CN109097063B - Soil remediation agent and preparation method thereof - Google Patents
Soil remediation agent and preparation method thereof Download PDFInfo
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- CN109097063B CN109097063B CN201811111527.6A CN201811111527A CN109097063B CN 109097063 B CN109097063 B CN 109097063B CN 201811111527 A CN201811111527 A CN 201811111527A CN 109097063 B CN109097063 B CN 109097063B
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- 239000002689 soil Substances 0.000 title claims abstract description 90
- 238000005067 remediation Methods 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 241000195474 Sargassum Species 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000004927 clay Substances 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000003895 organic fertilizer Substances 0.000 claims abstract description 26
- 230000000813 microbial effect Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 109
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 96
- 239000000203 mixture Substances 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 49
- 238000000967 suction filtration Methods 0.000 claims description 42
- 238000001291 vacuum drying Methods 0.000 claims description 42
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 37
- 235000019441 ethanol Nutrition 0.000 claims description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 241000894006 Bacteria Species 0.000 claims description 22
- 229920000858 Cyclodextrin Polymers 0.000 claims description 20
- 239000001116 FEMA 4028 Substances 0.000 claims description 20
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 20
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 20
- 229960004853 betadex Drugs 0.000 claims description 20
- 239000004698 Polyethylene Substances 0.000 claims description 18
- 229920000573 polyethylene Polymers 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 10
- UJIQFNIGENNTDY-UHFFFAOYSA-N (3-chloro-2-oxopropyl) diethyl phosphate Chemical compound P(=O)(OCC)(OCC)OCC(CCl)=O UJIQFNIGENNTDY-UHFFFAOYSA-N 0.000 claims description 9
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 9
- 229960002089 ferrous chloride Drugs 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 244000063299 Bacillus subtilis Species 0.000 claims description 7
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000000243 photosynthetic effect Effects 0.000 claims description 7
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 description 12
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 241000282414 Homo sapiens Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000035558 fertility Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003802 soil pollutant Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Soil Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Mycology (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a soil remediation agent, which consists of the following raw materials in parts by weight: the composite organic fertilizer modified Ti-Fe-B-O20-30 parts, the polyaspartic acid potassium 5-10 parts, the composite microbial agent 0.5-1 part, the modified sargassum powder 10-15 parts and the modified activated clay 5-10 parts. The invention also discloses a preparation method of the soil remediation agent. The soil remediation agent disclosed by the invention is simple to prepare, low in cost, safe and environment-friendly to use, good in soil remediation effect, high in remediation efficiency and small in usage amount.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a soil remediation agent and a preparation method thereof.
Background
Soil is one of the main natural resources on which human beings rely for survival, and is also an important component of the human ecological environment. In recent years, with the development of modern industrialization and urbanization, the problem of soil pollution is increasingly prominent, and the pollution area is continuously enlarged. As a basic material foundation of human social production activities, once soil is polluted, the soil can cause adverse effects on human survival. Therefore, the development of efficient, environmentally friendly and economical soil remediation techniques has become an urgent task in the field of soil remediation.
Soil pollutants mainly include organic compounds and heavy metals. The organic compounds can reduce or eliminate harmfulness through self physical, chemical or biological purification in nature; heavy metals are rich and difficult to degrade in the environment, are concentrated by thousands of times under the action of biological amplification of a food chain, enter a human body, are difficult to naturally discharge or completely remove, and are generally irreversible in life. Therefore, the remediation of heavy metal pollution in soil is far from the heavy task.
The physical and chemical methods in the conventional heavy metal contaminated soil remediation method have direct and quick effect, but have poor persistence and high treatment cost, and if the method is not used properly, the remediation effect cannot be achieved, but new pollution can be caused. The microbial technology and organic matter treatment are adopted, so that the effects of safety, lasting effect and comprehensiveness can be achieved, but the general repairing agent only has a single function, has no insect prevention, bacterium prevention and fertility increasing effects, and has little improvement on the structure of soil.
Therefore, the development of a novel soil remediation technology which is low in cost, simple, convenient, efficient and environment-friendly is of great significance.
Disclosure of Invention
The invention aims to solve the problems and provides a soil remediation agent which is simple to prepare, low in cost, safe and environment-friendly to use and good in soil remediation effect, and a preparation method of the soil remediation agent.
In order to achieve the purpose, the invention adopts the technical scheme that:
a soil remediation agent comprises the following raw materials in parts by weight: the composite organic fertilizer modified Ti-Fe-B-O20-30 parts, the polyaspartic acid potassium 5-10 parts, the composite microbial agent 0.5-1 part, the modified sargassum powder 10-15 parts and the modified activated clay 5-10 parts.
Preferably, the compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
Preferably, the preparation method of the modified sargassum powder comprises the following steps:
i, dispersing sargassum powder in an organic solvent, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the organic solvent, stirring the mixture at the temperature of 50-70 ℃ to react for 5-7 hours, then carrying out suction filtration, washing the mixture for 3-6 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 10-15 hours at the temperature of 80-90 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
and II, adding the gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder prepared in the step I, mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and an alkaline catalyst into N, N-dimethylformamide, stirring and reacting for 8-10 hours at the temperature of 80-90 ℃, then performing suction filtration, washing for 3-5 times with water, and then placing in a vacuum drying box for drying at the temperature of 100 ℃ and 110 ℃ to constant weight to obtain the modified sargassum powder.
Preferably, the mass ratio of the sargassum powder, the organic solvent and the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane in the step I is (3-5): (10-15): 1.
Preferably, the organic solvent is selected from one or more of ethanol, acetonitrile, acetone and chloroform.
Preferably, in the step II, the mass ratio of the gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder to the mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin to the basic catalyst to the N, N-dimethylformamide is 1:1 (0.3-0.5) to (10-15).
Preferably, the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the preparation method of the modified activated clay comprises the following steps:
step D1: dispersing activated clay into acetonitrile, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of between 50 and 70 ℃ for reaction for 5 to 7 hours, then carrying out suction filtration, washing the mixture for 3 to 6 times by using ethanol, and then placing the mixture in a vacuum drying oven for drying the mixture for 10 to 15 hours at the temperature of between 80 and 90 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: and (2) adding the gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane modified activated clay prepared in the step (I), mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and sodium carbonate into N, N-dimethylformamide, stirring and reacting for 8-10 hours at the temperature of 80-90 ℃, then carrying out suction filtration, washing for 3-5 times by using water, and then placing in a vacuum drying oven for drying at the temperature of 100 ℃ and 110 ℃ to constant weight to obtain the modified activated clay.
Preferably, the mass ratio of the activated clay to the acetonitrile to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane in the step D1 is (3-5): (10-15): 1.
Preferably, the mass ratio of the gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, the mono (6-polyethylene polyamine-6-deoxidation) betacyclodextrin, the sodium carbonate and the N, N-dimethylformamide in the step D2 is 1:1 (0.3-0.5) to (10-15).
Preferably, the preparation method of the Ti-Fe-B-O modified by the compound organic fertilizer comprises the following steps:
step S1: adding titanium tetrachloride, ferrous chloride and sodium borate into a beaker filled with ethanol, stirring for 2-3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15-18 hours at the temperature of 180-; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3-5 times after the reaction system is cooled, finally drying in a vacuum drying oven at the temperature of 100-110 ℃ for 18-22 hours, cooling to room temperature, grinding, and sieving with a 200-400-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing the Ti-Fe-B-O prepared in the step S1 in acetonitrile, adding bis [3- (triethoxysilyl) propyl ] amine into the acetonitrile, stirring the mixture at the temperature of between 50 and 70 ℃ for reaction for 5 to 7 hours, then carrying out suction filtration, washing the reaction product with ethanol, and drying the reaction product to obtain modified Ti-Fe-B-O;
step S3: dispersing the modified Ti-Fe-B-O prepared in the step S2 in dimethyl sulfoxide, adding diethyl (3-chloro-2-oxopropyl) phosphate into the solution, stirring the solution at 40-60 ℃ for reaction for 6-8 hours, and performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (4) soaking the surface ionized Ti-Fe-B-O prepared in the step (S3) in 10-20% by mass of diethylenetriamine pentamethylene phosphonic acid at 50-60 ℃ for 18-24 hours, then carrying out suction filtration, washing with water for 3-5 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the composite organic fertilizer.
Preferably, the mass ratio of the titanium tetrachloride, the ferrous chloride, the sodium borate and the ethanol in the step S1 is 2:0.5:0.02 (20-30).
Preferably, the mass ratio of the Ti-Fe-B-O, the acetonitrile and the bis [3- (triethoxysilyl) propyl ] amine in the step S2 is 1 (5-10): 0.5.
Preferably, the mass ratio of the modified Ti-Fe-B-O, the dimethyl sulfoxide and the diethyl (3-chloro-2-oxopropyl) phosphate in the step S3 is 1 (5-10): 1.
Preferably, the mass ratio of the surface ionized Ti-Fe-B-O to the diethylenetriamine pentamethylene phosphonic acid in the step S4 is 1 (20-30).
Preferably, the preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 200-mesh and 300-mesh sieve to obtain the soil remediation agent.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the soil remediation agent provided by the invention has the advantages of simple and feasible preparation method, easily available raw materials, low preparation cost and suitability for large-scale production.
2) The soil remediation agent provided by the invention overcomes the technical problems of poor remediation effect, low remediation efficiency, large dosage, high cost and easy secondary pollution caused by the traditional soil remediation agent, and has the advantages of simple preparation, low cost, safe and environment-friendly use, small dosage and good soil remediation effect.
3) According to the soil remediation agent provided by the invention, the Ti-Fe-B-O is modified by adding the compound organic fertilizer, on one hand, the Ti-Fe-B-O has an excellent effect of degrading soil organic matters through photocatalysis, and in addition, the compound organic fertilizer is introduced, so that the soil fertility and nutrition can be effectively improved, and the soil remediation agent has an improvement effect on soil; secondly, iron is introduced through modification, so that ferrite is formed, heavy metals in soil are adsorbed and fixed, and meanwhile, through ion exchange, a diethylenetriamine pentamethylenephosphonic acid structure and more amino and carboxyl structures are introduced, so that the complexing and fixing capacity of the heavy metals is improved; in addition, the composite biological agent is added, and the organic fertilizer and the added potassium polyaspartate are used for reducing heavy metal ions, so that the soil remediation effect is achieved.
4) The soil remediation agent provided by the invention has synergistic effect of the components, not only can reduce the toxicity of soil, but also can complex and fix heavy metal ions in the soil, reduce the biological activity of the soil remediation agent and reduce the hazard of the soil remediation agent. The soil remediation effect and efficiency are obviously improved, the self-degradable components of the potassium polyaspartate, the sargassum powder and the mono (6-polyethylene polyamine-6-deoxygenized) beta-cyclodextrin are provided, secondary pollution is avoided, the soil can be loosened, the soil is prevented from hardening, and the soil fertility is improved.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Mono (6-polyethylenepolyamine-6-deoxy) betacyclodextrin used in the following examples of the present invention was obtained from Zhiyuan Biotech Co., Ltd, Bin, Shandong, and other materials were obtained from Shanghai spring Xin import and export trade Co., Ltd.
Example 1
A soil remediation agent comprises the following raw materials in parts by weight: 20 parts of composite organic fertilizer modified Ti-Fe-B-O, 5 parts of polyaspartic acid potassium, 0.5 part of composite microbial agent, 10 parts of modified sargassum powder and 5 parts of modified activated clay.
The compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
The preparation method of the modified sargassum powder comprises the following steps:
dispersing 30g of sargassum powder into 100g of ethanol, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the mixture, stirring the mixture to react for 5 hours at the temperature of 50 ℃, then performing suction filtration, washing the mixture for 3 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 10 hours at the temperature of 80 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
and II, adding 10g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 3g of sodium hydroxide which are prepared in the step I into 100g of N, N-dimethylformamide, stirring and reacting for 8 hours at 80 ℃, then carrying out suction filtration, washing for 3 times by using water, and then placing in a vacuum drying oven to dry to constant weight at 100 ℃ to obtain the modified sargassum powder.
The preparation method of the modified activated clay comprises the following steps:
step D1: dispersing 30g of activated clay into 100g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of 50 ℃ to react for 5 hours, then performing suction filtration, washing the mixture for 3 times by using ethanol, and then placing the mixture in a vacuum drying oven to be dried for 10 hours at the temperature of 80 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 3g of sodium carbonate which are prepared in the step I into 100g of N, N-dimethylformamide, stirring and reacting for 8 hours at 80 ℃, then carrying out suction filtration, washing for 3 times by using water, and then placing in a vacuum drying oven to dry to constant weight at 100 ℃ to obtain the modified activated clay.
The preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding 20g of titanium tetrachloride, 5g of ferrous chloride and 0.2g of sodium borate into a beaker filled with 200g of ethanol, stirring for 2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15 hours at 180 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3 times after the reaction system is cooled, finally drying in a vacuum drying oven at 100 ℃ for 18 hours, cooling to room temperature, grinding, and sieving with a 200-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing 10g of Ti-Fe-B-O prepared in the step S1 in 50g of acetonitrile, adding 5g of bis [3- (triethoxysilyl) propyl ] amine, stirring at 50 ℃ for reaction for 5 hours, performing suction filtration, washing with ethanol, and drying to obtain modified Ti-Fe-B-O;
step S3: dispersing 10g of modified Ti-Fe-B-O prepared in the step S2 in 50g of dimethyl sulfoxide, adding 10g of (3-chloro-2-oxopropyl) diethyl phosphate, stirring and reacting at 40 ℃ for 6 hours, and then performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (3) soaking 10g of the surface ionized Ti-Fe-B-O prepared in the step (S3) in 200g of 10 mass percent diethylenetriamine pentamethylene phosphonic acid at 50 ℃ for 18 hours, then carrying out suction filtration, washing with water for 3 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the composite organic fertilizer.
The preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 200-mesh sieve to obtain the soil remediation agent.
Example 2
A soil remediation agent comprises the following raw materials in parts by weight: 23 parts of composite organic fertilizer modified Ti-Fe-B-O, 6 parts of polyaspartic acid potassium, 0.7 part of composite microbial agent, 12 parts of modified sargassum powder and 6 parts of modified activated clay.
The compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
The preparation method of the modified sargassum powder comprises the following steps:
i, dispersing 35g of sargassum powder in 115g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of 55 ℃ to react for 5.5 hours, then carrying out suction filtration, washing the mixture for 4 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 11 hours at the temperature of 83 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
II, adding 10g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 3.5g of potassium hydroxide which are prepared in the step I into 115g of N, N-dimethylformamide, stirring and reacting for 8.5 hours at 83 ℃, then carrying out suction filtration, washing with water for 4 times, and then placing in a vacuum drying oven for drying at 103 ℃ to constant weight to obtain the modified sargassum powder.
The preparation method of the modified activated clay comprises the following steps:
step D1: dispersing 35g of activated clay into 115g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of 55 ℃ to react for 5.5 hours, then performing suction filtration, washing the mixture for 4 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 11 hours at the temperature of 83 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay prepared in the step I, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 3.5g of sodium carbonate into 115g of N, N-dimethylformamide, stirring and reacting for 8.5 hours at 83 ℃, then carrying out suction filtration, washing with water for 4 times, and then placing in a vacuum drying oven to dry at 103 ℃ to constant weight to obtain the modified activated clay.
The preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding 20g of titanium tetrachloride, 5g of ferrous chloride and 0.2g of sodium borate into a beaker filled with 230g of ethanol, stirring for 2.3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 16 hours at 185 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 4 times after the reaction system is cooled, finally drying in a vacuum drying oven at 103 ℃ for 19 hours, cooling to room temperature, grinding, and sieving with a 250-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing 10g of Ti-Fe-B-O prepared in the step S1 in 65g of acetonitrile, adding 5g of bis [3- (triethoxysilyl) propyl ] amine, stirring and reacting at 55 ℃ for 5.5 hours, performing suction filtration, washing with ethanol, and drying to obtain modified Ti-Fe-B-O;
step S3: dispersing 10g of modified Ti-Fe-B-O prepared in the step S2 in 65g of dimethyl sulfoxide, adding 10g of (3-chloro-2-oxopropyl) diethyl phosphate, stirring and reacting at 45 ℃ for 6.5 hours, and then performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (4) soaking 10g of the surface ionized Ti-Fe-B-O prepared in the step (S3) in 235g of diethylenetriamine pentamethylene phosphonic acid with the mass fraction of 13% at 53 ℃ for 20 hours, then carrying out suction filtration, washing with water for 4 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the composite organic fertilizer.
The preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 230-mesh sieve to obtain the soil remediation agent.
Example 3
A soil remediation agent comprises the following raw materials in parts by weight: 25 parts of composite organic fertilizer modified Ti-Fe-B-O, 7 parts of polyaspartic acid potassium, 0.8 part of composite microbial agent, 13 parts of modified sargassum powder and 7 parts of modified activated clay.
The compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
The preparation method of the modified sargassum powder comprises the following steps:
i, dispersing 40g of sargassum powder in 130g of acetone, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetone, stirring the mixture at the temperature of 60 ℃ to react for 6 hours, then carrying out suction filtration, washing the mixture for 5 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 12 hours at the temperature of 85 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
II, adding 10g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 4g of sodium carbonate which are prepared in the step I into 130g of N, N-dimethylformamide, stirring and reacting for 9 hours at 86 ℃, then carrying out suction filtration, washing with water for 4 times, and then placing in a vacuum drying oven to dry at 105 ℃ to constant weight to obtain the modified sargassum powder.
The preparation method of the modified activated clay comprises the following steps:
step D1: dispersing 40g of activated clay into 130g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of 60 ℃ to react for 6 hours, then performing suction filtration, washing the mixture for 5 times by using ethanol, and then placing the mixture in a vacuum drying oven to be dried for 12 hours at the temperature of 85 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 4g of sodium carbonate which are prepared in the step I into 130g of N, N-dimethylformamide, stirring and reacting for 9 hours at 86 ℃, then carrying out suction filtration, washing for 4 times with water, and then placing in a vacuum drying oven for drying at 105 ℃ to constant weight to obtain the modified activated clay.
The preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding 20g of titanium tetrachloride, 5g of ferrous chloride and 0.2g of sodium borate into a beaker filled with 270g of ethanol, stirring for 2.6 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 16.5 hours at 190 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 5 times after the reaction system is cooled, finally drying in a vacuum drying oven at 106 ℃ for 20 hours, cooling to room temperature, grinding, and sieving with a 300-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing 10g of Ti-Fe-B-O prepared in the step S1 in 85g of acetonitrile, adding 5g of bis [3- (triethoxysilyl) propyl ] amine, stirring and reacting at 60 ℃ for 6 hours, performing suction filtration, washing with ethanol, and drying to obtain modified Ti-Fe-B-O;
step S3: dispersing 10g of modified Ti-Fe-B-O prepared in the step S2 in 85g of dimethyl sulfoxide, adding 10g of (3-chloro-2-oxopropyl) diethyl phosphate, stirring at 50 ℃ for reaction for 7 hours, and then performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (4) soaking 10g of the surface ionized Ti-Fe-B-O prepared in the step (S3) in 270g of diethylenetriamine pentamethylenephosphonic acid with the mass fraction of 16% at 56 ℃ for 22 hours, then carrying out suction filtration, washing for 5 times with water, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the composite organic fertilizer.
The preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 260-mesh sieve to obtain the soil remediation agent.
Example 4
A soil remediation agent comprises the following raw materials in parts by weight: 28 parts of composite organic fertilizer modified Ti-Fe-B-O, 9 parts of polyaspartic acid potassium, 0.9 part of composite microbial agent, 14 parts of modified sargassum powder and 9 parts of modified activated clay.
The compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
The preparation method of the modified sargassum powder comprises the following steps:
i, dispersing 45g of sargassum powder in 140g of an organic solvent, adding 10g of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane into the organic solvent, stirring the mixture to react for 6.5 hours at 65 ℃, then performing suction filtration, washing the mixture for 5 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 14 hours at 88 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane modified sargassum powder; the organic solvent is a mixture formed by mixing ethanol, acetonitrile, acetone and chloroform according to the mass ratio of 2:1:3: 2;
II, adding 10g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder prepared in the step I, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 4.5g of sodium carbonate into 140g of N, N-dimethylformamide, stirring and reacting for 9.5 hours at 88 ℃, then carrying out suction filtration, washing with water for 5 times, and drying in a vacuum drying oven at 108 ℃ to constant weight to obtain the modified sargassum powder.
The preparation method of the modified activated clay comprises the following steps:
step D1: dispersing 45g of activated clay into 145g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of 65 ℃ to react for 6.5 hours, then performing suction filtration, washing the mixture for 5 times by using ethanol, and then placing the mixture in a vacuum drying oven to be dried for 14 hours at the temperature of 88 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay prepared in the step I, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 4.5g of sodium carbonate into 143g of N, N-dimethylformamide, stirring and reacting for 9.5 hours at 89 ℃, then carrying out suction filtration, washing for 5 times by using water, and then placing in a vacuum drying oven to dry at 108 ℃ to constant weight to obtain the modified activated clay.
The preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding 20g of titanium tetrachloride, 5g of ferrous chloride and 0.2g of sodium borate into a beaker filled with 285g of ethanol, stirring for 2.8 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 17 hours at 195 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 5 times after the reaction system is cooled, finally drying in a vacuum drying oven at 108 ℃ for 21 hours, cooling to room temperature, grinding, and sieving with a 350-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing 10g of Ti-Fe-B-O prepared in the step S1 in 95g of acetonitrile, adding 5g of bis [3- (triethoxysilyl) propyl ] amine, stirring and reacting at 65 ℃ for 6.5 hours, performing suction filtration, washing with ethanol, and drying to obtain modified Ti-Fe-B-O;
step S3: dispersing the modified Ti-Fe-B-O10g prepared in the step S2 in 98g of dimethyl sulfoxide, adding 10g of (3-chloro-2-oxopropyl) diethyl phosphate, stirring and reacting at 58 ℃ for 7.5 hours, and then performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (4) soaking the surface ionized Ti-Fe-B-O10g prepared in the step S3 in 285g of diethylenetriamine pentamethylene phosphonic acid with the mass fraction of 19% at 58 ℃ for 23 hours, then carrying out suction filtration, washing with water for 4 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the compound organic fertilizer.
The preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 290-mesh sieve to obtain the soil remediation agent.
Example 5
A soil remediation agent comprises the following raw materials in parts by weight: 30 parts of composite organic fertilizer modified Ti-Fe-B-O, 10 parts of polyaspartic acid potassium, 1 part of composite microbial agent, 15 parts of modified sargassum powder and 10 parts of modified activated clay.
The compound microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria and bacillus subtilis.
The preparation method of the modified sargassum powder comprises the following steps:
dispersing 50g of sargassum powder into 150g of chloroform, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the chloroform, stirring the mixture at 70 ℃ to react for 7 hours, then carrying out suction filtration, washing the mixture for 6 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 15 hours at 90 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
and II, adding 10g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 5g of potassium carbonate which are prepared in the step I into 150g of N, N-dimethylformamide, stirring and reacting for 10 hours at 90 ℃, then carrying out suction filtration, washing with water for 5 times, and drying in a vacuum drying oven at 110 ℃ to constant weight to obtain the modified sargassum powder.
The preparation method of the modified activated clay comprises the following steps:
step D1: dispersing 50g of activated clay into 150g of acetonitrile, adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at 70 ℃ for reaction for 7 hours, then carrying out suction filtration, washing the mixture for 6 times by using ethanol, and then placing the mixture in a vacuum drying oven for drying at 90 ℃ for 15 hours to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding 10g of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay, 10g of mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and 5g of sodium carbonate which are prepared in the step I into 150g of N, N-dimethylformamide, stirring and reacting for 10 hours at 90 ℃, then carrying out suction filtration, washing for 5 times with water, and then placing in a vacuum drying oven to dry to constant weight at 110 ℃ to obtain the modified activated clay.
The preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding 20g of titanium tetrachloride, 5g of ferrous chloride and 0.2g of sodium borate into a beaker filled with 300g of ethanol, stirring for 3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 18 hours at 200 ℃; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 5 times after the reaction system is cooled, finally drying in a vacuum drying oven at 110 ℃ for 22 hours, cooling to room temperature, grinding, and sieving with a 400-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing Ti-Fe-B-O10g prepared in the step S1 in 100g of acetonitrile, adding 5g of bis [3- (triethoxysilyl) propyl ] amine, stirring at 70 ℃ for reaction for 7 hours, performing suction filtration, washing with ethanol, and drying to obtain modified Ti-Fe-B-O;
step S3: dispersing the modified Ti-Fe-B-O10g prepared in the step S2 in 100g of dimethyl sulfoxide, adding 10g of (3-chloro-2-oxopropyl) diethyl phosphate, stirring and reacting at 60 ℃ for 8 hours, and then performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (3) soaking the surface ionized Ti-Fe-B-O10g prepared in the step (S3) in 300g of 20 mass percent diethylenetriamine pentamethylene phosphonic acid at 60 ℃ for 24 hours, then carrying out suction filtration, washing with water for 5 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the compound organic fertilizer.
The preparation method of the soil remediation agent comprises the following steps: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 300-mesh sieve to obtain the soil remediation agent.
Comparative example 1
This example provides a soil remediation agent, formulation and method of preparation similar to example 1, except that no potassium polyaspartate is added.
Comparative example 2
The present example provides a soil remediation agent, which is formulated and prepared in the same manner as example 1, except that modified sargassum powder is not added.
Comparative example 3
The present example provides a soil remediation agent, which has the same formulation and preparation method as example 1, except that the Ti-Fe-B-O surface is not modified by a compound organic fertilizer.
Comparative example 4
The present example provides a soil remediation agent, which has the same formulation as that of example 1 of the Chinese invention patent CN 107686431A.
In order to visually reflect the effect of the repairing agent, a chemical polluted area is taken as a repairing object, and the heavy metal content of the soil surface layer of the area is higher than the third-level standard of soil environment quality standard. And carrying out a harmless treatment test according to the actual condition of pollution.
The soil to be tested is polluted soil near a chemical plant in Changsha, and the sampling depth is 0-10 cm from the surface layer. Removing the covering on the soil surface before sampling, placing the retrieved soil sample on a plastic cloth for air drying, crushing soil blocks after the soil sample is half-dry, removing impurities such as stones, and paving the soil sample into a thin layer for air drying. After air drying, sieving for standby. The soil remediation agents prepared in the above examples 1-5 and comparative examples are subjected to remediation effect tests, specifically, 1 wt% of the soil remediation agents are uniformly mixed and scattered on the surface of contaminated soil, then soil is ploughed to fully and uniformly mix the soil remediation agents and heavy metal contaminated soil, the soil remediation process is completed after 3 days, and the content of various toxic substances in the soil before and after remediation is measured.
TABLE 1
As can be seen from the above Table 1, the soil remediation agent prepared by the embodiments of the present invention has more excellent soil remediation effect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The soil remediation agent is characterized by comprising the following raw materials in parts by weight: 20-30 parts of composite organic fertilizer modified Ti-Fe-B-O, 5-10 parts of polyaspartic acid potassium, 0.5-1 part of composite microbial agent, 10-15 parts of modified sargassum powder and 5-10 parts of modified activated clay;
the preparation method of the modified sargassum powder comprises the following steps:
i, dispersing sargassum powder in an organic solvent, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the organic solvent, stirring the mixture at the temperature of 50-70 ℃ to react for 5-7 hours, then carrying out suction filtration, washing the mixture for 3-6 times by using ethanol, and then placing the mixture in a vacuum drying oven to dry the mixture for 10-15 hours at the temperature of 80-90 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified sargassum powder;
II, adding the gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder prepared in the step I, mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and an alkaline catalyst into N, N-dimethylformamide, stirring and reacting for 8-10 hours at the temperature of 80-90 ℃, then performing suction filtration, washing for 3-5 times with water, and then placing in a vacuum drying box for drying at the temperature of 100 ℃ and 110 ℃ to constant weight to obtain modified sargassum powder;
the preparation method of the modified activated clay comprises the following steps:
step D1: dispersing activated clay into acetonitrile, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into the acetonitrile, stirring the mixture at the temperature of between 50 and 70 ℃ for reaction for 5 to 7 hours, then carrying out suction filtration, washing the mixture for 3 to 6 times by using ethanol, and then placing the mixture in a vacuum drying oven for drying the mixture for 10 to 15 hours at the temperature of between 80 and 90 ℃ to obtain gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay;
step D2: adding the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane modified activated clay, the mono (6-polyethylene polyamine-6-deoxy) beta-cyclodextrin and the sodium carbonate which are prepared in the step I into N, N-dimethylformamide, stirring and reacting for 8-10 hours at the temperature of 80-90 ℃, then carrying out suction filtration, washing for 3-5 times by using water, and then placing in a vacuum drying box for drying at the temperature of 100 ℃ and 110 ℃ to constant weight to obtain the modified activated clay;
the preparation method of the Ti-Fe-B-O modified by the composite organic fertilizer comprises the following steps:
step S1: adding titanium tetrachloride, ferrous chloride and sodium borate into a beaker filled with ethanol, stirring for 2-3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 15-18 hours at the temperature of 180-; taking out the reaction kettle, respectively washing with deionized water and absolute ethyl alcohol for 3-5 times after the reaction system is cooled, finally drying in a vacuum drying oven at the temperature of 100-110 ℃ for 18-22 hours, cooling to room temperature, grinding, and sieving with a 200-400-mesh sieve to obtain Ti-Fe-B-O;
step S2: dispersing the Ti-Fe-B-O prepared in the step S1 in acetonitrile, adding bis [3- (triethoxysilyl) propyl ] amine into the acetonitrile, stirring the mixture at the temperature of between 50 and 70 ℃ for reaction for 5 to 7 hours, then carrying out suction filtration, washing the reaction product with ethanol, and drying the reaction product to obtain modified Ti-Fe-B-O;
step S3: dispersing the modified Ti-Fe-B-O prepared in the step S2 in dimethyl sulfoxide, adding diethyl (3-chloro-2-oxopropyl) phosphate into the solution, stirring the solution at 40-60 ℃ for reaction for 6-8 hours, and performing rotary evaporation to remove the dimethyl sulfoxide to obtain surface ionized Ti-Fe-B-O;
step S4: and (4) soaking the surface ionized Ti-Fe-B-O prepared in the step (S3) in 10-20% by mass of diethylenetriamine pentamethylene phosphonic acid at 50-60 ℃ for 18-24 hours, then carrying out suction filtration, washing with water for 3-5 times, and then placing in a vacuum drying oven to be dried to constant weight at 105 ℃ to obtain the Ti-Fe-B-O modified by the composite organic fertilizer.
2. The soil remediation agent of claim 1 wherein said complex microbial agent comprises photosynthetic bacteria, lactic acid bacteria, sulfurous bacteria, bacillus subtilis.
3. The soil remediation agent of claim 1 wherein in step i the mass ratio of sargassum powder, organic solvent, gamma- (2, 3-glycidoxy) propyltrimethoxysilane is (3-5): (10-15): 1; the organic solvent is selected from one or more of ethanol, acetonitrile, acetone and chloroform.
4. The soil remediation agent of claim 1 wherein in step ii said γ - (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, mono (6-polyethylenepolyamine-6-deoxy) betacyclodextrin, basic catalyst, N-dimethylformamide are present in a mass ratio of 1:1 (0.3-0.5) to (10-15); the alkaline catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
5. The soil remediation agent of claim 1 wherein in step D1 the ratio by mass of activated clay, acetonitrile, γ - (2, 3-glycidoxy) propyltrimethoxysilane, is (3-5): (10-15): 1; in the step D2, the mass ratio of the gamma- (2, 3-glycidoxy) propyltrimethoxysilane modified sargassum powder, the mono (6-polyethylene polyamine-6-deoxidation) beta-cyclodextrin, the sodium carbonate and the N, N-dimethylformamide is 1:1 (0.3-0.5) to (10-15).
6. The soil remediation agent of claim 1, wherein in step S1 the mass ratio of titanium tetrachloride, ferrous chloride, sodium borate, and ethanol is 2:0.5:0.02 (20-30); in the step S2, the mass ratio of Ti-Fe-B-O, acetonitrile to bis [3- (triethoxysilyl) propyl ] amine is 1 (5-10) to 0.5; in the step S3, the mass ratio of the modified Ti-Fe-B-O to the dimethyl sulfoxide to the diethyl (3-chloro-2-oxopropyl) phosphate is 1 (5-10) to 1; the mass ratio of the surface ionized Ti-Fe-B-O to the diethylenetriamine pentamethylene phosphonic acid in the step S4 is 1 (20-30).
7. The soil remediation agent of any one of claims 1 to 6, wherein said soil remediation agent is prepared by a method comprising the steps of: adding the raw materials into a mixer, uniformly mixing, grinding, and sieving with a 200-mesh and 300-mesh sieve to obtain the soil remediation agent.
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| CN111944536B (en) | 2021-12-28 |
| CN109097063A (en) | 2018-12-28 |
| CN111944536A (en) | 2020-11-17 |
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