CN108722365B - Heavy metal ion adsorption material and preparation method thereof - Google Patents
Heavy metal ion adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heavy metal ion adsorption material which is prepared from the following components in parts by weight: 50-60 parts of cyclodextrin-based cucurbituril triazine copolymer, 20-30 parts of hyperbranched polyethyleneimine and 5-10 parts of graphene oxide. The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at the temperature of 230-250 ℃ to obtain the heavy metal ion adsorbing material. The heavy metal ion adsorption material disclosed by the invention has the advantages of low cost, good heavy metal ion adsorption effect, large adsorption capacity and easiness in desorption.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a material suitable for efficiently adsorbing heavy metal ions in wastewater and a preparation method thereof.
Background
With the development of economy and the promotion of global industrialization process, the production activities in the industries such as mining and metallurgy, mechanical manufacturing, chemical engineering, electronics, instruments and the like are increased year by year, the environmental problem is increasingly prominent, a large amount of wastewater rich in heavy metal ions comes, the heavy metal ions cannot be automatically degraded in water and can be enriched in organisms through food chains, the threat to the living environment, the ecology and the health of human beings is great, the development of economy and the progress of society are restricted, and the method becomes a great barrier for hindering the development of society. Therefore, the search for effective measures to remove and enrich the heavy metal ions in the recovered wastewater becomes one of the problems facing and urgently waiting to be solved in the current global environmental protection field.
At present, the treatment method of the heavy metal ion polluted water body mainly comprises the following steps: chemical precipitation, electrochemical methods, exchange resin methods, adsorption methods, membrane separation methods, photocatalytic methods, and supercritical fluid extraction methods. Chemical precipitation methods are mostly adopted in industry, but the chemical precipitation methods easily cause secondary pollution, are not thorough in treatment of low-concentration heavy metal ions, and are difficult to be applied to treatment of flowing water bodies; the electrochemical method has large power consumption and is not suitable for large-scale treatment; the ion exchange resin method can transfer heavy metal ions to the resin, but the resin and the heavy metal ions are difficult to separate, and the cyclic utilization of the resin and the heavy metal ions cannot be realized; although the membrane separation method has high treatment efficiency, the treatment cost of the membrane material is high; the photocatalysis method is an environment-friendly treatment method, but has higher cost and lower efficiency; although the supercritical fluid extraction method has simple flow, high extraction speed and low energy consumption, the cost is too high, and the large-scale sewage treatment cannot be realized. The adsorption method is the most applied method, the simplest operation and the most ideal treatment effect at present. However, the adsorption materials on the market at present have the defects of lower adsorption capacity, poor reproducibility and high price.
Therefore, the novel adsorption material which is low in price, good in heavy metal ion adsorption effect, large in adsorption capacity and easy to desorb is developed, meets market demands, and has wide market value and application prospect.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a heavy metal ion adsorption material and a preparation method thereof, wherein the preparation method is simple and easy to implement, the raw materials are easy to obtain, the price is low, the dependence on equipment is not large, and the preparation method is suitable for industrial production; the heavy metal ion adsorption material prepared by the preparation method overcomes the defects of high price, poor adsorption effect, small adsorption capacity, difficult desorption, complex equipment, easy secondary pollution, high operation cost and difficult waste treatment of the heavy metal ion adsorption material in the prior art, and has the advantages of low cost, good heavy metal ion adsorption effect, large adsorption capacity and easy desorption.
In order to achieve the aim, the invention adopts the technical scheme that the heavy metal ion adsorption material is prepared from the following components in parts by weight: 50-60 parts of cyclodextrin-based cucurbituril triazine copolymer, 20-30 parts of hyperbranched polyethyleneimine and 5-10 parts of graphene oxide.
Preferably, the preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: dissolving allyl cucurbituril, allyl-beta-cyclodextrin, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, an initiator and an emulsifier in a high-boiling point solvent, stirring and reacting for 3-4 hours at 65-75 ℃ in the atmosphere of nitrogen or inert gas, then precipitating in water, filtering, and then placing in a vacuum drying oven at 100-110 ℃ for drying for 12-15 hours to obtain the cyclodextrin cucurbituril triazine copolymer.
Preferably, the mass ratio of the allyl cucurbituril to the allyl-beta-cyclodextrin to the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the initiator to the emulsifier to the high-boiling-point solvent is 1:1 (3-4): 0.03-0.05): 0.04-0.06): 12-15.
Preferably, the allyl cucurbituril is prepared in advance, and the preparation method refers to the following steps: ACS Nano 2012,6(4),2960-8DOI 10.1021/nn204123 p; the allyl- β -cyclodextrin was purchased from Zhiyuan Biotech, Inc., Shandong, Binzhou.
Preferably, the emulsifier is one or more selected from sodium dodecyl benzene sulfonate, polyoxypropylene polyethylene glycerol ether and nonylphenol polyoxyethylene ether.
Preferably, the initiator is selected from one or more of tert-butyl hydroperoxide, dicumyl peroxide, tert-butyl peroxypivalate, cyclohexanone peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the inert gas is selected from one or more of helium, neon and argon.
Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at the temperature of 230-250 ℃ to obtain the heavy metal ion adsorbing material.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the heavy metal ion adsorption material provided by the invention has the advantages of simple and feasible preparation method, easily available raw materials, low price and low dependence on equipment, and is suitable for industrial production.
2) The heavy metal ion adsorption material provided by the invention overcomes the defects of high price, poor adsorption effect, small adsorption capacity, difficult desorption, complex equipment, easy secondary pollution, high operation cost and difficult waste treatment of the heavy metal ion adsorption material in the prior art, and has the advantages of low cost, good heavy metal ion adsorption effect, large adsorption capacity and easy desorption.
3) The heavy metal ion adsorption material provided by the invention combines excellent adsorption properties of cyclodextrin, graphene oxide and cucurbituril, and the graphene oxide has more active groups on the surface, is good in compatibility with macromolecular materials and is linked by chemical bonds, so that the heavy metal ion adsorption material is beneficial to fixing of various materials and can better exert the adsorption effect on heavy metal ions; the hyperbranched polyethyleneimine structure is introduced, the adsorption capacity of the material on heavy metal ions can be improved by more amino structures, and the branched structure exposes active amino groups and other groups, so that the heavy metal ions can be better adsorbed; the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione structure is introduced, on one hand, the conjugated structure is favorable for carrying out photocatalytic treatment on organic matters in sewage, and on the other hand, the epoxy group in the structure and the amino group in the hyperbranched polyethyleneimine and the active agent on the surface of graphene oxide are subjected to chemical connection reaction, so that the material forms a three-dimensional network structure, the structure is more compact, and the mechanical property and the weather resistance are more excellent.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The allyl cucurbituril used in the following examples of the present invention was prepared in advance, and the preparation method was referred to: ACS Nano 2012,6(4),2960-8DOI 10.1021/nn204123 p; the allyl- β -cyclodextrin was obtained from Zhiyuan Biotech GmbH, Shandong Bingzhou, and other materials were obtained from Shanghai spring Xin import and export commerce GmbH.
Example 1
The heavy metal ion adsorption material is prepared from the following components in parts by weight: 50 parts of cyclodextrin-based cucurbituril triazine copolymer, 20 parts of hyperbranched polyethyleneimine and 5 parts of graphene oxide.
The preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: dissolving 10g of allyl cucurbituril, 10g of allyl-beta-cyclodextrin, 30g of 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 0.3g of tert-butyl hydroperoxide and 0.4g of sodium dodecyl benzene sulfonate in 120g of dimethyl sulfoxide, stirring and reacting for 3 hours at 65 ℃ under the atmosphere of nitrogen, precipitating in water, filtering, and drying for 12 hours at 100 ℃ in a vacuum drying oven to obtain the cyclodextrin cucurbituril triazine copolymer.
The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at 230 ℃ to obtain the heavy metal ion adsorbing material.
Example 2
The heavy metal ion adsorption material is prepared from the following components in parts by weight: 53 parts of cyclodextrin-based cucurbituril triazine copolymer, 23 parts of hyperbranched polyethyleneimine and 6 parts of graphene oxide.
The preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: 10g of allyl cucurbituril, 10g of allyl-beta-cyclodextrin, 33g of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 0.35g of dicumyl peroxide and 0.45g of polyoxypropylene polyethylene glycerol ether are dissolved in 130g of N, N-dimethylformamide, stirred and reacted at 69 ℃ for 3.4 hours under the atmosphere of helium, then precipitated in water, filtered and placed in a vacuum drying oven for 13 hours at 103 ℃ to obtain the cyclodextrin cucurbituril triazine copolymer.
The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at 235 ℃ to obtain the heavy metal ion adsorbing material.
Example 3
The heavy metal ion adsorption material is prepared from the following components in parts by weight: 55 parts of cyclodextrin-based cucurbituril triazine copolymer, 26 parts of hyperbranched polyethyleneimine and 7 parts of graphene oxide.
The preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: dissolving 10g of allyl cucurbituril, 10g of allyl-beta-cyclodextrin, 36g of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 0.4g of azodiisobutyronitrile and 0.5g of nonylphenol polyoxyethylene ether in 135g of N-methylpyrrolidone, stirring and reacting at 70 ℃ in a neon atmosphere for 3.6 hours, then precipitating in water, filtering, and drying at 105 ℃ in a vacuum drying oven for 13.5 hours to obtain the cyclodextrin cucurbituril triazine copolymer.
The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at the temperature of 242 ℃ to obtain the heavy metal ion adsorbing material.
Example 4
The heavy metal ion adsorption material is prepared from the following components in parts by weight: 58 parts of cyclodextrin-based cucurbituril triazine copolymer, 28 parts of hyperbranched polyethyleneimine and 9 parts of graphene oxide.
The preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: dissolving 10g of allyl cucurbituril, 10g of allyl-beta-cyclodextrin, 38g of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 0.45g of initiator and 0.55g of emulsifier in 145g of high-boiling-point solvent, stirring and reacting for 3.8 hours at 73 ℃ under argon atmosphere, precipitating in water, filtering, and drying for 14.5 hours at 108 ℃ in a vacuum drying oven to obtain the cyclodextrin cucurbituril triazine copolymer; the emulsifier is a mixture formed by mixing sodium dodecyl benzene sulfonate, polyoxypropylene polyethylene glycerol ether and nonylphenol polyoxyethylene ether according to a mass ratio of 2:3: 4; the initiator is a mixture formed by mixing tert-butyl peroxypivalate, cyclohexanone peroxide and azobisisobutyronitrile according to a mass ratio of 3:5: 4; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to the mass ratio of 2:3: 5.
The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded and molded at 245 ℃ to obtain the heavy metal ion adsorbing material.
Example 5
The heavy metal ion adsorption material is prepared from the following components in parts by weight: 60 parts of cyclodextrin-based cucurbituril triazine copolymer, 30 parts of hyperbranched polyethyleneimine and 10 parts of graphene oxide.
The preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: 10g of allyl cucurbituril, 10g of allyl-beta-cyclodextrin, 40g of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 0.5g of azodiisoheptanonitrile and 0.6g of polyoxypropylene polyvinyl glycerol ether are dissolved in 150g of N-methylpyrrolidone, stirred and reacted for 4 hours at 75 ℃ in a nitrogen atmosphere, then precipitated in water, filtered and placed in a vacuum drying oven for 15 hours at 110 ℃ to obtain the cyclodextrin cucurbituril triazine copolymer.
The preparation method of the heavy metal ion adsorption material comprises the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at the temperature of 250 ℃ to obtain the heavy metal ion adsorbing material.
Comparative example
The present example provides a heavy metal composite adsorption material, and the formula and the preparation method refer to Chinese invention patents: 200810150856.1 example 1.
The heavy metal ion adsorption material prepared by the embodiment and the comparative example of the invention adopts the following method to determine the adsorption capacity of the heavy metal ions: placing a certain mass of adsorption material in a conical flask with a plug, respectively adding a certain volume of heavy metal ion solution, vibrating in a constant-temperature oscillator at a constant temperature of 25 ℃ for a certain time, and calculating adsorption capacity according to the change of the concentration of heavy metal ions in the feed liquid; the concentration of heavy metal ions is measured by using a UV2450 type ultraviolet-visible spectrophotometer and calculated according to the adsorption capacity formula (1):
qeq-adsorption capacity of heavy metal ions, mg/g; cO-initial concentration of feed solution, mg/mL;
Ct-concentration of feed liquid at time t, mg/mL; vfVolume of feed liquid, mL; w-weight of adsorbent, g.
The desorption rate was determined as follows: washing the adsorption material after adsorption balance with distilled water until no metal ions exist in the filtrate, then mixing with a certain volume of 2% sulfuric acid solution, oscillating for a certain time at constant temperature in a constant temperature oscillator, measuring the concentration of heavy metal ions in the solution, and calculating the desorption rate according to the formula (2):
wherein eta is the desorption rate, and C is the concentration of metal ions in the eluate (mg. L)-1) V is the volume of the eluent (L), Q is the adsorption capacity of the membrane adsorbent before elution (mg. g)-1) And m is the mass (g) of the adsorbent.
This example selects Pb2+、Cu2+、Cd3+The adsorption capacity and desorption rate were determined and the test results are shown in table 1.
As can be seen from table 1, compared with graphene oxide alone and the heavy metal ion adsorption material in the prior art, the heavy metal ion adsorption material disclosed in the embodiment of the present invention has greatly improved adsorption amount and desorption rate for heavy metal ions.
TABLE 1
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The heavy metal ion adsorption material is characterized by being prepared from the following components in parts by weight: 50-60 parts of cyclodextrin-based cucurbituril triazine copolymer, 20-30 parts of hyperbranched polyethyleneimine and 5-10 parts of graphene oxide.
2. The heavy metal ion adsorption material of claim 1, wherein the preparation method of the cyclodextrin-based cucurbituril triazine copolymer comprises the following steps: dissolving allyl cucurbituril, allyl-beta-cyclodextrin, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, an initiator and an emulsifier in a high-boiling point solvent, stirring and reacting for 3-4 hours at 65-75 ℃ in the atmosphere of nitrogen or inert gas, then precipitating in water, filtering, and then placing in a vacuum drying oven at 100-110 ℃ for drying for 12-15 hours to obtain the cyclodextrin cucurbituril triazine copolymer.
3. The heavy metal ion adsorption material of claim 2, wherein the mass ratio of the allyl cucurbituril, the allyl-beta-cyclodextrin, the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, the initiator, the emulsifier and the high boiling point solvent is 1:1 (3-4) (0.03-0.05) (0.04-0.06) (12-15).
4. The heavy metal ion adsorption material of claim 2, wherein the emulsifier is one or more selected from sodium dodecyl benzene sulfonate, polyoxypropylene polyethylene glycerol ether and nonylphenol polyoxyethylene ether.
5. The heavy metal ion adsorbing material according to claim 2, wherein the initiator is selected from one or more of tert-butyl hydroperoxide, dicumyl peroxide, tert-butyl peroxypivalate, cyclohexanone peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
6. The heavy metal ion adsorbing material according to claim 2, wherein the inert gas is selected from one or more of helium, neon and argon.
7. The heavy metal ion adsorption material of claim 2, wherein the high boiling point solvent is one or more selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
8. A method for preparing the heavy metal ion adsorbing material according to any one of claims 1 to 7, comprising the following steps: all the raw materials are added into a screw extruder according to the weight ratio, and are mixed and extruded to be molded at the temperature of 230-250 ℃ to obtain the heavy metal ion adsorbing material.
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| CN110746608B (en) * | 2019-10-20 | 2021-11-05 | 陕西理工大学 | Nitrogen-containing cyclodextrin polymer porous material and preparation method and application thereof |
| CN111229181B (en) * | 2020-03-18 | 2020-10-30 | 王晓景 | Material for adsorbing heavy metal Pb2+ ions |
| CN112915985A (en) * | 2021-02-03 | 2021-06-08 | 江苏新视界先进功能纤维创新中心有限公司 | Easy-to-remove regenerated open-chain cucurbituril-based material for treating phenolic wastewater and preparation method thereof |
| CN112915984A (en) * | 2021-02-03 | 2021-06-08 | 江苏新视界先进功能纤维创新中心有限公司 | Easily-desorbed regenerated open-chain cucurbituril-based material for treating heavy metal water pollution and preparation method thereof |
| CN116750779B (en) * | 2023-08-18 | 2023-12-15 | 深圳新宙邦科技股份有限公司 | Preparation method of hexafluorophosphate, electrolyte and secondary battery |
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| CN105647119A (en) * | 2016-01-13 | 2016-06-08 | 辽宁工程技术大学 | Preparation method of three-dimensional porous-graphene-reinforced epoxy resin composite material |
| CN107892733A (en) * | 2017-12-12 | 2018-04-10 | 成都育芽科技有限公司 | A kind of heavy metal wastewater thereby nonionic adsorption resin and preparation method thereof |
| CN107913677A (en) * | 2017-12-12 | 2018-04-17 | 成都育芽科技有限公司 | A kind of nanometer heavy metal wastewater thereby ionic adsorption microballoon and preparation method thereof |
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| CN112480316A (en) | 2021-03-12 |
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