CN113651764A - Synthesis method and application of heavy metal stabilizer - Google Patents
Synthesis method and application of heavy metal stabilizer Download PDFInfo
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- CN113651764A CN113651764A CN202110958853.6A CN202110958853A CN113651764A CN 113651764 A CN113651764 A CN 113651764A CN 202110958853 A CN202110958853 A CN 202110958853A CN 113651764 A CN113651764 A CN 113651764A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 41
- 239000003381 stabilizer Substances 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 23
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 23
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 23
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002689 soil Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 17
- 238000000967 suction filtration Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000008098 formaldehyde solution Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/64—Condensation products of melamine with aldehydes; Derivatives thereof
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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
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
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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
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/16—Soil-conditioning materials or soil-stabilising materials containing organic compounds only applied in a physical form other than a solution or a grout, e.g. as platelets or granules
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method and application of a heavy metal stabilizer, which comprises the following steps: heating cardanol to 40-70 ℃, adding sodium hydroxide after the cardanol is fully melted, and stirring at constant temperature to obtain reaction liquid; adding a formaldehyde aqueous solution and DMF into the obtained reaction solution, heating, and stirring at constant temperature; adding melamine into the obtained reaction liquid, after the reaction liquid is subjected to aftertreatment A, slowly adding thiourea in batches, after the reaction is completed, heating to 90-125 ℃, stirring at constant temperature for reaction for 9-16h, and after the reaction liquid is subjected to aftertreatment B, obtaining a white solid; and adding a sodium sulfite aqueous solution into the obtained white solid, heating to 90-120 ℃, carrying out constant-temperature reflux stirring for 1.5-4h, and carrying out post-treatment C on the reaction liquid after the reaction is finished to obtain a final product. The method has the advantages of simple synthesis process, mild reaction conditions, green and easily-obtained raw material cardanol, and high selectivity of the prepared compound to heavy metals.
Description
Technical Field
The invention relates to the field of heavy metal stabilizers in soil heavy metal pollution treatment, and particularly relates to a synthesis method and application of a heavy metal stabilizer.
Background
In recent decades, the increase of urban population and the rapid development of modern industry cause increasingly serious soil heavy metal pollution, which not only causes the destruction of ecological environment, but also brings along with the phenomenon of biological enrichment, and finally endangers human beings. Meanwhile, heavy metals are leached under the condition of higher migration activity, so that underground water is polluted to cause secondary pollution, and the difficulty of soil remediation is greatly increased. Wherein the migration activity of metal elements such as Cu, Cd, Ni and the like is relatively small, and the migration activity of Pb is larger than that of the metal elements. Therefore, the leaching problem of Pb during soil remediation cannot be ignored.
In order to solve the threat of heavy metal leaching to underground water, the heavy metal in the polluted soil needs to be stabilized by a stabilizer. Traditional stabilizers, such as sepiolite, limestone, biochar and other adsorbing materials, show good repairing effect on heavy metals in the polluted soil. However, the adsorption effect on heavy metals is not selective, and the adsorption sites on the stabilizer can be occupied by other non-target heavy metals, so that a higher dosage of the stabilizer is needed to achieve the stabilizing effect, if the high dosage of the stabilizer is added into soil for a long time, the environment quality of the soil is adversely affected, various functions of the soil are destroyed, and the enrichment effect of plants on other non-target metals is also affected. Therefore, the development of a stabilizer with higher selectivity is needed, which can meet the requirement of stabilizing target heavy metals and simultaneously does not influence the enrichment effect of plants on other heavy metals.
At present, the stabilizing agent is mainly selected for removing heavy metals in aqueous solution. For example, fully inorganic bimetallic Mo-Fe-S clusters for Pb in water2+The functionalized sepiolite is used for removing cadmium in soil, and the TA @ Zr is used for removing Pb in aqueous solution2+Higher selectivity and the like. The material has better selectivity and larger target heavy metalThe adsorption capacity, however, the process for synthesizing the material is complicated, the raw materials are expensive, and part of the raw materials have high toxicity to the environment and human body. Therefore, in the process of repairing heavy metal pollution by the stabilizer, the stabilizer which has the advantages of stable effect, high selectivity to heavy metal, simple and feasible synthesis process, green and nontoxic raw materials and low cost needs to be explored.
Disclosure of Invention
The invention aims to provide a synthesis method and application of a heavy metal stabilizer, the synthesis method is simple in synthesis process, mild in reaction conditions, environment-friendly and easily available in raw material cardanol, and the prepared compound has high selectivity on heavy metals.
The technical scheme adopted by the invention is that the synthesis method of the heavy metal stabilizer comprises the following steps:
step (1): heating cardanol to 40-70 ℃, adding sodium hydroxide after the cardanol is fully melted, and stirring at constant temperature to obtain reaction liquid;
step (2): adding a formaldehyde water solution and DMF (N, N-dimethylformamide) into the reaction liquid obtained in the step (1), heating, and stirring at constant temperature;
and (3): adding melamine into the reaction liquid obtained in the step (2), after the reaction liquid is subjected to post-treatment A, slowly adding thiourea in batches, after the reaction is completed, heating to 90-125 ℃, stirring at constant temperature for reaction for 9-16h, and performing post-treatment B on the reaction liquid to obtain a white solid;
and (4): and (4) adding a sodium sulfite aqueous solution into the white solid obtained in the step (3), heating to 90-120 ℃, carrying out constant-temperature reflux stirring for 1.5-4h, and carrying out post-treatment C on the reaction liquid after the reaction is finished to obtain a final product.
Further, in the step (1), the constant-temperature stirring time is 15-30 min.
Further, in the step (2), the temperature of the temperature rise is 60-90 ℃, and the constant-temperature stirring time is 30-70 min.
Further, in the step (3), the post-treatment A is carried out according to the following steps: firstly heating to 80-110 ℃, stirring at constant temperature for reaction for 30-60min, and then cooling to 30-70 ℃.
Further, in the step (3), the post-treatment B is performed as follows: cooling the reaction solution, filtering, washing the product with acetone and deionized water, and stoving the solid in an oven at 70-100 deg.c.
Further, in the step (4), the post-treatment C is performed according to the following steps: cooling the reaction solution, filtering, washing the product with ethanol and deionized water, and drying the obtained solid in an oven at 60-100 ℃.
Further, in the step (4), the mass ratio of the white solid to the sodium sulfite is 1: 1.5-3.2.
Further, in the step (1), the step (2) and the step (3), the charging molar ratio of cardanol, formaldehyde, melamine, thiourea and sodium hydroxide is 1.0:3.8-4.1:2.3-2.6:1.8-2.2: 0.9-1.2.
Further, in the step (1), the step (2) and the step (3), the charging mass ratio of cardanol, formaldehyde, melamine, thiourea and sodium hydroxide is 8-12: 3-5: 7-11: 3-6: 0.5-2.
The heavy metal stabilizer can be used for absorbing heavy metal in the heavy metal pollution treatment of soil, and the heavy metal is Pb.
Compared with the prior art, the invention has the following advantages:
the preparation method adopts cardanol, thiourea, formaldehyde and melamine as reaction raw materials to synthesize the heavy metal stabilizer containing sulfydryl. The raw material cardanol is extracted and refined from natural cashew shell oil, belongs to an environment-friendly industrial raw material, and has the advantages of low price, degradability, rich sources, excellent performance, reproducibility and the like. The metal stabilizer has the advantages of no influence on soil environment quality, simple synthesis process, mild reaction conditions, high efficiency, rapidness, selective adsorption of Pb and the like, can realize effective control on the high leaching risk element Pb, and only reduces the bioavailability of Pb on the premise of not reducing the bioavailability of other heavy metals.
Drawings
FIG. 1 is an SEM photograph of a product produced in example 1 of the present invention;
FIG. 2 is an SEM photograph of a product prepared in example 2 of the present invention.
FIG. 3 is an SEM photograph of a product prepared in example 3 of the present invention.
FIG. 4 is an SEM photograph of a product prepared in example 4 of the present invention.
FIG. 5 is an SEM photograph of a product prepared in example 5 of the present invention.
FIG. 6 is an XRD spectrum of the products prepared in examples 1, 2, 3, 4 and 5 of the present invention.
FIG. 7 shows the product obtained in example 5 for Pb2+Adsorption equilibrium curve of (1).
FIG. 8 shows the product obtained in example 5 for Pb2+Adsorption kinetics curve of (1).
Detailed Description
The invention is described in more detail below with reference to the figures and the examples, but the scope of the invention is not limited thereto.
Example 1
In a three-necked flask equipped with a stirrer, a spherical condenser and a thermometer, 10.00g of cardanol was added under oil bath conditions, and the temperature was raised to 40 ℃. After the cardanol is fully melted, 1.05g of sodium hydroxide is added, and the mixture is stirred at constant temperature for reaction for 30 min. Adding 7g of formaldehyde water solution with the mass fraction of 37% and 50ml of DMF solution, heating to 60 ℃, stirring at constant temperature for reaction for 70min, and then adding 2.85g of formaldehyde water solution with the mass fraction of 37%. 9.11g of melamine is added, the temperature is raised to 80 ℃, the reaction is carried out for 30min under constant temperature stirring, and then the temperature is reduced to 30 ℃. Adding 4.50g of thiourea in batches, heating to 90 ℃, and stirring at constant temperature for reaction for 9 hours. And cooling, performing suction filtration, washing the product with acetone and deionized water, and drying the obtained white solid in a 70 ℃ drying oven.
Putting 4g of the white solid product into a three-neck flask, adding an aqueous solution prepared by completely dissolving 10.68g of sodium sulfite with deionized water, heating to 90 ℃, carrying out constant-temperature reflux stirring for 4 hours, cooling the reaction solution after the reaction is finished, carrying out suction filtration, washing the solid with ethanol and deionized water, and finally drying in a 60 ℃ drying oven to obtain the final stabilizing agent.
Example 2
12.00g of cardanol was added to a three-necked flask equipped with a stirrer, a spherical condenser tube and a thermometer under oil bath conditions, and the temperature was raised to 70 ℃. After the cardanol is fully melted, 1.89g of sodium hydroxide is added, and the mixture is stirred at constant temperature for reaction for 15 min. Adding 9.5g of formaldehyde solution with the mass fraction of 37% and 60ml of DMF solution, heating to 90 ℃, stirring at constant temperature for reaction for 30min, and then adding 4.24g of formaldehyde solution with the mass fraction of 37%. Adding 13.92g of melamine, heating to 110 ℃, stirring at constant temperature for reaction for 45min, and then cooling to 70 ℃. Adding 6.60g of thiourea in batches, heating to 125 ℃, and stirring at constant temperature for reaction for 12 hours. And cooling, performing suction filtration, washing the product with acetone and deionized water, and drying the obtained white solid in an oven at 80 ℃.
And (3) putting 4g of the white solid product into a three-neck flask, adding an aqueous solution prepared by completely dissolving 10.68g of sodium sulfite with deionized water, heating to 120 ℃, carrying out constant-temperature reflux stirring for 1.5h, cooling the reaction solution, carrying out suction filtration, washing the solid with ethanol and deionized water, and finally putting the solid into a 100 ℃ drying oven for drying to obtain the final stabilizing agent.
Example 3
In a three-necked flask equipped with a stirrer, a spherical condenser and a thermometer, 10.00g of cardanol was added under oil bath conditions, and the temperature was raised to 60 ℃. After the cardanol is fully melted, 1.05g of sodium hydroxide is added, and the mixture is stirred at constant temperature for reaction for 20 min. Adding 7g of formaldehyde solution with the mass fraction of 37% and 60ml of DMF solution, heating to 90 ℃, stirring at constant temperature for reaction for 50min, and then adding 2.85g of formaldehyde solution with the mass fraction of 37%. 9.11g of melamine is added, the temperature is raised to 100 ℃, the reaction is carried out for 40min under constant temperature stirring, and then the temperature is reduced to 45 ℃. Adding 4.50g of thiourea in batches, heating to 110 ℃, and stirring at constant temperature for reaction for 14 h. And cooling, performing suction filtration, washing the product with acetone and deionized water, and drying the obtained white solid in an oven at 100 ℃.
Putting 4g of the white solid product into a three-neck flask, adding an aqueous solution prepared by completely dissolving 10.68g of sodium sulfite with deionized water, heating to 100 ℃, refluxing and stirring for 3 hours, cooling the reaction solution after the reaction is finished, performing suction filtration, washing the solid with ethanol and deionized water, and finally drying in a 90 ℃ drying oven to obtain the final stabilizing agent.
Example 4
In a three-necked flask equipped with a stirrer, a spherical condenser and a thermometer, 10.00g of cardanol was added under oil bath conditions, and the temperature was raised to 55 ℃. After the cardanol is fully melted, 1.05g of sodium hydroxide is added, and the mixture is stirred at constant temperature for reaction for 30 min. Adding 7g of formaldehyde solution with the mass fraction of 37% and 60ml of DMF solution, heating to 75 ℃, stirring at constant temperature for reaction for 50min, and then adding 2.85g of formaldehyde solution with the mass fraction of 37%. 9.11g of melamine is added, the temperature is raised to 105 ℃, the reaction is carried out for 60min under constant temperature stirring, and then the temperature is reduced to 50 ℃. Adding 4.50g of thiourea in batches, heating to 110 ℃, and stirring at constant temperature for reacting for 16 h. And cooling, performing suction filtration, washing the product with acetone and deionized water, and drying the obtained white solid in a 70 ℃ drying oven.
Putting 4g of the white solid product into a three-neck flask, adding an aqueous solution prepared by completely dissolving 10.68g of sodium sulfite with deionized water, heating to 95 ℃, refluxing and stirring for 2 hours, cooling the reaction solution after the reaction is finished, performing suction filtration, washing the solid with ethanol and deionized water, and finally drying in a 90 ℃ drying oven to obtain the final stabilizing agent.
Example 5
In a three-necked flask equipped with a stirrer, a spherical condenser and a thermometer, 10.00g of cardanol was added under oil bath conditions, and the temperature was raised to 50 ℃. After the cardanol is fully melted, 1.05g of sodium hydroxide is added, and the mixture is stirred at constant temperature for reaction for 20 min. Adding 7g of formaldehyde solution with the mass fraction of 37% and 60ml of DMF solution, heating to 65 ℃, stirring at constant temperature for reaction for 60min, and then adding 2.85g of formaldehyde solution with the mass fraction of 37%. 9.11g of melamine is added, the temperature is raised to 90 ℃, the reaction is carried out for 60min under constant temperature stirring, and then the temperature is reduced to 50 ℃. Adding 4.50g of thiourea in batches, heating to 100 ℃, and stirring at constant temperature for reaction for 15 h. And cooling, performing suction filtration, washing the product with acetone and deionized water, and drying the obtained white solid in a 70 ℃ drying oven.
Putting 4g of the white solid product into a three-neck flask, adding an aqueous solution prepared by completely dissolving 10.68g of sodium sulfite with deionized water, heating to 90 ℃, refluxing and stirring for 3 hours, cooling the reaction solution after the reaction is finished, performing suction filtration, washing the solid with ethanol and deionized water, and finally drying in an oven at 80 ℃ to obtain the final stabilizing agent.
Example 6
0.10g of the product prepared in example 5 are charged with 250ml of Pb2+Shaking the solution with concentration of 0, 25, 50, 75, 100, 125, 150, 175, 200, 250, 300mg/L at 25 deg.C for 12h, diluting the adsorbed solution 10 times after adsorption is finished, and measuring Pb2+Concentration of Pb in each of the different concentrations2+The amount of adsorption. According to Pb2+Concentration and corresponding Pb2+And (5) drawing an adsorption equilibrium curve according to the adsorption amount. Example 5 preparation of product Pb under selected conditions2+The maximum adsorption was 588.2 mg/g.
0.02g of the product prepared in example 5 are charged with 500ml of Pb2+Shaking at room temperature in solutions with concentrations of 0.5, 1.5, and 2.0mg/L, respectively, sampling at intervals of 0, 2, 5, 8, 15, 25, 40, 60, 90, and 120min to measure Pb2+And (4) concentration. According to the measured Pb2+The concentration was plotted as adsorption kinetics.
As shown in fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5, the products prepared in examples 1, 2, 3, 4 and 5 show a plurality of scaly block-shaped objects outside the particles under a Scanning Electron Microscope (SEM), and the surface part of the particles has small pores, which not only facilitate the metal adsorption of the stabilizer, but also enhance the selective adsorption capability of the stabilizer on the heavy metal.
As shown in fig. 6, the products prepared in examples 2, 3, 4 and 5 all have obvious peaks at specific positions, indicating that they have better crystal structure. In addition, the prepared product has larger characteristic peak area and peak intensity, which shows that the prepared product has very high crystalline phase and developed crystalline structure, and is a crystalline material with relatively obvious spatial structure characteristics.
As shown in FIG. 7, 0.10g of the product prepared in example 5 was added to 250ml of solutions with a concentration of 0, 25, 50, 75, 100, 125, 150, 175, 200, 250, 300Pb, respectively2+After shaking the solution at 25 ℃ for 12h, the Pb pair of the product prepared in example 5 was determined2+The maximum adsorption amount was 588.2 mgPb/g.
As shown in FIG. 8, under different initial lead concentrations (0.5, 1.5 and 2mg/L), the adsorption of the product prepared in example 5 on lead does not change within 2-120 min, which shows that the speed is high, and the adsorption equilibrium can be reached quickly within 2 min.
Claims (10)
1. A method for synthesizing a heavy metal stabilizer is characterized by comprising the following steps:
step (1): heating cardanol to 40-70 ℃, adding sodium hydroxide after the cardanol is fully melted, and stirring at constant temperature to obtain reaction liquid;
step (2): adding a formaldehyde aqueous solution and N, N-dimethylformamide into the reaction liquid obtained in the step (1), heating, and stirring at constant temperature;
and (3): adding melamine into the reaction liquid obtained in the step (2), after the reaction liquid is subjected to post-treatment A, slowly adding thiourea in batches, after the reaction is completed, heating to 90-125 ℃, stirring at constant temperature for reaction for 9-16h, and performing post-treatment B on the reaction liquid to obtain a white solid;
and (4): and (4) adding a sodium sulfite aqueous solution into the white solid obtained in the step (3), heating to 90-120 ℃, carrying out constant-temperature reflux stirring for 1.5-4h, and carrying out post-treatment C on the reaction liquid after the reaction is finished to obtain a final product.
2. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein the constant-temperature stirring time in the step (1) is 15-30 min.
3. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein in the step (2), the temperature is raised to 60-90 ℃, and the constant-temperature stirring time is 30-70 min.
4. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein the post-treatment A in the step (3) comprises: firstly heating to 80-110 ℃, stirring at constant temperature for reaction for 30-60min, and then cooling to 30-70 ℃.
5. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein the post-treatment B in the step (3) comprises: cooling the reaction solution, filtering, washing the product with acetone and deionized water, and stoving the solid in an oven at 70-100 deg.c.
6. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein in the step (4), the post-treatment C comprises: cooling the reaction solution, filtering, washing the product with ethanol and deionized water, and drying the obtained solid in an oven at 60-100 ℃.
7. The method for synthesizing a heavy metal stabilizer according to claim 1, wherein in the step (4), the mass ratio of the white solid to the sodium sulfite is 1: 1.5-3.2.
8. The synthesis method of the heavy metal stabilizer according to claim 1, wherein in the step (1), the step (2) and the step (3), the charging molar ratio of cardanol, formaldehyde, melamine, thiourea and sodium hydroxide is 1.0:3.8-4.1:2.3-2.6:1.8-2.2: 0.9-1.2.
9. The application of the heavy metal stabilizer prepared by the synthesis method according to any one of claims 1 to 8 in the treatment of heavy metal pollution of soil.
10. The use according to claim 9, wherein the heavy metal absorbed in the soil heavy metal pollution treatment is Pb.
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