Multi-effect soil conditioner for soil polluted by organic matters and preparation method of multi-effect soil conditioner

Abstract

The invention discloses a multi-effect soil conditioner for organic matter contaminated soil and a preparation method thereof, and relates to the technical field of compound fertilizers, the multi-effect soil conditioner comprises the following raw materials by weight: 5-7 parts of urea, 25-30 parts of calcium superphosphate, 7.5-8.5 parts of potassium sulfate, 13-17 parts of farmyard manure, 8-9 parts of perlite, 50-60 parts of straw biochar, and 8-10 parts of an organic pollutant adsorbent. The organic pollutant adsorbent is a MOFs-based composite material, and the stability, oxidation resistance and high-temperature stability of the organic pollutant adsorbent in wet soil are improved, so that the prepared multi-effect soil conditioner has relatively high organic pollutant adsorption capacity, and the soil conditioner has relatively good soil quality on the basis of meeting the nutritional requirements of soil. The organic pollutants can be adsorbed and gathered in cooperation with the straw biochar, subsequent pollutant removal is facilitated, and the method is worthy of application and popularization.

Description

Technical Field

[0001] The invention relates to the technical field of compound fertilizers, and in particular to a multi-effect soil conditioner for organic matter-contaminated soil and a preparation method thereof. Background Art

[0002] A large amount of organic pollutants generated by industrial production, agricultural activities and daily life emissions cause far-reaching and serious pollution to the soil. The accumulated organic pollutants will destroy the soil structure, pollute the environment, and affect food safety and human health. Therefore, for the conditioning of soil contaminated by organic matter, on the basis of meeting basic nutritional needs, it is more important to adsorb and aggregate organic pollutants for easy removal. Usually, straw biochar in soil treatment agents can not only improve soil structure, increase soil fertility, regulate soil pH, and improve soil microbial activity and stress resistance, but also adsorb pollutants such as organic pollutants in the soil, but the adsorption capacity is limited.

[0003] Previously, studies have used metal organic frameworks (MOFs) in the adsorption and removal of various organic pollutants. Among them, green and environmentally friendly metal organic frameworks such as cyclodextrin-MOFs have been widely studied in the removal of organic pollutants in water. However, cyclodextrin-MOFs have poor water stability, so their use in soils with high water content is limited and needs to be improved. In addition, the cyclodextrin in cyclodextrin-MOFs has a weak antioxidant effect, which makes it easy to lose its structural characteristics when oxidized, which is not conducive to the adsorption of organic pollutants.

[0004] Therefore, a suitable modification method is needed to improve the water stability and antioxidant properties of cyclodextrin-MOFs, so as to obtain a more stable organic pollutant adsorbent that synergistically adsorbs organic pollutants with straw biochar, and apply it to soil conditioners to obtain a multi-effect soil conditioner suitable for organic contaminated soils. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a multi-effect soil conditioner for organic polluted soil and a preparation method thereof.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A multi-effect soil conditioner for organic polluted soil, comprising the following raw materials in parts by weight: 5-7 parts of urea, 25-30 parts of superphosphate, 7.5-8.5 parts of potassium sulfate, 13-17 parts of farmyard manure, 8-9 parts of perlite, 50-60 parts of straw biochar, and 8-10 parts of an organic pollutant adsorbent;

[0008] The multi-effect soil conditioner for organic matter-contaminated soil comprises the following steps for preparation:

[0009] Urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar and organic pollutant adsorbent are stirred for 15-25 minutes to obtain a mixture, and then the mixture is transferred to an extrusion granulator for extrusion molding, and then dried and sieved to obtain a multi-effect soil conditioner for organic polluted soil;

[0010] Furthermore, the drying is carried out using a far-infrared dryer at 70-80°C for 2-3h, and the sieved particle size is 10-12mm;

[0011] The preparation of the organic pollutant adsorbent comprises the following steps:

[0012] Step A1, add taraxasterol to toluene, start stirring, then add sodium hydroxide solution, stir for 5-10 minutes, then dropwise add epichlorohydrin, stir and react at room temperature for 6-7 hours to obtain an epoxy product;

[0013] Furthermore, the dosage ratio of taraxasterol, toluene, sodium hydroxide solution and epichlorohydrin is 43-45 g: 100-120 mL: 10-15 mL: 10-11 g, and the mass fraction of the sodium hydroxide solution is 5-10%;

[0014] During the reaction of step A1, the hydroxyl group in taraxasterol reacts with epichlorohydrin to first open the ring and then close the ring to generate an epoxy product containing a five-ring structure;

[0015] Step A2, in a protective gas atmosphere, add 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid to toluene, heat to 45-50° C., add pyridine, start stirring, then add the epoxy product, stir to react for 8-10 hours, then heat to 100-110° C., stir for 1-2 hours to obtain a hydroxyl product;

[0016] Further, the ratio of 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, toluene, pyridine and epoxidation product is 20-22 g: 170-180 mL: 4-6 g: 53-55 g;

[0017] During the reaction of step A2, 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid reacts with the epoxy group of the epoxy product to form a hydroxyl product containing a five-ring structure and a hindered amine;

[0018] Step A3, add dodec-11-enoic acid to DMF, add dichlorothionyl under stirring, reflux and stir at 50-55° C. for 5-6 hours to obtain an acyl chloride product; stir and mix the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain a mixed solution 1; add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 in an ice-water bath, raise the temperature to 40-45° C. after the addition is complete, stir and react at a constant temperature for 8-10 hours, and distill under reduced pressure to obtain a monomer s;

[0019] Further, the dosage ratio of dodeca-11-enoic acid, DMF, and dichlorothionyl is 20-22 g: 50-55 mL: 15-17 mL; the dosage ratio of the hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution 1 is 7.5-8.5 g: 2-3 mL: 5-7 mL: 20-25 mL; the dosage ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 21-23 g: 45-50 mL; the dosage ratio of the mixed solution 1 and the mixed solution 2 is 35-45 mL: 8-10 mL;

[0020] During the reaction of step A3, dodecyl-11-enoic acid reacts with thionyl chloride to obtain an acyl chloride product, and the acyl chloride product reacts with a hydroxyl product containing a pentacyclic structure and a hindered amine to obtain a monomer s containing a long alkane chain, a pentacyclic structure and a hindered amine;

[0021] Step A4, cyclodextrin, potassium hydroxide and deionized water are mixed and stirred for 45-60 minutes, methanol is added, the temperature is raised to 60-75°C, stirring is continued for 8-10 hours, and then a surfactant solution is added, stirred for 10-15 minutes, and then allowed to stand at room temperature for 24-26 hours, centrifuged, washed with isopropanol, and the precipitate is dried to obtain cyclodextrin-MOF;

[0022] Furthermore, the cyclodextrin is one of α-cyclodextrin and γ-cyclodextrin; the dosage ratio of cyclodextrin to potassium hydroxide is 4-6g:1g, deionized water is added to control the concentration of potassium hydroxide to 2-3mol / L, the dosage ratio of deionized water, methanol, and surfactant solution is 1mL:10-15mL:200-300mL, the surfactant solution is obtained by adding hexadecyltrimethylammonium bromide to water and stirring and mixing, and the concentration of the surfactant solution is 7-9g / L;

[0023] During the reaction of step A4, cyclodextrin-MOF is prepared by a solvothermal method;

[0024] Step A5, adding cyclodextrin-MOF to ethanol, ultrasonically dispersing for 30-35 minutes to obtain a mixed solution 3; then adding monomer s and silane containing terminal double bonds to ethanol and stirring for 20-25 minutes to obtain a mixed solution 4; in a protective gas atmosphere, mixing the mixed solution 3 with the mixed solution 4, then adding an ethanol solution of azobisisobutyronitrile, stirring and reacting at 70-75° C. for 5-5.5 hours, then washing with methanol and drying in a vacuum drying oven at 50-60° C. overnight to obtain an organic pollutant adsorbent;

[0025] Further, the dosage ratio of cyclodextrin-MOF and ethanol in the mixed solution 3 is 1-1.2 g: 100-110 mL; the dosage ratio of monomer s, silane containing terminal double bonds, and ethanol in the mixed solution 4 is 30-32 g: 7-9 g: 250-260 mL; the dosage ratio of the mixed solution 3, the mixed solution 4, and the ethanol solution of azobisisobutyronitrile is 10-12 mL: 3-3.5 mL: 1-1.2 mL, and the ethanol solution of azobisisobutyronitrile is obtained by adding azobisisobutyronitrile to ethanol and stirring and mixing, and the concentration of the ethanol solution of azobisisobutyronitrile is 0.04 mol / L;

[0026] During the reaction of step A5, under the initiation of azobisisobutyronitrile, the monomer s containing a long alkane chain, a five-ring structure and a hindered amine is copolymerized with a silane containing a terminal double bond to obtain a polymer coated on the surface of cyclodextrin MOFs to obtain an organic pollutant adsorbent.

[0027] Beneficial effects of the invention: The invention discloses a multi-effect soil conditioner for organic polluted soil and a preparation method thereof, wherein the multi-effect soil conditioner for organic polluted soil comprises raw materials such as urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar, and organic pollutant adsorbent. The urea, superphosphate, potassium sulfate, and farmyard manure in the multi-effect soil conditioner of the invention provide basic nutrients for the soil, and the combination of perlite and straw biochar can improve soil structure, increase soil fertility, and promote plant growth.

[0028] The organic pollutant adsorbent belongs to a MOFs-based composite material, which is prepared by coating a polymer obtained by copolymerizing a monomer s containing a long alkane chain, a five-ring structure and a hindered amine with a silane containing a terminal double bond on the surface of a cyclodextrin MOFs. The polymer obtained by the copolymerization does not affect the pore size of the cyclodextrin MOFs, and therefore does not affect the adsorption of organic pollutants by the cyclodextrin MOFs; the long alkane chain and the hydrophobic five-ring structure of the copolymerized polymer synergistically improve the hydrophobicity of the cyclodextrin MOFs, thereby improving the stability of the organic pollutant adsorbent in soils with a high water content, and the hydrophobic five-ring structure is composed of the natural product taraxasterol. The introduction of hindered amine-containing polymers can enhance environmental protection and make the organic pollutant adsorbent more applicable in the soil; the coating of polymers containing hindered amines can improve the antioxidant properties of polymers and cyclodextrin MOFs, avoiding the polymers being unable to effectively coat cyclodextrin MOFs due to oxidation, and the cyclodextrins being oxidized and losing their structural characteristics, resulting in a decrease in the adsorption capacity for organic pollutants; the introduction of silanes containing terminal double bonds can improve the thermal stability of the copolymerized polymers, avoiding the soil being exposed to high temperature in summer, and losing the stability-enhancing effect on cyclodextrin MOFs in high temperature and high humidity environments due to the decrease in polymer stability.

[0029] Therefore, the multi-effect soil conditioner of the present invention can not only provide nutrients for the soil, improve soil structure and promote plant growth, but the organic pollutant adsorbent can also cooperate with straw biochar to strongly adsorb bisphenols, organic dyes, antibiotics and other drug-like organic pollutants, thereby preventing organic pollutants from destroying the soil structure, polluting the environment, and affecting food safety and human health. Aggregating organic matter makes it more convenient to remove organic pollutants in the subsequent remediation process. It has high applicability in soil contaminated by organic matter and is worthy of popularization and use. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] Example 1

[0032] An organic pollutant adsorbent, the preparation of which comprises the following steps:

[0033] Step A1, adding taraxasterol to toluene, stirring, adding sodium hydroxide solution, stirring for 5 minutes, and then dropping epichlorohydrin, stirring and reacting at room temperature for 6 hours to obtain an epoxy product; the dosage ratio of taraxasterol, toluene, sodium hydroxide solution and epichlorohydrin is 43g:100mL:10mL:10g, and the mass fraction of the sodium hydroxide solution is 5%;

[0034] Step A2, in a nitrogen atmosphere, add 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid to toluene, heat to 45°C, add pyridine, start stirring, then add the epoxy product, stir and react for 8h, then heat to 100°C, stir for 1h to obtain a hydroxyl product; the amount ratio of 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, toluene, pyridine and epoxy product is 20g:170mL:4g:53g;

[0035] Step A3, add dodec-11-enoic acid to DMF, add dichlorothionyl under stirring, reflux and stir at 50°C for 5h to obtain an acyl chloride product; stir and mix the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain a mixed solution 1; add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 in an ice-water bath, after the addition is complete, heat to 40°C, stir and react at a constant temperature for 8h, and distill under reduced pressure to obtain a monomer s; the amount ratio of dodec-11-enoic acid, DMF, and dichlorothionyl is 20g:50mL:15mL; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide in the mixed solution 1 is 7.5g:2mL:5mL:20mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 21g:45mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 35mL:8mL;

[0036] Step A4, α-cyclodextrin (supplier: Qianhui Bio), potassium hydroxide, and deionized water were mixed and stirred for 45 minutes, and then methanol was added, the temperature was raised to 60°C, and the reaction was continued with stirring for 8 hours, and then the surfactant solution was added, stirred for 10 minutes, and then allowed to stand at room temperature for 24 hours, centrifuged, and the precipitate was washed with isopropanol and dried to obtain cyclodextrin-MOF; the dosage ratio of α-cyclodextrin and potassium hydroxide was 4g:1g, and deionized water was added to control the concentration of potassium hydroxide to 2mol / L, and the dosage ratio of deionized water, methanol, and surfactant solution was 1mL:10mL:200mL, and the surfactant solution was obtained by adding hexadecyltrimethylammonium bromide to water and stirring and mixing, and the concentration of the surfactant solution was 7g / L;

[0037] Step A5, add cyclodextrin-MOF to ethanol, ultrasonically disperse for 30 minutes to obtain a mixed solution 3; then add monomer s and silane containing terminal double bonds to ethanol and stir for 20 minutes to obtain a mixed solution 4; in a nitrogen atmosphere, mix the mixed solution 3 with the mixed solution 4, then add an ethanol solution of azobisisobutyronitrile, stir and react at 70°C for 5 hours, then wash with methanol and dry in a vacuum drying oven at 50°C overnight to obtain an organic pollutant adsorbent; the cyclodextrin-MOF and ethanol in the mixed solution 3 The dosage ratio is 1g:100mL; the dosage ratio of monomer s, silane containing terminal double bonds, and ethanol in mixed solution 4 is 30g:7g:250mL; the dosage ratio of mixed solution 3, mixed solution 4, and ethanol solution of azobisisobutyronitrile is 10mL:3mL:1mL, the ethanol solution of azobisisobutyronitrile is obtained by adding azobisisobutyronitrile to ethanol and stirring and mixing, and the concentration of the ethanol solution of azobisisobutyronitrile is 0.04mol / L; the ethanol is ethanol with a volume fraction of 95%.

[0038] Example 2

[0039] An organic pollutant adsorbent, the preparation of which comprises the following steps:

[0040] Step A1, adding taraxasterol to toluene, stirring, adding sodium hydroxide solution, stirring for 7 minutes, and then dropping epichlorohydrin, stirring and reacting at room temperature for 6.5 hours to obtain an epoxy product; the amount ratio of taraxasterol, toluene, sodium hydroxide solution and epichlorohydrin is 44g:110mL:13mL:10.5g, and the mass fraction of the sodium hydroxide solution is 7%;

[0041] Step A2, in a nitrogen atmosphere, add 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid to toluene, heat to 47°C, add pyridine, start stirring, then add the epoxy product, stir and react for 9 hours, then heat to 105°C, stir for 1.5 hours to obtain a hydroxyl product; the amount ratio of 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, toluene, pyridine and epoxy product is 21g:175mL:5g:54g;

[0042] Step A3, add dodec-11-enoic acid to DMF, add dithionyl chloride under stirring, reflux and stir at 53°C for 5.5h to obtain an acyl chloride product; stir and mix the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain a mixed solution 1; add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 in an ice-water bath, after the addition is complete, heat to 42°C, stir and react at a constant temperature for 9h, and distill under reduced pressure to obtain a monomer s; the amount ratio of dodec-11-enoic acid, DMF, and dithionyl chloride is 21g:53mL:16mL; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide in the mixed solution 1 is 8g:2.5mL:6mL:23mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 22g:47mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 40mL:9mL;

[0043] Step A4, γ-cyclodextrin (supplier: Qianhui Bio), potassium hydroxide, and deionized water were mixed and stirred for 52 minutes, and then methanol was added, the temperature was raised to 68°C, and the reaction was continued with stirring for 9 hours, and then the surfactant solution was added, stirred for 13 minutes, and then allowed to stand at room temperature for 25 hours, centrifuged, and the precipitate was washed with isopropanol and dried to obtain cyclodextrin-MOF; the dosage ratio of γ-cyclodextrin and potassium hydroxide was 5g:1g, and deionized water was added to control the concentration of potassium hydroxide to 2.5mol / L, and the dosage ratio of deionized water, methanol, and surfactant solution was 1mL:13mL:250mL, and the surfactant solution was obtained by adding hexadecyltrimethylammonium bromide to water and stirring and mixing, and the concentration of the surfactant solution was 8g / L;

[0044] Step A5, adding cyclodextrin-MOF to ethanol, ultrasonically dispersing for 33 minutes to obtain a mixed solution 3; then adding monomer s and silane containing terminal double bonds to ethanol and stirring for 23 minutes to obtain a mixed solution 4; in a nitrogen atmosphere, mixing the mixed solution 3 with the mixed solution 4, then adding an ethanol solution of azobisisobutyronitrile, stirring and reacting at 73°C for 5.3 hours, then washing with methanol and drying in a vacuum drying oven at 55°C overnight to obtain an organic pollutant adsorbent; the cyclodextrin-MOF in the mixed solution 3 The usage ratio of MOF and ethanol is 1.1g:105mL; the usage ratio of monomer s, silane containing terminal double bonds, and ethanol in mixed solution 4 is 31g:8g:255mL; the usage ratio of mixed solution 3, mixed solution 4, and ethanol solution of azobisisobutyronitrile is 11mL:3.3mL:1.1mL, and the ethanol solution of azobisisobutyronitrile is obtained by adding azobisisobutyronitrile to ethanol and stirring and mixing, and the concentration of the ethanol solution of azobisisobutyronitrile is 0.04mol / L.

[0045] Example 3

[0046] An organic pollutant adsorbent, the preparation of which comprises the following steps:

[0047] Step A1, adding taraxasterol to toluene, stirring, adding sodium hydroxide solution, stirring for 10 minutes, and then dropping epichlorohydrin, stirring and reacting at room temperature for 7 hours to obtain an epoxy product; the amount ratio of taraxasterol, toluene, sodium hydroxide solution and epichlorohydrin is 45g:120mL:15mL:11g, and the mass fraction of the sodium hydroxide solution is 10%;

[0048] Step A2, in a nitrogen atmosphere, add 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid to toluene, heat to 50°C, add pyridine, start stirring, then add the epoxy product, stir to react for 10 hours, then heat to 110°C, stir for 2 hours to obtain a hydroxyl product; the amount ratio of 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, toluene, pyridine and epoxy product is 22g:180mL:6g:55g;

[0049] Step A3, add dodec-11-enoic acid to DMF, add dichlorothionyl under stirring, reflux and stir at 55°C for 6h to obtain an acyl chloride product; stir and mix the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide to obtain a mixed solution 1; add the acyl chloride product to dimethyl sulfoxide to obtain a mixed solution 2, add the mixed solution 2 dropwise to the mixed solution 1 in an ice-water bath, after the addition is complete, heat to 45°C, stir and react at a constant temperature for 10h, and distill under reduced pressure to obtain a monomer s; the amount ratio of dodec-11-enoic acid, DMF, and dichlorothionyl is 22g:55mL:17mL; the amount ratio of the hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide in the mixed solution 1 is 8.5g:3mL:7mL:25mL; the amount ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 23g:50mL; the amount ratio of the mixed solution 1 to the mixed solution 2 is 45mL:10mL;

[0050] Step A4, γ-cyclodextrin (supplier: Qianhui Bio), potassium hydroxide, and deionized water were mixed and stirred for 60 minutes, and then methanol was added, the temperature was raised to 75°C, and the reaction was continued with stirring for 10 hours, and then a surfactant solution was added, stirred for 15 minutes, and then allowed to stand at room temperature for 26 hours, centrifuged, and the precipitate was washed with isopropanol and dried to obtain cyclodextrin-MOF; the dosage ratio of γ-cyclodextrin and potassium hydroxide was 6g:1g, and deionized water was added to control the concentration of potassium hydroxide to 3 mol / L. The dosage ratio of deionized water, methanol, and surfactant solution was 1mL:15mL:300mL, and the surfactant solution was obtained by adding hexadecyltrimethylammonium bromide to water and stirring and mixing, and the concentration of the surfactant solution was 9g / L;

[0051] Step A5, adding cyclodextrin-MOF to ethanol, ultrasonically dispersing for 35 minutes to obtain a mixed solution 3; then adding monomer s and silane containing terminal double bonds to ethanol and stirring for 25 minutes to obtain a mixed solution 4; in a nitrogen atmosphere, mixing the mixed solution 3 with the mixed solution 4, then adding an ethanol solution of azobisisobutyronitrile, stirring and reacting at 75°C for 5.5 hours, then washing with methanol and drying in a vacuum drying oven at 60°C overnight to obtain an organic pollutant adsorbent; the cyclodextrin-MOF in the mixed solution 3 The usage ratio of MOF and ethanol is 1.2g:110mL; the usage ratio of monomer s, silane containing terminal double bonds, and ethanol in mixed solution 4 is 32g:9g:260mL; the usage ratio of mixed solution 3, mixed solution 4, and ethanol solution of azobisisobutyronitrile is 12mL:3.5mL:1.2mL, and the ethanol solution of azobisisobutyronitrile is obtained by adding azobisisobutyronitrile to ethanol and stirring and mixing, and the concentration of the ethanol solution of azobisisobutyronitrile is 0.04mol / L.

[0052] Example 4

[0053] A multi-effect soil conditioner for organic polluted soil, comprising the following raw materials in parts by weight: 5 parts of urea, 25 parts of superphosphate, 7.5 parts of potassium sulfate, 13 parts of farmyard manure, 8 parts of perlite, 50 parts of straw biochar, and 8 parts of an organic pollutant adsorbent;

[0054] The multi-effect soil conditioner for organic matter-contaminated soil comprises the following steps for preparation:

[0055] Urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar and organic pollutant adsorbent were stirred for 15 minutes to obtain a mixture, which was then transferred to an extrusion granulator for extrusion molding, and then dried and sieved to obtain a multi-effect soil conditioner for organic polluted soil; a far-infrared dryer was used for drying at 70°C for 2 hours, and the sieved particle size was 10 mm.

[0056] Example 5

[0057] A multi-effect soil conditioner for organic polluted soil, comprising the following raw materials in parts by weight: 6 parts of urea, 27 parts of superphosphate, 8.0 parts of potassium sulfate, 15 parts of farmyard manure, 8.5 parts of perlite, 55 parts of straw biochar, and 9 parts of an organic pollutant adsorbent;

[0058] The multi-effect soil conditioner for organic matter-contaminated soil comprises the following steps for preparation:

[0059] Urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar and organic pollutant adsorbent are stirred for 20 minutes to obtain a mixture, which is then transferred to an extrusion granulator for extrusion molding, and then dried and sieved to obtain a multi-effect soil conditioner for organic polluted soil; a far-infrared dryer is used for drying at 75°C for 2.5 hours, and the sieved particle size is 11 mm.

[0060] Example 6

[0061] A multi-effect soil conditioner for organic polluted soil, comprising the following raw materials in parts by weight: 7 parts of urea, 30 parts of superphosphate, 8.5 parts of potassium sulfate, 17 parts of farmyard manure, 9 parts of perlite, 60 parts of straw biochar, and 10 parts of an organic pollutant adsorbent;

[0062] The multi-effect soil conditioner for organic matter-contaminated soil comprises the following steps for preparation:

[0063] Urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar and organic pollutant adsorbent are stirred for 25 minutes to obtain a mixture, which is then transferred to an extrusion granulator for extrusion molding, and then dried and sieved to obtain a multi-effect soil conditioner for organic polluted soil; a far-infrared dryer is used for drying at 80°C for 3 hours, and the sieved particle size is 12 mm.

[0064] Comparative Example 1

[0065] Compared with Example 6, during the preparation of the organic pollutant adsorbent, the taraxasterol in step A1 was replaced with cyclohexyl alcohol, and the rest was exactly the same as Example 6 to prepare a multi-effect soil conditioner.

[0066] Comparative Example 2

[0067] Compared with Example 6, in the process of preparing the organic pollutant adsorbent, the dodecyl-11-enoic acid in step A3 is replaced with acrylic acid, and the rest is exactly the same as Example 6 to prepare a multi-effect soil conditioner.

[0068] Comparative Example 3

[0069] Compared with Example 6, in the preparation process of the organic pollutant adsorbent, the 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid in step A2 is replaced with propionic acid, and the rest is exactly the same as Example 6 to obtain a multi-effective soil conditioner.

[0070] Comparative Example 4

[0071] Compared with Example 6, during the preparation of the organic pollutant adsorbent, the silane containing terminal double bonds in step A5 is replaced with ethyl acrylate, and the rest is exactly the same as Example 6 to prepare a multi-effect soil conditioner.

[0072] Comparative Example 5

[0073] Compared with Example 6, the organic pollutant adsorbent is replaced with straw biochar, and the rest is exactly the same as Example 6 to prepare a multi-effect soil conditioner.

[0074] The multi-effect soil conditioner prepared by the present invention is further tested for its effect, and the test results are as follows.

[0075] The multi-effect soil treatment agent of the present invention and a solution of organic pollutants (bisphenol F, methylene blue, tetracycline) with a concentration of 50 mg / L were stirred and mixed uniformly, and then placed in an air oven at room temperature and in an air oven at 50° C. for 7 days and treated by a catalytic degradation method, and then the degradation rate was measured, where the degradation rate (%) = (50-concentration of the organic pollutant solution after 7 days) / 50*100, and the results are recorded in Table 1;

[0076] The test results are recorded in Table 1;

[0077] Table 1: Test results

[0078]

[0079] According to the data in Table 1, the multi-effect soil conditioner of the present invention has excellent ability to adsorb organic pollutants such as bisphenol F, methylene blue and tetracycline. After the organic pollutants are aggregated, it is more convenient to remove them by catalytic degradation method, so as to obtain a better degradation rate of organic pollutants. As shown in Example 6 compared with Comparative Example 1, cyclohexyl alcohol is used instead of taraxasterol, and the hydrophobic five-ring structure is not introduced to synergistically enhance the stability of the organic pollutant adsorbent in an environment with a large water content with the alkane long chain, and the adsorption and aggregation of organic pollutants are reduced, and the degradation rate at room temperature is reduced, which also leads to a decrease in environmental protection. As shown in Example 6 compared with Comparative Example 2, acrylic acid is used instead of dodecyl-11-enoic acid, and the alkane long chain and the hydrophobic five-ring structure are not introduced to synergistically enhance the stability of the organic pollutant adsorbent in an environment with a large water content, and the adsorption and aggregation of organic pollutants are reduced, and the degradation rate at room temperature is reduced. Comparison between Example 6 and Comparative Example 3 shows that when propionic acid replaces 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, the antioxidant properties of the polymer and cyclodextrin MOFs decrease. Under the oxidative action of oxygen in the air, the adsorption and aggregation of organic pollutants by the organic pollutant adsorbent decreases, and the degradation rate at room temperature decreases. Comparison between Example 6 and Comparative Example 4 shows that when ethyl acrylate replaces the silane containing terminal double bonds, the thermal stability of the polymer obtained by copolymerization decreases. In an air oven at 80°C, due to the decrease in the thermal stability of the polymer, the stability of the cyclodextrin MOFs in the organic pollutant adsorbent decreases, the adsorption and aggregation of organic pollutants by the organic pollutant adsorbent decreases, and the degradation rate decreases at 80°C. Comparison between Example 6 and Comparative Example 5 shows that when the organic pollutant adsorbent is replaced with straw biochar, only the straw biochar plays the role of adsorbing organic pollutants, and the adsorption and aggregation of organic pollutants is insufficient, and the degradation rate decreases significantly.

[0080] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A multi-effect soil conditioner for organic polluted soil, characterized in that: The invention comprises the following raw materials in parts by weight: 5-7 parts of urea, 25-30 parts of superphosphate, 7.5-8.5 parts of potassium sulfate, 13-17 parts of farmyard manure, 8-9 parts of perlite, 50-60 parts of straw biochar, and 8-10 parts of organic pollutant adsorbent; The preparation of the organic pollutant adsorbent comprises the following steps: Step A1, adding taraxasterol to toluene, stirring, then adding sodium hydroxide solution, adding epichlorohydrin dropwise, stirring and reacting at room temperature to obtain an epoxy product; Step A2, in a protective gas atmosphere, add 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid to toluene, add pyridine, and then add the epoxy product, and stir to react to obtain a hydroxyl product; Step A3, adding dodec-11-enoic acid to DMF, adding thionyl chloride under stirring, stirring and reacting to obtain an acyl chloride product; The hydroxyl product, pyridine, triethylamine and dimethyl sulfoxide are stirred and mixed to obtain a mixed solution 1; the acyl chloride product is added to dimethyl sulfoxide to obtain a mixed solution 2, and the mixed solution 2 is added dropwise to the mixed solution 1, and the mixture is stirred and reacted to obtain a monomer s; Step A4, mixing cyclodextrin, potassium hydroxide and deionized water, adding methanol, and then adding a surfactant solution, stirring and standing at room temperature to obtain cyclodextrin-MOF; Step A5, adding cyclodextrin-MOF to ethanol and ultrasonically dispersing to obtain a mixed solution 3; then adding monomer s and silane containing terminal double bonds to ethanol to obtain a mixed solution 4; in a protective gas atmosphere, mixing the mixed solution 3 with the mixed solution 4, then adding an ethanol solution of azobisisobutyronitrile, stirring the reaction to obtain an organic pollutant adsorbent.

2. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A1, the dosage ratio of taraxasterol, toluene, sodium hydroxide solution and epichlorohydrin is 43-45 g: 100-120 mL: 10-15 mL: 10-11 g, and the mass fraction of the sodium hydroxide solution is 5-10%.

3. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A2, the ratio of 2-(2,2,6,6-tetramethylpiperidin-4-yl)acetic acid, toluene, pyridine and epoxide product is 20-22 g: 170-180 mL: 4-6 g: 53-55 g.

4. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A3, the usage ratio of dodecaned-11-enoic acid, DMF, and dichlorothionyl is 20-22 g: 50-55 mL: 15-17 mL; the usage ratio of the hydroxyl product, pyridine, triethylamine, and dimethyl sulfoxide in the mixed solution 1 is 7.5-8.5 g: 2-3 mL: 5-7 mL: 20-25 mL.

5. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A3, the usage ratio of the acyl chloride product and dimethyl sulfoxide in the mixed solution 2 is 21-23 g:45-50 mL; the usage ratio of the mixed solution 1 and the mixed solution 2 is 35-45 mL:8-10 mL.

6. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A4, the cyclodextrin is one of α-cyclodextrin and γ-cyclodextrin; the dosage ratio of cyclodextrin to potassium hydroxide is 4-6g:1g, and deionized water is added to control the concentration of potassium hydroxide to 2-3 mol / L.

7. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A4, the usage ratio of deionized water, methanol and surfactant solution is 1 mL: 10-15 mL: 200-300 mL. The surfactant solution is obtained by adding hexadecyltrimethylammonium bromide to water and stirring and mixing. The concentration of the surfactant solution is 7-9 g / L.

8. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A5, the usage ratio of cyclodextrin-MOF and ethanol in the mixed solution 3 is 1-1.2 g: 100-110 mL; the usage ratio of monomer s, silane containing terminal double bonds, and ethanol in the mixed solution 4 is 30-32 g: 7-9 g: 250-260 mL.

9. The multi-effect soil conditioner for organic polluted soil according to claim 1, characterized in that: In step A5, the dosage ratio of the mixed solution 3, the mixed solution 4, and the ethanol solution of azobisisobutyronitrile is 10-12 mL: 3-3.5 mL: 1-1.2 mL, the ethanol solution of azobisisobutyronitrile is obtained by adding azobisisobutyronitrile to ethanol and stirring and mixing, and the concentration of the ethanol solution of azobisisobutyronitrile is 0.04 mol / L; the volume fraction of ethanol is 95%.

10. A method for preparing the multi-effect soil conditioner for organic polluted soil according to claims 1-9, characterized in that: The steps include: Urea, superphosphate, potassium sulfate, farmyard manure, perlite, straw biochar and organic pollutant adsorbent are stirred for 15-25 minutes to obtain a mixture, and then the mixture is transferred to an extrusion granulator for extrusion molding, and then dried and sieved to obtain a multi-effect soil conditioner for organic polluted soil; the drying is carried out using a far-infrared dryer at 70-80°C for 2-3 hours, and the sieved particle size is 10-12mm.

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