CN110615500A - Composite material with high adsorption performance for sewage treatment - Google Patents

Composite material with high adsorption performance for sewage treatment Download PDF

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Publication number
CN110615500A
CN110615500A CN201910841700.6A CN201910841700A CN110615500A CN 110615500 A CN110615500 A CN 110615500A CN 201910841700 A CN201910841700 A CN 201910841700A CN 110615500 A CN110615500 A CN 110615500A
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adsorption
fiber
stirring
heavy metal
organic phosphorus
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CN110615500B (en
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骆瑜
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Suzhou Qingxi Environmental Protection Technology Co Ltd
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Suzhou Qingxi Environmental Protection Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
    • C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01—Natural vegetable fibres
    • D10B2201/02—Cotton
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides

Abstract

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.

Description

Composite material with high adsorption performance for sewage treatment
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
Example 1:
the specific preparation process of the heavy metal adsorption fiber is as follows:
step 1: adding 24.9g of triallyl isocyanurate into 225mL of ethanol solution, uniformly stirring, adjusting the pH =1 of the solution by using acetic acid, then adding 29.14g of 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 10g of thiotriallyl isocyanurate prepared in the first step into 250mL of ethanol, stirring and dissolving, then adding 8.6g of azodiisobutyronitrile, heating to 90-95 ℃, then dropwise adding 6.6g of acrylic acid into a reaction container through a dropping funnel, controlling the dropwise adding speed to be 9-10mL/min, stirring and reacting for 1-1.5h after completely dropwise adding, then heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent therein to obtain a carboxyl nitrogen-sulfur polymer;
and step 3: adding 10g of carboxyl nitrogen sulfur polymer into 80g of 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.
Example 2:
the specific preparation process of the heavy metal adsorption fiber is as follows:
step 1: adding 24.9g of triallyl isocyanurate into 225mL of ethanol solution, uniformly stirring, adjusting the pH =1 of the solution by using acetic acid, then adding 19.41g of 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 10g of thiotriallyl isocyanurate prepared in the first step into 250mL of ethanol, stirring and dissolving, then adding 8.6g of azodiisobutyronitrile, heating to 90-95 ℃, then dropwise adding 6.6g of acrylic acid into a reaction container through a dropping funnel, controlling the dropwise adding speed to be 9-10mL/min, stirring and reacting for 1-1.5h after completely dropwise adding, then heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent therein to obtain a carboxyl nitrogen-sulfur polymer;
and step 3: adding 10g of carboxyl nitrogen sulfur polymer into 80g of 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.
Example 3:
the specific preparation process of the heavy metal adsorption fiber is as follows:
step 1: adding 10g of triallyl isocyanurate into 250mL of ethanol, stirring and dissolving, then adding 8.6g of azobisisobutyronitrile, heating to 90-95 ℃, then dropwise adding 6.6g of 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, then heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent therein to obtain a carboxyl nitrogen polymer;
and step 3: adding 10g of carboxyl nitrogen polymer into 80g of 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.
Example 4:
the specific preparation process of the heavy metal adsorption fiber is as follows:
step 1: adding 10g of triallyl isocyanurate into 250mL of ethanol, stirring and dissolving, then adding 8.6g of azodiisobutyronitrile, heating to 90-95 ℃, stirring and reacting for 1-1.5h, heating to 120-125 ℃, stirring and reacting for 5-6h, and evaporating the obtained product solution to remove the solvent to obtain a polymer;
step 2: adding 10g of polymer into 80g of 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.
Example 5:
the specific preparation process of the organophosphorus adsorbing fiber is as follows:
adding 30mL of ammonia water and 100mL of 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 6g of beta-cyclodextrin and 1.2g of sodium hydroxide into the reaction container, heating to 120 ℃ and 125 ℃, carrying out reflux reaction for 10-12h, and then carrying out evaporation to remove the solvent therein, thus obtaining solid powder;
adding 9.2g of glycerol and 79mL of water into a reaction container, adding 3.95g of p-toluenesulfonic acid and 9.8g of maleic anhydride into the reaction container, heating to 250 ℃ and 270 ℃, carrying out reflux reaction for 12-13h, adding 12.05g of solid powder prepared in the step I into the reaction container, stirring and dissolving, adding 11.2g of toluene diisocyanate dropwise into the reaction container while carrying out vigorous stirring, and carrying out stirring reaction for 2-3h at constant temperature after complete dropwise addition 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.
Example 6:
the specific preparation process of the organophosphorus adsorbing fiber is as follows:
adding 30mL of ammonia water and 100mL of 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 6g of beta-cyclodextrin and 1.2g of sodium hydroxide into the reaction container, heating to 120 ℃ and 125 ℃, carrying out reflux reaction for 10-12h, and then carrying out evaporation to remove the solvent therein, thus obtaining solid powder;
adding 10g of solid powder into an acetone solution, stirring and dissolving, then adding 11.2g of toluene diisocyanate dropwise while stirring vigorously, and stirring and reacting at constant temperature for 2-3h after complete dropwise addition 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.
Example 7:
a composite material with high adsorption performance for sewage treatment is prepared by mixing the heavy metal adsorption fiber prepared in example 1 and the organic phosphorus adsorption fiber prepared in example 4 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; 10mL of omethoate organic pesticide with the concentration of 300g/L is added into 10mg of prepared yarn, the vibration is carried out for 2h at normal temperature, the content of organic phosphorus before and after adsorption is measured by an ultraviolet spectrophotometer, and then the adsorption rate of the yarn to omethoate is calculated to be 96.7 percent, so that the organic phosphorus adsorption fiber in the yarn has higher adsorption performance to the organic phosphorus in the omethoate, and the toxicity of water is further reduced.
Example 8:
a composite material for sewage treatment having high adsorption performance, which was prepared in the same manner as in example 7 except that the heavy metal-adsorbing fiber prepared in example 1 used in example 7 was replaced with the heavy metal-adsorbing fiber prepared in example 2.
Example 9:
a composite material for sewage treatment having high adsorption performance, which was prepared in the same manner as in example 7 except that the heavy metal-adsorbing fiber prepared in example 1 used in example 7 was replaced with the heavy metal-adsorbing fiber prepared in example 3.
Example 10:
a composite material for sewage treatment having high adsorption performance, which was prepared in the same manner as in example 7 except that the heavy metal-adsorbing fiber prepared in example 1 used in example 7 was replaced with the heavy metal-adsorbing fiber prepared in example 4.
Example 11:
a composite material for sewage treatment having high adsorption performance was prepared in the same manner as in example 7 except that the organic phosphorus-adsorbing fiber prepared in example 4 used in example 7 was replaced with the organic phosphorus-adsorbing fiber prepared in example 5.
Example 12:
preparing heavy metal ion solutions with different concentrations, wherein the concentration of lead ions is 50mg/L, the concentration of mercury ions is 100mg/L, and the concentration of chromium ions is 100mg/L, then weighing 10mg, adding the yarns prepared in the embodiments 6-9 into a shaking bottle, respectively adding 10mL of different heavy metal ions into the shaking bottle, shaking for 3-4h at normal temperature, and then, shaking for 3-4h at normal temperatureRespectively measuring the concentrations of the corresponding heavy metal ions in different oscillation bottles before and after oscillation by using an atomic absorption spectrophotometer, wherein the concentration of the original heavy metal ions is marked as C0And the concentration of the adsorbed heavy metal ion is recorded as C1The adsorption rate P = (C) of the yarn to the respective heavy metal ion0-C1)/C0Multiplying by 100%, calculating the adsorption rate of the yarns in the embodiments 6 to 9 on each heavy metal ion, drying the adsorbed yarns, soaking the yarns in a dilute sulfuric acid solution with the concentration of 1%, soaking and heating to 60-70 ℃, soaking for 3-4h, filtering, washing to be neutral, drying, repeating the adsorption experiment for 8 times, and measuring the adsorption rate of the yarns on each heavy metal ion when the yarns are repeated for 8 times, wherein the specific results are shown in table 1;
TABLE 1 adsorption rate of heavy metal ions after various times of cyclic adsorption%
As can be seen from table 1, the yarn prepared in example 7 has high adsorption performance for lead ions, mercury ions and chromium ions, and since heavy metal adsorption fibers contain a large amount of amino and sulfur elements, the heavy metal adsorption fibers 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 the heavy metal ions in the sewage is reduced, and meanwhile, since amide groups and hydroxyl groups on the carboxyl nitrogen sulfur polymer layer on the surface of the fibers have high hydrophilic performance, the hydrophilic performance of the fibers can be improved, so that the sewage can be directly contacted with the fibers, and the adsorption amount of the heavy metal ions is improved, meanwhile, the organic phosphorus adsorption fibers contained in the yarn have hyperbranched network structures, and modified beta-cyclodextrin with cage-shaped structures is arranged on nodes of each network structure, the modified beta-cyclodextrin contains amino, so that a large number of amino groups are uniformly distributed on the surface of the prepared fiber, and the adsorption performance of the yarn is further improved; the adsorption performance of the yarns in examples 8 and 9 is reduced, the adsorption performance of the heavy metal adsorption fibers is reduced due to the reduction of the sulfur content on the adsorption film on the surface of the heavy metal adsorption fibers, the polymer prepared in example 10 does not contain carboxyl, the water absorption of the surface of the heavy metal fibers is reduced, the approaching effect between the adsorption film on the surface of the fibers and heavy metal ions is reduced, and the adsorption rate is reduced; meanwhile, the adsorption film on the surface of the organophosphorus adsorption fiber in the embodiment 11 is directly prepared by polymerizing the modified beta-cyclodextrin, the prepared glue solution has low bonding performance, and the adsorption film is easy to peel off from the surface of the fiber after repeated use for many times, so that the adsorption performance is reduced.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (6)

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.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110818504A (en) * 2019-11-15 2020-02-21 福建师范大学福清分校 Organic fertilizer capable of reducing heavy metal pollution of soil and preparation and application thereof
CN113882152A (en) * 2021-12-09 2022-01-04 天津市职业大学 Preparation method of antibacterial easily-regenerated fiber material for treating oily sewage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104548949A (en) * 2013-10-11 2015-04-29 中国石油化工股份有限公司 Preparation method of polymer porous membrane for removing water pollutants
KR20170045454A (en) * 2015-10-16 2017-04-27 서울대학교산학협력단 Method of producing an ion-exchange fiber Plaited thread Micro chip filter
CN106621838A (en) * 2016-12-31 2017-05-10 天津汉晴环保科技有限公司 Hyperbranch-modified PVDF (polyvinylidene fluoride) separation membrane and preparation method thereof
CN108393074A (en) * 2018-03-19 2018-08-14 哈尔滨工程大学 The preparation method of hyperbranched amine polymer-modified cotton fiber sorbing material
WO2018200857A1 (en) * 2017-04-26 2018-11-01 Cornell University Grafted porous cyclodextrin polymeric material and methods of making and using same
CN109351210A (en) * 2018-09-27 2019-02-19 南昌大学 It is a kind of for simultaneously go water removal in the nano fibrous membrane of micro heavy ion and organic pollutant preparation method
CN109569527A (en) * 2018-12-14 2019-04-05 北京化工大学 A kind of multifunctional ceiling enclosure material based on cellulose base and preparation method thereof and its application
CN109864341A (en) * 2019-04-12 2019-06-11 滁州卷烟材料厂 A kind of cigarette composite filter tip and its recovery process of recoverable

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104548949A (en) * 2013-10-11 2015-04-29 中国石油化工股份有限公司 Preparation method of polymer porous membrane for removing water pollutants
KR20170045454A (en) * 2015-10-16 2017-04-27 서울대학교산학협력단 Method of producing an ion-exchange fiber Plaited thread Micro chip filter
CN106621838A (en) * 2016-12-31 2017-05-10 天津汉晴环保科技有限公司 Hyperbranch-modified PVDF (polyvinylidene fluoride) separation membrane and preparation method thereof
WO2018200857A1 (en) * 2017-04-26 2018-11-01 Cornell University Grafted porous cyclodextrin polymeric material and methods of making and using same
CN108393074A (en) * 2018-03-19 2018-08-14 哈尔滨工程大学 The preparation method of hyperbranched amine polymer-modified cotton fiber sorbing material
CN109351210A (en) * 2018-09-27 2019-02-19 南昌大学 It is a kind of for simultaneously go water removal in the nano fibrous membrane of micro heavy ion and organic pollutant preparation method
CN109569527A (en) * 2018-12-14 2019-04-05 北京化工大学 A kind of multifunctional ceiling enclosure material based on cellulose base and preparation method thereof and its application
CN109864341A (en) * 2019-04-12 2019-06-11 滁州卷烟材料厂 A kind of cigarette composite filter tip and its recovery process of recoverable

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALAAEDDIN ALSBAIEE: "Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer", 《NATURE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110818504A (en) * 2019-11-15 2020-02-21 福建师范大学福清分校 Organic fertilizer capable of reducing heavy metal pollution of soil and preparation and application thereof
CN113882152A (en) * 2021-12-09 2022-01-04 天津市职业大学 Preparation method of antibacterial easily-regenerated fiber material for treating oily sewage

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