A method for preparing a cationic organic polymer flocculant
By preparing a cationic organic polymer flocculant, using specific raw materials and multi-step reaction process, the problem of unsatisfactory effects of the existing flocculant is solved, and efficient and economical flocculation effect is achieved, which is suitable for solid-liquid separation in water treatment and industrial production.
Patent Information
- Application Number
- CN202411399833.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-09
- Publication Date
- 2025-05-09
- Estimated Expiration
- 2044-10-09
AI Technical Summary
At this stage, there are fewer successful varieties of cationic polymer flocculants, with unsatisfactory flocculation results, and fewer excellent and economical flocculants, which affects the solid-liquid separation efficiency in water treatment and industrial production.
By preparing a cationic organic polymer flocculant, using raw materials such as N,N-dimethylethanolamine, propyltriethoxysilane isocyanate, and after multiple steps of reaction, including reaction, filtration, reduced pressure rotary vaporization and polymerization, a flocculant with excellent flocculation performance is obtained.
The prepared cationic organic polymer flocculant has stronger adsorption bridge and settlement efficiency, which significantly improves the flocculation effect. It has a simple process and low cost, which is suitable for efficient and economical flocculation operations.
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Figure CN119264326B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of flocculants, in particular to a method for preparing a cationic organic polymer flocculant. Background Art
[0002] With the worsening of water pollution around the world, my country currently mainly uses biological methods and flocculation sedimentation methods to treat urban domestic sewage and industrial wastewater. The flocculation sedimentation method has been more widely used due to its advantages such as simple process, convenient operation and low energy consumption. Flocculants play a decisive role in the flocculation sedimentation method, and their quality will determine the effect after treatment. Therefore, the preparation of efficient and cheap flocculants has always been one of the research topics of scientific researchers.
[0003] Cationic polymer flocculants have the advantages of uniform charge distribution, small dosage in water treatment, fast flocculation speed and high treatment efficiency. They are widely used in the treatment of various industrial and domestic wastewaters. However, at this stage, few successful varieties have been developed, and the flocculation effect is not ideal. There are few types of excellent and economical flocculants. Therefore, strengthening the development and application research of cationic flocculants is of great significance to my country's water production and wastewater treatment as well as solid-liquid separation in industrial production. Summary of the invention
[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide a method for preparing a cationic organic polymer flocculant. The flocculant prepared by this method has excellent flocculation performance.
[0005] The object of the present invention can be achieved by the following technical scheme: a method for preparing a cationic organic polymer flocculant, the method for preparing the cationic organic polymer flocculant is as follows:
[0006] (1) Under nitrogen conditions, N,N-dimethylethanolamine and dibutyltin dilaurate are added to a toluene solvent, stirred and mixed evenly, and a toluene solution containing triethoxypropyl isocyanatesilane is added thereto at 70-80° C., and the mixture is kept warm for 3-5 hours. After the reaction is completed, the mixture is filtered, vacuum evaporated, and dried to obtain an intermediate product 1;
[0007] (2) The intermediate product 1 and trans-1,4-dichloro-2-butene are added to an isopropanol solvent, and the mixture is refluxed at 75-85° C. for 8-14 hours. After the reaction is completed, the mixture is distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate having the structural formula:
[0008] (3) Add tridecafluorooctanol, trans-1,4-dichloro-2-butene and a phase transfer catalyst to a toluene solvent, stir and mix evenly, then add a sodium hydroxide aqueous solution, react at 40-45° C. for 20-35 hours, and after the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene, whose structural formula is:
[0009] (4) Under nitrogen conditions, acrylamide and a disilane gemini quaternary ammonium salt intermediate are added to deionized water, stirred to dissolve, and then trans-1,4-bis(tridecafluorooctyloxy)but-2-ene is added thereto and stirred evenly, and ammonium persulfate initiator is added thereto, and the polymerization reaction is carried out at 55-70° C. for 5-10 hours. After the reaction is completed, acetone precipitation is performed, and the mixture is filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0010] As a further solution of the present invention: in (1), the molar ratio of N,N-dimethylethanolamine to isocyanatepropyltriethoxysilane is 1:1-1.2.
[0011] As a further embodiment of the present invention: in (2), the molar ratio of the intermediate product 1 to trans-1,4-dichloro-2-butene is 2-2.5:1.
[0012] As a further embodiment of the present invention: in (3), the molar ratio of tridecafluorooctanol to trans-1,4-dichloro-2-butene is 1.8-2.4:1.
[0013] As a further solution of the present invention: in (3), the phase transfer catalyst is tetrabutylammonium bromide.
[0014] As a further solution of the present invention: in said (3), the mass fraction of the sodium hydroxide aqueous solution is 70-80%.
[0015] As a further embodiment of the present invention: in said (4), the molar ratio of acrylamide, the bis-silane gemini quaternary ammonium salt intermediate, and trans-1,4-bis(tridecafluorooctyloxy)but-2-ene is 1:0.2-0.5:0.02-0.1.
[0016] Beneficial effects of the present invention: The present invention uses N,N-dimethylethanolamine and isocyanatepropyltriethoxysilane as raw materials to obtain an intermediate product 1, and uses trans-1,4-dichloro-2-butene to react with the intermediate product 1 and tridecafluorooctanol twice in sequence to obtain a disilane gemini quaternary ammonium salt intermediate and trans-1,4-bis(tridecafluorooctyloxy)but-2-ene, and finally initiates polymerization with acrylamide to obtain a cationic organic polymer flocculant.
[0017] The bisilane gemini quaternary ammonium salt intermediate prepared by the present invention has a simple and novel structure and a simple preparation method. The quaternary ammonium salt contained therein contains a positive charge. When the quaternary ammonium salt is introduced into a flocculant and used, it is adsorbed on suspended particles with negative charges or water-soluble organic colloids containing anionic groups through electrostatic action. When the surface charge of the particles is neutralized to make them coagulate and unstable, the adsorption and bridging effect of its long chain is utilized to make the suspended particles coagulate and achieve the effect of flocculation and sedimentation. The siloxane structure contained therein is hydrolyzed to produce silanol groups that can be combined with inorganic substances to form chemical bonds and improve sedimentation efficiency. The cationic organic polymer flocculant prepared by the present invention contains a fluorine-containing hydrophobic group, and the hydrophobic association enhances the interaction between polymer molecular chains, thereby having a stronger adsorption and bridging effect and improving the flocculation effect. In addition, the introduction of the hydrophobic group can enhance the interaction between the polymer and the organic matter, reduce the hydrophilicity of the flocs, and accelerate the floc sedimentation speed. The flocculant prepared by the present invention has the advantages of simple preparation process of the flocculant, low cost, high flocculation efficiency, etc., and is convenient for realizing efficient and economical flocculation operation. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is the reaction principle of the bis-silane gemini quaternary ammonium salt intermediate;
[0019] Figure 2 It is the reaction principle of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene;
[0020] Figure 3 This is a solid powder scan of Example 1. DETAILED DESCRIPTION
[0021] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.
[0022] Example 1
[0023] (1) Under nitrogen conditions, 20 mmol of N,N-dimethylethanolamine and 4 drops of dibutyltin dilaurate were added to a toluene solvent and stirred to mix evenly. A toluene solution containing 20 mmol of triethoxypropyl isocyanate was added thereto at 75°C and the mixture was kept warm for 4 hours. After the reaction was completed, the mixture was filtered, evaporated under reduced pressure, and dried to obtain an intermediate 1.
[0024] (2) 25 mmol of the intermediate product 1 and 12 mmol of trans-1,4-dichloro-2-butene were added to an isopropanol solvent and refluxed at 80° C. for 10 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate.
[0025] (3) Add 20 mmol of tridecafluorooctanol, 10 mmol of trans-1,4-dichloro-2-butene, and 2 mmol of TBAB to a toluene solvent, stir and mix evenly, then add 10 mL of a 72% sodium hydroxide aqueous solution, react at 40° C. for 32 h. After the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0026] (4) Under nitrogen conditions, 50 mmol of acrylamide and 10 mmol of a disilane gemini quaternary ammonium salt intermediate were added to deionized water and stirred to dissolve. Then, 1 mmol of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene was added thereto and stirred evenly. Then, 0.1 mmol of ammonium persulfate initiator was added thereto. The polymerization reaction was carried out at 70° C. for 5 h. After the reaction was completed, acetone precipitation was performed, and the mixture was filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0027] Example 2
[0028] (1) Under nitrogen conditions, 20 mmol of N,N-dimethylethanolamine and 6 drops of dibutyltin dilaurate were added to a toluene solvent and stirred to mix evenly. A toluene solution containing 22 mmol of triethoxypropyl isocyanate was added thereto at 80°C and the mixture was kept warm for 3 hours. After the reaction was completed, the mixture was filtered, evaporated under reduced pressure, and dried to obtain an intermediate 1.
[0029] (2) 26 mmol of the intermediate product 1 and 12 mmol of trans-1,4-dichloro-2-butene were added to an isopropanol solvent and refluxed at 80° C. for 12 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate.
[0030] (3) Add 22 mmol of tridecafluorooctanol, 10 mmol of trans-1,4-dichloro-2-butene, and 1 mmol of TBAB to toluene solvent, stir and mix evenly, then add 10 mL of 80% sodium hydroxide aqueous solution, react at 45° C. for 20 h. After the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0031] (4) Under nitrogen conditions, 50 mmol of acrylamide and 15 mmol of a disilane gemini quaternary ammonium salt intermediate were added to deionized water and stirred to dissolve. Then, 2 mmol of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene was added thereto and stirred evenly. Then, 0.1 mmol of ammonium persulfate initiator was added thereto. The polymerization reaction was carried out at 65° C. for 6 h. After the reaction was completed, acetone precipitation was performed, and the mixture was filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0032] Example 3
[0033] (1) Under nitrogen conditions, 20 mmol of N,N-dimethylethanolamine and 8 drops of dibutyltin dilaurate were added to a toluene solvent and stirred to mix evenly. A toluene solution containing 24 mmol of triethoxypropyl isocyanate was added thereto at 70°C and the mixture was kept warm for 5 hours. After the reaction was completed, the mixture was filtered, evaporated under reduced pressure, and dried to obtain an intermediate 1.
[0034] (2) 24 mmol of the intermediate product 1 and 12 mmol of trans-1,4-dichloro-2-butene were added to an isopropanol solvent and refluxed at 80° C. for 14 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate.
[0035] (3) Add 24 mmol of tridecafluorooctanol, 10 mmol of trans-1,4-dichloro-2-butene, and 1 mmol of TBAB to a toluene solvent, stir and mix evenly, then add 10 mL of a 70% sodium hydroxide aqueous solution, react at 40° C. for 20 h. After the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0036] (4) Under nitrogen conditions, 50 mmol of acrylamide and 20 mmol of a disilane gemini quaternary ammonium salt intermediate were added to deionized water and stirred to dissolve. Then, 3 mmol of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene was added thereto and stirred evenly. Then, 0.2 mmol of ammonium persulfate initiator was added thereto. The polymerization reaction was carried out at 55° C. for 10 h. After the reaction was completed, acetone precipitation was performed, and the mixture was filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0037] Example 4
[0038] (1) Under nitrogen conditions, 20 mmol of N,N-dimethylethanolamine and 8 drops of dibutyltin dilaurate were added to a toluene solvent and stirred to mix evenly. A toluene solution containing 22 mmol of triethoxypropyl isocyanate was added thereto at 75°C and the mixture was kept warm for 4 hours. After the reaction was completed, the mixture was filtered, evaporated under reduced pressure, and dried to obtain an intermediate 1.
[0039] (2) 25 mmol of the intermediate product 1 and 12 mmol of trans-1,4-dichloro-2-butene were added to an isopropanol solvent and refluxed at 75° C. for 14 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate.
[0040] (3) Add 20 mmol of tridecafluorooctanol, 10 mmol of trans-1,4-dichloro-2-butene, and 1 mmol of TBAB to toluene solvent, stir and mix evenly, then add 10 mL of 80% sodium hydroxide aqueous solution, react at 40° C. for 24 h. After the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0041] (4) Under nitrogen conditions, 50 mmol of acrylamide and 22 mmol of a disilane gemini quaternary ammonium salt intermediate were added to deionized water and stirred to dissolve. Then, 4 mmol of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene was added thereto and stirred evenly. Then, 0.3 mmol of ammonium persulfate initiator was added thereto. The polymerization reaction was carried out at 70° C. for 5 h. After the reaction was completed, acetone was used for precipitation, which was then filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0042] Example 5
[0043] (1) Under nitrogen conditions, 20 mmol of N,N-dimethylethanolamine and 6 drops of dibutyltin dilaurate were added to a toluene solvent and stirred to mix evenly. A toluene solution containing 24 mmol of triethoxypropyl isocyanate was added thereto at 75°C and the mixture was kept warm for 4 hours. After the reaction was completed, the mixture was filtered, evaporated under reduced pressure, and dried to obtain an intermediate 1.
[0044] (2) 30 mmol of the intermediate product 1 and 12 mmol of trans-1,4-dichloro-2-butene were added to isopropanol solvent and refluxed at 85° C. for 8 h. After the reaction was completed, the mixture was distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate.
[0045] (3) 18 mmol of tridecafluorooctanol, 10 mmol of trans-1,4-dichloro-2-butene, and 2 mmol of TBAB were added to a toluene solvent and stirred to mix evenly. Then, 10 mL of a 75% sodium hydroxide aqueous solution was added thereto. The mixture was reacted at 45° C. for 35 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, the oil layer was separated, washed, dried, and distilled under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0046] (4) Under nitrogen conditions, 50 mmol of acrylamide and 25 mmol of a disilane gemini quaternary ammonium salt intermediate were added to deionized water and stirred to dissolve. Then, 5 mmol of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene was added thereto and stirred evenly. Then, 0.2 mmol of ammonium persulfate initiator was added thereto. The polymerization reaction was carried out at 60° C. for 8 h. After the reaction was completed, acetone precipitation was performed, and the mixture was filtered, washed, and dried to obtain a cationic organic polymer flocculant.
[0047] Comparative Example 1
[0048] The difference between this comparative example and Example 1 is that in step (4), methacryloyloxyethyl trimethylammonium chloride is used instead of the disilane gemini quaternary ammonium salt intermediate.
[0049] Comparative Example 2
[0050] The difference between this comparative example and Example 1 is that in step (4), trifluoroethyl methacrylate is used instead of trans-1,4-bis(tridecafluorooctyloxy)but-2-ene.
[0051] 3 g of diatomaceous earth was dispersed in 100 g of water, stirred and mixed for 10 min, a flocculant was added thereto, stirred and mixed for 10 min, the dosage of the flocculant was controlled to be 10 mg / L, and the mixture was allowed to stand for 30 min. The supernatant was taken out with a pipette at a distance of 20 mm from the liquid surface, and the transmittance of the supernatant was measured on a spectrophotometer with a wavelength of 590 nm; the Zeta potential of the diatomaceous earth suspension surface was measured using a nanoparticle surface potential analyzer.
[0052] Table 1:
[0053] Supernatant permeability (%) Zeta potential / mV Example 1 83.63 -2.45 Example 2 88.49 -1.05 Example 3 95.28 -0.52 Example 4 98.40 -0.08 Example 5 94.02 0.10 Comparative Example 1 74.25 -10.36 Comparative Example 2 67.48 -8.05
[0054] The greater the supernatant permeability, the better the flocculation effect. As can be seen from the table, the supernatant permeability of Examples 1-5 is greater than that of Comparative Example 1-2, and can reach a maximum of 98.40%. The closer the Zeta potential is to 0, the better the flocculation effect. The diatomite suspended particles are negatively charged, and the particles have a larger Zeta potential. The repulsive force between the charges prevents the suspended particles from approaching each other, and eliminating or reducing the Zeta potential can cause the particles to collide and aggregate and lose stability. Therefore, a cationic organic polymer flocculant is added thereto. Because it contains a positively charged quaternary ammonium group, it is adsorbed on the diatomite, which can change the surface charge of the diatomite, reduce the Zeta potential, and make the particles easy to approach and connect together to form flocs, thereby achieving a flocculation effect. The Zeta potential of Examples 1-5 is closer to 0. Therefore, the flocculant prepared by the present invention has a better flocculation effect.
[0055] The above description of the embodiments is to facilitate the understanding and application of the present invention by those skilled in the art. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the embodiments herein, and modifications made to the present invention by those skilled in the art based on the disclosure of the present invention should be within the scope of protection of the present invention.
Claims
1. A method for preparing a cationic organic polymer flocculant, characterized in that: The preparation method of the cationic organic polymer flocculant is as follows: (1) Under nitrogen conditions, N,N-dimethylethanolamine and dibutyltin dilaurate are added to a toluene solvent, stirred and mixed evenly, and a toluene solution containing triethoxypropyl isocyanatesilane is added thereto at 70-80° C., and the mixture is kept warm for 3-5 hours. After the reaction is completed, the mixture is filtered, vacuum evaporated, and dried to obtain an intermediate product 1; (2) The intermediate product 1 and trans-1,4-dichloro-2-butene are added to an isopropanol solvent, and the mixture is refluxed at 75-85° C. for 8-14 hours. After the reaction is completed, the mixture is distilled under reduced pressure, washed, and recrystallized to obtain a disilane gemini quaternary ammonium salt intermediate having the structural formula: (3) Add tridecafluorooctanol, trans-1,4-dichloro-2-butene and a phase transfer catalyst to a toluene solvent, stir and mix evenly, then add a sodium hydroxide aqueous solution, react at 40-45° C. for 20-35 hours, and after the reaction is completed, cool to room temperature, filter, separate the oil layer, wash, dry, and distill under reduced pressure to obtain trans-1,4-bis(tridecafluorooctyloxy)but-2-ene, whose structural formula is: (4) Under nitrogen conditions, acrylamide and a disilane gemini quaternary ammonium salt intermediate are added to deionized water, stirred to dissolve, and then trans-1,4-bis(tridecafluorooctyloxy)but-2-ene is added thereto and stirred evenly, wherein the molar ratio of acrylamide, disilane gemini quaternary ammonium salt intermediate and trans-1,4-bis(tridecafluorooctyloxy)but-2-ene is 1:0.2-0.5:0.02-0.1, and ammonium persulfate initiator is added thereto, and the polymerization reaction is carried out at 55-70° C. for 5-10 hours. After the reaction is completed, acetone precipitation is performed, suction filtration is performed, washing is performed, and drying is performed to obtain a cationic organic polymer flocculant.
2. The method for preparing a cationic organic polymer flocculant according to claim 1, characterized in that: In the above (1), the molar ratio of N,N-dimethylethanolamine to isocyanatepropyltriethoxysilane is 1:1-1.
2.
3. The method for preparing a cationic organic polymer flocculant according to claim 1, characterized in that: In the above (2), the molar ratio of the intermediate product 1 to trans-1,4-dichloro-2-butene is 2-2.5:
1.
4. The method for preparing a cationic organic polymer flocculant according to claim 1, characterized in that: In the above (3), the molar ratio of tridecafluorooctanol to trans-1,4-dichloro-2-butene is 1.8-2.4:
1.
5. The method for preparing a cationic organic polymer flocculant according to claim 1, characterized in that: In the above (3), the phase transfer catalyst is tetrabutylammonium bromide.
6. The method for preparing a cationic organic polymer flocculant according to claim 1, characterized in that: In the above (3), the mass fraction of the sodium hydroxide aqueous solution is 70-80%.
Citation Information
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