Advanced treatment agent and treatment method for textile printing and dyeing wastewater

Abstract

The invention discloses an advanced treatment agent for textile printing and dyeing wastewater and a treatment method. The advanced treatment agent comprises a component A and a component B, the component A comprises modified graphene oxide and an enzyme treatment agent; the component B comprises magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methyl cellulose and chitosan, and the hydroxyapatite is coated with the magnesium aluminum silicate to form a core-shell structure. By adopting a modified graphene oxide immobilized enzyme structure, harmful components in water can be effectively adsorbed, so that the effect of greatly improving sewage purification is achieved, and meanwhile, the adsorption effect of the harmful components can be further improved by matching with aluminum-magnesium silicate coated hydroxyapatite, hydroxypropyl methyl cellulose and chitosan; meanwhile, bonding with the modified graphene oxide is beneficial to agglomeration and flocculation of substances, so that the flocculation capacity is improved, and floc separation is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of sewage treatment, and in particular to an advanced treatment agent and a treatment method for textile printing and dyeing wastewater. Background Art

[0002] The printing and dyeing of textile fabrics will generate a lot of sewage, causing very serious environmental pollution, which is the pain point and difficulty of environmental protection work. The reason is that the printing and dyeing sewage generated is large in volume, the water quality changes greatly, the acidity and alkalinity are strong, the content of organic pollutants is high, biodegradation is difficult, and the water color is high. Even after the treated sewage is discharged, it will still cause eutrophication of the water in the river, thereby leading to the crazy growth of plants such as water hyacinth and blue algae, affecting the entire ecosystem.

[0003] The relatively excellent purification methods currently available include chemical oxidation, electrochemical method and biodegradation method, which have high purification degree, but low efficiency, high cost and are difficult to apply industrially. Therefore, the commonly used industrial measure is still the traditional flocculation method.

[0004] The positively (negatively) charged groups in the flocculant and some negatively (positively) charged particles or granules in the water that are difficult to separate are brought close to each other, reducing their electric potential and making them unstable. The aggregation of these particles is achieved by using their polymerization properties and then separated by physical or chemical methods. There are many types of flocculants, from low molecular weight to high molecular weight, from single type to composite type. The general trend is to develop in the direction of cheap, practical, non-toxic and efficient. Inorganic flocculants are cheap, but they will have adverse effects on human health and the ecological environment. Although organic polymer flocculants are used in small amounts, have low scum production, strong flocculation ability, easy floc separation, and good oil removal and suspended solids removal effects, the residual monomers of this type of polymer have "three-cause" effects (causing cancer, causing cancer, and causing mutations), and their application range is limited.

[0005] In view of this, this application is hereby filed. Summary of the invention

[0006] The technical problem to be solved by the present invention is that the existing flocculants have poor removal effect and are easy to introduce other pollution. The purpose is to provide a deep treatment agent and treatment method for textile printing and dyeing wastewater. By adopting modified graphene oxide to fix the enzyme structure, harmful components in the water can be effectively adsorbed, thereby greatly improving the effect of sewage purification. At the same time, magnesium aluminum silicate is used to coat hydroxyapatite, hydroxypropyl methylcellulose and chitosan, which can further improve the adsorption effect of harmful components. At the same time, it can be bonded with modified graphene oxide to facilitate the agglomeration and flocculation of substances, thereby improving the flocculation ability and facilitating floc separation.

[0007] The present invention is achieved through the following technical solutions:

[0008] In a first aspect, the present invention provides a deep treatment agent for textile printing and dyeing wastewater, comprising component A and component B;

[0009] The component A comprises modified graphene oxide and an enzyme treatment agent;

[0010] The B component comprises magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methylcellulose and chitosan, and the magnesium aluminum silicate is coated on the outside of the hydroxyapatite to form a core-shell structure.

[0011] The printing and dyeing wastewater treatment agent of the present invention firstly adopts graphene oxide as one of the main adsorption components. The graphene oxide is an ultra-thin two-dimensional nanosheet with the atomic thickness modified with various hydroxyl groups, carboxyl groups, epoxy groups and carbonyl groups on the surface and edge of the graphene. The graphene oxide has a large specific surface area, and the oxygen-containing functional groups on the surface are negatively charged and can adsorb harmful components in water, thereby significantly improving the overall adsorption performance of the flocculant. The enzyme treatment agent is fixed on the graphene oxide by physical or chemical bonding, which can improve the stability and full utilization rate of the enzyme. The addition of the enzyme treatment agent can decompose macromolecules such as proteins in sewage into small molecules, and the decomposed small molecules can be quickly locked and adsorbed by the bonded graphene oxide. At the same time, the graphene oxide has good hydrophilicity and can be fully dispersed and spread in the sewage, thereby carrying the enzyme treatment agent to contact with more protein substances, thereby improving the decomposition and adsorption effect.

[0012] Secondly, the present invention adopts magnesium aluminum silicate coated hydroxyapatite as one of the other main adsorption components. As a typical biological material, hydroxyapatite has the advantages of good fluidity, large specific surface area, small particle size, high activity, good hydrophilicity, etc. Therefore, it can adsorb a large amount of organic dye ion pollutants in sewage, but it has a big problem that the flocculation effect is poor. Although flocculation precipitation can be produced, the mutual dispersion and agglomeration effect between the flocculation precipitation are poor, and it is difficult to separate. Therefore, the present application coats the magnesium aluminum silicate layer on the outside of the hydroxyapatite. After contacting water, magnesium aluminum silicate can form a gel layer with a certain thickness, and its interior has a large specific surface area and porous structure. Therefore, the gel layer can not only adsorb harmful components, but also produce a "binding" effect on the adsorbed harmful components and hydroxyapatite, on the one hand, improving the adsorption effect, on the other hand, improving the flocculation effect of hydroxyapatite, and at the same time, the magnesium aluminum silicate coated hydroxyapatite particles and the particles, the generated gel layer fuses with each other, can aggregate the dispersed and suspended floccules as a whole for sedimentation, and further strengthen the flocculation effect, which is convenient for the subsequent separation of floccules. In addition, during the gradual gelation process, the gel layer of magnesium aluminum silicate coated hydroxyapatite can enclose the flocculants formed by the adsorbed modified graphene oxide and enzymes through its porous three-dimensional network structure, and realize the coupled flocculation of component A and component B through the covalent bonding of the active groups on the surfaces of hydroxyapatite and graphene oxide, so that all flocculation products can be fully aggregated and settled in the water, thereby ensuring the removal of flocculants and flocculants and avoiding the introduction of new pollutants.

[0013] Finally, hydroxypropyl methylcellulose and chitosan are added to the B component of the flocculant of the present invention. The hydroxypropyl methylcellulose can also form a gel-like substance in water, and plays the role of an intermediate "adhesive" in the gel layer between the magnesium aluminum silicate-coated hydroxyapatite particles and the particles, thereby improving the overall flocculation and sedimentation ability of the B component. Chitosan has excellent heavy metal adsorption capacity, and its surface has abundant primary amine groups. After the B component is added to the sewage, it can quickly form a film with the hydroxypropyl methylcellulose and adsorb a large amount of anions. At the same time, its surface is also rich in a large number of hydrogen bonds, which can bond with the active groups of graphene oxide, thereby improving the overall flocculation and sedimentation effect, and can ensure the overall separation and treatment of the flocculant, i.e., the flocculation product, to avoid the introduction of new pollutants.

[0014] In a specific embodiment, the modified graphene oxide is sequentially subjected to amination with 4,4'-diaminodiphenyl ether and aldehyde modification with glutaraldehyde.

[0015] In a specific embodiment, the steps of amination treatment of the modified graphene oxide are as follows:

[0016] Take nano graphene oxide powder and add it into an appropriate amount of N-methylpyrrolidone (NMP) to fully dissolve;

[0017] Then, an appropriate amount of 4,4'-diaminodiphenyl ether (ODA) is added, and the mixture is stirred and dispersed under a nitrogen atmosphere. The mixture is filtered, washed, and dried to obtain amino-modified graphene oxide.

[0018] In a specific embodiment, the steps of the formaldehyde treatment of the modified graphene oxide are as follows:

[0019] Ultrasonic dispersion of the amino-modified graphene oxide in a phosphate buffer solution forms a dispersion system;

[0020] Nitrogen was introduced, and glutaraldehyde was added, the mass percentage of glutaraldehyde in the dispersed system was 0.5%, and the mixture was stirred at 30° C., and then filtered, washed, and dried to obtain modified graphene oxide.

[0021] In a specific embodiment, the preparation method of component A is as follows:

[0022] (1) redispersing the modified graphene oxide in a phosphate buffer solution, wherein the concentration of the graphene oxide in the phosphate buffer solution is 0.9 mg / mL, to obtain a modified graphene oxide dispersion solution;

[0023] (2) preparing an enzyme treatment agent into an aqueous solution, adding the solution to the modified graphene oxide dispersion, stirring at 4° C. to immobilize the enzyme on the surface of the modified graphene oxide, washing the protease immobilized on the surface of the modified graphene oxide with a phosphate buffer, and freeze-drying to obtain a component A enzyme-graphene oxide complex;

[0024] The concentration of the enzyme in the modified graphene oxide dispersion is 2.0 mg / mL, and the enzyme may be protease, amylase, or the like.

[0025] The modified graphite oxide of the present invention is respectively aminated with 4,4'-diaminodiphenyl ether, and is modified by aldehyde group with glutaraldehyde, wherein the graphene oxide after amination can improve the surface charge of its nano material, so that it can be fully dispersed, improve its ability of suspension flocculation in water, and is not easy to settle, and can also physically fix the enzyme protein in combination with the adsorption capacity of graphene oxide and the amination group; and after the aldehyde group modification, the graphene oxide surface can be covalently bound to the enzyme protein to realize the chemical fixation of the enzyme protein, improve the stability of the connection between the enzyme preparation and the graphene oxide, so that the graphene oxide and the enzyme preparation are fixed in an integrated structure, greatly improving the treatment effect of waste water. In addition, the graphene oxide after amination and aldehyde group modification can further improve the combination with the B component hydroxyapatite and the chitosan active group, thereby ensuring the subsequent flocculation and sedimentation effect.

[0026] In a specific embodiment, the preparation method of magnesium aluminum silicate coated hydroxyapatite is as follows:

[0027] (1) 250 mL, 0.025 mol / L calcium nitrate and 30 mL, 0.3 mol / L ammonium bicarbonate were mixed evenly by mechanical stirring, 150 mL, 0.20 mol / L ammonium hydrogen phosphate were slowly added, the pH of the system was maintained at 10 with ammonia water, the reaction was maintained at 45° C. in a water bath for 40 min, and the system after the reaction was aged for 24 h to obtain an aged system;

[0028] (2) 10 parts by weight of methyl orthosilicate, 0.5 parts by weight of 4 mol / L hydrochloric acid, and 30 parts by weight of water were mixed and stirred for 15 minutes to form a gel, 25 parts by weight of a solution containing 3 parts by weight of aluminum chloride and 1 part by weight of magnesium chloride were added dropwise, the mixture was stirred and mixed for 15 minutes, and 10 parts by weight of 25 wt% ammonia water were added dropwise to prepare a magnesium aluminum silicate sol;

[0029] (3) The aging system was added to the magnesium aluminum silicate sol, stirred and mixed for 15 minutes, aged for 2 hours, washed with clean water, calcined at 500° C. for 1 hour, and ball milled for 2 hours to obtain magnesium aluminum silicate-coated hydroxyapatite.

[0030] In a specific embodiment, component B also includes magnetic ferrosoferric oxide, which is added during the preparation of the aging system.

[0031] The present invention adds magnetic ferrosoferric oxide in the process of preparing hydroxyapatite, and after the flocculant of the present invention completes sewage treatment, the flocculation and sedimentation products can be conveniently collected and separated.

[0032] In a specific embodiment, the content ratio of magnesium aluminum silicate coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan is 30-35:5-10:3-5.

[0033] In a specific embodiment, the added mass ratio of the aging system to the magnesium aluminum silicate sol is 1:2 to 2.5.

[0034] In a second aspect, the present invention provides a method for treating textile printing and dyeing wastewater, comprising the following steps:

[0035] (1) Add component A to the wastewater to be treated and continue stirring for 15 to 20 minutes;

[0036] (2) Add component B to the wastewater in 2 to 3 times in sequence, stirring continuously, with an interval of 5 to 10 minutes between each addition. After component B is added, let it stand for 60 to 80 minutes;

[0037] (3) Using magnetic adsorption to remove flocculent substances;

[0038] The mass ratio of component A to component B is 1:1.2-1.5.

[0039] The flocculation treatment agent of the present invention is used to sequentially add component A and component B to the sewage to be treated. First, after the graphene oxide immobilized enzyme mixture of component A is added to the sewage, it can be quickly dispersed and spread to achieve the decomposition and adsorption of harmful components. Secondly, after the treatment of component A is stable, component B is added in small amounts for multiple times. The component B added in small amounts at the beginning will first adsorb harmful components of the wastewater to form flocculation of the component B itself. As the amount of component B gradually increases, hydroxyapatite and chitosan in component B gradually combine with graphene oxide, and at the same time, the gel penetration effect of magnesium aluminum silicate and hydroxypropyl methylcellulose gradually increases. Finally, the suspended flocculation products of components A and B gradually agglomerate and accelerate sedimentation, so that the adsorbed flocculation products and the flocculant are synchronously sedimented and removed, thereby avoiding the introduction of new pollution into the wastewater.

[0040] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0041] 1. A deep treatment agent and treatment method for textile printing and dyeing wastewater provided in an embodiment of the present invention adopts graphene oxide as one of the main adsorption components, and the surface and edge are modified with various hydroxyl groups, carboxyl groups, epoxy groups and carbonyl groups, which significantly improves the overall adsorption performance of the flocculant;

[0042] 2. An embodiment of the present invention provides a deep treatment agent and treatment method for textile printing and dyeing wastewater. The enzyme treatment agent is fixed on graphene oxide by physical or chemical bonding, which can improve the stability and full utilization rate of the enzyme. The addition of the enzyme treatment agent can decompose macromolecules such as proteins in sewage into small molecules. The decomposed small molecules can be quickly locked and adsorbed by the bonded graphene oxide. At the same time, graphene oxide has good hydrophilicity and can be fully dispersed and spread in sewage, thereby carrying the enzyme treatment agent to contact more protein substances, thereby improving the decomposition and adsorption effect;

[0043] 3. A deep treatment agent and treatment method for textile printing and dyeing wastewater provided in an embodiment of the present invention adopts magnesium aluminum silicate coated hydroxyapatite as another main adsorption component. Hydroxyapatite has the advantages of good fluidity, large specific surface area, small particle size, high activity, good hydrophilicity, etc., so it can adsorb a large amount of organic dye plasma pollutants in sewage;

[0044] 4. A deep treatment agent and treatment method for textile printing and dyeing wastewater provided in an embodiment of the present invention, wherein a magnesium aluminum silicate layer is coated on the outside of hydroxyapatite, and the magnesium aluminum silicate can form a gel layer with a certain thickness after contacting water, and the inside of the gel layer has a large specific surface area and a porous structure. Therefore, the gel layer can not only adsorb harmful components, but also produce a "binding" effect on the adsorbed harmful components and hydroxyapatite, on the one hand, improving the adsorption effect, and on the other hand, improving the flocculation effect of hydroxyapatite. At the same time, the magnesium aluminum silicate coated hydroxyapatite particles and the particles, the generated gel layer fuses with each other, and the dispersed and suspended floccules are aggregated and settled as a whole, thereby further strengthening the flocculation effect and facilitating the subsequent separation of floccules;

[0045] 5. An embodiment of the present invention provides a deep treatment agent and treatment method for textile printing and dyeing wastewater. During the gradual gelation process, the porous three-dimensional network structure of the gel layer of magnesium aluminum silicate coated hydroxyapatite can enclose the floccules formed by the modified graphene oxide and the enzyme that have been adsorbed, and the coupled flocculation of component A and component B is achieved through the covalent bonding of the active groups on the surfaces of hydroxyapatite and graphene oxide, so that all flocculation products are fully aggregated and precipitated in the water, thereby ensuring the removal of floccules and flocculants and avoiding the introduction of new pollutants.

[0046] 6. A deep treatment agent and treatment method for textile printing and dyeing wastewater provided in an embodiment of the present invention also add hydroxypropyl methylcellulose and chitosan. Hydroxypropyl methylcellulose can also form a gel-like substance in water, which plays the role of an intermediate "adhesive" in the gel layer between the magnesium aluminum silicate-coated hydroxyapatite particles and the particles, thereby improving the overall flocculation and sedimentation ability of component B; chitosan has excellent heavy metal adsorption capacity, and its surface has abundant primary amine groups. After component B is added to the sewage, it can quickly form a film with hydroxypropyl methylcellulose and adsorb a large amount of anions. At the same time, its surface is also rich in a large number of hydrogen bonds, which can bond with the active groups of graphene oxide, thereby improving the overall flocculation and sedimentation effect, and can ensure the overall separation and treatment of the flocculant, i.e., the flocculation product. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The illustrative embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0048] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present invention. However, it is apparent to one of ordinary skill in the art that these specific details need not be employed to practice the present invention. In other embodiments, in order to avoid confusing the present invention, well-known structures are not specifically described.

[0049] Throughout the specification, references to "one embodiment," "an embodiment," "an example," or "an example" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment or example is included in at least one embodiment of the present invention. Therefore, the phrases "one embodiment," "an embodiment," "an example," or "an example" appearing in various places throughout the specification do not necessarily all refer to the same embodiment or example. Furthermore, particular features, structures, or characteristics may be combined in one or more embodiments or examples in any appropriate combinations and / or subcombinations.

[0050] In a first aspect, the present invention provides a deep treatment agent for textile printing and dyeing wastewater, comprising component A and component B;

[0051] The component A comprises modified graphene oxide and an enzyme treatment agent;

[0052] The B component comprises magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methylcellulose and chitosan, and the magnesium aluminum silicate is coated on the outside of the hydroxyapatite to form a core-shell structure.

[0053] The printing and dyeing wastewater treatment agent of the present invention firstly adopts graphene oxide as one of the main adsorption components. The graphene oxide is an ultra-thin two-dimensional nanosheet with the atomic thickness modified with various hydroxyl groups, carboxyl groups, epoxy groups and carbonyl groups on the surface and edge of the graphene. The graphene oxide has a large specific surface area, and the oxygen-containing functional groups on the surface are negatively charged and can adsorb harmful components in water, thereby significantly improving the overall adsorption performance of the flocculant. The enzyme treatment agent is fixed on the graphene oxide by physical or chemical bonding, which can improve the stability and full utilization rate of the enzyme. The addition of the enzyme treatment agent can decompose macromolecules such as proteins in sewage into small molecules, and the decomposed small molecules can be quickly locked and adsorbed by the bonded graphene oxide. At the same time, the graphene oxide has good hydrophilicity and can be fully dispersed and spread in the sewage, thereby carrying the enzyme treatment agent to contact with more protein substances, thereby improving the decomposition and adsorption effect.

[0054] Secondly, the present invention adopts magnesium aluminum silicate coated hydroxyapatite as one of the other main adsorption components. As a typical biological material, hydroxyapatite has the advantages of good fluidity, large specific surface area, small particle size, high activity, good hydrophilicity, etc. Therefore, it can adsorb a large amount of organic dye ion pollutants in sewage, but it has a big problem that the flocculation effect is poor. Although flocculation precipitation can be produced, the mutual dispersion and agglomeration effect between the flocculation precipitation are poor, and it is difficult to separate. Therefore, the present application coats the magnesium aluminum silicate layer on the outside of the hydroxyapatite. After contacting water, magnesium aluminum silicate can form a gel layer with a certain thickness, and its interior has a large specific surface area and porous structure. Therefore, the gel layer can not only adsorb harmful components, but also produce a "binding" effect on the adsorbed harmful components and hydroxyapatite, on the one hand, improving the adsorption effect, on the other hand, improving the flocculation effect of hydroxyapatite, and at the same time, the magnesium aluminum silicate coated hydroxyapatite particles and the particles, the generated gel layer fuses with each other, can aggregate the dispersed and suspended floccules as a whole for sedimentation, and further strengthen the flocculation effect, which is convenient for the subsequent separation of floccules. In addition, during the gradual gelation process, the gel layer of magnesium aluminum silicate coated hydroxyapatite can enclose the flocculants formed by the adsorbed modified graphene oxide and enzymes through its porous three-dimensional network structure, and realize the coupled flocculation of component A and component B through the covalent bonding of the active groups on the surfaces of hydroxyapatite and graphene oxide, so that all flocculation products can be fully aggregated and settled in the water, thereby ensuring the removal of flocculants and flocculants and avoiding the introduction of new pollutants.

[0055] Finally, hydroxypropyl methylcellulose and chitosan are added to the B component of the flocculant of the present invention. The hydroxypropyl methylcellulose can also form a gel-like substance in water, and plays the role of an intermediate "adhesive" in the gel layer between the magnesium aluminum silicate-coated hydroxyapatite particles and the particles, thereby improving the overall flocculation and sedimentation ability of the B component. Chitosan has excellent heavy metal adsorption capacity, and its surface has abundant primary amine groups. After the B component is added to the sewage, it can quickly form a film with the hydroxypropyl methylcellulose and adsorb a large amount of anions. At the same time, its surface is also rich in a large number of hydrogen bonds, which can bond with the active groups of graphene oxide, thereby improving the overall flocculation and sedimentation effect, and can ensure the overall separation and treatment of the flocculant, i.e., the flocculation product, to avoid the introduction of new pollutants.

[0056] In a specific embodiment, the modified graphene oxide is sequentially subjected to amination with 4,4'-diaminodiphenyl ether and aldehyde modification with glutaraldehyde.

[0057] In a specific embodiment, the steps of amination treatment of the modified graphene oxide are as follows:

[0058] Take nano graphene oxide powder and add it into an appropriate amount of N-methylpyrrolidone (NMP) to fully dissolve;

[0059] Then, an appropriate amount of 4,4'-diaminodiphenyl ether (ODA) is added, and the mixture is stirred and dispersed under a nitrogen atmosphere. The mixture is filtered, washed, and dried to obtain amino-modified graphene oxide.

[0060] In a specific embodiment, the steps of the formaldehyde treatment of the modified graphene oxide are as follows:

[0061] Ultrasonic dispersion of the amino-modified graphene oxide in a phosphate buffer solution forms a dispersion system;

[0062] Nitrogen was introduced, and glutaraldehyde was added, the mass percentage of glutaraldehyde in the dispersed system was 0.5%, and the mixture was stirred at 30° C., and then filtered, washed, and dried to obtain modified graphene oxide.

[0063] In a specific embodiment, the preparation method of component A is as follows:

[0064] (1) redispersing the modified graphene oxide in a phosphate buffer solution, wherein the concentration of the graphene oxide in the phosphate buffer solution is 0.9 mg / mL, to obtain a modified graphene oxide dispersion solution;

[0065] (2) preparing an enzyme treatment agent into an aqueous solution, adding the solution to the modified graphene oxide dispersion, stirring at 4° C. to immobilize the enzyme on the surface of the modified graphene oxide, washing the protease immobilized on the surface of the modified graphene oxide with a phosphate buffer, and freeze-drying to obtain a component A enzyme-graphene oxide complex;

[0066] The concentration of the enzyme in the modified graphene oxide dispersion is 2.0 mg / mL, and the enzyme may be protease, amylase, or the like.

[0067] The modified graphite oxide of the present invention is respectively aminated with 4,4'-diaminodiphenyl ether, and is modified by aldehyde group with glutaraldehyde, wherein the graphene oxide after amination can improve the surface charge of its nano material, so that it can be fully dispersed, improve its ability of suspension flocculation in water, and is not easy to settle, and can also physically fix the enzyme protein in combination with the adsorption capacity of graphene oxide and the amination group; and after the aldehyde group modification, the graphene oxide surface can be covalently bound to the enzyme protein to realize the chemical fixation of the enzyme protein, improve the stability of the connection between the enzyme preparation and the graphene oxide, so that the graphene oxide and the enzyme preparation are fixed in an integrated structure, greatly improving the treatment effect of waste water. In addition, the graphene oxide after amination and aldehyde group modification can further improve the combination with the B component hydroxyapatite and the chitosan active group, thereby ensuring the subsequent flocculation and sedimentation effect.

[0068] In a specific embodiment, the preparation method of magnesium aluminum silicate coated hydroxyapatite is as follows:

[0069] (1) 250 mL, 0.025 mol / L calcium nitrate and 30 mL, 0.3 mol / L ammonium bicarbonate were mixed evenly by mechanical stirring, 0.10-0.20 g of magnetic ferroferric oxide was added, and the magnetic ferroferric oxide was evenly dispersed by ultrasonication for 5 min, and 150 mL, 0.20 mol / L ammonium hydrogen phosphate was slowly added, and the pH of the system was maintained at 10 with ammonia water, and the reaction was maintained at 45° C. in a water bath for 40 min. The system after the reaction was aged for 24 h to obtain an aged system;

[0070] (2) 10 parts by weight of methyl orthosilicate, 0.5 parts by weight of 4 mol / L hydrochloric acid, and 30 parts by weight of water were mixed and stirred for 15 minutes to form a gel, 25 parts by weight of a solution containing 3 parts by weight of aluminum chloride and 1 part by weight of magnesium chloride were added dropwise, the mixture was stirred and mixed for 15 minutes, and 10 parts by weight of 25 wt% ammonia water were added dropwise to prepare a magnesium aluminum silicate sol;

[0071] (3) The aging system was added to the magnesium aluminum silicate sol, stirred and mixed for 15 minutes, aged for 2 hours, washed with clean water, calcined at 500° C. for 1 hour, and ball milled for 2 hours to obtain magnesium aluminum silicate-coated hydroxyapatite.

[0072] In a specific embodiment, component B also includes magnetic ferrosoferric oxide, which is added during the preparation of the aging system.

[0073] The present invention adds magnetic ferrosoferric oxide in the process of preparing hydroxyapatite, and after the flocculant of the present invention completes sewage treatment, the flocculation and sedimentation products can be conveniently collected and separated.

[0074] In a specific embodiment, the content ratio of magnesium aluminum silicate coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan is 30-35:5-10:3-5.

[0075] In a specific embodiment, the added mass ratio of the aging system to the magnesium aluminum silicate sol is 1:2 to 2.5.

[0076] In a second aspect, the present invention provides a method for treating textile printing and dyeing wastewater, comprising the following steps:

[0077] (1) Add component A to the wastewater to be treated and continue stirring for 15 to 20 minutes;

[0078] (2) Add component B to the wastewater in 2 to 3 times in sequence, stirring continuously, with an interval of 5 to 10 minutes between each addition. After component B is added, let it stand for 60 to 80 minutes;

[0079] (3) Using magnetic adsorption to remove flocculent substances;

[0080] The mass ratio of component A to component B is 1:1.2-1.5.

[0081] The flocculation treatment agent of the present invention is used to sequentially add component A and component B to the sewage to be treated. First, after the graphene oxide immobilized enzyme mixture of component A is added to the sewage, it can be quickly dispersed and spread to achieve the decomposition and adsorption of harmful components. Secondly, after the treatment of component A is stable, component B is added in small amounts for multiple times. The component B added in small amounts at the beginning will first adsorb harmful components of the wastewater to form flocculation of the component B itself. As the amount of component B gradually increases, hydroxyapatite and chitosan in component B gradually combine with graphene oxide, and at the same time, the gel penetration effect of magnesium aluminum silicate and hydroxypropyl methylcellulose gradually increases. Finally, the suspended flocculation products of components A and B gradually agglomerate and accelerate sedimentation, so that the adsorbed flocculation products and the flocculant are synchronously sedimented and removed, thereby avoiding the introduction of new pollution into the wastewater.

[0082] Example 1

[0083] The embodiment of the present invention provides a deep treatment agent for textile printing and dyeing wastewater, comprising component A and component B, wherein the mass ratio of component A to component B is 1:1.2;

[0084] The component A comprises modified graphene oxide and an enzyme treatment agent;

[0085] (1) dispersing the modified graphene oxide in a phosphate buffer solution, wherein the concentration of the graphene oxide in the phosphate buffer solution is 0.9 mg / mL, to obtain a modified graphene oxide dispersion solution;

[0086] (2) preparing an enzyme treatment agent into an aqueous solution, adding the solution to the modified graphene oxide dispersion, wherein the concentration of the enzyme in the modified graphene oxide dispersion is 2.0 mg / mL, stirring at 4° C. to achieve immobilization of the enzyme on the surface of the modified graphene oxide, washing the protease immobilized on the surface of the modified graphene oxide with a phosphate buffer solution, and freeze-drying to obtain a component A enzyme-graphene oxide complex;

[0087] The B component includes magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methylcellulose and chitosan;

[0088] (1) 250 mL, 0.025 mol / L calcium nitrate and 30 mL, 0.3 mol / L ammonium bicarbonate were mixed evenly by mechanical stirring, 0.10-0.20 g of magnetic ferroferric oxide was added, and the magnetic ferroferric oxide was evenly dispersed by ultrasonication for 5 min, and 150 mL, 0.20 mol / L ammonium hydrogen phosphate was slowly added, and the pH of the system was maintained at 10 with ammonia water, and the reaction was maintained at 45° C. in a water bath for 40 min. The system after the reaction was aged for 24 h to obtain an aged system;

[0089] (2) 10 parts by weight of methyl orthosilicate, 0.5 parts by weight of 4 mol / L hydrochloric acid, and 30 parts by weight of water were mixed and stirred for 15 minutes to form a gel, 25 parts by weight of a solution containing 3 parts by weight of aluminum chloride and 1 part by weight of magnesium chloride were added dropwise, the mixture was stirred and mixed for 15 minutes, and 10 parts by weight of 25 wt% ammonia water were added dropwise to prepare a magnesium aluminum silicate sol;

[0090] (3) adding the aging system at a mass ratio of 1:2 to the magnesium aluminum silicate sol, stirring and mixing for 15 minutes, aging for 2 hours, washing with water, calcining at 500°C for 1 hour, and ball milling for 2 hours to obtain magnesium aluminum silicate-coated hydroxyapatite;

[0091] (4) Mixing magnesium aluminum silicate-coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan in a mass ratio of 30:5:3 to obtain component B.

[0092] Example 2

[0093] The embodiment of the present invention provides a deep treatment agent for textile printing and dyeing wastewater, comprising component A and component B, wherein the mass ratio of component A to component B is 1:1.5;

[0094] The component A comprises modified graphene oxide and an enzyme treatment agent;

[0095] (1) dispersing the modified graphene oxide in a phosphate buffer solution, wherein the concentration of the graphene oxide in the phosphate buffer solution is 0.9 mg / mL, to obtain a modified graphene oxide dispersion solution;

[0096] (2) preparing an enzyme treatment agent into an aqueous solution, adding the solution to the modified graphene oxide dispersion, wherein the concentration of the enzyme in the modified graphene oxide dispersion is 2.0 mg / mL, stirring at 4° C. to achieve immobilization of the enzyme on the surface of the modified graphene oxide, washing the protease immobilized on the surface of the modified graphene oxide with a phosphate buffer solution, and freeze-drying to obtain a component A enzyme-graphene oxide complex;

[0097] The B component includes magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methylcellulose and chitosan;

[0098] (1) 250 mL, 0.025 mol / L calcium nitrate and 30 mL, 0.3 mol / L ammonium bicarbonate were mixed evenly by mechanical stirring, 0.10-0.20 g of magnetic ferroferric oxide was added, and the magnetic ferroferric oxide was evenly dispersed by ultrasonication for 5 min, and 150 mL, 0.20 mol / L ammonium hydrogen phosphate was slowly added, and the pH of the system was maintained at 10 with ammonia water, and the reaction was maintained at 45° C. in a water bath for 40 min. The system after the reaction was aged for 24 h to obtain an aged system;

[0099] (2) 10 parts by weight of methyl orthosilicate, 0.5 parts by weight of 4 mol / L hydrochloric acid, and 30 parts by weight of water were mixed and stirred for 15 minutes to form a gel, 25 parts by weight of a solution containing 3 parts by weight of aluminum chloride and 1 part by weight of magnesium chloride were added dropwise, the mixture was stirred and mixed for 15 minutes, and 10 parts by weight of 25 wt% ammonia water were added dropwise to prepare a magnesium aluminum silicate sol;

[0100] (3) adding the aging system at a mass ratio of 1:2.5 to the magnesium aluminum silicate sol, stirring and mixing for 15 minutes, aging for 2 hours, washing with water, calcining at 500° C. for 1 hour, and ball milling for 2 hours to obtain magnesium aluminum silicate-coated hydroxyapatite;

[0101] (4) Mixing magnesium aluminum silicate-coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan in a mass ratio of 35:10:5 to obtain component B.

[0102] Comparative Example 1

[0103] This comparative example provides a printing and dyeing wastewater treatment agent, including component A, wherein component A includes a modified graphene oxide-immobilized enzyme treatment agent complex.

[0104] Comparative Example 2

[0105] This comparative example provides a printing and dyeing wastewater treatment agent, including component A, wherein component A includes modified graphene oxide and an enzyme treatment agent (the two are directly mixed).

[0106] Comparative Example 3

[0107] This comparative example provides a dyeing wastewater treatment agent, including a B component, wherein the B component includes magnesium aluminum silicate-coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan.

[0108] Comparative Example 4

[0109] This comparative example provides a dyeing wastewater treatment agent, which includes a B component, wherein the B component includes hydroxyapatite, hydroxypropyl methylcellulose and chitosan.

[0110] Comparative Example 5

[0111] This comparative example provides a dyeing wastewater treatment agent, including a component A and a component B, wherein the component A includes common graphene oxide, and the component B includes magnesium aluminum silicate-coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan.

[0112] Comparative Example 6

[0113] This comparative example provides a dyeing wastewater treatment agent, including a component A and a component B, wherein the component A includes a modified graphene oxide immobilized enzyme treatment agent complex, and the component B includes hydroxyapatite, hydroxypropyl methylcellulose and chitosan.

[0114] Comparative Example 7

[0115] This comparative example provides a printing and dyeing wastewater treatment agent, including a component A and a component B, wherein the component A includes a modified graphene oxide immobilized enzyme treatment agent complex, and the component B includes hydroxypropyl methylcellulose and chitosan.

[0116] The flocculation treatment agents prepared in Examples 1-2 and Comparative Examples 1-7 were tested for their treatment effects on printing and dyeing wastewater, and the data results are shown in Table 1 below.

[0117] Table 1

[0118]

[0119] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A deep treatment agent for textile printing and dyeing wastewater, characterized in that: It includes component A and component B; The component A comprises modified graphene oxide and an enzyme treatment agent; The B component comprises magnesium aluminum silicate, hydroxyapatite, hydroxypropyl methylcellulose and chitosan, and the magnesium aluminum silicate is coated on the outside of the hydroxyapatite to form a core-shell structure.

2. The deep treatment agent for textile printing and dyeing wastewater according to claim 1, characterized in that: The modified graphene oxide is prepared by sequentially using 4,4'-diaminodiphenyl ether for amination and using glutaraldehyde for formaldehyde modification.

3. The deep treatment agent for textile printing and dyeing wastewater according to claim 1, characterized in that: The amination treatment steps of the modified graphene oxide are as follows: Take nano graphene oxide powder and add it into an appropriate amount of N-methylpyrrolidone (NMP) to fully dissolve; Then, an appropriate amount of 4,4'-diaminodiphenyl ether (ODA) is added, and the mixture is stirred and dispersed under a nitrogen atmosphere. The mixture is filtered, washed, and dried to obtain amino-modified graphene oxide.

4. A deep treatment agent for textile printing and dyeing wastewater according to claim 3, characterized in that: The steps of the aldehyde treatment of the modified graphene oxide are as follows: Ultrasonic dispersion of the amino-modified graphene oxide in a phosphate buffer solution forms a dispersion system; Nitrogen was introduced, and glutaraldehyde was added, the mass percentage of glutaraldehyde in the dispersed system was 0.5%, and the mixture was stirred at 30° C., and then filtered, washed, and dried to obtain modified graphene oxide.

5. A deep treatment agent for textile printing and dyeing wastewater according to claim 4, characterized in that: The preparation method of component A is as follows: (1) redispersing the modified graphene oxide in a phosphate buffer to obtain a modified graphene oxide dispersion; (2) The enzyme treatment agent is prepared into an aqueous solution, added to the modified graphene oxide dispersion, and stirred at 4° C. to achieve the fixation of the enzyme on the surface of the modified graphene oxide. The protease fixed on the surface of the modified graphene oxide is washed with phosphate buffer, and freeze-dried to obtain a component A enzyme-graphene oxide complex.

6. The deep treatment agent for textile printing and dyeing wastewater according to claim 1, characterized in that: The preparation method of magnesium aluminum silicate coated hydroxyapatite is as follows: (1) Calcium nitrate and ammonium bicarbonate were mixed evenly by mechanical stirring, and ammonium hydrogen phosphate was slowly added. The pH value of the system was maintained at 10 with aqueous ammonia, and the reaction was maintained in a water bath for 40 minutes. The system after the reaction was aged for 24 hours to obtain an aged system; (2) Methyl orthosilicate, 4 mol / L hydrochloric acid and water were mixed and stirred for 15 min to form a gel, a solution containing aluminum chloride and magnesium chloride was added dropwise, the mixture was stirred and mixed for 15 min, and aqueous ammonia was added dropwise to obtain a magnesium aluminum silicate sol; (3) The aging system was added to the magnesium aluminum silicate sol, stirred and mixed for 15 minutes, aged for 2 hours, washed with clean water, calcined at 500° C. for 1 hour, and ball milled for 2 hours to obtain magnesium aluminum silicate-coated hydroxyapatite.

7. The deep treatment agent for textile printing and dyeing wastewater according to claim 6, characterized in that: Component B also includes magnetic ferrosoferric oxide, which is added during the preparation of the aging system.

8. The deep treatment agent for textile printing and dyeing wastewater according to claim 6, characterized in that: The component content ratio of magnesium aluminum silicate coated hydroxyapatite, hydroxypropyl methylcellulose and chitosan is 30-35:5-10:3-5.

9. The deep treatment agent for textile printing and dyeing wastewater according to claim 6, characterized in that: The added mass ratio of the aging system to the magnesium aluminum silicate sol is 1:2 to 2.

5.

10. A method for treating textile printing and dyeing wastewater, characterized in that: The steps include: (1) Adding the component A described in any one of claims 1 to 9 into the wastewater to be treated and stirring continuously for 15 to 20 minutes; (2) Add the component B described in any one of claims 1 to 9 to the wastewater in 2 to 3 times in sequence, stirring continuously, with an interval of 5 to 10 minutes between each addition. After the addition of the component B is completed, let it stand for 60 to 80 minutes; (3) Using magnetic adsorption to remove flocculent substances; The mass ratio of component A to component B is 1:1.2-1.5.

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