CN109319895B - Nano chitosan modified polyaluminum chloride and preparation method thereof - Google Patents
Nano chitosan modified polyaluminum chloride and preparation method thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 119
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 15
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000009775 high-speed stirring Methods 0.000 claims abstract description 9
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 230000008859 change Effects 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- -1 fatty acid sulfoalkyl ester Chemical class 0.000 claims description 12
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 25
- 230000016615 flocculation Effects 0.000 abstract description 25
- 239000002245 particle Substances 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
Landscapes
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses nano chitosan modified polyaluminum chloride and a preparation method thereof, and relates to the technical field of environment-friendly water treatment. The method comprises the following steps: dissolving chitosan in dilute acid solution, adding EDTA disodium salt, adding absolute ethyl alcohol under stirring to change the solution into milk white, transferring the solution into a reaction kettle, and reacting at the temperature of 180 ℃ and 220 ℃ for 4-6h to obtain nano chitosan solution; carrying out heat preservation activation by an anionic surfactant under ultrasonic to obtain an active nano chitosan solution; dissolving polyaluminium chloride in deionized water to obtain a polyaluminium chloride solution, adding an active nano chitosan solution at a constant speed under high-speed stirring, carrying out heat preservation reaction for 1-2h, then aging for 2-4h under ice bath, adding absolute ethyl alcohol, completely precipitating, taking the precipitate, and drying to obtain the final product. The invention utilizes the nano chitosan particles to modify the polyaluminium chloride, maintains the electric neutralization effect of the polyaluminium chloride, strengthens the electrostatic cluster effect of the polyaluminium chloride, and introduces the flocculation effect of chitosan, thereby improving the flocculation effect.
Description
Technical Field
The invention relates to the technical field of environment-friendly water treatment, in particular to a sewage flocculant and a preparation method thereof, and specifically relates to nano chitosan modified polyaluminium chloride and a preparation method thereof.
Background
With the continuous acceleration of the industrialization process in China, more and more industrial sewage is generated, the industrial sewage contains a large amount of toxic and harmful substances, and if the industrial sewage is directly discharged without being treated, the water body pollution is caused. Therefore, various wastewater treatment methods are applied to reduce toxic and harmful substances in industrial wastewater, such as flocculation, sedimentation, evaporation, adsorption, and the like. Among these methods, flocculation is an environmentally friendly, efficient method for wastewater treatment.
Flocculants are essential agents in the flocculation process and include inorganic flocculants and organic flocculants. The inorganic polymeric flocculant becomes the most widely used flocculant at present due to the advantages of good sedimentation performance, high safety, wide application range and the like. Among them, polyaluminium chloride is the most well-developed inorganic polymeric flocculant. It is generally accepted that Al in the polyaluminium13The flocculant has high morphological charge amount, strong point neutralization capacity and strong adsorption bridging capacity, and is the optimal flocculation form in the polyaluminium chloride flocculant.
Recent studies have shown that the form of polyaluminium chloride has a certain particle size distribution, which not only fully exerts a simple electrical neutralization effect, but also is advantageous to exert an electrostatic clustering effect due to various space and charge combinations. Therefore, how to fully exert various flocculation effects of the polyaluminium chloride and enable the various flocculation effects to be cooperated so as to present a more efficient flocculation effect becomes a problem which needs to be solved urgently.
Disclosure of Invention
The first invention of the invention is that: aiming at the existing problems, the nano chitosan modified polyaluminium chloride is provided, wherein the polyaluminium chloride is modified by using nano chitosan particles, the electric neutralization effect of the polyaluminium chloride is kept, and the electrostatic cluster effect of the polyaluminium chloride is enhanced at the same time, so that the flocculation effect of chitosan is introduced, and the flocculation effect is improved.
The second purpose of the invention is to provide a preparation method of nano chitosan modified polyaluminium chloride, which is simple and feasible and is used for preparing the nano chitosan modified polyaluminium chloride.
The technical scheme adopted by the invention is as follows:
a preparation method of nano chitosan modified polyaluminium chloride comprises the following steps:
(1) dissolving chitosan in a dilute acid solution to obtain a chitosan solution; adding EDTA disodium salt into the chitosan solution, adding absolute ethyl alcohol under the stirring condition to change the solution into milk white, then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-220 ℃ to obtain a nano chitosan solution;
(2) adding a sodium tripolyphosphate solution into the nano chitosan solution under an ultrasonic condition, then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution;
(3) dissolving polyaluminium chloride in deionized water to obtain a polyaluminium chloride solution, then adding the active nano chitosan solution into the polyaluminium chloride solution at a constant speed under the condition of high-speed stirring, and continuously carrying out heat preservation reaction for 1-2 hours to obtain a crude product solution;
(4) and aging the crude product solution for 2-4h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate after complete precipitation to obtain the product.
The invention relates to a preparation method of nano chitosan modified polyaluminum chloride, wherein the mass ratio of chitosan to polyaluminum chloride is 1: 3-5.
The invention relates to a preparation method of nano chitosan modified polyaluminium chloride, in the step (1), dilute acid solution is selected from any one of dilute nitric acid, dilute hydrochloric acid, dilute acetic acid, dilute sulfuric acid and dilute formic acid, and the concentration is 5-10 wt%; the concentration of the chitosan solution is 20-35%. .
The invention relates to a preparation method of nano chitosan modified polyaluminium chloride, wherein the mass ratio of EDTA disodium to chitosan is 1: 60-80; the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9-12: 1.
The invention relates to a preparation method of nano chitosan modified polyaluminum chloride, in the step (2), the ultrasonic power is 500-1000w, and the frequency is 22-24 KHz; the mass ratio of the sodium tripolyphosphate to the chitosan is 1: 50-70.
According to the preparation method of the nano chitosan modified polyaluminum chloride, the anionic surfactant is selected from any one of alkyl sulfonate, fatty acid alkyl sulfonate, alkyl glyceryl ether sulfonate, fatty alcohol sulfate and alkyl alcohol polyoxyethylene ether phosphate, and the mass ratio of the anionic surfactant to the chitosan is 1: 30-40.
The invention relates to a preparation method of nano chitosan modified polyaluminium chloride, in the step (3), the concentration of a polyaluminium chloride solution is 20-30%; the high-speed stirring is 1800-3000 r/min.
The preparation method of the nano chitosan modified polyaluminum chloride provided by the invention comprises the step (4), wherein the drying temperature is not more than 70 ℃.
The nano chitosan modified polyaluminum chloride is prepared by adopting the preparation method of any one of the nano chitosan modified polyaluminum chloride.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) the nano chitosan particles with flocculation function are used for modifying the polyaluminium chloride, so that the electric neutralization function of the aluminium chloride is kept, the electrostatic cluster function of the aluminium chloride is enhanced, the flocculation function of the chitosan is introduced, namely, the flocculation effect of the polyaluminium chloride is enhanced through various ways, and the polyaluminium chloride has wide application prospect.
(2) The nano chitosan modifies huge amount of aluminum chloride and aluminum chloride through two modes of physical modification and chemical modification: physical modification, namely embedding the modified product into polyaluminium chloride under the condition of high-speed stirring; chemical modification, namely chemical combination between the active nano chitosan particles and the polyaluminium chloride. The two modes are combined, so that the modification efficiency is effectively improved, and the flocculation effect is further enhanced.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification (including any accompanying claims, abstract) may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The embodiment provides nano chitosan modified polyaluminum chloride and a preparation method thereof, and the preparation method improves the flocculation effect of the polyaluminum chloride through various ways and effectively improves the flocculation effect. The method comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in a dilute acid solution to obtain a chitosan solution; adding EDTA disodium salt into the chitosan solution, adding absolute ethyl alcohol under the stirring condition to change the solution into milk white, then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-220 ℃ to obtain the nano chitosan solution.
Step two: adding a sodium tripolyphosphate solution into the nano chitosan solution under the ultrasonic condition, then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution.
Step three: dissolving polyaluminium chloride in deionized water to obtain a polyaluminium chloride solution, then adding the active nano chitosan solution into the polyaluminium chloride solution at a constant speed under the condition of high-speed stirring, and continuously carrying out heat preservation reaction for 1-2h to obtain a crude product solution.
Step four: and aging the crude product solution for 2-4h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate after complete precipitation to obtain the product.
Example 2
The embodiment provides nano chitosan modified polyaluminum chloride and a preparation method thereof, and the preparation method improves the flocculation effect of the polyaluminum chloride through various ways and effectively improves the flocculation effect. The method comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in dilute acid solution to obtain chitosan solution with concentration of 20-35 wt%; wherein the dilute acid solution is selected from any one of dilute nitric acid, dilute hydrochloric acid, dilute acetic acid, dilute sulfuric acid and dilute formic acid, and the concentration is 5-10 wt%. Adding disodium EDTA salt into the chitosan solution according to the mass ratio of disodium EDTA to chitosan of 1:60-80, adding absolute ethyl alcohol under the condition of stirring speed of 120-180r/min to make the solution milk white, wherein the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9-12: 1. Then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-.
Step two: adding a sodium tripolyphosphate solution into the nano chitosan solution under the ultrasonic condition, then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution.
Step three: and (2) taking polyaluminum chloride according to the mass ratio of the chitosan to the polyaluminum chloride of 1:3-5, dissolving the polyaluminum chloride in deionized water to obtain a polyaluminum chloride solution, then adding the active nano chitosan solution into the polyaluminum chloride solution at a constant speed under the condition of high-speed stirring, and continuously carrying out heat preservation reaction for 1-2 hours to obtain a crude product solution.
Step four: and aging the crude product solution for 2-4h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate after complete precipitation to obtain the product.
Example 3
The embodiment provides nano chitosan modified polyaluminum chloride and a preparation method thereof, and the preparation method improves the flocculation effect of the polyaluminum chloride through various ways and effectively improves the flocculation effect. The method comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in dilute acid solution to obtain chitosan solution with concentration of 20-35 wt%; wherein the dilute acid solution is selected from any one of dilute nitric acid, dilute hydrochloric acid, dilute acetic acid, dilute sulfuric acid and dilute formic acid, and the concentration is 5-10 wt%. Adding disodium EDTA salt into the chitosan solution according to the mass ratio of disodium EDTA to chitosan of 1:60-80, adding absolute ethyl alcohol under the condition of stirring speed of 120-180r/min to make the solution milk white, wherein the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9-12: 1. Then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-.
Step two: adding a sodium tripolyphosphate solution into the nano chitosan solution under the ultrasonic conditions of power of 500-1000w and frequency of 22-24KHz, wherein the mass ratio of the sodium tripolyphosphate to the chitosan is 1: 50-70. Then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution. Wherein the anionic surfactant is selected from any one of alkyl sulfonate, fatty acid alkyl sulfonate, alkyl glyceryl ether sulfonate, fatty alcohol sulfate and alkyl alcohol polyoxyethylene ether phosphate, and the mass ratio of the anionic surfactant to the chitosan is 1: 30-40.
Step three: and (2) taking polyaluminum chloride according to the mass ratio of the chitosan to the polyaluminum chloride of 1:3-5, dissolving the polyaluminum chloride in deionized water to obtain a polyaluminum chloride solution, then adding the active nano chitosan solution into the polyaluminum chloride solution at a constant speed under the condition of high-speed stirring, and continuously carrying out heat preservation reaction for 1-2 hours to obtain a crude product solution.
Step four: and aging the crude product solution for 2-4h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate after complete precipitation to obtain the product.
Example 4
The embodiment provides nano chitosan modified polyaluminum chloride and a preparation method thereof, and the preparation method improves the flocculation effect of the polyaluminum chloride through various ways and effectively improves the flocculation effect. The method comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in dilute acid solution to obtain chitosan solution with concentration of 20-35 wt%; wherein the dilute acid solution is selected from any one of dilute nitric acid, dilute hydrochloric acid, dilute acetic acid, dilute sulfuric acid and dilute formic acid, and the concentration is 5-10 wt%. Adding disodium EDTA salt into the chitosan solution according to the mass ratio of disodium EDTA to chitosan of 1:60-80, adding absolute ethyl alcohol under the condition of stirring speed of 120-180r/min to make the solution milk white, wherein the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9-12: 1. Then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-.
Step two: adding a sodium tripolyphosphate solution into the nano chitosan solution under the ultrasonic conditions of power of 500-1000w and frequency of 22-24KHz, wherein the mass ratio of the sodium tripolyphosphate to the chitosan is 1: 50-70. Then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution. Wherein the anionic surfactant is selected from any one of alkyl sulfonate, fatty acid alkyl sulfonate, alkyl glyceryl ether sulfonate, fatty alcohol sulfate and alkyl alcohol polyoxyethylene ether phosphate, and the mass ratio of the anionic surfactant to the chitosan is 1: 30-40.
Step three: and (2) taking polyaluminium chloride according to the mass ratio of the chitosan to the polyaluminium chloride of 1:3-5, dissolving the polyaluminium chloride in deionized water to obtain a polyaluminium chloride solution with the concentration of 20-30%, then adding the active nano chitosan solution into the polyaluminium chloride solution at a constant speed under the stirring condition of 1800-.
Step four: aging the crude product solution for 2-4h under ice bath condition, adding anhydrous ethanol for precipitation, completely precipitating, and drying the precipitate at a temperature not higher than 70 ℃.
Example 5
The embodiment provides nano chitosan modified polyaluminum chloride and a preparation method thereof, and the preparation method improves the flocculation effect of the polyaluminum chloride through various ways and effectively improves the flocculation effect. The method comprises the following specific steps:
the method comprises the following steps: dissolving chitosan in a 10% dilute acetic acid solution to obtain a 30% wt chitosan solution; adding disodium EDTA into the chitosan solution according to the mass ratio of 1:75 of disodium EDTA to chitosan, adding absolute ethyl alcohol under the condition of stirring speed of 150r/min to make the solution milk white, wherein the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9: 1. Then transferring the solution into a reaction kettle, and reacting for 6 hours at the temperature of 200 ℃ to obtain the nano chitosan solution.
Step two: adding a sodium tripolyphosphate solution into the nano chitosan solution under the ultrasonic condition of 800w of power and 24KHz of frequency, wherein the mass ratio of the sodium tripolyphosphate to the chitosan is 1: 60. Then adding sodium dodecyl benzene sulfonate according to the mass ratio of the sodium dodecyl benzene sulfonate to the chitosan of 1: 40, and carrying out heat preservation and activation for 4 hours at the temperature of 60 ℃ to obtain an active nano chitosan solution.
Step three: and (2) taking polyaluminum chloride according to the mass ratio of the chitosan to the polyaluminum chloride of 1:4, dissolving the polyaluminum chloride in deionized water to obtain a polyaluminum chloride solution with the concentration of 20%, then adding the active nano chitosan solution into the polyaluminum chloride solution at a constant speed under the stirring condition of 2400r/min, and continuing to perform heat preservation reaction for 2 hours to obtain a crude product solution.
Step four: and aging the crude product solution for 2h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate at 60 ℃ after complete precipitation.
Example 6
This example demonstrates the flocculation of the nano-chitosan-modified polyaluminum chloride prepared in example 5 to provide a basis for its application.
Water for experiment: the waste water from metal smelting has no smell and light petroleum hydrocarbon smell. There were very small white particles present. The main components are rare earth oxides and metal ion complexes. The pH value is about 1.23. The water temperature was 19 ℃.
Flocculating agent: (1) ordinary polyaluminum chlorides; (2) the nano chitosan-modified polyaluminum chloride (hereinafter referred to as modified polyaluminum chloride) provided in example 5.
The experimental water was treated with two flocculants, the results of which are shown in table 1:
as can be seen from Table 1, the treatment efficiency of the nano chitosan modified polyaluminum chloride provided by the invention on various pollutants in sewage is higher than that of common aluminum chloride.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (9)
1. A preparation method of nano chitosan modified polyaluminium chloride is characterized by comprising the following steps:
(1) dissolving chitosan in a dilute acid solution to obtain a chitosan solution; adding EDTA disodium salt into the chitosan solution, adding absolute ethyl alcohol under the stirring condition to change the solution into milk white, then transferring the solution into a reaction kettle, and reacting for 4-6h at the temperature of 180-220 ℃ to obtain a nano chitosan solution;
(2) adding a sodium tripolyphosphate solution into the nano chitosan solution under an ultrasonic condition, then adding an anionic surfactant, and carrying out heat preservation and activation for 2-4h at the temperature of 40-60 ℃ to obtain an active nano chitosan solution;
(3) dissolving polyaluminium chloride in deionized water to obtain a polyaluminium chloride solution, then adding the active nano chitosan solution into the polyaluminium chloride solution at a constant speed under the condition of high-speed stirring, and continuously carrying out heat preservation reaction for 1-2 hours to obtain a crude product solution;
(4) and aging the crude product solution for 2-4h under an ice bath condition, adding absolute ethyl alcohol for precipitation, and drying the precipitate after complete precipitation to obtain the product.
2. The method for preparing nano chitosan modified polyaluminum chloride as claimed in claim 1, wherein the mass ratio of chitosan to polyaluminum chloride is 1: 3-5.
3. The method for preparing nano chitosan modified polyaluminum chloride as claimed in claim 2, wherein the dilute acid solution in step (1) is selected from any one of dilute nitric acid, dilute hydrochloric acid, dilute acetic acid, dilute sulfuric acid and dilute formic acid, and the concentration is 5-10 wt%; the concentration of the chitosan solution is 20-35% wt.
4. The preparation method of nano chitosan modified polyaluminum chloride as claimed in claim 3, wherein the mass ratio of EDTA disodium to chitosan is 1: 60-80; the volume ratio of the absolute ethyl alcohol to the chitosan solution is 9-12: 1.
5. The method for preparing nano chitosan modified polyaluminum chloride as claimed in claim 1, wherein in the step (2), the ultrasonic power is 500-1000w, and the frequency is 22-24 KHz; the mass ratio of the sodium tripolyphosphate to the chitosan is 1: 50-70.
6. The method for preparing nano chitosan modified polyaluminum chloride as claimed in claim 5, wherein the anionic surfactant is selected from any one of alkyl sulfonate, fatty acid sulfoalkyl ester, alkyl glyceryl ether sulfonate, fatty alcohol sulfate and alkyl alcohol polyoxyethylene ether phosphate, and the mass ratio of the anionic surfactant to the chitosan is 1: 30-40.
7. The method for preparing nano-chitosan modified polyaluminum chloride as claimed in claim 6, wherein in the step (3), the concentration of the polyaluminum chloride solution is 20-30%; the high-speed stirring is 1800-3000 r/min.
8. The method for preparing nano chitosan-modified polyaluminum chloride as claimed in claim 7, wherein in the step (4), the drying temperature is not more than 70 ℃.
9. A nano chitosan modified polyaluminum chloride, characterized in that, it is prepared by the method of any one of claims 1-8.
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