Sewage treatment agent after cracking of waste tires and preparation method of sewage treatment agent

Abstract

The invention relates to the technical field of sewage treatment, and discloses a treatment agent for sewage generated after cracking of waste tires and a preparation method of the treatment agent. The sewage treatment agent obtained after cracking of the waste tires is obtained by mixing polyferric silicate sulfate, polyaluminum chloride, thioureido sulfobetaine modified chitosan and imidazoline quaternary ammonium salt modified graphene oxide. Sulfur and amino in the thiourea group can form a stable multidentate coordination complex with heavy metal ions, so that efficient adsorption is realized; a thiourea group and sulphobetaine structure is introduced to a chitosan molecular chain, so that the adsorption sites of chitosan are increased, and the sewage treatment effect is improved; nitrogen atoms on an imidazoline ring can form hydrogen bonds in the flocculation process, so that the interaction between the sewage treatment agent and colloidal particles is enhanced, and the aggregation of the colloidal particles is promoted; by introducing imidazoline quaternary ammonium salt into graphene oxide, agglomeration of graphene oxide lamellas is reduced, and the sewage treatment effect is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage treatment, and particularly to a sewage treatment agent after pyrolysis of waste tires and a preparation method thereof. Background Art

[0002] With the rapid development of the automotive industry, the large-scale treatment of waste tires has become a global environmental protection problem. The pyrolysis technology has attracted much attention because it can realize the resource utilization of tires. However, the pyrolysis wastewater generated in its production process has complex components, containing harmful components such as organic matter, inorganic salts, heavy metals, polycyclic aromatic hydrocarbons, and oil substances, and has characteristics such as high toxicity and poor biodegradability. If directly discharged without effective treatment, it will pose a serious threat to the water ecosystem and human health. Patent CN104478097A discloses a water purification agent and a sewage treatment method for the sewage generated in the recycling of waste tires. The water purification agent for sewage treatment of this invention has high safety and does not cause secondary pollution. Using a material with adsorption capacity as the raw material, supplemented by microorganisms to treat sewage, it has a wide range of uses and can be recycled, but its treatment effect on the pyrolysis sewage of waste tires still needs to be improved. Summary of the Invention

[0003] (1) Technical Problem to be Solved Aiming at the deficiencies of the prior art, the present invention provides a sewage treatment agent after pyrolysis of waste tires and a preparation method thereof, which has a good treatment effect on the sewage after pyrolysis of waste tires.

[0004] (2) Technical Solution To achieve the above object, the present invention provides the following technical solution: A sewage treatment agent after pyrolysis of waste tires, comprising the following weight components: 4.5 - 7.5 parts by weight of polysilicon ferric sulfate, 10 - 18 parts by weight of polyaluminum chloride, 4 - 8 parts by weight of thiourea-based sulfobetaine modified chitosan, 1.2 - 1.8 parts by weight of imidazoline quaternary ammonium salt modified graphene oxide.

[0005] Preferably, the preparation method of the thiourea-based sulfobetaine modified chitosan comprises the following steps: (1) Add 3 - 3.2 g of 1,3 - propane sultone to 40 - 60 mL of acetone solvent, stir and dissolve at 30 - 35 °C, dissolve 4.4 - 4.6 g of [3 - (dimethylamino)propyl]thiourea in 60 - 80 mL of acetone solvent, and drop it into the 1,3 - propane sultone solution. After dropping, raise the temperature to the reaction temperature and react for 2.5 - 3.5 h. After the reaction is completed, carry out vacuum filtration and drying to obtain thiourea-based sulfobetaine; (2) Add 15 - 25 mL of glacial acetic acid and 80 - 100 mL of deionized water to the reactor. Add 1.3 - 1.8 g of chitosan and 1.4 - 1.6 g of thiourea - based sulfobetaine thereto, stir and mix. Dropwise add 1.8 - 2.2 mL of formaldehyde solution thereto, react at 24 - 30 °C for 10 - 14 h. After the reaction is completed, adjust the pH to 7.5 - 8 with a sodium hydroxide solution with a mass fraction of 4% - 8%. Wash the precipitate, filter it under reduced pressure, and dry it in vacuo to obtain thiourea - based sulfobetaine - modified chitosan.

[0006] Preferably, in the step (1), the reaction temperature is 38 - 44 °C.

[0007] Preferably, in the step (2), the mass fraction of the formaldehyde solution is 37% - 38%.

[0008] Preferably, the preparation method of the imidazoline quaternary ammonium salt - modified graphene oxide includes the following steps: S1. Add 3.7 - 4.3 g of lauric acid to the reactor, heat up to 160 - 170 °C, add 1.8 - 2.4 mL of water - carrying agent and 4.8 - 5.2 g of triethylenetetramine thereto, reflux and react for 2 - 3 h, then heat up to 220 - 230 °C and continue to react for 3.5 - 4 h. After the reaction is completed, distill under reduced pressure to obtain lauric acid imidazoline intermediate; S2. Add 4.6 - 5.2 g of lauric acid imidazoline intermediate to 50 - 80 mL of anhydrous ethanol solvent, stir and dissolve it. Add 1.8 - 2.2 g of benzyl chloride thereto, heat up to 50 - 65 °C and react for 7 - 10 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize and dry it in vacuo to obtain lauric acid imidazoline quaternary ammonium salt; S3. Add 1.2 - 1.8 g of graphene oxide to 180 - 200 mL of deionized water, ultrasonically disperse it for 40 - 50 min, adjust the pH to 5.5 - 6 with a potassium hydroxide solution with a mass fraction of 1.5% - 2%. Add 0.5 - 0.9 g of condensing agent and react for 1 - 1.5 h, then add 1.3 - 1.4 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen for protection, heat up to 65 - 75 °C and react for 7 - 10 h. After the reaction is completed, centrifuge, wash and dry it in vacuo to obtain imidazoline quaternary ammonium salt - modified graphene.

[0009] Preferably, the water - carrying agent in S1 is xylene.

[0010] Preferably, the condensing agent in S3 is 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide.

[0011] Preferably, the preparation method of the sewage treatment agent after pyrolysis of waste tires is as follows: Add polyferric silicate sulfate, polyaluminum chloride, thiourea-based sulfobetaine modified chitosan, and imidazoline quaternary ammonium salt modified graphene oxide into a mixer, and mix at 200 - 400 rpm for 10 - 15 min to obtain the sewage treatment agent after pyrolysis of waste tires.

[0012] (III) Beneficial technical effects In the present invention, a sewage treatment agent after pyrolysis of waste tires is obtained by mixing polyferric silicate sulfate, polyaluminum chloride, thiourea-based sulfobetaine modified chitosan, and imidazoline quaternary ammonium salt modified graphene oxide.

[0013] Sulfur and amino groups in thiourea have strong coordination abilities and can form stable multidentate coordination complexes with heavy metal ions to achieve efficient adsorption; sulfonic acid groups are strong anionic groups and can undergo electrostatic attraction with positively charged metal ions or positively charged colloidal particles in sewage to promote flocculation precipitation; many particles in sewage carry negative charges, and the positive charges carried by quaternary ammonium salt cations can neutralize these negative charges, thereby reducing the electrostatic repulsion between particles and making it easier for particles to approach and aggregate with each other to form larger flocs; by introducing thiourea groups and sulfobetaine structures onto the chitosan molecular chain, the adsorption sites of chitosan are increased and the sewage treatment effect is improved; nitrogen atoms on the imidazoline ring can form hydrogen bonds during the flocculation process, and this hydrogen bond effect helps to enhance the interaction between the sewage treatment agent and colloidal particles, enabling it to better adsorb on the surface of colloidal particles and promoting the aggregation between colloidal particles; by introducing imidazoline quaternary ammonium salt into graphene oxide, the distance between graphene oxide sheets is enlarged, the mutual attraction between sheets is weakened, the aggregation of sheets is reduced, the dispersion of graphene oxide in sewage is promoted, and the sewage treatment effect is further improved. Description of the drawings

[0014] Figure 1 is the synthesis reaction formula of thiourea-based sulfobetaine modified chitosan.

[0015] Figure 2 is the synthesis reaction formula of lauric acid imidazoline quaternary ammonium salt. Specific embodiments

[0016] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0017] To better understand the above technical solution, the above technical solution will be described in detail below in conjunction with the accompanying drawings of the specification and specific embodiments. Example 1

[0018] (1) Add 3 g of 1,3 - propane sultone to 40 mL of acetone solvent, stir and dissolve at 30 °C. Dissolve 4.4 g of [3 - (dimethylamino)propyl]thiourea in 60 mL of acetone solvent, and drop it into the 1,3 - propane sultone solution. After the dropping is completed, raise the temperature to 38 °C and react for 2.5 h. After the reaction is completed, filter under reduced pressure and dry to obtain thiourea - based sulfobetaine. (2) Add 15 mL of glacial acetic acid and 80 mL of deionized water to the reactor. Add 1.3 g of chitosan and 1.4 g of thiourea - based sulfobetaine, stir and mix. Drop 1.8 mL of formaldehyde solution with a mass fraction of 37% into it, and react at 24 °C for 10 h. After the reaction is completed, adjust the pH to 7.5 with a sodium hydroxide solution with a mass fraction of 4%. Wash the precipitate, filter under reduced pressure, and dry in vacuum to obtain thiourea - based sulfobetaine - modified chitosan. (3) Add 3.7 g of lauric acid to the reactor, raise the temperature to 160 °C, add 1.8 mL of xylene water - carrying agent and 4.8 g of triethylenetetramine, reflux and react for 2 h, then raise the temperature to 220 °C and continue to react for 3.5 h. After the reaction is completed, distill under reduced pressure to obtain lauric acid imidazoline intermediate. (4) Add 4.6 g of lauric acid imidazoline intermediate to 50 mL of anhydrous ethanol solvent, stir and dissolve. Add 1.8 g of benzyl chloride to it, raise the temperature to 50 °C and react for 7 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize and dry in vacuum to obtain lauric acid imidazoline quaternary ammonium salt. (5) Add 1.2 g of graphene oxide to 180 mL of deionized water, ultrasonically disperse for 40 min, adjust the pH to 5.5 with a potassium hydroxide solution with a mass fraction of 1.5%. Add 0.5 g of 1 - (3 - dimethylaminopropyl)-3 - ethylcarbodiimide condensing agent and react for 1 h, then add 1.3 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen protection, raise the temperature to 65 °C and react for 7 h. After the reaction is completed, centrifuge, wash and dry in vacuum to obtain imidazoline quaternary ammonium salt - modified graphene. (6) Add 4.5 parts by weight of polysilicon ferric sulfate, 10 parts by weight of polyaluminum chloride, 4 parts by weight of thiourea - based sulfobetaine - modified chitosan, and 1.2 parts by weight of imidazoline quaternary ammonium salt - modified graphene oxide to the mixer, and mix at 200 rpm for 10 min to obtain a sewage treatment agent for the treatment of waste tire pyrolysis. Example 2

[0019] (1) Add 3.2 g of 1,3 - propane sultone to 60 mL of acetone solvent, stir and dissolve at 35 °C. Dissolve 4.6 g of [3 - (dimethylamino)propyl]thiourea in 80 mL of acetone solvent, and add it dropwise to the 1,3 - propane sultone solution. After the dropwise addition, raise the temperature to 44 °C and react for 3.5 h. After the reaction is completed, perform suction filtration and drying to obtain thiourea - based sulfobetaine; (2) Add 25 mL of glacial acetic acid and 100 mL of deionized water to the reactor. Add 1.8 g of chitosan and 1.6 g of thiourea - based sulfobetaine thereto, stir and mix. Dropwise add 2.2 mL of 38% formaldehyde solution by mass fraction, and react at 30 °C for 14 h. After the reaction is completed, adjust the pH to 8 with 8% sodium hydroxide solution by mass fraction. Wash the precipitate, perform suction filtration, and dry in vacuum to obtain thiourea - based sulfobetaine - modified chitosan; (3) Add 4.3 g of lauric acid to the reactor, raise the temperature to 170 °C, add 2.4 mL of xylene water - carrying agent and 5.2 g of triethylenetetramine thereto, reflux and react for 3 h, then raise the temperature to 230 °C and continue to react for 4 h. After the reaction is completed, perform vacuum distillation to obtain lauric acid imidazoline intermediate; (4) Add 5.2 g of lauric acid imidazoline intermediate to 80 mL of anhydrous ethanol solvent, stir and dissolve. Add 2.2 g of benzyl chloride thereto, raise the temperature to 65 °C and react for 10 h. After the reaction is completed, remove the solvent by rotary evaporation, perform recrystallization and dry in vacuum to obtain lauric acid imidazoline quaternary ammonium salt; (5) Add 1.8 g of graphene oxide to 200 mL of deionized water, ultrasonically disperse for 50 min, adjust the pH to 6 with 2% potassium hydroxide solution by mass fraction. Add 0.9 g of 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide condensing agent and react for 1.5 h, then add 1.4 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen for protection, raise the temperature to 75 °C and react for 10 h. After the reaction is completed, centrifuge, wash and dry in vacuum to obtain imidazoline quaternary ammonium salt - modified graphene; (6) Add 7.5 parts by weight of polysilicon ferric sulfate, 18 parts by weight of polyaluminum chloride, 8 parts by weight of thiourea - based sulfobetaine - modified chitosan, and 1.8 parts by weight of imidazoline quaternary ammonium salt - modified graphene oxide to the mixer, and mix at 400 rpm for 15 min to obtain the sewage treatment agent for the pyrolysis of waste tires. Example 3

[0020] (1) Add 3.1 g of 1,3 - propane sultone to 50 mL of acetone solvent, stir and dissolve at 32 °C. Dissolve 4.5 g of [3 - (dimethylamino)propyl]thiourea in 70 mL of acetone solvent, and drop it into the 1,3 - propane sultone solution. After the dropping is completed, raise the temperature to 41 °C and react for 3 h. After the reaction is completed, filter under reduced pressure and dry to obtain thiourea - based sulfobetaine; (2) Add 20 mL of glacial acetic acid and 90 mL of deionized water to the reactor. Add 1.55 g of chitosan and 1.5 g of thiourea - based sulfobetaine thereto, stir and mix. Drop 2 mL of formaldehyde solution with a mass fraction of 37.5% into it, and react at 27 °C for 12 h. After the reaction is completed, adjust the pH to 7.8 with a 6% sodium hydroxide solution by mass. Wash the precipitate, filter under reduced pressure, and dry in vacuum to obtain thiourea - based sulfobetaine - modified chitosan; (3) Add 4 g of lauric acid to the reactor, raise the temperature to 165 °C, add 2.1 mL of xylene water - carrying agent and 5 g of triethylenetetramine thereto, reflux and react for 2.5 h, then raise the temperature to 225 °C and continue to react for 3.8 h. After the reaction is completed, distill under reduced pressure to obtain lauric acid imidazoline intermediate; (4) Add 4.9 g of lauric acid imidazoline intermediate to 65 mL of anhydrous ethanol solvent, stir and dissolve. Add 2 g of benzyl chloride thereto, raise the temperature to 58 °C and react for 8.5 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize and dry in vacuum to obtain lauric acid imidazoline quaternary ammonium salt; (5) Add 1.5 g of graphene oxide to 190 mL of deionized water, ultrasonically disperse for 45 min, adjust the pH to 5.7 with a 1.7% potassium hydroxide solution by mass. Add 0.7 g of 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide condensing agent and react for 1.2 h, then add 1.35 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen protection, raise the temperature to 70 °C and react for 8.5 h. After the reaction is completed, centrifuge, wash and dry in vacuum to obtain imidazoline quaternary ammonium salt - modified graphene; (6) Add 6 parts by weight of polysilicon ferric sulfate, 14 parts by weight of polyaluminum chloride, 6 parts by weight of thiourea - based sulfobetaine - modified chitosan, and 1.5 parts by weight of imidazoline quaternary ammonium salt - modified graphene oxide to the mixer, and mix at 300 rpm for 12 min to obtain the sewage treatment agent for the pyrolysis of waste tires. Example 4

[0021] (1) Add 3 g of 1,3 - propane sultone to 40 mL of acetone solvent, stir and dissolve at 30 °C. Dissolve 4.4 g of [3 - (dimethylamino)propyl]thiourea in 60 mL of acetone solvent, and add it dropwise to the 1,3 - propane sultone solution. After the addition is complete, raise the temperature to 38 °C and react for 2.5 h. After the reaction is completed, filter under reduced pressure and dry to obtain thiourea - based sulfobetaine; (2) Add 15 mL of glacial acetic acid and 80 mL of deionized water to the reactor. Add 1.3 g of chitosan and 1.4 g of thiourea - based sulfobetaine, stir and mix. Dropwise add 1.8 mL of formaldehyde solution with a mass fraction of 37%, and react at 24 °C for 10 h. After the reaction is completed, adjust the pH to 7.5 with a 4% sodium hydroxide solution, wash the precipitate, filter under reduced pressure, and dry in vacuum to obtain thiourea - based sulfobetaine - modified chitosan; (3) Add 4.3 g of lauric acid to the reactor, raise the temperature to 170 °C, add 2.4 mL of xylene water - carrying agent and 5.2 g of triethylenetetramine, reflux and react for 3 h, then raise the temperature to 230 °C and continue to react for 4 h. After the reaction is completed, distill under reduced pressure to obtain lauric acid imidazoline intermediate; (4) Add 5.2 g of lauric acid imidazoline intermediate to 80 mL of anhydrous ethanol solvent, stir and dissolve. Add 2.2 g of benzyl chloride, raise the temperature to 65 °C and react for 10 h. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize and dry in vacuum to obtain lauric acid imidazoline quaternary ammonium salt; (5) Add 1.5 g of graphene oxide to 190 mL of deionized water, ultrasonically disperse for 45 min, adjust the pH to 5.7 with a 1.7% potassium hydroxide solution, add 0.7 g of 1 - (3 - dimethylaminopropyl)-3 - ethylcarbodiimide condensing agent and react for 1.2 h, then add 1.35 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen protection, raise the temperature to 70 °C and react for 8.5 h. After the reaction is completed, centrifuge, wash and dry in vacuum to obtain imidazoline quaternary ammonium salt - modified graphene; (6) Add 6 parts by weight of polysilicon ferric sulfate, 14 parts by weight of polyaluminum chloride, 6 parts by weight of thiourea - based sulfobetaine - modified chitosan, and 1.5 parts by weight of imidazoline quaternary ammonium salt - modified graphene oxide to the mixer, and mix at 300 rpm for 12 min to obtain the sewage treatment agent for the pyrolysis of waste tires. Example 5

[0022] (1) Add 3.2 g of 1,3 - propane sultone to 60 mL of acetone solvent, stir and dissolve it at 35 °C. Dissolve 4.6 g of [3 - (dimethylamino)propyl]thiourea in 80 mL of acetone solvent, and drop it into the 1,3 - propane sultone solution. After the dropping is completed, raise the temperature to 44 °C and react for 3.5 h. After the reaction is completed, filter under reduced pressure and dry to obtain thiourea - based sulfobetaine; (2) Add 25 mL of glacial acetic acid and 100 mL of deionized water to the reactor. Add 1.8 g of chitosan and 1.6 g of thiourea - based sulfobetaine thereto, stir and mix. Drop 2.2 mL of 38% formaldehyde solution into it, and react at 30 °C for 14 h. After the reaction is completed, adjust the pH to 8 with 8% sodium hydroxide solution, wash the precipitate, filter under reduced pressure, and dry in vacuum to obtain thiourea - based sulfobetaine - modified chitosan; (3) Add 4 g of lauric acid to the reactor, raise the temperature to 165 °C, add 2.1 mL of xylene water - carrying agent and 5 g of triethylenetetramine thereto, reflux and react for 2.5 h, then raise the temperature to 225 °C and continue to react for 3.8 h. After the reaction is completed, distill under reduced pressure to obtain lauric acid imidazoline intermediate; (4) Add 4.9 g of lauric acid imidazoline intermediate to 65 mL of anhydrous ethanol solvent, stir and dissolve it. Add 2 g of benzyl chloride thereto, raise the temperature to 58 °C and react for 8.5 h. After the reaction is completed, rotary evaporate to remove the solvent, recrystallize and dry in vacuum to obtain lauric acid imidazoline quaternary ammonium salt; (5) Add 1.2 g of graphene oxide to 180 mL of deionized water, ultrasonically disperse for 40 min, adjust the pH to 5.5 with 1.5% potassium hydroxide solution. Add 0.5 g of 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide condensing agent and react for 1 h, then add 1.3 g of lauric acid imidazoline quaternary ammonium salt, introduce nitrogen protection, raise the temperature to 65 °C and react for 7 h. After the reaction is completed, centrifuge, wash and dry in vacuum to obtain imidazoline quaternary ammonium salt - modified graphene; (6) Add 4.5 parts by weight of polysilicon ferric sulfate, 10 parts by weight of polyaluminum chloride, 4 parts by weight of thiourea - based sulfobetaine - modified chitosan, and 1.2 parts by weight of imidazoline quaternary ammonium salt - modified graphene oxide to the mixer, and mix at 200 rpm for 10 min to obtain the sewage treatment agent after pyrolysis of waste tires.

[0023] Comparative Example 1 Compared with Example 1, this comparative example is different in that step (6) does not contain thiourea - based sulfobetaine - modified chitosan.

[0024] Comparative Example 2 Compared with Example 1, this comparative example is different in that step (6) does not contain imidazoline quaternary ammonium salt - modified graphene oxide.

[0025] Pour 1 L of the wastewater after pyrolysis of waste tires into a beaker, add a predetermined amount of sewage treatment agent, set the stirrer at 200 r / min, stir rapidly for 2 min, then adjust to 50 r / min and stir slowly for 15 min. After sedimentation for 40 min, take the supernatant, measure the COD and turbidity, compare the measurement results with the initial data, and calculate the COD removal rate and turbidity removal rate; the test results are shown in Table 1; use an atomic absorption spectrophotometer to measure the concentrations of Cd 2+ , Pb 2+ , Zn 2+ , compare the measurement results with the initial data, and calculate the removal rates of Cd 2+ , Pb 2+ , Zn 2 + . The removal rates are shown in Table 2. The dosage of the sewage treatment agent is 30 mg / L.

[0026] Table 1: Tests on COD removal rate and turbidity removal rate.

[0027] Item COD Removal Rate (%) Turbidity Removal Rate (%) Example 1 99.8 95.4 Example 2 99.6 93.8 Example 3 98.5 95.2 Example 4 99.7 94.5 Example 5 99.4 95.0 Comparative Example 1 90.2 87.2 Comparative Example 2 92.8 89.3 Table 2: Tests on the removal rates of Cd 2+ , Pb 2+ , Zn 2+ .

[0028] Item <![CDATA[Cd 2+ Removal rate (%)]]> <![CDATA[Pb 2+ Removal rate (%)]]> <![CDATA[Zn 2+ Removal rate (%)]]> Example 1 98.2 97.3 97.2 Example 2 97.6 96.7 96.2 Example 3 97.9 96.9 96.5 Example 4 98.0 97.0 96.8 Example 5 98.4 97.5 97.4 Comparative Example 1 94.3 93.6 90.7 Comparative Example 2 88.7 86.8 86.0 As can be seen from Table 1 and Table 2, the sewage treatment agents in Examples 1-5 of the present invention have better treatment effects on the wastewater after pyrolysis of waste tires compared with the sewage treatment agents in Comparative Examples 1-2.

[0029] It should be noted that in this article, the term "including", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or device. Without further limitations, an element defined by the phrase "including a..." does not exclude the existence of additional identical elements in the process, method, article or device including the said element.

[0030] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

[0031] Those skilled in the art should understand that the above are only several specific embodiments of the present invention, rather than all embodiments. It should be noted that many modifications and improvements can be made by those of ordinary skill in the art, and all modifications or improvements that do not exceed the scope described in the claims shall be regarded as the protection scope of the present invention.

Claims

1. A wastewater treatment agent after waste tire pyrolysis, characterized in that: The invention comprises the following components by weight: 4.5-7.5 parts by weight of polyferric silicate sulfate, 10-18 parts by weight of polyaluminium chloride, 4-8 parts by weight of thiourea sulfobetaine modified chitosan, and 1.2-1.8 parts by weight of imidazoline quaternary ammonium salt modified graphene oxide.

2. The wastewater treatment agent after the cracking of waste tires according to claim 1, characterized in that: The method for preparing thiourea sulfobetaine modified chitosan comprises the following steps: (1) Add 3-3.2 g of 1,3-propane sultone to 40-60 mL of acetone solvent, stir and dissolve at 30-35° C., dissolve 4.4-4.6 g of [3-(dimethylamino)propyl]thiourea in 60-80 mL of acetone solvent, and add it dropwise to the 1,3-propane sultone solution. After the addition is complete, heat to the reaction temperature and react for 2.5-3.5 hours. After the reaction is completed, filter under reduced pressure and dry to obtain thiourea sulfobetaine; (2) Add 15-25 mL of glacial acetic acid and 80-100 mL of deionized water into the reactor, add 1.3-1.8 g of chitosan and 1.4-1.6 g of thiourea sulfobetaine, stir and mix, add 1.8-2.2 mL of formaldehyde solution dropwise thereto, react at 24-30° C. for 10-14 h, after the reaction is completed, adjust the pH to 7.5-8 with a sodium hydroxide solution with a mass fraction of 4%-8%, wash the precipitate, filter it under reduced pressure, and vacuum dry it to obtain thiourea sulfobetaine modified chitosan.

3. The wastewater treatment agent after the waste tire pyrolysis according to claim 2 is characterized in that: The reaction temperature in step (1) is 38-44°C.

4. The sewage treatment agent after the waste tire pyrolysis according to claim 2 is characterized in that: The mass fraction of the formaldehyde solution in step (2) is 37%-38%.

5. The wastewater treatment agent after the cracking of waste tires according to claim 1, characterized in that: The preparation method of the imidazoline quaternary ammonium salt modified graphene oxide comprises the following steps: S1. Add 3.7-4.3 g of lauric acid to the reactor, heat it to 160-170 ° C, add 1.8-2.4 mL of a water-carrying agent and 4.8-5.2 g of triethylenetetramine, reflux for 2-3 hours, heat it to 220-230 ° C and continue to react for 3.5-4 hours. After the reaction is completed, distill under reduced pressure to obtain a lauric acid imidazoline intermediate; S2. Add 4.6-5.2 g of lauric acid imidazoline intermediate to 50-80 mL of anhydrous ethanol solvent, stir to dissolve, add 1.8-2.2 g of benzyl chloride thereto, heat to 50-65 ° C and react for 7-10 hours. After the reaction is completed, remove the solvent by rotary evaporation, recrystallize and vacuum dry to obtain lauric acid imidazoline quaternary ammonium salt; S3. Add 1.2-1.8g of graphene oxide to 180-200mL of deionized water, ultrasonically disperse for 40-50min, adjust the pH to 5.5-6 with 1.5%-2% potassium hydroxide solution, add 0.5-0.9g of condensation agent and react for 1-1.5h, then add 1.3-1.4g of lauric acid imidazoline quaternary ammonium salt, pass nitrogen protection, heat to 65-75℃ and react for 7-10h. After the reaction, centrifuge, wash and vacuum dry to obtain imidazoline quaternary ammonium salt modified graphene.

6. The wastewater treatment agent after the waste tire pyrolysis according to claim 5 is characterized in that: The water-carrying agent in S1 is xylene.

7. The wastewater treatment agent after the waste tire pyrolysis according to claim 5 is characterized in that: The condensing agent in S3 is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

8. A method for preparing a sewage treatment agent after pyrolysis of waste tires according to any one of claims 1 to 7, characterized in that: The preparation method of the wastewater treatment agent after the waste tire is cracked is as follows: polysilicate ferric sulfate, polyaluminium chloride, thiourea sulfobetaine modified chitosan and imidazoline quaternary ammonium salt modified graphene oxide are added into a mixer, and mixed at 200-400 rpm for 10-15 minutes to obtain the wastewater treatment agent after the waste tire is cracked.

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