CN106903147B - Leaching material capable of adsorbing and degrading organochlorine pollutants and preparation method thereof - Google Patents
Leaching material capable of adsorbing and degrading organochlorine pollutants and preparation method thereof Download PDFInfo
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- CN106903147B CN106903147B CN201710136576.4A CN201710136576A CN106903147B CN 106903147 B CN106903147 B CN 106903147B CN 201710136576 A CN201710136576 A CN 201710136576A CN 106903147 B CN106903147 B CN 106903147B
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Abstract
The invention provides a leaching material capable of adsorbing and degrading organochlorine pollutants and a preparation method thereof, belonging to the technical field of organochlorine pollutant degradation. The leaching material is a multifunctional leaching material which is composed of zero-valent iron and esterified and etherified humic acid and can adsorb and degrade organic chlorine pollutants. Humic acid, glycerol and organic acid are used to generate humic acid ester under the action of an acid catalyst; and then, carboxyl, hydroxyl, amino and the like in the glycidyl ether and the esterified humic acid are utilized to carry out cross-linking reaction and etherification modification, so that hydrophobic ether groups and hydrophobic chains are introduced. And then carrying out coordination complexation or micro-mesoporous loading on iron ions and hydroxyl groups and carboxyl groups in the etherified humic acid ester, and finally reducing the iron ions into zero-valent iron to prepare the Fenton-like oxidation material which has the adsorption and hydrophobicity of the etherified humic acid ester and the zero-valent iron, and is a super-strong leaching material capable of simultaneously realizing adsorption and degradation, efficient separation of chlorobenzene POPs from soil and recycling of leaching media.
Description
Technical Field
The invention belongs to the technical field of leaching materials, and particularly relates to a leaching material capable of adsorbing and degrading organochlorine pollutants and a preparation method thereof.
Background
The chlorine-containing organic pollutants are widely used in the industries of pesticides, manufacturing industry, cleaning industry, chemical production and the like, and are artificially synthesized persistent organic pollutants which have long-term residue, biological accumulation, semi-volatility and high toxicity and can seriously harm human health and ecological environment through various environmental media. The chlorobenzene pesticide contaminated site is repaired by using the method for the purposes of pollution removal, quality recovery, reutilization and safety and health protection. In the numerous restoration technologies for chlorobenzene POPs highly polluted soil, the advantages of large heterogeneity, poor fluidity, large mass transfer resistance, difficult restoration material recovery and the like of soil media can be broken through by adopting the ectopic deep washing, so that the method is considered to be an effective restoration method and also a soil restoration technology based on environmental functional materials.
In order to improve the washing and removing efficiency of POPs, researchers at home and abroad develop various researches on related washing materials. The main classification is two main categories: one is a leaching material based on solubilization and curling effects on POPs, namely a chemical surfactant, a biological surfactant, an organic solvent, a special leaching agent, a compound leaching agent and the like; another class is oxidation enhanced leaching materials based on chemical morphology modification of POPs.
However, the ex-situ leaching technology still has a technical bottleneck in the application process of the remediation of the highly polluted soil in the chlorobenzene pesticide field. The reason is that the mass transfer direction of the dissolved phase consisting of water and the surfactant is from soil to water, the mass transfer power is mainly desorbed by the curling action of the surfactant on the soil fixed-state POPs, and the POPs are promoted to be dissolved into the water phase by the solubilization action, so that the POPs are separated from the soil, and the remediation of the soil polluted by the POPs is realized. However, its leaching action is limited in two ways: firstly, chlorobenzene POPs have low solubility and limited solubilization of surfactants, so that the concentration of desorption-dissolution equilibrium of soil POPs is still low, and the single leaching efficiency is low; and secondly, the high-pollution soil fixed-state POPs are in a multilayer adsorption state, the POPs in the inner-layer adsorption state are aged for a long time, the soil forms combined residual-state POPs by virtue of micropore inlaying effect and chemical effects such as covalent bond, molecular bond, charge transfer and the like, and the residual-state POPs are difficult to elute and remove by virtue of crimping effect. Although studies have reported that enhanced washing with surfactants in combination with Fenton oxidation can enhance the removal of residual states of POPs. However, for highly polluted soil, the soil residual amount is still large, and the oxidation material cannot be recovered, which is likely to cause secondary pollution of the soil. In a word, the leaching material has the limitation of single function (only elution), even though the washing is carried out for multiple times, the removal of the POPs in the highly polluted soil is difficult to reach the standard, tens of times or even hundreds of times of the soil leaching solution is generated, and the subsequent 'purification treatment of the leaching solution' and 'safety treatment of the POPs' are very difficult due to the large amount and complex composition of the leaching solution.
Disclosure of Invention
The invention aims to provide a leaching material capable of adsorbing and degrading organochlorine pollutants and a preparation method thereof, aiming at the problems in the prior art. The method is characterized in that the chemical reaction characteristic of the structure of humic acid ester and glycidyl ether is utilized to enable esterified and etherified humic acid to have hydrophobicity, then metallic iron ions are loaded on the etherified humic acid ester, and the etherified humic acid ester loaded with zero-valent iron metal is obtained through reduction. The leaching material has the characteristics of adsorption of etherified humic acid ester, hydrophobicity and Fenton-like oxidation of zero-valent iron, and is a super-strong leaching material which can realize adsorption and degradation, efficient separation of chlorobenzene POPs from soil and recycling of leaching media. The purpose of the invention is realized by the following technical scheme:
the leaching material is a multifunctional leaching material which consists of zero-valent iron and esterified and etherified humic acid and can adsorb and degrade organic chloride pollutants.
As a specific example of the leaching material capable of adsorbing and degrading organochlorine pollutants, the leaching material is Fe2+Or Fe3+Loaded on esterified and etherified humic acid, and then prepared by a reduction method.
As a specific example of the leaching material capable of adsorbing and degrading organic chlorine pollutants, the esterified and etherified humic acid is prepared by preparing esterified humic acid from humic acid, glycerol and organic acid under the action of an acid catalyst, and then etherifying the esterified humic acid under the action of glycidyl ether.
The invention also relates to a preparation method of the leaching material for adsorbing and degrading the organochlorine pollutants, which comprises the following steps:
1) humic acid esterification: adding glycerol and organic acid into a reactor, adding humic acid into an oil bath, then adding an acid catalyst, and performing suction filtration, washing and drying after reaction to obtain esterified humic acid;
2) and (3) humic acid ester etherification: putting the esterified humic acid into a water bath, adjusting the pH to 4-7, adding acetone mixed glycidyl ether, performing suction filtration, washing and drying after reaction to obtain etherified humic acid ester;
3) preparation of leaching materials: and adding the etherified humic acid ester into a solution containing iron ions, putting the solution into a water bath, adjusting the pH value to 2-7, and performing suction filtration, reduction, suction filtration again, washing and vacuum drying after reaction to obtain the leaching material.
The invention takes humic acid as raw material, glycerin and organic acid are added to carry out esterification reaction under the action of acid catalyst to generate esterified humic acid; and then, performing crosslinking reaction and etherification modification by utilizing the glycidyl ether and carboxyl, hydroxyl, amino and the like in the esterified humic acid under the weakly acidic and neutral conditions, thereby introducing hydrophobic ether groups and hydrophobic chains. And then carrying out coordination complexation or micro-mesoporous loading on iron ions and hydroxyl groups and carboxyl groups in the etherified humic acid ester, and finally reducing the iron ions into zero-valent iron to prepare the Fenton-like oxidation material which has the adsorption and hydrophobicity of the etherified humic acid ester and the zero-valent iron, and is a super-strong leaching material capable of simultaneously realizing adsorption and degradation, efficient separation of chlorobenzene POPs from soil and recycling of leaching media. Different from the traditional inorganic oxide carrier, a large amount of organic functional groups (such as hydroxyl, carbonyl and the like) contained in the etherified humic acid ester carrier can interact with the reduced zero-valent iron nano particles through electron losing/obtaining, and play a good stabilizing role on the zero-valent iron nano particles, so that the zero-valent iron nano particles are anchored on the hydrophobic humic acid carrier. In addition, the humic acid contains a large amount of rigid benzene ring structures, and can also effectively disperse and reduce the formed zero-valent iron nanoparticles, thereby ensuring better dispersibility of the humic acid.
As a specific embodiment of the preparation method of the leaching material capable of adsorbing and degrading organochlorine pollutants, the organic acid is any one of palmitic acid, oleic acid, linoleic acid or C8-20 organic acid; the acid catalyst is one of concentrated sulfuric acid or solid acid catalyst.
As a specific example of the preparation method of the leaching material capable of adsorbing and degrading organochlorine pollutants, in step 1), the humic acid is sieved before being added, wherein the mesh size of the mesh is preferably 100-500 meshes.
As a specific embodiment of the preparation method of the leaching material capable of adsorbing and degrading organochlorine pollutants, in the step 1), the volume ratio of the organic acid to the glycerol is 2-6; further, the volume ratio of the organic acid to the glycerol is preferably 3-5; the mass ratio of the total volume of the organic acid and the glycerol to the humic acid is 3-7, and further, the mass ratio of the total volume of the organic acid and the glycerol to the humic acid is preferably 4-6. The adding amount of the acid catalyst is 1-5% of the total volume of the reaction. The addition of the acid catalyst can promote the esterification reaction and improve the esterification rate, but when the amount of the acid catalyst is higher than the amount limited by the invention, although the catalytic effect is enhanced, the reverse reaction speed can be accelerated at the moment, and a series of side reactions such as polymerization, etherification and the like are increased, so that the esterification rate is reduced; the oil bath temperature is 100-200 ℃, more preferably 120-180 ℃, and most preferably 140-160 ℃; the reaction time is 20 to 30 hours, more preferably 22 to 28 hours, and still more preferably 24 to 26 hours.
As a specific embodiment of the preparation method of the leaching material capable of adsorbing and degrading organic chlorine pollutants, step 2) further comprises adding esterified humic acid into water, and then reacting in a water bath, wherein the volume ratio of water to the total volume of acetone and glycidyl ether is 20-30. Further, the volume ratio of water to the total volume of acetone and glycidyl ether is preferably 22 to 28, and more preferably 24 to 26. The addition of the humic acid into water plays a role in dispersing the esterified humic acid, so that the etherification degree is improved. If the water amount is too much, a waste phenomenon occurs, the concentration of the glycidyl ether is reduced, and the etherification degree is reduced; if the amount of water is too small, the material is not uniformly dispersed, and incomplete etherification may result.
As a specific embodiment of the preparation method of the leaching material capable of adsorbing and degrading the organic chlorine pollutants, the volume ratio of the acetone to the glycidyl ether is 5-10. Further, the volume ratio of acetone to glycidyl ether is preferably 6 to 9, and more preferably 7 to 8. Since the glycidyl ether is hardly soluble in water, acetone is added to increase the solubility of the glycidyl ether in water, so that the etherification degree is increased. If the amount of acetone is too large, the properties of the solution are changed, and side reactions are caused; if the amount of acetone is too small, the effect of changing the solubility of the glycidyl ether cannot be achieved.
As a specific example of the preparation method of the leaching material capable of adsorbing and degrading organic chlorine pollutants, in step 2), the glycidyl ether is one of glycerol ether, glycol ether or allyl ether, and the mass ratio of the glycidyl ether to esterified humic acid is 10% -50%; further, the mass ratio of the glycidyl ether to the esterified humic acid is preferably 15% to 40%, more preferably 25% to 30%. And the excessive glycidyl ether is supersaturated and etherified, so that the glycidyl ether is wasted. If the amount of the glycidyl ether is too small, the etherification is incomplete. The water bath temperature is 40 ℃ to 80 ℃, more preferably 50 ℃ to 70 ℃, and still more preferably 55 ℃ to 65 ℃. The reaction time is 5 to 10 hours, and more preferably 7 to 9 hours.
As a specific embodiment of the preparation method of the leaching material capable of adsorbing and degrading organochlorine pollutants, in the step 3), the solution of the iron ions is one of a ferrous sulfate solution or a ferric sulfate solution, and the mass ratio of the iron ions to etherified humic acid ester is 0.01-0.5; more preferably 0.05 to 0.35, and still more preferably 0.1 to 0.2. If the mass of iron is too low, the ability to degrade contaminants is poor, and if the mass of iron is too high, the weight of the eluted material is increased, hydrophobic groups are masked, and the hydrophobic effect cannot be achieved. The temperature of the water bath is 20-40 ℃, and the more preferable temperature is 25-35 ℃; the reaction time is 2 to 12 hours, more preferably 4 to 10 hours, and still more preferably 6 to 8 hours; the reducing agent used for the reduction is NaBH4Or KBH4One of (1); the molar mass ratio of the reducing agent to the iron ions is 0.5-2, preferably 0.8-1.5, and preferably 1.0-1.2; the temperature of the vacuum drying is 40-80 ℃, more preferably 50-70 ℃, and still more preferably 55-65 ℃.
The invention adopts dilute HNO in the synthesis steps 2) and 3)3And dilute NaOH solution to adjust pH. The reason why the pH value of the etherification reaction is adjusted to 4-7 is that only esterified humic acid can react with active groups of glycidyl ether under weakly acidic and neutral conditions to etherify the esterified humic acid, so that the prepared etherified humic acid ester adsorbing material has hydrophobic property, and if the pH value is not within the range set by the invention, the etherification effect cannot be achieved, and the hydrophobic property of the material can be greatly reduced. In the preparation process of the leaching material (step 3), the pH is adjusted to 2-7, and if the pH is less than 2, the solution is peracid, which can affect etherified clodate and Fe2+Or Fe3+Complexation of ions; if basic, then Fe2+Or Fe3+The ions will hydrolyze and hinder complexation.
The suction filtration, washing and drying in the synthesis steps are all conventional operations in the technical field, and the purpose of the invention can be realized only according to the conventional operations, which is not described in detail and specifically limited herein.
The invention has the beneficial effects that:
1. the leaching material loads zero-valent metallic iron, has good Fenton-like oxidation characteristic, can be oxidized and degraded to change the chemical form of POPs (persistent organic pollutants) and desorb the residual state of the POPs in soil, thereby effectively improving the adsorption and leaching removal rate of the POPs in the soil;
2. the esterified and etherified humic acid in the leaching material has high-efficiency solid phase extraction capacity, has the characteristics of large adsorption capacity, selectivity and broad-spectrum compatibility on various aromatic POPs (including intermediates generated by oxidation enhanced leaching), continuously adsorbs chlorobenzene POPs washed from soil, continuously breaks through the dissolving-adsorbing balance of the POPs between a water phase and the soil in a leaching system, promotes the POPs in the polluted soil to be finally enriched on the leaching material, and realizes a synergistic enhanced leaching mechanism of oxidation and adsorption;
3. the leaching material has the hydrophobic property of etherified humic acid ester, can realize the effective separation of soil, water and material three phases, the POPs enriched on the leaching material are desorbed and concentrated by a small amount of organic solvent, the subsequent safe treatment of chemical or biochemical degradation is convenient, and the leaching material is deoxidized, regenerated and reused after being desorbed. Therefore, the chlorobenzene POPs and the soil are efficiently separated and enriched, and the leaching materials are efficiently recovered.
Drawings
FIG. 1 is an XPS survey of the iron ion-loaded etherified humic acid ester prepared in example 1;
FIG. 2 is an XPS survey of the zero-valent iron-loaded etherified humic acid ester prepared in example 1;
FIG. 3 is a single spectrum diagram of the iron element of the iron ion-loaded etherified humic acid ester prepared in example 1;
FIG. 4 is a single spectrum diagram of the iron element of the zero-valent iron-loaded etherified humic acid ester prepared in example 1;
FIG. 5 is a graph showing the hydrophobic angle of the zero-valent iron-loaded etherified humic acid ester prepared in example 1, wherein β represents the hydrophobic angle.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and palmitic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 200-mesh sieve into an oil bath at 150 ℃, then adding a concentrated sulfuric acid catalyst for reaction for 20 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of the palmitic acid to the glycerol is 3; the mass ratio of the total volume of the palmitic acid and the glycerol to the humic acid is 5ml/g, and the volume of the concentrated sulfuric acid catalyst is 2% of the total volume of the reaction.
2) Etherifying esterified humic acid: adding esterified humic acid into water at 50 deg.C, reacting in water bath, and adding diluted HNO3And regulating the pH value to 5 with a dilute NaOH solution, adding glycerol ether mixed with acetone, reacting for 8 hours, and performing suction filtration, washing and drying to obtain etherified humic acid ester. Wherein the volume ratio of the acetone to the glycerol ether is 8; the ratio of water to the total volume of acetone and glycerol ether was 20; the mass ratio of the glyceryl ether to the esterified humic acid was 20%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfite solution, placing into water bath at 30 deg.C, and adding diluted HNO3Adjusting pH to 3 with dilute NaOH solution, performing suction filtration after 6h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load2+Etherified humic acid esters of (4), then loading Fe2+The etherified humic acid ester is put into deionized water solution, NaBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 50 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe2+The mass ratio of the sodium borohydride to the etherified humic acid ester is 0.01, and the molar mass ratio of the sodium borohydride to the iron ions is 0.5.
Fig. 1 is an XPS full spectrum of the iron ion-loaded etherified humic acid ester prepared in this example, and fig. 2 is an XPS full spectrum of the zero-valent iron-loaded etherified humic acid ester prepared in this example. As can be seen from the full spectrum diagrams in fig. 1 and 2, most of the peaks generated by reduction with the reducing agent are iron elements, but only a small amount of impurities of sodium element and boron element are contained, because the catalyst is reduced by using sodium borohydride, a small amount of impurities remain on the catalyst after reduction, but the catalytic activity of the catalyst is not affected.
Fig. 3 is a single spectrogram of an iron element of the iron ion-loaded etherified humic acid ester prepared in the embodiment, and fig. 3 is a single spectrogram of an iron element of the zero-valent iron-loaded etherified humic acid ester prepared in the embodiment. As can be seen from the single spectrograms of fig. 3 and fig. 4, the bond energy of the reduced iron element is significantly higher than that of the unreduced iron element, which indicates that a large amount of Fe ions on the catalyst are reduced to zero-valent iron by the reducing agent sodium borohydride or potassium borohydride.
FIG. 5 is a graph showing the hydrophobic angle of the iron-supporting etherified humic acid ester prepared in this example. The prepared etherified humic acid ester adsorbing material has a hydrophobic angle of 104.7 degrees and more than 90 degrees, and has hydrophobicity.
Example 2
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and oleic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 300-mesh sieve into oil bath at 180 ℃, then adding a concentrated sulfuric acid catalyst for reaction for 25 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of the oleic acid to the glycerol is 2; the mass ratio of the total volume of the oleic acid and the glycerol to the humic acid is 4ml/g, and the volume of the concentrated sulfuric acid catalyst is 1 percent of the total volume of the reaction.
2) Etherifying esterified humic acid: adding the esterified humic acid into a certain amount of water, reacting in a water bath at 60 ℃, and using diluted HNO3And adjusting the pH value of the solution and a dilute NaOH solution to 6, adding glycidyl ether mixed with acetone, reacting for 6 hours, and performing suction filtration, washing and drying to obtain the humic acid adsorbing material. Wherein the volume ratio of the acetone to the glycidyl ether is 6; the ratio of water to the total volume of acetone and glycidyl ether was 25; the mass ratio of the glycidyl ether to the esterified humic acid was 30%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfite solution, placing into water bath at 40 deg.C, and adding diluted HNO3Adjusting pH to 5 with dilute NaOH solution, performing suction filtration after 6h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load2+Etherified humic acid esters of (4), then loading Fe2+The etherified humic acid ester is put into deionized water solution, NaBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 65 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe2+The mass ratio of the sodium borohydride to the etherified humic acid ester is 0.03, and the molar mass ratio of the sodium borohydride to the iron ions is 1.
Example 3
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and linoleic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 400-mesh sieve into oil bath at 120 ℃, then adding a concentrated sulfuric acid catalyst into the mixture to react for 28 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of the linoleic acid to the glycerol is 6; the mass ratio of the total volume of linoleic acid and glycerol to the humic acid is 7ml/g, and the volume of the concentrated sulfuric acid catalyst is 5 percent of the total volume of the reaction.
2) Etherifying esterified humic acid: adding the esterified humic acid into a certain amount of water, reacting in 80 ℃ water bath, and using diluted HNO3And adjusting the pH value of the solution and a dilute NaOH solution to be 4, adding glycidyl ether mixed with acetone, reacting for 9 hours, and performing suction filtration, washing and drying to obtain the humic acid adsorbing material. Wherein the volume ratio of the acetone to the glycidyl ether is 5; the ratio of water to the total volume of acetone and glycidyl ether was 30; the mass ratio of the glycidyl ether to the esterified humic acid was 50%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfate solution, placing into 35 deg.C water bath, and adding diluted HNO3Adjusting pH to 6 with dilute NaOH solution, performing suction filtration after 10h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load3 +Etherified humic acid esters of (4), then loading Fe3+The etherified humic acid ester is put into deionized water solution, NaBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 70 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe3+The mass ratio of the sodium borohydride to the etherified humic acid ester is 0.1, and the molar mass ratio of the sodium borohydride to the iron ions is 1.5.
Example 4
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and oleic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 150-mesh sieve into an oil bath at 200 ℃, then adding a concentrated sulfuric acid catalyst for reaction for 22 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of the oleic acid to the glycerol is 5; the mass ratio of the total volume of the oleic acid and the glycerol to the humic acid is 4ml/g, and the volume of the concentrated sulfuric acid catalyst is 3 percent of the total volume of the reaction.
2) Etherifying esterified humic acid: adding esterified humic acid into a certain amount of water, reacting in 70 deg.C water bath, and adding diluted HNO3And adjusting the pH value of the solution and a dilute NaOH solution to 5, adding glycidyl ether mixed with acetone, reacting for 8 hours, and performing suction filtration, washing and drying to obtain the humic acid adsorbing material. Wherein the volume ratio of the acetone to the glycidyl ether is 10; the ratio of water to the total volume of acetone and glycidyl ether was 22; the mass ratio of the glycidyl ether to the esterified humic acid was 10%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfate solution, placing the solution into a water bath at 25 ℃, and adding diluted HNO3Adjusting pH to 4 with dilute NaOH solution, performing suction filtration after 8h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load3+Etherified humic acid esters of (4), then loading Fe3+The etherified humic acid ester is put into deionized water solution, and KBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 55 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe3+The mass ratio of the humic acid to the etherified humic acid ester is 0.3, and the molar mass ratio of the potassium borohydride to the iron ions is 0.5-2
Example 5
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and linoleic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 250-mesh sieve into oil bath at 130 ℃, then adding a concentrated sulfuric acid catalyst for reaction for 27 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of the linoleic acid to the glycerol is 3; the mass ratio of the total volume of linoleic acid and glycerol to the humic acid is 6ml/g, and the volume of the concentrated sulfuric acid catalyst is 1 percent of the total volume of the reaction.
2) Etherifying esterified humic acid: adding esterified humic acid into water, reacting in 75 deg.C water bath, dilutingHNO3And adjusting the pH value of the solution and a dilute NaOH solution to be 4, adding glycidyl ether mixed with acetone, reacting for 8 hours, and performing suction filtration, washing and drying to obtain the humic acid adsorbing material. Wherein the volume ratio of the acetone to the glycidyl ether is 10; the ratio of water to the total volume of acetone and glycidyl ether was 22; the mass ratio of the glycidyl ether to the esterified humic acid was 15%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfate solution, placing the solution into a water bath at 25 ℃, and adding diluted HNO3Adjusting pH to 2 with dilute NaOH solution, performing suction filtration after 5h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load3+Etherified humic acid esters of (4), then loading Fe3+The etherified humic acid ester is put into deionized water solution, and KBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 65 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe3+The mass ratio of the sodium hydrogen borate to the etherified humic acid ester is 0.5, and the molar mass ratio of the potassium borohydride to the iron ions is 2.
Example 6
The preparation method of the leaching material of this example is as follows:
1) humic acid esterification: and (2) adding glycerol and palmitic acid into the round-bottom flask slowly in sequence, stirring and adding humic acid which is sieved by a 350-mesh sieve into oil bath at 170 ℃, then adding a concentrated sulfuric acid catalyst for reaction for 30 hours, and after the reaction, carrying out suction filtration, washing and drying to obtain esterified humic acid. Wherein the volume ratio of palmitic acid to glycerol is 6; the mass ratio of the total volume of the palmitic acid and the glycerol to the humic acid is 4ml/g, and the volume of the concentrated sulfuric acid catalyst is 4% of the total volume of the reaction.
2) Etherifying esterified humic acid: adding esterified humic acid into water, reacting in 75 deg.C water bath, and adding diluted HNO3And adjusting the pH value of the solution and a dilute NaOH solution to 4, adding glycidyl ether mixed with acetone, reacting for 7 hours, and performing suction filtration, washing and drying to obtain the humic acid adsorbing material. Wherein the volume ratio of the acetone to the glycidyl ether is 8; the ratio of water to the total volume of acetone and glycidyl ether was 28; the mass ratio of the glycidyl ether to the esterified humic acid was 40%.
3) Preparation of leaching materials: adding the etherified humic acid ester into ferric sulfate solution, placing the solution into a water bath at 25 ℃, and adding diluted HNO3Adjusting pH to 7 with dilute NaOH solution, performing suction filtration after 5h of reaction, and performing vacuum drying at 40 ℃ to obtain Fe load3+Etherified humic acid esters of (4), then loading Fe3+The etherified humic acid ester is put into deionized water solution, and KBH is added4Standing at room temperature for reduction reaction for 12h, then performing suction filtration and washing, and performing vacuum drying at the temperature of 65 ℃ to obtain the etherified humic acid ester supported zero-valent iron leaching material. Wherein, Fe3+The mass ratio of the sodium humate to the etherified humic acid ester is 0.4, and the molar mass ratio of the potassium borohydride to the iron ions is 0.8.
Performance testing of the Leaching materials prepared in examples 1 to 6
1.2, 4, 6-trichlorophenol degradation:
0.02g of the leaching material prepared in the above examples 1 to 4 was added to 50ml of a 10 mg/L2, 4, 6-trichlorophenol solution, the mixture was reacted for 3 hours on a light-shielding oscillator, the adsorbing material was filtered off, the remaining 2,4, 6-trichlorophenol solution was extracted and concentrated with n-hexane, and the degradation rate of the 2,4, 6-trichlorophenol by the leaching material prepared in the examples was measured and calculated by a gas chromatograph.
2. Hydrophobic property of leaching material
And (3) tabletting the leaching materials prepared in the above embodiments 1 to 6, and placing the tabletting into a corresponding hydrophobic angle measuring instrument to measure the hydrophobic angle of the prepared leaching materials.
The degradation performance of the leaching materials prepared in examples 1 to 6 to 2,4, 6-trichlorophenol and the results of the hydrophobic property test thereof are shown in the following table 1:
TABLE 1 degradation and hydrophobicity of the leached materials prepared in examples 1 to 6
| Leaching material | Degradation rate of 2,4, 6-trichlorophenol | Hydrophobic angle | Hydrophobicity |
| Example 1 | 95.65％ | 104.7° | Hydrophobic |
| Example 2 | 96.21％ | 101.2° | Hydrophobic |
| Example 3 | 95.33％ | 104.1° | Hydrophobic |
| Example 4 | 96.15％ | 101.6° | Hydrophobic |
| Example 5 | 95.97％ | 102.6° | Hydrophobic |
| Example 6 | 96.23％ | 100.3° | Hydrophobic |
From the above table 1, it can be seen that humic acid is esterified and etherified in sequence, then iron ions are loaded, and finally reduction is performed to obtain the etherified humic acid ester leaching material loaded with zero-valent iron, wherein the degradation rate of the leaching material to 2,4, 6-trichlorophenol can reach more than 95%, which indicates that the leaching material has good degradation performance to organic chlorine pollutants, because zero-valent iron is loaded in the prepared leaching material, the chemical form of 2,4, 6-trichlorophenol can be changed by oxidative degradation through Fenton-like oxidation of zero-valent iron, and the degradation rate to 2,4, 6-trichlorophenol is improved. Meanwhile, the hydrophobic angles of the leaching materials prepared by the method are all larger than 100 degrees, which shows that the leaching materials synthesized by the method have good hydrophobic property, can well realize the effective separation of three phases of water, soil and the leaching materials, and after adsorbing the organic chlorine pollutants, the leaching materials are separated from the soil and water by utilizing the hydrophobic property, thereby realizing the high-efficiency separation and enrichment of the organic chlorine pollutants and the soil and the high-efficiency recovery of the leaching materials.
Comparative example 1 influence of the volume ratio of organic acid to Glycerol on the Performance of rinsing Material
The volume ratio of the organic acid to the oleic acid (acid-oil ratio) was changed as shown in the following table, the other preparation steps were the same as those in example 1, the adsorption rate of the prepared leaching material to 2,4, 6-trichlorophenol was measured according to the above method, and the hydrophobic angle and hydrophobic property of the prepared leaching material were measured. The test results are shown in table 2 below.
TABLE 2 degradation and hydrophobic Properties of the Leaching materials prepared at different acid to oil ratios
| Volume ratio of sour oil | 0.5 | 1.5 | 8 | 12 | 20 |
| Degradation rate of 2,4, 6-trichlorophenol | 82.23％ | 80.48％ | 80.25％ | 84.67％ | 83.19％ |
| Drip washing material hydrophobic angle | 88.2° | 70.3° | 59.3° | 42.6° | 25.2° |
| Hydrophobicity | Hydrophilic | Hydrophilic | Hydrophilic | Hydrophilic | Hydrophilic |
As can be seen from Table 2, the degradation rate of 2,4, 6-trichlorophenol is reduced when the volume ratio of the acid oil is changed. The reason is that when the volume ratio of the acid oil is reduced, the esterification degree is not enough, the esterified humic acid is not complete, the subsequent etherification reaction is influenced, the adsorption performance of the etherified humic acid ester is reduced, and the loading capacity of iron ions on the etherified humic acid ester is also influenced, so that the Fenton-like oxidation performance of the finally prepared leaching material loaded with zero-valent iron ions is caused, and the degradation rate of 2,4, 6-trichlorophenol is reduced. When the volume ratio of the acid oil is too large, the organic acid is excessive, the pH reaction environment of the esterification reaction can be changed, and the smooth proceeding of the reaction is influenced, so that the subsequent load of iron ions on the etherified humic acid ester is influenced, the Fenton-like oxidation performance of zero-valent iron ions is reduced, and the degradation rate of 2,4, 6-trichlorophenol is reduced.
When the specific volume of the acid oil is increased or decreased, the esterification reaction is incomplete, so that the subsequent etherification reaction is influenced, the normal synthesis of the hydrophobic ether group and the hydrophobic chain is influenced, the hydrophobic property of the prepared leaching material is reduced, the leaching material is changed from hydrophobic to hydrophilic, the separation of the leaching material from soil and a water phase is influenced, and the recovery of the leaching material is not facilitated.
Comparative example 2 influence of pH ratio on rinsing Material Performance during rinsing Material preparation
The pH value in the preparation process of the leaching material (step 3) was changed according to the following table, the other preparation steps were the same as the preparation method of example 1, and the degradation rate of the prepared leaching material to 2,4, 6-trichlorophenol was tested according to the above method, and the hydrophobic angle and hydrophobic property of the prepared leaching material were tested. The test results are shown in table 3 below.
TABLE 3 degradation Rate and hydrophobic Properties of the Leaching materials prepared at different pH's in step 3)
| Step 3) |
1 | 8 | 10 | 12 |
| Degradation rate of 2,4, 6-trichlorophenol | 50.26％ | 80.60％ | 76.43％ | 71.35％ |
| Drip washing material hydrophobic angle | 79.1° | 86.2° | 84.3° | 80.1° |
| Hydrophobicity | Hydrophilic | Hydrophilic | Hydrophilic | Hydrophilic |
As can be seen from Table 3, the degradation rate of 2,4, 6-trichlorophenol is reduced when the pH value is changed during iron loading. The reason is that when the solution is too acid, humic acid ester and Fe are affected2+Or Fe3+Complexation of ions; if basic, then Fe2+Or Fe3+The ions will hydrolyze, hinder complexation and reduce Fe0The formation of (2) reduces the progress of the Fenton-like reaction, so the degradation rate is reduced.
As can be seen from table 3, the hydrophobicity of the eluted material also decreases when the pH is changed during iron loading, because the peracid or overbase conditions break the hydrophobic groups of the eluted material and result in a decrease in hydrophobicity and a decrease in the hydrophobic angle.
Comparative example 3 influence of the mass ratio of iron ions to etherified humic acid esters on the Properties of the rinsing Material
The mass ratio of the ferric ions to the etherified humic acid ester is changed according to the following table, other preparation steps are the same as the preparation method of the embodiment 1, the degradation rate of the prepared leaching material to the 2,4, 6-trichlorophenol is tested according to the method, and the hydrophobic angle and the hydrophobic performance of the prepared leaching material are tested. The test results are shown in table 4 below.
TABLE 4 degradation Rate and hydrophobic Properties of Leaching materials prepared with the mass ratio of iron ions to etherified humic acid esters
| Mass ratio of iron ion to etherified humic acid ester | 0.005 | 0.008 | 0.7 | 1.5 |
| Degradation rate of 2,4, 6-trichlorophenol | 79.95％ | 85.78％ | 96.36％ | 97.58％ |
| Drip washing material hydrophobic angle | 106.5° | 103.7° | 87.2° | 80.2° |
| Hydrophobicity | Hydrophobic | Hydrophobic | Hydrophilic | Hydrophilic |
As can be seen from Table 4, the degradation rate of 2,4, 6-trichlorophenol was changed when the mass ratio of iron ions to etherified humic acid esters was changed. When the ratio is decreased, the degradation rate is decreased because the ability to degrade the contaminant is poor if the mass of iron is too small, and conversely, if the mass of iron is too large, Fe, which is a contaminant, can be degraded0The degradation rate is increased, but the iron loading is increased, which increases the weight of the leaching material, masks the hydrophobic groups and does not play a role in hydrophobicity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The preparation method of the leaching material capable of adsorbing and degrading the organochlorine pollutants is characterized by comprising the following steps of:
1) humic acid esterification: adding glycerol and organic acid into a reactor, adding humic acid into an oil bath, then adding an acid catalyst, and performing suction filtration, washing and drying after reaction to obtain esterified humic acid; the volume ratio of the organic acid to the glycerol is 2-6;
2) and (3) humic acid ester etherification: putting the esterified humic acid into a water bath, adjusting the pH to 4-7, adding acetone mixed glycidyl ether, performing suction filtration, washing and drying after reaction to obtain etherified humic acid ester;
3) preparation of leaching materials: adding the etherified humic acid ester into a solution containing iron ions, putting the solution into a water bath, adjusting the pH to 2-7, and performing suction filtration, reduction, suction filtration again, washing and vacuum drying after reaction to obtain a leaching material; the mass ratio of the iron ions to the etherified humic acid ester is 0.01-0.5.
2. The preparation method of the leaching material capable of adsorbing and degrading organochlorine pollutants as claimed in claim 1, wherein the organic acid is any one of palmitic acid, oleic acid, linoleic acid or an organic acid with 8-20C atoms; the acid catalyst is concentrated sulfuric acid.
3. The method for preparing the leaching material capable of adsorbing and degrading the organochlorine pollutants according to claim 2, wherein in the step 1), the mass ratio of the total volume of the organic acid and the glycerol to the humic acid is 3-7; the oil bath temperature is 100-200 ℃, and the reaction time is 20-30 h.
4. The method for preparing the leaching material capable of adsorbing and degrading the organochlorine pollutants according to claim 2, wherein the step 2) further comprises adding the esterified humic acid into water, and then reacting in a water bath, wherein the volume ratio of the water to the total volume of the acetone and the glycidyl ether is 20-30.
5. The method for preparing the leaching material capable of adsorbing and degrading the organochlorine pollutants according to claim 2, wherein the volume ratio of the acetone to the glycidyl ether is 5-10.
6. The method for preparing the leaching material capable of adsorbing and degrading the organochlorine pollutants according to claim 2, wherein in the step 2), the glycidyl ether is one of glycerol ether, glycol ether or allyl ether, and the mass ratio of the glycidyl ether to the esterified humic acid is 10% -50%; the water bath temperature is 40-80 ℃, and the reaction time is 5-10 h.
7. The method for preparing the leaching material capable of adsorbing and degrading the organochlorine pollutants according to claim 2, wherein in the step 3), the solution of the iron ions is one of a ferrous sulfate solution or a ferric sulfate solution, the water bath temperature is 20 ℃ to 40 ℃, and the reaction time is 2h to 12 h; the above-mentionedThe reducing agent used for the reduction is NaBH4Or KBH4One of (1); the molar mass ratio of the reducing agent to the iron ions is 0.5-2; the temperature of the vacuum drying is 40-80 ℃.
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