阅读说明：本技术 一种具有高吸附性能的污水处理用复合材料 (Composite material with high adsorption performance for sewage treatment ) 是由 骆瑜 于 2019-09-06 设计创作，主要内容包括：本发明公开了一种具有高吸附性能的污水处理用复合材料,是由重金属吸附纤维和有机磷吸附纤维按照质量比为4：1的比例复合纺织形成纱线制备,然后纱线纺织成过滤纱布,然后将过滤纱布固定在MBR组件的固定架上,制成MBR组件的平板过滤膜。本发明通过重金属吸附纤维和有机磷吸附纤维复合纺织制备过滤膜,然后将过滤膜与现有的MBR组件中的平板膜交替安装在MBR组件上,由于过滤膜不仅能够对金属离子进行吸附,同时能够对有机磷化合物进行吸附,不仅实现过滤并且能够有效的对污水中的重金属离子和有机磷进行吸附处理,解决了现有的MBR工艺不能实现对小分子重金属离子和有机磷的清除的问题。(The invention discloses a composite material with high adsorption performance for sewage treatment, which is prepared from heavy metal adsorption fibers and organic phosphorus adsorption fibers in a mass ratio of 4: 1, preparing yarns, spinning the yarns into filtering gauze, fixing the filtering gauze on a fixing frame of the MBR assembly, and manufacturing a flat filtering membrane of the MBR assembly. According to the invention, the filtering membrane is prepared by compounding and spinning the heavy metal adsorption fiber and the organic phosphorus adsorption fiber, and then the filtering membrane and the flat plate membrane in the conventional MBR component are alternately arranged on the MBR component, so that the filtering membrane can adsorb metal ions and organic phosphorus compounds, not only is filtering realized, but also heavy metal ions and organic phosphorus in sewage can be effectively adsorbed, and the problem that the conventional MBR process cannot remove small-molecule heavy metal ions and organic phosphorus is solved.)

1. The composite material with high adsorption performance for sewage treatment is characterized by comprising heavy metal adsorption fibers and organic phosphorus adsorption fibers in a mass ratio of 4: 1, preparing yarns, spinning the yarns into filter gauze, fixing the filter gauze on a fixing frame of the MBR assembly, and preparing a flat filtering membrane of the MBR assembly;

the specific preparation process of the organophosphorus adsorbing fiber is as follows:

adding ammonia water and epoxy chloropropane into a reaction container at the same time, carrying out reflux reaction for 4-5h at the temperature of 60-65 ℃, then adding beta-cyclodextrin and sodium hydroxide into the reaction container, heating to the temperature of 120-125 ℃, carrying out reflux reaction for 10-12h, and then carrying out evaporation to remove the solvent therein, thus obtaining solid powder;

adding glycerol and acetone into a reaction container, adding p-toluenesulfonic acid and maleic anhydride into the reaction container, heating to 250-270 ℃, performing reflux reaction for 12-13h, adding the solid powder prepared in the step I into the reaction container, stirring for dissolving, adding toluene diisocyanate dropwise into the reaction container while stirring vigorously, and after complete dropwise addition, performing constant-temperature stirring reaction for 2-3h to obtain a loaded glue solution;

thirdly, soaking the cotton fiber in the loading glue solution for 10-15min, then fishing out, and drying at 70-80 ℃ to obtain the organic phosphorus adsorption fiber, wherein a layer of organic phosphorus adsorption film is compounded on the surface of the cotton fiber.

2. The composite material as claimed in claim 1, wherein 30-35mL ammonia water, 6-7g β -cyclodextrin and 1.2g sodium hydroxide are added to 100mL epichlorohydrin in step (i).

3. The composite material for sewage treatment with high adsorption performance according to claim 1, wherein the ratio of glycerol to maleic anhydride in the step (c) is 1: 1, adding 0.24-0.25g of p-toluenesulfonic acid into per gram of maleic anhydride, adding 8-9mL of water, adding 1.23-1.25g of solid powder, and adding 1.14-1.18g of toluene diisocyanate.

4. The composite material for sewage treatment with high adsorption performance as claimed in claim 1, wherein the heavy metal adsorption fiber is prepared by the following specific steps:

step 1: adding triallyl isocyanurate into an ethanol solution, uniformly stirring, adjusting the pH =1 of the solution by using acetic acid, then adding ethanedithiol into a reaction vessel, stirring and reacting for 7-8h at normal temperature, and then evaporating to remove the solvent and the ethanedithiol which is not completely reacted to obtain the thiotriallyl isocyanurate;

step 2: adding the thiotriallyl isocyanurate prepared in the first step into ethanol, stirring and dissolving, then adding azodiisobutyronitrile, heating to 90-95 ℃, then dropwise adding acrylic acid into the reaction container through a dropping funnel, controlling the dropwise adding speed to be 9-10mL/min, stirring and reacting for 1-1.5h after the dropwise adding is completed, heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent therein to obtain the carboxyl nitrogen sulfur polymer;

and step 3: adding carboxyl nitrogen sulfur polymer into water, stirring and dissolving to obtain an adsorption solution, adding polyamide fiber into the adsorption solution, simultaneously heating to 60-70 ℃, cooking for 2-3h, and then filtering to obtain the heavy metal adsorption fiber.

5. The composite material for sewage treatment with high adsorption performance as claimed in claim 4, wherein the ratio of the amount of the triallyl isocyanurate and the ethanedithiol is 1: 3.1, and simultaneously adding 9-10mL of ethanol solution into each gram of triallyl isocyanurate.

6. The composite material for sewage treatment with high adsorption performance as claimed in claim 4, wherein 0.86-0.89g of azobisisobutyronitrile, 25-30mL of ethanol and 0.66-0.67g of acrylic acid are added to each gram of thiotriallyl isocyanurate.

Technical Field

The invention belongs to the field of sewage treatment, and relates to a composite material with high adsorption performance for sewage treatment.

Background

The sewage mostly contains factory wastewater and domestic sewage at the same time, the ammonia nitrogen content in the sewage is higher, the ammonia nitrogen content in the sewage is reduced by generally treating the sewage through an MBR process, but the adsorption performance of the sewage to micromolecule heavy metal ions and organic phosphorus compounds is lower, the heavy metal ions exist in the water body, certain harm is caused to a human body after reaching certain concentration, meanwhile, the organic phosphorus compounds are generally derived from main components in pesticides and have great harm to the human body in the water body, and the organic phosphorus compounds cannot be cleared through the conventional MBR process.

Disclosure of Invention

The invention aims to provide a composite material with high adsorption performance for sewage treatment, which is characterized in that a filtering membrane is prepared by compounding and spinning heavy metal adsorption fibers and organic phosphorus adsorption fibers, and then the filtering membrane and a flat plate membrane in the conventional MBR component are alternately arranged on the MBR component.

The purpose of the invention can be realized by the following technical scheme:

a composite material with high adsorption performance for sewage treatment is prepared from heavy metal adsorption fibers and organic phosphorus adsorption fibers according to a mass ratio of 4: 1, preparing yarns, weaving the yarns into filter gauze, fixing the filter gauze on a fixing frame of an MBR (membrane bioreactor) assembly to prepare a flat filter membrane of the MBR assembly, wherein the flat filter membrane and the flat membrane in the conventional MBR assembly can be alternately arranged on the MBR assembly in the using process, so that not only is filtration realized, but also the heavy metal ions and organic phosphorus in sewage can be effectively adsorbed;

the preparation process of the heavy metal adsorption fiber comprises the following steps:

step 1: adding triallyl isocyanurate into an ethanol solution, uniformly stirring, adjusting the pH =1 of the solution by using acetic acid, then adding ethanedithiol into a reaction vessel, stirring and reacting for 7-8h at normal temperature, and then evaporating to remove the solvent and the ethanedithiol which is not completely reacted to obtain the thiotriallyl isocyanurate; wherein the ratio of the amount of the triallyl isocyanurate to the ethylene glycol is 1: 3.1, simultaneously adding 9-10mL of ethanol solution into each gram of triallyl isocyanurate, wherein ketone groups contained in the triallyl isocyanurate can react with ethanedithiol under an acidic condition to generate thioketal, and further leading sulfur elements to be introduced into a product;

step 2: adding the thiotriallyl isocyanurate prepared in the first step into ethanol, stirring and dissolving, then adding azodiisobutyronitrile, heating to 90-95 ℃, then dropwise adding acrylic acid into the reaction container through a dropping funnel, controlling the dropwise adding speed to be 9-10mL/min, stirring and reacting for 1-1.5h after the dropwise adding is completed, heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent therein to obtain the carboxyl nitrogen sulfur polymer; wherein 0.86-0.89g of azobisisobutyronitrile is added into each gram of the thiotriallyl isocyanurate, 25-30mL of ethanol is added, and 0.66-0.67g of acrylic acid is added;

and step 3: adding carboxyl nitrogen sulfur polymer into water, stirring and dissolving to obtain an adsorption solution, adding polyamide fiber into the adsorption solution, simultaneously heating to 60-70 ℃, cooking for 2-3h, and then filtering to obtain heavy metal adsorption fiber, wherein the carboxyl nitrogen sulfur polymer contains a large amount of carboxyl and can react with amino in the polyamide fiber, so that the carboxyl nitrogen sulfur polymer is firmly loaded on the surface of the polyamide fiber, the surface of the polyamide fiber is loaded with a carboxyl nitrogen sulfur polymer layer, and the carboxyl nitrogen sulfur polymer contains a large amount of amino and sulfur elements, and can be combined with heavy metal copper ions, nickel ions, lead ions, mercury ions, chromium ions and iron ions through chelation, so that the heavy metal ions are adsorbed on the carboxyl nitrogen sulfur polymer layer on the surface of the cellulose, the content of heavy metal ions in the sewage is reduced, and meanwhile, because both the amide groups and the hydroxyl groups on the carboxyl nitrogen-sulfur polymer layer on the surface of the fiber have higher hydrophilic performance, the hydrophilic capability of the fiber can be improved, so that the sewage can be directly contacted with the fiber, and the adsorption quantity of the heavy metal ions is further improved;

the specific preparation process of the organophosphorus adsorbing fiber is as follows:

adding ammonia water and epoxy chloropropane into a reaction container at the same time, carrying out reflux reaction for 4-5h at the temperature of 60-65 ℃, then adding beta-cyclodextrin and sodium hydroxide into the reaction container, heating to the temperature of 120-125 ℃, carrying out reflux reaction for 10-12h, and then carrying out evaporation to remove the solvent therein, thus obtaining solid powder; wherein 30-35mL of ammonia water, 6-7g of beta-cyclodextrin and 1.2g of sodium hydroxide are added into every 100mL of epoxy chloropropane; ammonia water and epoxy chloropropane are subjected to ring opening reaction to generate alkyl chloride containing amino, wherein the alkyl chloride and primary alcohol groups in beta-cyclodextrin are subjected to substitution reaction under alkaline conditions, so that the epoxy chloropropane subjected to ring opening of the amino is grafted on a beta-cyclodextrin chain, and because the beta-cyclodextrin is in a cage shape, a large number of primary alcohol groups are distributed outside the cage shape, and a large number of epoxy chloropropane subjected to ring opening of the amino is introduced into a grafted product;

adding glycerol and acetone into a reaction container, adding p-toluenesulfonic acid and maleic anhydride into the reaction container, heating to 250-270 ℃, performing reflux reaction for 12-13h, adding the solid powder prepared in the step I into the reaction container, stirring for dissolving, adding toluene diisocyanate dropwise into the reaction container while stirring vigorously, and after complete dropwise addition, performing constant-temperature stirring reaction for 2-3h to obtain a loaded glue solution; wherein the ratio of glycerol to maleic anhydride by mass is 1: 1, adding 0.24-0.25g of p-toluenesulfonic acid into per gram of maleic anhydride, adding 8-9mL of water, adding 1.23-1.25g of solid powder, and adding 1.14-1.18g of toluene diisocyanate; the glycerol contains three hydroxyl groups, two of the hydroxyl groups can be subjected to polymerization reaction with maleic anhydride to generate an unsaturated polymer containing hydroxyl groups as branched chains, the solid powder substance prepared in the step I contains a large amount of amino groups, and the amino groups can be subjected to polymerization reaction with the hydroxyl groups on the unsaturated polymer branched chains under the action of toluene diisocyanate, so that the prepared load glue solution is polymerized in different directions on the peripheral sides by the cage-shaped beta-cyclodextrin, the prepared polymer is further connected with the linear unsaturated polymer in different directions by the cage-shaped beta-cyclodextrin to form a hyperbranched structure, the unsaturated polymer has certain adhesive property, the polymer generated after polymerization has certain adhesive property, can be firmly adhered to the surface of fibers, and contains a large amount of cage-shaped structures, the cage-shaped structure can be used for clathrating organic phosphorus in the sewage, so that the organic phosphorus is adsorbed;

soaking the cotton fiber in the loaded glue solution for 10-15min, taking out, drying at 70-80 ℃ to obtain organic phosphorus adsorption fiber, and compounding a layer of organic phosphorus adsorption film on the surface of the cotton fiber; because the cotton fiber has higher water absorption performance, a large amount of loading glue solution can be adsorbed on the surface and the inside of the cotton fiber, so that the prepared organic phosphorus adsorption fiber has higher adsorption performance on the surface and the inside.

The invention has the beneficial effects that:

1. according to the invention, the filtering membrane is prepared by compounding and spinning the heavy metal adsorption fiber and the organic phosphorus adsorption fiber, and then the filtering membrane and the flat plate membrane in the conventional MBR component are alternately arranged on the MBR component, so that the filtering membrane can adsorb metal ions and organic phosphorus compounds, not only is filtering realized, but also heavy metal ions and organic phosphorus in sewage can be effectively adsorbed, and the problem that the conventional MBR process cannot remove small-molecule heavy metal ions and organic phosphorus is solved.

2. The heavy metal adsorption fiber prepared by the invention contains a large amount of amino and sulfur elements which can be combined with heavy metal copper ions, nickel ions, lead ions, mercury ions, chromium ions and iron ions through chelation, so that the heavy metal ions are adsorbed on a carboxyl nitrogen sulfur polymer layer on the surface of cellulose, the content of the heavy metal ions in sewage is reduced, meanwhile, because amide groups and hydroxyl groups on the carboxyl nitrogen sulfur polymer layer on the surface of the fiber have higher hydrophilic performance, the hydrophilic capability of the fiber can be improved, so that the sewage can be directly contacted with the fiber, the adsorption quantity of the heavy metal ions is improved, meanwhile, the adsorption fiber containing organic phosphorus in the yarn has a hyperbranched net structure, modified beta-cyclodextrin with a cage-shaped structure is arranged on each node of the net structure, and the modified beta-cyclodextrin contains amino, and then make the fibre surface equipartition of preparation have a large amount of amino, further improved the adsorption efficiency of yarn, and then can solve the lower problem of MBR membrane to heavy metal ion adsorption efficiency among the prior art.

3. The organic phosphorus adsorption fiber prepared by the invention is characterized in that the surface of the fiber is coated with a layer of loading glue solution, wherein the loading glue solution is polymerized in different directions of the peripheral side by cage-shaped beta-cyclodextrin, so that the prepared polymer is formed into a hyperbranched structure by connecting linear unsaturated polymers in different directions through the cage-shaped beta-cyclodextrin, and because the glycerol contains three hydroxyl groups, two of the hydroxyl groups can be polymerized with maleic anhydride to generate the unsaturated polymer containing hydroxyl groups as branched chains, the unsaturated polymer has certain adhesive property, the polymer generated after polymerization has certain adhesive property and can be firmly adhered to the surface of the fiber, so that an adsorption film on the surface of the fiber can not be peeled off after the prepared fiber is repeatedly used for many times, and the repeated use performance of the yarn is further improved, and the polymer contains a large amount of cage structures, and the cage structures can be used for clathrating organic phosphorus in sewage, so that the organic phosphorus is adsorbed, and the problem of low organic phosphorus removal efficiency of an MBR (membrane bioreactor) membrane in the prior art is solved.

Detailed Description