阅读说明：本技术 一种防结垢的高浓度有机废水输运改性管材及其制备方法 (Anti-scaling high-concentration organic wastewater transport modified pipe and preparation method thereof ) 是由 赵锐 李敏 于 2020-07-10 设计创作，主要内容包括：本发明提供了一种防结垢的高浓度有机废水输运改性管材及其制备方法,防结垢的高浓度有机废水输运改性管材,包括以下重量份原料：高密度聚乙烯树脂75-90份、含氟聚甲基环氧丙烯酸酯聚合物12-19份和疏水改性纳米二氧化硅1-7份。本发明中的含氟聚甲基环氧丙烯酸酯聚合物由甲基丙烯酸六氟丁酯、甲基丙烯酸丁酯和甲基丙烯酸缩水甘油酯通过两步本体聚合制得,其具有很好的抗结垢性能、耐酸碱性能,而且在制备过程中全程无有机溶剂加入,绿色环保,且与高密度聚乙烯树脂和疏水改性纳米二氧化硅共混时具有很好的相容性,有效解决了现有技术中材料表面防污性能不好、易造成二次污染和易结垢等问题,便于推广使用。(The invention provides an anti-scaling high-concentration organic wastewater transport modified pipe and a preparation method thereof, wherein the anti-scaling high-concentration organic wastewater transport modified pipe comprises the following raw materials in parts by weight: 75-90 parts of high-density polyethylene resin, 12-19 parts of fluorine-containing polymethyl epoxy acrylate polymer and 1-7 parts of hydrophobic modified nano silicon dioxide. The fluorine-containing polymethyl epoxy acrylate polymer is prepared by two-step bulk polymerization of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate, has good anti-scaling performance and acid and alkali resistance, is free of organic solvent in the whole preparation process, is green and environment-friendly, has good compatibility when being blended with high-density polyethylene resin and hydrophobic modified nano silicon dioxide, effectively solves the problems of poor surface anti-fouling performance, easy secondary pollution, easy scaling and the like of materials in the prior art, and is convenient to popularize and use.)

1. An anti-scaling high-concentration organic wastewater transport modified pipe is characterized by comprising the following raw materials in parts by weight: 75-90 parts of high-density polyethylene resin, 12-19 parts of fluorine-containing polymethyl epoxy acrylate polymer and 1-7 parts of hydrophobic modified nano silicon dioxide;

wherein, the fluorine-containing polymethyl epoxy acrylate polymer is prepared by two-step bulk polymerization of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate; the mass ratio of the hexafluorobutyl methacrylate to the butyl methacrylate to the glycidyl methacrylate is 9-12: 6-9: 2-4.

2. The anti-scaling high-concentration organic wastewater transportation modified pipe material as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight: 78 parts of high-density polyethylene resin, 17 parts of fluorine-containing polymethyl epoxy acrylate polymer and 5 parts of hydrophobic modified nano silicon dioxide.

3. The anti-fouling high-concentration organic wastewater transport modified pipe material as claimed in claim 1 or 2, wherein the mass ratio of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate is 10: 6: 3.

4. the anti-fouling high-concentration organic wastewater transport modified pipe material as claimed in claim 3, wherein the fluorine-containing polymethacrylate polymer is prepared by the following method:

(1) mixing 1/3 times weight of hexafluorobutyl methacrylate and 0.25-0.4 times weight of butyl methacrylate, and adding azodibutylnitrile with a total mass of 0.1-0.3% of the two components;

(2) mixing the residual hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate, then adding azodibutylnitrile accounting for 0.1-0.3% of the total mass of the residual hexafluorobutyl methacrylate, the residual butyl methacrylate, the butyl methacrylate and the glycidyl methacrylate, mixing, then dropwise adding the mixture into the product obtained in the step (1), stirring the mixture at the constant temperature of 75-78 ℃ for 90-100min, and stopping the reaction;

(3) transferring the reactant in the step (2) to a thin-layer reactor, reacting at the temperature of 72-77 ℃ for 20-25h, then continuing to react at the temperature of 100-120 ℃ for 1-3h, and cooling to room temperature to obtain the catalyst.

5. The anti-scaling high-concentration organic wastewater transport modified pipe material as claimed in claim 4, wherein the mass ratio of the hexafluorobutyl methacrylate to the butyl methacrylate in the step (1) is 3:2, and the addition amount of the azodibutylnitrile is 0.2% of the total mass of the hexafluorobutyl methacrylate and the butyl methacrylate.

6. The anti-scaling high-concentration organic wastewater transport modified pipe material as claimed in claim 4, wherein the addition amount of the azodibutylnitrile in the step (2) is 0.2% of the total mass of the remaining hexafluorobutyl methacrylate, the remaining butyl methacrylate and the remaining glycidyl methacrylate.

7. The anti-scaling high-concentration organic wastewater conveying modified pipe material as claimed in claim 4 or 6, wherein the dropwise adding is completed within 1h in the step (2).

8. The anti-scaling high-concentration organic wastewater transport modified pipe material as claimed in claim 4, wherein the hydrophobically modified nano-silica is prepared by modifying nano-silica with vinyltrimethoxysilane.

9. The method for preparing the anti-scaling high-concentration organic wastewater transport modified pipe material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:

the fluorine-containing polymethyl epoxy acrylate polymer, the hydrophobic modified nano silicon dioxide and the high-density polyethylene resin are uniformly mixed, and then are subjected to granulation and injection molding in sequence to obtain the fluorine-containing polymethyl epoxy acrylate resin.

10. The method as claimed in claim 9, wherein the extrusion temperature is 180-200 ℃ and the injection molding temperature is 170-190 ℃.

Technical Field

The invention belongs to the technical field of transport pipes and preparation, and particularly relates to an anti-scaling high-concentration organic wastewater transport modified pipe and a preparation method thereof.

Background

The high-concentration organic wastewater has the characteristics of large pollution load and complex components, and is generally collected by a pipeline system and then conveyed to a treatment facility for advanced treatment and discharge after reaching the standard. The common waste water conveying pipe is mainly made of polyvinyl chloride (PVC) and high-density polyethylene (HDPE), wherein the common waste water conveying pipe is mainly added with lead salt stabilizer, acrylate processing aid, calcium carbonate filler, lubricant and the like, and the common waste water conveying pipe is mainly added with coupling agent, antioxidant, calcium carbonate, carbon black and other fillers, wherein the carbon black and the calcium carbonate filler have strong hydrophilicity. The two types of pipes are used in the waste water transportation process, and can easily cause the biomembrane adhesion and mineral deposition on the inner wall of the pipeline, thereby generating scaling. The scale formation seriously affects the transportation efficiency, shortens the service life of the pipe, and even can cause the overlarge pressure of the pipe, thereby causing the leakage of waste water and generating secondary pollution to the environment.

The scale prevention technology of the existing wastewater conveying pipeline mainly comprises the measures of adding a scale inhibitor, surface coating, ultrasonic or high-frequency electromagnetic field scale removal and the like, but the scale inhibitor is possibly added to generate secondary chemical pollution, the problem that a surface coating film is easy to peel off is solved, and the ultrasonic or high-frequency electromagnetic field scale removal technology is difficult to adapt to the reality that the operation mileage of the pipeline is long and the yield of wastewater is large, and is difficult to be applied in engineering practice.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides an anti-scaling high-concentration organic wastewater transport modified pipe and a preparation method thereof, which can effectively solve the problems that a wastewater transport pipeline has poor anti-scaling technical effect, is easy to cause secondary pollution and cannot be popularized and used.

In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: the anti-scaling high-concentration organic wastewater transport modified pipe comprises the following raw materials in parts by weight:

75-90 parts of high-density polyethylene resin, 12-19 parts of fluorine-containing polymethyl epoxy acrylate polymer and 1-7 parts of hydrophobic modified nano silicon dioxide;

wherein, the fluorine-containing polymethyl epoxy acrylate polymer is prepared by two-step bulk polymerization of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate; the mass ratio of the hexafluorobutyl methacrylate to the butyl methacrylate to the glycidyl methacrylate is 9-12: 6-9: 2-4.

Further, the anti-scaling high-concentration organic wastewater transport modified pipe comprises the following raw materials in parts by weight: 78 parts of high-density polyethylene resin, 17 parts of fluorine-containing polymethyl epoxy acrylate polymer and 5 parts of hydrophobic modified nano silicon dioxide.

Further, the mass ratio of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate is 10: 6: 3.

further, the fluorine-containing polymethyl epoxy acrylate polymer is prepared by the following method:

(1) mixing 1/3 times weight of hexafluorobutyl methacrylate and 0.25-0.4 times weight of butyl methacrylate, and adding azodibutylnitrile with a total mass of 0.1-0.3% of the two components;

(2) mixing the residual hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate, then adding azodibutylnitrile accounting for 0.1-0.3% of the total mass of the residual hexafluorobutyl methacrylate, the residual butyl methacrylate, the butyl methacrylate and the glycidyl methacrylate, mixing, then dropwise adding the mixture into the product obtained in the step (1), stirring the mixture at the constant temperature of 75-78 ℃ for 90-100min, and stopping the reaction; the temperature of the liquid begins to rise, and the temperature is immediately reduced when the viscosity of the reaction liquid is increased, so that the reaction is stopped;

(3) transferring the reactant in the step (2) to a thin-layer reactor, reacting at the temperature of 72-77 ℃ for 20-25h, then continuing to react at the temperature of 100-120 ℃ for 1-3h, and cooling to room temperature to obtain the catalyst.

Further, in the step (1), the mass ratio of the hexafluorobutyl methacrylate to the butyl methacrylate is 3:2, and the addition amount of the azobisbutylnitrile is 0.2% of the total mass of the hexafluorobutyl methacrylate and the butyl methacrylate.

Further, the adding amount of the azodicarbonitrile in the step (2) is 0.2 percent of the total mass of the residual hexafluorobutyl methacrylate, the residual butyl methacrylate and the residual glycidyl methacrylate.

Further, in the step (2), the dropwise addition is completed within 1 hour.

Further, the hydrophobically modified nano-silica is prepared by modifying nano-silica with vinyl trimethoxy silane, and specifically comprises the following steps:

(1) preparing nano silicon dioxide suspension by using nano silicon dioxide; the method specifically comprises the following steps: adding the nano silicon dioxide into ethanol, stirring or ultrasonically dispersing for 25-30min to obtain 20-30g/L nano silicon dioxide suspension;

(2) preparing a vinyltrimethoxysilane hydrolysis solution by using vinyltrimethoxysilane; the method specifically comprises the following steps: dissolving vinyltrimethoxysilane in an ethanol aqueous solution to ensure that the concentration of the vinyltrimethoxysilane is 130-150g/L, then adding acetic acid to adjust the pH value to 4 +/-0.5, and stirring for 20-40min to obtain a vinyltrimethoxysilane hydrolysis solution; wherein the ethanol aqueous solution is a mixed solution formed by mixing ethanol and water according to the volume ratio of 3: 1;

(3) dropwise adding the vinyltrimethoxysilane hydrolyzed solution obtained in the step (2) into the nano-silica suspension obtained in the step (1) in a stirring state at a constant speed for 1 hour, then adjusting the pH value to 9-10, stirring for 3-4 hours at the temperature of 50-70 ℃, then sequentially cooling, centrifuging, drying and grinding, and finally sequentially washing, centrifuging, drying and grinding the ground powder with ethanol to obtain modified nano-silica; wherein the volume ratio of the vinyltrimethoxysilane hydrolyzed solution to the nano-silica suspension is 4: 5.

The preparation method of the anti-scaling high-concentration organic wastewater transport modified pipe comprises the following steps:

the fluorine-containing polymethyl epoxy acrylate polymer, the hydrophobic modified nano silicon dioxide and the high-density polyethylene resin are uniformly mixed, and then are subjected to granulation and injection molding in sequence to obtain the fluorine-containing polymethyl epoxy acrylate resin.

Further, the granulation extrusion temperature is 180-200 ℃, and the injection molding temperature is 170-190 ℃.

In summary, the invention has the following advantages:

1. the invention relates to a high-concentration organic wastewater, in particular to an organic wastewater with COD (chemical oxygen demand) of more than 2000mg/L, such as papermaking, leather, food industry wastewater, landfill leachate and the like, which is generally collected by a pipeline system and then conveyed to a treatment facility for advanced treatment and standard discharge, and a common wastewater conveying pipe is easy to scale in the wastewater conveying process.

The fluorine-containing polymethyl epoxy acrylate polymer is prepared by two-step bulk polymerization of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate, the synthesis process comprises two stages of a reaction kettle and a thin-layer reactor, no organic solvent is added in the whole reaction process, the method is green and environment-friendly, and the prepared fluorine-containing polymethyl epoxy acrylate polymer has excellent scale resistance. A high-molecular polymerization initiator such as azodibutylnitrile is used in the synthesis process, and the reaction is stable, has no side reaction and is easy to control; the hexafluorobutyl methacrylate serving as a reaction raw material is used for reducing the surface energy of a polymer material and improving the ageing resistance, corrosion resistance, hydrophobicity and anti-scaling performance of the material; butyl methacrylate is used for improving the antifouling performance of the polymer and increasing the flexibility of the material; the glycidyl methacrylate has two functional groups of active vinyl and epoxy group with ionic reaction, is used for improving the ageing resistance, toughening and corrosion resistance of the polymer, improving the formability and bending strength of the material and simultaneously improving the compatibility of the polymer and a high-density polyethylene resin blending system. According to the invention, through the synergistic effect of hexafluorobutyl methacrylate, butyl methacrylate and glycidyl methacrylate, not only is the excellent scale-resistant characteristic shown, but also the flexibility and strength of the pipe can be dispersed or improved by coordinating with other components in the preparation of the pipe, so that the pipe has excellent comprehensive performances such as scale resistance, corrosion resistance, mechanical property, ageing resistance and the like.

In addition, the nano silicon dioxide increases the wear resistance, mechanical strength, toughness and density of the composite material, has good ageing resistance and antibacterial performance, and can inhibit the adhesion of a biological film on the surface of the material; the vinyltrimethoxysilane has high oleophilic degree when used for modifying the nano-silica, and the modified nano-silica has super-hydrophobicity, so that the dispersibility of the silica powder in a blending system can be improved, and the bonding force and the compatibility of a polymer, polyethylene resin and a powder material during blending are increased.

2. The anti-scaling wastewater conveying pipeline material has good anti-scaling performance, and the surface energy is as low as 26.5 mN/m; the material has good acid and alkali resistance and strong adaptability to the extreme environment, and the corrosion resistance of the material is obviously superior to that of a PVC pipe; the surface wear resistance of the material is good, the hydrophobic property of the surface of the material after being worn is improved, and the anti-scaling property of the material is obviously superior to that of common polyvinyl chloride and high-density polyethylene materials.

3. The preparation method is simple, the synthesis of the low-surface-energy fluorine-containing polymethyl epoxy acrylate polymer adopts a bulk polymerization mode, and no organic solvent is used in the whole process, so that the environmental pollution caused by the synthesis mode is reduced, and the secondary pollution possibly caused by using a scale inhibitor is avoided; during preparation, the fluorine-containing polymethyl epoxy acrylate bulk polymer with low surface energy and the cross-linked hybrid composite pipeline material are successfully prepared. The invention adopts a melt crosslinking mode to overcome the defect of short service life caused by the falling off of a film layer in a common antifouling surface coating mode, does not need to additionally add a processing aid in the processing process, and has low cost of the used monomer and better economic benefit compared with the measures of ultrasonic wave or high-frequency electromagnetic field descaling and the like.

Drawings

FIG. 1 is an infrared spectrum of a fluorine-containing polymethacrylate polymer;

FIG. 2 is an infrared spectrogram of an anti-scaling high-concentration organic wastewater transport modified pipe;

FIG. 3 is a plot of polymer polarization;

FIG. 4 is a drawing showing the adhesion of surface biofilms when different pipes are immersed in simulated weak acid wastewater for 14 days;

FIG. 5 is a graph showing surface scaling of different pipes after being soaked in simulated weak acid wastewater for 14 days;

in the figures 4-5, a, b and c are respectively an anti-scaling high-concentration organic wastewater transportation modified pipe, an HDPE pipe and a PVC pipe.

Detailed Description

The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by manufacturers, and are all conventional products sold in the market.