CN114774132B - Garden soil ecological restoration agent and preparation method thereof - Google Patents
Garden soil ecological restoration agent and preparation method thereof Download PDFInfo
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- CN114774132B CN114774132B CN202210359020.2A CN202210359020A CN114774132B CN 114774132 B CN114774132 B CN 114774132B CN 202210359020 A CN202210359020 A CN 202210359020A CN 114774132 B CN114774132 B CN 114774132B
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- scandium
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- vermiculite
- diboride
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- 239000002689 soil Substances 0.000 title claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 94
- 239000010455 vermiculite Substances 0.000 claims abstract description 94
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 94
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 58
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 49
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims abstract description 28
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960001082 trimethoprim Drugs 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- -1 scandium acyl chloride Chemical class 0.000 claims abstract description 12
- 239000008247 solid mixture Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 46
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 9
- 231100001240 inorganic pollutant Toxicity 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 229910001385 heavy metal Inorganic materials 0.000 description 12
- 238000005067 remediation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000003516 soil conditioner Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 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
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a preparation method of a garden soil ecological restoration agent, which comprises the following steps: step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder; step 2, after dissolving diboron trioxide in acid liquor, mixing the solution with scandium trichloride under the condition of an adhesive; step 3, placing the solid mixture into a tube furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite; step 4, scandium diboride/expanded vermiculite is treated by dicarboxylic acid; step 5, acylating and chlorinating carboxylated scandium diboride/expanded vermiculite; and 6, reacting trimethoprim with scandium acyl chloride diboride/expanded vermiculite to obtain the garden soil ecological restoration agent. The ecological restoration agent obtained by the invention has a good restoration effect on soil, and can restore inorganic pollutants and organic pollutants in the soil at the same time.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to a garden soil ecological restoration agent and a preparation method thereof.
Background
The soil is a loose surface layer for providing plant growth fertility on the surface of continents, various industrial waste water, harmful gas and other pollutants enter the soil along with the development of modern industry and agriculture, the accumulated harmful substances in the soil are also increasing, agricultural production activities on the polluted soil tend to form food safety problems, living and the like can directly endanger human health, besides, part of harmful cost also participates in natural and ecological system circulation in various forms such as solid, liquid, gas and the like, and damage is caused to human bodies and the natural world in a wider range.
Common pollution forms of garden soil comprise inorganic pollutants and organic pollutants, wherein the inorganic pollutants are most obvious and most harmful to heavy metal elements, and the organic pollutants are most obvious and most harmful to chemical fertilizers, pesticides and the like. The inorganic pollutants mainly contain heavy metals, and are represented by five heavy metal elements of lead, cadmium, mercury, arsenic and chromium; organic pollutants are various, and benzene organic pollutants such as benzene, toluene, xylene and ethylbenzene are serious pollutants. If the organic pollutants and the inorganic pollutants in the garden soil are not removed in time, plants in the garden can be damaged to a greater extent, and meanwhile, groundwater and surface water sources can be endangered, so that the health of human bodies is endangered.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a garden soil ecological restoration agent and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a preparation method of a garden soil ecological restoration agent, which comprises the following steps:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder to obtain vermiculite powder;
step 2, after dissolving diboron trioxide in acid liquor, mixing the solution with scandium trichloride under the condition of an adhesive to obtain a solid mixture;
step 3, placing the solid mixture into a tube furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite;
step 4, treating scandium diboride/expanded vermiculite with dicarboxylic acid to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing carboxylated scandium diboride/expanded vermiculite in an organic solvent, and then reacting with thionyl chloride to generate scandium diboride chloride/expanded vermiculite;
and 6, preparing trimethoprim into a solution, and reacting with scandium acyl chloride/expanded vermiculite under the action of a catalyst to obtain the ecological restoration agent for garden soil.
Preferably, in the step 1, the mesh number of the vermiculite particles after grinding and sieving is 300-500 mesh.
Preferably, in the step 2, the acid solution which is compatible with the diboron trioxide is hydrochloric acid, and the concentration of the hydrochloric acid is 1.8-2.4 mol/L; the mass ratio of the diboron trioxide to the hydrochloric acid is 1:10-15.
Preferably, in the step 2, scandium trichloride solution is obtained by dissolving scandium trichloride in deionized water, and the mass ratio of scandium trichloride to deionized water is 0.89-1.35:10.
Preferably, in the step 2, the binder is polyvinyl alcohol, the addition amount of the binder is 12% -18% of the mass of scandium trichloride solution, and the mass ratio of the diboron trioxide to the scandium trichloride solution is 1:12-16.
Preferably, in the step 3, an inert gas is required as a shielding gas during the roasting in the tube furnace, and the inert gas includes one of helium, neon and argon.
Preferably, in the step 3, the roasting temperature of the tube furnace is 950-1050 ℃, the roasting time is 2-4 hours, and the tube furnace needs to be washed with water and then dried after the roasting is finished.
Preferably, in the step 4, the dicarboxylic acid includes one of oxalic acid, malonic acid, adipic acid and azelaic acid.
Preferably, in the step 4, after scandium diboride/expanded vermiculite is dispersed with deionized water, dicarboxylic acid is added, and then stirring and dispersing treatment is carried out for 1-2 hours at 75-80 ℃; wherein the mass ratio of scandium diboride/expanded vermiculite, dicarboxylic acid and deionized water is 1:0.2-0.4:8-12.
Preferably, in the step 5, the organic solvent is chloroform, the mass ratio of carboxylated scandium diboride/expanded vermiculite to chloroform is 1:15-25, and the addition amount of thionyl chloride is 6% -10% of the mass of chloroform.
Preferably, in the step 5, the reaction condition with thionyl chloride is as follows: the thionyl chloride is added dropwise, ice water bath conditions are adopted before and during the dripping, stirring and mixing are carried out for 0.5-1 h after the dripping is finished, and then the temperature is raised to room temperature for reaction for 4-6 h.
Preferably, in the step 6, trimethoprim is mixed with absolute ethyl alcohol, glacial acetic acid is added, and after stirring and mixing are carried out uniformly, a solution is prepared; wherein the mass ratio of trimethoprim, glacial acetic acid and absolute ethyl alcohol is 1.15-1.42:0.4-0.6:5-10.
Preferably, in the step 6, the catalyst is triethylamine, scandium diboride chloride/expanded vermiculite is firstly dispersed in chloroform and then reacts with trimethoprim solution, wherein the mass ratio of scandium diboride chloride/expanded vermiculite, triethylamine, chloroform and trimethoprim solution is 1:0.02-0.04:5-10:6.2-8.6.
Preferably, in the step 6, the reaction conditions are as follows: under the protection of inert gas, the temperature is raised to 45-50 ℃ and the reflux reaction is carried out for 5-8 h.
In a second aspect, the invention provides a garden soil ecological restoration agent prepared by the preparation method.
The beneficial effects of the invention are as follows:
1. the invention discloses a garden soil ecological restoration agent, which is prepared by using scandium diboride modified vermiculite as a base material and combining grafted trimethoprim and carboxyl.
2. In the process of modifying vermiculite by scandium diboride, a compound containing scandium and boron is adsorbed on the surface of vermiculite powder after being mixed, then high-temperature sintering treatment is carried out, the vermiculite is dehydrated and swelled in the sintering process to generate more pores, scandium diboride is gradually generated in the sintering process, scandium diboride can be gradually generated on the surface of the vermiculite and in the generated pores, and the specific surface area of the vermiculite is increased in the generating process. The vermiculite is a soil conditioner with good water absorbability and cation exchange property, and subsequent tests show that the scandium diboride modified vermiculite has better adsorptivity to heavy metal, can reduce the water soluble and exchangeable heavy metal content in soil, and reduces the bioavailability and migration of heavy metal in soil.
3. The invention uses trimethoprim to modify carboxylated scandium diboride/expanded vermiculite, and forms a conjugate to be fixed in the scandium diboride/expanded vermiculite by generating more stable amide groups. Trimethoprim contains a large amount of methoxy and amino, amino and scandium diboride acyl chloride/expanded vermiculite generate amide groups, and methoxy and carboxyl easily form a hydrogen bond structure. When heavy metal ions are adsorbed, the heavy metal ions can be combined and coordinated with methoxy, amino and amido, so that a complex is generated and fixed by the ecological restoration agent.
4. In addition, the conjugate formed by trimethoprim and carboxylated scandium diboride/expanded vermiculite contains rich aromatic carbon, so that the conjugate has stronger adsorption affinity to HOCs compounds such as organic benzene, the adsorption affinity of the conjugate on the surface of the ecological restoration agent is stronger, and the adsorption affinity of the internal conjugate is weaker, so that the internal conjugate needs longer adsorption balance, the adsorbed organic benzene compounds are difficult to break loose, and a locking phenomenon is generated, so that the external conjugate of the ecological restoration agent is easier to adsorb, and the internal conjugate has stronger fixity, and a benign adsorption state is formed.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic view of a Scanning Electron Microscope (SEM) of a soil ecological restoration agent for gardens, prepared in example 1 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The expanded vermiculite can be used as a soil conditioner, and has good cation exchange property and adsorptivity, so that the structure of soil can be improved, water storage and soil moisture conservation can be realized, the air permeability and the water content of the soil can be improved, and the acid soil can be changed into neutral soil; vermiculite can also play a role in buffering, preventing rapid change of PH value, enabling fertilizer to be slowly released in crop growth medium, and allowing fertilizer to be used in a slightly excessive amount without harm to plants; vermiculite can also provide K, mg, ca, fe and trace Mn, cu, zn and other elements contained in the vermiculite to crops. The vermiculite has the characteristics of water absorption, cation exchange property and chemical components, so that the vermiculite plays multiple roles of fertilizer preservation, water storage, ventilation, mineral fertilizer and the like.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
A garden soil ecological restoration agent is prepared by the following steps:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder through a 400-mesh sieve to obtain vermiculite powder; dissolving diboron trioxide in 2.1mol/L hydrochloric acid, wherein the mass ratio of the diboron trioxide to the hydrochloric acid is 1:12, so as to obtain a diboron trioxide solution; scandium trichloride is dissolved in deionized water, and the mass ratio of scandium trichloride to deionized water is 1.14:10, so that scandium trichloride solution is obtained;
step 2, mixing scandium trichloride solution and diboron trioxide solution, wherein the mass ratio of the diboron trioxide to the scandium trichloride solution is 1:14, adding polyvinyl alcohol accounting for 15% of the mass of the scandium trichloride solution, heating to 60 ℃, stirring and mixing uniformly, adding vermiculite powder, mixing uniformly, drying under reduced pressure, and obtaining a solid mixture after complete drying;
step 3, placing the solid mixture into a crucible, placing the crucible into a tube furnace, introducing inert gas as a protective gas, heating the tube furnace to 1000 ℃, roasting for 3 hours, washing with water for at least three times, and drying to obtain scandium diboride/expanded vermiculite;
step 4, after scandium diboride/expanded vermiculite and deionized water are dispersed, malonic acid is added, and the mass ratio of scandium diboride/expanded vermiculite to malonic acid to deionized water is 1:0.3:10; stirring and uniformly mixing, stirring and dispersing for 2 hours at 80 ℃, filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, stirring the carboxylated scandium diboride/expanded vermiculite and the chloroform in an ice water bath until the temperature is constant, dropwise adding thionyl chloride, wherein the addition amount of the thionyl chloride is 8% of the mass of the chloroform, stirring and mixing for 1h, removing the ice water bath, simultaneously starting timing, reacting for 5h at room temperature, filtering out solids, and drying under reduced pressure to obtain scandium diboride chloride/expanded vermiculite;
step 6, mixing trimethoprim with absolute ethyl alcohol, dropwise adding glacial acetic acid, and uniformly stirring and mixing to obtain trimethoprim solution, wherein the mass ratio of trimethoprim to glacial acetic acid to absolute ethyl alcohol is 1.27:0.5:8;
step 7, scandium acyl chloride/expanded vermiculite is dispersed in chloroform, triethylamine is added, the mixture is poured into reflux equipment for magnetic stirring, inert gas is introduced for protection, the temperature is raised to 50 ℃, trimethoprim solution is dropwise added, after all the solutions are dropwise added, the heat preservation and stirring treatment are continued for 6 hours, solids are filtered out, and the solution is dried under reduced pressure, so that the garden soil ecological restoration agent is obtained; wherein the mass ratio of scandium acyl chloride/expanded vermiculite, triethylamine, chloroform and trimethoprim solution is 1:0.03:8:7.4.
Example 2
A garden soil ecological restoration agent, an SEM image is shown in figure 1, and the preparation method comprises the following steps:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder with a 300-mesh sieve to obtain vermiculite powder; dissolving diboron trioxide in 1.8mol/L hydrochloric acid, wherein the mass ratio of the diboron trioxide to the hydrochloric acid is 1:10, so as to obtain a diboron trioxide solution; scandium trichloride is dissolved in deionized water, and the mass ratio of scandium trichloride to deionized water is 0.89:10, so that scandium trichloride solution is obtained;
step 2, mixing scandium trichloride solution and diboron trioxide solution, wherein the mass ratio of the diboron trioxide to the scandium trichloride solution is 1:12, adding polyvinyl alcohol accounting for 12% of the mass of the scandium trichloride solution, heating to 55 ℃, stirring and mixing uniformly, adding vermiculite powder, mixing uniformly, drying under reduced pressure, and obtaining a solid mixture after complete drying;
step 3, placing the solid mixture into a crucible, placing the crucible into a tube furnace, introducing inert gas as a protective gas, heating the tube furnace to 950 ℃, roasting for 2 hours, washing with water for at least three times, and drying to obtain scandium diboride/expanded vermiculite;
step 4, dispersing scandium diboride/expanded vermiculite and deionized water, then adding oxalic acid, wherein the mass ratio of scandium diboride/expanded vermiculite to oxalic acid to deionized water is 1:0.2:8, stirring and mixing uniformly, stirring and dispersing for 1h at 75 ℃, and then filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, stirring the carboxylated scandium diboride/expanded vermiculite and the chloroform in an ice water bath until the temperature is constant, dropwise adding thionyl chloride, wherein the addition amount of the thionyl chloride is 6% of the mass of the chloroform, stirring and mixing for 0.5h, removing the ice water bath, simultaneously starting timing, reacting for 4h at room temperature, filtering out solids, and drying under reduced pressure to obtain scandium diboride chloride/expanded vermiculite;
step 6, mixing trimethoprim with absolute ethyl alcohol, dropwise adding glacial acetic acid, and uniformly stirring and mixing to obtain trimethoprim solution, wherein the mass ratio of trimethoprim to glacial acetic acid to absolute ethyl alcohol is 1.15:0.4:5;
step 7, scandium acyl chloride/expanded vermiculite is dispersed in chloroform, triethylamine is added, the mixture is poured into reflux equipment for magnetic stirring, inert gas is introduced for protection, the temperature is raised to 45 ℃, trimethoprim solution is dropwise added dropwise, after all the solutions are dropwise added, the heat preservation and stirring treatment are continued for 5 hours, solids are filtered out, and the solution is dried under reduced pressure, so that the garden soil ecological restoration agent is obtained; wherein the mass ratio of scandium acyl chloride to expanded vermiculite, triethylamine, chloroform and trimethoprim solution is 1:0.02:5:6.2.
Example 3
A garden soil ecological restoration agent is prepared by the following steps:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder with a 500-mesh sieve to obtain vermiculite powder; dissolving diboron trioxide in 2.4mol/L hydrochloric acid, wherein the mass ratio of the diboron trioxide to the hydrochloric acid is 1:15, so as to obtain a diboron trioxide solution; scandium trichloride is dissolved in deionized water, and the mass ratio of scandium trichloride to deionized water is 1.35:10, so that scandium trichloride solution is obtained;
step 2, mixing scandium trichloride solution and diboron trioxide solution, wherein the mass ratio of the diboron trioxide to the scandium trichloride solution is 1:16, adding polyvinyl alcohol accounting for 18% of the mass of the scandium trichloride solution, heating to 60 ℃, stirring and mixing uniformly, adding vermiculite powder, mixing uniformly, drying under reduced pressure, and obtaining a solid mixture after complete drying;
step 3, placing the solid mixture into a crucible, placing the crucible into a tube furnace, introducing inert gas as a protective gas, heating the tube furnace to 1050 ℃, roasting for 4 hours, washing with water for at least three times, and drying to obtain scandium diboride/expanded vermiculite;
step 4, dispersing scandium diboride/expanded vermiculite and deionized water, then adding adipic acid, uniformly stirring and mixing, stirring and dispersing for 2 hours at 80 ℃, filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, stirring the carboxylated scandium diboride/expanded vermiculite and the chloroform in an ice water bath until the temperature is constant, dropwise adding thionyl chloride, wherein the addition amount of the thionyl chloride is 10% of the mass of the chloroform, stirring and mixing for 1h, removing the ice water bath, simultaneously starting timing, reacting for 6h at room temperature, filtering out solids, and drying under reduced pressure to obtain scandium diboride chloride/expanded vermiculite;
step 6, mixing trimethoprim with absolute ethyl alcohol, dropwise adding glacial acetic acid, and uniformly stirring and mixing to obtain trimethoprim solution, wherein the mass ratio of trimethoprim to glacial acetic acid to absolute ethyl alcohol is 1.42:0.6:10;
step 7, scandium acyl chloride/expanded vermiculite is dispersed in chloroform, triethylamine is added, the mixture is poured into reflux equipment for magnetic stirring, inert gas is introduced for protection, the temperature is raised to 50 ℃, trimethoprim solution is dropwise added, after all the solutions are dropwise added, the heat preservation and stirring treatment are continued for 8 hours, solids are filtered out, and the solution is dried under reduced pressure, so that the garden soil ecological restoration agent is obtained; wherein the mass ratio of scandium acyl chloride to expanded vermiculite, triethylamine, chloroform and trimethoprim solution is 1:0.04:10:8.6.
Comparative example
A garden soil ecological restoration agent is prepared by the following steps:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder through a 400-mesh sieve to obtain vermiculite powder;
and 2, placing vermiculite powder in a crucible, placing the crucible in a tube furnace, introducing inert gas as a protective gas, heating the tube furnace to 500 ℃, roasting for 3 hours, washing with water for at least three times, and drying to obtain the expanded vermiculite.
In order to facilitate clear understanding of the present invention, the inventors also conducted experimental applications for the soil ecological restoration agents prepared in examples 1 to 3 and comparative examples, specifically as follows:
(1) 40kg of garden soil (red soil) polluted by the same area is collected, the content of heavy metals (lead, cadmium, mercury, arsenic and chromium) and the content of organic pollutants (organic benzene) in the soil are detected, the content is recorded as an initial value, and then the soil is evenly divided into four parts and then is respectively poured into four open containers with vent holes at the bottoms, numbered and reserved.
(2) The soil ecological restoration agents prepared in examples 1 to 3 and comparative example are respectively weighed, the weighed weight is 200g (2% of the soil weight), then the weighed soil ecological restoration agents are respectively scattered into a soil container with a number, uniformly mixed with the soil (the restoration agents are scattered while the soil is mixed), watered, the soil humidity is kept to be (25+/-1)%, the soil is kept under the condition of 25 ℃ for shading and standing for 30 days, the soil humidity is kept by continuous watering, and the heavy metal content (lead, cadmium, mercury, arsenic and chromium) and the organic pollutant content (organic benzene) in the soil are detected again after 30 days, and the soil ecological restoration agents are recorded as restoration values.
The test results are shown in table 1 below:
TABLE 1 Performance of soil ecological restoration agent
(3) And (3) calculating by a formula to obtain the restoration rate of the heavy metal content (lead, cadmium, mercury, arsenic and chromium) and the content of organic pollutants (organic benzene) in the polluted soil.
(4) The calculation formula is as follows: repair rate (%) = (1-repair value/initial value) ×100%;
the calculation results are shown in table 2 below:
TABLE 2 repair rate of soil ecological restoration agent
The results in table 1 and table 2 show that the remediation rate of heavy metal lead in the embodiment 1 of the invention can reach 81%, the remediation rate of cadmium can reach 68%, the remediation rate of mercury can reach 79%, the remediation rate of arsenic can reach 81%, the remediation rate of chromium can reach 67%, and the remediation rate of organic benzene can reach 74%, which are far higher than various values in the comparative example, so that the soil ecological remediation agent prepared by the invention has better remediation effect.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the ecological restoration agent for garden soil is characterized by comprising the following steps of:
step 1, cleaning vermiculite particles, grinding the cleaned vermiculite particles into powder, and sieving the powder to obtain vermiculite powder;
step 2, after dissolving diboron trioxide in acid liquor, mixing the solution with scandium trichloride under the condition of an adhesive to obtain a solid mixture;
step 3, placing the solid mixture into a tube furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite;
step 4, treating scandium diboride/expanded vermiculite with dicarboxylic acid to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing carboxylated scandium diboride/expanded vermiculite in an organic solvent, and then reacting with thionyl chloride to generate scandium diboride chloride/expanded vermiculite;
and 6, preparing trimethoprim into a solution, and reacting with scandium acyl chloride/expanded vermiculite under the action of a catalyst to obtain the ecological restoration agent for garden soil.
2. The method for preparing a garden soil ecological restoration agent according to claim 1, wherein in the step 1, the mesh number of the vermiculite particles after grinding and sieving is 300-500 meshes.
3. The method for preparing a garden soil ecological restoration agent according to claim 1, wherein in the step 2, the acid solution which is compatible with the diboron trioxide is hydrochloric acid, and the concentration of the hydrochloric acid is 1.8-2.4 mol/L; the adhesive is polyvinyl alcohol, and the addition amount of the adhesive is 12-18% of the mass of scandium trichloride solution.
4. The method for preparing a soil ecological restoration agent for gardens according to claim 1, wherein in the step 3, inert gas is required to be used as a shielding gas during roasting in a tube furnace, and the inert gas comprises one of helium, neon and argon.
5. The method for preparing a soil ecological restoration agent for gardens according to claim 1, wherein in the step 3, the roasting temperature of the tube furnace is 950-1050 ℃, the roasting time is 2-4 hours, and the water washing and drying treatment are needed after the roasting is finished.
6. The method for preparing ecological restoration agent for garden soil according to claim 1, wherein in the step 4, the dicarboxylic acid comprises one of oxalic acid, malonic acid, adipic acid and azelaic acid.
7. The method for preparing a garden soil ecological restoration agent according to claim 1, wherein in the step 4, scandium diboride/expanded vermiculite is dispersed with deionized water, dicarboxylic acid is added, and then stirring and dispersing treatment are carried out for 1-2 h at 75-80 ℃.
8. The method for preparing the ecological restoration agent for garden soil according to claim 1, wherein in the step 5, the organic solvent is chloroform, and the addition amount of thionyl chloride is 6% -10% of the mass of chloroform; the reaction conditions with thionyl chloride are as follows: the thionyl chloride is added dropwise, ice water bath conditions are adopted before and during the dripping, stirring and mixing are carried out for 0.5-1 h after the dripping is finished, and then the temperature is raised to room temperature for reaction for 4-6 h.
9. The method for preparing a garden soil ecological restoration agent according to claim 1, wherein in the step 6, trimethoprim is mixed with absolute ethyl alcohol, glacial acetic acid is added, and the mixture is stirred and mixed uniformly to prepare a solution; the catalyst is triethylamine, scandium chloride diboride/expanded vermiculite is firstly dispersed in chloroform and then reacts with trimethoprim solution, and the reaction conditions are as follows: under the protection of inert gas, the temperature is raised to 45-50 ℃ and the reflux reaction is carried out for 5-8 h.
10. A garden soil ecological restoration agent, which is characterized in that the garden soil ecological restoration agent is prepared by the preparation method of the garden soil ecological restoration agent according to any one of claims 1 to 9.
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