtain a solvent B, adding the solvent B into the intermediate product a by using a constant-pressure dropping funnel, stirring while dropping, controlling the rotation speed to be 40r/min, stirring and reacting for 24h at room temperature after dropping is finished, washing with deionized water after the reaction is finished, centrifuging, and drying the obtained solid in vacuum at 60 ℃ to obtain modified Fe3O4。
Example 5
Modified Fe3O4The preparation method comprises the following steps:
step B1, adding 0.1mol of Fe3O4Adding the powder, 190mL of absolute ethyl alcohol and 200mL of deionized water into a three-neck flask, ultrasonically dispersing for 30min under the condition of frequency of 30kHz, adding 0.1mol of coupling agent KH-560 into the three-neck flask under the condition of rotating speed of 80r/min, heating to 47 ℃, and stirring for reacting for 24h to obtain an intermediate product a;
step B2, adding 0.1mol of arginine into 108mL of deionized water, stirring at 50 ℃ and 70r/min for 10min to obtain a solvent B, adding the solvent B into the intermediate product a by using a constant-pressure dropping funnel, stirring while dropping, controlling the rotation speed to be 40r/min, stirring and reacting for 24h at room temperature after dropping is finished, washing with deionized water after the reaction is finished, centrifuging, and drying the obtained solid in vacuum at 60 ℃ to obtain modified Fe3O4。
Example 6
Modified Fe3O4The preparation method comprises the following steps:
step B1, adding 0.1mol of Fe3O4Adding the powder, 200mL of absolute ethyl alcohol and 200mL of deionized water into a three-neck flask, ultrasonically dispersing for 30min under the condition of frequency of 30kHz, adding 0.1mol of coupling agent KH-560 into the three-neck flask under the condition of rotating speed of 80r/min, heating to 47 ℃, and stirring for reacting for 24h to obtain an intermediate product a;
step B2, adding 0.1mol of arginine into 110mL of deionized water, stirring at 50 ℃ and 70r/min for 10min to obtain a solvent B, adding the solvent B into the intermediate product a by using a constant-pressure dropping funnel, stirring while dropping, controlling the rotation speed to be 40r/min, stirring and reacting for 24h at room temperature after dropping is finished, washing with deionized water after the reaction is finished, centrifuging, and drying the obtained solid in vacuum at 60 ℃ to obtain modified Fe3O4。
Comparative example 2
This comparative example was a ferroferric oxide powder purchased from bio-technologies ltd, wokay, beijing.
Example 7
A preparation process of an environment-friendly adsorption material comprises the following specific steps:
1g of modified chitosan of example 1, 5mL of deionized water and 5mL of anhydrous ethanol were added to a reactor, and after magnetic stirring for 2 hours, 0.25g of modified Fe of example 4 was added3O4And continuously stirring for reaction for 2 hours, adding 0.15mL of 25 mass percent glutaraldehyde solution, stirring for reaction for 8 hours at 40 ℃, filtering after the reaction is finished, drying a filter cake in a 60 ℃ oven for 12 hours, washing a dried product with 2 mass percent acetic acid solution and distilled water sequentially for one time, and finally drying at 50 ℃ to constant weight to obtain the environment-friendly adsorbing material.
Example 8
1g of the modified chitosan of example 2, 5mL of deionized water and 5mL of anhydrous ethanol were added to a reactor, and after magnetic stirring for 3 hours, 0.30g of the modified Fe of example 5 was added3O4And continuously stirring for reaction for 2 hours, adding 0.20mL of glutaraldehyde solution with the mass fraction of 25%, stirring for reaction for 8 hours at 42 ℃, filtering after the reaction is finished, drying a filter cake in a 60 ℃ drying oven for 12 hours, washing a dried product with acetic acid solution with the mass fraction of 2% and distilled water sequentially for one time, and finally drying at 50 ℃ to constant weight to obtain the environment-friendly adsorbing material.
Example 9
1g of the modified chitosan of example 3, 5mL of deionized water and 5mL of anhydrous ethanol were added to a reactor, and after magnetic stirring for 4 hours, 0.35g of the modified Fe of example 6 was added3O4And continuously stirring for reaction for 2 hours, adding 0.25mL of glutaraldehyde solution with the mass fraction of 25%, stirring for reaction for 8 hours at 45 ℃, filtering after the reaction is finished, drying a filter cake in a 60 ℃ drying oven for 12 hours, washing a dried product with acetic acid solution with the mass fraction of 2% and distilled water sequentially for one time, and finally drying at 50 ℃ to constant weight to obtain the environment-friendly adsorbing material.
Comparative example 3
The modified chitosan in example 7 was replaced with the chitosan in comparative example 1, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 4
Modified Fe in example 83O4By replacement withThe ferroferric oxide powder, the rest raw materials and the preparation process in the comparative example 2 are unchanged.
Comparative example 5
Modified Chitosan from example 9 was replaced with Chitosan from comparative example 1 to modify Fe3O4The ferroferric oxide powder in the paired proportion 2 is replaced, and the rest raw materials and the preparation process are unchanged.
Example 10
The performance of the adsorbing materials prepared in examples 7 to 9 and comparative examples 3 to 5 was measured in the following manner: respectively adding the same amount of adsorbing materials in the examples and the comparative examples into a copper chloride solution with the mass fraction of 0.5%, then adding dilute hydrochloric acid to adjust the pH value to 5, uniformly stirring and shaking for 6h, and detecting Cl by using a silver nitrate titration method-Concentration, calculation of Cl-Adsorption rate, and testing Cu by using UV752 digital display ultraviolet visible light photometer2+Concentration, calculation of Cu2+The adsorption rate is tested according to GB/T21510-2+Each group of the adsorbing materials is added to Na2Desorbing in EDTA eluent, collecting the adsorbing material under the action of an external magnetic field, washing the adsorbing material for 5 times by deionized water, then drying the adsorbing material in vacuum at 50 ℃ for the next round of adsorption, and calculating the adsorption rate of 6 times of repeated use, wherein the test results of each group are shown in the following table:
as can be seen from the above table, Cu of examples 7 to 92+The adsorption rate is 99.6-99.8%, Cl-The adsorption rate is 60.9-61.2%, the antibacterial rate is 90.8-92.3%, and Cu is adsorbed after 6 times of use2+The adsorption rate is 87.9-88.2%, the performance measurement results are superior to those of comparative examples 3-5, which shows that the chitosan is modified to graft a quaternary ammonium salt structure and an amidoxime group on the chitosan molecule, so that the adsorbing material of the invention has excellent antibacterial performance and excellent adsorption performance on metal ions, and the characteristic that the amino and the epoxy can perform a ring-opening reaction is utilized to obtain the adsorbing material grafted with alcoholic hydroxyl, carboxyl, primary amino and secondary aminoModified Fe3O4Particles of modified Fe3O4The magnetic adsorption material has magnetism, is grafted with various active chemical groups, and can adsorb anionic and cationic pollutants together, so that the adsorption material prepared by the invention has excellent adsorption effect, antibacterial property and regeneration property, and has high utilization value in water pollution remediation.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. A preparation process of an environment-friendly adsorption material is characterized by comprising the following specific steps:
adding modified chitosan, deionized water and absolute ethyl alcohol into a reactor, magnetically stirring for 2-4h, and adding modified Fe3O4Continuously stirring for reaction for 2h, adding a glutaraldehyde solution with the mass fraction of 25%, stirring for reaction for 8h at 40-45 ℃, filtering after the reaction is finished, and purifying and drying a filter cake to obtain the environment-friendly adsorbing material;
wherein the modified Fe3O4The preparation method comprises the following steps:
step B1, mixing Fe3O4Adding the powder, absolute ethyl alcohol and deionized water into a three-neck flask, ultrasonically dispersing for 30min, adding a coupling agent KH-560 into the three-neck flask, heating to 45-48 ℃, and stirring for reacting for 24h to obtain an intermediate product a;
step B2, adding arginine into deionized water, stirring for 10min at 50 ℃ to obtain a solvent B, adding the solvent B into the intermediate product a by using a constant-pressure dropping funnel, stirring and reacting for 24h at room temperature after the dropwise addition is finished, and washing, centrifuging and drying after the reaction is finished to obtain modified Fe3O4。
2. The preparation process of the environment-friendly adsorbing material as claimed in claim 1, wherein the modified chitosan, deionized water, absolute ethyl alcohol and modified Fe3O4And the dosage ratio of the glutaraldehyde solution is 1 g: 5mL of: 5mL of: 0.25-0.35 g: 0.15-0.25 mL.
3. The preparation process of the environment-friendly adsorbing material as claimed in claim 1, wherein Fe in step B13O4The dosage ratio of the powder, the absolute ethyl alcohol, the deionized water and the coupling agent KH-560 is 0.1 mol: 180-200 mL: 200mL of: 0.1 mol; the dosage ratio of arginine to deionized water in the step B2 is 0.1 mol: 100-110mL, the volume ratio of the intermediate product a to the solvent b is 4-4.1: 1.
4. the preparation process of the environment-friendly adsorption material according to claim 1, wherein the modified chitosan is prepared by the following steps:
step A1, adding chitosan and acetic acid solution with the mass fraction of 1% into a round-bottom flask, stirring for 4-6h at room temperature, then adding sodium hydroxide solution to adjust the pH value to 7-8, controlling the reaction temperature to be 0-5 ℃, dropwise adding 2-chloroethyl acetonitrile into the round-bottom flask by using a constant-pressure dropping funnel, after dropwise adding, heating to 60 ℃, continuing stirring for reaction for 4-6h, after the reaction is finished, adding sodium hydroxide solution into the round-bottom flask to adjust the pH value to 7-8, purifying, washing and drying to obtain an intermediate 1;
step A2, adding the intermediate 1 and a methanol aqueous solution of hydroxylamine hydrochloride with the mass fraction of 3% into a three-neck flask, controlling the reaction temperature to be 85 ℃, carrying out reflux reaction for 2 hours, then adding a sodium hydroxide solution into the three-neck flask to adjust the pH value to be 7, carrying out rotary evaporation, repeatedly washing with ethanol, and finally drying to obtain an intermediate 2;
and A3, adding the intermediate 2 and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into a sodium hydroxide solution with the pH value of 9, stirring and reacting for 10-12h at 80 ℃, adding acetone with the volume being 3 times that of the mixture after the reaction is finished, separating out floccules, carrying out suction filtration, washing a filter cake for 3-5 times by using ethanol with the volume fraction of 80%, and finally carrying out vacuum drying at 30 ℃ to constant weight to obtain the modified chitosan.
5. The preparation process of the environment-friendly adsorption material according to claim 4, wherein the dosage ratio of the chitosan, the acetic acid solution and the 2-chloroethoxy acetonitrile in the step A1 is 0.1 mol: 160-220 mL: 0.1mol, the methanol aqueous solution in the step A2 is prepared from methanol and deionized water according to the volume ratio of 1: 1, and the dosage ratio of the intermediate 1 to a methanol aqueous solution of hydroxylamine hydrochloride with the mass fraction of 3% is 1 g: 28-35mL, the ratio of the amounts of intermediate 2, 3-chloro-2-hydroxypropyltrimethylammonium chloride and sodium hydroxide solution in step A3 was 1 g: 3.8-4.2 g: 100 mL.
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