Composite improved saline-alkali soil composition based on biomass charcoal and preparation method of composite improved saline-alkali soil composition

Abstract

The invention relates to the technical field of saline-alkali soil improvement, and discloses a composite improved saline-alkali soil composition based on biomass charcoal and a preparation method thereof.Biomass charcoal, glucose, lactic acid bacteria, saccharomycetes, aluminum sulfate and a quaternary ammonium salt modifier are added into a stirrer to be stirred and mixed, stirring is conducted, and a mixture is obtained; and obtaining the composite improved saline-alkali soil composition based on the biomass charcoal. A quaternary ammonium salt group in the quaternary ammonium salt modifier can reduce the pH value of the soil and reduce the alkalinity of the soil, so that the salinization condition of the soil is improved, and quaternary ammonium salt can promote the activity of soil microorganisms and improve the fertility of the soil and the growth environment of crops; the siloxane is converted to be neutral by adjusting the pH value of the soil, the siloxane is beneficial to reducing the alkalinity of the soil, and a more suitable growth environment is provided for plants; wherein the contained boric acid group reduces the pH value of the soil by neutralizing alkaline substances in the soil, and has a relatively good improvement effect on the saline-alkali soil.

Description

Technical Field

[0001] The invention relates to the technical field of saline-alkali land improvement, and in particular to a biomass charcoal-based composite improved saline-alkali soil composition and a preparation method thereof. Background Art

[0002] Saline-alkali land is a general term for saline soil and alkaline soil. Saline soil mainly refers to salinized soil with high chloride or sulfate content and alkaline soil. Alkaline soil refers to soil containing carbonate or biphosphate, with high pH value and alkaline soil. Saline-alkali soil has less organic matter and is not conducive to the growth of crops. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN108966718A discloses a saline-alkali land improvement method. The invention can significantly improve the physical structure of saline-alkali soil, reduce the total salt content of saline-alkali soil, activate the soil, retain water and fertilizer, increase the organic matter content of the soil, and change the physical and chemical properties of saline-alkali soil, thereby realizing a long-term virtuous cycle of saline-alkali soil. However, its operation is cumbersome and the cost is high. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a biochar-based composite improved saline-alkali soil composition and a preparation method thereof, which has a good repair effect on saline-alkali soil.

[0005] (II) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a biochar-based composite improved saline-alkali soil composition, comprising the following components by weight: 40-90 parts by weight of biochar, 8-15 parts by weight of glucose, 0.6-0.8 parts by weight of lactic acid bacteria, 0.7-1 parts by weight of yeast, 0.3-0.8 parts by weight of aluminum sulfate, and 1-2 parts by weight of a quaternary ammonium salt improver.

[0007] Preferably, the preparation method of the quaternary ammonium salt modifier is:

[0008] (1) Add 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor containing acetone solvent, react at 80-95° C. for 7-12 hours, cool after the reaction, concentrate under reduced pressure, wash, and recrystallize from ethanol to obtain intermediate 1;

[0009] (2) Under nitrogen atmosphere, intermediate 1 and ε-caprolactone are added to a reactor and stirred evenly, and then stannous octoate catalyst is added to react at 120-130° C. for 3-6 hours. After the reaction is completed, the crude product is first dissolved in chloroform and then precipitated with anhydrous ether. The dissolution and precipitation are repeated 3-5 times, and the product is vacuum dried to obtain caprolactone-modified quaternary ammonium phenol;

[0010] (3) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introducing nitrogen protection, and then continuing to add tetramethylammonium hydroxide catalyst, reacting at 110-140° C. for 2-5 hours, cooling and discharging after the reaction, to obtain a double-terminal epoxy silicone oil;

[0011] (4) adding the double-terminal epoxy silicone oil and the caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride ether catalyst thereto, reacting at 80-95° C. for 6-10 hours, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2;

[0012] (5) Add boric acid to toluene solvent, stir and disperse, then add intermediate 2, raise the temperature to 110-125° C., react for 8-12 hours, and after the reaction is completed, perform vacuum distillation to obtain a quaternary ammonium salt modifier.

[0013] Preferably, the mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol in (1) is 1:1.2-1.4.

[0014] Preferably, the mass ratio of the intermediate 1, ε-caprolactone and stannous octoate catalyst in (2) is 1:1.1-1.3:0.01-0.03.

[0015] Preferably, the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst in (3) is 1.2-1.6:1:0.02-0.04.

[0016] Preferably, the mass ratio of the double-ended epoxy silicone oil, the caprolactone-modified quaternized phenol, and the boron trifluoride etherate catalyst in (4) is 1:0.8-1.4:0.02-0.03.

[0017] Preferably, the mass ratio of boric acid to intermediate 2 in (5) is 1:2.1-2.4.

[0018] Preferably, the preparation method of the biochar-based composite improved saline-alkali soil composition is: add biochar, glucose, lactic acid bacteria, yeast, aluminum sulfate, and quaternary ammonium salt improver into a stirrer, stir and mix, and stir for 20-35 minutes to obtain the biochar-based composite improved saline-alkali soil composition.

[0019] (III) Beneficial technical effects

[0020] The invention adds biomass charcoal, glucose, lactic acid bacteria, yeast, aluminum sulfate and quaternary ammonium salt improver into a stirrer, stirs and mixes, and after stirring, obtains a composite improved saline-alkali soil composition based on biomass charcoal.

[0021] The tertiary amino group of 4-((dimethylamino)methyl)phenol reacts with the chlorine in chloroethanol to generate a quaternary ammonium salt group and introduce a hydroxyl group to obtain intermediate 1; intermediate 1 reacts with ε-caprolactone to obtain caprolactone-modified quaternary ammonium phenol; the epoxy group in the double-terminal epoxy silicone oil and the phenolic hydroxyl group of the caprolactone-modified quaternary ammonium phenol are subjected to an addition reaction to increase the degree of substitution of the quaternary ammonium salt and introduce a large amount of intermediate 2; boric acid reacts with the hydroxyl group of intermediate 2 to obtain a quaternary ammonium salt modifier.

[0022] The quaternary ammonium salt groups in quaternary ammonium salt improvers can improve the structure and properties of the soil by interacting with the negative charges in the soil, which can reduce the pH value of the soil and reduce the alkalinity of the soil, thereby improving the salinization of the soil. Quaternary ammonium salts can also promote the activity of soil microorganisms, improve soil fertility and the growth environment of crops; the si-o-si bonds and hydroxyl groups in the siloxane molecules can produce complexation and adsorption with soil particles to cause the soil particles to aggregate. By adjusting the pH value of the soil to neutral, siloxane helps to reduce the alkalinity of the soil and provide a more suitable growth environment for plants; the boric acid groups contained therein reduce the pH value of the soil by neutralizing the alkaline substances in the soil, and have a good improvement effect on saline-alkali soil. DETAILED DESCRIPTION

[0023] Example 1

[0024] (1) adding 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor filled with acetone solvent, wherein the mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol is 1:1.2, reacting at 80° C. for 7 h, cooling after the reaction, concentrating under reduced pressure, washing, and recrystallizing with ethanol to obtain intermediate 1;

[0025] (2) Under a nitrogen atmosphere, intermediate 1 and ε-caprolactone were added to a reactor and stirred evenly, and then stannous octoate catalyst was added, wherein the mass ratio of intermediate 1, ε-caprolactone, and stannous octoate catalyst was 1:1.1:0.01, and the reaction was carried out at 120°C for 3 hours. After the reaction was completed, the crude product was first dissolved in chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 3 times. The product was vacuum dried to obtain caprolactone-modified quaternary ammonium phenol;

[0026] (3) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introducing nitrogen protection, and then continuing to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1.2:1:0.02, reacting at 110° C. for 2 hours, cooling and discharging after completion, and obtaining double-terminal epoxy silicone oil;

[0027] (4) adding double-ended epoxy silicone oil and caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, caprolactone-modified quaternary ammonium phenol, and boron trifluoride etherate catalyst is 1:0.8:0.02, reacting at 80-95° C. for 6 h, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2;

[0028] (5) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 2 thereto, wherein the mass ratio of boric acid to intermediate 2 is 1:2.1, heating to 110° C., reacting for 8 hours, and after the reaction is completed, distilling under reduced pressure to obtain a quaternary ammonium salt modifier;

[0029] (6) 40 parts by weight of biochar, 8 parts by weight of glucose, 0.6 parts by weight of lactic acid bacteria, 0.7 parts by weight of yeast, 0.3 parts by weight of aluminum sulfate, and 1 part by weight of quaternary ammonium salt improver are added into a blender, stirred and mixed, and stirred for 20 minutes to obtain a composite improved saline-alkali soil composition based on biochar.

[0030] Example 2

[0031] (1) adding 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor filled with acetone solvent, wherein the mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol is 1:1.4, reacting at 95° C. for 12 h, cooling after the reaction, concentrating under reduced pressure, washing, and recrystallizing from ethanol to obtain intermediate 1;

[0032] (2) Under a nitrogen atmosphere, intermediate 1 and ε-caprolactone were added to a reactor and stirred evenly, and then stannous octoate catalyst was added, wherein the mass ratio of intermediate 1, ε-caprolactone, and stannous octoate catalyst was 1:1.3:0.03, and the reaction was carried out at 130°C for 6 hours. After the reaction was completed, the crude product was first dissolved in chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 5 times. The product was vacuum dried to obtain caprolactone-modified quaternary ammonium phenol;

[0033] (3) Add octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introduce nitrogen protection, and then continue to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1.6:1:0.04, react at 140° C. for 5 hours, and cool and discharge after the reaction to obtain a double-terminal epoxy silicone oil;

[0034] (4) adding double-ended epoxy silicone oil and caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, caprolactone-modified quaternary ammonium phenol, and boron trifluoride etherate catalyst is 1:1.4:0.03, reacting at 95°C for 10 hours, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2;

[0035] (5) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 2 thereto, wherein the mass ratio of boric acid to intermediate 2 is 1:2.4, heating to 125° C., reacting for 12 h, and after the reaction is completed, distilling under reduced pressure to obtain a quaternary ammonium salt modifier;

[0036] (6) 90 parts by weight of biochar, 15 parts by weight of glucose, 0.8 parts by weight of lactic acid bacteria, 1 part by weight of yeast, 0.8 parts by weight of aluminum sulfate, and 2 parts by weight of quaternary ammonium salt improver were added into a blender, stirred and mixed, and stirred for 35 minutes to obtain a biochar-based composite improved saline-alkali soil composition.

[0037] Example 3

[0038] (1) Adding 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor filled with acetone solvent, wherein the mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol is 1:1.3, reacting at 85° C. for 10 h, cooling after the reaction, concentrating under reduced pressure, washing, and recrystallizing from ethanol to obtain intermediate 1;

[0039] (2) Under a nitrogen atmosphere, intermediate 1 and ε-caprolactone were added to a reactor and stirred evenly, and then stannous octoate catalyst was added, wherein the mass ratio of intermediate 1, ε-caprolactone, and stannous octoate catalyst was 1:1.2:0.02, and the reaction was carried out at 125°C for 5 hours. After the reaction was completed, the crude product was first dissolved in chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 4 times. The product was vacuum dried to obtain caprolactone-modified quaternary ammonium phenol;

[0040] (3) Add octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introduce nitrogen protection, and then continue to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1.4:1:0.03, react at 125° C. for 4 hours, cool and discharge after completion, and obtain double-terminal epoxy silicone oil;

[0041] (4) adding double-ended epoxy silicone oil and caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, caprolactone-modified quaternary ammonium phenol, and boron trifluoride etherate catalyst is 1:1.2:0.02, reacting at 86°C for 8h, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2;

[0042] (5) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 2 thereto, wherein the mass ratio of boric acid to intermediate 2 is 1:2.3, heating to 115° C., reacting for 10 h, and after the reaction is completed, distilling under reduced pressure to obtain a quaternary ammonium salt modifier;

[0043] (6) 75 parts by weight of biochar, 10 parts by weight of glucose, 0.7 parts by weight of lactic acid bacteria, 0.9 parts by weight of yeast, 0.6 parts by weight of aluminum sulfate, and 1 part by weight of quaternary ammonium salt improver were added into a blender, stirred and mixed, and stirred for 25 minutes to obtain a biochar-based composite improved saline-alkali soil composition.

[0044] Example 4

[0045] (1) adding 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor filled with acetone solvent, wherein the mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol is 1:1.2, reacting at 80° C. for 7 h, cooling after the reaction, concentrating under reduced pressure, washing, and recrystallizing with ethanol to obtain intermediate 1;

[0046] (2) Under a nitrogen atmosphere, intermediate 1 and ε-caprolactone were added to a reactor and stirred evenly, and then stannous octoate catalyst was added, wherein the mass ratio of intermediate 1, ε-caprolactone, and stannous octoate catalyst was 1:1.1:0.01, and the reaction was carried out at 120°C for 3 hours. After the reaction was completed, the crude product was first dissolved in chloroform and then precipitated with anhydrous ether, and the dissolution and precipitation were repeated 3 times. The product was vacuum dried to obtain caprolactone-modified quaternary ammonium phenol;

[0047] (3) Add octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introduce nitrogen protection, and then continue to add tetramethylammonium hydroxide catalyst, wherein the mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst is 1.6:1:0.04, react at 140° C. for 5 hours, and cool and discharge after the reaction to obtain a double-terminal epoxy silicone oil;

[0048] (4) adding double-ended epoxy silicone oil and caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride etherate catalyst thereto, wherein the mass ratio of double-ended epoxy silicone oil, caprolactone-modified quaternary ammonium phenol, and boron trifluoride etherate catalyst is 1:1.4:0.03, reacting at 95°C for 10 hours, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2;

[0049] (5) adding boric acid to toluene solvent, stirring and dispersing, and then adding intermediate 2 thereto, wherein the mass ratio of boric acid to intermediate 2 is 1:2.3, heating to 115° C., reacting for 10 h, and after the reaction is completed, distilling under reduced pressure to obtain a quaternary ammonium salt modifier;

[0050] (6) 75 parts by weight of biochar, 10 parts by weight of glucose, 0.7 parts by weight of lactic acid bacteria, 0.9 parts by weight of yeast, 0.6 parts by weight of aluminum sulfate, and 1 part by weight of quaternary ammonium salt improver were added into a blender, stirred and mixed, and stirred for 25 minutes to obtain a biochar-based composite improved saline-alkali soil composition.

[0051] Comparative Example 1

[0052] 75 parts by weight of biochar, 10 parts by weight of glucose, 0.7 parts by weight of lactic acid bacteria, 0.9 parts by weight of yeast, and 0.6 parts by weight of aluminum sulfate were added into a blender, stirred and mixed, and stirred for 25 minutes to obtain a composite improved saline-alkali soil composition based on biochar.

[0053] The present invention was used to carry out saline-alkali soil remediation test, and the test results are shown in Table 1.

[0054] Table 1: Soil remediation tests.

[0055]

[0056] It can be seen from Table 1 that Examples 1-4 of the present invention have better repair effects than Comparative Example 1.

[0057] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A composite improved saline-alkali soil composition based on biomass charcoal, characterized in that: The invention comprises the following components by weight: 40-90 parts by weight of biochar, 8-15 parts by weight of glucose, 0.6-0.8 parts by weight of lactic acid bacteria, 0.7-1 parts by weight of yeast, 0.3-0.8 parts by weight of aluminum sulfate and 1-2 parts by weight of a quaternary ammonium salt improver.

2. The biochar-based composite improved saline-alkali soil composition according to claim 1, characterized in that: The preparation method of the quaternary ammonium salt modifier is: (1) Add 4-((dimethylamino)methyl)phenol and chloroethanol to a reactor containing acetone solvent, react at 80-95° C. for 7-12 hours, cool after the reaction, concentrate under reduced pressure, wash, and recrystallize from ethanol to obtain intermediate 1; (2) Under a nitrogen atmosphere, the intermediate 1 and ε-caprolactone are added to a reactor and stirred evenly, and then a stannous octoate catalyst is added to react at 120-130° C. for 3-6 hours. After the reaction is completed, the crude product is first dissolved in chloroform and then precipitated with anhydrous ether. The dissolution and precipitation are repeated 3-5 times, and the product is vacuum dried to obtain caprolactone-modified quaternary ammonium phenol; . (3) adding octamethylcyclotetrasiloxane and 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reaction kettle, introducing nitrogen protection, and then continuing to add tetramethylammonium hydroxide catalyst, reacting at 110-140° C. for 2-5 hours, cooling and discharging after the reaction, to obtain a double-terminal epoxy silicone oil; (4) adding the double-terminal epoxy silicone oil and the caprolactone-modified quaternary ammonium phenol to a solvent containing N,N-dimethylformamide, stirring and mixing, and continuously adding boron trifluoride ether catalyst thereto, reacting at 80-95° C. for 6-10 hours, filtering after completion, washing with deionized water and ethanol in turn, and drying to obtain intermediate 2; (5) Add boric acid to toluene solvent, stir and disperse, then add intermediate 2, raise the temperature to 110-125° C., react for 8-12 hours, and after the reaction is completed, perform vacuum distillation to obtain a quaternary ammonium salt modifier.

3. The biochar-based composite improved saline-alkali soil composition according to claim 2, characterized in that: The mass ratio of 4-((dimethylamino)methyl)phenol to chloroethanol in (1) is 1:1.2-1.

4.

4. The biochar-based composite improved saline-alkali soil composition according to claim 2, characterized in that: The mass ratio of the intermediate 1, ε-caprolactone and stannous octoate catalyst in (2) is 1:1.1-1.3:0.01-0.

03.

5. The biochar-based composite improved saline-alkali soil composition according to claim 2, characterized in that: The mass ratio of octamethylcyclotetrasiloxane, 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane and tetramethylammonium hydroxide catalyst in (3) is 1.2-1.6:1:0.02-0.

04.

6. The biochar-based composite improved saline-alkali soil composition according to claim 2, characterized in that: The mass ratio of the double-terminal epoxy silicone oil, the caprolactone-modified quaternized phenol, and the boron trifluoride etherate catalyst in (4) is 1:0.8-1.4:0.02-0.

03.

7. The biochar-based composite improved saline-alkali soil composition according to claim 2, characterized in that: The mass ratio of boric acid to intermediate 2 in (5) is 1:2.1-2.

4.

8. A method for preparing a composite improved saline-alkali soil composition based on biochar according to any one of claims 1 to 7, characterized in that: The preparation method of the biochar-based composite improved saline-alkali soil composition is as follows: biochar, glucose, lactic acid bacteria, yeast, aluminum sulfate, and quaternary ammonium salt improver are added into a stirrer, stirred and mixed, and stirred for 20-35 minutes to obtain the biochar-based composite improved saline-alkali soil composition.

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