Organic wastewater treatment agent and preparation method thereof

Abstract

The invention discloses an organic wastewater treatment agent and a preparation method thereof, and relates to the field of organic wastewater treatment. When preparing the organic wastewater treatment agent, the present invention etches zeolite powder with sodium hydroxide and tetrapropylammonium hydroxide to obtain porous zeolite powder; then tetrabutyl titanate is loaded on porous zeolite powder by a solution gel method to obtain loaded nano titanium dioxide zeolite; the loaded nano titanium dioxide zeolite and allyltrimethoxysilane are reacted to obtain a pre-modified zeolite; then the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride and allyl chloride are copolymerized to obtain a modified zeolite; p-hydroxybenzaldehyde, benzaldehyde and pyrrole are reacted to obtain hydroxyporphyrin; the modified zeolite and hydroxyporphyrin are reacted to obtain an organic wastewater treatment agent. The organic wastewater treatment agent prepared by the present invention has excellent heavy metal complexation and photocatalytic degradation.

Description

Technical Field

[0001] The invention relates to the field of organic wastewater treatment, in particular to an organic wastewater treating agent and a preparation method thereof. Background Art

[0002] Since heavy metal ions and organic pollutants are difficult to be biodegraded, they are enriched in organisms by participating in the circulation of the food chain, thereby endangering human health. How to effectively remove organic pollutants and heavy metal ions from wastewater has far-reaching significance for promoting economic development and maintaining environmental sustainable development. In order to effectively remove organic pollutants from water, people have proposed many solutions, among which photocatalysis technology is the most green, effective and sustainable. Among them, TiO2 is widely used as a semiconductor for photocatalysis because of its high activity, light corrosion resistance, low price and easy availability, chemical stability, etc., but TiO2 only responds strongly to ultraviolet light with a wavelength below 390nm, and the catalytic efficiency is low. Therefore, the present invention prepares a kind of organic wastewater treatment agent with a wide light response range. Summary of the invention

[0003] The purpose of the present invention is to provide an organic wastewater treating agent and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] An organic wastewater treating agent is prepared by reacting modified zeolite and hydroxyporphyrin.

[0006] As an optimization, the modified zeolite is obtained by reacting the loaded nano-titanium dioxide zeolite with allyltrimethoxysilane and then copolymerizing with 1-allyl-3-methylimidazolium chloride and allyl chloride.

[0007] As an optimization, the nano-titanium dioxide loaded zeolite is obtained by etching zeolite powder with sodium hydroxide and tetrapropylammonium hydroxide and then loading tetrabutyl titanate through a solution gel method.

[0008] As an optimization, the zeolite powder model is YQNW893823, which comes from Chifeng Hengshuo Silica Processing Co., Ltd.

[0009] As an optimization, the hydroxyporphyrin is obtained by reacting p-hydroxybenzaldehyde, benzaldehyde and pyrrole.

[0010] A method for preparing an organic wastewater treatment agent comprises the following preparation steps:

[0011] (1) zeolite powder and sodium hydroxide solution with a mass fraction of 5-10% are mixed in a mass ratio of 1:(29-31), stirred at 60-70°C and 100-200 rpm for 25-35 min, cooled to room temperature in deionized water at 0-2°C and centrifuged, washed with deionized water for 3-5 times, dried at 85-95°C for 23-25 ​​h, added with 0.5-1.5 mol / L tetrapropylammonium hydroxide solution with a mass of 99-101 times of the zeolite powder, stirred at 75-85°C and 200-300 rpm for 3-5 h, centrifuged, washed with deionized water for 3-5 times, dried at 75-85°C for 23-25 ​​h, repeatedly stirred and centrifuged with 0.5-1.5 mol / L ammonium chloride solution for 2-4 times, transferred into a muffle furnace, and calcined at 500-600°C for 3-5 h to obtain porous zeolite powder;

[0012] (2) Tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:(8-10), stirred at 20-30°C and 400-500 rpm for 30-40 min, 0.9-1.1 times the mass of tetrabutyl titanate glacial acetic acid is added, stirring is continued for 35-45 min, porous zeolite powder is added in an amount of 6-7 times the mass of tetrabutyl titanate, stirring is continued for 2-3 h, pH is adjusted to 2-4 by uniform speed addition of the mixed solution within 1-2 h, stirring is continued for 55-65 min, allowed to stand for 4-6 h, dried at 100-110°C for 6-8 h, ground and sieved to 100-200 mesh, calcined at 450-550°C for 1-3 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0013] (3) The nano-titanium dioxide zeolite, polyvinyl alcohol and anhydrous ethanol were added in a mass ratio

[0014] 1: (0.1-0.3): (9-11) mix well, disperse by ultrasonic at 20-30°C for 1-2h, add 0.04-0.06 times the mass of allyltrimethoxysilane loaded with nano-titanium dioxide zeolite, heat to 70-80°C, stir at 400-500rpm for 1-3h, cool naturally to room temperature and filter, wash with anhydrous ethanol for 3-5 times, dry at 55-65°C for 7-9h to obtain pre-modified zeolite; pre-modified zeolite, 1-allyl-3-methylimidazolium chloride, allyl chloride, benzoyl peroxide and toluene are mixed in a mass ratio of 1:(1-2):(1.3-1.5):(0.1-0.2):(8-10), stirred in a nitrogen atmosphere at 80-90° C. and 200-300 rpm for 5-7 hours, rotary evaporated at 40-50° C. for 1-2 hours, washed with anhydrous ethanol for 3-5 times, and dried at 65-75° C. for 11-13 hours to obtain a modified zeolite;

[0015] (4) p-hydroxybenzaldehyde, benzaldehyde and propionic acid are mixed in a molar ratio of 1:3:(13-14), stirred at 135-145° C. and 200-300 rpm for 1-2 hours, pyrrole is added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, the reaction is continued for 1-3 hours, purified by elution with chloroform, rotary evaporated at 60-70° C. for 1-2 hours, and dried at 45-55° C. for 23-25 ​​hours to obtain hydroxyporphyrin;

[0016] (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran are mixed in proportion, stirred at 15-25° C. and 200-300 rpm for 23-25 ​​h in a nitrogen atmosphere, rotary evaporated at 40-50° C. for 1-2 h, washed with anhydrous ethanol and deionized water for 3-5 times respectively, and dried at 55-65° C. for 23-25 ​​h to obtain an organic wastewater treatment agent.

[0017] As an optimization, the mixed solution in step (2) is obtained by mixing deionized water and anhydrous ethanol in a mass ratio of 1:7, and then adding a 65% mass fraction nitric acid aqueous solution to adjust the pH to 4.

[0018] As an optimization, the reaction equation of the pre-modified zeolite in step (3) is:

[0019]

[0020] Where R is TiO2.

[0021] As an optimization, the reaction equation of the modified zeolite in step (3) is:

[0022]

[0023] Where R is TiO2.

[0024] As an optimization, the reaction equation of the hydroxyporphyrin in step (4) is:

[0025]

[0026] As an optimization, the mixing in proportion in step (5) is to mix the modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran in a mass ratio of 1:1.45:0.35:25.

[0027] As an optimization, the reaction equation of the organic wastewater treatment agent in step (5) is:

[0028]

[0029] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0030] When preparing the organic wastewater treatment agent, the present invention comprises the following steps: etching zeolite powder with sodium hydroxide and tetrapropylammonium hydroxide to obtain porous zeolite powder; then loading tetrabutyl titanate on the porous zeolite powder by a solution gel method to obtain loaded nano titanium dioxide zeolite; reacting the loaded nano titanium dioxide zeolite with allyltrimethoxysilane to obtain pre-modified zeolite; then copolymerizing the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride and allyl chloride to obtain modified zeolite; reacting p-hydroxybenzaldehyde, benzaldehyde and pyrrole to obtain hydroxyporphyrin; and reacting the modified zeolite with hydroxyporphyrin to obtain the organic wastewater treatment agent.

[0031] Firstly, zeolite powder is etched with sodium hydroxide and tetrapropylammonium hydroxide to obtain porous zeolite powder; then tetrabutyl titanate is loaded on the porous zeolite powder by a solution gel method to obtain loaded nano titanium dioxide zeolite; nano titanium dioxide is loaded on the etched porous zeolite, and the specific surface area and pore structure of the zeolite itself are used to compound with the nano titanium dioxide, so as to further increase the effective adsorption active sites and pore structure, enhance the adsorption of heavy metal ions and organic pollutants, and improve the adsorption of the organic wastewater treatment agent; at the same time, the nano titanium dioxide can absorb the ultraviolet light region with a wavelength less than 380nm, and catalytically degrade organic molecules through photocatalytic hydrolysis and redox reaction. The use of zeolite to immobilize nano titanium dioxide can effectively prevent its free release or aggregation in water, enhance the stability of the nano titanium dioxide structure, and improve the photocatalytic degradability and recyclability of the organic wastewater treatment agent.

[0032] Secondly, the nano-titanium dioxide-loaded zeolite and allyl trimethoxysilane are reacted to obtain a pre-modified zeolite; the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride and allyl chloride are copolymerized to obtain a modified zeolite; p-hydroxybenzaldehyde, benzaldehyde and pyrrole are reacted to obtain hydroxyporphyrin; the modified zeolite and hydroxyporphyrin are reacted to obtain an organic wastewater treatment agent; by grafting allyl trimethoxysilane, a carbon-carbon double bond structure is introduced on the surface of the nano-titanium dioxide-loaded zeolite, and 1-allyl-3-methylimidazolium chloride is reacted with the modified zeolite to obtain an organic wastewater treatment agent. The imidazolium chloride and allyl chloride are copolymerized. The electrostatic effect of the imidazolium salt structure can adsorb and complex heavy metal ions in organic wastewater, thereby improving the heavy metal complexing property of the organic wastewater treatment agent. At the same time, the chlorine atom retained at the end of the allyl chloride is used to graft hydroxyporphyrin to form a coordination bond with the empty orbital of the metal ion, complex and fix the heavy metal ions, enhance the photocatalytic activity of porphyrin under light conditions, expand the absorption wavelength range, and further improve the heavy metal complexing property and photocatalytic degradation property of the organic wastewater treatment agent. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0036] (1) Zeolite powder and 5% sodium hydroxide solution were mixed in a mass ratio of 1:29, stirred at 60°C and 100 rpm for 35 min, cooled to room temperature in deionized water at 0°C and centrifuged, washed with deionized water for 3 times, dried at 85°C for 25 h, added with 1.5 mol / L tetrapropylammonium hydroxide solution (99 times the mass of the zeolite powder), stirred at 75°C and 200 rpm for 5 h, centrifuged, washed with deionized water for 3 times, dried at 75°C for 25 h, repeatedly stirred and centrifuged with 1.5 mol / L ammonium chloride solution for 2 times, transferred into a muffle furnace, and calcined at 500°C for 5 h to obtain porous zeolite powder;

[0037] (2) Tetrabutyl titanate and anhydrous ethanol were mixed in a mass ratio of 1:8, stirred at 20°C and 400 rpm for 40 min, 0.9 times the mass of butyl titanate of glacial acetic acid was added, stirring was continued for 45 min, porous zeolite powder was added in an amount of 6 times the mass of butyl titanate, stirring was continued for 3 h, and the mixed solution was added at a uniform speed within 1 h to adjust the pH to 2, stirring was continued for 65 min, standing for 6 h, drying at 100°C for 8 h, grinding and sieving 100 mesh, calcining at 450°C for 3 h, and naturally cooling to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0038] (3) Mix the nano-titanium dioxide-loaded zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:0.1:9, ultrasonically disperse at 20°C for 2h, add allyl trimethoxysilane (0.04 times the mass of the nano-titanium dioxide-loaded zeolite), heat to 70°C, stir at 400rpm for 3h, cool naturally to room temperature and filter, wash with anhydrous ethanol 3 times, and dry at 55°C for 9h to obtain a pre-modified zeolite; mix the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride, allyl chloride, benzoyl peroxide and toluene in a mass ratio of 1:1:1.3:0.1:8, stir at 80°C and 200rpm in a nitrogen atmosphere for 7h, rotary evaporate at 40°C for 2h, wash with anhydrous ethanol 3 times, and dry at 65°C for 13h to obtain a modified zeolite;

[0039] (4) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid were mixed in a molar ratio of 1:3:13, stirred at 135°C and 200 rpm for 2 h, pyrrole was added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, and the reaction was continued for 3 h. The mixture was purified by elution with chloroform, rotary evaporated at 60°C for 2 h, and dried at 45°C for 25 h to obtain hydroxyporphyrin;

[0040] (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 15°C and 200 rpm for 25 h in a nitrogen atmosphere, rotary evaporated at 40°C for 2 h, washed with anhydrous ethanol and deionized water for 3 times respectively, and dried at 55°C for 25 h to obtain an organic wastewater treatment agent.

[0041] Example 2

[0042] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0043] (1) Zeolite powder and 7.5% sodium hydroxide solution were mixed at a mass ratio of 1:30, stirred at 65°C and 150 rpm for 30 min, cooled to room temperature in deionized water at 1°C and centrifuged, washed with deionized water for 4 times, dried at 90°C for 24 h, added with 1 mol / L tetrapropylammonium hydroxide solution (100 times the mass of the zeolite powder), stirred at 80°C and 250 rpm for 4 h, centrifuged, washed with deionized water for 4 times, dried at 80°C for 24 h, repeatedly stirred and centrifuged with 1 mol / L ammonium chloride solution for 3 times, transferred into a muffle furnace, and calcined at 550°C for 4 h to obtain porous zeolite powder;

[0044] (2) Tetrabutyl titanate and anhydrous ethanol were mixed in a mass ratio of 1:9, stirred at 25°C and 450 rpm for 35 min, glacial acetic acid was added in an amount of 1 times the mass of butyl titanate, stirring was continued for 40 min, porous zeolite powder was added in an amount of 6.5 times the mass of butyl titanate, stirring was continued for 2.5 h, and the mixed solution was added at a uniform speed within 1.5 h to adjust the pH to 3, stirring was continued for 60 min, standing for 5 h, dried at 105°C for 7 h, ground and sieved to 150 mesh, calcined at 500°C for 2 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0045] (3) Mix the nano-titanium dioxide zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:0.2:10, ultrasonically disperse at 25°C for 1.5 hours, add allyl trimethoxysilane (0.05 times the mass of the nano-titanium dioxide zeolite), heat to 75°C, stir at 450rpm for 2 hours, cool naturally to room temperature and filter, wash with anhydrous ethanol 4 times, and dry at 60°C for 8 hours to obtain a pre-modified zeolite; mix the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride, allyl chloride, benzoyl peroxide and toluene in a mass ratio of 1:1.5:1.4:0.15:9, stir at 85°C and 250rpm for 6 hours in a nitrogen atmosphere, rotary evaporate at 45°C for 1.5 hours, wash with anhydrous ethanol 4 times, and dry at 70°C for 12 hours to obtain a modified zeolite;

[0046] (4) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid were mixed in a molar ratio of 1:3:13.5, stirred at 140°C and 250 rpm for 1.5 h, pyrrole was added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, the reaction was continued for 2 h, purified by elution with chloroform, rotary evaporated at 65°C for 1.5 h, and dried at 50°C for 24 h to obtain hydroxyporphyrin;

[0047] (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 20°C and 250 rpm for 24 h in a nitrogen atmosphere, rotary evaporated at 45°C for 1.5 h, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 24 h to obtain an organic wastewater treatment agent.

[0048] Example 3

[0049] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0050] (1) zeolite powder and sodium hydroxide solution with a mass fraction of 0% were mixed in a mass ratio of 1:31, stirred at 70°C and 200 rpm for 25 min, cooled to room temperature in deionized water at 2°C and centrifuged, washed with deionized water 5 times, dried at 95°C for 23 h, added with 0.5 mol / L tetrapropylammonium hydroxide solution with a mass of 101 times that of the zeolite powder, stirred at 85°C and 300 rpm for 3 h, centrifuged, washed with deionized water 5 times, dried at 85°C for 23 h, repeatedly stirred and centrifuged with 0.5 mol / L ammonium chloride solution for 4 times, transferred into a muffle furnace, and calcined at 600°C for 3 h to obtain porous zeolite powder;

[0051] (2) Tetrabutyl titanate and anhydrous ethanol were mixed in a mass ratio of 1:10, stirred at 30°C and 500 rpm for 30 min, glacial acetic acid was added in an amount 1.1 times the mass of tetrabutyl titanate, stirring was continued for 35 min, porous zeolite powder was added in an amount 7 times the mass of tetrabutyl titanate, stirring was continued for 2 h, the mixed solution was added at a uniform speed within 2 h to adjust the pH to 4, stirring was continued for 55 min, allowed to stand for 4 h, dried at 110°C for 6 h, ground and sieved through 200 mesh, calcined at 550°C for 1 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0052] (3) Mix the nano-titanium dioxide zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:0.3:11, ultrasonically disperse at 30°C for 1 hour, add 0.06 times the mass of the nano-titanium dioxide zeolite, heat to 80°C, stir at 500rpm for 1 hour, cool naturally to room temperature and filter, wash with anhydrous ethanol 5 times, and dry at 65°C for 7 hours to obtain a pre-modified zeolite; mix the pre-modified zeolite, 1-allyl-3-methylimidazolium chloride, allyl chloride, benzoyl peroxide and toluene in a mass ratio of 1:2:1.5:0.2:10, stir at 90°C and 300rpm for 5 hours in a nitrogen atmosphere, rotary evaporate at 50°C for 1 hour, wash with anhydrous ethanol 5 times, and dry at 75°C for 11 hours to obtain a modified zeolite;

[0053] (4) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid were mixed in a molar ratio of 1:3:13, stirred at 145°C and 300 rpm for 1 hour, pyrrole was added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, and the reaction was continued for 1 hour, eluted and purified with chloroform, rotary evaporated at 70°C for 1 hour, and dried at 55°C for 23 hours to obtain hydroxyporphyrin;

[0054] (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 25°C and 300 rpm for 23 h in a nitrogen atmosphere, rotary evaporated at 50°C for 1 h, washed with anhydrous ethanol and deionized water for 5 times respectively, and dried at 65°C for 23 h to obtain an organic wastewater treatment agent.

[0055] Comparative Example 1

[0056] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0057] (1) Zeolite powder and 7.5% sodium hydroxide solution were mixed at a mass ratio of 1:30, stirred at 65°C and 150 rpm for 30 min, cooled to room temperature in deionized water at 1°C and centrifuged, washed with deionized water for 4 times, dried at 90°C for 24 h, added with 1 mol / L tetrapropylammonium hydroxide solution (100 times the mass of the zeolite powder), stirred at 80°C and 250 rpm for 4 h, centrifuged, washed with deionized water for 4 times, dried at 80°C for 24 h, repeatedly stirred and centrifuged with 1 mol / L ammonium chloride solution for 3 times, transferred into a muffle furnace, and calcined at 550°C for 4 h to obtain porous zeolite powder;

[0058] (2) The porous zeolite powder, polyvinyl alcohol and anhydrous ethanol were mixed in a mass ratio of 1:0.2:10, ultrasonically dispersed at 25°C for 1.5 hours, allyl trimethoxysilane (0.05 times the mass of the supported nano-titanium dioxide zeolite) was added, the temperature was raised to 75°C, stirred at 450 rpm for 2 hours, naturally cooled to room temperature and filtered, washed with anhydrous ethanol for 4 times, and dried at 60°C for 8 hours to obtain a modified zeolite;

[0059] (3) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid were mixed in a molar ratio of 1:3:13.5, stirred at 140°C and 250 rpm for 1.5 h, pyrrole was added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, the reaction was continued for 2 h, purified by elution with chloroform, rotary evaporated at 65°C for 1.5 h, and dried at 50°C for 24 h to obtain hydroxyporphyrin;

[0060] (4) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 20°C and 250 rpm for 24 h in a nitrogen atmosphere, rotary evaporated at 45°C for 1.5 h, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 24 h to obtain an organic wastewater treatment agent.

[0061] Comparative Example 2

[0062] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0063] (1) Zeolite powder and 7.5% sodium hydroxide solution were mixed at a mass ratio of 1:30, stirred at 65°C and 150 rpm for 30 min, cooled to room temperature in deionized water at 1°C and centrifuged, washed with deionized water for 4 times, dried at 90°C for 24 h, added with 1 mol / L tetrapropylammonium hydroxide solution (100 times the mass of the zeolite powder), stirred at 80°C and 250 rpm for 4 h, centrifuged, washed with deionized water for 4 times, dried at 80°C for 24 h, repeatedly stirred and centrifuged with 1 mol / L ammonium chloride solution for 3 times, transferred into a muffle furnace, and calcined at 550°C for 4 h to obtain porous zeolite powder;

[0064] (2) Tetrabutyl titanate and anhydrous ethanol were mixed in a mass ratio of 1:9, stirred at 25°C and 450 rpm for 35 min, glacial acetic acid was added in an amount of 1 times the mass of butyl titanate, stirring was continued for 40 min, porous zeolite powder was added in an amount of 6.5 times the mass of butyl titanate, stirring was continued for 2.5 h, and the mixed solution was added at a uniform speed within 1.5 h to adjust the pH to 3, stirring was continued for 60 min, standing for 5 h, dried at 105°C for 7 h, ground and sieved to 150 mesh, calcined at 500°C for 2 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0065] (3) Mix the nano-titanium dioxide-loaded zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:0.2:10, ultrasonically disperse at 25°C for 1.5 hours, add 0.05 times the mass of the nano-titanium dioxide-loaded zeolite of allyltrimethoxysilane, heat to 75°C, stir at 450 rpm for 2 hours, cool naturally to room temperature and filter, wash with anhydrous ethanol 4 times, and dry at 60°C for 8 hours to obtain a modified zeolite;

[0066] (4) The modified zeolite, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 20°C and 250 rpm for 24 h in a nitrogen atmosphere, rotary evaporated at 45°C for 1.5 h, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 24 h to obtain an organic wastewater treatment agent.

[0067] Comparative Example 3

[0068] A method for preparing an organic wastewater treatment agent, the method comprising the following preparation steps:

[0069] (1) Zeolite powder and 7.5% sodium hydroxide solution were mixed at a mass ratio of 1:30, stirred at 65°C and 150 rpm for 30 min, cooled to room temperature in deionized water at 1°C and centrifuged, washed with deionized water for 4 times, dried at 90°C for 24 h, added with 1 mol / L tetrapropylammonium hydroxide solution (100 times the mass of the zeolite powder), stirred at 80°C and 250 rpm for 4 h, centrifuged, washed with deionized water for 4 times, dried at 80°C for 24 h, repeatedly stirred and centrifuged with 1 mol / L ammonium chloride solution for 3 times, transferred into a muffle furnace, and calcined at 550°C for 4 h to obtain porous zeolite powder;

[0070] (2) Tetrabutyl titanate and anhydrous ethanol were mixed in a mass ratio of 1:9, stirred at 25°C and 450 rpm for 35 min, glacial acetic acid was added in an amount of 1 times the mass of butyl titanate, stirring was continued for 40 min, porous zeolite powder was added in an amount of 6.5 times the mass of butyl titanate, stirring was continued for 2.5 h, and the mixed solution was added at a uniform speed within 1.5 h to adjust the pH to 3, stirring was continued for 60 min, standing for 5 h, dried at 105°C for 7 h, ground and sieved to 150 mesh, calcined at 500°C for 2 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite;

[0071] (3) Mix the nano-titanium dioxide-loaded zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:0.2:10, ultrasonically disperse at 25°C for 1.5 hours, add 0.05 times the mass of the nano-titanium dioxide-loaded zeolite of allyltrimethoxysilane, heat to 75°C, stir at 450 rpm for 2 hours, cool naturally to room temperature and filter, wash with anhydrous ethanol 4 times, and dry at 60°C for 8 hours to obtain a modified zeolite;

[0072] (4) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid were mixed in a molar ratio of 1:3:13.5, stirred at 140°C and 250 rpm for 1.5 h, pyrrole was added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, the reaction was continued for 2 h, purified by elution with chloroform, rotary evaporated at 65°C for 1.5 h, and dried at 50°C for 24 h to obtain hydroxyporphyrin;

[0073] (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 20°C and 250 rpm for 24 h in a nitrogen atmosphere, rotary evaporated at 45°C for 1.5 h, washed with anhydrous ethanol and deionized water for 4 times respectively, and dried at 60°C for 24 h to obtain an organic wastewater treatment agent.

[0074] Test Example 1

[0075] Heavy metal ion complexation

[0076] Test method: Use zinc nitrate, copper nitrate, lead nitrate and deionized water to prepare 50 mg / L (c0) zinc, copper and lead standard solutions, respectively. Mix the organic wastewater treatment agent obtained in each embodiment and the comparative example with the zinc, lead and copper standard solutions at a mass ratio of 1:20, shake at 25 ° C and pH 5 for 24 hours and then filter. Use HPLC to determine the concentration of metal ions in the filtrate c1 (Zn1, Cu1, Pb1), and calculate the adsorption rate

[0077] =c0-c1 / c0*100%.

[0078] Table 1 below shows the analysis results of the heavy metal complexing properties of the organic wastewater treatment agents of Examples 1 to 3 of the present invention and Comparative Examples 1 to 3.

[0079] Table 1

[0080]

[0081]

[0082] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the organic wastewater treatment agent prepared by the present invention has good heavy metal complexing properties.

[0083] By comparison, the zinc, copper and lead ion adsorption rates of Examples 1, 2 and 3 are higher than those of Comparative Example 1, which indicates that the specific surface area and pore structure of zeolite itself are utilized and compounded with nano-titanium dioxide to further increase the effective adsorption active sites and pore structure, enhance the adsorption of heavy metal ions, and improve the adsorption of organic wastewater treatment agents.

[0084] By comparison, the adsorption rates of zinc, copper and lead ions of Examples 1, 2 and 3 are higher than those of Comparative Example 2, which indicates that the chlorine atom retained at the end of the allyl chloride is used to graft hydroxyporphyrin, form coordination bonds with the empty orbitals of metal ions, complex and fix heavy metal ions, and improve the heavy metal complexing property of the organic wastewater treatment agent.

[0085] By comparison, the zinc, copper and lead ion adsorption rates of Examples 1, 2 and 3 are higher than those of Comparative Example 3, indicating that a carbon-carbon double bond structure is introduced on the surface of the nano-titanium dioxide zeolite by grafting allyltrimethoxysilane, copolymerizing with 1-allyl-3-methylimidazolium chloride and allyl chloride, and the electrostatic effect of the imidazolium salt structure can adsorb and complex heavy metal ions in organic wastewater, thereby improving the heavy metal complexing property of the organic wastewater treatment agent.

[0086] Test Example 2

[0087] Photocatalytic degradation

[0088] Test method: 20 mg / L (c0) ciprofloxacin hydrochloride solution and 50 mg / L zinc solution were mixed at a mass ratio of 1:1 to obtain a liquid to be treated; the organic wastewater treatment agent obtained in each embodiment and the comparative example were mixed with the liquid to be treated at a mass ratio of 1:2, stirred in the dark for 30 minutes, and a test sample was obtained. The test sample was respectively exposed to a 300W xenon lamp with a 420nm cut-off filter and an irradiation intensity of 157.8×10 3 μW / cm 2 After treating for 5 hours under the conditions of , the mixture was filtered and the concentration c1 of ciprofloxacin hydrochloride in the filtrate was determined. The degradation rate was calculated as c0-c1 / c0*100%. Table 2 below shows the analysis results of the photocatalytic degradation of the organic wastewater treatment agents of Examples 1 to 3 of the present invention and Comparative Examples 1 to 3.

[0089] Table 2

[0090] Degradation rate % Degradation rate % Example 1 98.5 Comparative Example 1 86.9 Example 2 98.9 Comparative Example 2 32.4 Example 3 98.2 Comparative Example 3 96.6

[0091] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the organic wastewater treatment agent prepared by the present invention has good photocatalytic degradation.

[0092] By comparison, the degradation rates of Examples 1, 2, and 3 are lower than those of Comparative Example 1, which illustrates that the specific surface area and pore structure of zeolite itself are utilized to compound with nano-titanium dioxide to further increase the effective adsorption active sites and pore structure, enhance the adsorption of organic pollutants, and improve the adsorption of the organic wastewater treatment agent; at the same time, nano-titanium dioxide can absorb ultraviolet light with a wavelength of less than 380nm, and catalytically degrade organic molecules through photocatalytic hydrolysis and redox reactions. The use of zeolite to immobilize nano-titanium dioxide can effectively prevent its free release or aggregation in water, enhance the stability of the nano-titanium dioxide structure, and improve the photocatalytic degradation of the organic wastewater treatment agent.

[0093] By comparison, the degradation rates of Examples 1, 2, and 3 are lower than those of Comparative Example 2, which indicates that the chlorine atom retained at the end of the allyl chloride group is used to graft hydroxyporphyrin, form coordination bonds with the empty orbitals of metal ions, complex and fix heavy metal ions, enhance the photocatalytic activity of porphyrin under light conditions, expand the absorption wavelength range, and improve the photocatalytic degradability of the organic wastewater treatment agent.

[0094] 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 method for preparing an organic wastewater treatment agent, characterized in that: The organic wastewater treatment agent is prepared by reacting modified zeolite and hydroxyporphyrin; The modified zeolite is obtained by reacting a loaded nano-titanium dioxide zeolite with allyltrimethoxysilane, and then copolymerizing with 1-allyl-3-methylimidazolium chloride and allyl chloride; The nano-titanium dioxide loaded zeolite is obtained by etching zeolite powder with sodium hydroxide and tetrapropylammonium hydroxide and then loading tetrabutyl titanate through a solution gel method; The hydroxyporphyrin is obtained by reacting p-hydroxybenzaldehyde, benzaldehyde and pyrrole; The method comprises the following preparation steps: (1) Mix zeolite powder and sodium hydroxide solution with a mass fraction of 5-10% in a mass ratio of 1:(29-31), stir at 60-70°C and 100-200 rpm for 25-35 min, cool to room temperature in deionized water at 0-2°C and centrifuge, wash with deionized water for 3-5 times, dry at 85-95°C for 23-25 ​​h, add 0.5-1.5 mol / L tetrapropylammonium hydroxide solution (99-101 times the mass of zeolite powder), stir at 75-85°C and 200-300 rpm for 3-5 h, centrifuge, wash with deionized water for 3-5 times, dry at 75-85°C for 23-25 ​​h, repeat stirring and centrifuging with 0.5-1.5 mol / L ammonium chloride solution for 2-4 times, transfer to a muffle furnace, and calcine at 500-600°C for 3-5 h to obtain porous zeolite powder; (2) Tetrabutyl titanate and anhydrous ethanol are mixed in a mass ratio of 1:(8-10), stirred at 20-30°C and 400-500 rpm for 30-40 min, 0.9-1.1 times the mass of tetrabutyl titanate of glacial acetic acid is added, stirring is continued for 35-45 min, 6-7 times the mass of tetrabutyl titanate of porous zeolite powder is added, stirring is continued for 2-3 h, pH is adjusted to 2-4 by uniform speed addition of the mixed solution within 1-2 h, stirring is continued for 55-65 min, allowed to stand for 4-6 h, dried at 100-110°C for 6-8 h, ground and sieved to 100-200 mesh, calcined at 450-550°C for 1-3 h, and naturally cooled to room temperature to obtain nano-titanium dioxide-loaded zeolite; (3) Mix the nano-titanium dioxide zeolite, polyvinyl alcohol and anhydrous ethanol in a mass ratio of 1:(0.1-0.3):(9-11), disperse them by ultrasonic at 20-30°C for 1-2h, add 0.04-0.06 times the mass of the nano-titanium dioxide zeolite, heat to 70-80°C, stir at 400-500rpm for 1-3h, cool naturally to room temperature and filter, wash with anhydrous ethanol for 3-5 times, and dry at 55-65°C for 7-9h to obtain to pre-modified zeolite; pre-modified zeolite, 1-allyl-3-methylimidazolium chloride, allyl chloride, benzoyl peroxide and toluene are mixed in a mass ratio of 1:(1-2):(1.3-1.5):(0.1-0.2):(8-10), stirred in a nitrogen atmosphere at 80-90°C and 200-300rpm for 5-7h, rotary evaporated at 40-50°C for 1-2h, washed with anhydrous ethanol for 3-5 times, and dried at 65-75°C for 11-13h to obtain modified zeolite; (4) p-Hydroxybenzaldehyde, benzaldehyde and propionic acid are mixed in a molar ratio of 1:3:(13-14), stirred at 135-145°C and 200-300 rpm for 1-2 hours, pyrrole is added in an amount 4 times the molar amount of p-hydroxybenzaldehyde, the reaction is continued for 1-3 hours, purified by elution with chloroform, rotary evaporated at 60-70°C for 1-2 hours, and dried at 45-55°C for 23-25 ​​hours to obtain hydroxyporphyrin; (5) The modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran were mixed in proportion, stirred at 15-25°C and 200-300 rpm for 23-25 ​​h in a nitrogen atmosphere, rotary evaporated at 40-50°C for 1-2 h, washed with anhydrous ethanol and deionized water for 3-5 times respectively, and dried at 55-65°C for 23-25 ​​h to obtain an organic wastewater treatment agent.

2. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The mixed solution in step (2) is obtained by mixing deionized water and anhydrous ethanol in a mass ratio of 1:7, and then adding a 65% mass fraction nitric acid aqueous solution to adjust the pH to 4.

3. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The reaction equation of the pre-modified zeolite in step (3) is: ； Where R is TiO2.

4. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The reaction equation of the modified zeolite in step (3) is: ； Where R is TiO2.

5. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The reaction equation of the hydroxyporphyrin in step (4) is: 。 6. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The mixing in proportion in step (5) is to mix the modified zeolite, hydroxyporphyrin, potassium hydroxide and tetrahydrofuran in a mass ratio of 1:1.45:0.35:

25.

7. The method for preparing an organic wastewater treatment agent according to claim 1, characterized in that: The reaction equation of the organic wastewater treatment agent in step (5) is: 。

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