CN111848859A - Micro-crosslinked cationic polyacrylamide flocculant and preparation method and application thereof - Google Patents
Micro-crosslinked cationic polyacrylamide flocculant and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a micro-crosslinked cationic polyacrylamide flocculant and a preparation method and application thereof. The micro-crosslinked cationic polyacrylamide flocculant is prepared by taking acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride as main comonomers and vinyl alkoxy silane as a copolymerization crosslinking monomer by adopting an inverse emulsion free radical polymerization method. Wherein, the vinyl alkoxy silane is taken as a copolymerization crosslinking monomer, which can generate micro-crosslinking on polymer molecular chains in the process of inverse emulsion polymerization and promote the flocculation and sedimentation of chemical oil displacement agents, crude oil, suspended matters, inorganic salts and the like in the oil extraction sewage; the method of inverse emulsion free radical polymerization is adopted, the polymerization reaction condition and the addition amount of the crosslinking monomer are controlled, the molecular weight of the polymer is improved without influencing the water solubility of the polymer, the adsorption, bridging, electric neutralization and hydrophobic association of the polymer are stronger, and the flocculation separation effect on the oily sewage is better.
Description
Technical Field
The invention relates to a micro-crosslinked cationic polyacrylamide flocculant, a preparation method and application thereof, and belongs to the technical field of oil-containing sewage treatment of oil fields.
Background
In the process of oil exploitation, with the wide application of chemical combination flooding oil extraction technology, a large amount of crude oil sewage generated after produced liquid separation gathers chemical oil displacement agents, crude oil, suspended matters, inorganic salts and the like, and has the characteristics of complex components, high stability, high oil content and the like. The common treatment method for the oily sewage comprises the following steps: the method comprises the steps of gravity settling, flotation, membrane separation, emulsion breaking, flocculation and the like, wherein the flocculation method is one of the methods which are widely applied at present, and an organic polymeric flocculant or an organic-inorganic composite polymeric flocculant, particularly a modified cationic polyacrylamide flocculant, is an effective oily sewage treating agent and has the characteristics of small dosage, good flocculation effect and the like.
In recent years, researchers in China develop various modified polyacrylamide flocculants by using acrylamide as a main chain and copolymerizing acrylamide with other functional monomers. Such as: according to the method, acrylamide, dimethyl diallyl ammonium chloride, butyl acrylate, a surfactant and deionized water are used as raw materials in Chinese patent document CN103319653A, acrylamide, acryloyloxyethyl trimethyl ammonium chloride, perfluoro octyl ethyl acrylate, the surfactant and the deionized water are used as raw materials in Chinese patent document CN103319652A, hydrophobic modified cationic polyacrylamide flocculant is respectively prepared, and hydrophobic groups are introduced into macromolecules of the flocculant, so that the adsorption capacity of a polymer on suspended particles, particularly organic matters in water, can be improved, the hydrophilic performance of flocs can be reduced, and the sedimentation speed of the flocs is accelerated. Chinese patent CN103881006A adopts a reverse emulsion polymerization method, and simultaneously, a third monomer of methacrylamide sodium aminosalicylate and a redox initiator are respectively fed, so that the high-solid-content high-molecular-weight anion modified polyacrylamide emulsion which can meet the fields of mineral mining and separation, red mud sedimentation, oil extraction, municipal domestic sewage treatment and the like is prepared, and the flocculation effect and the clarity of suspension are improved. Wulinjian and the like use acrylamide, cationic monomer acryloyloxyethyl trimethyl ammonium chloride and self-made surface active hydrophobic monomer dodecyl-dimethyl- (3-methacrylamide) propyl ammonium bromide to carry out aqueous solution free radical copolymerization to synthesize a novel terpolymer hydrophobic modified cationic polyacrylamide flocculant (the synthesis of novel hydrophobic modified cationic polyacrylamide and the application research of sewage treatment [ D ]. Beijing university of chemical industry, 2015 ]).
The modified polyacrylamide flocculant has a good flocculation effect on laboratory simulated oily wastewater, but has an undefined treatment effect on field oily wastewater. In the process of oil exploitation, in particular to on-site oily sewage generated by an offshore drilling and production platform, the requirement on the flocculation effect of a flocculating agent is higher, the oil-water separation effect is good, the separation speed is high, and the structural strength of flocs is moderate.
Disclosure of Invention
Aiming at the defects of the prior art and the requirements of high oil-water separation speed, good effect and moderate floc structural strength in on-site crude oil sewage treatment, the invention provides a micro-crosslinked cationic polyacrylamide flocculant and a preparation method and application thereof.
Description of terms:
room temperature: having a meaning well known in the art, typically 25. + -. 2 ℃.
The technical scheme of the invention is as follows:
a micro-crosslinked cationic polyacrylamide flocculant is prepared by taking acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride as main comonomers and vinyl alkoxy silane as a copolymerization crosslinking monomer by adopting an inverse emulsion free radical polymerization method; wherein, the mol ratio of the acrylamide to the methacryloyloxyethyl dimethyl benzyl ammonium chloride is (1-2) to 1, and the mol number of the vinyl alkoxy silane is 0.5 to 2.5 percent of the total mol number of the three monomers.
According to the invention, the vinyl alkoxy silane is any one of vinyl triethoxysilane, vinyl methyldiethoxysilane and vinyl dimethylethoxysilane.
In the invention, an alkoxysilane unit which is easy to hydrolyze and crosslink is introduced into the molecular chain structure of the polymer of acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride, so that the molecular chain of the polymer can generate micro-crosslinking.
According to the invention, the weight average molecular weight of the micro-crosslinked cationic polyacrylamide flocculant is (1.14-8.32) multiplied by 106。
The preparation method of the micro-crosslinked cationic polyacrylamide flocculant comprises the following steps:
(1) preparing a monomer aqueous solution: dissolving acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride in deionized water according to a molar ratio of (1-2):1 to prepare a monomer aqueous solution with the total monomer content of 40-45 wt% for later use;
(2) preparation of inverse emulsion: uniformly mixing the hydrophobic continuous phase, the vinyl alkoxy silane and the compound emulsifier to prepare an oil phase, transferring the monomer aqueous solution in the step (1) into the oil phase, and shearing and uniformly mixing for 10-15 minutes to obtain uniform and stable emulsion;
(3) inverse emulsion polymerization: introducing N into the emulsion prepared in the step (2)2Deoxidizing; heating to 55-65 ℃, slowly dripping initiator aqueous solution under the condition of stirring, continuously stirring at constant temperature for reaction for 4-6h, then cooling to room temperature, stopping introducing nitrogen, and finishing the reaction;
(4) and (3) post-treatment: and (4) pouring the reaction emulsion obtained in the step (3) into acetone, stirring, filtering, washing with acetone, and carrying out vacuum drying and crushing on the solid to obtain the micro-crosslinked cationic polyacrylamide flocculant with white powder appearance.
According to the invention, the mole number of the vinyl alkoxy silane in the step (2) is 0.5-2.5% of the total mole number of the three monomers of acrylamide, methacryloyloxyethyl dimethyl benzyl ammonium chloride and vinyl alkoxy silane.
Preferably according to the invention, the hydrophobic continuous phase in step (2) is one of kerosene or cyclohexane.
According to the invention, the mass ratio of the hydrophobic continuous phase to the total water in the reaction system in the step (2) is (0.4-1.0): 1.0. Wherein the total water of the reaction system comprises the solvent water of the monomer aqueous solution in the step (1) and the solvent water of the initiator aqueous solution in the step (3).
According to the invention, the dosage of the compound emulsifier in the step (2) is 8-15% of the total mass of the three monomers, and the mass ratio of the Tween80 to the Span80 is (0.05-0.5): 1.0.
In the preparation of the inverse emulsion, firstly, the dyeing method and the dilution method are adopted to determine that the type of the emulsion is the water-in-oil emulsion; the influence of the type of the hydrophobic continuous phase (oil phase), the HLB (hydrophile-lipophile balance) value of the emulsion, the dosage of the emulsifier, the mass ratio of oil to water and the reaction temperature on the stability of the inverse emulsion is researched through an orthogonal experiment, and according to the orthogonal experiment result and the stability evaluation of the inverse emulsion, the factors which have the greatest influence on the stability of the inverse emulsion are the mass ratio of oil to water and the HLB value of the emulsion, and the influence of the type of the hydrophobic continuous phase (oil phase), the reaction temperature and the dosage of the emulsifier on the stability of.
Preferably, according to the present invention, the rotation speed of the shearing in the step (2) is 1000-2000 rpm.
According to the invention, the initiator in the step (3) is azobisisobutyrimidazoline hydrochloride, and the amount of the initiator is 0.6-0.8% of the total mass of the three monomers.
According to the invention, preferably, the initiator aqueous solution in the step (3) is prepared by dissolving the initiator in deionized water to prepare an aqueous solution with a mass percentage of 1.0-1.5%.
According to the invention, the vacuum drying condition in the step (4) is preferably 60-70 ℃ for 12-24 h.
The micro-crosslinked cationic polyacrylamide flocculant is applied to the treatment of oil extraction wastewater.
The invention has the technical characteristics and beneficial effects that:
1. the micro-crosslinked cationic polyacrylamide flocculant is prepared by using acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride as main comonomers and vinyl alkoxy silane as a copolymerized crosslinking monomer, firstly preparing a monomer aqueous solution containing the acrylamide and the methacryloyloxyethyl dimethyl benzyl ammonium chloride, then preparing an oil phase containing the vinyl alkoxy silane, and then preparing the flocculant by adopting an inverse emulsion free radical polymerization method. The vinyl alkoxy silane is used as a copolymerization crosslinking monomer, and can generate micro-crosslinking on polymer molecular chains in the inverse emulsion polymerization reaction process, so as to promote flocculation and sedimentation of chemical oil displacement agents, crude oil, suspended matters, inorganic salts and the like in the oil extraction sewage.
2. The invention adopts the method of inverse emulsion free radical polymerization in the preparation method of the micro-crosslinked cationic polyacrylamide flocculant, controls the polymerization reaction condition and the addition amount of the crosslinking monomer, can ensure that the hydrolysis speed and the crosslinking degree of the alkoxy silane unit are easy to control, realizes the improvement of the molecular weight of the polymer without influencing the water solubility of the polymer, ensures that the adsorption, bridging, electric neutralization and hydrophobic association of the polymer are stronger, has better flocculation separation effect on oily sewage, and can meet the requirements of high oil-water separation speed, good effect and moderate floc structural strength in the field crude oil sewage treatment. Any condition beyond that required by the present invention, such as increasing the amount of crosslinking monomer added, increasing the reaction temperature or extending the reaction time, results in a decrease in the water solubility of the polymer and a decrease in flocculant performance.
3. The flocculant is used for oil field oily wastewater with complex components, high stability and large oil content, and when the usage amount of the flocculant is 300 mg.L-1The deoiling rate can reach about 95 percent.
Drawings
FIG. 1 is a NMR spectrum of PADS30-2 prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope. The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
The weight average molecular weight Mw of the polymer was determined using a DAMN HELEOS 18 angle laser light scattering apparatus from Wyatt, USA.
In the examples, the copolymeric crosslinking monomer was vinyltriethoxysilane, the product being labelled PADS 30; the copolymerized crosslinking monomer is vinyl methyl diethoxysilane, and the product is marked as PADS 20; the co-crosslinking monomer was vinyldimethylethoxysilane and the product was designated PADS 10.
EXAMPLE 1 preparation of PADS30-2
A preparation method of a micro-crosslinked cationic polyacrylamide flocculant PADS30-2 comprises the following steps:
(1) preparing a monomer aqueous solution: accurately weighing 3.19g (44.43mmol) of Acrylamide (AM) and 6.04g (22.40mmol) of methacryloyloxyethyl dimethyl benzyl ammonium chloride (DBC), dissolving in 12.22g of deionized water, and stirring uniformly to prepare a monomer aqueous solution;
(2) preparing an inverse emulsion: weighing 0.15g (0.78mmoL, which accounts for 1.15% of the total mole of the three monomers of acrylamide, methacryloxyethyldimethylbenzyl ammonium chloride and vinyltriethoxysilane) of Vinyltriethoxysilane (VTS), 0.28g of Tween80 and 0.92g of Span80 in 15.00g of kerosene, uniformly mixing to prepare an oil phase, transferring the oil phase into a high-speed shearing machine, starting the high-speed shearing machine, dripping the monomer aqueous solution prepared in the step (1) into the oil phase, and shearing at the rotating speed of 1000rpm for 15min to obtain uniform and stable emulsion;
(3) inverse emulsion polymerization: transferring the emulsion prepared in the step (2) to a device provided with a stirrer, a thermometer, a reflux condenser pipe and N2Into a 100mL four-necked flask with a guide tube, N was introduced2Deoxidizing for 30 min; starting stirring, heating to 60 ℃, slowly dripping the prepared initiator aqueous solution (0.075g of azobisisobutyronitrile hydrochloride is dissolved in 5.00g of deionized water), taking about 2 hours, continuously stirring at constant temperature for reaction for 4 hours, then cooling, stopping introducing nitrogen, and finishing the reaction;
(4) and (3) post-treatment: pouring the emulsion obtained after the inverse emulsion polymerization into 500mL of acetone, stirring, filtering, washing with acetone to obtain a solid, vacuum-drying at 60-70 ℃ for 12h, and pulverizing to obtain the final productTo 7.92g of micro-crosslinked cationic polyacrylamide flocculant PADS30-2, weight average molecular weight Mw: 2.404X 106The yield thereof was found to be 84.38%.
The NMR spectrum of PADS30-2 is shown in FIG. 1, and the two peaks at chemical shifts 1.90ppm and 0.68ppm correspond to-CH in the VTS monomer2methine-CH on-CH-2The proton peaks in- (j) and methylene-CH- (k), the two peaks appearing at chemical shifts of 1.50ppm and 2.15ppm respectively correspond to the-CH peaks in the monomeric AM2methine-CH on-CH-2Proton peaks in- (a) and methylene-CH- (b); the peak at chemical shift 3.06ppm corresponds to-N in DBC monomer+(CH3)2(e) Proton peaks in the upper two equivalent methyl groups; the peak appearing at chemical shift 7.45ppm is the proton peak on the benzene ring in the DBC monomer.
Example 2: preparation of PADS30-3
The procedure of example 1 was followed except that 0.30g of Vinyltriethoxysilane (VTS), 2.27% of the total moles of acrylamide, methacryloxyethyldimethylbenzylammonium chloride and vinyltriethoxysilane, and otherwise conditions were completely the same as those in example 1 to obtain a product, namely, a micro-crosslinked cationic polyacrylamide flocculant PADS 30-3.
Example 3: preparation of PADS30-1
The procedure of example 1 was followed except that 0.075g of Vinyltriethoxysilane (VTS), 0.58% of the total moles of acrylamide, methacryloxyethyldimethylbenzylammonium chloride and vinyltriethoxysilane, otherwise exactly in accordance with example 1, to give the product, slightly crosslinked, cationic polyacrylamide flocculant PADS 30-1.
Example 4: preparation of PADS30-4
The preparation according to example 1 is carried out with the difference that the molar ratio n of the monomers Acrylamide (AM) to methacryloyloxyethyldimethylbenzylammonium chloride (DBC) (AM/DBC) is 1: 1, the other conditions are completely consistent with those of the example 1, and the product of the micro-crosslinked cationic polyacrylamide flocculant PADS30-4 is obtained.
Example 5: preparation of PADS20-1
The procedure of example 3 was followed except that 0.063g of Vinylmethyldiethoxysilane (VDS) was used as the crosslinking monomer and the other conditions were completely the same as in example 3 to give the product, slightly crosslinked, cationic polyacrylamide flocculant PADS 20-1.
Example 6: preparation of PADS20-2
The procedure of example 1 was followed except that 0.126g of Vinylmethyldiethoxysilane (VDS) was used as the crosslinking monomer and the other conditions were completely the same as in example 1 to obtain a product, a micro-crosslinked cationic polyacrylamide flocculant PADS 20-2.
Example 7: preparation of PADS20-3
The procedure of example 1 was followed except that 0.25g of Vinylmethyldiethoxysilane (VDS) was used as the crosslinking monomer and the other conditions were completely the same as in example 1 to obtain a product, a micro-crosslinked cationic polyacrylamide flocculant PADS 20-3.
Example 8: preparation of PADS10-1
The preparation method of example 1 was followed, except that the crosslinking monomer was 0.052g of Vinyldimethylethoxysilane (VES) and the other conditions were completely the same as those of example 1, to obtain a product, namely, a slightly crosslinked cationic polyacrylamide flocculant PADS 10-1.
Example 9: preparation of PADS10-2
The procedure of example 1 was followed except that 0.103g of Vinyldimethylethoxysilane (VES) was used as a crosslinking monomer, and the other conditions were completely the same as those in example 1, to give a product, a slightly crosslinked cationic polyacrylamide flocculant PADS 10-2.
Example 10: preparation of PADS10-3
The procedure of example 1 was followed except that 0.21g of Vinyldimethylethoxysilane (VES) was used as a crosslinking monomer, and the other conditions were completely the same as those in example 1, to give a product, a slightly crosslinked cationic polyacrylamide flocculant, PADS 10-3.
Comparative example 1: preparation of PAD
Without any addition of silane crosslinking monomer, otherwise exactly the same conditions as in example 1 gave the product PAD.
The experimental conditions and characteristics of the prepared products of examples 1-10 and comparative examples are summarized in table 1.
Table 1: examples 1-10, comparative examples Experimental conditions and results
Note: n (AM/DBC): (ii) the molar ratio of Acrylamide (AM) to methacryloyloxyethyldimethylbenzylammonium chloride (DBC); n silane: molar vinyl alkoxysilane, toto: total monomer moles.
The yield of the micro-crosslinked cationic polyacrylamide flocculant is 81-88%, and the weight average molecular weight is more than 1.0 multiplied by 106。
Test example: evaluation of flocculation separation performance of flocculant on oily sewage
The oily wastewater used in the test examples was derived from the wastewater generated at the crude oil extraction site of an offshore oil field, and the oil content in the wastewater was 60288 mg.L-1；
The oil content in the sewage is measured by adopting a portable oil content detector of United states Tera TD-500D, and the deoiling rate is calculated by the following formula:
the method for evaluating the flocculation separation performance of the flocculant on the oily sewage comprises the following steps:
1) deionized water is taken to prepare the prepared micro-crosslinked cationic polyacrylamide flocculant with the concentration of 10.0 g.L-1The aqueous flocculant solution of (1);
2) shaking up oily sewage from an oil field, and putting 10.0mL of the oily sewage into a test tube; adding 300 or 400 mu L of prepared flocculant aqueous solution into the sewage, fully shaking the test tube for 1 minute, and standing for 2 hours at normal temperature;
3) after oil-water separation, extracting the separated sewage by using chromatographically pure hexane, measuring the oil content in the water by using a portable oil content detector of America Terna TD-500D, and obtaining the deoiling rate by calculation.
The flocculation separation performance of the oily sewage was evaluated using the products prepared in examples 1 to 10 and comparative example 1, and the results are shown in Table 2.
Table 2: comparison of flocculation Effect of flocculants of examples 1 to 10 and comparative example 1 on oily wastewater
As can be seen from the table, the flocculant prepared in the example has an addition concentration of 300 mg.L in the oily sewage-1When the oil removal rate reaches 82.78-94.97%, the addition concentration of the flocculant prepared in the example in the oily sewage is 400 mg.L-1When the flocculant is used, the deoiling rate reaches 89.36-96.87%, and the flocculant prepared in the comparative example is used at 400 mg.L-1When the oil-containing sewage is treated by the additive concentration of (2), the deoiling rate is only 84.80%. The above results show that: in the process of preparing the flocculant, a proper amount of vinyl alkoxy silane crosslinking monomer is added to perform copolymerization crosslinking reaction with acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride, compared with a comparative example, the flocculation effect of the flocculant on oily sewage can be obviously improved, wherein the effects of vinyl triethoxysilane and vinyl methyl diethoxysilane are more obvious, the deoiling rate of the oily sewage can be improved, and the adding amount can be reduced.
Claims (9)
1. The micro-crosslinked cationic polyacrylamide flocculant is characterized by being prepared by taking acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride as main comonomers and vinyl alkoxy silane as a copolymerization crosslinking monomer by adopting an inverse emulsion free radical polymerization method; wherein, the mol ratio of the acrylamide to the methacryloyloxyethyl dimethyl benzyl ammonium chloride is (1-2) to 1, and the mol number of the vinyl alkoxy silane is 0.5 to 2.5 percent of the total mol number of the three monomers.
2. The micro-crosslinked cationic polyacrylamide flocculant of claim 1, wherein the vinyl alkoxy silane is any one of vinyl triethoxysilane, vinyl methyldiethoxysilane, and vinyl dimethylethoxy silane.
3. The micro-crosslinked cationic polyacrylamide flocculant of claim 1, wherein the micro-crosslinked cationic polyacrylamide flocculant has a weight average molecular weight of (1.14-8.32) x 106。
4. The preparation method of the micro-crosslinked cationic polyacrylamide flocculant of claim 1, characterized by comprising the steps of:
(1) preparing a monomer aqueous solution: dissolving acrylamide and methacryloyloxyethyl dimethyl benzyl ammonium chloride in deionized water according to a molar ratio of (1-2):1 to prepare a monomer aqueous solution with the total monomer content of 40-45 wt% for later use;
(2) preparation of inverse emulsion: uniformly mixing the hydrophobic continuous phase, the vinyl alkoxy silane and the compound emulsifier to prepare an oil phase, transferring the monomer aqueous solution in the step (1) into the oil phase, and shearing and uniformly mixing for 10-15 minutes to obtain uniform and stable emulsion;
(3) inverse emulsion polymerization: introducing N into the emulsion prepared in the step (2)2Deoxidizing; heating to 55-65 ℃, slowly dripping initiator aqueous solution under the condition of stirring, continuously stirring at constant temperature for reaction for 4-6h, then cooling to room temperature, stopping introducing nitrogen, and finishing the reaction;
(4) and (3) post-treatment: and (4) pouring the reaction emulsion obtained in the step (3) into acetone, stirring, filtering, washing with acetone, and carrying out vacuum drying and crushing on the solid to obtain the micro-crosslinked cationic polyacrylamide flocculant with white powder appearance.
5. The method of claim 4, wherein step (2) satisfies one or more of the following conditions:
i. the mole number of the vinyl alkoxy silane is 0.5 to 2.5 percent of the total mole number of three monomers of acrylamide, methacryloyloxyethyl dimethyl benzyl ammonium chloride and vinyl alkoxy silane;
the hydrophobic continuous phase is one of kerosene or cyclohexane;
the mass ratio of the hydrophobic continuous phase to the total water of the reaction system is (0.4-1.0): 1.0;
the dosage of the compound emulsifier is 8-15% of the total mass of the three monomers, the compound emulsifier is Tween80 and Span80, and the mass ratio of the Tween80 to the Span80 is (0.05-0.5): 1.0;
v. the rotation speed of the shearing is 1000-2000 rpm.
6. The method according to claim 4, wherein the initiator in the step (3) is azobisisobutyrimidazoline hydrochloride, and the amount of the initiator is 0.6 to 0.8% by mass based on the total mass of the three monomers.
7. The preparation method of claim 4, wherein the initiator aqueous solution in the step (3) is prepared by dissolving the initiator in deionized water to prepare an aqueous solution with a mass percent of 1.0-1.5%.
8. The method according to claim 4, wherein the vacuum drying in the step (4) is carried out under vacuum drying conditions of 60 to 70 ℃ for 12 to 24 hours.
9. The use of a micro-crosslinked cationic polyacrylamide flocculant of claim 1 in the treatment of oil production wastewater.
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| CN113831450A (en) * | 2021-10-27 | 2021-12-24 | 山东大学 | Branched cationic polyacrylamide flocculant and preparation method and application thereof |
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| CN114685711A (en) * | 2022-05-31 | 2022-07-01 | 东营市北陆生物科技有限公司 | Modified flocculant and preparation method thereof |
| CN116948089A (en) * | 2023-09-21 | 2023-10-27 | 河南博源新材料有限公司 | Cationic polyacrylamide terpolymer and preparation method thereof |
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| CN113831450A (en) * | 2021-10-27 | 2021-12-24 | 山东大学 | Branched cationic polyacrylamide flocculant and preparation method and application thereof |
| CN113896911A (en) * | 2021-11-10 | 2022-01-07 | 武汉鑫恒顺科技有限公司 | PPR gray pipe color master batch and preparation method thereof |
| CN114685711A (en) * | 2022-05-31 | 2022-07-01 | 东营市北陆生物科技有限公司 | Modified flocculant and preparation method thereof |
| CN116948089A (en) * | 2023-09-21 | 2023-10-27 | 河南博源新材料有限公司 | Cationic polyacrylamide terpolymer and preparation method thereof |
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