WO2018121165A1 - 选择性吸附金离子的中空纤维膜及其制备方法与应用 - Google Patents

选择性吸附金离子的中空纤维膜及其制备方法与应用 Download PDF

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WO2018121165A1
WO2018121165A1 PCT/CN2017/113524 CN2017113524W WO2018121165A1 WO 2018121165 A1 WO2018121165 A1 WO 2018121165A1 CN 2017113524 W CN2017113524 W CN 2017113524W WO 2018121165 A1 WO2018121165 A1 WO 2018121165A1
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hollow fiber
fiber membrane
film
gold ions
selectively adsorbing
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PCT/CN2017/113524
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English (en)
French (fr)
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刘长坤
刘吉安
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深圳大学
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Publication of WO2018121165A1 publication Critical patent/WO2018121165A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/28—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
    • 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
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the invention relates to the field of precious metal recovery, in particular to a hollow fiber membrane for selectively adsorbing gold ions, a preparation method and application thereof.
  • gold is unique in nature and has a wide range of applications. It is mainly concentrated in many technical fields such as electronic technology, communication technology, and medical technology. At a certain concentration, the state of the compound may cause great harm to the organism and the environment. At the same time, the content of gold in the earth's crust is very low. Based on this status quo, the treatment and recycling of gold in heavy metal wastewater is more practical. In the gold-containing waste liquid produced in the industry, the content of gold is generally low. Therefore, their recovery is technically difficult and costly, so they are often directly discharged in the early stage. At present, not only because of the high price of gold and the scarcity of resources, it is necessary to recover gold in wastewater, and in order to meet environmental protection requirements, it is necessary to carry out harmless treatment of heavy metal wastewater.
  • methods for recycling gold-containing wastewater in industrial production include a precipitation method, an ion exchange method, a solvent extraction method, and an electrodeposition method.
  • these methods generally have the disadvantages of high energy consumption, high processing cost, secondary pollution, and low processing efficiency.
  • heavy metal wastewater in industrial production is often not a single component, but a variety of heavy metals coexist.
  • traditional gold-containing wastewater treatment methods are not selective, this makes gold difficult to recycle.
  • gold-containing electroplating wastewater often contains other heavy metal ions, such as copper and zinc.
  • Traditional treatment methods cannot selectively capture gold ions, but need to be separated by multiple experiments.
  • the object of the present invention is to provide a hollow fiber membrane for selectively adsorbing gold ions and a preparation method and application thereof, thereby solving the problem that the traditional gold-containing wastewater treatment method cannot selectively capture gold ions. .
  • a method for preparing a hollow fiber membrane for selectively adsorbing gold ions comprising the steps of:
  • A, 0.1-0.5g polypropylene hollow fiber membrane is placed in a plasma cleaning machine, and washed in an air atmosphere for 5-10min to obtain an activated PP film;
  • the activated PP film obtained in the step A is placed in a test tube, and after adding dichloromethane, ⁇ -bromoisobutyryl bromide and pyridine are added in an ice water bath, and then the test tube is sealed and transferred to a magnetic stirrer at room temperature. The reaction was stirred for 5 to 48 hours to obtain a brominated PP film with impurities, and then the brominated PP film with impurities was taken out, washed, and dried in an oven to obtain a clean brominated PP film;
  • step C Add the cleaned brominated PP film obtained in step B to the tube filled with argon, and then add cuprous bromide, copper bromide and 2,2-bipyridine, respectively, and then add deionized water, N, N- Dimethylformamide and glycidyl methacrylate, then argon gas was introduced into the solution in the test tube for 10-30 min, then the test tube was sealed and placed on a magnetic stirrer, and the reaction was stirred for 1-12 h in a constant temperature water bath to obtain an attached Impurity PP-PGMA film, after which the PP-PGMA film with impurities is taken out, washed and placed in an oven to be dried to obtain a clean PP-PGMA film;
  • step D Add the clean PP-PGMA film obtained in step C to the test tube, then add tetrahydrofuran and acyclic polyamine compound, seal the test tube and place it on a magnetic stirrer, and stir the reaction at room temperature for 10-48 hours to obtain the attached
  • the aminated PP film with impurities is then taken out, and the aminated PP film with impurities is taken out, washed, and dried in an oven to finally obtain a hollow fiber membrane selectively adsorbing gold ions.
  • step B 0.1-0.5 g of the activated PP membrane obtained in the step A is placed in a test tube, and 5-50 mL of dichloromethane is added thereto. 1-10 mL of ⁇ -bromoisobutyryl bromide and 0.5-5 mL of pyridine were added to the ice water bath.
  • the method for preparing a hollow fiber membrane for selectively adsorbing gold ions wherein in the step B, the test tube is sealed and transferred to a magnetic stirrer, and the stirring speed is 200-400 r/min when the reaction is stirred at normal temperature. .
  • the method for preparing a hollow fiber membrane for selectively adsorbing gold ions wherein in the step C, 0.1-0.5 g of the cleaned brominated PP film obtained in the step B is added to the tube filled with argon gas, and then separately added. 0.01-0.5g cuprous bromide, 0.1-1g copper bromide and 0.1-1g 2,2-bipyridine, then add 1-10mL deionized water, 1-10mL N,N-dimethylformamide and 1- 10 mL of glycidyl methacrylate.
  • the method for preparing a hollow fiber membrane for selectively adsorbing gold ions wherein in the step C, the test tube is sealed and placed on a magnetic stirrer, and the temperature is 30-60 ° C while stirring in a constant temperature water bath, stirring The speed is 100-200r/min.
  • step D 0.1-0.5 g of the clean PP-PGMA membrane obtained in the step C is added to the test tube, and then 2-15 mL of tetrahydrofuran is added. 2-15 mL of diethylenetriamine.
  • the method for preparing a hollow fiber membrane for selectively adsorbing gold ions wherein in the step D, the test tube is sealed and placed on a magnetic stirrer, and the stirring speed is 100-200 r/min when the reaction is stirred at normal temperature. .
  • the acyclic polyamine compound comprises ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene-5 Amine, polyethene polyamine.
  • a hollow fiber membrane selectively adsorbing gold ions wherein the hollow fiber membrane selectively adsorbing gold ions is prepared by the method for preparing a hollow fiber membrane for selectively adsorbing gold ions according to any of the above.
  • the present invention provides a hollow fiber membrane for selectively adsorbing gold ions, a preparation method and application thereof, and a method for preparing a hollow fiber membrane for selectively adsorbing gold ions, comprising: first performing a polypropylene hollow fiber membrane The surface is activated to obtain an activated PP film, and then the activated PP film is subjected to bromination reaction to obtain a brominated PP film, and then the brominated PP film is subjected to SI-ATRP reaction, followed by amination, thereby finally obtaining a hollow selective adsorption gold ion. Fiber membrane.
  • the hollow fiber membrane selectively adsorbing gold ions prepared by the preparation method of the invention has the properties of physically retaining particulate matter and selectively chemisorbing precious metal gold, and has high adsorption amount of gold ions in water body, and can selectively recover gold content. Gold ions in wastewater.
  • the present invention provides a hollow fiber membrane for selectively adsorbing gold ions, a preparation method and application thereof, and the present invention will be further described in detail below in order to clarify and clarify the objects, technical solutions and effects of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • Polypropylene (PP) hollow fiber membrane is a membrane material widely used in the field of water treatment. It has the advantages of impact resistance, good wear resistance, corrosion resistance, large unit membrane area and high separation efficiency.
  • the invention expands the application range of the polypropylene hollow fiber membrane by retaining the excellent performance of the polypropylene hollow fiber membrane while grafting the polymer polymer brush having the ability to selectively adsorb the noble metal.
  • the invention provides a method for preparing a hollow fiber membrane for selectively adsorbing gold ions, which comprises the steps of:
  • step S200 the activated PP film obtained in step S100 is placed in a test tube, and after adding dichloromethane, ⁇ -bromoisobutyryl bromide and pyridine are added in an ice water bath, and then the test tube is sealed and transferred to a magnetic stirrer at room temperature. Stir the reaction for 5-48 h to obtain a brominated PP film with impurities, and then the brominated PP film with impurities is taken out, washed, and dried in an oven to obtain a clean brominated PP film;
  • step S300 adding the cleaned brominated PP film obtained in step S200 to the argon-filled test tube, and then adding cuprous bromide, copper bromide and 2,2-bipyridine, respectively, and adding deionized water, N, N- Dimethylformamide and glycidyl methacrylate, then argon gas was introduced into the test tube for 10-30 min, then the test tube was sealed and placed on a magnetic stirrer, and the reaction was stirred for 1-12 h in a constant temperature water bath to obtain impurities.
  • PP-PGMA film after which the PP-PGMA film with impurities is taken out, washed and placed in an oven to be dried to obtain a clean PP-PGMA film;
  • step S400 adding the clean PP-PGMA film obtained in step S300 to the test tube, then adding tetrahydrofuran and acyclic polyamine compound, sealing the test tube and placing it on a magnetic stirrer, and stirring the reaction at normal temperature for 10-48 hours to obtain a
  • the aminated PP film with impurities is then taken out, and the aminated PP film with impurities is taken out, washed, and dried in an oven to finally obtain a hollow fiber membrane selectively adsorbing gold ions.
  • the step S100 is to perform an activation reaction.
  • the original polypropylene hollow fiber membrane is washed with a plasma cleaner to activate it, and a hydroxyl group is generated in the surface layer to obtain an activated polypropylene hollow fiber membrane, that is, an activated PP membrane.
  • the polypropylene hollow fiber membrane is cleaned by a plasma cleaning machine to activate the surface, enhance the hydrophilic property, and generate active groups such as hydroxyl groups, which is beneficial to the subsequent chemical modification of the polypropylene hollow fiber membrane.
  • step S200 the bromination reaction is carried out, and the hydroxyl group on the activated polypropylene hollow fiber membrane is replaced by a halogen element bromine (Br) to prepare a brominated polypropylene hollow fiber membrane, that is, a brominated PP membrane.
  • a halogen element bromine Br
  • the step S300 is a SI-ATRP reaction using a surface-initiated atom transfer radical polymerization (SI-ATRP) method: using N,N-dimethylformamide (DMF) as a solvent.
  • SI-ATRP surface-initiated atom transfer radical polymerization
  • DMF N,N-dimethylformamide
  • PGMA Polyglycidyl methacrylate
  • GMA glycidyl methacrylate
  • the step S400 is to perform an amination reaction, and the PP-PGMA film is chemically modified by an acyclic polyamine compound by a ring-opening reaction of an epoxy group with an amine group to prepare an aminated modified polypropylene hollow.
  • the fiber membrane that is, the aminated PP membrane (aminated PP membrane), and the aminated PP membrane is the final product: a hollow fiber membrane that selectively adsorbs gold ions.
  • the preparation method of the hollow fiber membrane for selectively adsorbing gold ions of the invention realizes the multifunctionalization of the polypropylene hollow fiber membrane, and retains the physical properties of the original retained particulate matter while imparting the chemical modification method thereof Gold ion Chemical adsorption properties.
  • the invention adopts the SI-ATRP method and the acyclic polyamine amination to chemically modify the polypropylene hollow fiber membrane, and the operation is simple and easy to control.
  • the activated PP film obtained in the step S100 is placed in a test tube, 5-50 mL of dichloromethane is added, and 1-10 mL of ⁇ -bromoisobutyryl bromide and 0.5-5 mL of pyridine are added in an ice water bath.
  • the test tube is sealed and transferred to a magnetic stirrer, and the stirring speed is 200-400 r/min (rev/min) when the reaction is stirred at normal temperature.
  • 0.1-0.5 g of the cleaned brominated PP film obtained in the step S200 is added to the argon-filled test tube, and then 0.01-0.5 g of cuprous bromide and 0.1-1 g of copper bromide are respectively added. And 0.1-1 g of 2,2-bipyridine, further adding 1-10 mL of deionized water, 1-10 mL of N,N-dimethylformamide and 1-10 mL of glycidyl methacrylate.
  • the test tube is sealed and placed on a magnetic stirrer, and the temperature is 30-60 ° C when the reaction is stirred in a constant temperature water bath, and the stirring speed is 100-200 r/min.
  • step S400 0.1-0.5 g of the clean PP-PGMA film obtained in the step S300 is added to the test tube, and then 2-15 mL of tetrahydrofuran and 2-15 mL of diethylenetriamine are added.
  • the test tube is sealed and placed on a magnetic stirrer, and the stirring speed is 100-200 r/min when the reaction is stirred at normal temperature.
  • the acyclic polyamine compound comprises ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethenepolyamine.
  • the polyethene polyamine is a co-product of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
  • the acyclic polyamine compound is preferably diethylenetriamine.
  • the method of washing the brominated PP film with impurities is: washing with acetone and deionized water in sequence, specifically, washing with acetone several times, and then washing the number with deionized water. Times.
  • the PP-PGMA film with impurities is washed by sequentially washing with tetrahydrofuran, 0.1 M HCl, 0.1 M NaOH and deionized water.
  • 0.1 M is 0.1 mol/L.
  • the method for washing the aminated PP film with impurities is: sequentially washing with acetone and deionized water, specifically, washing with acetone several times, and then washing the number with deionized water. Times.
  • the preparation method of the hollow fiber membrane for selectively adsorbing gold ions of the invention adopts a convenient and controllable surface initiation-atomic transfer radical polymerization method, and uses a polypropylene hollow fiber microfiltration membrane as a substrate to first graft a methyl group on the surface of the material.
  • the glycidyl acrylate polymer brush is further added by an acyclic polyamine compound and an epoxy group on polyglycidyl methacrylate.
  • an aminated modified polypropylene hollow fiber membrane is obtained, thereby finally obtaining a hollow fiber membrane selectively adsorbing gold ions.
  • the hollow fiber membrane selectively adsorbing gold ions prepared by the preparation method of the invention has the properties of physically retaining particulate matter and selectively chemisorbing precious metal gold, and has high adsorption amount of gold ions in water body, and can selectively recover gold content. Gold ions in wastewater.
  • the present invention also provides a hollow fiber membrane selectively adsorbing gold ions, wherein the hollow fiber membrane selectively adsorbing gold ions is prepared by using any of the above-mentioned hollow fiber membranes for selectively adsorbing gold ions.
  • the method is prepared.
  • the acyclic polyamine introduced on the surface of the polypropylene hollow fiber membrane has high adsorption amount to gold ions, and exhibits selective adsorption capacity to gold ions in the gold zinc ion system. Therefore, the hollow fiber membrane selectively adsorbing gold ions prepared by the invention has the properties of physically trapping particulate matter and selectively chemisorbing precious metal gold, and can selectively recover gold ions in the gold-containing wastewater.
  • the present invention also provides an application of a hollow fiber membrane for selectively adsorbing gold ions, that is, the above-mentioned hollow fiber membrane selectively adsorbing gold ions is used for selective adsorption.
  • Gold ions in gold wastewater are used for selective adsorption.
  • a 0.1 g polypropylene hollow fiber membrane was placed in a plasma cleaner and washed in an air atmosphere for 5 minutes to obtain an activated PP membrane.
  • the PP-PGMA film with impurities is taken out, and then tetrahydrofuran, 0.1 M HCl, 0.1 M NaOH and After the ionized water was washed, it was dried in an oven to obtain a clean PP-PGMA film.
  • the adsorption performance test of the hollow fiber membrane selectively adsorbing gold ions prepared in the present example was carried out as follows:
  • Adsorption experiment The aminated PP film prepared in this example was subjected to an adsorption experiment, and the adsorption amount was measured as follows: the aminated PP film was added as an adsorbent to an aqueous solution containing gold ions, and shaken at room temperature and protected from light to equilibrium after adsorption. Determine the concentration of gold ions in the solution. Calculate the amount of adsorption according to the following formula:
  • q (mmol g -1 ) is the equilibrium adsorption amount
  • C 0 and C e are the original solution concentration and adsorption equilibrium concentration (mmol/L) of gold ions
  • V is the volume of the adsorption solution (L);
  • m is adsorption The quality of the agent aminated PP film.
  • the adsorption amount of the aminated PP film to other metal ions (for example, zinc) in the aqueous solution containing gold ions is also calculated by referring to the above formula.
  • the aminated PP film adsorbent prepared in this embodiment is placed in an aqueous solution containing gold ions and zinc ions (chlorogold-zinc nitrate mixed solution) for adsorption test, and the adsorption conditions are:
  • the amount of adsorbent: 0.03g, the concentration of Au 3+ and Zn 2+ is 4mmol / L, pH 1.0, the temperature is 25 ° C, the rotation speed is 150r / min, after adsorption for 24h, the aminated PP membrane adsorbent is measured for Au
  • the adsorption amount of 3+ was 1.176 mmol/g, and the adsorption amount to Zn 2+ was 0.064 mmol/g.
  • the aminated PP film has a high amount of gold ions adsorbed in the water, and the aminated PP film adsorbs the gold ions much more than the zinc ions. Therefore, the aminated PP film prepared in this example It is possible to selectively adsorb gold ions in an aqueous solution containing gold zinc, thereby achieving separation of gold and zinc.
  • the PP-PGMA film with impurities is taken out, and then tetrahydrofuran, 0.1 M HCl, 0.1 M NaOH and After the ionized water was washed, it was dried in an oven to obtain a clean PP-PGMA film.
  • Example 1 the hollow fiber membrane selectively adsorbing gold ions prepared in the present example was subjected to adsorption performance test.
  • the aminated PP film adsorbent prepared in this embodiment is placed in an aqueous solution containing gold ions and zinc ions (chlorogold-zinc nitrate mixed solution) for adsorption test, and the adsorption conditions are:
  • the amount of adsorbent: 0.03g, the concentration of Au 3+ and Zn 2+ is 4mmol / L, pH 1.0, the temperature is 25 ° C, the rotation speed is 150r / min, after adsorption for 24h, the aminated PP membrane adsorbent is measured for Au
  • the adsorption amount of 3+ was 1.057 mmol/g, and the adsorption amount to Zn 2+ was 0.049 mmol/g.
  • the aminated PP film has a high amount of gold ions adsorbed in the water, and the aminated PP film adsorbs the gold ions much more than the zinc ions. Therefore, the aminated PP film prepared in this example It is possible to selectively adsorb gold ions in an aqueous solution containing gold zinc, thereby achieving separation of gold and zinc.
  • a 0.3 g polypropylene hollow fiber membrane was placed in a plasma cleaner and washed in an air atmosphere for 8 minutes to obtain an activated PP membrane.
  • the rotation speed is 150r/min, and the reaction is carried out in a constant temperature water bath at 50 °C for 8 hours to obtain a PP-PGMA film with impurities. Then, the PP-PGMA film with impurities is taken out, and tetrahydrofuran, 0.1 M HCl, 0.1 M NaOH and deionized are sequentially used. After the water was washed clean, it was dried in an oven to obtain a clean PP-PGMA film.
  • Example 1 the hollow fiber membrane selectively adsorbing gold ions prepared in the present example was subjected to adsorption performance test.
  • the gold ion ion adsorption experiment was carried out separately: the aminated PP film prepared in this example was used as an adsorbent in an aqueous solution containing only gold ions (without other metal impurities) for adsorption test, and the adsorption conditions were: adsorbent dosage: 0.03 g
  • the aminated PP film adsorbent prepared in this embodiment is placed in an aqueous solution containing gold ions and zinc ions (chlorogold-zinc nitrate mixed solution) for adsorption test, and the adsorption conditions are:
  • the amount of adsorbent: 0.03g, the concentration of Au 3+ and Zn 2+ is 4mmol / L, pH 1.0, the temperature is 25 ° C, the rotation speed is 150r / min, after adsorption for 24h, the aminated PP membrane adsorbent is measured for Au
  • the adsorption amount of 3+ was 1.245 mmol/g, and the adsorption amount to Zn 2+ was 0.071 mmol/g.
  • the aminated PP film has a high adsorption amount of gold ions in the water, and the adsorption amount of the aminated polyurethane film on the gold ions. It is much larger than the adsorption amount of zinc ions. Therefore, the aminated PP film prepared in this embodiment can selectively adsorb gold ions in an aqueous solution containing gold zinc, thereby achieving separation of gold and zinc.
  • a 0.5 g polypropylene hollow fiber membrane was placed in a plasma cleaner and washed in an air atmosphere for 10 minutes to obtain an activated PP membrane.
  • the PP-PGMA film with impurities was taken out, and tetrahydrofuran, 0.1 M HCl, 0.1 M NaOH and deionized water were sequentially used. After washing, it was dried in an oven to obtain a clean PP-PGMA film.
  • Example 1 the hollow fiber membrane selectively adsorbing gold ions prepared in the present example was subjected to adsorption performance test.
  • the aminated PP film adsorbent prepared in this embodiment is placed in an aqueous solution containing gold ions and zinc ions (chlorogold-zinc nitrate mixed solution) for adsorption test, and the adsorption conditions are:
  • the amount of adsorbent: 0.03g, the concentration of Au 3+ and Zn 2+ is 4mmol / L, pH 1.0, the temperature is 25 ° C, the rotation speed is 150r / min, after adsorption for 24h, the aminated PP membrane adsorbent is measured for Au
  • the adsorption amount of 3+ was 1.259 mmol/g, and the adsorption amount to Zn 2+ was 0.076 mmol/g.
  • the aminated PP film has a high amount of gold ions adsorbed in the water, and the aminated PP film adsorbs the gold ions much more than the zinc ions. Therefore, the aminated PP film prepared in this example It is possible to selectively adsorb gold ions in an aqueous solution containing gold zinc, thereby achieving separation of gold and zinc.
  • the present invention provides a hollow fiber membrane for selectively adsorbing gold ions, a preparation method and application thereof, and a method for preparing a hollow fiber membrane for selectively adsorbing gold ions, comprising: firstly, polypropylene hollow fiber The membrane is surface-activated to obtain an activated PP membrane, and then the activated PP membrane is subjected to bromination reaction to obtain a brominated PP membrane, and then the brominated PP membrane is subjected to SI-ATRP reaction, followed by amination to finally obtain selective adsorption of gold ions. Hollow fiber membrane.
  • the hollow fiber membrane selectively adsorbing gold ions prepared by the preparation method of the invention has the properties of physically retaining particulate matter and selectively chemisorbing precious metal gold, and has high adsorption amount of gold ions in water body, and can selectively recover gold content. Gold ions in wastewater.

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Abstract

一种选择性吸附金离子的中空纤维膜的制备方法，包括：先对聚丙烯中空纤维膜进行表面活化，得到活化PP膜，然后将活化PP膜进行溴化反应，得到溴化PP膜，再将溴化PP膜进行SI-ATRP反应，然后进行胺化，最终得到选择性吸附金离子的中空纤维膜。还包括一种选择性吸附金离子的中空纤维膜及其应用。

Description

选择性吸附金离子的中空纤维膜及其制备方法与应用 技术领域
本发明涉及贵金属回收领域，尤其涉及一种选择性吸附金离子的中空纤维膜及其制备方法与应用。
背景技术
金作为贵金属元素，性质特异，应用范围广，主要集中在电子技术、通讯技术、医疗技术等多个技术领域。金在一定的浓度下，其化合物状态有可能会对生物体和环境造成极大的危害。同时，金在地壳中的含量非常低。基于这种现状，对重金属废水中金的处理及回收利用更具有现实意义。在工业中所产生的含金废液中，金的含量一般较低。因此它们的回收在技术上比较困难，成本较高，所以在早期常被直接排放。当前，不仅是因为黄金价格昂贵和资源稀少，需要对废水中的金进行回收，而且为了满足环保要求，必须对重金属废水进行无害化处理。
目前工业生产中含金废水回收利用的方法有沉淀法、离子交换法、溶剂萃取法和电沉积法等。但这些方法普遍存在能耗高、处理费用高、二次污染、处理效率低等缺点。大多数情况下，工业生产中的重金属废水往往不是单一组分的，而是多种重金属共存的。由于传统的含金废水处理方法是不具备选择性的，这就使得金在回收再利用时造成困难。例如，含金电镀废水中往往还含有其他重金属离子，如铜，锌等，传统处理方法不能有选择性的捕捉金离子，而是需要通过多步实验分离。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种选择性吸附金离子的中空纤维膜及其制备方法与应用，从而解决传统的含金废水处理方法不能选择性的捕捉金离子的问题。
本发明的技术方案如下：
一种选择性吸附金离子的中空纤维膜的制备方法，包括步骤：
A、将0.1-0.5g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗5-10min，得到活化PP膜；
B、将步骤A得到的活化PP膜放入试管中，加入二氯甲烷后，在冰水浴中加入α-溴异丁酰溴和吡啶，然后将试管密封并转移至磁力搅拌器上，常温下搅拌反应5-48h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，洗涤干净后置于烘箱中干燥，得到洁净的溴化PP膜；
C、在充满氩气的试管中加入步骤B得到的洁净的溴化PP膜，然后分别加入溴化亚铜、溴化铜和2,2-联吡啶，再加入去离子水、N,N-二甲基甲酰胺和甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气10-30min，再将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应1-12h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，洗涤干净后置于烘箱中干燥，得到洁净的PP-PGMA膜；
D、在试管中加入步骤C得到的洁净的PP-PGMA膜，然后加入四氢呋喃和无环多聚胺化合物，再将试管密封并置于磁力搅拌器上，常温下搅拌反应10-48h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，洗涤干净后置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤B中，将步骤A得到的0.1-0.5g活化PP膜放入试管中，加入5-50mL二氯甲烷，在冰水浴中加入1-10mLα-溴异丁酰溴和0.5-5mL吡啶。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤B中，将试管密封并转移至磁力搅拌器上，常温下搅拌反应时，搅拌的转速为200-400r/min。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤C中，在充满氩气的试管中加入0.1-0.5g步骤B得到的洁净的溴化PP膜，然后分别加入0.01-0.5g溴化亚铜、0.1-1g溴化铜和0.1-1g 2,2-联吡啶，再加入1-10mL去离子水、1-10mL N,N-二甲基甲酰胺和1-10mL甲基丙烯酸缩水甘油酯。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤C中，将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应时，温度为30-60℃，搅拌的转速为100-200r/min。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤D中，在试管中加入0.1-0.5g步骤C得到的洁净的PP-PGMA膜，然后加入2-15mL四氢呋喃和2-15mL二乙烯三胺。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤D中，将试管密封并置于磁力搅拌器上，常温下搅拌反应时，搅拌的转速为100-200r/min。
所述的选择性吸附金离子的中空纤维膜的制备方法，其中，所述步骤D中，所述无环多聚胺化合物包括乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺。
一种选择性吸附金离子的中空纤维膜，所述选择性吸附金离子的中空纤维膜采用以上任一所述的选择性吸附金离子的中空纤维膜的制备方法制备而成。
一种选择性吸附金离子的中空纤维膜的应用，将以上所述选择性吸附金离子的中空纤维膜用于选择性吸附含金废水中的金离子。
有益效果：本发明提供了一种选择性吸附金离子的中空纤维膜及其制备方法与应用，所述选择性吸附金离子的中空纤维膜的制备方法，包括：先对聚丙烯中空纤维膜进行表面活化，得到活化PP膜，然后将活化PP膜进行溴化反应，得到溴化PP膜，再将溴化PP膜进行SI-ATRP反应，然后进行胺化，最终得到选择性吸附金离子的中空纤维膜。通过本发明制备方法制备的选择性吸附金离子的中空纤维膜，兼具物理截留颗粒物和选择性化学吸附贵金属金的性能，其对水体中的金离子吸附量高，能够选择性的回收含金废水中的金离子。
具体实施方式
本发明提供一种选择性吸附金离子的中空纤维膜及其制备方法与应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
聚丙烯(PP)中空纤维膜是一种广泛应用于水处理领域的膜材料，它具有抗冲击、耐磨性能好、耐腐蚀、单位膜面积大和分离效率高等优点。本发明在保留聚丙烯中空纤维膜的优良性能同时，通过接枝具有选择性吸附贵金属能力的高分子聚合物刷，拓展了聚丙烯中空纤维膜的应用范围。
本发明提供的一种选择性吸附金离子的中空纤维膜的制备方法，其包括步骤：
S100、将0.1-0.5g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗5-10min，得到活化PP膜；
S200、将步骤S100得到的活化PP膜放入试管中，加入二氯甲烷后，在冰水浴中加入α-溴异丁酰溴和吡啶，然后将试管密封并转移至磁力搅拌器上，常温下搅拌反应5-48h，得到 附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，洗涤干净后置于烘箱中干燥，得到洁净的溴化PP膜；
S300、在充满氩气的试管中加入步骤S200得到的洁净的溴化PP膜，然后分别加入溴化亚铜、溴化铜和2,2-联吡啶，再加入去离子水、N,N-二甲基甲酰胺和甲基丙烯酸缩水甘油酯，随后对试管中溶液通入氩气10-30min，再将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应1-12h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，洗涤干净后置于烘箱中干燥，得到洁净的PP-PGMA膜；
S400、在试管中加入步骤S300得到的洁净的PP-PGMA膜，然后加入四氢呋喃和无环多聚胺化合物，再将试管密封并置于磁力搅拌器上，常温下搅拌反应10-48h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，洗涤干净后置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
所述步骤S100也就是进行活化反应，首先用等离子清洗机清洗原始聚丙烯中空纤维膜，使其活化，在表层产生羟基，得到活化的聚丙烯中空纤维膜，即活化PP膜。利用等离子清洗机对聚丙烯中空纤维膜进行清洗，使其表面活化，增强亲水性能，并且产生羟基等活性基团，有利于后续对聚丙烯中空纤维膜的化学改性。
所述步骤S200也就是进行溴化反应，以卤族元素溴(Br)取代活化后聚丙烯中空纤维膜上的羟基，制得溴化的聚丙烯中空纤维膜，即溴化PP膜。
所述步骤S300为采用表面引发-原子转移自由基聚合(Surface-initiated atom transfer radical polymerization，SI-ATRP)方法进行SI-ATRP反应：以N,N-二甲基甲酰胺(DMF)为溶剂，甲基丙烯酸缩水甘油酯(GMA)为单体制备出聚甲基丙烯酸缩水甘油酯(PGMA)PP膜，也即是在聚丙烯中空纤维膜表面接枝甲基丙烯酸缩水甘油酯聚合物刷，制得表面接枝聚甲基丙烯酸缩水甘油酯的聚丙烯中空纤维膜，即PP-PGMA膜。
所述步骤S400也就是进行胺化反应，通过环氧基团与胺基的开环反应,利用无环多聚胺化合物对PP-PGMA膜进行化学改性，制备胺化改性的聚丙烯中空纤维膜，即胺化PP膜(胺基化PP膜)，而胺化PP膜即是最终产物：选择性吸附金离子的中空纤维膜。
本发明选择性吸附金离子的中空纤维膜的制备方法，实现了聚丙烯中空纤维膜的多功能化，在保留其原有截留颗粒物的物理特性的同时，通过化学改性方法，赋予了其对金离子的 化学吸附性能。本发明采用SI-ATRP方法和无环多聚胺胺化对聚丙烯中空纤维膜进行化学改性，操作简单且易于控制。
优选地，所述步骤S200中，将步骤S100得到的活化PP膜放入试管中，加入5-50mL二氯甲烷，在冰水浴中加入1-10mLα-溴异丁酰溴和0.5-5mL吡啶。
优选地，所述步骤S200中，将试管密封并转移至磁力搅拌器上，常温下搅拌反应时，搅拌的转速为200-400r/min(转/分钟)。
优选地，所述步骤S300中，在充满氩气的试管中加入0.1-0.5g步骤S200得到的洁净的溴化PP膜，然后分别加入0.01-0.5g溴化亚铜、0.1-1g溴化铜和0.1-1g 2,2-联吡啶，再加入1-10mL去离子水、1-10mL N,N-二甲基甲酰胺和1-10mL甲基丙烯酸缩水甘油酯。
优选地，所述步骤S300中，将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应时，温度为30-60℃，搅拌的转速为100-200r/min。
优选地，所述步骤S400中，在试管中加入0.1-0.5g步骤S300得到的洁净的PP-PGMA膜，然后加入2-15mL四氢呋喃和2-15mL二乙烯三胺。
优选地，所述步骤S400中，将试管密封并置于磁力搅拌器上，常温下搅拌反应时，搅拌的转速为100-200r/min。
优选地，所述步骤S400中，所述无环多聚胺化合物包括乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺。其中，多乙烯多胺是乙二胺、二乙烯三胺、三乙烯四胺和四乙烯五胺的联产物。所述无环多聚胺化合物优选为二乙烯三胺。
优选地，所述步骤S200中，对附有杂质的溴化PP膜进行洗涤的方法为：依次用丙酮和去离子水洗涤，具体的，先用丙酮洗涤数次，再用去离子水冲洗数次。
优选地，所述步骤S300中，对附有杂质的PP-PGMA膜进行洗涤的方法为：依次用四氢呋喃、0.1M HCl、0.1M NaOH和去离子水洗涤。其中，0.1M为0.1mol/L。
优选地，所述步骤S400中，对附有杂质的胺化PP膜进行洗涤的方法为：依次用丙酮和去离子水洗涤，具体的，先用丙酮洗涤数次，再用去离子水冲洗数次。
本发明选择性吸附金离子的中空纤维膜的制备方法，利用方便可控的表面引发-原子转移自由基聚合方法，以聚丙烯中空纤维微滤膜为基材，先在材料表面接枝甲基丙烯酸缩水甘油酯聚合物刷，再通过无环多聚胺化合物与聚甲基丙烯酸缩水甘油酯上的环氧基团进行加成反 应，得到胺化改性的聚丙烯中空纤维膜，从而最终制备得到选择性吸附金离子的中空纤维膜。通过本发明制备方法制备的选择性吸附金离子的中空纤维膜，兼具物理截留颗粒物和选择性化学吸附贵金属金的性能，其对水体中的金离子吸附量高，能够选择性的回收含金废水中的金离子。
基于上述方法，本发明还提供了一种选择性吸附金离子的中空纤维膜，所述选择性吸附金离子的中空纤维膜采用以上任一所述的选择性吸附金离子的中空纤维膜的制备方法制备而成。本发明在聚丙烯中空纤维膜表面引入的无环多聚胺对金离子吸附量高，在金锌离子体系中对金离子表现出明显的选择性吸附能力。因此，本发明制备的选择性吸附金离子的中空纤维膜兼具物理截留颗粒物和选择性化学吸附贵金属金的性能，能够选择性的回收含金废水中金离子。
基于上述选择性吸附金离子的中空纤维膜，本发明还提供了一种选择性吸附金离子的中空纤维膜的应用，即将以上所述选择性吸附金离子的中空纤维膜用于选择性吸附含金废水中的金离子。
下面以具体实施例对本发明做详细说明：
实施例1：
(1)、将0.1g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗5min，得到活化PP膜。
(2)、将0.1g步骤(1)得到的活化PP膜放入试管中，加入15mL二氯甲烷，在冰水浴中加入3mLα-溴异丁酰溴和1mL吡啶，然后将试管密封并转移至磁力搅拌器上，转速为300r/min，常温下反应24h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，得到洁净的溴化PP膜。
(3)、在充满氩气的试管中加入0.1g步骤(2)得到的洁净的溴化PP膜，然后分别加入0.03g溴化亚铜、0.11g溴化铜和0.2g 2,2-联吡啶，再加入2mL去离子水、4mL N,N-二甲基甲酰胺和6mL甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气20min，再将试管密封并置于磁力搅拌器上，转速为150r/min，45℃恒温水浴反应4h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，并依次用四氢呋喃、0.1M HCl、0.1M NaOH和去离子水洗涤干净后，置于烘箱中干燥，得到洁净的PP-PGMA膜。
(4)、在试管中加入0.1g步骤(3)得到的洁净的PP-PGMA膜，然后加入6mL四氢呋喃和10mL二乙烯三胺，再将试管密封并置于磁力搅拌器上，转速为150r/min，常温下反应24h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，用丙酮洗涤数次，再用去离子水冲洗数次后，置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜(胺化PP膜)。
下面对本实施例制备的选择性吸附金离子的中空纤维膜进行吸附性能测试：
吸附实验：将本实施例制备的胺化PP膜进行吸附实验，吸附量的测算方法如下：将胺化PP膜作为吸附剂加入到含金离子的水溶液中，室温且避光振荡至吸附平衡后，测定溶液中的金离子浓度。依下式计算吸附量：
q＝(C0－Ce)V/m
式中，q(mmol g-1)为平衡吸附量；C0和Ce为金离子的原始溶液浓度和吸附平衡浓度(mmol/L)；V为吸附溶液的体积(L)；m为吸附剂胺化PP膜的质量。
需要说明的是，对于胺化PP膜对含金离子水溶液中其他金属离子(例如锌)的吸附量也参照上式进行计算。
首先进行单独吸附金离子实验：将本实施例制备的胺化PP膜作为吸附剂放入只含金离子的水溶液中(没有其他金属杂质)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+浓度为4mmol/L，pH＝2.5，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.666mmol/g。
然后进行选择性吸附金离子实验：将本实施例制备的胺化PP膜吸附剂放入含有金离子和锌离子的水溶液中(氯金酸-硝酸锌混合溶液)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+和Zn2+浓度均为4mmol/L，pH＝1.0，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.176mmol/g，对Zn2+的吸附量为0.064mmol/g。
由实验结果可知，胺化PP膜对水体中的金离子吸附量高，胺化PP膜对金离子的吸附量远远大于对锌离子的吸附量，因此，本实施例制备的胺化PP膜能够在含金锌的水溶液中选择性的吸附金离子，从而实现金和锌的分离。
实施例2：
(1)、将0.1g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗5min，得到活 化PP膜。
(2)、将0.1g步骤(1)得到的活化PP膜放入试管中，加入5mL二氯甲烷，在冰水浴中加入1mLα-溴异丁酰溴和0.5mL吡啶，然后将试管密封并转移至磁力搅拌器上，转速为400r/min，常温下反应5h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，得到洁净的溴化PP膜。
(3)、在充满氩气的试管中加入0.1g步骤(2)得到的洁净的溴化PP膜，然后分别加入0.01g溴化亚铜、0.1g溴化铜和0.1g 2,2-联吡啶，再加入1mL去离子水、1mL N,N-二甲基甲酰胺和1mL甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气10min，再将试管密封并置于磁力搅拌器上，转速为200r/min，30℃恒温水浴反应1h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，并依次用四氢呋喃、0.1M HCl、0.1M NaOH和去离子水洗涤干净后，置于烘箱中干燥，得到洁净的PP-PGMA膜。
(4)、在试管中加入0.1g步骤(3)得到的洁净的PP-PGMA膜，然后加入2mL四氢呋喃和2mL 乙二胺，再将试管密封并置于磁力搅拌器上，转速为200r/min，常温下反应10h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
参照实施例1，将本实施例制备的选择性吸附金离子的中空纤维膜进行吸附性能测试。
首先进行单独吸附金离子实验：将本实施例制备的胺化PP膜作为吸附剂放入只含金离子的水溶液中(没有其他金属杂质)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+浓度为4mmol/L，pH＝2.5，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.534mmol/g。
然后进行选择性吸附金离子实验：将本实施例制备的胺化PP膜吸附剂放入含有金离子和锌离子的水溶液中(氯金酸-硝酸锌混合溶液)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+和Zn2+浓度均为4mmol/L，pH＝1.0，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.057mmol/g，对Zn2+的吸附量为0.049mmol/g。
由实验结果可知，胺化PP膜对水体中的金离子吸附量高，胺化PP膜对金离子的吸附量远远大于对锌离子的吸附量，因此，本实施例制备的胺化PP膜能够在含金锌的水溶液中选择性的吸附金离子，从而实现金和锌的分离。
实施例3：
(1)、将0.3g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗8min，得到活化PP膜。
(2)、将0.3g步骤(1)得到的活化PP膜放入试管中，加入30mL二氯甲烷，在冰水浴中加入6mLα-溴异丁酰溴和3mL吡啶，然后将试管密封并转移至磁力搅拌器上，转速为300r/min，常温下反应30h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，得到洁净的溴化PP膜。
(3)、在充满氩气的试管中加入0.3g步骤(2)得到的洁净的溴化PP膜，然后分别加入0.3g溴化亚铜、0.6g溴化铜和0.6g 2,2-联吡啶，再加入6mL去离子水、6mL N,N-二甲基甲酰胺和6mL甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气20min，再将试管密封并置于磁力搅拌器上，转速为150r/min，50℃恒温水浴反应8h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，并依次用四氢呋喃、0.1M HCl、0.1MNaOH和去离子水洗涤干净后，置于烘箱中干燥，得到洁净的PP-PGMA膜。
(4)、在试管中加入0.3g步骤(3)得到的洁净的PP-PGMA膜，然后加入10mL四氢呋喃和10mL三乙烯四胺，再将试管密封并置于磁力搅拌器上，转速为150r/min，常温下反应30h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
参照实施例1，将本实施例制备的选择性吸附金离子的中空纤维膜进行吸附性能测试。
首先进行单独吸附金离子实验：将本实施例制备的胺化PP膜作为吸附剂放入只含金离子的水溶液中(没有其他金属杂质)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+浓度为4mmol/L，pH＝2.5，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.723mmol/g。
然后进行选择性吸附金离子实验：将本实施例制备的胺化PP膜吸附剂放入含有金离子和锌离子的水溶液中(氯金酸-硝酸锌混合溶液)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+和Zn2+浓度均为4mmol/L，pH＝1.0，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.245mmol/g，对Zn2+的吸附量为0.071mmol/g。
由实验结果可知，胺化PP膜对水体中的金离子吸附量高，胺化PP膜对金离子的吸附量 远远大于对锌离子的吸附量，因此，本实施例制备的胺化PP膜能够在含金锌的水溶液中选择性的吸附金离子，从而实现金和锌的分离。
实施例4：
(1)、将0.5g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗10min，得到活化PP膜。
(2)、将0.5g步骤(1)得到的活化PP膜放入试管中，加入50mL二氯甲烷，在冰水浴中加入10mLα-溴异丁酰溴和5mL吡啶，然后将试管密封并转移至磁力搅拌器上，转速为200r/min，常温下反应48h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，得到洁净的溴化PP膜。
(3)、在充满氩气的试管中加入0.5g步骤(2)得到的洁净的溴化PP膜，然后分别加入0.5g溴化亚铜、1g溴化铜和1g 2,2-联吡啶，再加入10mL去离子水、10mL N,N-二甲基甲酰胺和10mL甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气30min，再将试管密封并置于磁力搅拌器上，转速为100r/min，60℃恒温水浴反应12h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，并依次用四氢呋喃、0.1M HCl、0.1M NaOH和去离子水洗涤干净后，置于烘箱中干燥，得到洁净的PP-PGMA膜。
(4)、在试管中加入0.5g步骤(3)得到的洁净的PP-PGMA膜，然后加入15mL四氢呋喃和15mL多乙烯多胺，再将试管密封并置于磁力搅拌器上，转速为100r/min，常温下反应48h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，用丙酮洗涤3次，再用去离子水冲洗3次后，置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
参照实施例1，将本实施例制备的选择性吸附金离子的中空纤维膜进行吸附性能测试。
首先进行单独吸附金离子实验：将本实施例制备的胺化PP膜作为吸附剂放入只含金离子的水溶液中(没有其他金属杂质)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+浓度为4mmol/L，pH＝2.5，温度为25℃，转速为150r/min，吸附24h后，测得胺化PP膜吸附剂对Au3+的吸附量为1.745mmol/g。
然后进行选择性吸附金离子实验：将本实施例制备的胺化PP膜吸附剂放入含有金离子和锌离子的水溶液中(氯金酸-硝酸锌混合溶液)进行吸附试验，吸附条件为：吸附剂用量：0.03g，Au3+和Zn2+浓度均为4mmol/L，pH＝1.0，温度为25℃，转速为150r/min，吸附24h后，测得 胺化PP膜吸附剂对Au3+的吸附量为1.259mmol/g，对Zn2+的吸附量为0.076mmol/g。
由实验结果可知，胺化PP膜对水体中的金离子吸附量高，胺化PP膜对金离子的吸附量远远大于对锌离子的吸附量，因此，本实施例制备的胺化PP膜能够在含金锌的水溶液中选择性的吸附金离子，从而实现金和锌的分离。
综上所述，本发明提供了一种选择性吸附金离子的中空纤维膜及其制备方法与应用，所述选择性吸附金离子的中空纤维膜的制备方法，包括：先对聚丙烯中空纤维膜进行表面活化，得到活化PP膜，然后将活化PP膜进行溴化反应，得到溴化PP膜，再将溴化PP膜进行SI-ATRP反应，然后进行胺化，最终得到选择性吸附金离子的中空纤维膜。通过本发明制备方法制备的选择性吸附金离子的中空纤维膜，兼具物理截留颗粒物和选择性化学吸附贵金属金的性能，其对水体中的金离子吸附量高，能够选择性的回收含金废水中的金离子。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

  1. 一种选择性吸附金离子的中空纤维膜的制备方法，其特征在于，包括步骤：
    A、将0.1-0.5g聚丙烯中空纤维膜置于等离子清洗机中，在空气气氛下清洗5-10min，得到活化PP膜；
    B、将步骤A得到的活化PP膜放入试管中，加入二氯甲烷后，在冰水浴中加入α-溴异丁酰溴和吡啶，然后将试管密封并转移至磁力搅拌器上，常温下搅拌反应5-48h，得到附有杂质的溴化PP膜，之后取出附有杂质的溴化PP膜，洗涤干净后置于烘箱中干燥，得到洁净的溴化PP膜；
    C、在充满氩气的试管中加入步骤B得到的洁净的溴化PP膜，然后分别加入溴化亚铜、溴化铜和2,2-联吡啶，再加入去离子水、N,N-二甲基甲酰胺和甲基丙烯酸缩水甘油酯，随后对试管中的溶液通入氩气10-30min，再将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应1-12h，得到附有杂质的PP-PGMA膜，之后取出附有杂质的PP-PGMA膜，洗涤干净后置于烘箱中干燥，得到洁净的PP-PGMA膜；
    D、在试管中加入步骤C得到的洁净的PP-PGMA膜，然后加入四氢呋喃和无环多聚胺化合物，再将试管密封并置于磁力搅拌器上，常温下搅拌反应10-48h，得到附有杂质的胺化PP膜，之后取出附有杂质的胺化PP膜，洗涤干净后置于烘箱中干燥，最终得到选择性吸附金离子的中空纤维膜。
  2. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤B中，将步骤A得到的0.1-0.5g活化PP膜放入试管中，加入5-50mL二氯甲烷，在冰水浴中加入1-10mLα-溴异丁酰溴和0.5-5mL吡啶。
  3. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤B中，将试管密封并转移至磁力搅拌器上，常温下搅拌反应时，搅拌的转速为200-400r/min。
  4. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤C中，在充满氩气的试管中加入0.1-0.5g步骤B得到的洁净的溴化PP膜，然后分别加入0.01-0.5g溴化亚铜、0.1-1g溴化铜和0.1-1g 2,2-联吡啶，再加入1-10mL去离子水、1-10mL N,N-二甲基甲酰胺和1-10mL甲基丙烯酸缩水甘油酯。
  5. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤C中，将试管密封并置于磁力搅拌器上，恒温水浴搅拌反应时，温度为30-60℃，搅拌的 转速为100-200r/min。
  6. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤D中，在试管中加入0.1-0.5g步骤C得到的洁净的PP-PGMA膜，然后加入2-15mL四氢呋喃和2-15mL二乙烯三胺。
  7. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤D中，将试管密封并置于磁力搅拌器上，常温下搅拌反应时，搅拌的转速为100-200r/min。
  8. 根据权利要求1所述的选择性吸附金离子的中空纤维膜的制备方法，其特征在于，所述步骤D中，所述无环多聚胺化合物包括乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺。
  9. 一种选择性吸附金离子的中空纤维膜，其特征在于，所述选择性吸附金离子的中空纤维膜采用如权利要求1-8任一所述的选择性吸附金离子的中空纤维膜的制备方法制备而成。
  10. 一种选择性吸附金离子的中空纤维膜的应用，其特征在于，将如权利要求9所述选择性吸附金离子的中空纤维膜用于选择性吸附含金废水中的金离子。
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CA2857444A1 (en) * 2011-12-08 2013-06-13 University Of Fukui Conjugated fiber and structural fiber product comprising the conjugated fiber
CN102553531A (zh) * 2012-01-13 2012-07-11 同济大学 一种具有微纳复合结构的多孔碳质吸附材料的制备方法
CN103755900A (zh) * 2013-12-31 2014-04-30 上海交通大学 一种具有金属阳离子吸附能力的梯度分子刷聚合物及其制备方法
CN106745457A (zh) * 2016-12-26 2017-05-31 深圳大学 选择性吸附金离子的中空纤维膜及其制备方法与应用

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WO2020120306A1 (de) * 2018-12-12 2020-06-18 Carl Freudenberg Kg Membran für den selektiven stofftransport

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