CN109266363A - A kind of green soil renovation agent and preparation method thereof and application method - Google Patents
A kind of green soil renovation agent and preparation method thereof and application method Download PDFInfo
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- CN109266363A CN109266363A CN201811332769.8A CN201811332769A CN109266363A CN 109266363 A CN109266363 A CN 109266363A CN 201811332769 A CN201811332769 A CN 201811332769A CN 109266363 A CN109266363 A CN 109266363A
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- 239000002689 soil Substances 0.000 title claims abstract description 116
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 86
- 238000009418 renovation Methods 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000004021 humic acid Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 235000015097 nutrients Nutrition 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 241000196324 Embryophyta Species 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 21
- 235000008011 Alhagi graecorum Nutrition 0.000 claims description 20
- 235000017398 Alhagi maurorum Nutrition 0.000 claims description 20
- 241000214035 Alhagi maurorum Species 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015702 Artemisia filifolia Nutrition 0.000 claims description 6
- 241001670242 Artemisia filifolia Species 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 230000002045 lasting effect Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 41
- 230000000694 effects Effects 0.000 abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 230000008439 repair process Effects 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract description 5
- 230000004060 metabolic process Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000813 microbial effect Effects 0.000 abstract description 4
- 230000008635 plant growth Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004936 stimulating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 239000007787 solid Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000227 grinding Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052793 cadmium Inorganic materials 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 description 6
- 229960001545 hydrotalcite Drugs 0.000 description 6
- 238000005065 mining Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005067 remediation Methods 0.000 description 6
- 239000007836 KH2PO4 Substances 0.000 description 5
- 239000009798 Shen-Fu Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 231100001261 hazardous Toxicity 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 231100000584 environmental toxicity Toxicity 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000004162 soil erosion Methods 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B79/00—Methods for working soil
- A01B79/02—Methods for working soil combined with other agricultural processing, e.g. fertilising, planting
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Environmental Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Fertilizers (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of green soil renovation agent and preparation method thereof and application method, by by modified humic acid and magnetic Fe3O4/ MgAl-LDH reaction is made, one side magnetic Fe3O4/ MgAl-LDH, which carries the humic acid containing nutrient, improves the structure and composition ingredient of soil, promotes plant growth；One side Fe3O4/ MgAl-LDH and humic acid under the action of rhizosphere microbial can mutual stimulating activity group, improve soil enzyme activities, at the same these active function groups be easy to again with heavy metal-polluted soil generation complex compound, reduce the biological effectiveness of heavy metal.The raw material that this method uses are cheap and easily-available compound, and preparation method and process are also very easy, on the one hand the renovation agent of acquisition can provide the necessary nutrient of metabolism of plant, on the one hand again can heavy metal-passivated pollutant；The plant of healthy fast-growth again can it is stable in turn, improve aeolian sandy soil, be finally reached repair aeolian sandy soil, greening environment purpose.
Description
Technical field
The invention belongs to soil remediation field, it is related to a kind of green soil renovation agent and preparation method thereof and application method.
Background technique
Shaanxi Province northern mining area mineral resources are highly enriched, and water resource is relatively deficient；Prolonged drought, high wind and of short duration, no simultaneously
Regular heavy rainfall weather causes area's soil erosion and desertification extremely serious, and ecology is extremely fragile.Recently as derived energy chemical base
Ground construction like a raging fire, a large amount of hazardous contaminants are discharged into environment, and polluted soil area expands year by year.It moves back in soil
Problems of ecological security caused by change, soil pollution is increasingly prominent, reinforces extremely urgent to area's soil remediation research.
It is in progress significantly currently, soil restoring technology has achieved, common and effective recovery technique there are 3 major class: 1. dropping
Hazardous contaminant total amount in low soil, 2. by changing the occurrence patterns or and soil of hazardous contaminant in the soil
Combination, reduce the migration of hazardous contaminant in the soil and biological effectiveness, 3. by changing area's kind
Plant mode and system, avoid hazardous contaminant from transmitting in food chain.Specific contaminated soil remediation method has chemical remediation
(such as microbial remediation method is planted for method (utilizing soil-repairing agent), physical restoration (such as Soil leaching repairing method), biological restoration
Object repairing method), engineering repairing method (such as covering method, soil dilution method).In these recovery technique, chemosetting/stabilization is repaired
Recovering technology is the soil pollution recovery technique for comparing efficient and cost-effective.
Common renovation agent can be divided into 2 classes in chemical stabilization recovery technique: organic renovation agent and inorganic renovation agent.Its
In, organic renovation agent such as organic fertilizer, organic clay etc.；Inorganic renovation agent such as lime, cement, modified cellulose, slag etc..These
Renovation agent or increase-volume are big, or cause water eutrophication or repairing effect unstable, or there are secondary pollution, make soil property
Deteriorate or at high cost.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of green soil renovation agent and its
Preparation method and application method, which is easy to get, easy to operate；The soil-repairing agent on the one hand can rehabilitating soil dirt
Status is contaminated, on the one hand can improve soil nutrient, while also Ke Xunhuanliyong, side effect will not be generated to soil, is had green, high
The features such as imitating, be inexpensive, without security risk
In order to achieve the above object, the present invention is achieved by the following scheme:
A kind of preparation method of green soil renovation agent, comprising the following steps:
1) in the ratio of (5~20) mg:100mL, humic acid is added in nutrient solution, is sufficiently mixed uniformly, by mixture
12~15min is irradiated under the dose of radiation of 12.5~15.5kGy, then is centrifuged, dried, being ground up, sieved processing, is made pre-
Handle humic acid；
2) humic acid, magnetic Fe will be pre-processed3O4/ MgAl-LDH and water press the amount ratio of (0.5~2) g:2g:100mL, fill
Divide after mixing, adjusting pH value is 6.9~7.6, then by mixture washing, centrifugal treating up to removing residue humic acid,
Obtained product is freeze-dried, be ground up, sieved, isolated solid product；
3) solid product that will be obtained repeats step 2) and operates 2~5 times, green soil renovation agent is made.
Preferably, in step 1), being sufficiently mixed is uniformly that humic acid is added in nutrient solution, stirs 6~10h.
Preferably, 100mg L is contained in every 100mL nutrient solution-1KH2PO4、450mg L-1KNO3、500mg L-1MgSO4With
1000mg L-1Ca(NO3)2·4H2O。
Preferably, in step 2), being sufficiently mixed is uniformly the oscillation treatment 6~for 24 hours at 55~75 DEG C.
Preferably, in step 2), the HCl of 0.05M or NaOH solution is used to adjust solution ph as 6.9~7.6；Then will
50% ethanol washing of mixture is centrifuged 20min with 13400 × g, and lasting centrifugation is for several times until remove humic acid.
Preferably, in step 1 and step 2), be sieved for 200 meshes.
The invention also discloses using green soil renovation agent made from above-mentioned preparation method.
The invention also discloses the application methods of above-mentioned green soil renovation agent, by the green soil renovation agent and are contaminated
Aeolian sandy soil mixes rear bearing kind desert dominant plant, and green soil renovation agent accounts for the 5.5%~20.5% of contaminated aeolian sandy soil quality.
Further, desert dominant plant selection sand sagebrush (Artemisia filifolia) or camel thorn.
Compared with prior art, the invention has the following advantages:
The preparation method of green soil renovation agent disclosed by the invention, by by modified humic acid and magnetic Fe3O4/MgAl-
LDH reaction is made, and has combined magnetic Fe3O4The good characteristic of/MgAl-LDH and humic acid, one side magnetic Fe3O4/MgAl-
LDH, which carries the humic acid containing nutrient, improves the structure and composition ingredient of soil, promotes plant growth；One side Fe3O4/MgAl-
LDH and humic acid under the action of rhizosphere microbial can mutual stimulating activity group, improve soil enzyme activities, while these activity
Functional group is easy to generate complex compound with heavy metal-polluted soil again, reduces the biological effectiveness of heavy metal.The raw material that this method uses
It is cheap and easily-available compound, preparation method and process are also very easy, on the one hand the renovation agent of acquisition can provide plant
The necessary nutrient of metabolism, on the one hand again can heavy metal-passivated pollutant；The plant of healthy fast-growth again can be steady in turn
Fixed, improvement aeolian sandy soil, is finally reached the purpose for repairing aeolian sandy soil, greening environment.
The soil-repairing agent can not only play during soil remediation improves the soil organism, CEC, the work for adjusting pH
With nutrient contained therein may additionally facilitate plant growth, while the distinctive layer structure of hydrotalcite, also help soil root
Water conservation is suitble to the reparation of arid area soil, and after imposing on heavy metal pollution aeolian sandy soil, hydrotalcite and humic acid are conducive to weight
The stabilization of metal ion, while the activity that hydrotalcite and humic acid can also mutually in excitation structure under the action of rhizosphere microbial
Group, the combination of promotion and heavy metal, and can also improve soil enzymatic activities, facilitate the growth of plant.Fertility exhaust while
The renovation agent for having adsorbed plurality of heavy metal can be taken out by the magnetism of carrier by magnetic separation technique.Therefore the renovation agent not only may be used
Improve soil physico-chemical property, also can effectively reduce bioavailability of heavy metals, wind can be effectively improved after planting desert dominant plant
The barren and pollution situation of sandy soil, is finally reached the purpose of aeolian sandy soil reparation, environmental greening, has novel, unique, environmental protection, letter
Easily, the features such as at low cost.
Detailed description of the invention
Fig. 1 is the growing state comparison diagram of renovation agent cultivated plant made from embodiment 1；
Fig. 2 is the growing state comparison diagram of renovation agent cultivated plant made from embodiment 2；
Fig. 3 is the growing state comparison diagram of renovation agent cultivated plant made from embodiment 3.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein can in addition to illustrating herein or
Sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that cover
Cover it is non-exclusive include, for example, the process, method, system, product or equipment for containing a series of steps or units are not necessarily limited to
Step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, product
Or other step or units that equipment is intrinsic.
The invention will be described in further detail with reference to the accompanying drawing:
Embodiment 1
(1) it samples:
Humic acid is purchased in market, and aeolian sandy soil is derived from shenfu coal mining area；Nutrient solution is by 100mg L-1KH2PO4, 450mg L- 1KNO3, 500mg L-1MgSO4, 1000mg L-1Ca(NO3)2·4H2O and deionized water are formulated.
Sand sagebrush (Artemisia filifolia), camel thorn etc. may be selected in desert dominant plant.
Nano-magnetic Fe3O4Self-control, magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation, and required drug is point
It analyses pure.Method is as follows:
Fe is synthesized first3O4Nanoparticle, 2.0g FeCl3·6H2O is dissolved in 20mL ethylene glycol solvent, is stirred in magnetic force
Mix lower addition 6mL N2H4·H2O (80wt%) and 3.0g NaOH.Then mixture is sealed in 50mL polytetrafluoroethyllining lining
Stainless steel cauldron in, in 90 DEG C of heating 10h.It then cools to room temperature, resulting black powder is cleaned 3 with deionized water
It is secondary, it is then dried in vacuo in 55 ± 5 DEG C, obtains Fe3O4Nanoparticle.
Magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation: taking 9.38g Al (NO3)3·9H2O and 12.80g Mg
(NO3)2·6H2O is dissolved in the distilled water of 150mL, then by the Fe of above-mentioned preparation3O4(1.93g) is added in the solution.It will mix
It closes solution and quickly stirs 10s with magnetic stirring apparatus under 60 DEG C of water-baths.Then mixed liquor is slowly added into containing Na2CO3
In the 200mL lye of (5.29g) and NaOH (6.75g), vigorous magnetic stirs 40min.Suspension is under conditions of 80 DEG C of stirrings
Aging 10h.Sediment is collected by filtration, and is cleaned with decarburization water to neutrality.Then sample is ground in 60 DEG C (oil bath) dry a few hours
Mill, screening (200 mesh), obtain magnetic Fe3O4/MgAl-LDH。
(2) preparation of renovation agent:
100mL nutrient solution is taken, 5mg humic acid is added thereto and is sufficiently mixed, stirs 6h, then mixture exists
12min is irradiated under 12.5kGy dosage.It is then centrifuged for separating, the humic acid of acquisition is dried at room temperature, is then ground, is sieved
(200 mesh)；
Take the humic acid of 0.5g step (1) and the magnetic Fe of the above-mentioned preparation of 2g3O4/ MgAl-LDH is placed in 100mL redistilled water
In, 6h is vibrated in oscillator at 55 DEG C, adjusting pH value of solution with 0.05M HCl or NaOH solution is 6.9.Then, it will mix
Object 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20 minutes, is continued for several times until removing remaining humic acid.
The solid isolated is freeze-dried, grinding, and sieves (200 mesh).And 0.5g the solid of acquisition repeats the above process 3 times, i.e.,
The mixing of pretreated humic acid is placed in 100mL redistilled water, and 6h is vibrated in oscillator at 55 DEG C, with 0.05M HCl or
It is 6.9 that NaOH solution, which adjusts pH value of solution,.Then, by mixture 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20
Minute, continue for several times until removing remaining humic acid.The solid isolated is freeze-dried, grinding, and sieves (200 mesh).
HA-LDH renovation agent is obtained, the renovation agent of acquisition is stored under conditions of being protected from light and feeling nice and cool in case application；
(3) renovation agent is matched and is applied:
Obtained HA-LDH renovation agent and contaminated aeolian sandy soil is refitted in terrine according to 5.5% ratio.By what is screened
Desert dominant plant (grow fine, height is identical, strain age is consistent, this research is by taking camel thorn as an example) plantation is in terrine, every tank
One is planted, is grown 80 days under natural lighting.Observation of plant growing state and soil property variation.Growing state is referring to Fig. 1, from Fig. 1
In as can be seen that blank control group relative to not renovation agent, the plant height of plant, hat in one group of addition HA-LDH renovation agent
Wide, biological quality is obviously higher by very much.
Table 1-1, which matches, applies heavy metal in soil content
Only have the content of Cu, Cd to exceed it is found that renovation agent matches the heavy metal applied after aeolian sandy soil in soil by table 1-1 data
National standard GB15618-1995.
Table 1-2 Cu occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
Table 1-3 Cd occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
By table 1-2 and table 1-3 it is found that after camel thorn plantation, the residual form of Cu, Cd increase obvious in Soil-in-Root, especially
Residual form containing renovation agent has respectively reached 79%, 83%, this shows that renovation agent can effectively reduce the biology of heavy metal Cu, Cd
Validity and eco-toxicity.
Table 1-4 repairs front and back aeolian sandy soil nutritional ingredient variation
By table 1-4 data it is found that the physicochemical property of the aeolian sandy soil after repairing is obviously improved, after planting camel thorn, stability
Also it is ensured, by the metabolism of plant, the soil property of aeolian sandy soil, which will turn to, to circulate benignly.Therefore the technology can be effectively
Aeolian sandy soil is repaired, contains desert extending.
Renovation agent after failure can be separated from soil by magnetic separation technique, then pass through hydrotalcite preparation process
It lives again and continues to apply, effect does not subtract originally.
Embodiment 2
(1) humic acid is purchased in market, and aeolian sandy soil is derived from shenfu coal mining area；Nutrient solution is by 100mg L-1KH2PO4, 450mg
L-1KNO3, 500mg L-1MgSO4, 1000mg L-1Ca(NO3)2·4H2O and deionized water are formulated.Nano-magnetic Fe3O4From
System, magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation, and required drug is that analysis is pure.Method is as follows:
Synthesizing magnetic Fe3O4/ MgAl-LDH: synthesis Fe first3O4Nanoparticle, 2.0g FeCl3·6H2O is dissolved in 20mL
In ethylene glycol solvent, 6mL N is added under magnetic stirring2H4·H2O (80wt%) and 3.0g NaOH.Then mixture is sealed
In the stainless steel cauldron of 50mL polytetrafluoroethyllining lining, in 90 DEG C of heating 10h.It then cools to room temperature, it will be resulting black
Color powder is cleaned 3 times with deionized water, is then dried in vacuo in 55 ± 5 DEG C, is obtained Fe3O4Nanoparticle.Second, magnetic Fe3O4/
The synthesis of MgAl-LDH uses coprecipitation.Take 9.38g Al (NO3)3·9H2O and 12.80g Mg (NO3)2·6H2O is dissolved in
In the distilled water of 150mL, then by Fe obtained by step 13O4(1.93g) is added in the solution.By mixed solution in 60 DEG C of water-baths
It is lower quickly to stir 10s with magnetic stirring apparatus.Then mixed liquor is slowly added into containing Na2CO3(5.29g) and NaOH (6.75g)
200mL lye in, vigorous magnetic stir 40min.Suspension aging 10h under conditions of 80 DEG C of stirrings.Precipitating is collected by filtration
Object, and cleaned with decarburization water to neutrality.Then sample grinds in 60 DEG C (oil bath) dry a few hours, sieves (200 mesh), obtain magnetic
Property Fe3O4/ MgAl-LDH sample.
Desert dominant plant selects camel thorn.
(2) preparation of renovation agent:
100mL nutrient solution is taken, 8mg humic acid is added thereto and is sufficiently mixed, 7h is stirred, then by mixture in 13kGy
12.5min is irradiated under dosage.It is then centrifuged for separating, the humic acid of acquisition is dried at room temperature, is then ground, is sieved (200 mesh)；
Take the humic acid of 0.8g step (1) and the magnetic Fe of the laboratory 2g synthesis3O4/ MgAl-LDH is placed in 100mL redistilled water
In, 8h is vibrated in oscillator at 60 DEG C, adjusting pH value of solution with 0.05M HCl or NaOH solution is 7.0.Then, it will mix
Object 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20 minutes, is continued for several times until removing remaining humic acid.
The solid isolated is freeze-dried, grinding, and sieves (200 mesh).And 0.8g the solid of acquisition repeats the above process 3 times, i.e.,
The mixing of pretreated humic acid is placed in 100mL redistilled water, and 8h is vibrated in oscillator at 60 DEG C, with 0.05M HCl or
It is 7.0 that NaOH solution, which adjusts pH value of solution,.Then, by mixture 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20
Minute, continue for several times until removing remaining humic acid.The solid isolated is freeze-dried, grinding, and sieves (200 mesh).
HA-LDH renovation agent is obtained, the renovation agent of acquisition is stored under conditions of being protected from light and feeling nice and cool in case application.
(3) renovation agent, which is matched, applies aeolian sandy soil:
HA-LDH renovation agent and contaminated aeolian sandy soil obtained in (2) is taken to be refitted in terrine according to 9.5% ratio.It will sieve
The desert dominant plant (growing fine, height is identical, strain age is consistent) chosen is planted in terrine, and every tank plants one, in nature
It is grown 85 days under illumination.Observation of plant growing state and soil property variation.
As a result referring to fig. 2, as shown in Figure 2, the blank control group relative to not renovation agent adds HA-LDH renovation agent
One group in the plant height of plant, hat be wide, biological quality is obviously higher by very much.
Table 2-1, which matches, applies heavy metal in soil content
Matching the heavy metal after applying aeolian sandy soil in soil by renovation agent known to table 2-1 data only has Cu, Cd content to have exceeded
National standard GB15618-1995.
Table 2-2 Cu occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
Table 2-3 Cd occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
By table 2-2 and table 2-3 it is found that after camel thorn plantation, the residual form of Cu, Cd increase obvious in Soil-in-Root, especially
Residual form containing renovation agent has respectively reached 80%, 90%, this shows that renovation agent can effectively reduce the biology of heavy metal Cu, Cd
Validity and eco-toxicity.In conclusion security risk is not present in the technology of the present invention.
Table 2-4 repairs front and back aeolian sandy soil nutritional ingredient variation
By table 2-4 data it is found that the physicochemical property of the aeolian sandy soil after repairing is obviously improved, after planting camel thorn, stability
Also it is ensured, by the metabolism of plant, the soil property of aeolian sandy soil, which will turn to, to circulate benignly.Therefore the technology can be effectively
Aeolian sandy soil is repaired, contains desert extending.
Renovation agent after failure can be separated from soil by magnetic separation technique, then pass through hydrotalcite preparation process
It lives again and continues to apply, effect does not subtract originally.
Embodiment 3
(1) humic acid is purchased in market, and aeolian sandy soil is derived from shenfu coal mining area；Nutrient solution is by 100mg L-1KH2PO4, 450mg
L-1KNO3, 500mg L-1MgSO4, 1000mg L-1Ca(NO3)2·4H2O and deionized water are formulated.Nano-magnetic Fe3O4From
System, magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation, and required drug is that analysis is pure, the method is as follows:
Synthesizing magnetic Fe3O4/ MgAl-LDH: synthesis Fe first3O4Nanoparticle, 2.0g FeCl3·6H2O is dissolved in 20mL
In ethylene glycol solvent, 6mL N is added under magnetic stirring2H4·H2O (80wt%) and 3.0g NaOH.Then mixture is sealed
In the stainless steel cauldron of 50mL polytetrafluoroethyllining lining, in 90 DEG C of heating 10h.It then cools to room temperature, it will be resulting black
Color powder is cleaned 3 times with deionized water, is then dried in vacuo in 55 ± 5 DEG C, is obtained Fe3O4Nanoparticle.Second, magnetic Fe3O4/
The synthesis of MgAl-LDH uses coprecipitation.Take 9.38g Al (NO3)3·9H2O and 12.80g Mg (NO3)2·6H2O is dissolved in
In the distilled water of 150mL, then by Fe obtained by step 13O4(1.93g) is added in the solution.By mixed solution in 60 DEG C of water-baths
It is lower quickly to stir 10s with magnetic stirring apparatus.Then mixed liquor is slowly added into containing Na2CO3(5.29g) and NaOH (6.75g)
200mL lye in, vigorous magnetic stir 40min.Suspension aging 10h under conditions of 80 DEG C of stirrings.Precipitating is collected by filtration
Object, and cleaned with decarburization water to neutrality.Then sample grinds in 60 DEG C (oil bath) dry a few hours, sieves (200 mesh), obtain magnetic
Property Fe3O4/ MgAl-LDH sample.
Desert dominant plant selects camel thorn.
(2) preparation of renovation agent:
100mL nutrient solution is taken, 10mg humic acid is added thereto and is sufficiently mixed, stirs 8h, then mixture exists
13min is irradiated under 13.5kGy dosage.It is then centrifuged for separating, the humic acid of acquisition is dried at room temperature, is then ground, is sieved
(200 mesh)；
Take the humic acid of 1.2g step (1) and the magnetic Fe of the laboratory 2g synthesis3O4/ MgAl-LDH is placed in 100mL redistilled water
In, 12h is vibrated in oscillator at 65 DEG C, adjusting pH value of solution with 0.05M HCl or NaOH solution is 7.1.Then, it will mix
Object 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20 minutes, is continued for several times until removing remaining humic acid.
The solid isolated is freeze-dried, grinding, and sieves (200 mesh).And 1.2g the solid of acquisition repeats the above process 3 times, i.e.,
The mixing of pretreated humic acid is placed in 100mL redistilled water, and 12h is vibrated in oscillator at 65 DEG C, with 0.05M HCl or
It is 7.1 that NaOH solution, which adjusts pH value of solution,.Then, by mixture 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20
Minute, continue for several times until removing remaining humic acid.The solid isolated is freeze-dried, grinding, and sieves (200 mesh).
HA-LDH renovation agent is obtained, the renovation agent of acquisition is stored under conditions of being protected from light and feeling nice and cool in case application.
(3) renovation agent, which is matched, applies aeolian sandy soil:
HA-LDH renovation agent and contaminated aeolian sandy soil obtained in (2) is taken to be refitted in terrine according to 13% ratio.It will sieve
The desert dominant plant (growing fine, height is identical, strain age is consistent) chosen is planted in terrine, and every tank plants one, in nature
It is grown 90 days under illumination.Observation of plant growing state and soil property variation.
Growing state is referring to Fig. 3, as shown in Figure 3, relative to the blank control group of not renovation agent, adds HA-LDH and repairs
The plant height of plant, hat width, biological quality are obviously higher by much in one group of multiple agent.
Table 3-1, which matches, applies heavy metal in soil content
Matching the heavy metal after applying aeolian sandy soil in soil by renovation agent known to table 3-1 data only has Cu, Cd content to have exceeded
National standard GB15618-1995.
Table 3-2 Cu occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
Table 3-3 Cd occurrence patterns variation in soil before and after camel thorn plantation under renovation agent effect
By table 3-2 and table 3-3 it is found that after camel thorn plantation, the residual form of Cu, Cd increase obvious in Soil-in-Root, especially
Residual form containing renovation agent has respectively reached 87%, 87%, this shows that renovation agent can effectively reduce the biology of heavy metal Cu, Cd
Validity and eco-toxicity.
By table 3-4 data it is found that the physicochemical property of the aeolian sandy soil after repairing is obviously improved, after planting camel thorn, stability
Also it is ensured, by the metabolism of plant, the soil property of aeolian sandy soil, which will turn to, to circulate benignly.Therefore the technology can be effectively
Aeolian sandy soil is repaired, contains desert extending.
Table 3-4 repairs front and back aeolian sandy soil nutritional ingredient variation
Renovation agent after failure can be separated from soil by magnetic separation technique, then pass through hydrotalcite preparation process
It lives again and continues to apply, effect does not subtract originally.
Embodiment 4
Humic acid is purchased in market, and aeolian sandy soil is derived from shenfu coal mining area；Nutrient solution is by 100mg L-1KH2PO4, 450mg L- 1KNO3, 500mg L-1MgSO4, 1000mg L-1Ca(NO3)2·4H2O and deionized water are formulated.Fe3O4Nanoparticle is certainly
System, magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation, and required drug is that analysis is pure.Desert dominant plant selects white horse with a black mane
Camel thorn.100mL nutrient solution is taken, 18mg humic acid is added thereto and is sufficiently mixed, 9h is stirred, then by mixture in 15kGy agent
Amount is lower to irradiate 14.5min.It is then centrifuged for separating, the humic acid of acquisition is dried at room temperature, is then ground, is sieved (200 mesh)；It takes
The magnetic Fe of the pretreated humic acid of 1.5g and the synthesis of the laboratory 2g3O4/ MgAl-LDH is placed in 100mL redistilled water, at 70 DEG C
Under 20h is vibrated in oscillator, adjusting pH value of solution with 0.05M HCl or NaOH solution is 7.4.Then, by mixture 100mL
50% ethanol washing, and with 13,400 × g is centrifuged 20 minutes, is continued for several times until removing remaining humic acid.By what is isolated
Solid freeze-drying, grinding, and sieve (200 mesh).The solid of acquisition repeats the above process 3 times, i.e., pretreated with 1.5g
Humic acid mixing is placed in 100mL redistilled water, 20h is vibrated in oscillator at 70 DEG C, with 0.05M HCl or NaOH solution tune
Saving pH value of solution is 7.4.Then, by mixture 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20 minutes, is continued
For several times until removing remaining humic acid.The solid isolated is freeze-dried, grinding, and sieves (200 mesh).HA-LDH is obtained to repair
Multiple agent.Obtained HA-LDH renovation agent and contaminated aeolian sandy soil are refitted in terrine according to 18% ratio.The sand that will have been screened
In terrine, every tank plants one, raw under natural lighting for unconcerned dominant plant (growing fine, height is identical, strain age is consistent) plantation
It is 95 days long.Observation of plant growing state and soil property variation.
Embodiment 5
Humic acid is purchased in market, and aeolian sandy soil is derived from shenfu coal mining area；Nutrient solution is by 100mg L-1KH2PO4, 450mg L- 1KNO3, 500mg L-1MgSO4, 1000mg L-1Ca(NO3)2·4H2O and deionized water are formulated.Fe3O4Nanoparticle is certainly
System, magnetic Fe3O4The synthesis of/MgAl-LDH uses coprecipitation, and required drug is that analysis is pure.Desert dominant plant selects white horse with a black mane
Camel thorn.100mL nutrient solution is taken, 20mg humic acid is added thereto and is sufficiently mixed, 10h is stirred, then by mixture in 15.5kGy
15min is irradiated under dosage.It is then centrifuged for separating, the humic acid of acquisition is dried at room temperature, is then ground, is sieved (200 mesh)；It takes
The magnetic Fe of the pretreated humic acid of 2g and the synthesis of the laboratory 2g3O4/ MgAl-LDH is placed in 100mL redistilled water, at 75 DEG C
It is vibrated in oscillator for 24 hours, adjusting pH value of solution with 0.05M HCl or NaOH solution is 7.6.Then, by mixture 100mL
50% ethanol washing, and with 13,400 × g is centrifuged 20 minutes, is continued for several times until removing remaining humic acid.By what is isolated
Solid freeze-drying, grinding, and sieve (200 mesh).The solid of acquisition repeats the above process 3 times, i.e., with the pretreated corruption of 2g
Phytic acid mixing is placed in 100mL redistilled water, is vibrated in oscillator at 75 DEG C for 24 hours, is adjusted with 0.05M HCl or NaOH solution
PH value of solution is 7.6.Then, by mixture 50% ethanol washing of 100mL, and with 13,400 × g is centrifuged 20 minutes, lasting number
It is secondary until removing remaining humic acid.The solid isolated is freeze-dried, grinding, and sieves (200 mesh).HA-LDH is obtained to repair
Agent.Obtained HA-LDH renovation agent and contaminated aeolian sandy soil are refitted in terrine according to 20.5% ratio.The sand that will have been screened
In terrine, every tank plants one, raw under natural lighting for unconcerned dominant plant (growing fine, height is identical, strain age is consistent) plantation
It is 100 days long.Observation of plant growing state and soil property variation.
The unlimited sprawling of aeolian sandy soil had both been contained in the preparation of above-mentioned renovation agent, reduced heavy metal-polluted soil total amount and a huge sum of money
The biological effectiveness of category, and solve the handling problems that fertility exhausts rear renovation agent, this method is at low cost, without security risk, green
Colour circle is protected, and renovation agent, which is made, can be recycled, and long-time service will not cause burden or secondary pollution to soil, is effectively realized
The reparation recycled with barren contaminated soil of resource.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (9)
1. a kind of preparation method of green soil renovation agent, which comprises the following steps:
1) in the ratio of (5~20) mg:100mL, humic acid is added in nutrient solution, is sufficiently mixed uniformly, mixture is existed
12~15min is irradiated under the dose of radiation of 12.5~15.5kGy, then is centrifuged, dried, being ground up, sieved processing, and pre- place is made
Manage humic acid；
2) humic acid, magnetic Fe will be pre-processed3O4/ MgAl-LDH and water press the amount ratio of (0.5~2) g:2g:100mL, sufficiently mixed
After conjunction is uniform, adjusting pH value is 6.9~7.6, then by mixture washing, centrifugal treating up to removing residue humic acid, will
To product it is freeze-dried, be ground up, sieved, isolated solid product；
3) solid product that will be obtained repeats step 2) and operates 2~5 times, green soil renovation agent is made.
2. the preparation method of green soil renovation agent according to claim 1, which is characterized in that sufficiently mixed in step 1)
Conjunction is uniformly that humic acid is added in nutrient solution, stirs 6~10h.
3. the preparation method of green soil renovation agent according to claim 1, which is characterized in that in step 1), every 100mL
Contain 100mg L in nutrient solution-1KH2PO4、450mg L-1KNO3、500mg L-1MgSO4With 1000mg L-1Ca(NO3)2·
4H2O。
4. the preparation method of green soil renovation agent according to claim 1, which is characterized in that sufficiently mixed in step 2)
Conjunction is uniformly the oscillation treatment 6~for 24 hours at 55~75 DEG C.
5. the preparation method of green soil renovation agent according to claim 1, which is characterized in that in step 2), use
It is 6.9~7.6 that the HCl or NaOH solution of 0.05M, which adjusts solution ph,；Then by 50% ethanol washing of mixture, with 13400
× g is centrifuged 20min, and lasting centrifugation is for several times until remove humic acid.
6. the preparation method of green soil renovation agent according to claim 1, which is characterized in that in step 1 and step 2),
Sieving was 200 meshes.
7. using green soil renovation agent made from preparation method described in any one of claim 1~6.
8. the application method of green soil renovation agent as claimed in claim 7, which is characterized in that by the green soil renovation agent with
Contaminated aeolian sandy soil mixes rear bearing kind desert dominant plant, green soil renovation agent account for contaminated aeolian sandy soil quality 5.5%~
20.5%.
9. application method according to claim 8, which is characterized in that desert dominant plant selects sand sagebrush (Artemisia filifolia) or camel thorn.
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Cited By (5)
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| CN110404512A (en) * | 2019-06-25 | 2019-11-05 | 兰州大学 | A kind of preparation method and modification humic acid of modified humic acid |
| CN113287385A (en) * | 2021-06-04 | 2021-08-24 | 北京化工大学 | Method for improving soda saline-alkali soil by forming hydrotalcite-like compound in soil |
| CN115627172A (en) * | 2022-10-26 | 2023-01-20 | 湖南农业大学 | Compound conditioner for medium and light cadmium-polluted soil and application |
| CN115647023A (en) * | 2022-12-05 | 2023-01-31 | 湖南农业大学 | Method for compositely repairing cadmium-polluted rice field soil |
| US11970648B1 (en) * | 2021-02-18 | 2024-04-30 | Patric N. Galvin | Method for increasing water permeability in fire affected soils |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404512A (en) * | 2019-06-25 | 2019-11-05 | 兰州大学 | A kind of preparation method and modification humic acid of modified humic acid |
| US11970648B1 (en) * | 2021-02-18 | 2024-04-30 | Patric N. Galvin | Method for increasing water permeability in fire affected soils |
| CN113287385A (en) * | 2021-06-04 | 2021-08-24 | 北京化工大学 | Method for improving soda saline-alkali soil by forming hydrotalcite-like compound in soil |
| CN115627172A (en) * | 2022-10-26 | 2023-01-20 | 湖南农业大学 | Compound conditioner for medium and light cadmium-polluted soil and application |
| CN115647023A (en) * | 2022-12-05 | 2023-01-31 | 湖南农业大学 | Method for compositely repairing cadmium-polluted rice field soil |
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