CN118027280B - Water-dispersible cationic polyacrylamide material and preparation method thereof - Google Patents
Water-dispersible cationic polyacrylamide material and preparation method thereof Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 69
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims abstract description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 abstract description 14
- 230000016615 flocculation Effects 0.000 abstract description 14
- 239000010865 sewage Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012688 inverse emulsion polymerization Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a water-dispersible cationic polyacrylamide material and a preparation method thereof, comprising the following steps: s1, dissolving acrylamide, methacryloxyethyl trimethyl ammonium chloride, polyvinylpyrrolidone and ammonium sulfate in deionized water to prepare a homogeneous solution A; s2-6, preparing water-dispersed cationic polyacrylamide; the water-dispersible cationic polyacrylamide material prepared by the method has excellent sewage treatment performance, excellent flocculation performance, good fluidity and good stability, and the preparation process is simple to operate, low in energy consumption, energy-saving, environment-friendly and safe.
Description
Technical Field
The invention relates to the technical field of polymer material synthesis, in particular to a water-dispersible cationic polyacrylamide material and a preparation method thereof.
Background
The structural formula of Polyacrylamide (PAM) is [ -CH2-CH (CONH 2) ] n-, the molecular weight is 400 ten thousand-2000 ten thousand, and the polyacrylamide is divided into cationic, anionic, zwitterionic and nonionic according to the structure. Cationic polyacrylamide is a copolymer consisting of polyacrylamide and cationic structural units. The molecular chain of the cationic polyacrylamide is usually provided with quaternary ammonium groups, and the cationic polyacrylamide is positively charged in both an acidic system and a basic system. In industrial wastewater, colloid particles are usually negatively charged, and cationic polyacrylamide can be used for adsorbing suspended particles in water, so that the particles are aggregated into larger flocs through mechanisms such as electric neutralization, adsorption bridging and the like, and pollutants in water are removed by sedimentation. Moreover, the cationic polyacrylamide has the advantages of small dosage, low toxicity, easy post-treatment and the like, and is widely applied to industries such as water treatment, oil fields, papermaking and the like.
In the current high-tech age, the industrialization process is accelerated, the water consumption is rapidly increased, and meanwhile, a large amount of industrial wastewater causes serious water pollution. Among the many sewage treatment methods, flocculation is the most widely used water treatment method because of its advantages of simplicity and economy. At present, the flocculant has various varieties and can be roughly divided into organic flocculant, inorganic flocculant, microbial flocculant and composite flocculant. The synthetic organic polymeric flocculant has the characteristics of high flocculation efficiency, easy water dissolution, convenient subsequent treatment and the like, so that the synthetic organic polymeric flocculant is widely applied, the polyacrylamide is low in production cost, easy to modify and modify, has strong adsorption performance, small consumption and large formed floccules, and is one of the floccules with the largest consumption at present. Cationic polyacrylamide is more commonly used in wastewater treatment because most of the particles in the wastewater are negatively charged.
The product types of the cationic polyacrylamide comprise four dosage forms of hydrosol, dry powder, water-in-oil emulsion and water-in-water emulsion. The method for producing the cationic polyacrylamide product by the copolymerization method can be classified into aqueous solution polymerization, inverse emulsion polymerization, water dispersion polymerization and the like. The main methods adopted in the current industrial production are aqueous solution polymerization and inverse emulsion polymerization, but the problems that the solid content and the molecular weight of hydrosol are low are difficult to overcome, the product is difficult to dissolve, the hydrosol is used as dry powder for convenient transportation and dissolution, and the hydrosol is obtained through the procedures of granulation, drying, crushing, sieving and the like. However, when the polymer is used in the form of dry powder, a lot of energy is consumed for drying, and large-scale equipment is required for dissolution, so that the cost is high. For inverse emulsion polymerization, the use of some surfactants and organic solvents during the synthesis process can lead to problems of environmental pollution and difficult recovery. Aiming at the problems, the cationic polyacrylamide is prepared by adopting water-dispersible polymerization, has the advantages of environmental protection, energy conservation, convenient transportation, quick dissolution, economy and the like, has wide application prospect in the aspect of sewage treatment, but researches related to the cationic polyacrylamide are freshly reported.
Therefore, the preparation method of the water-dispersible cationic polyacrylamide material has obvious guiding value for solving the problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a water-dispersible cationic polyacrylamide material and a preparation method thereof, and the water-dispersible cationic polyacrylamide material prepared by the method has excellent sewage treatment performance. Compared with the commercial products, the water-dispersible cationic polyacrylamide prepared by the method has the characteristics of high solid content, large molecular weight and instant dissolution. The water-dispersible cationic polyacrylamide prepared by the method has excellent flocculation performance, good fluidity and good stability, and the preparation process is simple to operate, low in energy consumption, energy-saving, environment-friendly and safe.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
S1, dissolving acrylamide, methacryloxyethyl trimethyl ammonium chloride, polyvinylpyrrolidone and ammonium sulfate in deionized water to prepare a homogeneous solution A;
s2, introducing nitrogen into the homogeneous solution A to remove oxygen;
s3, adding an initiator azo diisobutylamidine hydrochloride into deionized water to prepare a solution B;
S4, dispersing the nano copper powder, the trimesic acid and the nitrogen-doped graphene oxide into DMF, and stirring for 0.5-1 h to prepare a solution C;
S5, adding the solution B into the homogeneous solution A, sealing and stirring, heating for 0.5-1 h, adding the solution C after the polymerization reaction is initiated, slowly dropwise adding the dilute nitric acid solution, and continuously heating for 5-10 h after the dropwise adding of the dilute nitric acid solution is completed to prepare the polyacrylamide emulsion;
S6, purifying and drying the polyacrylamide emulsion, grinding and screening to obtain the water-dispersed cationic polyacrylamide.
Preferably, in the step S1, the molar ratio of the acrylamide to the methacryloyloxyethyl trimethyl ammonium chloride is 2:1-6:1.
Preferably, in the step S1, the total solid content of the acrylamide and the methacryloyloxyethyl trimethyl ammonium chloride is added according to the mass fraction of 10% -30%; the polyvinyl pyrrolidone and the ammonium sulfate are respectively added according to the mass percent of 0.5-1.0% and the mass percent of 20-30%, and the balance is deionized water.
Preferably, in the step S2, the time for introducing nitrogen and removing oxygen is limited to 10min-30min;
And step S3, the concentration of the initiator azo diisobutylamidine hydrochloride solution is 1g/L-10g/L.
Preferably, in step S4, the total solid content of the nano copper powder and the trimesic acid is added according to 30% -40% of the mass fraction, wherein the molar ratio of the nano copper powder to the trimesic acid is 2-3:1, a step of; the nitrogen-doped graphene oxide is added according to the mass percentage of 10% -15%, and the balance is DMF.
Preferably, the preparation method of the nitrogen-doped graphene oxide comprises the following steps: according to the mass ratio of 1:2-1: and 4, dispersing graphene oxide in an ammonia water solution, heating to 120-140 ℃, performing hydrothermal reaction for 1-2 h, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide.
Preferably, in the step S5, the concentration of the dilute nitric acid is 3-6 mol/L; the molar ratio of the dilute nitric acid to the nanometer copper powder is 6:1-8:1.
Preferably, in step S5, the temperature of the heating reaction is limited to 40-50 ℃; the temperature of the continued heating reaction is defined as 80-100 ℃.
Preferably, in step S6, the solvent used for the purification is an alcohol-water mixed solution.
A water-dispersible cationic polyacrylamide material is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, nitric acid reacts with nano copper powder to generate nitric oxide by controlling the molar ratio of dilute nitric acid to nano copper powder, nitric oxide bulges out of cationic polyacrylamide, and the prepared cationic polyacrylamide has a porous structure except for absorbing oxygen which is possibly not exhausted in the solution, and copper nitrate generated by the reaction exists in a solution system and can be subjected to coordination reaction with functional groups on the polyacrylamide to generate a gel structure through crosslinking, so that the viscosity of the polyacrylamide is improved, and Cu-MOF material generated by the reaction with trimesic acid exists in the cationic polyacrylamide to improve the flocculation effect of the cationic polyacrylamide on wastewater;
2. the water-dispersible cationic polyacrylamide flocculant product prepared by the method has excellent sewage treatment performance, and compared with the commercial product, the water-dispersible cationic polyacrylamide prepared by the method has the characteristics of high solid content, large molecular weight and quick dissolution. The preparation method has the advantages of excellent flocculation performance, good fluidity, good stability, simple preparation process operation, low energy consumption, energy conservation, environmental protection and safety.
Drawings
FIG. 1 is a flow chart of a preparation process of a water-dispersible cationic polyacrylamide material of the present invention;
FIG. 2 is an infrared spectrum of a water-dispersible cationic polyacrylamide material of the present invention;
FIG. 3 is a scanning electron microscope image A of a water-dispersed cationic polyacrylamide material of the present invention;
FIG. 4 is a scanning electron microscope image B of a water-dispersed cationic polyacrylamide material of the present invention;
FIG. 5 is a scanning electron microscope image of a Cu-MOF material in a separately prepared water-dispersible cationic polyacrylamide material;
FIG. 6 is an x-ray powder diffraction pattern of a water-dispersed cationic polyacrylamide material of the present invention;
FIG. 7 is a graph of thermogravimetric analysis of a water dispersible cationic polyacrylamide material of the present invention.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, to illustrate some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-7, the present invention provides a technical solution:
Example 1:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
(1) 6.09g of acrylamide, 8.91g of methacryloxyethyl trimethyl ammonium chloride, 0.7g of polyvinylpyrrolidone and 24.5g of ammonium sulfate were weighed into a flask, and 59.8g of deionized water was added thereto and mixed with thorough stirring to prepare a homogeneous solution A. Nitrogen was introduced into the homogeneous solution a for half an hour while stirring, and oxygen was removed from the homogeneous solution a.
(2) 0.005G of initiator azobisisobutyrimidine hydrochloride was dissolved in deionized water to prepare solution B having a concentration of 5 g/L. Dispersing 10g of graphene oxide in 23ml of ammonia water solution, heating to 120 ℃, performing hydrothermal reaction for 1h, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide. 8.4g of nano copper powder, 10.5g of trimesic acid and 7g of nitrogen-doped graphene oxide are dispersed in 37.1ml of DMF and stirred for half an hour to prepare a solution C.
(3) Slowly dropwise adding the solution B into the homogeneous solution A while stirring, continuously introducing nitrogen and stirring for half an hour when the dropwise adding is completed, heating to the reaction temperature of 45 ℃, reacting for half an hour, stopping introducing nitrogen, adding the solution C, slowly dropwise adding 150ml of 6mol/L dilute nitric acid solution, sealing a reaction container, heating to 80 ℃, reacting for 8 hours, stopping reacting to obtain a milky water-in-water emulsion with good fluidity, purifying, drying, crushing and sieving the emulsion with an alcohol-water mixed solution, and obtaining powder which is the target water-dispersible cationic polyacrylamide product.
Example 2:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
(1) 7.60g of acrylamide, 7.40g of methacryloxyethyl trimethyl ammonium chloride, 0.7g of polyvinylpyrrolidone and 24.5g of ammonium sulfate were weighed into a flask, and 59.8g of deionized water was added thereto and mixed with thorough stirring to prepare a homogeneous solution A. Nitrogen was introduced into the homogeneous solution a for half an hour while stirring, and oxygen was removed from the homogeneous solution a.
(2) 0.005G of initiator azobisisobutyrimidine hydrochloride was dissolved in deionized water to prepare solution B having a concentration of 5 g/L. Dispersing 8g of graphene oxide in 21ml of ammonia water solution, heating to 140 ℃, performing hydrothermal reaction for 2 hours, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide. 5.6g of nano copper powder, 10.5g of trimesic acid and 5.5g of nitrogen-doped graphene oxide are dispersed in 18.65ml of DMF and stirred for half an hour to prepare solution C.
(3) Slowly dropwise adding the solution B into the homogeneous solution A while stirring, continuously introducing nitrogen and stirring for half an hour when the dropwise adding is completed, heating to the reaction temperature of 45 ℃, reacting for half an hour, stopping introducing nitrogen, adding the solution C, slowly dropwise adding 134ml of 6mol/L dilute nitric acid solution, sealing a reaction container, heating to 100 ℃, reacting for 8 hours, stopping reacting to obtain a milky water-in-water emulsion with good fluidity, purifying, drying, crushing and sieving the emulsion with an alcohol-water mixed solution, and obtaining powder, namely the target water-dispersible cationic polyacrylamide product.
Example 3:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
(1) 8.67g of acrylamide, 6.33g of methacryloxyethyl trimethyl ammonium chloride, 0.7g of polyvinylpyrrolidone and 24.5g of ammonium sulfate were weighed into a flask, and 59.8g of deionized water was added thereto and mixed with thorough stirring to prepare a homogeneous solution A. Nitrogen was introduced into the homogeneous solution a for half an hour while stirring, and oxygen was removed from the homogeneous solution a.
(2) 0.005G of initiator azobisisobutyrimidine hydrochloride was dissolved in deionized water to prepare solution B having a concentration of 5 g/L. Dispersing 10g of graphene oxide in 23ml of ammonia water solution, heating to 120 ℃, performing hydrothermal reaction for 1h, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide. 8.4g of nano copper powder, 12.6g of trimesic acid and 9g of nitrogen-doped graphene oxide are dispersed into 30ml of DMF and stirred for half an hour to prepare solution C.
(3) Slowly dropwise adding the solution B into the homogeneous solution A while stirring, continuously introducing nitrogen and stirring for half an hour when the dropwise adding is completed, heating to the reaction temperature of 45 ℃, reacting for half an hour, stopping introducing nitrogen, adding the solution C, slowly dropwise adding 117ml of 6mol/L dilute nitric acid solution, sealing a reaction container, heating to 80 ℃, reacting for 8 hours, stopping reacting to obtain a milky water-in-water emulsion with good fluidity, purifying, drying, crushing and sieving the emulsion with an alcohol-water mixed solution, and obtaining powder which is the target water-dispersible cationic polyacrylamide product.
Example 4:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
(1) 9.47g of acrylamide, 5.53g of methacryloxyethyl trimethyl ammonium chloride, 0.7g of polyvinylpyrrolidone and 24.5g of ammonium sulfate were weighed into a flask, and 59.8g of deionized water was added thereto and mixed with thorough stirring to prepare a homogeneous solution A. Nitrogen was introduced into the homogeneous solution a for half an hour while stirring, and oxygen was removed from the homogeneous solution a.
(2) 0.005G of initiator azobisisobutyrimidine hydrochloride was dissolved in deionized water to prepare solution B having a concentration of 5 g/L. Dispersing 10g of graphene oxide in 23ml of ammonia water solution, heating to 120 ℃, performing hydrothermal reaction for 1h, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide. 8.4g of nano copper powder, 10.5g of trimesic acid and 7g of nitrogen-doped graphene oxide are dispersed in 37.1ml of DMF and stirred for half an hour to prepare a solution C.
(3) Slowly dropwise adding the solution B into the homogeneous solution A while stirring, continuously introducing nitrogen and stirring for half an hour when the dropwise adding is completed, heating to the reaction temperature of 45 ℃, reacting for half an hour, stopping introducing nitrogen, adding the solution C, slowly dropwise adding 150ml of 6mol/L dilute nitric acid solution, sealing a reaction container, heating to 80 ℃, reacting for 8 hours, stopping reacting to obtain a milky water-in-water emulsion with good fluidity, purifying, drying, crushing and sieving the emulsion with an alcohol-water mixed solution, and obtaining powder which is the target water-dispersible cationic polyacrylamide product.
Example 5:
the preparation method of the water-dispersible cationic polyacrylamide material comprises the following steps:
(1) 10.09g of acrylamide, 4.91g of methacryloxyethyl trimethyl ammonium chloride, 0.7g of polyvinylpyrrolidone and 24.5g of ammonium sulfate were weighed into a flask, and 59.8g of deionized water was added thereto and mixed with thorough stirring to prepare a homogeneous solution A. Nitrogen was introduced into the homogeneous solution a for half an hour while stirring, and oxygen was removed from the homogeneous solution a.
(2) 0.005G of initiator azobisisobutyrimidine hydrochloride was dissolved in deionized water to prepare solution B having a concentration of 5 g/L. Dispersing 8g of graphene oxide in 21ml of ammonia water solution, heating to 140 ℃, performing hydrothermal reaction for 2 hours, centrifuging, washing and drying to obtain the nitrogen-doped graphene oxide. 5.6g of nano copper powder, 10.5g of trimesic acid and 5.5g of nitrogen-doped graphene oxide are dispersed in 18.65ml of DMF and stirred for half an hour to prepare solution C.
(3) Slowly dropwise adding the solution B into the homogeneous solution A while stirring, continuously introducing nitrogen and stirring for half an hour when the dropwise adding is completed, heating to the reaction temperature of 45 ℃, reacting for half an hour, stopping introducing nitrogen, adding the solution C, slowly dropwise adding 134ml of 6mol/L dilute nitric acid solution, sealing a reaction container, heating to 100 ℃, reacting for 8 hours, stopping reacting to obtain a milky water-in-water emulsion with good fluidity, purifying, drying, crushing and sieving the emulsion with an alcohol-water mixed solution, and obtaining powder, namely the target water-dispersible cationic polyacrylamide product.
Comparative example 1:
Comparative example 1 was identical to example 3 except that the "water in water" emulsion prepared in comparative example 1 was not purified with aqueous alcohol, directly dried, broken and sieved to obtain the corresponding powder product.
Comparative example 2:
comparative example 2 is identical to comparative example 1 except that trimesic acid was not added in comparative example 2, and the remaining steps are exactly the same as in comparative example 1 in comparative example 2.
Comparative example 3:
Comparative example 3 is identical to comparative example 1 except that no nano copper powder, trimesic acid, nitrogen-doped graphene oxide, nitric acid are added in comparative example 3, and the remaining steps are exactly the same as in comparative example 1 in comparative example 3.
The water-dispersible cationic polyacrylamide flocculated materials prepared in examples 1 to 5 and comparative examples 1 to 3 were each tested for sewage treatment ability.
The water purification test method comprises the following steps: 1.2L of turbid water samples (turbidity is 138.5mg.L < -1 >) are measured, the average is divided into 8 groups, the 8 groups of water samples are simultaneously stirred for 5 minutes at the same rotating speed, the flocculating agents prepared in the examples 1-5 and the products prepared in the comparative examples 1-3 are respectively added into the 8 groups of water samples, and the flocculation effect of the 8 groups of samples is detected, and the results are shown in Table 1:
TABLE 1 flocculation effect detection of the flocculants prepared in examples 1-5 and the products prepared in comparative examples 1-3
The results show that the water-dispersible cationic polyacrylamide flocculation materials prepared in the examples 1-5 have very low residual turbidity after turbid water treatment, and have excellent flocculation effects, and the water-dispersible cationic polyacrylamide materials provided by the application are proved to be reliable. And the remarkable difference between the flocculation effects of the embodiments 1-5 and the comparative examples 1-3 can prove that the water-dispersible cationic polyacrylamide flocculation material prepared by the method has good flocculation effects, can obtain excellent flocculation effects under the condition of using only a small amount of medicaments, has strong sewage treatment capability and good stability, is environment-friendly in preparation process, and has obvious guiding value on the research direction of the brand-new water-dispersible cationic polyacrylamide material.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The preparation method of the water-dispersible cationic polyacrylamide material is characterized by comprising the following steps of:
S1, dissolving acrylamide, methacryloxyethyl trimethyl ammonium chloride, polyvinylpyrrolidone and ammonium sulfate in deionized water to prepare a homogeneous solution A;
s2, introducing nitrogen into the homogeneous solution A to remove oxygen;
s3, adding an initiator azo diisobutylamidine hydrochloride into deionized water to prepare a solution B;
S4, dispersing the nano copper powder, the trimesic acid and the nitrogen-doped graphene oxide into DMF, and stirring for 0.5-1 h to prepare a solution C;
S5, adding the solution B into the homogeneous solution A, sealing and stirring, heating for 0.5-1 h, adding the solution C after the polymerization reaction is initiated, slowly dropwise adding the dilute nitric acid solution, and continuously heating for 5-10 h after the dropwise adding of the dilute nitric acid solution is completed to prepare the polyacrylamide emulsion;
s6, purifying and drying the polyacrylamide emulsion, grinding and screening to obtain water-dispersed cationic polyacrylamide;
The molar ratio of the acrylamide to the methacryloyloxyethyl trimethyl ammonium chloride is 2:1-6:1;
Step S1, adding 10-30% of total solid content of the acrylamide and the methacryloyloxyethyl trimethyl ammonium chloride according to mass fraction; polyvinyl pyrrolidone and ammonium sulfate are respectively added according to the mass percent of 0.5-1.0% and the mass percent of 20-30%, and the balance is deionized water;
in the step S4, the total solid content of the nano copper powder and the trimesic acid is added according to 30-40% of the mass fraction, wherein the molar ratio of the nano copper powder to the trimesic acid is 2-3:1, a step of; adding 10-15% of nitrogen-doped graphene oxide according to mass fraction, wherein the rest is DMF;
The preparation method of the nitrogen-doped graphene oxide comprises the following steps: according to the mass ratio of 1:2-1: dispersing graphene oxide in an ammonia water solution, heating to 120-140 ℃, performing hydrothermal reaction for 1-2 h, centrifuging, washing and drying to obtain nitrogen-doped graphene oxide;
In the step S5, the concentration of the dilute nitric acid is 3-6 mol/L; the molar ratio of the dilute nitric acid to the nanometer copper powder is 6:1-8:1.
2. The method for preparing water-dispersible cationic polyacrylamide according to claim 1, wherein in step S2, the time for introducing nitrogen and removing oxygen is defined as 10min-30min;
And step S3, the concentration of the initiator azo diisobutylamidine hydrochloride solution is 1g/L-10g/L.
3. The method for preparing water-dispersible cationic polyacrylamide according to claim 1, wherein in step S5, the temperature of the heating reaction is defined as 40-50 ℃; the temperature of the continued heating reaction is defined as 80-100 ℃.
4. The method for preparing water-dispersible cationic polyacrylamide according to claim 1, wherein in step S6, the solvent used for purification is an alcohol-water mixed solution.
5. A water-dispersible cationic polyacrylamide material prepared by the preparation method of any one of claims 1 to 4.
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