CN108160054B - Preparation method of nylon membrane for adsorbing heavy metals - Google Patents
Preparation method of nylon membrane for adsorbing heavy metals Download PDFInfo
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- CN108160054B CN108160054B CN201711456259.7A CN201711456259A CN108160054B CN 108160054 B CN108160054 B CN 108160054B CN 201711456259 A CN201711456259 A CN 201711456259A CN 108160054 B CN108160054 B CN 108160054B
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a preparation method of a modified nylon membrane for adsorbing heavy metals, which comprises the steps of acidifying the nylon membrane, activating the nylon membrane with an activating agent, reacting the nylon membrane with a diethylenetriamine solution, washing the nylon membrane to be neutral after the reaction is finished, and drying the nylon membrane to obtain the modified nylon membrane. The method increases the active sites on the surface of the membrane by hydrolysis and activation, and improves the heavy metal adsorption capacity of the membrane. The modified nylon membrane for adsorbing heavy metals, which is prepared by the method, comprises Cu2+、Cd2+And Pb2+To Cu2+、Cd2+And Pb2+The adsorption amount of (a) is remarkably higher than that of the unmodified original membrane. In Cu2+、Cd2+And Pb2+For Cu in mixed binary mixed solution adsorption experiment2+And Pb2+Has high adsorption capacity and selective adsorption, and good reusability and regeneration performance.
Description
Technical Field
The invention belongs to the field of nylon membranes, and particularly relates to a preparation method of a nylon membrane for adsorbing heavy metals.
Background
In recent years, with the acceleration of the industrialization process, a large amount of industrial wastewater and urban domestic sewage containing heavy metals are discharged into the environment, which brings serious harm to the atmosphere, soil and water environment, especially human health, and lead, cadmium, chromium, mercury and arsenic are mainly harmful to human bodies. At present, a plurality of methods for treating heavy metal ions are available, such as a chemical precipitation method, an ion exchange method and the like, but the application is limited because a large amount of sludge is generated and secondary pollution is caused, and a membrane adsorption method has the advantages of simplicity and convenience in operation, low cost and the like. Therefore, the membrane is an important means with great potential for adsorbing and purifying heavy metal ions in industrial wastewater.
Materials which can be used as membrane matrix are cellulose, polysaccharide media, polyamides and derivatives thereof, chemically modified polysulfones, ethylene copolymers, polyalkylhydroxymethylacrylates, trimethylolamides, and porous nylon membranes, glass, ceramics, etc., which have a molecular structure with more or less reactive groups capable of chemically reacting with the spacer and the ligand, such as hydroxyl, amino, thiol, carboxyl, etc. Wherein, nylon (PA) has good film forming property and better mechanical and chemical stability; nylon 66 is a fiber formed by polycondensation of adipic acid and hexamethylene diamine, the molecular main chain contains repeated amide groups, and the prepared membrane can resist acid, alkali and various organic solvents, and is widely applied to laboratories and industry.
In recent years, Immobilized Metal Affinity Chromatography (IMAC) using a compound chelating a metal ion as a ligand has been developed. Ginger and sea Rong, etc. uses nylon membrane as base membrane, and makes covalent bond coupling with hydroxyethyl cellulose and chitosan to prepare nylon-hydroxyethyl fibre composite membrane and nylon-chitosan composite membrane, then makes them covalently couple with chelating ligand iminodiacetic acid (IDA), and makes the immobilized metal chelating ligand be used for separating and purifying protein. It is studied to introduce a side chain containing cyano group into the main chain of nylon 66 by acrylonitrile grafting reaction, and the cyano group is converted into an amidoxime group by hydroxylamine reaction to form a chelate with copper ions. Nielihua and the like hydrolyze a nylon membrane with dilute hydrochloric acid, modify chitosan, take papain as a ligand of an affinity membrane, activate glutaraldehyde, and bond the ligand on the nylon membrane by a covalent bonding method, so as to obtain the nylon affinity membrane with specific adsorption property. Ganzhou and the like take a flat nylon membrane as a substrate, and the nylon membrane is modified by ethyl cellulose (HEC) and then bonded with L-phenylalanine and L-tryptophan (Trp) genin, so that high-purity gamma-globulin is purified from human plasma.
The successfully modified nylon membrane has a plurality of active functional groups, which is not only beneficial to the application of affinity chromatography, but also beneficial to chelating different heavy metal ions so as to remove the heavy metal ions in the solution, but a chelating membrane material with good heavy metal adsorption performance and taking the nylon membrane as a base membrane is not reported.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a modified nylon membrane for adsorbing heavy metals, comprising the following steps:
and (2) placing the nylon membrane in an HCl solution, heating and refluxing, washing to be neutral after the reaction is finished, activating with an activating agent, reacting the activated nylon membrane with a diethylenetriamine solution, washing to be neutral after the reaction is finished, and drying to obtain the modified nylon membrane.
Preferably, in the preparation method of the modified nylon membrane for adsorbing heavy metals, the HCl solution is 1mol/L HCl solution, and the ratio of the HCl solution to the nylon membrane is 0.004-0.006 g/mL.
Preferably, in the preparation method of the modified nylon membrane for adsorbing heavy metals, the activating agent comprises glutaraldehyde.
Preferably, in the preparation method of the modified nylon membrane for adsorbing heavy metals, the activating agent is 2.5% of glutaraldehyde, and the mass-to-volume ratio of the nylon membrane to the 2.5% of glutaraldehyde is 0.011-0.013 g/mL.
Preferably, in the method for preparing a modified nylon membrane capable of adsorbing heavy metals according to the present invention, the crosslinking agent includes diethylenetriamine.
Preferably, in the preparation method of the modified nylon membrane for adsorbing heavy metals, the method comprises the following steps:
adding a nylon 66 membrane into a 1mol/LHCl solution, heating in a water bath, condensing and refluxing, reacting for 24 hours, cooling, washing with deionized water to be neutral, drying at 60 ℃, and sealing and storing for later use;
adding the acidified nylon membrane into 2.5% glutaraldehyde solution (v/v), carrying out water bath at 40 ℃ for 50min, drying after the reaction is finished, and sealing and storing for later use;
adding the activated nylon membrane into a Diethylenetriamine (DETA) solution, carrying out oscillation reaction for 5h at 40 ℃, washing the activated nylon membrane to be neutral by using deionized water after the reaction is finished, and drying the activated nylon membrane at 60 ℃ to obtain the modified nylon 66 membrane.
Preferably, in the preparation method of the modified nylon membrane for adsorbing heavy metals, the method increases the active sites on the surface of the membrane by hydrolysis and activation, so as to improve the heavy metal adsorption capacity of the membrane.
Another aspect of the present invention is to provide a modified nylon membrane for adsorbing heavy metals including Cu obtained by the above method2+、Cd2+And Pb2+One or more of (a).
Preferably, in the modified nylon membrane for adsorbing heavy metals, the main raw materials of the modified nylon membrane comprise a nylon 66 membrane, hydrochloric acid and glutaraldehyde are used as hydrolysis and activating agents, and the cross-linking agent is diethylenetriamine.
Compared with the prior art, the invention takes the nylon 66 membrane as the raw material, takes hydrochloric acid and glutaraldehyde solution as hydrolysis and activating agent, takes diethylenetriamine as cross-linking agent, obtains the membrane material for absorbing heavy metal by synthesis, and treats Cu2+、Cd2+And Pb2 +The adsorption amount of (a) is remarkably higher than that of the unmodified original membrane. In Cu2+、Cd2+And Pb2+For Cu in mixed binary mixed solution adsorption experiment2+And Pb2+Has high adsorption capacity and selective adsorption, and good reusability and regeneration performance.
Drawings
FIG. 1 adsorption of Cu by activated and unactivated nylon membranes2+、Cd2+、Pb2+Comparing the images;
FIG. 2 shows Cu adsorption of modified nylon membrane2+、Cd2+、Pb2+Adsorption kinetics graph of (a);
FIG. 3 shows Cu adsorption of modified nylon membrane2+、Cd2+、Pb2+Adsorption isotherm diagram of (1).
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1 preparation of modified Nylon Membrane
a. 1.9000g of nylon membrane (nylon 66, purchased from Tianjin Koilong laboratory instruments Co., Ltd.) was accurately weighed into a 500mL round-bottom flask, 350mL of 1mol/L HCl solution was added, the flask was placed in a constant temperature water bath at 55 ℃, heated and condensed under reflux, reacted for 24 hours, cooled, washed to neutral with deionized water, dried at 60 ℃, sealed and stored for later use.
b. Putting a proper amount of nylon membrane treated by hydrochloric acid into a 150mL triangular conical flask with a plug, adding 150mL (v/v) of 2.5% glutaraldehyde solution, oscillating and reacting in water bath at 40 ℃ for 50min, sucking off the redundant solution by using filter paper after the reaction is finished, and drying at 60 ℃ for later use.
c. And (3) placing the activated nylon membrane into a 150mL conical flask with a plug, adding 20mL of Diethylenetriamine (DETA) solution, carrying out oscillation reaction for 5h at 40 ℃ in a water bath, washing the reaction product to be neutral by using deionized water after the reaction is finished, drying the reaction product at 60 ℃, and keeping the reaction product dry and in a dark place for later use.
The modified nylon membrane obtained by the experimental steps is applied to heavy metal ion Cu2+、Cd2+And Pb2+And (4) performing an adsorption experiment, and calculating the adsorption amount. As shown in FIG. 1, which is a graph of adsorption of the modified nylon membrane against a control nylon membrane (nylon membrane purchased directly, untreated), the modified nylon membrane was seen to be Cu-resistant2+、Cd2+And Pb2+The adsorption of (a) is much higher than the adsorption capacity of a comparative untreated nylon membrane.
Example 2 static saturation adsorption capacity of modified Nylon Membrane for heavy Metal ions
Accurately weighing 120.0mg of the modified nylon membrane prepared in example 1, placing the modified nylon membrane in a 150mL conical flask with a plug, adding 10mL of HAc-NaAc buffer solution (pH 2-6) with a certain pH range, soaking for 12h, then adding 15mL of metal ion solution with a certain concentration (0.5-2.5 mmol/L), carrying out constant-temperature oscillation reaction at a certain temperature (25-45 ℃), enabling the adsorption to reach adsorption balance within a certain time (0-180 min), transferring the adsorbed water sample, treating the water sample, and adding 4-sulfophenyl porphyrin (TPPS4, C)44H34N4O20S6) And after the derivatization, the concentration of the heavy metal ions in the derivatized sample is measured by adopting HPLC, and the corresponding static saturated adsorption capacity of the modified nylon membrane to the heavy metal ions is calculated.
The experimental result shows that the modified nylon membrane adsorbs Cu2+The optimum pH value of the solution is 4.6, Pb2+And Cd2+The optimal pH value of the solution is 5.8 (as shown in figure 2), and the adsorption equilibrium is reached when the adsorption time is 90 min, 120min and 120min respectively (as shown in figure 3); the adsorption amount increases with the increase of temperature and concentration, and reaches the highest at 45 deg.C and 2.5mmol/L concentration, and for Cu2+、Cd2+And Pb2+The maximum adsorption amounts of (A) are 35.7830mg/g, 13.2156mg/g and 16.2862mg/g, respectively.
Example 3 adsorption selectivity experiment
Weighing 120mg of the modified nylon membrane prepared in the example 1, placing the modified nylon membrane in a binary mixed heavy metal ion solution, wherein the concentration of each heavy metal ion in the binary mixed heavy metal ion solution is 2.5mmol/L, oscillating and adsorbing at a constant temperature of 25 ℃, and measuring the concentration of each heavy metal ion in the binary mixed solution after adsorption balance to obtain the adsorption capacity.
The experimental result shows that the adsorption capacity of the copper-based copper alloy on three binary mixed heavy metal solutions is compared with that of the copper-based copper-2+And Pb2+In binary mixed solution, modified nylon membrane is used for Cu2+And Pb2+The adsorption amounts of (A) are 18.7264mmol/100g and 4.1559mmol/100g respectively; in Cu2+And Cd2+In binary mixed solution, modified nylon membrane is used for Cu2+And Cd2+The adsorption amounts of (A) are 22.5611mmol/100g and 2.5736mmol/100g respectively; at Pb2+And Cd2+In binary mixed solution, modified nylon membrane is used for Pb2+And Cd2+The adsorption capacity of the modified nylon membrane is 10.3160mmol/100g and 3.5393mmol/100g respectively, and the modified nylon membrane can be used for selectively separating Cu2+And Cd2+Binary mixed solution and Pb2+And Cd2+Binary mixed solution of Cu2+And Pb2+The adsorption capacity of the catalyst is more than that of Cd2+The amount of adsorption of (3). (see Table 1)
TABLE 1 adsorption capacity of modified Nylon Membrane to binary Mixed solution
Example 4: regeneration test
The adsorbed Cu prepared in example 32+Washing 120mg of saturated modified nylon membrane with HAc-NaAc buffer solution for several times, drying for later use, adding an eluent disodium ethylene diamine tetraacetate with a certain volume of 1mol/L, oscillating at constant temperature of 25 ℃, washing the modified nylon membrane with disodium ethylene diamine tetraacetate solution until the heavy metal Cu is reached2+Completely eluting ions, washing with deionized water for several times, oven drying at 60 deg.C, and adsorbing Cu at optimum temperature, pH and concentration2+The experiment of (3) is repeated five times, and then sampling detection is carried out respectively.
The experimental result shows that after five times of regeneration, the adsorption capacity of each time is 35.7731mg/g, 34.6985mg/g, 34.3624mg/g, 34.2325mg/g and 34.1128mg/g respectively, and the modified nylon membrane has good reusability and reproducibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a modified nylon membrane for adsorbing heavy metals comprises the following steps:
adding a nylon 66 membrane into a 1mol/LHCl solution, heating in a water bath, condensing and refluxing, reacting for 24 hours, cooling, washing with deionized water to be neutral, drying at 60 ℃, and sealing and storing for later use;
adding an acidified nylon 66 membrane into a glutaraldehyde solution with the volume ratio of 2.5%, performing water bath at 40 ℃ for 50min, drying after the reaction is finished, and sealing and storing for later use;
adding the activated nylon 66 film into a diethylenetriamine solution, carrying out oscillation reaction for 5h at 40 ℃, washing the activated nylon 66 film to be neutral by deionized water after the reaction is finished, and drying the activated nylon 66 film at 60 ℃ to obtain a modified nylon 66 film;
the mass-volume ratio of the nylon 66 membrane to 2.5% glutaraldehyde is 0.011-0.013 g/mL;
the ratio of the HCl solution to the nylon 66 membrane is 0.004-0.006 g/mL.
2. The method for preparing a modified nylon membrane capable of adsorbing heavy metals according to claim 1, wherein the method is to increase the active sites on the surface of the membrane by hydrolysis and activation so as to improve the heavy metal adsorption capacity of the membrane.
3. The modified nylon membrane for adsorbing heavy metal prepared by the preparation method according to any one of claims 1-2, wherein the heavy metal comprises Cu2+、Cd2+And Pb2+One or more of (a); the main raw materials of the modified nylon membrane comprise a nylon 66 membrane, hydrochloric acid and glutaraldehyde are used as hydrolysis and activating agents, and a cross-linking agent is diethylenetriamine.
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