CN115093517B - Nanometer NiO/MnFe 2 O 4 Preparation method of supported hydrophobically associating cationic polyacrylamide flocculant - Google Patents
Nanometer NiO/MnFe 2 O 4 Preparation method of supported hydrophobically associating cationic polyacrylamide flocculant Download PDFInfo
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Abstract
The invention discloses a nano NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps: s1: preparing nano nickel oxide and modifying: modifying the nano nickel oxide by adopting a vinyl silane coupling agent and acrylic acid; s2: preparing hexadecyl dimethyl allyl ammonium chloride; s3: adding modified nano nickel oxide, cetyl dimethyl allyl ammonium chloride, acrylamide, methacryloxyethyl trimethyl ammonium chloride, manganese acetate tetrahydrate, ferric nitrate nonahydrate, organic salt and urea into deionized water, stirring and dissolving, cooling to 0-2 ℃, introducing nitrogen, adding a composite initiator system for reaction for 3-5 h, heating to 100 ℃, preserving heat and crystallizing for 1-2 h, and hydrolyzing. The invention introduces nano NiO and MnFe into the molecular chain of polyacrylamide 2 O 4 And cationic monomer and hydrophobic monomer, which endows the polymer with photodegradation property and magnetic response property and improves the adsorption and flocculation sedimentation properties.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and hasThe body relates to a nanometer NiO/MnFe 2 O 4 A preparation method of a supported hydrophobic association cationic polyacrylamide flocculant.
Background
The cationic polyacrylamide polymer is a flocculant which is most widely used and has the greatest prospect in the current water treatment field, and the cationic flocculant has the advantages of high positive charge density, good water solubility and the like, wherein the cationic polymer with quaternary amine groups is the development trend of the product. The hydrophobic group can form a net structure in the aqueous solution due to hydrophobic association, the structure can reduce the hydrophilicity of the polymer and the flocs, enhance the phase transformation capability, enhance the adsorption capability of the polymer and the flocs on suspended particles, and enable the flocs to be separated from the water body more easily and be settled rapidly, so that the application of the hydrophobic association polyacrylamide as a flocculating agent in the field of water treatment is developed rapidly.
The hydrophobic association polyacrylamide enhances the adsorption bridging capability between the polymer and the solid particles due to strong intermolecular hydrophobic association, has good flocculation effect, and has better flocculation effect under the combined action of electrostatic action and hydrophobic association bridging if the hydrophobic monomer, acrylamide and cationic monomer are polymerized to prepare the cationic hydrophobic association polyacrylamide terpolymer. However, the existing polyacrylamide flocculant mainly depends on the attaching capability to achieve the effect of removing suspended particles in a water body, and when colloidal particles of the flocculant reach adsorption saturation, the flocculant does not have a flocculation function, and in addition, the existing flocculant has the problems that the separation of floccules is difficult, the recycling is not facilitated, and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nano NiO/MnFe 2 O 4 Preparation method of loaded hydrophobically associating cationic polyacrylamide flocculant, by introducing NiO and MnFe with magnetic response capability into hydrophobic monomer-cationic monomer-acrylamide terpolymer 2 O 4 NanoparticlesUnder the action of an externally applied magnetic field, the rapid magnetic separation of the floccules is realized, and the recycling of the floccules is realized; secondly, the introduction of inorganic nano particles improves the sedimentation power of floccules, thereby improving the sedimentation speed and shortening the solid-liquid separation time; again, mn 2+ 、Fe 3+ The nanometer NiO grafted on the polymer molecular chain is used as a crystal nucleus, and is self-assembled into a heterojunction photocatalysis structure, so that the photo-generated electrons and photo-generated holes are efficiently and quickly separated, the polyacrylamide flocculant also has excellent visible light catalytic degradation performance, the synchronous performance of flocculant adsorption and degradation is further realized, the occurrence of adsorption saturation balance is inhibited, and the polyacrylamide flocculant can continuously purify a water body.
The technical scheme of the invention is summarized as follows:
nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: 2-4 parts by mass of nickel acetate tetrahydrate is dissolved in 100-150 parts by mass of deionized water, ammonia water is added dropwise to adjust the pH value to 9.7-10 under the condition of continuous stirring, and stirring is continued until light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 4-6 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping a vinyl silane coupling agent onto the surface of nano nickel oxide, uniformly stirring, adding acrylic acid, and controlling the mass ratio of the vinyl silane coupling agent to the nano nickel oxide to the acrylic acid to be (0.4-0.8): 5: (0.6-1), stirring and reacting for 1-2 h to obtain vinyl modified nano nickel oxide; the vinyl silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane or methacryloxypropyl trimethoxy silane;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating 4-6 parts of allyl chloride, 12-20 parts of hexadecyl dimethyl tertiary amine and 18-25 parts of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, then distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 2 to 4 parts by mass of vinyl modified nano nickel oxide, 6 to 8 parts by mass of cetyl dimethyl allyl ammonium chloride, 60 to 110 parts by mass of acrylamide, 100 to 140 parts by mass of methacryloxyethyl trimethyl ammonium chloride, 2 to 3 parts by mass of manganese acetate tetrahydrate, 3.3 to 4.9 parts by mass of ferric nitrate nonahydrate, 4 to 6 parts by mass of organic salt and 5 to 10 parts by mass of urea into 150 to 240 parts by mass of deionized water, fully stirring and dissolving, then reducing the temperature to 0 to 2 ℃, transferring the mixture into a polymerization kettle and adding the mixture into a reaction kettle at a temperature of 60m 3 Introducing nitrogen at the flow rate of/h for 1-1.5 h, adding 8-12 parts of a composite initiator system to initiate polymerization reaction, polymerizing for 3-5 h, heating to 100 ℃, preserving heat and crystallizing for 1-2 h to obtain a polymer gel block;
s302: cutting the obtained polymer gel block, adding caustic soda flakes with a certain mass, kneading uniformly, carrying out hydrolysis reaction for 2-3 h, drying, crushing and sieving to obtain the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
The organic salt is selected from one or more of sodium acetate, sodium benzoate and sodium ethoxide;
the composite initiator system comprises the following components in percentage by weight: (a) 0.2% -20% of persulfate; (b) 0.5% -30% of sulfite; (c) 0.1% -20% of azo compound; (d) 0.5-15% of N, N-dimethylaminoethyl methacrylate; (e) 0.5% -30% of methylamine or ethylenediamine; (f) 5% -20% of isopropanol or pentaerythritol; (f) deionized water is complemented;
the persulfate is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate;
the sulfite is one or more of sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite;
the azo compound is one or more selected from azodiisobutyronitrile, dimethyl azodiisobutyrate and azodiisobutylamidine hydrochloride.
Preferably, the addition amount of the caustic soda flakes is 15-20% of the mass of the polymer gel block.
Preferably, the temperature of the hydrolysis reaction is 80 to 85 ℃, and the temperature of the drying after the hydrolysis reaction is finished is 75 ℃.
Preferably, the purity of the nitrogen is ∈ 99.99%.
The invention has the beneficial effects that:
1. the invention introduces NiO and MnFe with magnetic response capability into the hydrophobic monomer-cationic monomer-acrylamide terpolymer for the first time 2 O 4 The nano particles realize the rapid magnetic separation of floccules under the action of an externally applied magnetic field, and realize the recycling of floccules; secondly, the introduction of inorganic nano particles improves the sedimentation power of floccules, thereby improving the sedimentation speed and shortening the solid-liquid separation time; again, mn 2+ 、Fe 3+ The nanometer NiO grafted on the polymer molecular chain is used as a crystal nucleus, and is self-assembled into a heterojunction photocatalysis structure, so that the photo-generated electrons and photo-generated holes are efficiently and quickly separated, the polyacrylamide flocculant also has excellent visible light catalytic degradation performance, the synchronous performance of flocculant adsorption and degradation is further realized, the occurrence of adsorption saturation balance is inhibited, and the polyacrylamide flocculant can continuously purify a water body.
2. The invention utilizes the vinyl silane coupling agent and the acrylic acid to carry out surface modification reaction on the nano nickel oxide, so that the nano nickel oxide is connected into a polyacrylamide molecular chain through unsaturated-C=C-polymerization reaction, and meanwhile, because the acrylic acid exists on the surface of the nano nickel oxide, mn is reacted with Mn 2+ 、Fe 3+ Has chelating effect and is staticAdsorption of charges to Mn in the reaction system 2+ 、Fe 3+ Further takes nano nickel oxide as crystal nucleus, and is easy to nano MnFe in the later stage of the polymerization reaction (the reaction temperature in the later stage of the polymerization reaction is higher) 2 O 4 Is formed) and crystallization reaction period, self-assembling to form nano MnFe grafted on polyacrylamide chain 2 O 4 The NiO heterojunction structure ensures that the prepared polyacrylamide flocculant has excellent photocatalytic degradation performance, magnetic response performance, stronger flocculation capacity and adsorption capacity, and can be widely applied to the field of water treatment.
3. According to the invention, the hydrophobic monomer and the cationic monomer are introduced into the polyacrylamide chain, so that the hydrophobic association capability among polymer molecular chains is enhanced, the interaction between the organic polymer and the solid particles is enhanced, and the flocculation sedimentation of the solid particles is facilitated.
Drawings
FIG. 1 is a flow chart of a preparation method of the nano NiO supported hydrophobically associating cationic polyacrylamide flocculant.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides an embodiment of nano NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: 2-4 parts by mass of nickel acetate tetrahydrate is dissolved in 100-150 parts by mass of deionized water, ammonia water is added dropwise to adjust the pH value to 9.7-10 under the condition of continuous stirring, and stirring is continued until light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 4-6 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping a vinyl silane coupling agent onto the surface of nano nickel oxide, uniformly stirring, adding acrylic acid, and controlling the mass ratio of the vinyl silane coupling agent to the nano nickel oxide to the acrylic acid to be (0.4-0.8): 5: (0.6-1), stirring and reacting for 1-2 h to obtain vinyl modified nano nickel oxide; the vinyl silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane or methacryloxypropyl trimethoxy silane;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating 4-6 parts of allyl chloride, 12-20 parts of hexadecyl dimethyl tertiary amine and 18-25 parts of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, then distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 2 to 4 parts by mass of vinyl modified nano nickel oxide, 6 to 8 parts by mass of cetyl dimethyl allyl ammonium chloride, 60 to 110 parts by mass of acrylamide, 100 to 140 parts by mass of methacryloxyethyl trimethyl ammonium chloride, 2 to 3 parts by mass of manganese acetate tetrahydrate, 3.3 to 4.9 parts by mass of ferric nitrate nonahydrate, 4 to 6 parts by mass of organic salt and 5 to 10 parts by mass of urea into 150 to 240 parts by mass of deionized water, fully stirring and dissolving, then reducing the temperature to 0 to 2 ℃, transferring the mixture into a polymerization kettle and adding the mixture into a reaction kettle at a temperature of 60m 3 Introducing nitrogen with the purity of not less than 99.99% for 1-1.5 h at the flow rate of/h, adding 8-12 parts of a composite initiator system to initiate polymerization reaction, polymerizing for 3-5 h, heating to 100 ℃, preserving heat and crystallizing for 1-2 h to obtain a polymer gel block;
the vinyl silane coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane or methacryloxypropyl trimethoxy silane; the organic salt is selected from one or more of sodium acetate, sodium benzoate and sodium ethoxide; the composite initiator system comprises the following components in percentage by weight: (a) 0.2% -20% of persulfate; (b) 0.5% -30% of sulfite; (c) 0.1% -20% of azo compound; (d) 0.5-15% of N, N-dimethylaminoethyl methacrylate; (e) 0.5% -30% of methylamine or ethylenediamine; (f) 5% -20% of isopropanol or pentaerythritol; (f) deionized water is complemented; the persulfate is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate; the sulfite is one or more of sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite; the azo compound is one or more selected from azodiisobutyronitrile, dimethyl azodiisobutyrate and azodiisobutylamidine hydrochloride;
s302: cutting the obtained polymer gel block, adding caustic soda flakes accounting for 15% -20% of the mass of the polymer gel block, kneading uniformly, carrying out hydrolysis reaction for 2-3 h, drying, crushing and sieving to obtain the nano NiO/MnFe 2 O 4 Loading hydrophobic association cationic polyacrylamide; the temperature of the hydrolysis reaction is 80-85 ℃, and the drying temperature after the hydrolysis reaction is finished is 75 ℃.
This example is accomplished by first incorporating NiO and MnFe with magnetic response capability into a hydrophobic monomer-cationic monomer-acrylamide terpolymer 2 O 4 The nano particles realize the rapid magnetic separation of floccules under the action of an externally applied magnetic field, and realize the recycling of floccules; secondly, the introduction of inorganic nano particles improves the sedimentation power of floccules, thereby improving the sedimentation speed and shortening the solid-liquid separation time; again, mn 2+ 、Fe 3+ The nanometer NiO grafted on the polymer molecular chain is used as a crystal nucleus, and is self-assembled into a heterojunction photocatalysis structure, so that the photo-generated electrons and photo-generated holes are efficiently and quickly separated, the polyacrylamide flocculant also has excellent visible light catalytic degradation performance, the synchronous performance of flocculant adsorption and degradation is further realized, the occurrence of adsorption saturation balance is inhibited, and the polyacrylamide flocculant can continuously purify a water body.
This example uses vinylThe silane coupling agent and the acrylic acid carry out surface modification reaction on the nano nickel oxide, so that the nano nickel oxide is connected into a polyacrylamide molecular chain through unsaturated-C=C-polymerization reaction, and meanwhile, the acrylic acid exists on the surface of the nano nickel oxide to Mn 2+ 、Fe 3+ Has chelation and electrostatic charge adsorption, and can make Mn in reaction system 2+ 、Fe 3+ Further takes nano nickel oxide as crystal nucleus, and is easy to nano MnFe in the later stage of the polymerization reaction (the reaction temperature in the later stage of the polymerization reaction is higher) 2 O 4 Is formed) and crystallization reaction period, self-assembling to form nano MnFe grafted on polyacrylamide chain 2 O 4 The NiO heterojunction structure ensures that the prepared polyacrylamide flocculant has excellent photocatalytic degradation performance, magnetic response performance, stronger flocculation capacity and adsorption capacity, and can be widely applied to the field of water treatment.
According to the embodiment, the hydrophobic monomer and the cationic monomer are introduced into the polyacrylamide chain, so that the hydrophobic association capability among polymer molecular chains is enhanced, the interaction between the organic polymer and the solid particles is enhanced, and the flocculation and sedimentation of the solid particles are facilitated.
Example 1
Nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: dissolving 4g of nickel acetate tetrahydrate into 200g of deionized water, dropwise adding ammonia water to adjust the pH to 9.7 under the condition of continuous stirring, and continuously stirring until a light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 4 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping 0.08g of vinyl trimethoxy silane onto the surface of 1g of nano nickel oxide, uniformly stirring, adding 0.12g of acrylic acid, and stirring for reacting for 1h to obtain vinyl modified nano nickel oxide;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: 26g of allyl chloride, 78g of hexadecyl dimethyl tertiary amine and 117g of absolute ethyl alcohol are heated to 55 ℃ under continuous stirring, heated and refluxed for 24 hours at 55 ℃, then absolute ethyl alcohol is distilled out under reduced pressure at 50 ℃, then the product is poured into acetone to be frozen overnight and then subjected to suction filtration washing, and the suction filtration product is placed into a baking oven at 40 ℃ to be dried, thus obtaining the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 0.5g of vinyl modified nano nickel oxide, 1.5g of cetyl dimethyl allyl ammonium chloride, 15g of acrylamide, 25g of methacryloxyethyl trimethyl ammonium chloride, 0.5g of manganese acetate tetrahydrate, 0.825g of ferric nitrate nonahydrate, 1g of sodium acetate and 1.25g of urea into 37.5g of deionized water, fully stirring and dissolving, cooling to 0 ℃, transferring into a polymerization kettle and adding 60m of solution 3 Introducing nitrogen with the purity of not less than 99.99% at the flow rate of/h for 1h, adding 2g of a composite initiator system to initiate polymerization reaction, polymerizing for 3h, heating to 100 ℃, preserving heat and crystallizing for 1h to obtain a polymer gel block;
the composite initiator system comprises the following components in percentage by weight: (a) 0.2% ammonium persulfate; (b) 0.5% sodium sulfite; (c) 0.1% azobisisobutyronitrile; (d) 0.5% N, N-dimethylaminoethyl methacrylate; (e) 0.5% methylamine; (f) 5% isopropyl alcohol; (f) the deionized water is supplemented.
S302: cutting 20g of the obtained polymer gel block, adding 3g of caustic soda flakes, kneading uniformly, hydrolyzing at 80 ℃ for 2h, drying in a 75 ℃ oven, pulverizing by a pulverizer, sieving by a 60-mesh screen, and obtaining the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
Example two
Nanometer NiO/MnFe 2 O 4 Supported hydrophobically associating cationic polyacrylamide flocculantThe preparation method of (2) comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: dissolving 6g of nickel acetate tetrahydrate into 250g of deionized water, dropwise adding ammonia water to adjust the pH to 9.8 under the condition of continuous stirring, and continuously stirring until a light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 5 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping 0.2g of vinyl methyl dimethoxy silane onto the surface of 1.5g of nano nickel oxide, uniformly stirring, adding 0.26g of acrylic acid, and stirring for reacting for 1.5h to obtain vinyl modified nano nickel oxide;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating 26-39 g of allyl chloride, 105g of hexadecyl dimethyl tertiary amine and 140g of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 0.75g of vinyl modified nano nickel oxide, 1.75g of cetyl dimethyl allyl ammonium chloride, 21.5g of acrylamide, 30g of methacryloxyethyl trimethyl ammonium chloride, 0.65g of manganese acetate tetrahydrate, 1.1g of ferric nitrate nonahydrate, 1.25g of sodium benzoate and 2.0g of urea into 50g of deionized water, fully stirring and dissolving, cooling to 1 ℃ after dissolving, transferring into a polymerization kettle and adding 60m of sodium benzoate into the polymerization kettle 3 Introducing nitrogen with the purity of not less than 99.99% at the flow rate of/h for 1.5h, adding 2.5g of a composite initiator system to initiate polymerization, polymerizing for 4h, heating to 100 ℃ and preserving heat for crystallization for 1.5h to obtainA polymer gel block;
the composite initiator system comprises the following components in percentage by weight: (a) 10% potassium persulfate; (b) 15% potassium sulfite; (c) 20% dimethyl azodiisobutyrate; (d) 10% N, N-dimethylaminoethyl methacrylate; (e) 15% ethylenediamine; (f) 20% pentaerythritol; (f) deionized water is complemented;
s302: cutting 20g of the obtained polymer gel block, adding 3.5g of caustic soda flakes, kneading uniformly, carrying out hydrolysis reaction at 85 ℃ for 2.5h, drying in a 75 ℃ oven, crushing by a crusher, sieving by a 60-mesh screen, and obtaining the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
Example III
Nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: 8g of nickel acetate tetrahydrate is dissolved in 300g of deionized water, ammonia water is added dropwise to adjust the pH to 10 under the condition of continuous stirring, and stirring is continued until light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 6 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dropwise adding 0.32g of methacryloxypropyl trimethoxysilane onto the surface of 2g of nano nickel oxide, uniformly stirring, adding 0.4g of acrylic acid, and stirring for reacting for 2h to obtain vinyl modified nano nickel oxide;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating 39g of allyl chloride, 130g of hexadecyl dimethyl tertiary amine and 162.5g of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: 1g of vinyl modified nano nickel oxide, 2g of hexadecyl dimethyl allyl ammonium chloride, 27.5g of acrylamide, 35g of methacryloxyethyl trimethyl ammonium chloride, 0.75g of manganese acetate tetrahydrate, 1.225g of ferric nitrate nonahydrate, 1.5g of sodium ethoxide and 2.5g of urea are added into 60g of deionized water, after being fully stirred and dissolved, the temperature is reduced to 2 ℃, and then the mixture is transferred into a polymerization kettle and treated with 60m 3 Introducing nitrogen with the purity of not less than 99.99% at the flow rate of/h for 1.5h, adding 3g of a composite initiator system to initiate polymerization reaction, polymerizing for 5h, heating to 100 ℃, preserving heat and crystallizing for 2h, and obtaining a polymer gel block;
the composite initiator system comprises the following components in percentage by weight: (a) 20% sodium persulfate; (b) 30% potassium hydrogen sulfite; (c) 10% azobisisobutylamidine hydrochloride; (d) 5% N, N-dimethylaminoethyl methacrylate; (e) 10% ethylenediamine; (f) 5% pentaerythritol; (f) the deionized water is supplemented.
S302: cutting 20g of the obtained polymer gel block, adding 4g of caustic soda flakes, kneading uniformly, carrying out hydrolysis reaction for 3h at 85 ℃, drying in a 75 ℃ oven, crushing by a crusher, sieving by a 60-mesh screen, and obtaining the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
Example IV
Nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: dissolving 5g of nickel acetate tetrahydrate into 210g of deionized water, dropwise adding ammonia water to adjust the pH to 9.85 under the condition of continuous stirring, and continuously stirring until a light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 5 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping 0.16g of vinyl trimethoxy silane onto the surface of 1g of nano nickel oxide, uniformly stirring, adding 0.2g of acrylic acid, and stirring for reacting for 1h to obtain vinyl modified nano nickel oxide;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating up 37.5g of allyl chloride, 108g of hexadecyl dimethyl tertiary amine and 158g of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 1.0g of vinyl modified nano nickel oxide, 1.75g of cetyl dimethyl allyl ammonium chloride, 25g of acrylamide, 35g of methacryloxyethyl trimethyl ammonium chloride, 0.65g of manganese acetate tetrahydrate, 1.1g of ferric nitrate nonahydrate, 1.25g of sodium acetate and 1.75g of urea into 55g of deionized water, fully stirring and dissolving, cooling to 1 ℃, transferring into a polymerization kettle and adding 60m of solution 3 Introducing nitrogen with the purity of not less than 99.99% at the flow rate of/h for 1h, adding 2.5g of a composite initiator system to initiate polymerization reaction, polymerizing for 4h, heating to 100 ℃, preserving heat and crystallizing for 1h to obtain a polymer gel block;
the composite initiator system comprises the following components in percentage by weight: (a) 5% ammonium persulfate; (b) 7.5% sodium sulfite; (c) 10% azobisisobutyronitrile; (d) 7.5% N, N-dimethylaminoethyl methacrylate; (e) 10% methylamine; (f) 8.5% pentaerythritol; (f) the deionized water is supplemented.
S302: after 20g of the resulting polymer gel pieces were sheared, 3.5g of tablets were addedAfter alkali is kneaded uniformly, hydrolysis reaction is carried out for 2 hours at 85 ℃, then drying is carried out in a baking oven at 75 ℃, a pulverizer is used for pulverizing, and a 60-mesh screen is used for sieving, thus obtaining the nano NiO/MnFe 2 O 4 Loaded hydrophobically associating cationic polyacrylamide
Example five
Nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant comprises the following steps:
s1: preparing nano nickel oxide, modifying and treating and S2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer the same as in example four;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: 0.75g of vinyl modified nano nickel oxide, 2.0g of hexadecyl dimethyl allyl ammonium chloride, 27.5g of acrylamide, 34.5g of methacryloxyethyl trimethyl ammonium chloride, 0.65g of manganese acetate tetrahydrate, 1.1g of ferric nitrate nonahydrate, 1.5g of sodium acetate and 1.5g of urea are added into 60g of deionized water, after the mixture is fully stirred and dissolved, the temperature is reduced to 1.5 ℃, and the mixture is transferred into a polymerization kettle and treated with 60m 3 Introducing nitrogen with the purity of not less than 99.99% at the flow rate of/h for 1.5h, adding 3.0g of a composite initiator system to initiate polymerization reaction, polymerizing for 4.5h, heating to 100 ℃, preserving heat and crystallizing for 1h to obtain a polymer gel block;
the composite initiator system comprises the following components in percentage by weight: (a) 10% ammonium persulfate; (b) 10% sodium sulfite; (c) 10% azobisisobutyronitrile; (d) 5% N, N-dimethylaminoethyl methacrylate; (e) 10% methylamine; (f) 5% pentaerythritol; (f) the deionized water is supplemented.
S302: cutting 20g of the obtained polymer gel block, adding 3.5g of caustic soda flakes, kneading uniformly, carrying out hydrolysis reaction for 2h at 85 ℃, drying in a 75 ℃ oven, crushing by a crusher, sieving by a 60-mesh screen, and obtaining the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
Comparative example a comparative example was identical to example one, except that: manganese acetate tetrahydrate and ferric nitrate nonahydrate are not added in the preparation process of S301.
The second comparative example is the same as the second example in that: and S103, the operation step of modifying nano nickel oxide is omitted, namely, unmodified nano nickel oxide is adopted to directly participate in subsequent polymerization reaction.
Comparative example three is identical to example one, except that: manganese acetate tetrahydrate, ferric nitrate nonahydrate and vinyl modified nano nickel oxide are not added in the preparation process of S301.
The wastewater treatment performance of the polyacrylamide flocculants prepared in examples one to five and comparative examples one to three was measured:
the polyacrylamide flocculants prepared in examples one to five and comparative examples one to three are respectively added into 8 groups of 1000mL industrial wastewater (the initial physicochemical parameters of the industrial wastewater are that the suspended matter content is 127.2mg/L, the nitrate nitrogen content is 32.5mg/L and the total phosphorus content is 9.4 mg/L) in the same batch according to the proportion of 1mg/100mL, after the physicochemical indexes of the water body after treatment are measured, the removal rates of the suspended matter, the nitrate nitrogen and the total phosphorus are calculated, and the test results are shown in the following table:
| suspended matter removal rate/% | Nitrate removal rate/% | Total phosphorus removal/% | |
| Example 1 | 91.5 | 91.3 | 90.8 |
| Example two | 94.7 | 94.8 | 94.5 |
| Example III | 99.6 | 99.4 | 99.1 |
| Example IV | 99.2 | 99.1 | 98.9 |
| Example five | 95.3 | 96.0 | 98.3 |
| Comparative example one | 79.5 | 64.6 | 64.4 |
| Comparative example two | 83.6 | 73.9 | 73.5 |
| Comparative example three | 74.8 | 58.5 | 59.2 |
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. Nanometer NiO/MnFe 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized by comprising the following steps of:
s1: preparing nano nickel oxide and modifying:
s101: preparing nickel hydroxide sol precursor: 2-4 parts by mass of nickel acetate tetrahydrate is dissolved in 100-150 parts by mass of deionized water, ammonia water is added dropwise to adjust the pH value to 9.7-10 under the condition of continuous stirring, and stirring is continued until light green nickel hydroxide sol is generated;
s102: preparing nano nickel oxide: transferring the nickel hydroxide sol obtained in the step S101 into a reaction kettle, placing the reaction kettle into a muffle furnace at 400 ℃ for heat preservation for 4-6 hours, carrying out suction filtration on a product, washing the product to be neutral by deionized water and absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain nano nickel oxide;
s103: modified nano nickel oxide: dripping a vinyl silane coupling agent onto the surface of nano nickel oxide, uniformly stirring, adding acrylic acid, and controlling the mass ratio of the vinyl silane coupling agent to the nano nickel oxide to the acrylic acid to be (0.4-0.8): 5: (0.6-1), stirring and reacting for 1-2 h to obtain vinyl modified nano nickel oxide;
s2: preparation of cetyl dimethylallyl ammonium chloride hydrophobic monomer: heating 4-6 parts of allyl chloride, 12-20 parts of hexadecyl dimethyl tertiary amine and 18-25 parts of absolute ethyl alcohol to 55 ℃ under continuous stirring, heating and refluxing for 24 hours at 55 ℃, then distilling the absolute ethyl alcohol under reduced pressure at 50 ℃, pouring the product into acetone, freezing overnight, performing suction filtration and washing, and drying the suction filtration product in a baking oven at 40 ℃ to obtain the hexadecyl dimethyl allyl ammonium chloride hydrophobic monomer;
s3: preparing nano nickel oxide/manganese ferrite loaded hydrophobically associating cationic polyacrylamide:
s301: adding 2 to 4 parts by mass of vinyl modified nano nickel oxide, 6 to 8 parts by mass of cetyl dimethyl allyl ammonium chloride, 60 to 110 parts by mass of acrylamide, 100 to 140 parts by mass of methacryloxyethyl trimethyl ammonium chloride, 2 to 3 parts by mass of manganese acetate tetrahydrate, 3.3 to 4.9 parts by mass of ferric nitrate nonahydrate, 4 to 6 parts by mass of organic salt and 5 to 10 parts by mass of urea into 150 to 240 parts by mass of deionized water, fully stirring and dissolving, then reducing the temperature to 0 to 2 ℃, transferring the mixture into a polymerization kettle and adding the mixture into a reaction kettle at a temperature of 60m 3 Introducing nitrogen at the flow rate of/h for 1-1.5 h, adding 8-12 parts of a composite initiator system to initiate polymerization reaction, polymerizing for 3-5 h, heating to 100 ℃, preserving heat and crystallizing for 1-2 h to obtain a polymer gel block;
s302: cutting the obtained polymer gel block, adding caustic soda flakes with a certain mass, kneading uniformly, carrying out hydrolysis reaction for 2-3 h, drying, crushing and sieving to obtain the nano NiO/MnFe 2 O 4 And loading hydrophobic association cationic polyacrylamide.
2. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobic association cationic polyacrylamide flocculant is characterized in that the vinyl silane coupling agent is one or more selected from vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane or methacryloxypropyl trimethoxy silane.
3. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the organic salt is one or more selected from sodium acetate, sodium benzoate and sodium ethoxide.
4. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the composite initiator system comprises the following components in percentage by weight: (a) 0.2% to20% of persulfate; (b) 0.5% -30% of sulfite; (c) 0.1% -20% of azo compound; (d) 0.5-15% of N, N-dimethylaminoethyl methacrylate; (e) 0.5% -30% of methylamine or ethylenediamine; (f) 5% -20% of isopropanol or pentaerythritol; (f) the deionized water is supplemented.
5. A nano NiO/MnFe according to claim 4 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that persulfate is selected from one or more of ammonium persulfate, potassium persulfate and sodium persulfate.
6. A nano NiO/MnFe according to claim 4 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the sulfite is one or more selected from sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.
7. A nano NiO/MnFe according to claim 4 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the azo compound is one or more selected from azodiisobutyronitrile, dimethyl azodiisobutyrate and azodiisobutylamidine hydrochloride.
8. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the addition amount of the caustic soda flakes is 15-20% of the mass of the polymer gel block.
9. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobic association cationic polyacrylamide flocculant is characterized in that the temperature of the hydrolysis reaction is 80-85 ℃, and the drying temperature after the hydrolysis reaction is finished is 75 ℃.
10. A nano NiO/MnFe according to claim 1 2 O 4 The preparation method of the supported hydrophobically associating cationic polyacrylamide flocculant is characterized in that the purity of the nitrogen is not less than 99.99%.
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| JP2013123699A (en) * | 2011-12-16 | 2013-06-24 | Mitsubishi Paper Mills Ltd | Magnetic cation exchange material |
| CN103804955A (en) * | 2014-02-11 | 2014-05-21 | 东华大学 | Method for preparing cubic-crystal-form manganese ferrite composite microsphere by virtue of suspension polymerization method |
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| JP2013123699A (en) * | 2011-12-16 | 2013-06-24 | Mitsubishi Paper Mills Ltd | Magnetic cation exchange material |
| CN103804955A (en) * | 2014-02-11 | 2014-05-21 | 东华大学 | Method for preparing cubic-crystal-form manganese ferrite composite microsphere by virtue of suspension polymerization method |
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