CN116554888B - Soil restoration agent suitable for heavy metal pollution of soil - Google Patents
Soil restoration agent suitable for heavy metal pollution of soil Download PDFInfo
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- CN116554888B CN116554888B CN202310841559.6A CN202310841559A CN116554888B CN 116554888 B CN116554888 B CN 116554888B CN 202310841559 A CN202310841559 A CN 202310841559A CN 116554888 B CN116554888 B CN 116554888B
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- hydroxyapatite
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- 239000002689 soil Substances 0.000 title claims abstract description 42
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 23
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 61
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 61
- 239000000440 bentonite Substances 0.000 claims abstract description 56
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 56
- 241000209094 Oryza Species 0.000 claims abstract description 55
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 55
- 235000009566 rice Nutrition 0.000 claims abstract description 55
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 230000004048 modification Effects 0.000 claims abstract description 30
- 238000012986 modification Methods 0.000 claims abstract description 30
- 230000001105 regulatory effect Effects 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 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 claims abstract description 18
- 239000002028 Biomass Substances 0.000 claims abstract description 18
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000003610 charcoal Substances 0.000 claims abstract description 18
- 239000004021 humic acid Substances 0.000 claims abstract description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 69
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 13
- 239000007983 Tris buffer Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 claims description 12
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 238000005067 remediation Methods 0.000 claims description 7
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 230000003750 conditioning effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The invention discloses a soil restoration agent suitable for soil heavy metal pollution, which comprises the following raw materials in parts by weight: 40-45 parts of bentonite regulating slurry, 15-25 parts of biomass charcoal, 5-10 parts of calcium hydroxy phosphate, 2-5 parts of humic acid, 3-6 parts of hydroxyapatite blending rice hull ash agent and 1-3 parts of calcium oxide. According to the invention, biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite are blended with rice hull ash and calcium oxide raw materials to be compounded and prepared, through coordination among various raw materials, bentonite adjustment slurry is used as matrix liquid to carry out coating modification, through coordination among bentonite adjustment slurry and the hydroxyapatite blending rice hull ash, the raw materials are synergistic, the heavy metal adsorption efficiency of the product is enhanced, sustainable adsorption can be realized, and meanwhile, the product has stable performance under the acid corrosion condition.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a soil remediation agent suitable for soil heavy metal pollution.
Background
Soil is one of the main natural resources that humans depend on to survive, and is also an important component of the human ecological environment. However, with the increase of industrial and urban pollution and the increase of the types and the quantity of agricultural chemical substances, the heavy metal pollution of soil is increasingly serious. Therefore, in order to protect natural resources and maintain good ecological environment, the soil polluted by heavy metals is repaired into unprecedented matters.
The existing soil repairing agent is easy to saturate in heavy metal adsorption, long-acting repairing efficiency is difficult to realize, meanwhile, the repairing agent is difficult to store under the acid corrosion condition, the adsorption effect is easy to influence after long-term storage, and the invention further improves the problem.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a soil restoration agent suitable for soil heavy metal pollution so as to solve the problems in the prior art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a soil restoration agent suitable for soil heavy metal pollution, which comprises the following raw materials in parts by weight:
40-45 parts of bentonite regulating slurry, 15-25 parts of biomass charcoal, 5-10 parts of calcium hydroxy phosphate, 2-5 parts of humic acid, 3-6 parts of hydroxyapatite blending rice hull ash agent and 1-3 parts of calcium oxide;
the preparation method of the repairing agent comprises the following steps: and (3) mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite with the rice hull ash agent, uniformly stirring and mixing the mixture, and then adding the mixture into bentonite-regulated slurry for continuous mixing to obtain the repairing agent.
Preferably, the soil restoration agent comprises the following raw materials in parts by weight:
42.5 parts of bentonite regulating slurry, 20 parts of biomass charcoal, 7.5 parts of calcium hydroxy phosphate, 3.5 parts of humic acid, 4.5 parts of hydroxyapatite blending rice hull ash agent and 2 parts of calcium oxide.
Preferably, the preparation method of the bentonite conditioning slurry comprises the following steps:
s01: feeding bentonite into 130-140 deg.C, heat treating for 10-15min, cooling to 45-55 deg.C at 1-3 deg.C/min, and maintaining for 5-10min;
s02: placing the S01 product into hydrochloric acid solution with the total amount of 3-5 times of the S01 product, then adding sodium dodecyl sulfate with the total amount of 2-5% of the S01 product and yttrium nitrate solution with the total amount of 1-5% of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 2-5% of the total amount of the S01 product and a Tris buffer solution accounting for 1-3% of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 3-5 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry.
Preferably, the mass fraction of the hydrochloric acid solution is 1-3%; the mass fraction of the yttrium nitrate solution is 2-5%.
Preferably, the rotational speed of the primary stirring pre-modification is 350-450r/min, the stirring temperature is 40-45 ℃, and the stirring time is 30-40min; the rotational speed of the secondary stirring pre-modification is 800-1000r/min, the stirring temperature is 46-48 ℃, and the stirring time is 20-30min.
Preferably, the Tris buffer is 12-15g/L, pH value 8.5-9.0, wherein the concentration of dopamine is 2-3mg/ml.
Preferably, the regulating compound liquid comprises the following raw materials in parts by weight:
3-6 parts of chitosan aqueous solution with the mass fraction of 5%, 1-3 parts of sodium alginate aqueous solution with the mass fraction of 2%, 5-10 parts of ethanol solvent, 1-4 parts of N, N-dimethylamide and 2-5 parts of nano magnesium oxide.
Preferably, the preparation method of the hydroxyapatite blended rice hull ash agent comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: delivering the rice hull ash into 3-5 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 10-20min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 5-10% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain the hydroxyapatite blended rice hull ash agent.
Preferably, the lanthanum nitrate solution has a mass fraction of 5-10%.
Preferably, the ultrasonic power is 300-400W.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite are blended with rice hull ash and calcium oxide raw materials to be compounded and prepared, through coordination among various raw materials, bentonite adjustment slurry is used as matrix liquid to carry out coating modification, through coordination among bentonite adjustment slurry and the hydroxyapatite blending rice hull ash, the raw materials are synergistic, the heavy metal adsorption efficiency of the product is enhanced, sustainable adsorption can be realized, and meanwhile, the product has stable performance under the acid corrosion condition.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The soil remediation agent suitable for soil heavy metal pollution comprises the following raw materials in parts by weight:
40-45 parts of bentonite regulating slurry, 15-25 parts of biomass charcoal, 5-10 parts of calcium hydroxy phosphate, 2-5 parts of humic acid, 3-6 parts of hydroxyapatite blending rice hull ash agent and 1-3 parts of calcium oxide;
the preparation method of the repairing agent comprises the following steps: and (3) mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite with the rice hull ash agent, uniformly stirring and mixing the mixture, and then adding the mixture into bentonite-regulated slurry for continuous mixing to obtain the repairing agent.
The soil restoration agent of the embodiment comprises the following raw materials in parts by weight:
42.5 parts of bentonite regulating slurry, 20 parts of biomass charcoal, 7.5 parts of calcium hydroxy phosphate, 3.5 parts of humic acid, 4.5 parts of hydroxyapatite blending rice hull ash agent and 2 parts of calcium oxide.
The preparation method of the bentonite conditioning slurry of the embodiment comprises the following steps:
s01: feeding bentonite into 130-140 deg.C, heat treating for 10-15min, cooling to 45-55 deg.C at 1-3 deg.C/min, and maintaining for 5-10min;
s02: placing the S01 product into hydrochloric acid solution with the total amount of 3-5 times of the S01 product, then adding sodium dodecyl sulfate with the total amount of 2-5% of the S01 product and yttrium nitrate solution with the total amount of 1-5% of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 2-5% of the total amount of the S01 product and a Tris buffer solution accounting for 1-3% of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 3-5 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry.
The mass fraction of the hydrochloric acid solution in the embodiment is 1-3%; the mass fraction of the yttrium nitrate solution is 2-5%.
The rotational speed of the primary stirring pre-modification is 350-450r/min, the stirring temperature is 40-45 ℃, and the stirring time is 30-40min; the rotational speed of the secondary stirring pre-modification is 800-1000r/min, the stirring temperature is 46-48 ℃, and the stirring time is 20-30min.
The Tris buffer of this example has a value of 12-15g/L, pH of 8.5-9.0, wherein the concentration of dopamine is 2-3mg/ml.
The adjusting composite liquid of the embodiment comprises the following raw materials in parts by weight:
3-6 parts of chitosan aqueous solution with the mass fraction of 5%, 1-3 parts of sodium alginate aqueous solution with the mass fraction of 2%, 5-10 parts of ethanol solvent, 1-4 parts of N, N-dimethylamide and 2-5 parts of nano magnesium oxide.
The preparation method of the hydroxyapatite blended rice hull ash agent in the embodiment comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: delivering the rice hull ash into 3-5 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 10-20min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 5-10% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain the hydroxyapatite blended rice hull ash agent.
The mass fraction of the lanthanum nitrate solution in the embodiment is 5-10%.
The ultrasonic power of this embodiment is 300-400W.
Example 1.
The soil remediation agent suitable for soil heavy metal pollution comprises the following raw materials in parts by weight:
40 parts of bentonite regulating slurry, 15 parts of biomass charcoal, 5 parts of calcium hydroxy phosphate, 2 parts of humic acid, 3 parts of hydroxyapatite blending rice hull ash agent and 1 part of calcium oxide;
the preparation method of the repairing agent comprises the following steps: and (3) mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite with the rice hull ash agent, uniformly stirring and mixing the mixture, and then adding the mixture into bentonite-regulated slurry for continuous mixing to obtain the repairing agent.
The preparation method of the bentonite conditioning slurry of the embodiment comprises the following steps:
s01: feeding bentonite into a reactor for heat treatment at 130 ℃ for 10min, cooling to 45 ℃ at a speed of 1 ℃/min, and preserving heat for 5min;
s02: placing the S01 product into hydrochloric acid solution with the total amount being 3 times that of the S01 product, then adding sodium dodecyl sulfate with the total amount being 2% of the S01 product and yttrium nitrate solution with the total amount being 1% of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 2-5% of the total amount of the S01 product and a Tris buffer solution accounting for 1% of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 3 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry.
The mass fraction of the hydrochloric acid solution of this example was 1%; the mass fraction of the yttrium nitrate solution is 2%.
The rotational speed of the primary stirring pre-modification is 350r/min, the stirring temperature is 40 ℃, and the stirring time is 30min; the rotational speed of the secondary stirring pre-modification is 800r/min, the stirring temperature is 46 ℃, and the stirring time is 20min.
The Tris buffer of this example had a 12g/L, pH value of 8.5, with a dopamine concentration of 2mg/ml.
The adjusting composite liquid of the embodiment comprises the following raw materials in parts by weight:
3 parts of chitosan aqueous solution with the mass fraction of 5%, 1 part of sodium alginate aqueous solution with the mass fraction of 2%, 5 parts of ethanol solvent, 1 part of N, N-dimethylamide and 2 parts of nano magnesium oxide.
The preparation method of the hydroxyapatite blended rice hull ash agent in the embodiment comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: sending the rice hull ash into 3 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 10min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 5% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain the hydroxyapatite blended rice hull ash agent.
The lanthanum nitrate solution of this example was 5% by mass.
The ultrasonic power of this example was 300W.
Example 2.
The soil remediation agent suitable for soil heavy metal pollution comprises the following raw materials in parts by weight:
45 parts of bentonite regulating slurry, 25 parts of biomass charcoal, 10 parts of calcium hydroxy phosphate, 5 parts of humic acid, 6 parts of hydroxyapatite blending rice hull ash agent and 3 parts of calcium oxide;
the preparation method of the repairing agent comprises the following steps: and (3) mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite with the rice hull ash agent, uniformly stirring and mixing the mixture, and then adding the mixture into bentonite-regulated slurry for continuous mixing to obtain the repairing agent.
The preparation method of the bentonite conditioning slurry of the embodiment comprises the following steps:
s01: feeding bentonite into a reactor at 140 ℃ for heat treatment for 15min, cooling to 55 ℃ at a speed of 3 ℃/min, and preserving heat for 10min;
s02: placing the S01 product into a hydrochloric acid solution which is 5 times of the total amount of the S01 product, then adding sodium dodecyl sulfate which is 5% of the total amount of the S01 product and yttrium nitrate solution which is 5% of the total amount of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 5 percent of the total amount of the S01 product and a Tris buffer solution accounting for 3 percent of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 5 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry.
The mass fraction of the hydrochloric acid solution of this example was 3%; the mass fraction of the yttrium nitrate solution is 5%.
The rotational speed of the primary stirring pre-modification is 450r/min, the stirring temperature is 45 ℃, and the stirring time is 40min; the rotational speed of the secondary stirring pre-modification is 1000r/min, the stirring temperature is 48 ℃, and the stirring time is 30min.
The Tris buffer of this example had a 15/L, pH value of 9.0, where the concentration of dopamine was 3mg/ml.
The adjusting composite liquid of the embodiment comprises the following raw materials in parts by weight:
6 parts of chitosan aqueous solution with the mass fraction of 5%, 3 parts of sodium alginate aqueous solution with the mass fraction of 2%, 10 parts of ethanol solvent, 4 parts of N, N-dimethylamide and 5 parts of nano magnesium oxide.
The preparation method of the hydroxyapatite blended rice hull ash agent in the embodiment comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: sending the rice hull ash into 5 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 20min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 10% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain the hydroxyapatite blended rice hull ash agent.
The lanthanum nitrate solution of this example has a mass fraction of 10%.
The ultrasonic power of this example was 400W.
Example 3.
The soil remediation agent suitable for soil heavy metal pollution comprises the following raw materials in parts by weight: 42.5 parts of bentonite regulating slurry, 20 parts of biomass charcoal, 7.5 parts of calcium hydroxy phosphate, 3.5 parts of humic acid, 4.5 parts of hydroxyapatite blending rice hull ash agent and 2 parts of calcium oxide.
The preparation method of the repairing agent comprises the following steps: and (3) mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite with the rice hull ash agent, uniformly stirring and mixing the mixture, and then adding the mixture into bentonite-regulated slurry for continuous mixing to obtain the repairing agent.
The preparation method of the bentonite conditioning slurry of the embodiment comprises the following steps:
s01: feeding bentonite into a reactor for heat treatment at 135 ℃ for 12min, cooling to 50 ℃ at a speed of 2 ℃/min, and preserving heat for 7.5min;
s02: placing the S01 product into a hydrochloric acid solution with the total amount of 4 times of the S01 product, then adding sodium dodecyl sulfate with the total amount of 3.5% of the S01 product and yttrium nitrate with the total amount of 3% of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 3.5 percent of the total amount of the S01 product and a Tris buffer solution accounting for 2 percent of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 4 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry.
The mass fraction of the hydrochloric acid solution in this example was 2%; the mass fraction of the yttrium nitrate solution is 3.5%.
The rotational speed of the primary stirring pre-modification is 400r/min, the stirring temperature is 42 ℃, and the stirring time is 35min; the rotational speed of the secondary stirring pre-modification is 900r/min, the stirring temperature is 47 ℃, and the stirring time is 25min.
The Tris buffer of this example had a value of 13.5g/L, pH of 8.8, with a dopamine concentration of 2.5mg/ml.
The adjusting composite liquid of the embodiment comprises the following raw materials in parts by weight:
4.5 parts of chitosan aqueous solution with the mass fraction of 5%, 2 parts of sodium alginate aqueous solution with the mass fraction of 2%, 7.5 parts of ethanol solvent, 2.5 parts of N, N-dimethylamide and 3.5 parts of nano magnesium oxide.
The preparation method of the hydroxyapatite blended rice hull ash agent in the embodiment comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: sending the rice hull ash into 4 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 15min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 7.5% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain the hydroxyapatite blended rice hull ash agent.
The lanthanum nitrate solution of this example has a mass fraction of 7.5%.
The ultrasonic power of this example was 350W.
Comparative example 1.
The difference from example 3 is that no bentonite conditioning slurry was added.
Comparative example 2.
The difference from example 3 is that the bentonite material used for the pre-modification in the preparation of bentonite conditioning slurry is replaced by bentonite.
Comparative example 3.
The modification process for the pre-modified bentonite differs from example 3:
putting bentonite into hydrochloric acid solution with the total amount of 4 times of bentonite, adding sodium dodecyl sulfate with the total amount of 3.5% of bentonite and yttrium nitrate solution with the total amount of 3% of bentonite, adding silane coupling agent KH560 with the total amount of 3.5% of bentonite and Tris buffer solution with the total amount of 2% of bentonite into the bentonite, stirring for pre-modification, wherein the stirring speed of the stirring for pre-modification is 900r/min, the stirring temperature is 47 ℃, the stirring time is 35min, stirring is full, and then washing and drying are carried out to obtain the pre-modified bentonite.
Comparative example 4.
The difference from example 3 is that the bentonite conditioning slurry is prepared by replacing the conditioning composite liquid with a chitosan aqueous solution with a mass fraction of 5%.
Comparative example 5.
Unlike example 3, no hydroxyapatite was added to blend the rice hull ash.
Comparative example 6.
Unlike example 3, the hydroxyapatite blended rice hull ash agent was prepared without adding modified rice hull ash.
The products of examples 1-3 and comparative examples 1-6 were tested for performance as follows:
from examples 1-3 and comparative examples 1-6, the adsorption rate of heavy metals in the embodiment 3 of the invention is excellent from 1h to 48h, and the product has excellent adsorption performance stability under the acid corrosion condition;
the product is not added with bentonite adjustment slurry or one of hydroxyapatite and rice hull ash agent, the performance of the product is obviously deteriorated, meanwhile, the stability of acid corrosion is obviously deteriorated, only the bentonite adjustment slurry and the hydroxyapatite are adopted for blending, the synergistic effect is obvious, the pre-modified bentonite in the preparation of the bentonite adjustment slurry is replaced by bentonite raw materials, the modification method of the pre-modified bentonite is different, the adjustment composite liquid in the preparation of the bentonite adjustment slurry is replaced by chitosan aqueous solution with the mass fraction of 5%, the performance of the product is in a deterioration trend, and only the bentonite adjustment slurry and the hydroxyapatite and rice hull ash agent prepared by the method have the most obvious synergistic effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. The soil restoration agent suitable for heavy metal pollution of soil is characterized by comprising the following raw materials in parts by weight:
40-45 parts of bentonite regulating slurry, 15-25 parts of biomass charcoal, 5-10 parts of calcium hydroxy phosphate, 2-5 parts of humic acid, 3-6 parts of hydroxyapatite blending rice hull ash agent and 1-3 parts of calcium oxide;
the preparation method of the repairing agent comprises the following steps: mixing biomass charcoal, calcium hydroxy phosphate, humic acid and hydroxyapatite to prepare rice hull ash agent and calcium oxide, stirring and mixing uniformly, adding into bentonite-regulated slurry, and continuing to mix thoroughly to obtain a repairing agent; the preparation method of the bentonite adjustment slurry comprises the following steps:
s01: feeding bentonite into 130-140 deg.C, heat treating for 10-15min, cooling to 45-55 deg.C at 1-3 deg.C/min, and maintaining for 5-10min;
s02: placing the S01 product into hydrochloric acid solution with the total amount of 3-5 times of the S01 product, then adding sodium dodecyl sulfate with the total amount of 2-5% of the S01 product and yttrium nitrate solution with the total amount of 1-5% of the S01 product, and then carrying out primary stirring and pre-modification;
s03: then adding a silane coupling agent KH560 accounting for 2-5% of the total amount of the S01 product and a Tris buffer solution accounting for 1-3% of the total amount of the S01 product into the S02, carrying out secondary stirring for pre-modification, stirring fully, washing with water, and drying to obtain pre-modified bentonite;
s04: adding the pre-modified bentonite into 3-5 times of the regulating composite liquid, and uniformly stirring to obtain bentonite regulating slurry;
the preparation method of the hydroxyapatite blended rice hull ash agent comprises the following steps:
s11: mixing a hydrogen peroxide solution with the mass fraction of 6% and a hydrochloric acid solution with the mass fraction of 2% according to the weight ratio of 1:3 to obtain a hydrochloric acid-hydrogen peroxide solution;
s12: delivering the rice hull ash into 3-5 times hydrochloric acid-hydrogen peroxide solution for ultrasonic dispersion for 10-20min, ending ultrasonic treatment, washing with water, and drying to obtain modified rice hull ash;
s13: adding hydroxyapatite into a lanthanum nitrate solution according to a weight ratio of 1:5, then adding glycol amine accounting for 5-10% of the total amount of the hydroxyapatite, and uniformly stirring to obtain a hydroxyapatite solution;
adding the modified rice hull ash into the hydroxyapatite liquid according to the weight ratio of 1:5, stirring fully, washing with water, and drying to obtain a hydroxyapatite blended rice hull ash agent; the adjusting composite liquid comprises the following raw materials in parts by weight:
3-6 parts of chitosan aqueous solution with the mass fraction of 5%, 1-3 parts of sodium alginate aqueous solution with the mass fraction of 2%, 5-10 parts of ethanol solvent, 1-4 parts of N, N-dimethylamide and 2-5 parts of nano magnesium oxide.
2. The soil restoration agent suitable for heavy metal pollution of soil according to claim 1, wherein the soil restoration agent is prepared from the following raw materials in parts by weight:
42.5 parts of bentonite regulating slurry, 20 parts of biomass charcoal, 7.5 parts of calcium hydroxy phosphate, 3.5 parts of humic acid, 4.5 parts of hydroxyapatite blending rice hull ash agent and 2 parts of calcium oxide.
3. The soil restoration agent suitable for heavy metal pollution of soil according to claim 1, wherein the mass fraction of the hydrochloric acid solution is 1-3%; the mass fraction of the yttrium nitrate solution is 2-5%.
4. The soil remediation agent suitable for heavy metal pollution of soil according to claim 1, wherein the primary stirring pre-modification speed is 350-450r/min, the stirring temperature is 40-45 ℃, and the stirring time is 30-40min; the rotational speed of the secondary stirring pre-modification is 800-1000r/min, the stirring temperature is 46-48 ℃, and the stirring time is 20-30min.
5. A soil restoration agent for soil heavy metal pollution according to claim 1, wherein said Tris buffer solution has a concentration of 12-15g/L, pH value of 8.5-9.0, and wherein the concentration of dopamine is 2-3mg/ml.
6. The soil restoration agent for soil heavy metal pollution according to claim 1, wherein the lanthanum nitrate solution has a mass fraction of 5-10%.
7. A soil restoration agent suitable for soil heavy metal pollution according to claim 1, wherein the power of said ultrasound is 300-400W.
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