CN101704928B - Preparation method of starch grafted acrylamide flocculating agent - Google Patents
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- 229920002472 Starch Polymers 0.000 title claims abstract description 30
- 239000008107 starch Substances 0.000 title claims abstract description 30
- 235000019698 starch Nutrition 0.000 title claims abstract description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000008394 flocculating agent Substances 0.000 title abstract description 4
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 14
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000003995 emulsifying agent Substances 0.000 abstract description 14
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 abstract description 7
- 239000003999 initiator Substances 0.000 abstract description 7
- -1 polyoxyethylene Polymers 0.000 abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 4
- 229920000578 graft copolymer Polymers 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 abstract description 4
- 229920000053 polysorbate 80 Polymers 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000012496 blank sample Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000012688 inverse emulsion polymerization Methods 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention provides a preparation method of a starch grafted acrylamide flocculating agent, which comprises the following concrete step of polymerizing starch and acrylamide in a reversed emulsion formed by liquid paraffin, water and a compounded emulsifying agent to form a graft copolymer of the starch and the acrylamide, wherein potassium permanganate is used as an initiator, and the compounded emulsifying agent comprises span 80, Tween 80 and alkylphenol polyoxyethylene (4) in a mass ratio of 7-9:0.1-0.5:0.9-2.5. The method adopts the compounded emulsifying agent comprising the span 80, the Tween 80 and the alkylphenol polyoxyethylene (4) for preparing the reversed emulsion, thereby stabilizing the system of the reversed emulsion, providing a stable reaction environment for polyreaction, and being helpful for improving the stability of products. In addition, in the method, the potassium permanganate is also selected as the initiator, thereby effectively improving the efficiency of initiating the polyreaction.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a macromolecular compound obtained by reaction of only carbon-carbon unsaturated bonds.
Background
Organic flocculants refer to natural or synthetic organic molecular substances capable of producing flocculation. The natural organic flocculant is protein or polysaccharide compound, such as starch, protein, animal glue, sodium alginate, sodium carboxymethylcellulose, etc.; the synthesized organic flocculant includes polyacrylamide, sodium polyacrylate, polyvinyl pyridine salt, polyethyleneimine, etc. The flocculating agent is a water-soluble linear high molecular substance, can be ionized in water, is a high molecular electrolyte, and can be classified into an anionic type, a cationic type, an amphoteric type and the like according to the characteristic of a dissociable group. After the flocculant is ionized in water, chain molecules of the flocculant can generate a bonding and bridging effect, and charged groups on the molecules play a role in charge neutralization and compression on a diffusion layer of a micelle, so that the flocculant can be used for treating wastewater with high concentration, high turbidity, high chroma and special odor.
The starch grafted acrylamide flocculant is a grafted copolymer of starch and acrylamide, and has the advantages of good flocculation effect, degradability, cheap and easily-obtained raw materials and the like, so that the starch grafted acrylamide flocculant becomes a hotspot of current research. The traditional method for preparing the starch grafted acrylamide flocculant is an aqueous solution polymerization method, for example, a method for synthesizing the starch grafted acrylamide flocculant by an aqueous solution polymerization method is disclosed in the text of synthesis and application of a polymeric flocculant, namely starch grafted acrylamide flocculant, and the method comprises the following steps: adding a certain amount of starch into 100ml of water, introducing nitrogen at 85 ℃, stirring and pasting for 1 hour, adjusting the temperature to 20-60 ℃, and sequentially adding acrylamide and Ce4+After reacting for 2-3 hours at constant temperature, precipitating by using acetone and separatingTaking out the precipitate and drying in vacuum to obtain a crude product; extracting the crude product with mixed solvent at volume ratio of 60: 40 to remove homopolymer and unreacted starch, washing with acetone to neutrality, and vacuum drying to obtain refined product. The authors of the article have studied the effect of 3 initiators, namely potassium permanganate, ammonium ceric nitrate and potassium persulfate, on the polymerization reaction, and thought that the conversion rate and the grafting rate of the initiator, which is potassium permanganate, are high, but the viscosity of the obtained polymer is low, because the chain grafted by potassium permanganate is short, the number of homopolymers is large, and the formation of grafted macromolecules is difficult; ammonium ceric nitrate is easy to initiate graft copolymerization of macromolecular chains, and the viscosity of the obtained polymer is the best among the three, but the conversion rate and the grafting rate are relatively low. The authors also found the optimum process parameters for the polymerization by orthogonal experiments: the dosage of the initiator is 1.1mmol/L, the dosage of the starch is 35g/L, the dosage of the acrylamide is 1.48mol/L, the reaction temperature is 25 ℃, and the reaction time is 2 hours. The viscosity of the polymer obtained under the above conditions can be as high as 587.83 ml/g. However, in the aqueous solution polymerization method, due to the existence of the difficulty in heat dissipation in the polymerization process, the control on the production process is not easy to cause implosion, and the number of byproducts is large, so that the stability of the obtained product is poor.
The inverse emulsion polymerization method is a new polymerization method which has attracted much attention in recent years and is characterized in that a monomer dissolved in water is dispersed in a nonpolar liquid with the aid of an emulsifier to form a water-in-oil state, and then polymerization is carried out. The method has the advantages of high polymerization rate, high solid content of the product, large molecular weight, narrow distribution, mild reaction conditions and the like. The research on graft copolymerization of starch acrylamide by inverse emulsion method discloses a method for preparing a starch acrylamide graft copolymer by using an inverse emulsion method, which comprises the following steps: mixing a compound emulsifier mainly comprising Span80 with liquid paraffin, adding a mixture of 30% of starch milk and 40% of monomer acrylamide under stirring to form inverse emulsion, introducing high-purity nitrogen for 30min, raising the temperature to 35-55 ℃, slowly dropwise adding an initiator ammonium persulfate to react for 4 hours, demulsifying with ethanol after the reaction is finished, repeatedly washing, performing suction filtration, and performing vacuum drying at 64 ℃; wherein the oil-water ratio of the inverse emulsion is 0.8-1.6, the concentration of the emulsifier is 2-10%, the concentration of the initiator is 1-7 mmol/L, and the ratio of the monomer to the starch is 0.8-1.8. The stability of the inverse emulsion system is the key to the success or failure of the inverse emulsion polymerization, and the determining factor of the stability of the emulsion system is the emulsification system. Although the emulsifying system in the method is claimed to be a compound emulsifier, only one component of the compound emulsifier, namely Span80, is disclosed, and the method cannot be repeated by a person skilled in the art without knowing the rest of the components of the emulsifier, and the effect claimed in the method can be achieved. In addition, the method adopts ammonium persulfate as a polymerization initiator, and the ammonium persulfate can effectively initiate the graft copolymerization reaction of the starch acrylamide, but the initiation reaction efficiency is low, so that the grafting rate (about 85 percent at most) and the grafting efficiency (less than 60 percent) of the copolymer are low.
Disclosure of Invention
The technical problem to be solved by the invention is to improve the stability of an emulsion system during the inverse emulsion polymerization reaction.
The technical scheme for solving the problems is as follows:
the preparation method of the starch grafted acrylamide flocculant comprises the following steps:
(1) taking 27-46 parts by weight of liquid paraffin and 1-4 parts by weight of compound emulsifier, and fully and uniformly mixing to obtain an oil phase; adding 5.3-13.8 parts by weight of starch into 26.5-62.2 parts by weight of water, uniformly mixing, adding the prepared oil phase, and fully stirring to form an inverse emulsion;
(2) introducing nitrogen to exhaust oxygen in the inverse emulsion, heating to 35-60 ℃, dropwise adding 1% by mass potassium permanganate solution with volume 0.6-3 times of the mass of the compound emulsifier under the condition of continuously introducing nitrogen and stirring, adding 10.8-26.8 parts by weight of 50% by mass acrylamide solution after uniformly stirring, and reacting for 1-7 hours; or
Introducing nitrogen to exhaust oxygen in the inverse emulsion, adding 10.8-26.8 parts by weight of acrylamide solution with the mass concentration of 50% under the conditions of continuously introducing nitrogen and stirring, heating to 35-60 ℃, dropwise adding potassium permanganate solution with the mass concentration of 1% and the volume of 0.6-3 times of the mass of the used compound emulsifier, and reacting for 1-7 hours;
(3) cooling to normal temperature, adding ethanol, stirring to separate out reaction product, filtering, taking filter residue, washing with ethanol and acetone in turn until the filter residue is loose small particles, and vacuum drying;
in the above step, the compound emulsifier in step (1) is composed of span80, tween 80 and alkylphenol polyoxyethylene (4) ether (i.e., OP-4) in a mass ratio of 7-9: 0.1-0.5: 0.9-2.5, wherein the mass ratio of span80, tween 80 and alkylphenol polyoxyethylene (4) ether is preferably 7: 0.5: 2.5.
The method of the invention has the following advantages:
(1) the invention adopts a composite emulsification system consisting of Span80, Tweet80 and OP-4 as an emulsifier for inverse emulsion polymerization reaction, and a stable inverse emulsion system can be formed in the reaction process; the graft copolymerization of the starch and the monomers is carried out in the oil phase in the inverse emulsion system, the reaction condition is mild, the polymerization rate is high, the occurrence of implosion is effectively prevented, and the reaction rate and the conversion rate are improved; the obtained product has high solid content, large molecular weight and narrow distribution, and has good flocculation performance;
(2) by adopting a potassium permanganate initiation system, the efficiency of initiating graft copolymerization can be effectively improved, and the grafting rate and the grafting efficiency can reach more than 97 percent.
Detailed Description
The grafting yield and grafting efficiency in the following examples were determined as follows:
the content (m ') of the monomer in the graft was determined by measuring the nitrogen content in the sample by the Kjeldahl method'M) Thereby, the grafting ratio (G,%) and the grafting efficiency (E,%) were calculated. MeterThe calculation formula is as follows:
in the formula: m'M-mass of monomers in the graft copolymer, g;
mGmass of graft copolymer, g;
mMmass of monomers used in the reaction, g
Example 1
Taking 40g of liquid paraffin, Span802.24g, 800.16 g of Tween and OP-40.80 g of liquid paraffin into a three-neck flask, stirring to dissolve, adding 30mL of water and 6.7g of starch, and stirring until an inverse emulsion is formed. The conductivity is measured to be close to 0, and the emulsion stability is measured to be close to 1.
Introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, heating to 50 ℃, continuously introducing nitrogen and stirring, dropwise adding 1mL of 1% potassium permanganate solution, stirring for 20min, adding 18.8g of 50% acrylamide solution, reacting for 3h, and stopping stirring; transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring until no solid product is formed, filtering to separate out the solid in the beaker, repeatedly washing with ethanol and acetone, filtering until the filter cake is loose small particles, and finally drying to the moisture content required by the product. The grafting rate and grafting efficiency were found to be 98.7% and 97.3%, respectively.
Example 2
46g of liquid paraffin, 803.6 g of Span, 800.1 g of Tween and 40.3 g of OP-40 are taken out of a three-neck flask, stirred for 4 to be dissolved, added with 29.2g of water and 6.7g of starch and stirred until an inverse emulsion is formed. The conductivity is measured to be close to 0, and the emulsion stability is measured to be close to 1.
And introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, continuously introducing nitrogen and stirring, adding 10.8g of 50% acrylamide solution, heating to 40 ℃, dropwise adding 0.6mL of 1% potassium permanganate solution, reacting for 7h, stopping stirring, transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring to obtain a solid product, filtering to separate the solid in the beaker from the mixture, repeatedly washing the filter cake with ethanol and acetone until the filter cake is loose small particles, and finally performing vacuum drying until the moisture content required by the product is reached. The grafting rate and the grafting efficiency are respectively 99.2 percent and 98.6 percent according to measurement
Example 3 liquid paraffin 27g, span 800.7 g, tween 800.05 g and OP-40.25 g were taken in a three-necked flask, stirred to dissolve, and then added with water 27.6g and starch 6.7g, stirred until an inverse emulsion was formed, and the conductivity was measured to be close to 0 and the emulsion stability was measured to be close to 1.
And introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, continuously introducing nitrogen and stirring, dropwise adding 3mL of 1% potassium permanganate solution, stirring for 20min, adding 26.8g of 50% acrylamide solution, heating to 60 ℃, reacting for 1h, stopping stirring, transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring to obtain a solid product, filtering to separate the solid in the beaker from the mixture, repeatedly washing the filter cake with ethanol and acetone until the filter cake is loose small particles, and finally, vacuum drying to the moisture content required by the product. The grafting rate and grafting efficiency were determined to be 98.7% and 98.2%, respectively.
Example 4
Dissolving 1g of the sample in example 1 in 1000mL of water to prepare a 1 per mill solution, simultaneously adding 5mL of the solution (experimental sample) and 5mL of distilled water (blank sample) into 1000mL of 2 parts of 0.2% kaolin suspension respectively, slowly and quickly stirring for 15min, and standing for 10min to obtain the experimental sample with the turbidity of 20% and the light transmittance of 85.5%; the haze of the blank was 61% and the light transmittance was 28%.
Example 5
Simultaneously, 8mL (experimental sample) of the sample solution in example 4 and 8mL (blank sample) of distilled water are respectively added into 1000mL of 2 wastewater samples from ditches in a certain living area, the mixture is stirred slowly and quickly for 15min and is kept stand for 10min, the removal rate of suspended matters and COD of the experimental sample is measured to be more than 85%, and the removal rate of suspended matters and COD of the blank sample are measured to be 25%.
Example 6
1g of the sample in example 2 is dissolved in 1000mL of water to prepare 1 per mill of solution, simultaneously 10mL (experimental sample) of the solution and 5mL of distilled water (blank sample) are respectively added into 1000mL of the yellow muddy water sample, the mixture is slowly and quickly stirred for 15min and is kept stand for 10min, the removal rate of suspended matters and COD of the experimental sample is measured to be more than 90%, and the removal rate of suspended matters and COD of the blank sample are measured to be 28%.
Claims (1)
1. The preparation method of the starch grafted acrylamide flocculant comprises the following steps:
(1) putting 40g of liquid paraffin, Span802.24g, 800.16 g of Tween and OP-40.80 g of liquid paraffin into a three-neck flask, stirring to dissolve, adding 30mL of water and 6.7g of starch, and stirring until an inverse emulsion is formed; the conductivity of the formed inverse emulsion is close to 0, and the stability of the emulsion is close to 1;
introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, heating to 50 ℃, continuously introducing nitrogen and stirring, dropwise adding 1mL of 1% potassium permanganate solution, stirring for 20min, adding 18.8g of 50% acrylamide solution, reacting for 3h, and stopping stirring; transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring until no solid product is formed, filtering to separate out the solid in the beaker, repeatedly washing with ethanol and acetone, filtering until the filter cake is loose small particles, and finally drying to the moisture content required by the product; or,
(2) putting 46g of liquid paraffin, 803.6 g of Span, 800.1 g of Tween and 40.3 g of OP-in a three-neck flask, stirring to dissolve, adding 29.2g of water and 6.7g of starch, and stirring until an inverse emulsion is formed; the conductivity of the formed inverse emulsion is close to 0, and the stability of the emulsion is close to 1;
introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, continuously introducing nitrogen and stirring, adding 10.8g of 50% acrylamide solution, heating to 40 ℃, dropwise adding 0.6mL of 1% potassium permanganate solution, reacting for 7h, and stopping stirring; transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring to obtain a solid product, filtering to separate the solid in the beaker from the mixture, repeatedly washing a filter cake with ethanol and acetone until the filter cake is loose small particles, and finally performing vacuum drying to the moisture content required by the product; or,
(3) placing 27g of liquid paraffin, 800.7 g of Span, 800.05 g of Tween and 40.25 g of OP-40 in a three-neck flask, stirring to dissolve, adding 27.6g of water and 6.7g of starch, and stirring until an inverse emulsion is formed; the conductivity of the formed inverse emulsion is close to 0, and the stability of the emulsion is close to 1;
introducing nitrogen into the emulsion until oxygen in the three-neck flask is completely removed, continuously introducing nitrogen and stirring, dropwise adding 3mL of 1% potassium permanganate solution, stirring for 20min, adding 26.8g of 50% acrylamide solution, heating to 60 ℃, reacting for 1h, and stopping stirring; transferring the mixture in the beaker into a 1000mL beaker, cooling to normal temperature, adding ethanol, stirring to obtain a solid product, filtering to separate the solid in the beaker from the mixture, repeatedly washing a filter cake with ethanol and acetone until the filter cake is loose small particles, and finally performing vacuum drying to the moisture content required by the product.
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| CN103435115B (en) * | 2013-08-26 | 2014-11-19 | 苏州富奇诺水治理设备有限公司 | Phenol-containing wastewater treatment agent |
| CN105061675A (en) * | 2015-03-24 | 2015-11-18 | 西北大学 | Starch flocculant, preparation method and applications thereof |
| CN106543364A (en) * | 2015-09-18 | 2017-03-29 | 上海东升新材料有限公司 | A kind of method for preparing acrylamide graft guar gum and its application |
| CN105618002B (en) * | 2016-02-18 | 2018-03-30 | 陕西科技大学 | modified starch/graphene oxide magnetic composite microsphere and preparation method thereof |
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| CN111320724B (en) * | 2020-04-16 | 2022-11-04 | 甘肃智仑新材料科技有限公司 | Temperature-sensitive poly-N-isopropyl acrylamide grafted guar gum, preparation method thereof and application thereof in oil field |
| CN111573801B (en) * | 2020-04-30 | 2023-01-06 | 云浮市郁南县春旭环保科技有限责任公司 | Organic composite aluminum sulfate water treatment agent and preparation method thereof |
| CN117384323B (en) * | 2023-12-12 | 2024-03-08 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
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