CN117625200A - Preparation method and application of contaminated soil heavy metal passivation material - Google Patents
Preparation method and application of contaminated soil heavy metal passivation material Download PDFInfo
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- CN117625200A CN117625200A CN202311441862.3A CN202311441862A CN117625200A CN 117625200 A CN117625200 A CN 117625200A CN 202311441862 A CN202311441862 A CN 202311441862A CN 117625200 A CN117625200 A CN 117625200A
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- attapulgite
- heavy metal
- passivation material
- contaminated soil
- dropwise adding
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 105
- 239000002689 soil Substances 0.000 title claims abstract description 98
- 238000002161 passivation Methods 0.000 title claims abstract description 92
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 102
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 229960000892 attapulgite Drugs 0.000 claims abstract description 78
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 78
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims abstract description 49
- 239000002699 waste material Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 33
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 tetramethyl ester Chemical class 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 144
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- 238000006243 chemical reaction Methods 0.000 claims description 32
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- 239000002245 particle Substances 0.000 claims description 10
- WYNNHRLBLIZWSW-UHFFFAOYSA-N dimethyl 2-iminobutanedioate Chemical compound COC(=O)CC(=N)C(=O)OC WYNNHRLBLIZWSW-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 230000009920 chelation Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 238000001291 vacuum drying Methods 0.000 description 24
- 241000209094 Oryza Species 0.000 description 18
- 241000237502 Ostreidae Species 0.000 description 17
- 235000020636 oyster Nutrition 0.000 description 17
- 239000002738 chelating agent Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 11
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- 238000012360 testing method Methods 0.000 description 6
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- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical class OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
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- 239000005995 Aluminium silicate Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- 235000019354 vermiculite Nutrition 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
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- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of soil heavy metal passivation, and discloses a preparation method and application of a contaminated soil heavy metal passivation material. The method comprises the following steps: reacting the attapulgite with gamma-aminopropyl triethoxysilane to prepare amino modified attapulgite; reacting the amino modified attapulgite with dimethyl maleate to obtain attapulgite-dimethyl iminosuccinate; reacting the attapulgite-iminosuccinic acid dimethyl ester with maleic acid dimethyl ester to prepare attapulgite-nitrilodisuccinic acid tetramethyl ester; after the attapulgite-tetramethyl nitrilodisuccinic acid reacts with sodium hydroxide aqueous solution, regulating the pH value to 2-3 to prepare the attapulgite-tetramethyl nitrilodisuccinic acid; and (3) crushing straw and aquatic wastes, and mixing with the attapulgite-nitrilodisuccinic acid to obtain the polluted soil heavy metal passivation material. The contaminated soil heavy metal passivation material can realize the stable passivation of the contaminated soil heavy metal by combining adsorption and chelation.
Description
Technical Field
The invention belongs to the technical field of soil heavy metal passivation, and particularly relates to a preparation method and application of a contaminated soil heavy metal passivation material.
Background
With the rapid development of modern economy and industry, the environmental pollution such as water pollution, air pollution, soil pollution and the like is increasingly severe. Heavy metal pollution is one of the most serious soil pollution, and heavy metal has extremely strong toxicity even under low concentration, cannot be decomposed by microorganisms or degraded by chemical processes after entering the soil, and can continuously exist in the soil environment. When crops such As grains and vegetables are planted on the soil polluted by the heavy metals, the heavy metals such As mercury (Hg), arsenic (As), cadmium (Cd), lead (Pb), chromium (Cr) and the like can be absorbed by the crops and enter a food chain, so that the heavy metals are enriched in animals or human bodies, and further the health of human beings is endangered. Therefore, the polluted soil needs to be repaired, and the biological effective state content of heavy metals in the soil is reduced.
Chinese patent application CN116116892A discloses a bioremediation method for heavy metal contaminated soil, which adopts sunflower and mustard to carry out wheel tillage, is matched with microbial agents, has strong adaptability to living environment and strong absorption and accumulation capacity to lead and chromium elements through two restoration modes of microbial agents and plants, and has strong removal capacity to chromium, cadmium and other heavy metal elements, so that two plants are matched with each other, and can extract and enrich heavy metal ions activated and dissociated by microorganisms, thereby realizing restoration of the heavy metal contaminated soil, but the heavy metal contaminated soil cannot be eaten after plant planting is finished, and harmless treatment is needed, otherwise, heavy metal can enter the soil environment again along with decay and decomposition of plants. Chinese patent CN104560047B discloses a soil heavy metal passivating agent which comprises humic acid, sulfhydryl compound, calcium phosphate and chitosan, is rich in functional groups such as sulfhydryl, amino, carboxyl and the like which can be subjected to complexation with heavy metals, and can be subjected to chelation and complexation reaction with heavy metal ions in soil, so that the activity of the heavy metals in the soil is reduced. However, the chelation and complexation operation of the functional groups and heavy metal ions are weak, and the passivation effect is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a heavy metal passivation material for contaminated soil, which solves the problem of poor passivation effect of the heavy metal in the contaminated soil in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing Attapulgite (ATP) in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, reacting after the dropwise adding is finished, filtering, washing and drying to obtain amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, reacting after the dropwise adding is finished, filtering, washing and drying after the reaction is finished to obtain the attapulgite-dimethyl iminosuccinate;
dispersing attapulgite-iminosuccinic acid dimethyl ester in N, N-dimethylformamide, dropwise adding dimethyl maleate, reacting after the dropwise adding is finished, filtering, washing and drying after the reaction is finished to obtain attapulgite-nitrilodisuccinic acid tetramethyl ester;
dispersing the attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding a sodium hydroxide aqueous solution, reacting after the dropwise adding is finished, adjusting the pH value to be 2-3 after the reaction is finished, filtering, washing and drying to obtain the attapulgite-tetramethyl nitrilodisuccinate;
and fifthly, crushing the straw and the aquatic wastes, mixing with the attapulgite-nitrilodisuccinic acid, and granulating to obtain the polluted soil heavy metal passivation material.
Preferably, in the first step, the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10 (80-100): 16-20, and the reaction condition is that the reaction is carried out for 3-5 hours at the temperature of 50-70 ℃.
Further, the dripping time of the gamma-aminopropyl triethoxysilane is 30-60min.
Preferably, the attapulgite clay in the first step can be replaced by other natural clay minerals including dolomite, diatomaceous earth, montmorillonite, kaolin, vermiculite.
Preferably, the attapulgite in the first step can be replaced by a composition formed by attapulgite and at least one of dolomite, diatomite, montmorillonite, kaolin and vermiculite.
Preferably, in the second step, the mass ratio of the amino modified attapulgite, the N, N-dimethylformamide and the dimethyl maleate is (95-115): (800-1200): (15-20), and the reaction condition is that the reaction is carried out for 20-30 hours at room temperature.
Further, the dropwise adding time of the dimethyl maleate is 30-60min.
Preferably, in the third step, the mass ratio of the attapulgite to the iminosuccinic acid dimethyl ester, the N, N-dimethylformamide to the maleic acid dimethyl ester is (105-125): (1000-1500): (15-20), and the reaction condition is that the reaction is carried out for 20-30 hours at room temperature.
Further, the dropwise adding time of the dimethyl maleate is 30-60min.
Preferably, in the fourth step, the mass ratio of the attapulgite to the tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the sodium hydroxide aqueous solution is (115-140): (1200-1500): (85-110), and the reaction condition is that the reaction is carried out for 2-3 hours at the temperature of 60-70 ℃.
Preferably, the aqueous sodium hydroxide solution is added dropwise for a period of 30 to 60 minutes.
Further, the aqueous sodium hydroxide solution comprises 10wt% aqueous sodium hydroxide solution,
preferably, in the fifth step, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is (25-50): (25-50): (50-100).
Preferably, the straw comprises corn straw, wheat straw and rice straw;
the mass ratio of the corn straw to the wheat straw to the rice straw is (10-20)/(5-10).
The aquatic waste comprises fish bones, crab shells and oyster shells;
the mass ratio of the fish bone, the crab shell and the oyster shell is (5-10)/(10-20).
Preferably, in the fifth step, the granulating mode is performed in a disc granulator; the particle size of the heavy metal passivation material for the polluted soil is 3.5-5mm.
Preferably, the application of the contaminated soil heavy metal passivation material prepared by the preparation method of the contaminated soil heavy metal passivation material to heavy metal contaminated soil is provided.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the natural clay mineral attapulgite, crop straws and aquatic wastes are used as preparation raw materials, and each raw material has a good adsorption effect, can effectively adsorb heavy metals in polluted soil, is wide in source and low in price, and can realize effective utilization of the wastes while solving the problem of passivation of the heavy metals in the polluted soil;
according to the invention, the attapulgite is modified, and the amino polycarboxylic acid chelating agent is introduced, so that the amino polycarboxylic acid chelating agent has a strong effect of chelating metal ions, the attapulgite, the straw and the aquatic waste can adsorb heavy metals in polluted soil into a passivation material, the amino polycarboxylic acid chelating agent can effectively chelate the adsorbed heavy metals, the heavy metals are prevented from being released into the soil environment again, and the stable passivation of the heavy metals in the polluted soil is realized by combining adsorption and chelation; secondly, the aminopolycarboxylic acid chelating agent is connected with the attapulgite through a stable chemical bond, so that dissolution loss of the chelating agent can be prevented; finally, the amino polycarboxylic acid chelating agent introduced in the invention is an environment-friendly chelating agent iminodisuccinic acid derivative, and can not bring non-degradable pollutants to the soil environment when being applied to the soil.
Drawings
FIG. 1 is a flow chart of a preparation process of a contaminated soil heavy metal passivation material in the invention;
FIG. 2 is a schematic illustration of the reaction of an amino modified attapulgite with dimethyl maleate to prepare attapulgite-tetramethyl nitrilodisuccinate according to the present invention;
FIG. 3 is a bar graph showing the results of the passivation capability test of heavy metal Pb of the contaminated soil heavy metal passivation materials prepared in examples 1 to 6 and comparative examples 1 to 2 according to the present invention;
FIG. 4 is a bar graph showing the results of the passivation capability test of heavy metal Cd of the contaminated soil heavy metal passivation materials prepared in examples 1-6 and comparative examples 1-2 of the present invention;
FIG. 5 is a bar graph showing the results of the passivation capability test of heavy metal passivation materials for heavy metal Cr in contaminated soil prepared in examples 1 to 6 and comparative examples 1 to 2 according to the present invention;
FIG. 6 is a bar graph showing the results of the passivation capability test of heavy metal As of the contaminated soil heavy metal passivation materials prepared in examples 1 to 6 and comparative examples 1 to 2 of the present invention;
fig. 7 is a bar graph showing the results of the passivation capability test of heavy metal Hg for the contaminated soil heavy metal passivation materials prepared in examples 1 to 6 and comparative examples 1 to 2 according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:80:16, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 30min, reacting for 5h at 50 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 95:800:15, the dropwise adding time of the dimethyl maleate is 30min, reacting at room temperature for 20h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 105:1000:15, the dropwise adding time of the dimethyl maleate is 30min, reacting at room temperature for 20h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 115:1200:85, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 30min, reacting for 3h at 60 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 2 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain attapulgite-amino disuccinic acid;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 25:25:100;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 10:20:10;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 5:20:20;
the particle size of the heavy metal passivation material for the polluted soil is 3.5mm.
Example 2
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:100:20, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 60min, reacting for 3h at 70 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 115:1200:20, the dropwise adding time of the dimethyl maleate is 60min, reacting at room temperature for 30h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 125:1500:20, the dropwise adding time of the dimethyl maleate is 60min, reacting at room temperature for 30h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 140:1500:110, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 60min, reacting for 2h at 70 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 3 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the attapulgite-tetramethyl nitrilodisuccinate;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 50:50:50;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 20:10:10;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 10:10:20;
the particle size of the heavy metal passivation material for the polluted soil is 5mm.
Example 3
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:84:17, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 35min, reacting for 4h at 60 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 100:880:16, the dropwise adding time of the dimethyl maleate is 35min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 110:1100:16, the dropwise adding time of the dimethyl maleate is 35min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 120:1260:90, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 35min, reacting for 2.5h at 65 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 2.5 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying box to obtain attapulgite-amino disuccinic acid;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 30:30:90;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 20:20:5;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 10:20:10;
the particle size of the heavy metal passivation material for the polluted soil is 4mm.
Example 4
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:88:18, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 40min, reacting for 4h at 60 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 105:960:17, the dropwise adding time of the dimethyl maleate is 40min, reacting at room temperature for 25h after the dropwise adding is finished, filtering after the reaction is finished, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 115:1200:17, the dropwise adding time of the dimethyl maleate is 40min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 125:1320:95, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 40min, reacting for 2.5h at 65 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 2.5 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the attapulgite-tetramethyl nitrilodisuccinate;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 35:35:80;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 10:10:10;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 5:10:20;
the particle size of the heavy metal passivation material for the polluted soil is 4mm.
Example 5
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:92:18, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 45min, reacting for 4h at 60 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 10:1050:18, the dropwise adding time of the dimethyl maleate is 45min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 115:1300:18, the dropwise adding time of the dimethyl maleate is 45min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 130:1380:100, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 45min, reacting for 2.5h at 65 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 2.5 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying box to obtain the attapulgite-amino disuccinic acid;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 40:40:70;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 10:10:5;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 5:10:10;
the particle size of the heavy metal passivation material for the polluted soil is 4.5mm.
Example 6
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the attapulgite to the dimethylbenzene to the gamma-aminopropyl triethoxysilane is 10:96:19, the dropwise adding time of the gamma-aminopropyl triethoxysilane is 50min, reacting for 4h at 60 ℃ after the dropwise adding is finished, filtering, washing with ethanol, and drying for 10h at 50 ℃ in a vacuum drying oven to obtain the amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the amino modified attapulgite to the N, N-dimethylformamide to the dimethyl maleate is 110:1120:19, the dropwise adding time of the dimethyl maleate is 50min, reacting at room temperature for 25h after the dropwise adding is finished, filtering after the reaction is finished, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-iminosuccinic acid dimethyl ester;
dispersing attapulgite-dimethyl iminosuccinate in N, N-dimethylformamide, dropwise adding dimethyl maleate, wherein the mass ratio of the attapulgite to the dimethyl iminosuccinate to the N, N-dimethylformamide to the dimethyl maleate is 120:1400:19, the dropwise adding time of the dimethyl maleate is 50min, reacting at room temperature for 25h after the dropwise adding is finished, filtering, washing with ethanol, and drying at 50 ℃ in a vacuum drying oven for 10h to obtain the attapulgite-tetramethyl iminodisuccinate;
dispersing attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding 10wt% of sodium hydroxide aqueous solution, wherein the mass ratio of the attapulgite-tetramethyl nitrilodisuccinate to the N, N-dimethylformamide to the 10wt% of sodium hydroxide aqueous solution is 135:1440:105, the dropwise adding time of the 10wt% of sodium hydroxide aqueous solution is 50min, reacting for 2.5h at 65 ℃ after the dropwise adding is finished, adding 2mol/L of hydrochloric acid aqueous solution to adjust the pH value to 2.5 after the reaction is finished, filtering, washing with deionized water, and drying for 10h at 50 ℃ in a vacuum drying box to obtain the attapulgite-amino disuccinic acid;
step five, crushing straw and aquatic wastes, mixing the crushed straw and aquatic wastes with attapulgite-nitrilodisuccinic acid, and granulating the mixture by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is 45:45:60;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 15:15:7.5;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 7.5:15:15;
the particle size of the heavy metal passivation material for the polluted soil is 4.5mm.
Comparative example 1
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
crushing straw and aquatic wastes, mixing with attapulgite, and granulating by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite is 50:50:50;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 20:10:10;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 10:10:20;
the particle size of the heavy metal passivation material for the polluted soil is 5mm.
Comparative example 2
The preparation method of the contaminated soil heavy metal passivation material comprises the following steps:
crushing straw and aquatic wastes, mixing with attapulgite and iminodisuccinic acid, and granulating by a disc granulator to obtain a polluted soil heavy metal passivation material;
wherein, the mass ratio of the straw to the aquatic waste to the attapulgite to the iminodisuccinic acid is 50:50:38:12;
the straw comprises corn straw, wheat straw and rice straw, wherein the mass ratio of the corn straw to the wheat straw to the rice straw is 20:10:10;
the aquatic waste comprises fish bones, crab shells and oyster shells, wherein the mass ratio of the fish bones to the crab shells to the oyster shells is 10:10:20;
the particle size of the heavy metal passivation material for the polluted soil is 5mm.
Test examples
The passivation ability of the prepared contaminated soil heavy metal passivation materials of examples 1 to 6 and comparative examples 1 to 2 to heavy metals in heavy metal contaminated soil was measured:
applying a heavy metal passivation material for the polluted soil to the heavy metal polluted agricultural land, wherein the application amount is 150 kg/mu, and the application depth is 15cm away from the soil surface; soil samples corresponding to examples 1 to 6 and comparative examples 1 to 2 were collected before applying the contaminated soil heavy metal passivation material, after applying the contaminated soil heavy metal passivation material for 1 month, and after applying the contaminated soil heavy metal passivation material for 12 months (the soil sample collection method was in accordance with standard HJ/T166-2004), and the effective Pb content, the effective Cd content, the effective Cr content, the effective As content, and the effective Hg content were measured, respectively, and the measurement results of the effective Pb content, the effective Cd content, the effective Cr content, the effective As content, the effective Hg content, the effective Pb reduction amount, the effective Cd reduction amount, the effective Cr reduction amount, the effective As reduction amount, and the effective Hg reduction amount were shown in table 1:
TABLE 1
As shown in Table 1, the heavy metal passivation material for contaminated soil prepared by the invention has good passivation capability on heavy metals in heavy metal contaminated soil. The attapulgite, straw and aquatic wastes in the passivation material can effectively adsorb heavy metals in polluted soil, the environment-friendly aminopolycarboxylic acid chelating agent introduced by modification of the attapulgite has strong chelating ability, the adsorbed heavy metals are effectively chelated, the passivation material has strong passivation ability by combining adsorption and chelation, along with the prolongation of passivation time, although the straw and the aquatic wastes can be gradually decomposed and the adsorption is weakened, the chelating agent connected with the attapulgite can still effectively chelate the heavy metals, and the passivation aging is prolonged. The heavy metal content in the agricultural soil after passivation treatment by the passivation material meets the requirements of agricultural soil pollution risk management and control standards, and normal agricultural planting can be performed. Compared with example 2, the passivation material in comparative example 1 only contains the material with adsorption effect, no chelating agent is introduced, the passivation capability is lower than that of the passivation material prepared in example 2, the effective Pb content, the effective Cd content, the effective Cr content, the effective As content and the effective Hg content in soil are high, and As the passivation time is prolonged, straws and aquatic wastes are gradually decomposed to lose adsorption effect, a large amount of adsorbed and passivated heavy metals are released into soil again, and the effective Pb content, the effective Cd content, the effective Cr content, the effective As content and the effective Hg content in soil are greatly increased. In comparison with example 2, the passivation material in comparative example 2, though containing the material having adsorption effect and the aminopolycarboxylic acid chelating agent iminodisuccinic acid, the chelating agent is not connected with the attapulgite by a stable chemical bond, the chelating agent is easy to dissolve and lose, the chelation effect is weakened, and thus the passivation capability of the passivation material is reduced, the effective Pb content, the effective Cd content, the effective Cr content, the effective As content and the effective Hg content in the soil are slightly higher than those in example 2, the adsorption material is further dissolved and lost while the decomposition of the adsorption material occurs along with the prolongation of the passivation time, and the effective heavy metal content in the soil after the passivation material is applied for 12 months is higher than that in the soil to which the passivation material of example 2 is applied.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the contaminated soil heavy metal passivation material is characterized by comprising the following steps of:
dispersing attapulgite in dimethylbenzene, dropwise adding gamma-aminopropyl triethoxysilane, reacting after the dropwise adding is finished, filtering, washing and drying after the reaction is finished to obtain amino modified attapulgite;
dispersing the amino modified attapulgite in N, N-dimethylformamide, dropwise adding dimethyl maleate, reacting after the dropwise adding is finished, filtering, washing and drying after the reaction is finished to obtain the attapulgite-dimethyl iminosuccinate;
dispersing attapulgite-iminosuccinic acid dimethyl ester in N, N-dimethylformamide, dropwise adding dimethyl maleate, reacting after the dropwise adding is finished, filtering, washing and drying after the reaction is finished to obtain attapulgite-nitrilodisuccinic acid tetramethyl ester;
dispersing the attapulgite-tetramethyl nitrilodisuccinate in N, N-dimethylformamide, dropwise adding a sodium hydroxide aqueous solution, reacting after the dropwise adding is finished, adjusting the pH value to be 2-3 after the reaction is finished, filtering, washing and drying to obtain the attapulgite-tetramethyl nitrilodisuccinate;
and fifthly, crushing the straw and the aquatic wastes, mixing with the attapulgite-nitrilodisuccinic acid, and granulating to obtain the polluted soil heavy metal passivation material.
2. The preparation method of the contaminated soil heavy metal passivation material according to claim 1, wherein in the first step, the mass ratio of the attapulgite, the dimethylbenzene and the gamma-aminopropyl triethoxysilane is 10 (80-100): 16-20, and the reaction condition is that the reaction is carried out for 3-5 hours at the temperature of 50-70 ℃.
3. The method for preparing the contaminated soil heavy metal passivation material according to claim 1, wherein in the second step, the mass ratio of the amino modified attapulgite, the N, N-dimethylformamide and the dimethyl maleate is (95-115): (800-1200): (15-20), and the reaction condition is that the reaction is carried out for 20-30 hours at room temperature.
4. The method for preparing the contaminated soil heavy metal passivation material according to claim 1, wherein in the third step, the mass ratio of the attapulgite to the dimethyl iminosuccinate, the N, N-dimethylformamide and the dimethyl maleate is (105-125): (1000-1500): (15-20), and the reaction condition is that the reaction is carried out for 20-30 hours at room temperature.
5. The method for preparing the contaminated soil heavy metal passivation material according to claim 1, wherein in the fourth step, the mass ratio of the attapulgite to the tetramethyl nitrilodisuccinate, the N, N-dimethylformamide to the aqueous solution of sodium hydroxide is (115-140): (1200-1500): (85-110), and the reaction condition is that the reaction is carried out at the temperature of 60-70 ℃ for 2-3 hours.
6. The method for preparing the contaminated soil heavy metal passivation material according to claim 1, wherein in the fifth step, the mass ratio of the straw to the aquatic waste to the attapulgite to the nitrilodisuccinic acid is (25-50): (25-50): (50-100).
7. The method for preparing the contaminated soil heavy metal passivation material according to claim 6, wherein the straw comprises corn straw, wheat straw and rice straw; the mass ratio of the corn straw to the wheat straw to the rice straw is (10-20)/(5-10).
8. The method for preparing a contaminated soil heavy metal passivation material according to claim 6, wherein the aquatic waste comprises fish bone, crab shell and oyster shell;
the mass ratio of the fish bone, the crab shell and the oyster shell is (5-10)/(10-20).
9. The method for preparing the passivation material for heavy metals in contaminated soil according to claim 1, wherein in the fifth step, the particle size of the passivation material for heavy metals in contaminated soil is 3.5-5mm.
10. Use of a contaminated soil heavy metal passivation material prepared by the method of any one of claims 1-9 in heavy metal contaminated soil.
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