CN113481015A - Mercury-contaminated soil remediation agent and preparation method thereof - Google Patents
Mercury-contaminated soil remediation agent and preparation method thereof Download PDFInfo
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- CN113481015A CN113481015A CN202110843774.0A CN202110843774A CN113481015A CN 113481015 A CN113481015 A CN 113481015A CN 202110843774 A CN202110843774 A CN 202110843774A CN 113481015 A CN113481015 A CN 113481015A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention discloses a mercury-polluted soil remediation agent and a preparation method thereof, and relates to the technical field of soil remediation. According to the invention, ferric chloride is firstly reacted with 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene to prepare a ferrous metal organic framework material, then nano manganese dioxide modified by grafting 3-bromo-4 aminobenzoic acid is connected to the ferrous metal organic framework material to prepare a composite metal organic material, finally the composite metal organic material is wrapped in a three-dimensional network structure formed by self-crosslinking of sodium hydrosulfide modified poly (perchloroethylene), and the mercury-polluted soil repairing agent is prepared after drying and dehydration. The mercury-polluted soil remediation agent prepared by the invention has excellent mercury ion adsorption capacity and adsorption stability.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a mercury-contaminated soil remediation agent and a preparation method thereof.
Background
Mercury is one of the heavy metal elements with very strong toxicity in the environment, and the toxicity of various mercury compounds is very different. Mercuric chloride in the inorganic mercury is a highly toxic substance; phenyl mercury in organic mercury is decomposed quickly and has low toxicity, and methyl mercury is absorbed easily in human body, is not easy to degrade and excrete slowly, and is easy to accumulate in brain and has maximum toxicity. With the rapid development of human society, the mercury pollutants generated by human activities are increased, and the mercury pollutants enter the soil and exceed the upper limit of soil self-regulation, thereby causing the quality of the soil to deteriorate.
Soil plays an important role in the biogeochemical cycle of mercury. The mercury in the atmosphere and the water body can enter the soil environment in various ways, and most of the mercury can be adsorbed by soil particles and retained in the soil. Mercury in the soil can be accumulated into the human body through a food chain, and damage to the nervous system and the liver and kidney functions of the human body is caused. Since the 20 th century, there have been many mercury poisoning incidents worldwide and the problem of mercury pollution has received a great deal of attention. Due to the diversity of forms of mercury in soil, the difficulty of prevention and control of soil mercury pollution is increased. Of course, for any contamination, eliminating the source of the contamination is the most fundamentally effective way to prevent contamination, but is not practical and therefore can only be minimized. For the soil polluted by mercury, effective measures should be actively taken to prevent and treat the soil.
Disclosure of Invention
The invention aims to provide a mercury-contaminated soil remediation agent and a preparation method thereof, and aims to solve the problems in the prior art.
The mercury-polluted soil remediation agent is characterized by mainly comprising the following components in parts by weight: 10-15 parts of iron metal organic framework material, 2-5 parts of modified nano manganese dioxide and 30-40 parts of sulfhydrylation poly perchloroethylene.
Preferably, the iron metal organic framework material is prepared by reacting ferric chloride and 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene in water.
Preferably, the modified nano manganese dioxide is prepared by grafting 3-bromo-4-aminobenzoic acid on the surface of nano calcium carbonate.
Preferably, the 3-bromo-4-aminobenzoic acid is prepared by reacting p-aminobenzoic acid with liquid bromine under the catalysis of ferric bromide.
Preferably, the sulfhydrylation polychloroethylene is prepared by sodium hydrosulfide and polychloroethylene substitution reaction.
As optimization, the mercury-contaminated soil remediation agent comprises the following raw material components in parts by mass: 10 parts of iron metal organic framework material, 4 parts of modified nano manganese dioxide and 35 parts of sulfhydrylation poly perchloroethylene.
As optimization, the preparation method of the mercury-contaminated soil remediation agent mainly comprises the following preparation steps:
(1) reacting ferric chloride with 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene in water, washing and drying to obtain the iron metal organic framework material;
(2) reacting p-aminobenzoic acid with liquid bromine under the catalysis of ferric bromide to prepare 3-bromine-4-aminobenzoic acid, metering the 3-bromine-4-aminobenzoic acid into the nano manganese dioxide dispersion liquid, and performing suction filtration, drying, crushing and sieving on the obtained product to prepare modified nano manganese dioxide;
(3) adding the modified nano manganese dioxide obtained in the step (2) into the iron metal organic framework material dispersion liquid obtained in the step (1) and stirring to obtain a composite metal organic material;
(4) and (3) reacting sodium hydrosulfide with polyperchloroethylene to obtain sulfhydrylated polyperchloroethylene, adding the composite metal organic material obtained in the step (3) into sulfhydrylated polyperchloroethylene alkali dispersion liquid, adding hydrogen peroxide and sodium pyrophosphate, carrying out suspension polymerization to form small balls, and washing and drying to obtain the mercury-polluted soil remediation agent.
As optimization, the preparation method of the mercury-contaminated soil remediation agent mainly comprises the following preparation steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing p-aminobenzoic acid and liquid bromine according to a mass ratio of 2: 3, uniformly mixing in a three-neck flask, adding a catalyst ferric bromide with the mass of 0.01 time of that of p-aminobenzoic acid, reacting for 1h at 20 ℃, adding deionized water, heating to 80 ℃, keeping for 10min, filtering, cooling the filtrate to 1-10 ℃, and performing cooling crystallization to obtain 3-bromo-4-aminobenzoic acid; mixing nano manganese dioxide and water according to a mass ratio of 1: 20, uniformly mixing, adding 3-bromo-4-aminobenzoic acid with the mass of 0.5 time of that of the nano silicon dioxide, stirring for 2 hours at the temperature of 80 ℃ at the rotating speed of 2000r/min, filtering, drying, crushing and sieving to obtain modified nano manganese dioxide;
(3) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding the modified nano manganese dioxide obtained in the step (2) with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to obtain a composite metal organic material;
(4) mixing the polychloroethylene and water according to the mass ratio of 1: 20, uniformly mixing, adding sodium hydrosulfide with the mass 1.2 times of that of the polyperchloroethylene, stirring for 1h at the rotating speed of 2000r/min under the nitrogen atmosphere at the temperature of 90 ℃, filtering, washing for 3 times by using deionized water, and carrying out vacuum freeze drying for 6h at the temperature of minus 10 ℃ to obtain the sulfhydrylation polyperchloroethylene; under the atmosphere of nitrogen, mixing the sulfhydrylation poly perchloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (3) with the mass of 0.4 time of that of the thiolated polyperchloroethylene, stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the thiolated polyperchloroethylene, stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the thiolated polyperchloroethylene, continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets for 3 times by deionized water, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury contaminated soil remediation agent.
Preferably, the drying mode in the step (2) is vacuum freeze drying, the drying time is 6 hours at the temperature of minus 10 ℃, the crushing mode is crushing by using a universal crusher, and the sieving mesh is 50 meshes.
Preferably, the dispersant in the step (4) is one or a mixture of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the mercury-polluted soil remediation agent takes an iron metal organic framework material prepared from ferric chloride and 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene as a core, modified nano manganese dioxide is added to prepare a composite metal organic material, the composite metal organic material is wrapped in a three-dimensional network structure crosslinked by sulfhydrylation poly (perchloroethylene) per se, and the composite metal organic material is suspended and polymerized into small balls to prepare the mercury-polluted soil remediation agent.
Firstly, dissolving ferric chloride in water, adding organic ligand 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene to prepare an iron metal organic framework material, wherein iron on the iron metal organic framework material forms an unsaturated metal site with lone pair electrons, so that the effect of iron on oxygen adsorption and dissociation is improved, and the dissociated oxygen can promote the oxidation of mercury to form Hg-O-Fe, thereby playing a role in repairing mercury-polluted soil; secondly, the 3-bromo-4-aminobenzoic acid is used for modifying the nano manganese dioxide, the carboxyl on the 3-bromo-4-aminobenzoic acid can react with the dissociated hydroxyl ions on the surface of the nano manganese dioxide in water so as to be grafted on the surface of the manganese dioxide, the acting force among nano particles is weakened, the nano manganese dioxide is not easy to agglomerate, the dispersity is improved, the catalytic oxidation effect of the nano manganese dioxide is improved, the dissociation speed of oxygen is accelerated, the oxidation speed of mercury is accelerated, and the adsorption speed of the iron metal organic framework material on mercury ions is improved; adding the modified nano manganese dioxide into the dispersion liquid of the iron metal organic framework material, wherein unsaturated metal sites on the iron metal organic framework material can adsorb amino on the surface of the modified nano manganese dioxide, and connecting the modified nano manganese dioxide to the iron metal organic framework material to obtain the composite metal organic material.
Finally, sodium hydrosulfide is used for modifying the polyperchloroethylene, the chlorine on the polyperchloroethylene is replaced by the hydrogen sulfide ions on the sodium hydrosulfide to generate sulfhydrylated polyperchloroethylene, and the sulfhydryls generated on the sulfhydrylated polyperchloroethylene can react with mercury ions to solidify the mercury ions, so that the mercury ions can be well removed; adding a composite metal organic material into a sulfhydrylation poly perchloroethylene dispersion liquid, wherein bromine on the composite metal organic material can generate nucleophilic substitution with sulfhydryl on the sulfhydrylation poly perchloroethylene, and then, two sulfhydryls between the sulfhydrylation poly perchloroethylene molecules are dehydrogenated to form a disulfide bond, so that a cross-linked network structure is formed, and the composite metal organic material is wrapped inside the cross-linked network; unreacted sulfydryl and disulfide bonds on the sulfhydrylation polychloroethylene are easy to be oxidized into sulfone and sulfoxide under the aerobic condition, so that the effect of storing oxygen is achieved, the sulfone and the sulfoxide can be reduced by mercury when adsorbing mercury under the anoxic condition, and the sulfone and the sulfoxide are reduced into thioether and sulfydryl under the catalysis of nano manganese dioxide, so that the effect of providing oxygen is achieved, and the adsorption performance of the mercury pollution soil repairing agent on mercury ions is more stable.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the invention, the method is described in detail by the following examples, and the method for testing each index of the mercury-contaminated soil remediation agent prepared in the following examples is as follows:
adsorption rate: the mercury contaminated soil remediation agent obtained in each example and a comparative product are put into a glass tube in the same mass, mercury vapor with certain mass passes through the glass tube at the same speed by using air, tail gas is introduced into nitric acid solution with the same mass, the molar concentration of mercury ions in the nitric acid solution is measured, and the adsorption rate under the air atmosphere is calculated to be 1-the molar concentration of mercury ions, the volume of the solution, the molar mass of mercury ions and the mass of mercury vapor.
Adsorption stability: placing the mercury-polluted soil remediation agent obtained in each example and a comparative product in the air for 6 hours, taking the same mass, placing the same mass into a glass tube, passing mercury vapor with the same mass through the glass tube at the same speed by using nitrogen, introducing tail gas into nitric acid solution with the same mass, measuring the concentration of mercury ions in the nitric acid solution, calculating the adsorption rate under the nitrogen atmosphere, and comparing the adsorption rate under the air atmosphere.
Example 1
A mercury contaminated soil remediation agent mainly comprises the following components in parts by weight: 10 parts of iron metal organic framework material, 4 parts of modified nano manganese dioxide and 35 parts of sulfhydrylation poly perchloroethylene.
The preparation method of the mercury-polluted soil remediation agent mainly comprises the following preparation steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing p-aminobenzoic acid and liquid bromine according to a mass ratio of 2: 3, uniformly mixing in a three-neck flask, adding a catalyst ferric bromide with the mass of 0.01 time of that of p-aminobenzoic acid, reacting for 1h at 20 ℃, adding deionized water, heating to 80 ℃, keeping for 10min, filtering, cooling the filtrate to 5 ℃, and cooling and crystallizing to obtain 3-bromo-4-aminobenzoic acid; mixing nano manganese dioxide and water according to a mass ratio of 1: 20, uniformly mixing, adding 3-bromo-4-aminobenzoic acid with the mass of 0.5 time of that of the nano silicon dioxide, stirring for 2 hours at the temperature of 80 ℃ at the rotating speed of 2000r/min, filtering, drying, crushing and sieving to obtain modified nano manganese dioxide;
(3) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding the modified nano manganese dioxide obtained in the step (2) with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to obtain a composite metal organic material;
(4) mixing the polychloroethylene and water according to the mass ratio of 1: 20, uniformly mixing, adding sodium hydrosulfide with the mass 1.2 times of that of the polyperchloroethylene, stirring for 1h at the rotating speed of 2000r/min under the nitrogen atmosphere at the temperature of 90 ℃, filtering, washing for 3 times by using deionized water, and carrying out vacuum freeze drying for 6h at the temperature of minus 10 ℃ to obtain the sulfhydrylation polyperchloroethylene; under the atmosphere of nitrogen, mixing the sulfhydrylation poly perchloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (3) with the mass of 0.4 time of that of the thiolated polyperchloroethylene, stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the thiolated polyperchloroethylene, stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the thiolated polyperchloroethylene, continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets for 3 times by deionized water, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury contaminated soil remediation agent.
Preferably, the drying mode in the step (2) is vacuum freeze drying, the drying time is 6 hours at the temperature of minus 10 ℃, the crushing mode is crushing by using a universal crusher, and the sieving mesh is 50 meshes.
Preferably, the dispersant in the step (4) is one or a mixture of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Example 2
A mercury contaminated soil remediation agent mainly comprises the following components in parts by weight: 10 parts of iron metal organic framework material, 4 parts of nano manganese dioxide and 35 parts of sulfhydrylated polyperchloroethylene.
The preparation method of the mercury-polluted soil remediation agent mainly comprises the following preparation steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding nano manganese dioxide with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to prepare the composite metal organic material;
(3) mixing the polychloroethylene and water according to the mass ratio of 1: 20, uniformly mixing, adding sodium hydrosulfide with the mass 1.2 times of that of the polyperchloroethylene, stirring for 1h at the rotating speed of 2000r/min under the nitrogen atmosphere at the temperature of 90 ℃, filtering, washing for 3 times by using deionized water, and carrying out vacuum freeze drying for 6h at the temperature of minus 10 ℃ to obtain the sulfhydrylation polyperchloroethylene; under the atmosphere of nitrogen, mixing the sulfhydrylation poly perchloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (2) with the mass of 0.4 time of that of the thiolated polyperchloroethylene, stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the thiolated polyperchloroethylene, stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the thiolated polyperchloroethylene, continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets for 3 times by deionized water, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury contaminated soil remediation agent.
Preferably, the dispersant in the step (3) is one or a mixture of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Example 3
A mercury contaminated soil remediation agent mainly comprises the following components in parts by weight: 10 parts of iron metal organic framework material, 4 parts of modified nano manganese dioxide and 35 parts of poly (perchloroethylene).
The preparation method of the mercury-polluted soil remediation agent mainly comprises the following preparation steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing p-aminobenzoic acid and liquid bromine according to a mass ratio of 2: 3, uniformly mixing in a three-neck flask, adding a catalyst ferric bromide with the mass of 0.01 time of that of p-aminobenzoic acid, reacting for 1h at 20 ℃, adding deionized water, heating to 80 ℃, keeping for 10min, filtering, cooling the filtrate to 5 ℃, and cooling and crystallizing to obtain 3-bromo-4-aminobenzoic acid; mixing nano manganese dioxide and water according to a mass ratio of 1: 20, uniformly mixing, adding 3-bromo-4-aminobenzoic acid with the mass of 0.5 time of that of the nano silicon dioxide, stirring for 2 hours at the temperature of 80 ℃ at the rotating speed of 2000r/min, filtering, drying, crushing and sieving to obtain modified nano manganese dioxide;
(3) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding the modified nano manganese dioxide obtained in the step (2) with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to obtain a composite metal organic material;
(4) under the atmosphere of nitrogen, mixing the polychloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (3) with the mass of 0.4 time of that of the poly (perchloroethylene), stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at the temperature of 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the poly (perchloroethylene), stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the poly (perchloroethylene), continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets with deionized water for 3 times, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury-polluted soil remediation agent.
Preferably, the drying mode in the step (2) is vacuum freeze drying, the drying time is 6 hours at the temperature of minus 10 ℃, the crushing mode is crushing by using a universal crusher, and the sieving mesh is 50 meshes.
Preferably, the dispersant in the step (4) is one or a mixture of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Comparative example
A mercury contaminated soil remediation agent mainly comprises the following components in parts by weight: 10 parts of iron metal organic framework material, 4 parts of nano manganese dioxide and 35 parts of poly (perchloroethylene).
The preparation method of the mercury-polluted soil remediation agent mainly comprises the following preparation steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding nano manganese dioxide with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to prepare the composite metal organic material;
(3) under the atmosphere of nitrogen, mixing the polychloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (2) with the mass of 0.4 time of that of the poly (perchloroethylene), stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at the temperature of 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the poly (perchloroethylene), stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the poly (perchloroethylene), continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets for 3 times by deionized water, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury-polluted soil remediation agent.
Preferably, the dispersant in the step (3) is one or a mixture of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
Examples of effects
The following table 1 shows the performance analysis results of the mercury contaminated soil remediation agents using examples 1, 2, 3 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| Adsorption rate of air environment | 99.8％ | 72.3％ | 85.2％ | 69.4％ |
| Adsorption rate in nitrogen environment | 98.2％ | 70.7％ | 64.5％ | 50.6％ |
From the experimental data of example 1 to example 3 in table 1, it can be seen that the adsorption rate of example 1 is higher and the change of the adsorption rate is much smaller than that of example 3 in the air and nitrogen environments, which illustrates that the thiolated polyperchloroethylene prepared by modifying the polyperchloroethylene with sodium hydrosulfide undergoes nucleophilic substitution with bromine on the composite metal organic material, and two sulfydryl groups between the sulfhydrylation polychloroethylene molecules are dehydrogenated to form a disulfide bond to form a cross-linked network structure, thereby improving the wrapping effect on the composite metal organic material, thereby improving the adsorption rate of the product, and in addition, the unreacted sulfydryl and disulfide bonds on the sulfhydrylation polychloroethylene are easy to be oxidized into sulfone and sulfoxide in the air, under the nitrogen environment, sulfone and sulfoxide can be reduced by mercury, and are reduced into thioether and sulfydryl under the catalysis of manganese dioxide, so that the effect of providing oxygen is achieved, and the stability of the product is improved; from the experimental data of the comparative example 2 and the comparative column of the examples 1 and 3, it can be seen that the adsorption rates of the comparative example 2 and the comparative column of the examples 1 and 3 are both improved, which illustrates that the modification of the nano manganese dioxide weakens the acting force among nano manganese dioxide particles, so that the manganese dioxide is not easy to agglomerate, the dispersibility is improved, and the adsorption effect is improved, thereby improving the catalytic oxidation effect of the nano manganese dioxide, accelerating the dissociation rate of oxygen and the oxidation rate of mercury, and further improving the adsorption 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 attributes 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. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The mercury-contaminated soil remediation agent is characterized by mainly comprising the following components in parts by weight: 10-15 parts of iron metal organic framework material, 2-5 parts of modified nano manganese dioxide and 30-40 parts of sulfhydrylation poly perchloroethylene.
2. The agent of claim 1, wherein said iron metal organic framework material is prepared by reacting ferric chloride with 1, 2, 4, 5-tetrakis (4-carboxyphenyl) benzene in water.
3. The agent of claim 2, wherein the modified nano manganese dioxide is prepared by grafting 3-bromo-4 amino benzoic acid on the surface of nano calcium carbonate.
4. The mercury-contaminated soil remediation agent of claim 3, wherein said 3-bromo-4-aminobenzoic acid is prepared by reacting p-aminobenzoic acid with liquid bromine under catalysis of ferric bromide.
5. The agent of claim 4, wherein said thiolated polyperchloroethylene is prepared by substitution of sodium hydrosulfide with polyperchloroethylene.
6. The mercury-contaminated soil remediation agent of claim 5, wherein the mercury-contaminated soil remediation agent comprises the following raw material components in parts by mass: 10 parts of iron metal organic framework material, 4 parts of modified nano manganese dioxide and 35 parts of sulfhydrylation poly perchloroethylene.
7. A preparation method of a mercury-contaminated soil remediation agent is characterized by mainly comprising the following preparation steps:
(1) reacting ferric chloride with 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene in water, washing and drying to obtain the iron metal organic framework material;
(2) reacting p-aminobenzoic acid with liquid bromine under the catalysis of ferric bromide to prepare 3-bromine-4-aminobenzoic acid, metering the 3-bromine-4-aminobenzoic acid into the nano manganese dioxide dispersion liquid, and performing suction filtration, drying, crushing and sieving on the obtained product to prepare modified nano manganese dioxide;
(3) adding the modified nano manganese dioxide obtained in the step (2) into the iron metal organic framework material dispersion liquid obtained in the step (1) and stirring to obtain a composite metal organic material;
(4) and (3) reacting sodium hydrosulfide with polyperchloroethylene to obtain sulfhydrylated polyperchloroethylene, adding the composite metal organic material obtained in the step (3) into sulfhydrylated polyperchloroethylene alkali dispersion liquid, adding hydrogen peroxide and sodium pyrophosphate, carrying out suspension polymerization to form small balls, and washing and drying to obtain the mercury-polluted soil remediation agent.
8. The method for preparing a mercury-contaminated soil remediation agent according to claim 7, wherein the method for preparing a mercury-contaminated soil remediation agent mainly comprises the following steps:
(1) 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene and water are mixed according to the mass ratio of 1: 20, uniformly mixing, adding ferric chloride with the mass of 0.4 time that of 1, 2, 4, 5-tetra (4-carboxyphenyl) benzene, reacting in a reaction kettle with polytetrafluoroethylene as a substrate for 12 hours at 150 ℃, putting in a centrifugal machine, centrifugally separating at the rotating speed of 8000r/min to obtain a product, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally drying at 120 ℃ for 6 hours to obtain the iron metal organic framework material;
(2) mixing p-aminobenzoic acid and liquid bromine according to a mass ratio of 2: 3, uniformly mixing in a three-neck flask, adding a catalyst ferric bromide with the mass of 0.01 time of that of p-aminobenzoic acid, reacting for 1h at 20 ℃, adding deionized water, heating to 80 ℃, keeping for 10min, filtering, cooling the filtrate to 1-10 ℃, and performing cooling crystallization to obtain 3-bromo-4-aminobenzoic acid; mixing nano manganese dioxide and water according to a mass ratio of 1: 20, uniformly mixing, adding 3-bromo-4-aminobenzoic acid with the mass of 0.5 time of that of the nano silicon dioxide, stirring for 2 hours at the temperature of 80 ℃ at the rotating speed of 2000r/min, filtering, drying, crushing and sieving to obtain modified nano manganese dioxide;
(3) mixing the iron metal organic framework material obtained in the step (1) with water according to the mass ratio of 1: 20, uniformly mixing, adding the modified nano manganese dioxide obtained in the step (2) with the mass of 0.4 time of that of the iron metal organic framework material, stirring at the rotating speed of 2000r/min for 3 hours at the temperature of 80 ℃, filtering, and carrying out vacuum freeze drying at the temperature of-10 ℃ for 6 hours to obtain a composite metal organic material;
(4) mixing the polychloroethylene and water according to the mass ratio of 1: 20, uniformly mixing, adding sodium hydrosulfide with the mass 1.2 times of that of the polyperchloroethylene, stirring for 1h at the rotating speed of 2000r/min under the nitrogen atmosphere at the temperature of 90 ℃, filtering, washing for 3 times by using deionized water, and carrying out vacuum freeze drying for 6h at the temperature of minus 10 ℃ to obtain the sulfhydrylation polyperchloroethylene; under the atmosphere of nitrogen, mixing the sulfhydrylation poly perchloroethylene with sodium hydroxide solution with the mass fraction of 20% according to the mass ratio of 1: 20, uniformly mixing, adding the composite metal organic material obtained in the step (3) with the mass of 0.4 time of that of the thiolated polyperchloroethylene, stirring for 3 hours at the rotating speed of 2000r/min under the condition of nitrogen protection at 20 ℃, adding a hydrogen peroxide solution with the mass fraction of 30% and the mass of 0.9 time of that of the thiolated polyperchloroethylene, stirring for 2 hours at the rotating speed of 2000r/min under the condition of 20 ℃, finally adding a dispersing agent with the mass of 0.01 time of that of the thiolated polyperchloroethylene, continuously stirring for 1 hour at the rotating speed of 100r/min to obtain product pellets, washing the product pellets for 3 times by deionized water, and carrying out vacuum freeze drying for 6 hours at the temperature of minus 10 ℃ to obtain the mercury contaminated soil remediation agent.
9. The method for preparing a mercury contaminated soil remediation agent as claimed in claim 8, wherein the drying in step (2) is vacuum freeze drying at-10 deg.C for 6h, and the pulverizing is performed by pulverizing with a universal pulverizer and sieving with a 50 mesh sieve.
10. The method for preparing a mercury contaminated soil remediation agent as claimed in claim 8, wherein the dispersant in step (4) is one or more of sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
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