CN114632498B - Hyperbranched sulfydryl sponge adsorbent and preparation method and application thereof - Google Patents
Hyperbranched sulfydryl sponge adsorbent and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a hyperbranched sulfydryl sponge adsorbent for efficiently removing heavy metal mercury in water and a preparation method thereof, and belongs to the field of water treatment technology and application. The invention firstly uses Hyperbranched Polyethyleneimine (HPEI) as a monomer and 1, 4-butanediol diglycidyl ether as a cross-linking agent to prepare a sponge with a three-dimensional porous structure by an ice template method, uses the sponge as a matrix material, uses high molecular weight HPEI containing rich amino functional groups as a branched chain to be connected on a sponge matrix, and uses mercaptoethanol and mercaptoethyl acetate to complete a substitution reaction between sulfydryl and amino to prepare the hyperbranched sponge with the sulfydryl as an end group. The prepared hyperbranched sulfhydryl sponge has rich sulfhydryl groups and large adsorption capacity, can form an extremely stable complex with mercury in water based on a soft and hard acid-base theory, has the advantages of strong selectivity, high removal rate, simple and low preparation cost, easy recovery and the like, and has wide application prospect in the field of water treatment.
Description
Technical Field
The invention belongs to the field of water treatment technology and application, and particularly relates to a hyperbranched sponge adsorbent for efficiently and selectively removing mercury in various water environments with high adsorption capacity, and a preparation method and application thereof.
Background
With the development of society and industry, the application range and the application amount of mercury are increasing day by day, however, mercury is a highly toxic heavy metal pollutant, and mercury remained in the atmosphere and water poses a serious threat to human health. One of the eight world public hazards occurring in japanese bear county in 1956 is responsible for the chief fate of the illness caused by mercury that is industrially emitted into water. The trace mercury is difficult to effectively remove in a sewage treatment plant, so that the mercury is accumulated in a water body and becomes a persistent water environment pollutant. In recent years, mercury in water has been detected to exceed standards many times and has proven to pose certain risks to the ecological environment and human health.
The common methods for removing heavy metals in wastewater include a chemical precipitation method, an electrochemical method, an ion exchange method, a chemical adsorption method and the like, but most of the methods have the defects of secondary pollution, high cost, higher lower limit of treatment, difficulty in recycling and the like. Currently, a chemical adsorption method is commonly used, wherein activated carbon adsorption is generally used, activated carbon has the advantages of large specific surface area, low price, high adsorption capacity and the like, activated carbon adsorption is one of the methods for removing mercury in water at present, but activated carbon has no selectivity for adsorbing mercury, and the adsorption effect is reversible and is easy to saturate, so that the consumption is large, and activated carbon has a minimum concentration for adsorbing mercury in water, and the activated carbon cannot play a role when the concentration is lower than the minimum concentration. Therefore, the method has very important significance in searching and developing the substitute adsorbent material with high efficiency, high adsorption capacity, high selectivity and no secondary pollution.
The hyperbranched polyethyleneimine sponge has unique properties of a net-shaped three-dimensional structure, high adsorption rate, a large number of terminal groups, intramolecular functional groups and the like, is convenient for wastewater to permeate into the sponge and is beneficial to full contact, so that target pollutants can be efficiently and rapidly adsorbed, and the thiol-functionalized high polymer material can be used for removing mercury with high selectivity through coordination, chelation and other effects based on a soft-hard acid-base theory.
Disclosure of Invention
In order to achieve the purpose of removing various forms of mercury in water with high adsorption capacity, the invention provides a preparation method of a hyperbranched sulfydryl sponge adsorbent with low cost, green and simple synthesis method, and obtains an adsorbent material for removing various forms of mercury in water with high efficiency, high adsorption capacity, high selectivity and no secondary pollution.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a hyperbranched sulfydryl sponge adsorbing material for removing mercury in water comprises the following steps:
(1) Dissolving polyethyleneimine into water, adding 1, 4-butanediol diglycidyl ether, mixing uniformly, then placing into a mold, reacting at-20 ℃ for 24 hours, thawing after the reaction is finished, and soaking and repeatedly cleaning by using a large amount of water and ethanol solution to obtain a sponge matrix;
(2) Dissolving the sponge matrix prepared in the step (1) in an alcohol-water mixed solution, adding polyethyleneimine with higher molecular weight for further hyperbranched, placing in a water bath at the temperature of 80 ℃, performing reflux reaction for 4 hours, and soaking and repeatedly cleaning by using a large amount of water and an ethanol solution after the reaction is finished to obtain hyperbranched amino sponge;
(3) And (3) placing the hyperbranched amino sponge prepared in the step (2) into a sulfydryl modified solvent, carrying out substitution reaction between sulfydryl and amino to obtain hyperbranched sponge with rich-end sulfydryl, repeatedly cleaning by using a large amount of water and ethanol solution after the reaction is finished, and drying to obtain the hyperbranched sulfydryl sponge.
Preferably, the weight average molecular weight of the polyethyleneimine in the step (1) is 10000 or 25000.
Preferably, the mass ratio of the polyethyleneimine, the 1, 4-butanediol diglycidyl ether and the water in the step (1) is 1 (1-10) to (20-50).
Preferably, the weight average molecular weight of the polyethyleneimine in the step (2) is any one of 25000 or 70000.
Preferably, the thiol-modified solvent in step (3) is a mixed solution of mercaptoethanol and one or two of ethyl thioglycolate.
Preferably, the volume ratio of mercaptoethanol to ethyl thioglycolate in step (3) is 1.
Preferably, the drying in the step (3) is vacuum drying, the drying temperature is 50-80 ℃, and the drying time is 24-48 h.
The invention also provides the hyperbranched mercapto-sponge prepared by the method, the sponge is divided into two parts, the first part is a polyethyleneimine sponge substrate, the further hyperbranched reaction is carried out on the sponge substrate, and the mercapto modification is carried out on the sponge substrate, and the modification reagent is a mixture of mercaptoethanol and ethyl thioglycolate in a certain molar ratio.
The invention also provides application of the hyperbranched sulfhydryl sponge in removing mercury ions in various forms in water.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the hyperbranched sulfhydryl sponge provided by the invention is simple, high in yield, low in raw material price and environment-friendly.
(2) The hyperbranched sulfhydryl sponge prepared by the invention has rich branched chains, is not tangled among molecules, has a large number of terminal sulfhydryl groups, and has strong binding capacity with mercury based on a soft and hard acid-base theory, so that mercury can be removed with high adsorption capacity and high selectivity, the purpose of water purification is achieved, and the problems of low adsorption efficiency and poor selectivity of traditional activated carbon adsorption on mercury ion compounds are fundamentally solved.
(3) The hyperbranched sulfhydryl sponge provided by the invention has high selectivity, stability and reuse rate, and has wide application prospects in the field of water treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described below.
FIG. 1 is a scanning electron micrograph of the hyperbranched mercaptosponge of example 1.
FIG. 2 is the recyclability of the hyperbranched thiol sponge of example 1.
Detailed Description
The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto, and it is obvious that the examples in the following description are only some examples of the present invention, and it is obvious for those skilled in the art to obtain other similar examples without inventive exercise and falling into the scope of the present invention.
Example 1:
a preparation method of a hyperbranched sulfydryl sponge adsorbing material for removing mercury in water comprises the following steps:
(1) Adding 0.1g of hyperbranched polyethyleneimine (purchased from Aladdin reagent (Shanghai) Co., ltd.) with the weight average molecular weight of 10000 into 2.3g of deionized water, uniformly mixing, adding 0.3g of 1, 4-butanediol diglycidyl ether, uniformly swirling, and immediately reacting at-20 ℃ for 24h; cleaning the prepared material with ethanol and water alternately, and repeating for six times;
(2) Placing 0.25g of the material prepared in the step (1) into 20mL of methanol aqueous solution (the volume ratio of methanol to water is 1;
(3) Placing the sponge material obtained in the step (2) in 20ml of mixed solution of mercaptoethanol and ethyl thioglycolate (the volume ratio of the mercaptoethanol to the ethyl thioglycolate is 1; and (3) alternately cleaning the prepared sponge material by using ethanol and water, repeating the cleaning for six times, and finally drying the sponge material in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain the hyperbranched sulfydryl sponge.
Example 2:
the hyperbranched sulfydryl sponge adsorbing material prepared in the embodiment 1 of the invention is applied to the experiment for removing mercury in water:
preparing 3 parts of mercury aqueous solution, wherein the initial concentration of mercury in water is 100ppm, the pH value is 5, the temperature is room temperature, then adding the hyperbranched sulfydryl sponge adsorbing material prepared in the example 1, and the adding amount of the adsorbing agent is 0.25g L -1 After 2h of adsorption on a shaker, the remaining mercury in the solution was finally detected by atomic fluorescence (see national environmental protection standard HJ 694-2014), each set of experiments was carried out three times, and the average of the three results was taken.
Through detection, the removal rate of mercury in water after the hyperbranched mercaptosponge adsorbing material prepared in the embodiment 1 is treated for 2 hours reaches 73.3%, and therefore, the hyperbranched mercaptosponge adsorbing material prepared in the invention can rapidly and efficiently remove mercury in water.
Example 3:
the hyperbranched sulfydryl sponge adsorbing material prepared in the embodiment 1 of the invention is applied to an adsorption time experiment for removing mercury in water:
preparing a mercury aqueous solution, wherein the initial concentration of mercury in the water is 100ppm, the pH value is 5, the temperature is room temperature, then adding the hyperbranched sulfydryl sponge adsorbing material prepared in the example 1, and the adding amount of the adsorbing agent is 0.25g L -1 40min,60min,90min,150min,270min,390min were adsorbed on a shaker, and the remaining mercury in the solution was finally detected by atomic fluorescence (see national standard HJ 694-2014), with each set of experiments performed in triplicate, and the average of the results was taken over the three times.
Through detection, the hyperbranched mercaptosponge adsorbing material prepared in the embodiment 1 can rapidly and efficiently adsorb mercury in water after oscillating and adsorbing for 40min, the removal rate of mercury in water after oscillating and adsorbing for 60min is 68.0%, the removal rate of mercury in water after oscillating and adsorbing for 90min is 72.4%, the removal rate of mercury in water after oscillating and adsorbing for 150min is 75.6%, the removal rate of mercury in water after oscillating and adsorbing for 270min is 84.2%, and the removal rate of mercury in water after oscillating and adsorbing for 390min is 88.0%.
Example 4:
the hyperbranched mercapto sponge adsorbing material prepared in embodiment 1 of the invention is applied to a reutilization experiment for removing mercury in water:
respectively preparing 4 parts of mercury aqueous solution with the initial concentration of 40ppm, the volume of 30ml, the pH value of 5 and the temperature of room temperature, firstly adding the hyperbranched mercaptosponge adsorbing material prepared in the embodiment 1 into the 1 st part of mercury aqueous solution, wherein the adding amount of the adsorbing agent is 10mg, adsorbing for 6 hours on an oscillator, detecting the residual mercury in the aqueous solution by an atomic fluorescence method, calculating the removal rate of the mercury in the aqueous solution, then filtering the hyperbranched mercaptosponge aqueous solution through filter paper to recover the hyperbranched mercaptosponge adsorbing material, then using 10ml and 3mol/L hydrochloric acid solution to perform oscillation soaking on the recovered mercaptohyperbranched sponge for 30min, then using pure water to wash off the residual hydrochloric acid attached to the surface, drying the mercaptohyperbranched sponge, then adding the hyperbranched sponge into the 2 nd part of mercury aqueous solution to perform adsorption experiments, repeating the operations in sequence, completing 4 times of adsorption experiments, and respectively calculating the removal rate of the mercury in the aqueous solution of each adsorption experiment.
After 4 repeated adsorption experiments, the hyperbranched mercaptosponge adsorbing material prepared in the embodiment 1 of the present invention still has an adsorption removal rate of 80.3% for mercury (see fig. 2), and thus, the hyperbranched mercaptosponge adsorbing material prepared in the present invention has excellent regeneration performance and reusability.
Example 5:
the hyperbranched sulfydryl sponge adsorbing material prepared in the embodiment 1 is applied to a selectivity experiment for removing mercury in water:
respectively preparing mercury aqueous solution and Cu 2+ Solution, zn 2+ Solution and Fe 3+ The solution, both at 20ppm initial concentration, 250mL volume, pH 5, room temperature, was then added to the hyperbranched mercaptosponge adsorbent material prepared in example 1 at a loading of 0.25g L adsorbent -1 And adsorbing the solution on an oscillator for 1h, detecting the amount of the remaining metal ions in the aqueous solution by inductively coupled plasma emission spectrometry, and calculating the removal rate of the metal ions in the aqueous solution.
Through detection, the removal rate of mercury in water treated by the hyperbranched mercaptosponge adsorbing material prepared in example 1 reaches 76.2%, and the removal rate of Cu in water treated by the hyperbranched mercaptosponge adsorbing material prepared in example 1 reaches 76.2% 2+ The removal rate of (1) is only 1.0%, and the Zn in the water treated by the hyperbranched sulfydryl sponge adsorbing material prepared in example 1 2+ The removal rate of (1) was only 0.6%, and Fe in the water treated by the hyperbranched sulfydryl sponge adsorbing material prepared in example 1 was 3+ The removal rate of (a) is only 0.9%, and therefore, the hyperbranched sulfydryl sponge adsorbing material prepared by the invention has very high selectivity on mercury adsorption.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. The preparation method of the hyperbranched sulfhydryl sponge is characterized by comprising the following steps:
(1) Uniformly mixing a hyperbranched polyethyleneimine aqueous solution and 1, 4-butanediol diglycidyl ether, and reacting at-20 ℃ for 12-24 h to obtain a polymer material;
(2) Dissolving the polymer material prepared in the step (1) in a mixed solution of alcohol and water, adding hyperbranched polyethyleneimine, and carrying out reflux reaction at the temperature of 60-100 ℃ for 4-10 h to obtain hyperbranched amino sponge;
(3) Adding the hyperbranched amino sponge prepared in the step (2) into a sulfydryl modified solvent, carrying out reflux reaction for 10-24 h at the temperature of 60-100 ℃, and drying to obtain hyperbranched sulfydryl sponge;
the weight average molecular weight of the polyethyleneimine obtained in the step (1) is 10000 or 25000; the weight average molecular weight of the polyethyleneimine obtained in the step (2) is 25000 or 70000;
the mass ratio of the polyethyleneimine, the 1, 4-butanediol diglycidyl ether and the water in the step (1) is 1 (1-10) to 20-50.
2. The method according to claim 1, wherein the mercapto-modified solvent in step (3) is a mixed solution of one or both of mercaptoethanol and ethyl thioglycolate.
3. The method according to claim 2, wherein the mercapto-modified solvent in step (3) is mercaptoethanol and ethyl thioglycolate, and the volume ratio of mercaptoethanol to ethyl thioglycolate is 1.
4. The process according to any one of claims 1 to 3, wherein the alcohol in the step (2) is one or more selected from methanol, ethanol, propanol and butanol.
5. The method according to claim 4, wherein the drying in step (3) is vacuum drying at 50-80 deg.C for 24-48 h.
6. Hyperbranched sulfhydryl sponge, characterized in that it is obtained by the process according to any one of claims 1 to 5.
7. Use of the hyperbranched sulfydryl sponge of claim 6 for removing mercury from water.
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