CN111454728A - Soil hardening improver capable of improving consistency of soil structure loosening degree - Google Patents
Soil hardening improver capable of improving consistency of soil structure loosening degree Download PDFInfo
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- 239000002689 soil Substances 0.000 title claims abstract description 102
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- 229920001661 Chitosan Polymers 0.000 claims abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003516 soil conditioner Substances 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- AXOFFTWUWPCDGJ-UHFFFAOYSA-N 2,2-dichloroethanamine;hydrochloride Chemical compound Cl.NCC(Cl)Cl AXOFFTWUWPCDGJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 9
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002907 Guar gum Polymers 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229960002154 guar gum Drugs 0.000 claims description 6
- 235000010417 guar gum Nutrition 0.000 claims description 6
- 239000000665 guar gum Substances 0.000 claims description 6
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims 2
- 230000035699 permeability Effects 0.000 abstract description 11
- 230000006872 improvement Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 206010016807 Fluid retention Diseases 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NWBJYWHLCVSVIJ-UHFFFAOYSA-N N-benzyladenine Chemical compound N=1C=NC=2NC=NC=2C=1NCC1=CC=CC=C1 NWBJYWHLCVSVIJ-UHFFFAOYSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000018343 nutrient deficiency Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003971 tillage Methods 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0464—Elimination of a polymeric phase using water or inorganic fluids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a soil hardening modifier capable of improving the consistency of soil structure loosening degree, and relates to the technical field of soil improvement, wherein the concrete preparation method comprises the following steps: 1) irradiating the prepared proton titanium dioxide by ultraviolet light to obtain pretreated proton titanium dioxide; 2) carrying out modification pretreatment on graphene oxide to obtain pretreated graphene oxide; 3) modifying the epoxy resin by using chitosan to obtain a chitosan modified epoxy resin precursor; 4) using polyethylene glycol as a pore-foaming agent to obtain porous polymer powder; 5) and uniformly mixing the obtained raw materials, drying and crushing to obtain the required soil conditioner. The modifier for improving the soil hardening, provided by the invention, can reduce the permeability difference existing in soil while improving the soil permeability, improve the consistency of the soil structure loosening degree, realize the reduction of the difference of the crop growth state in the soil, and has a promoting effect on the improvement of the crop yield and the quality.
Description
Technical Field
The invention belongs to the technical field of soil improvement, and particularly relates to a soil hardening improver capable of improving the consistency of soil structure loosening degree.
Background
The soil hardening refers to the phenomenon that the surface soil layer is poor in structure due to lack of organic matters, the structure is damaged and the soil is dispersed under the action of irrigation, rainfall and other external factors, and the surface soil is hardened under the action of cohesive force after drying. The main reasons for soil hardening in farmland are: (1) the farmland soil texture is too viscous, and the cultivated layer is shallow; (2) the application of the organic fertilizer is seriously insufficient, and the organic matter content of the soil is low; (3) fertilizer is applied in excess and unbalanced; (4) agricultural machinery is used for tillage and suppression; (5) excessive residues of plastic products; (6) water and soil loss; (7) accumulation of harmful substances. The main hazards caused by soil hardening of the farmland are as follows: (1) leading to poor growth of crop roots; (2) leading to the occurrence of nutrient deficiency of crop plants and reducing the yield and quality of agricultural products.
Therefore, how to maintain the soil quality and improve the soil hardening phenomenon to promote the growth of crops becomes a focus of attention. The application of the soil conditioner can relieve the agricultural production crisis to a certain extent, improve the soil structure and improve the permeability of the soil, so that the root system of crops can be healthily developed, and the quality of the crop yield is improved. For example, chinese patent CN201910508160X discloses a soil conditioner for soil hardening prevention and treatment and a preparation method thereof, in the technical scheme, a modification auxiliary material is added, the modification auxiliary material contains a gel structure sensitive to pH, after being added to soil, when the modification auxiliary material is near the isoelectric point of protein, the gel is in a shrinkage state, and when the gel deviates from the isoelectric point, the gel can expand or shrink along with the change of the pH of the environment, in the using process, the modification auxiliary material in the system attracts and absorbs a large amount of carbon dioxide, the large amount of carbon dioxide is dissolved in the system, so that the pH around the gel is reduced, amino groups on the gel molecular chains are protonated, the same kind of positive charges are mutually repelled, the gel expands, and in the expansion process, a good soil loosening effect is achieved, the permeability of the soil is improved, and the anti-caking capability of the soil system is enhanced; for example, chinese patent CN2017109844080 discloses a method for producing a soil conditioner for improving soil hardening and reducing salt damage, which comprises cross-linking and polymerizing acrylic acid, acrylamide and ethylene glycol diacrylate to obtain a polymer, loading plant nutrient 6-benzylaminopurine and vitamin B with the polymer as a carrier to obtain a high water-retention resin, and adding the high water-retention resin into the soil conditioner, wherein the high water-retention resin has strong water absorption and release capabilities, and can absorb and release water repeatedly, and the water absorption expansion of the high water-retention resin in soil is a contractile movement, which can improve soil permeability, thereby improving soil structure; above-mentioned technical scheme is all through taking place expansion or shrink in soil, produces the contractility motion to improve the permeability of soil, but this type of soil amendment exists the inhomogeneous phenomenon of distribution in soil, contains the region that the amendment is many in the soil, and soil permeability is big, the region that the amendment content is few, and soil permeability is less relatively, thereby makes the loose degree of soil structure differ, causes crops growth state easily to have the difference.
Disclosure of Invention
The invention aims to solve the existing problems and provides a soil hardening improver capable of improving the consistency of soil loosening degree.
The invention is realized by the following technical scheme:
a soil hardening improver capable of improving the consistency of soil structure loosening degree is specifically prepared by the following steps:
1) the preparation method comprises the steps of uniformly mixing cesium carbonate and titanium dioxide in a mass ratio of 5-5.5:7-7.5, putting the mixture into a crucible, heating the mixture in a muffle furnace at the temperature of 800-900 ℃ for 20-25h, taking out the crucible, cooling the crucible to room temperature, then pouring the mixture in the crucible into hydrochloric acid with the concentration of 1-1.5 mol/L according to the mass-volume ratio of the mixture to the hydrochloric acid of 1:45-55g/ml, continuously stirring the mixture for 10-15h at the speed of 80-150r/min, filtering the mixture, washing the mixture to be neutral by deionized water, drying a product, and then irradiating the product for 70-75h under ultraviolet light with the wavelength of 265nm to obtain pretreated protonic titanium dioxide;
2) adding 10-13 parts of acrylamide, 2-3 parts of butyl acrylate, 8-10 parts of methacryloyloxyethyl trimethyl ammonium chloride and 150 parts of distilled water, adding the mixture into a container, introducing nitrogen, heating to 50-60 ℃, then adding 20-25 parts of deionized water in which 0.05-0.07 part of N, N-methylene bisacrylamide is dissolved, stirring to fully mix the mixture, slowly dropwise adding 30-35 parts of deionized water in which 0.2-0.3 part of potassium persulfate is dissolved, heating to 65-70 ℃, reacting for 8-10h, after the reaction is finished, adding 1-1.5 parts of graphene oxide, continuing to react for 2-3h, filtering and drying the product to obtain pretreated graphene oxide; according to the method, the graphene oxide is pretreated, and an amide group and an ester group are introduced into the graphene oxide, so that a hydrogen bond effect can be generated between the graphene oxide and hydroxyl on the surface of clay existing in a large amount in soil, the graphene oxide can be adhered to the surface of the clay through the hydrogen bond effect to form a strong adhesive force, and the graphene oxide can be fixed in the soil and prevented from losing;
3) uniformly stirring epoxy resin and aniline in a weight ratio of 10:3-5, heating to 110-120 ℃, reacting for 45-50h, cooling to room temperature, purifying to obtain an epoxy resin precursor, adding chitosan into 10-15% by weight of sodium hydroxide solution, stirring for 30-40min at room temperature, adding dichloroethylamine hydrochloride, heating at 70-80 ℃ for reacting for 10-14h, acidifying a product after the reaction is finished, dialyzing for 3-4 days, freeze-drying to obtain a water-soluble chitosan derivative, and then heating to react according to a weight ratio of the epoxy resin precursor, N-dimethylformamide and the water-soluble chitosan derivative of 1:80-100:20-30, dissolving the epoxy resin precursor in N, N-dimethylformamide at room temperature, and adding a water-soluble chitosan derivative after the epoxy resin precursor is completely dissolved to obtain a chitosan modified epoxy resin precursor; according to the invention, chitosan is used for modifying the epoxy resin, so that the epoxy resin has positive charges, and self-assembly of the epoxy resin and the graphene oxide with negative charges is facilitated under the electrostatic action;
4) selecting at least one of PEG1000 and PEG2000 as polyethylene glycol, mixing a chitosan modified epoxy resin precursor, diethylenetriamine and polyethylene glycol in a weight ratio of 3-5:1:6-10 to obtain a clear and transparent viscous liquid, placing the viscous liquid in a constant temperature cabinet, reacting at 60-80 ℃ for 20-24h, cooling to room temperature after the reaction is finished, taking out a product, repeatedly soaking and washing the product by using deionized water until the polyethylene glycol is completely removed, drying the product in vacuum at 55-65 ℃ for 5-8h, and then grinding the product to obtain porous polymer powder with the average particle size of 30-50 um; in the invention, polyethylene glycol is used as a pore-foaming agent to form polymer powder with a porous structure, the polymer powder can take graphene oxide as a connecting junction point under the electrostatic action, the porous network structure of the continuous phase is formed by electrostatic self-assembly, can effectively loosen the soil, plays a role in improving the permeability of the soil, because the formed porous network structure is a continuous phase structure and the sizes of pores are similar, the porous network structure can be interpenetrated in soil and takes the clay adhered with the graphene oxide as a connection point, so that the formed porous network structure can be spread in the whole soil, the loosening degree of the soil can reach high consistency, therefore, the consistency of the soil structure loosening degree can be improved, the difference of the growth states of crops in the soil is reduced, and the improvement of the crop yield and the quality are promoted;
5) mixing 1-2 parts of pretreated proton titanium dioxide, 5-8 parts of pretreated graphene oxide and 50-60 parts of porous polymer powder, adding the mixture into a mixer, adding 4-7 parts of guar gum powder and 260 parts of deionized water, performing dispersion treatment at 60-70 ℃ for 30-50min at 800r/min of 600-plus-materials, filtering the product, spreading the product on a wire mesh of a hot air dryer, drying the product at 80-100 ℃ for 2-3h, and crushing the product into 200-mesh powder of 100-plus-materials by a vibration crusher to obtain the required soil conditioner.
Compared with the prior art, the invention has the following advantages:
according to the conditioner for improving the soil hardening phenomenon, the conditioner powder is mixed with water and then sprayed on the surface of hardened soil, the pretreated graphene oxide and the porous polymer powder in the conditioner powder are subjected to electrostatic self-assembly, the pretreated graphene oxide is used as a connecting and converging point, the porous polymer powder can be mutually and alternately connected in the soil, so that a continuous-phase porous network structure is formed, the formed porous network structure can be distributed in the whole soil, and the formed porous network structure has close pore sizes and smaller difference, so that the soil loosening degree can achieve high consistency, the consistency of the soil loosening degree can be improved, the difference reduction of the growth state of crops in the soil is realized, and the improvement of the crop yield and the quality is promoted.
Detailed Description
The present invention will be further described with reference to specific embodiments.
Example 1
A soil hardening improver capable of improving the consistency of soil structure loosening degree is specifically prepared by the following steps:
1) uniformly mixing cesium carbonate and titanium dioxide in a mass ratio of 5:7, putting the mixture into a crucible, heating the mixture in a muffle furnace at 800 ℃ for 20 hours, taking out the crucible, cooling the crucible to room temperature, then pouring the mixture in the crucible into hydrochloric acid with the concentration of 1 mol/L according to the mass-volume ratio of the mixture to the hydrochloric acid in the crucible of 1:45g/ml, continuously stirring the mixture for 10 hours at 80r/min, washing the mixture to be neutral by deionized water after filtering, drying the product, and irradiating the product for 70 hours under ultraviolet light with the wavelength of 265nm to obtain pretreated protonic titanium dioxide;
2) adding 10 parts of acrylamide, 2 parts of butyl acrylate, 8 parts of methacryloyloxyethyl trimethyl ammonium chloride and 120 parts of distilled water into a container, introducing nitrogen, heating to 50 ℃, adding 20 parts of deionized water in which 0.05 part of N, N-methylene bisacrylamide is dissolved, stirring to fully mix the mixture, slowly dropwise adding 30 parts of deionized water in which 0.2 part of potassium persulfate is dissolved, heating to 65 ℃, reacting for 8 hours, adding 1 part of graphene oxide after the reaction is finished, continuing to react for 2 hours, filtering and drying the product to obtain pretreated graphene oxide;
3) uniformly stirring epoxy resin and aniline in a weight ratio of 10:3, heating to 110 ℃ for reaction for 45h, cooling to room temperature, purifying to obtain an epoxy resin precursor, adding chitosan into a 10% sodium hydroxide solution in a weight ratio of 1:60:0.2 of chitosan, a sodium hydroxide solution and dichloroethylamine hydrochloride, stirring for 30min at room temperature, adding dichloroethylamine hydrochloride, heating for reaction for 10h at 70 ℃, acidifying a product after the reaction is finished, dialyzing for 3 days, freeze-drying to obtain a water-soluble chitosan derivative, dissolving the epoxy resin precursor in N, N-dimethylformamide and the water-soluble chitosan derivative in a weight ratio of 1:80:20 at room temperature, adding the water-soluble chitosan derivative after the epoxy resin precursor and the N, N-dimethylformamide are completely dissolved, obtaining a chitosan modified epoxy resin precursor;
4) selecting PEG1000 as polyethylene glycol for use, mixing a chitosan modified epoxy resin precursor, diethylenetriamine and polyethylene glycol in a weight ratio of 3:1:6 to obtain clear and transparent viscous liquid, placing the viscous liquid in a constant temperature box, reacting at 60 ℃ for 20 hours, cooling to room temperature after the reaction is finished, taking out a product, repeatedly soaking and washing the product by using deionized water until the polyethylene glycol is completely removed, drying the product in vacuum at 55 ℃ for 5 hours, and then grinding the product to obtain porous polymer powder with the average particle size of 30 microns;
5) mixing 1 part of pretreated proton titanium dioxide, 5 parts of pretreated graphene oxide and 50 parts of porous polymer powder, adding the mixture into a mixer, adding 4 parts of guar gum powder and 200 parts of deionized water, dispersing at 60 ℃ for 30min at 600r/min, filtering the product, spreading the product on a wire mesh of a hot air dryer, drying at 80 ℃ for 2h, and crushing the product into 200-mesh powder by a vibration crusher to obtain the required soil conditioner.
Example 2
A soil hardening improver capable of improving the consistency of soil structure loosening degree is specifically prepared by the following steps:
1) uniformly mixing cesium carbonate and titanium dioxide in a mass ratio of 5.2:7.3, putting the mixture into a crucible, heating the mixture in a muffle furnace at 850 ℃ for 23 hours, taking out the crucible, cooling the crucible to room temperature, then pouring the mixture in the crucible into hydrochloric acid with the concentration of 1.2 mol/L according to the mass-volume ratio of the mixture to the hydrochloric acid in the crucible of 1:50g/ml, continuously stirring the mixture for 12 hours at 120r/min, washing the mixture to be neutral by deionized water after filtering, drying the product, and irradiating the product for 73 hours under ultraviolet light with the wavelength of 265nm to obtain pretreated protonic titanium dioxide;
2) adding 11 parts of acrylamide, 2.5 parts of butyl acrylate, 9 parts of methacryloyloxyethyl trimethyl ammonium chloride and 130 parts of distilled water into a container, introducing nitrogen, heating to 55 ℃, adding 22 parts of deionized water in which 0.06 part of N, N-methylene bisacrylamide is dissolved, stirring to fully mix the mixture, slowly dropwise adding 32 parts of deionized water in which 0.25 part of potassium persulfate is dissolved, heating to 68 ℃, reacting for 9 hours, adding 1.2 parts of graphene oxide after the reaction is finished, continuing to react for 2-3 hours, filtering and drying the product to obtain pretreated graphene oxide;
3) uniformly stirring epoxy resin and aniline in a weight ratio of 10:4, heating to 115 ℃ for reaction for 47h, cooling to room temperature, purifying to obtain an epoxy resin precursor, adding chitosan into a sodium hydroxide solution with the mass percentage of 12% according to the weight ratio of the chitosan to the sodium hydroxide solution to the dichloroethylamine hydrochloride of 1:65:0.25, stirring for 35min at room temperature, adding dichloroethylamine hydrochloride, heating to react for 12h at 75 ℃, acidifying a product after the reaction is finished, dialyzing for 3 days, freeze-drying to obtain a water-soluble chitosan derivative, dissolving the epoxy resin precursor in N, N-dimethylformamide and the water-soluble chitosan derivative according to the weight ratio of the epoxy resin precursor to the N, N-dimethylformamide to the water-soluble chitosan derivative of 1:90:25 at room temperature, adding the water-soluble chitosan derivative after the epoxy resin precursor and the N, N-dimethylformamide are completely dissolved, obtaining a chitosan modified epoxy resin precursor; (ii) a
4) Selecting PEG1000 as polyethylene glycol, mixing a chitosan modified epoxy resin precursor, diethylenetriamine and polyethylene glycol in a weight ratio of 4:1:9 to obtain clear and transparent viscous liquid, placing the viscous liquid in a constant temperature box, reacting at 70 ℃ for 23h, cooling to room temperature after the reaction is finished, taking out a product, repeatedly soaking and washing the product by using deionized water until the polyethylene glycol is completely removed, drying the product in vacuum at 60 ℃ for 7h, and then grinding the product to obtain porous polymer powder with the average particle size of 40 um;
5) mixing 1.5 parts of pretreated proton titanium dioxide, 6 parts of pretreated graphene oxide and 55 parts of porous polymer powder, adding the mixture into a mixer, adding 5 parts of guar gum powder and 240 parts of deionized water, dispersing at 65 ℃ for 40min at 700r/min, filtering the product, spreading the product on a wire mesh of a hot air dryer, drying at 90 ℃ for 2.5h, and crushing the product into 150-mesh powder by a vibration crusher to obtain the required soil conditioner.
Example 3
A soil hardening improver capable of improving the consistency of soil structure loosening degree is specifically prepared by the following steps:
1) uniformly mixing cesium carbonate and titanium dioxide in a mass ratio of 5.5:7.5, putting the mixture into a crucible, heating the mixture in a muffle furnace at 900 ℃ for 25 hours, taking out the crucible, cooling the crucible to room temperature, then pouring the mixture in the crucible into hydrochloric acid with the concentration of 1.5 mol/L according to the mass-volume ratio of the mixture to the hydrochloric acid in the crucible of 1:55g/ml, continuously stirring the mixture for 15 hours at the speed of 150r/min, washing the mixture to be neutral by deionized water after filtering, drying the product, and irradiating the product for 75 hours under ultraviolet light with the wavelength of 265nm to obtain pretreated protonic titanium dioxide;
2) adding 13 parts of acrylamide, 3 parts of butyl acrylate, 10 parts of methacryloyloxyethyl trimethyl ammonium chloride and 150 parts of distilled water into a container, introducing nitrogen, heating to 60 ℃, adding 25 parts of deionized water in which 0.07 part of N, N-methylene bisacrylamide is dissolved, stirring to fully mix the mixture, slowly dropwise adding 35 parts of deionized water in which 0.3 part of potassium persulfate is dissolved, heating to 70 ℃, reacting for 10 hours, adding 1.5 parts of graphene oxide after the reaction is finished, continuing to react for 3 hours, filtering and drying the product to obtain pretreated graphene oxide;
3) uniformly stirring epoxy resin and aniline in a weight ratio of 10:5, heating to 120 ℃ for reaction for 50h, cooling to room temperature, purifying to obtain an epoxy resin precursor, adding chitosan into a sodium hydroxide solution with the mass percentage of 15% according to the weight ratio of the chitosan to the sodium hydroxide solution to the dichloroethylamine hydrochloride of 1:70:0.3, stirring for 40min at room temperature, adding dichloroethylamine hydrochloride, heating for reaction for 14h at 80 ℃, acidifying a product after the reaction is finished, dialyzing for 4 days, freeze-drying to obtain a water-soluble chitosan derivative, dissolving the epoxy resin precursor in N, N-dimethylformamide and the water-soluble chitosan derivative according to the weight ratio of the epoxy resin precursor to the N, N-dimethylformamide to the water-soluble chitosan derivative of 1:100:30 at room temperature, adding the water-soluble chitosan derivative after the epoxy resin precursor and the N, N-dimethylformamide are completely dissolved, obtaining a chitosan modified epoxy resin precursor;
4) selecting PEG2000 as polyethylene glycol, mixing a chitosan modified epoxy resin precursor, diethylenetriamine and polyethylene glycol according to a weight ratio of 5:1:10 to obtain a clear and transparent viscous liquid, placing the viscous liquid in a constant temperature box, reacting at 80 ℃ for 24 hours, cooling to room temperature after the reaction is finished, taking out a product, repeatedly soaking and washing the product by using deionized water until the polyethylene glycol is completely removed, drying the product in vacuum at 65 ℃ for 8 hours, and then grinding the product to obtain porous polymer powder with the average particle size of 50 um;
5) mixing 2 parts of pretreated proton titanium dioxide, 8 parts of pretreated graphene oxide and 60 parts of porous polymer powder, adding the mixture into a mixer, adding 7 parts of guar gum powder and 260 parts of deionized water, performing dispersion treatment at 70 ℃ at 800r/min for 50min, filtering the product, spreading the product on a wire mesh of a hot air dryer, drying the product at 100 ℃ for 3h, and crushing the product into 100-mesh powder by a vibration crusher to obtain the required soil conditioner.
Comparative example 1 the soil conditioner provided in the specific example of Chinese patent CN2017109844080 is adopted.
Comparative example 2 the soil conditioner provided in example 1 of chinese patent CN201910508160X was used.
The test method comprises the following steps:
selecting hardened soil with the area of 2 mu as a test site, evenly dividing the test soil into 4 areas, setting the areas as an area A, an area B, an area C and an area D, adding water into the soil conditioner provided by the embodiment 1, the comparative example 1 and the comparative example 2 according to the mass ratio of 1:200, and then adding 0.3kg/m2The amount of the composition is respectively sprayed in A, B, C area, zone D is not treated, and then the test is performed dailyThe soil surface in region sprays clear water, and soil surface is moist and soft can, so maintenance 20 days, then divide into 20 little regions respectively A, B, C, D regional subdividing, from every little region at random 20 soil samples of chooseing carry out the test of porosity, after the examination of awaiting measuring to accomplish completely, make statistics of the test result, the test result is found: the porosity of the soil sample selected in the area A is changed between 58.2 and 58.7 percent, and the ratio of the capillary porosity to the non-capillary porosity is 1.3 to 1.5 times; the porosity of the soil sample selected in the area B is changed between 45.3 and 53.7 percent, and the ratio of the capillary porosity to the non-capillary porosity is between 2.8 and 3.2 times; the porosity of the soil sample selected in the C area is changed between 48.2 and 55.9 percent, and the ratio of the capillary porosity to the non-capillary porosity is 2.1 to 2.4 times; and the porosity of the soil sample selected in the D area is changed between 40.3 percent and 45.6 percent, and the ratio of the capillary porosity to the non-capillary porosity is 9.2 to 12.7 times.
According to the test results, the soil conditioner provided by the comparative example 1 and the soil conditioner provided by the comparative example 2 can effectively improve the permeability of the soil, but the difference of the permeability of the soil in different areas is larger, and the soil after being improved mainly comprises capillary pores.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention.
Claims (10)
1. A soil hardening improver capable of improving the consistency of soil structure loosening degree is characterized by comprising the following specific preparation methods:
1) uniformly mixing a certain amount of cesium carbonate and titanium dioxide, placing the mixture into a crucible, heating the mixture in a muffle furnace at 900 ℃ for 20-25h, taking out the crucible, cooling the crucible to room temperature, pouring the mixture in the crucible into hydrochloric acid with the concentration of 1-1.5 mol/L, continuously stirring the mixture for 10-15h, washing the mixture to be neutral by deionized water after filtering, drying the product, and irradiating the product for 70-75h under ultraviolet light with the wavelength of 265nm to obtain pretreated protonic titanium dioxide;
2) adding a certain amount of acrylamide, butyl acrylate, methacryloxyethyl trimethyl ammonium chloride and distilled water into a container, introducing nitrogen, heating to 50-60 ℃, adding N, N-methylene bisacrylamide dissolved in deionized water, stirring to fully mix the N, N-methylene bisacrylamide, slowly dropwise adding a small amount of potassium persulfate dissolved in deionized water, heating to 65-70 ℃, reacting for 8-10 hours, adding a proper amount of graphene oxide after the reaction is finished, continuing to react for 2-3 hours, filtering the product, and drying to obtain pretreated graphene oxide;
3) uniformly stirring a certain amount of epoxy resin and aniline, heating to 110-120 ℃ for reaction for 45-50h, cooling to room temperature, purifying to obtain an epoxy resin precursor, adding a certain amount of chitosan into a sodium hydroxide solution, stirring at room temperature for 30-40min, adding a small amount of dichloroethylamine hydrochloride for heating reaction, acidifying a product after the reaction is finished, dialyzing for 3-4 days, freeze-drying to obtain a water-soluble chitosan derivative, dissolving the epoxy resin precursor in N, N-dimethylformamide at room temperature, and adding a proper amount of water-soluble chitosan derivative after the epoxy resin precursor is completely dissolved to obtain a chitosan modified epoxy resin precursor;
4) mixing a chitosan modified epoxy resin precursor, diethylenetriamine and polyethylene glycol according to a certain proportion to obtain clear and transparent viscous liquid, placing the viscous liquid in a constant temperature box, reacting for 20-24h at 60-80 ℃, cooling to room temperature after the reaction is finished, taking out a product, repeatedly soaking and washing the product by using deionized water until the polyethylene glycol is completely removed, and grinding the product after vacuum drying to obtain porous polymer powder;
5) mixing the pretreated proton titanium dioxide, the pretreated graphene oxide and the porous polymer powder according to a certain mass ratio, adding the mixture into a mixer, adding a proper amount of guar gum powder and deionized water, performing dispersion treatment at the temperature of 60-70 ℃ at 800r/min for 30-50min, filtering the product, spreading the product on a wire mesh of a hot air dryer, drying the product at the temperature of 80-100 ℃ for 2-3h, and crushing the product into 100-mesh powder with 200 meshes by a vibration crusher to obtain the required soil conditioner.
2. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 1), the mass ratio of the cesium carbonate to the titanium dioxide is 5-5.5: 7-7.5; the mass volume ratio of the mixture to the hydrochloric acid in the crucible is 1:45-55 g/ml.
3. The soil hardening improver for improving the consistency of the soil structure loosening degree according to claim 1, wherein the rotation speed of the continuous stirring in the step 1) is 80-150 r/min.
4. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 2), the weight parts of the raw materials are as follows: 10-13 parts of acrylamide, 2-3 parts of butyl acrylate, 8-10 parts of methacryloyloxyethyl trimethyl ammonium chloride, 150 parts of distilled water, 20-25 parts of deionized water for dissolving N, N-methylene bisacrylamide, 30-35 parts of deionized water for dissolving potassium persulfate, and 1-1.5 parts of graphene oxide.
5. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 2), the deionized water in which the N, N-methylene bisacrylamide is dissolved contains 0.05 to 0.07 part of the N, N-methylene bisacrylamide; the deionized water for dissolving the potassium persulfate contains 0.2-0.3 part of potassium persulfate.
6. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 3), the weight ratio of the epoxy resin to the aniline is 10: 3-5; the weight ratio of the chitosan to the sodium hydroxide solution to the dichloroethylamine hydrochloride is 1:60-70:0.2-0.3, wherein the mass percent of the sodium hydroxide solution is 10-15%; the weight ratio of the epoxy resin precursor to the N, N-dimethylformamide to the water-soluble chitosan derivative is 1:80-100: 20-30.
7. The soil hardening improver for improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 3), the heating reaction is carried out at 70-80 ℃ for 10-14 h.
8. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 4), the weight ratio of the chitosan modified epoxy resin precursor to diethylenetriamine to polyethylene glycol is 3-5:1: 6-10; the polyethylene glycol is at least one of PEG1000 and PEG 2000.
9. The soil hardening improver capable of improving the consistency of the soil structure loosening degree according to claim 1, wherein in the step 4), the vacuum drying temperature is 55-65 ℃, and the drying time is 5-8 h;
the average particle size of the grinding is 30-50 um.
10. The soil hardening improver capable of improving the consistency of the soil structure loosening degree as claimed in claim 1, wherein in the step 5), the raw materials comprise 1-2 parts of pretreated protonic titanium dioxide, 5-8 parts of pretreated graphene oxide, 50-60 parts of porous polymer powder, 4-7 parts of guar gum powder and 200-260 parts of deionized water.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112970366A (en) * | 2021-02-03 | 2021-06-18 | 刘韧 | Photothermal softening treatment method for caked soil |
| CN114711101A (en) * | 2022-04-08 | 2022-07-08 | 凯盛浩丰农业有限公司 | Application of water-retaining agent for vegetable transplantation in vegetable transplantation |
| CN114766317A (en) * | 2022-05-06 | 2022-07-22 | 甘肃农业大学 | Composition for covering soil, covering soil and preparation method thereof |
| CN115322789A (en) * | 2022-07-11 | 2022-11-11 | 杭州临安灵丰农业科技有限公司 | Soil conditioner for preventing and treating soil hardening and preparation method thereof |
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2020
- 2020-04-28 CN CN202010347070.XA patent/CN111454728A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112970366A (en) * | 2021-02-03 | 2021-06-18 | 刘韧 | Photothermal softening treatment method for caked soil |
| CN114711101A (en) * | 2022-04-08 | 2022-07-08 | 凯盛浩丰农业有限公司 | Application of water-retaining agent for vegetable transplantation in vegetable transplantation |
| CN114766317A (en) * | 2022-05-06 | 2022-07-22 | 甘肃农业大学 | Composition for covering soil, covering soil and preparation method thereof |
| CN114766317B (en) * | 2022-05-06 | 2023-05-26 | 甘肃农业大学 | Composition for coated soil, coated soil and preparation method of coated soil |
| CN115322789A (en) * | 2022-07-11 | 2022-11-11 | 杭州临安灵丰农业科技有限公司 | Soil conditioner for preventing and treating soil hardening and preparation method thereof |
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