CN114774132A - 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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- CN114774132A CN114774132A CN202210359020.2A CN202210359020A CN114774132A CN 114774132 A CN114774132 A CN 114774132A CN 202210359020 A CN202210359020 A CN 202210359020A CN 114774132 A CN114774132 A CN 114774132A
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- scandium
- ecological restoration
- vermiculite
- restoration agent
- garden soil
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- 239000002689 soil Substances 0.000 title claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 95
- 239000010455 vermiculite Substances 0.000 claims abstract description 95
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 95
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 55
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 45
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims abstract description 32
- 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 30
- 229960001082 trimethoprim Drugs 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 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
- 239000008247 solid mixture Substances 0.000 claims abstract description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 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 Chemical compound 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
- 238000001035 drying Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011261 inert gas Substances 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000003054 catalyst 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
- 238000010992 reflux Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000000203 mixture Substances 0.000 claims 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 231100001240 inorganic pollutant Toxicity 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 description 13
- 229910001385 heavy metal Inorganic materials 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001555 benzenes Chemical class 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
- -1 organic benzenes Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 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
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003516 soil conditioner Substances 0.000 description 2
- 238000006467 substitution reaction 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
- 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
- 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 238000010304 firing Methods 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- 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 vermiculite particles into powder, and sieving the powder; step 2, dissolving diboron trioxide in an acid solution, and mixing with a scandium trichloride solution under the condition of an adhesive; step 3, placing the solid mixture in a tubular furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite; step 4, treating scandium diboride/expanded vermiculite by using dicarboxylic acid; step 5, acylating and chlorinating carboxylated scandium diboride/expanded vermiculite; and 6, reacting trimethoprim with acyl chloride scandium 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 simultaneously restore inorganic pollutants and organic pollutants in soil.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to a garden soil ecological remediation agent and a preparation method thereof.
Background
The soil is a loose surface layer which is arranged on the surface of the continent and provides plant growth fertility, with the development of modern chemical industry and agriculture, various industrial wastewater, harmful gas and other pollutants enter the soil, the harmful substances accumulated in the soil are increased continuously, agricultural production activities carried out on the polluted soil tend to form food safety problems, living, life and the like on the polluted soil can directly harm human health, besides, part of harmful cost also participates in natural and ecological system circulation of various forms such as solid, liquid, gas and the like, and damages are caused to human bodies and nature in a wider range.
Common pollution forms of garden soil comprise inorganic pollutants and organic pollutants, wherein the inorganic pollutants are most obviously polluted and most harmful by heavy metal elements, and the organic pollutants are most obviously polluted and most harmful by chemical fertilizers, pesticides, weed killers and the like. The inorganic pollutants are mainly heavy metals, and typically represent five heavy metal elements of lead, cadmium, mercury, arsenic and chromium; the 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 are not removed in time in the garden soil, plants in the garden can be damaged to a great extent, and underground water and surface water sources can be harmed, so that the health of human bodies is harmed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a garden soil ecological restoration agent and a preparation method thereof.
The purpose 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, dissolving diboron trioxide in acid liquor, and mixing with a scandium trichloride solution under the condition of an adhesive to obtain a solid mixture;
step 3, placing the solid mixture in a tubular furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite;
step 4, treating scandium diboride/expanded vermiculite by using dicarboxylic acid to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing the 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 acyl chloride scandium diboride/expanded vermiculite under the action of a catalyst to obtain the garden soil ecological restoration agent.
Preferably, in the step 1, the screened mesh number of the ground vermiculite particles is 300-500 meshes.
Preferably, in the step 2, the acid solution 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, the 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 adhesive is polyvinyl alcohol, the addition amount of the adhesive is 12-18% of the weight of the scandium trichloride solution, and the weight ratio of the diboron trioxide to the scandium trichloride solution is 1: 12-16.
Preferably, in the step 3, during the firing in the tube furnace, an inert gas is used as a shielding gas, and the inert gas includes one of helium, neon and argon.
Preferably, in the step 3, the roasting temperature of the tubular furnace is 950-1050 ℃, the roasting time is 2-4 h, and after the roasting is finished, water washing and drying treatment are needed.
Preferably, in step 4, the dicarboxylic acid includes one of oxalic acid, malonic acid, adipic acid and azelaic acid.
Preferably, in the step 4, after the scandium diboride/expanded vermiculite and the deionized water are dispersed, adding dicarboxylic acid, and then stirring and dispersing for 1-2 hours at the temperature of 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 the carboxylated scandium diboride/expanded vermiculite to the chloroform is 1: 15-25, and the addition amount of the thionyl chloride is 6-10% of the mass of the chloroform.
Preferably, in the step 5, the reaction conditions with thionyl chloride are: and (3) dropwise adding thionyl chloride, wherein ice-water bath conditions are adopted before and during dropwise adding, stirring and mixing are carried out for 0.5-1 h after dropwise adding is finished, and then heating to room temperature for reacting for 4-6 h.
Preferably, in the step 6, trimethoprim is mixed with absolute ethyl alcohol, and after glacial acetic acid is added and stirred 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, and the scandium chloride diboride/expanded vermiculite is dispersed in chloroform and then reacts with the trimethoprim solution, wherein the mass ratio of the scandium chloride diboride/expanded vermiculite, the triethylamine, the chloroform and the 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: and under the protection of inert gas, heating to 45-50 ℃, and carrying out reflux reaction for 5-8 h.
In a second aspect, the invention provides a garden soil ecological restoration agent prepared by the preparation method.
The invention has the beneficial effects that:
1. the invention discloses an ecological restoration agent for garden soil, which is prepared by using vermiculite modified by scandium diboride as a base material and grafting trimethoprim and a carboxyl combination, and has a good restoration effect on soil, and inorganic pollutants and organic pollutants in the soil can be restored simultaneously.
2. In the process of modifying vermiculite by using scandium diboride, a compound containing scandium and boron is mixed and adsorbed on the surface of vermiculite powder, then high-temperature sintering treatment is carried out, dehydration expansion of vermiculite occurs in the sintering process, more pores are generated, scandium diboride is gradually generated in the sintering process, scandium diboride can be gradually generated on the surface of vermiculite and in the generated pores, and the specific surface area of vermiculite is increased in the generating process. The vermiculite is a soil conditioner with good water absorption and cation exchange performance, and subsequent tests show that the vermiculite modified by scandium diboride has better adsorbability on heavy metals, can reduce the content of water-soluble and exchangeable heavy metals in soil, and reduces the bioavailability and the mobility of the heavy metals in the soil.
3. The invention uses trimethoprim to modify carboxylated scandium diboride/expanded vermiculite, and forms a combination to be fixed in the scandium diboride/expanded vermiculite by generating more stable amide groups. Trimethoprim contains a large amount of methoxy and amino, the amino and acyl chloride scandium diboride/expanded vermiculite generate amide groups, and the methoxy and carboxyl easily form a hydrogen bond structure. When being adsorbed, the heavy metal ions can be combined and coordinated with methoxyl, amino and amido to generate complex which is fixed by the ecological restoration agent.
4. In addition, the combination generated by trimethoprim and carboxylated scandium diboride/expanded vermiculite contains rich aromatic carbon, has stronger adsorption affinity to HOCs compounds such as organic benzenes, the adsorption affinity of the combination on the surface of the ecological restoration agent is stronger, and the adsorption affinity of the internal combination is weaker, so that the adsorption balance of the internal combination needs longer time, the adsorbed organic benzenes are difficult to break loose, and the phenomenon of locking is generated, so that the combination outside the ecological restoration agent is easier to adsorb, and the phenomenon that the internal combination has stronger immobilization forms a benign adsorption state.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
Fig. 1 is a schematic view of a Scanning Electron Microscope (SEM) of the garden soil ecological restoration agent prepared in example 1 of the present invention.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
The expanded vermiculite can be used as a soil conditioner, and has good cation exchange property and adsorbability, so that the structure of soil can be improved, water can be stored, soil moisture can be preserved, the air permeability and water content of the soil can be improved, and the acid soil can be changed into neutral soil; the vermiculite can also play a role in buffering, prevent the rapid change of the pH value, slowly release the fertilizer in a crop growth medium, and allow the fertilizer to be used in a slight excess manner without harming the plants; the vermiculite can also provide K, Mg, Ca and Fe contained in the vermiculite and trace elements such as Mn, Cu, Zn and the like to crops. The vermiculite has the characteristics of water absorption, cation exchange and chemical components, so that the vermiculite has multiple functions of fertilizer retention, water storage, air permeability, mineral fertilizer and the like.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The invention is 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 with a 400-mesh sieve to obtain vermiculite powder; dissolving boron trioxide in 2.1mol/L hydrochloric acid, wherein the mass ratio of the boron trioxide to the hydrochloric acid is 1:12, so as to obtain a boron trioxide solution; dissolving scandium trichloride in deionized water, wherein the mass ratio of scandium trichloride to deionized water is 1.14:10, and obtaining a scandium trichloride solution;
step 2, mixing a scandium trichloride solution and a scandium trioxide solution, wherein the mass ratio of the boron 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 and mixing uniformly, drying under reduced pressure, and obtaining a solid mixture after complete drying;
step 3, placing the solid mixture in a crucible, placing the crucible in a tubular furnace, introducing inert gas as protective gas, heating the tubular 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, dispersing scandium diboride/expanded vermiculite and deionized water, and then adding malonic acid, wherein the mass ratio of scandium diboride/expanded vermiculite to malonic acid to deionized water is 1:0.3: 10; stirring and mixing uniformly, then stirring and dispersing at 80 ℃ for 2h, and then filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, wherein the mass ratio of the carboxylated scandium diboride/expanded vermiculite to the chloroform is 1:20, stirring 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, starting timing at the same time, reacting for 5h at room temperature, filtering out solids, and drying under reduced pressure to obtain acyl scandium diboride/expanded vermiculite;
step 6, mixing trimethoprim and absolute ethyl alcohol, dropwise adding glacial acetic acid, and stirring and mixing uniformly to obtain trimethoprim solution, wherein the mass ratio of trimethoprim, glacial acetic acid and absolute ethyl alcohol is 1.27:0.5: 8;
step 7, dispersing acyl chloride scandium diboride/expanded vermiculite in chloroform, adding triethylamine, pouring into a backflow device for magnetic stirring, introducing inert gas for protection, heating to 50 ℃, dropwise adding a trimethoprim solution, continuously preserving heat and stirring for 6 hours after all dropwise adding, filtering out solids, and drying under reduced pressure to obtain the garden soil ecological restoration agent; wherein the mass ratio of the scandium chloride diboride/expanded vermiculite, the triethylamine, the chloroform and the trimethoprim solution is 1:0.03:8: 7.4.
Example 2
A garden soil ecological restoration agent is shown in an SEM image 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 boron trioxide in 1.8mol/L hydrochloric acid, wherein the mass ratio of the boron trioxide to the hydrochloric acid is 1:10, so as to obtain a boron trioxide solution; dissolving scandium trichloride in deionized water, wherein the mass ratio of scandium trichloride to deionized water is 0.89:10, and obtaining a scandium trichloride solution;
step 2, mixing a scandium trichloride solution and a scandium trioxide solution, wherein the mass ratio of the boron 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 in a crucible, placing the crucible in a tubular furnace, introducing inert gas as protective gas, heating the tubular 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, oxalic acid and deionized water is 1:0.2:8, stirring and mixing uniformly, stirring and dispersing at 75 ℃ for 1h, filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, wherein the mass ratio of the carboxylated scandium diboride/expanded vermiculite to the chloroform is 1:15, stirring 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, starting timing at the same time, reacting for 4h at room temperature, filtering out solids, and drying under reduced pressure to obtain acyl scandium diboride/expanded vermiculite;
step 6, mixing trimethoprim and absolute ethyl alcohol, dropwise adding glacial acetic acid, and stirring and mixing uniformly to obtain trimethoprim solution, wherein the mass ratio of trimethoprim, glacial acetic acid and absolute ethyl alcohol is 1.15:0.4: 5;
step 7, dispersing acyl chloride scandium diboride/expanded vermiculite in chloroform, adding triethylamine, pouring into a reflux device, stirring under magnetic force, introducing inert gas for protection, heating to 45 ℃, dropwise adding a trimethoprim solution, continuously stirring for 5 hours under heat preservation after all the trimethoprim solution is dropwise added, filtering out solids, and drying under reduced pressure to obtain the garden soil ecological restoration agent; wherein the mass ratio of scandium chloride diboride/expanded vermiculite, triethylamine, chloroform to 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 vermiculite particles into powder, and sieving the powder with a 500-mesh sieve to obtain vermiculite powder; dissolving boron trioxide in 2.4mol/L hydrochloric acid, wherein the mass ratio of the boron trioxide to the hydrochloric acid is 1:15, so as to obtain a boron trioxide solution; dissolving scandium trichloride in deionized water, wherein the mass ratio of scandium trichloride to deionized water is 1.35:10, and obtaining a scandium trichloride solution;
step 2, mixing a scandium trichloride solution and a scandium trioxide solution, wherein the mass ratio of the boron trioxide to the scandium trichloride solution is 1:16, adding 18% of polyvinyl alcohol by 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 in a crucible, placing the crucible in a tubular furnace, introducing inert gas as protective gas, heating the tubular 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, adding adipic acid, wherein the mass ratio of scandium diboride/expanded vermiculite to adipic acid to deionized water is 1:0.4:12, stirring and mixing uniformly, stirring and dispersing at 80 ℃ for 2 hours, filtering and drying to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing carboxylated scandium diboride/expanded vermiculite in chloroform, wherein the mass ratio of the carboxylated scandium diboride/expanded vermiculite to the chloroform is 1:25, stirring 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, starting timing at the same time, reacting for 6h at room temperature, filtering out solids, and drying under reduced pressure to obtain acyl scandium diboride/expanded vermiculite;
step 6, mixing trimethoprim and absolute ethyl alcohol, dropwise adding glacial acetic acid, and stirring and mixing uniformly to obtain trimethoprim solution, wherein the mass ratio of trimethoprim, glacial acetic acid and absolute ethyl alcohol is 1.42:0.6: 10;
step 7, dispersing acyl chloride scandium diboride/expanded vermiculite in chloroform, adding triethylamine, pouring into a reflux device, stirring under magnetic force, introducing inert gas for protection, heating to 50 ℃, dropwise adding a trimethoprim solution, continuously stirring for 8 hours under heat preservation after all the trimethoprim solution is dropwise added, filtering out solids, and drying under reduced pressure to obtain the garden soil ecological restoration agent; wherein the mass ratio of the scandium chloride diboride/expanded vermiculite, the triethylamine, the chloroform and the 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 vermiculite particles into powder, and sieving the powder with a 400-mesh sieve to obtain vermiculite powder;
and 2, placing the vermiculite powder in a crucible, placing the crucible in a tubular furnace, introducing inert gas as protective gas, heating the tubular 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 make the content of the invention more clear, the inventor also carries out experimental application on the soil ecological restoration agent prepared in the examples 1-3 and the comparative example, specifically as follows:
(1) collecting 40kg of polluted garden soil (red soil) from the same area, detecting the content of heavy metals (lead, cadmium, mercury, arsenic and chromium) and the content of organic pollutants (organic benzenes) in the soil, recording the content as an initial value, dividing the soil into four parts, pouring the four parts into four open containers with air vents at the bottoms, and numbering the containers for later use.
(2) The soil ecological restoration agents prepared in the embodiments 1-3 and the comparative example are weighed respectively, the weighed weight is 200g (2% of the weight of the soil), then the weighed soil ecological restoration agents are respectively scattered into numbered soil containers, the soil ecological restoration agents are uniformly mixed with the soil (the soil is mixed while the restoration agents are scattered), watering is carried out, the soil humidity is kept to be (25 +/-1)%, the soil ecological restoration agents are placed in a dark place for 30 days under the condition of 25 ℃, watering is continuously carried out during the period to keep the soil humidity, the contents of heavy metals (lead, cadmium, mercury, arsenic and chromium) and the contents of organic pollutants (organic benzenes) in the soil are detected again after 30 days, and the contents are recorded as restoration values.
The results are shown in table 1 below:
TABLE 1 Performance of soil ecological remediation Agents
(3) And (4) calculating by a formula to obtain the restoration rate of the heavy metal content (lead, cadmium, mercury, arsenic and chromium) and the content of the organic pollutants (organic benzenes) in the polluted soil.
(4) The calculation formula is as follows: the repair rate (%) (1-repair value/initial value) × 100%;
the calculation results are shown in table 2 below:
TABLE 2 remediation rate of soil ecological remediation agent
The results in tables 1 and 2 show that the remediation rate of heavy metal lead in example 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 benzenes can reach 74%, which are far higher than the values in the comparative example, which indicates that the soil ecological remediation agent prepared by the invention has a good remediation effect.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is 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 on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is 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 solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a garden soil ecological restoration agent is characterized by comprising the following steps:
step 1, cleaning vermiculite particles, grinding the vermiculite particles into powder, and sieving the powder to obtain vermiculite powder;
step 2, dissolving diboron trioxide in an acid solution, and mixing with a scandium trichloride solution under the condition of an adhesive to obtain a solid mixture;
step 3, placing the solid mixture in a tubular furnace for high-temperature roasting treatment to obtain scandium diboride/expanded vermiculite;
step 4, treating scandium diboride/expanded vermiculite by using dicarboxylic acid to obtain carboxylated scandium diboride/expanded vermiculite;
step 5, dispersing the 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 acyl chloride scandium diboride/expanded vermiculite under the action of a catalyst to obtain the garden soil ecological restoration agent.
2. The preparation method of the garden soil ecological restoration agent according to claim 1, wherein in the step 1, the vermiculite particles are ground and sieved to obtain a mesh number of 300-500.
3. The preparation method of the garden soil ecological restoration agent according to claim 1, wherein in the step 2, the acid solution compatible with boron 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 weight of the scandium trichloride solution.
4. The method for preparing an ecological restoration agent for garden soil according to claim 1, wherein in step 3, an inert gas is used as a shielding gas during the roasting in the tube furnace, and the inert gas comprises one of helium, neon and argon.
5. The preparation method of the garden soil ecological restoration agent according to claim 1, wherein in the step 3, the roasting temperature of the tubular furnace is 950-1050 ℃, the roasting time is 2-4 h, and after the roasting, the treatment of washing and drying is required.
6. The method for preparing an 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 preparation method of the garden soil ecological restoration agent according to claim 1, wherein in the step 4, the dicarboxylic acid is added after the scandium diboride/expanded vermiculite is dispersed with the deionized water, and then the mixture is stirred and dispersed at 75-80 ℃ for 1-2 hours.
8. The preparation method of the garden soil ecological restoration agent according to claim 1, wherein in the step 5, the organic solvent is chloroform, and the addition amount of the thionyl chloride is 6% -10% of the mass of the chloroform; the conditions for the reaction with thionyl chloride were: and adding thionyl chloride dropwise, wherein ice-water bath conditions are adopted before and during the dropwise adding, stirring and mixing are carried out for 0.5-1 h after the dropwise adding is finished, and then heating to room temperature for reacting for 4-6 h.
9. The preparation method of the 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 diboride chloride/expanded vermiculite is firstly dispersed in chloroform and then reacts with trimethoprim solution, and the reaction conditions are as follows: and under the protection of inert gas, heating to 45-50 ℃, and carrying out reflux reaction for 5-8 h.
10. A garden soil ecological restoration agent, which is characterized by being prepared by using the preparation method of the garden soil ecological restoration agent according to any one of claims 1-9.
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