WO2020200289A1 - 一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法 - Google Patents

一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法 Download PDF

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WO2020200289A1
WO2020200289A1 PCT/CN2020/083027 CN2020083027W WO2020200289A1 WO 2020200289 A1 WO2020200289 A1 WO 2020200289A1 CN 2020083027 W CN2020083027 W CN 2020083027W WO 2020200289 A1 WO2020200289 A1 WO 2020200289A1
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membrane
organic
inorganic
ceramic membrane
ceramic
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PCT/CN2020/083027
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English (en)
French (fr)
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陈云强
洪昱斌
蓝伟光
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三达膜科技（厦门）有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/20—By influencing the flow
    • B01D2321/2066—Pulsated flow
    • B01D2321/2075—Ultrasonic treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/28—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by soaking or impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking

Definitions

  • the invention belongs to the technical field of nanofiltration membrane preparation, and specifically relates to a preparation method of an organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • Nanofiltration membrane is a new type of pressure-driven membrane with a pore size between ultrafiltration and reverse osmosis, and can be used for the separation of divalent and monovalent salts. Nanofiltration membranes have the characteristics of low operating pressure, strong anti-pollution ability, high flux and energy saving. Therefore, nanofiltration membranes are widely used in bioengineering, medicine, metallurgy, water treatment, electronics and other fields.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing an organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • a method for preparing an organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane The ceramic membrane is activated by a strong base with a crosslinking agent, followed by piperazine as the water phase monomer and trimesoyl chloride as the organic phase monomer , Using polyamines as acid acceptors to form an organic functional layer on the surface of the ceramic membrane through interfacial polymerization to obtain the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • the pores of the inorganic functional layer of the ceramic membrane are It is 10-100 nm, the material of the ceramic film is alumina, titania or zirconia, and the crosslinking agent is polyethylene glycol or cellulose crosslinking agent.
  • the ceramic membrane is soaked in a 1-10mol/L strong alkali solution for activation treatment, then dried, and then rinsed with cellulose after cooling, and then washed with ethanol and deionized water After drying, the activated ceramic membrane is obtained;
  • the grafted ceramic membrane immerse the grafted ceramic membrane in the organic phase monomer solution with a concentration of 0.2-2wt%, react at room temperature to remove the unreacted organic phase monomer solution, and then soak in the aqueous phase solution. React at room temperature to remove the unreacted aqueous phase solution, the aqueous phase solution contains 1-10wt% aqueous monomer and 0.5-5wt% acid acceptor, and the solvent is water;
  • step (3) After the material obtained in step (3) is air-dried, heat-treated at 50-80° C., and cooled naturally, the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane is obtained.
  • the time of ultrasonic treatment in the step (1) is 5-10 hours.
  • the activation treatment time in the step (1) is 10-24 hours.
  • the drying temperature in the step (1) is 100-150° C., and the time is 10-24 h.
  • the drying temperature in the step (2) is 80-100° C., and the time is 10-24 h.
  • reaction time at room temperature in the step (3) is 1-15 min.
  • the strong base is sodium hydroxide or potassium hydroxide.
  • the present invention uses self-assembly layer by layer, and directly grafts organic monomers on the ceramic interface by adding a coupling agent, and then performs interfacial polymerization with inorganic monomers, and grafts inorganic monomers on the ceramic support in the traditional way. It is different from the method of interfacial polymerization of organic monomers, and an acid acceptor is added to the reactants to reduce the influence of the reaction product hydrogen chloride; in the process of preparing the nanofiltration membrane by the interfacial polymerization method, the reaction between the monomers often releases hydrogen chloride , It is combined with the monomer in the water phase, resulting in a decrease in the polymerization rate and affecting the integrity of the membrane.
  • the present invention prepares an organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane on an inorganic ceramic membrane loaded with a cross-linking agent. Under the test conditions of room temperature and 0.6MPa, it has a higher resistance to 0.2wt% magnesium sulfate solution.
  • the rejection rate (94-96%) the pure water flux is 34-38LHM
  • the nitric acid solution with pH 2 and the sodium hydroxide solution with pH 12 are immersed for 168h at 85°C, and then at room temperature and 0.6MPa test conditions
  • the pure water flux is 34-39LHM
  • the 0.2wt% magnesium sulfate solution intercepts 92-94%, which basically remains unchanged.
  • the GE commercial membrane DK has a flux of 27LHM under 0.76MPa, and the acid and alkali resistance is The pH is 3-9.
  • Figure 1 is a scanning electron micrograph of the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane prepared in Example 1 of the present invention.
  • Figure 1(a) and (b) are the surface of the piperazine polyamide composite ceramic nanofiltration membrane, and Figure 1(c) is the cross section of the piperazine polyamide composite ceramic nanofiltration membrane;
  • Figure 2 shows the contact angle test of the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane in Example 1;
  • Figure 3 is a scanning electron micrograph of the composite ceramic nanofiltration membrane of the comparative example
  • Step 1 Soak the treated membrane tube in a TMC n-hexane solution with a mass fraction of 2wt%, react for 10 minutes at room temperature and take it out, soak in water and blow dry with an air gun;
  • Step 2 The membrane tube is immersed in an aqueous solution containing 1wt% piperazine, 1wt% PEG1000 and 1wt% diethylamine, reacted at room temperature for 10 minutes, then taken out, soaked in water and blown dry with an air gun;
  • Step 4 Place the membrane tube in a cool place at room temperature to air dry, then put it into an oven at 50°C for heat treatment for 15 minutes, and then cool in the furnace to prepare a complete organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane as shown in FIG. 1.
  • Membrane tube performance test Under the test conditions of room temperature and 0.6MPa pressure, the pure water flux is 38LHM, and the rejection rate of 0.2wt% magnesium sulfate solution is 94%.
  • Acid and alkali resistance test the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane prepared in this example was soaked in a nitric acid solution with a pH of 2 and a sodium hydroxide solution with a pH of 12 for 168h at 85°C, and then The pure water flux tested under the test conditions of room temperature and 0.6MPa pressure was 38.6LHM, and the rejection rate of 0.2wt% magnesium sulfate solution was 92.4%, which remained basically unchanged.
  • the GE commercial membrane DK has a flux of 27LHM at 0.76MPa and a pH of 3-9 in the acid and alkali resistance range.
  • Step 1 Immerse the treated membrane tube in a TMC n-hexane solution with a mass fraction of 1 wt%, react for 3 minutes at room temperature and take it out, soak in water and blow dry with an air gun;
  • Step 2 immerse the membrane tube in an aqueous solution containing 5wt% piperazine, 1wt% PEG1000 and 1wt% diethylamine, react for 3 minutes at room temperature, and then take it out, soak in water and blow dry with an air gun;
  • Step 4 Place the membrane tube in a cool place at room temperature to air dry, then put it into an 80°C oven for heat treatment for 15 minutes, and then cool it down in the furnace to prepare a complete organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • Membrane tube performance test Under the test conditions of room temperature and 0.6MPa pressure, the pure water flux is 34LHM, and the rejection rate of 0.2wt% magnesium sulfate solution is 96%.
  • Acid and alkali resistance test the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane prepared in this example was soaked in a nitric acid solution with a pH of 2 and a sodium hydroxide solution with a pH of 12 for 168h at 85°C, and then The pure water flux tested under the test conditions of room temperature and 0.6MPa pressure was 34.6LHM, and the rejection rate of 0.2wt% magnesium sulfate solution was 94%, which remained basically unchanged.
  • the GE commercial membrane DK has a flux of 27LHM at 0.76MPa and a pH of 3-9 in the acid and alkali resistance range.
  • the 10nm zirconia ceramic membrane tube with a length of about 50cm after being cut is ultrasonicated for 5h, soaked in 2mol/L sodium hydroxide for 24h, dried at 100°C for 10h, cooled and rinsed with cellulose, and then washed with ethanol and Rinse with deionized water several times, put it in an oven and dry for 12 hours at the set temperature of 100°C, and then cool down with the furnace;
  • Step 1 Soak the treated membrane tube in a 10wt% TMC n-hexane solution, react for 15 minutes at room temperature, and take it out, soak in water and blow dry with an air gun;
  • Step 2 immerse the membrane tube in an aqueous solution containing 0.2wt% piperazine, 1wt% PEG1000 and 1wt% diethylamine, react for 15 minutes at room temperature and take it out, soak in water and blow dry with an air gun;
  • Step 4 Place the membrane tube in a cool place at room temperature to air dry, and then put it into an oven at 50°C for heat treatment for 15 minutes, and then cool down in the furnace to prepare a complete organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • Membrane tube performance test Under the test conditions of room temperature and 0.6MPa pressure, the pure water flux is 36LHM, and the rejection rate of 0.2wt% magnesium sulfate solution is 95%.
  • Acid and alkali resistance test the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane prepared in this example was soaked in a nitric acid solution with a pH of 2 and a sodium hydroxide solution with a pH of 12 for 168h at 85°C, and then The pure water flux tested under the test conditions of room temperature and 0.6MPa pressure was 36.6LHM, and the rejection rate of 0.2wt% magnesium sulfate solution was 93.3%, which remained basically unchanged.
  • the GE commercial membrane DK has a flux of 27LHM at 0.76MPa and a pH of 3-9 in the acid and alkali resistance range.
  • Step 1 Soak the treated membrane tube in an aqueous solution containing 5wt% piperazine, 1wt% PEG1000 and 1wt% diethylamine, react at room temperature for 3 minutes, then take it out, soak in water and blow dry with an air gun ;
  • Step 2 The membrane tube is immersed in a 1wt% TMC n-hexane solution, reacted for 3 minutes at room temperature, and then taken out, soaked in water and blown dry with an air gun;
  • Step 3 Place the membrane tube in a cool place at room temperature to air dry, then put it into an oven at 80°C for heat treatment for 15 minutes, and then cool in the furnace to prepare a complete organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • Membrane tube performance test Under the test conditions of room temperature and 0.6MPa pressure, the pure water flux is 1800LHM, and the rejection rate of 0.2wt% magnesium sulfate solution is 0%.
  • the nanofiltration membrane prepared on the surface of the ceramic ultrafiltration base membrane forms a new dense functional layer of polyamide through interfacial polymerization; and the surface of the functional layer has no cracks, shedding, etc., indicating that the interfacial polymerization is uniform and complete ,
  • the thickness of the film is 300-400nm. Due to the formation of cross-linked structure during the interfacial polymerization process, the surface of the nanofiltration membrane is more rough and compact. The rougher surface film improves the hydrophilicity of the film, thereby increasing the flux of the film.
  • the film of the present invention has a rougher surface, a smaller water contact angle (38°), and a higher hydrophilicity.
  • the invention discloses a preparation method of an organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • a crosslinking agent is loaded on the ceramic membrane activated by strong alkali, followed by piperazine as the water phase monomer and trimesoyl chloride as the
  • the organic phase monomer uses a polyamine as an acid acceptor to form an organic functional layer on the surface of the ceramic membrane through interfacial polymerization to obtain the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane.
  • the invention prepares the organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane on the inorganic ceramic membrane loaded with the crosslinking agent. Under the test conditions at room temperature, it has a high rejection rate for the 2g/L magnesium sulfate solution, and The water flux is high and it has industrial applicability.

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Abstract

一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜及其制备方法，在经强碱活化陶瓷膜上负载交联剂，接着以哌嗪为水相单体，以均苯三甲酰氯为有机相单体，以多元胺为酸接受剂，通过界面聚合反应在陶瓷膜的表面形成有机功能层，即得有机无机哌嗪聚酰胺复合陶瓷纳滤膜，陶瓷膜的无机功能层的孔径为10-100nm，陶瓷膜的材质为氧化铝、氧化钛或氧化锆，交联剂为聚乙二醇或纤维素类交联剂；陶瓷膜的聚酰胺致密功能层膜层厚度为300-400nm，膜面具有的水接触角为38°。

Description

一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法 技术领域
本发明属于纳滤膜制备技术领域，具体涉及一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法。
背景技术
纳滤膜是一种新型的压力驱动膜，膜孔径介于超滤和反渗透之间，能够用于二价盐和一价盐的分离。纳滤膜具有操作压力低、较强的抗污染能力、高通量和节能等特点，因此，纳滤膜被广泛地应用于生物工程、医药、冶金、水处理、电子等领域。
从近年来纳滤膜的研究表明，纯无机纳滤膜和纯的机纳滤膜研究较多，但在实际应用中都存在一些问题。目前广泛使用的有机纳滤膜具有制备透气性高、密度低、成膜性好、成本低和柔韧性好等诸多优点，但因其耐高温、耐有机溶剂、耐酸碱性差而在很多领域失去了使用价值；无机纳滤膜具有机械强度高、耐腐蚀、耐溶剂、耐高温等优点，但制备成本较高，脆性大，加工困难。因此，如何将无机材料和有机材料的优点合二为一，开发兼具有机材料和无机材料特点的复合纳滤膜已成为国内外纳滤膜研究新的热点。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法。
本发明的技术方案如下：
一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法，在经强碱活化陶瓷膜上负载交联剂，接着以哌嗪为水相单体，以均苯三甲酰氯为有机相单体，以多元胺为酸接受剂，通过界面聚合反应在上述陶瓷膜的表面形成有机功能层，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜，上述陶瓷膜的无机功能层的孔经为10-100nm，上述陶瓷膜的材质为氧化铝、氧化钛或氧化锆，上述交联剂为聚乙二醇或纤维素类交联剂。
在本发明的一个优选实施方案中，包括如下步骤：
(1)将所述陶瓷膜经超声处理后，浸泡于1-10mol/L的强碱溶液中进行活化处理，然后烘干，冷却后用纤维素继续冲洗，然后用乙醇和去离子水进行洗涤，再经烘干后，获得活化后的陶瓷膜；
(2)将活化后的陶瓷膜用浓度为1-20wtwt％的交联剂溶液冲洗10-60min，然后烘干，获得接枝后的陶瓷膜；
(3)将接枝后的陶瓷膜浸泡于浓度为0.2-2wtwt％的有机相单体溶液中，于室温下反应，除去未反应的有机相单体溶液，然后浸泡于水相溶液中，于室温下反应，除去未反应的水相溶液，该水相溶液中含有1-10wtwt％的水相单体和0.5-5wtwt％的酸接受剂，溶剂为水；
(4)将步骤(3)所得的物料风干后，于50-80℃热处理，自然冷却后，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
进一步优选的，所述步骤(1)中的超声处理的时间为5-10h。
进一步优选的，所述步骤(1)中的活化处理的时间为10-24h。
进一步优选的，所述步骤(1)中的烘干的温度为100-150℃，时间为10-24h。
进一步优选的，所述步骤(2)中的烘干的温度为80-100℃，时间为10-24h。
进一步优选的，所述步骤(3)中的室温下的反应时间为1-15min。
在本发明的一个优选实施方案中，所述强碱为氢氧化钠或氢氧化钾。
本发明的有益效果是：
1、本发明通过先层层自组装，通过添加偶联剂后直接在陶瓷界面上接枝有机单体，再与无机单体进行界面聚合，与传统方式在陶瓷支撑体先接枝无机单体再与有机单体界面聚合的方式不同，并在反应物中加入酸接受剂，降低了反应产物氯化氢的影响；界面聚合法制备纳滤膜的过程中，单体之间的反应往往会释放氯化氢，其于水相单体结合，导致聚合速率下降，影响膜的完整性。
2、本发明通过在负载有交联剂的无机陶瓷膜上制备有机无机哌嗪聚酰胺复合陶瓷纳滤膜，在室温和0.6MPa的测试条件下，对0.2wt％的硫酸镁溶液具有较高的截留率(94-96％)，纯水通量为34-38LHM，在pH为2的硝酸溶液和pH为12的氢氧化钠溶液85℃下浸泡168h，然后在室温和0.6MPa的测试条件下测试其纯水通量为34-39LHM，对0.2wt％的硫酸镁溶液截留92-94％，基本保持不变，而GE商用膜DK在0.76MPa下的通量为27LHM，耐酸碱是pH为3-9。
附图说明
图1为本发明实施例1制备的有机无机哌嗪聚酰胺复合陶瓷纳滤膜的扫描电镜照片。
图1(a)、(b)为哌嗪聚酰胺复合陶瓷纳滤膜表面，图1(c)为哌嗪聚酰胺复合陶瓷 纳滤膜截面；
图2为本实施例1有机无机哌嗪聚酰胺复合陶瓷纳滤膜接触角测试；
图3为对比例的复合陶瓷纳滤膜的扫描电镜照片；
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
实施例1:
1、膜管处理
将切割后长度为50cm左右的100nm氧化铝陶瓷膜管超声5h后，用2mol/L氢氧化钠浸泡24h，100℃下烘干10h，冷却后使用纤维素冲洗陶瓷膜管，然后依次用乙醇和去离子水冲洗数次，放入烘箱中以温度设定值100℃干燥12h后随炉冷却；
2、纳滤膜制备
步骤1、将处理后的膜管浸泡于质量分数为2wt％的TMC正己烷溶液中，室温下反应10min后取出，进行泡水和气枪吹干；
步骤2、再将膜管浸泡于含有质量分数为1wt％的哌嗪、1wt％PEG1000及1wt％二乙胺的水相溶液中，室温下反应10min后取出，进行泡水和气枪吹干；
步骤3、重复步骤1及2；
步骤4、室温下将膜管放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，制备出完整的如图1所示的有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
膜管性能测试：在室温和0.6MPa的压力的测试条件下，纯水通量38LHM，对0.2wt％的硫酸镁溶液截留率94％。
耐酸碱性测试：85℃下，将本实施例制得的有机无机哌嗪聚酰胺复合陶瓷纳滤膜分别在pH为2的硝酸溶液和pH为12的氢氧化钠溶液浸泡168h后，然后于室温和0.6MPa的压力的测试条件下测试其纯水通量为38.6LHM，对0.2wt％的硫酸镁溶液截留率92.4％，基本保持不变。而GE商用膜DK在0.76MPa下的通量为27LHM，耐酸碱范围的pH为3-9。
实施例2:
1、膜管处理
将切割后长度为50cm左右的80nm氧化钛陶瓷膜管超声10h后，用5mol/L氢氧化钠浸泡24h，100℃下烘干10h，冷却后使用纤维素冲洗陶瓷膜管，然后依次用乙醇和去离子水冲洗数次，放入烘箱中以温度设定值100℃干燥12h后随炉冷却；
2、纳滤膜制备
步骤1、将处理后的膜管浸泡于质量分数为1wt％的TMC正己烷溶液中，室温下反应3min后取出，进行泡水和气枪吹干；
步骤2、再将膜管浸泡于含有质量分数为5wt％的哌嗪、1wt％PEG1000及1wt％二乙胺的水相溶液中，室温下反应3min后取出，进行泡水和气枪吹干；
步骤3、重复步骤1及2；
步骤4、室温下将膜管放置在阴凉处风干后放入80℃烘箱中热处理15min，之后随炉冷却，制备出完整的有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
膜管性能测试：在室温和0.6MPa的压力的测试条件下，纯水通量34LHM，对0.2wt％的硫酸镁溶液截留率96％。
耐酸碱性测试：85℃下，将本实施例制得的有机无机哌嗪聚酰胺复合陶瓷纳滤膜分别在pH为2的硝酸溶液和pH为12的氢氧化钠溶液浸泡168h后，然后于室温和0.6MPa的压力的测试条件下测试其纯水通量为34.6LHM，对0.2wt％的硫酸镁溶液截留率94％，基本保持不变。而GE商用膜DK在0.76MPa下的通量为27LHM，耐酸碱范围的pH为3-9。
实施例3:
1、膜管处理
将切割后长度为50cm左右的10nm氧化锆陶瓷膜管超声5h后，用2mol/L氢氧化钠浸泡24h，100℃下烘干10h，冷却后使用纤维素冲洗陶瓷膜管，然后依次用乙醇和去离子水冲洗数次，放入烘箱中以温度设定值100℃干燥12h后随炉冷却；
2、纳滤膜制备
步骤1、将处理后的膜管浸泡于质量分数为10wt％的TMC正己烷溶液中，室温下反应15min后取出，进行泡水和气枪吹干；
步骤2、再将膜管浸泡于含有质量分数为0.2wt％的哌嗪、1wt％PEG1000及1wt％ 二乙胺的水相溶液中，室温下反应15min后取出，进行泡水和气枪吹干；
步骤3、重复步骤1及2
步骤4、室温下将膜管放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，制备出完整的有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
膜管性能测试：在室温和0.6MPa的压力的测试条件下，纯水通量36LHM，对0.2wt％的硫酸镁溶液截留率95％。
耐酸碱性测试：85℃下，将本实施例制得的有机无机哌嗪聚酰胺复合陶瓷纳滤膜分别在pH为2的硝酸溶液和pH为12的氢氧化钠溶液浸泡168h后，然后于室温和0.6MPa的压力的测试条件下测试其纯水通量为36.6LHM，对0.2wt％的硫酸镁溶液截留率93.3％，基本保持不变。而GE商用膜DK在0.76MPa下的通量为27LHM，耐酸碱范围的pH为3-9。
对比例：
1、膜管处理
将切割后长度为50cm左右的80nm氧化钛陶瓷膜管超声10h后，用5mol/L氢氧化钠浸泡24h，100℃下烘干10h，冷却后使用纤维素冲洗陶瓷膜管，然后依次用乙醇和去离子水冲洗数次，放入烘箱中以温度设定值100℃干燥12h后随炉冷却；
2、纳滤膜制备
步骤1、将处理后的膜管浸泡于含有质量分数为5wt％的哌嗪、1wt％PEG1000及1wt％二乙胺的水相溶液中，室温下反应3min后取出，进行泡水和气枪吹干；
步骤2、再将膜管浸泡于质量分数为1wt％的TMC正己烷溶液中，室温下反应3min后取出，进行泡水和气枪吹干；
步骤3、室温下将膜管放置在阴凉处风干后放入80℃烘箱中热处理15min，之后随炉冷却，制备出完整的有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
膜管性能测试：在室温和0.6MPa的压力的测试条件下，纯水通量1800LHM，对0.2wt％的硫酸镁溶液截留率0％。
结果表明：在陶瓷表面先添加水相单体，再进行界面聚合形成的膜层不能很好的负载到陶瓷膜超滤膜上，膜层脱落。
下表为实施例1的膜与同类产品的性能对比
Figure PCTCN2020083027-appb-000001
由图1可知，陶瓷超滤基膜表面上制备的纳滤膜通过界面聚合形成了一层新的聚酰胺致密功能层；且该功能层表面均无裂痕、脱落等破损，表明界面聚合均匀完整，膜层厚度为300-400nm。由于界面聚合过程中交联结构的形成，纳滤膜表面更加粗糙紧实。表面膜层较粗糙提高了膜层的亲水性，从而增加了膜层的通量。
如图2所示，本发明的膜面较粗糙，具有较小的水接触角(38°)，较高的亲水性。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明公开了一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法，在经强碱活化陶瓷膜上负载交联剂，接着以哌嗪为水相单体，以均苯三甲酰氯为有机相单体，以多元胺为酸接受剂，通过界面聚合反应在上述陶瓷膜的表面形成有机功能层，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜。本发明通过在负载有交联剂的无机陶瓷膜上制备有机无机哌嗪聚酰胺复合陶瓷纳滤膜，在室温的测试条件下，对2g/L的硫酸镁溶液具有较高的截留率，纯水通量较高,具有工业实用性。

Claims (4)

  1. 一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法，其特征在于：在经强碱活化陶瓷膜上负载交联剂，接着以哌嗪为水相单体，以均苯三甲酰氯为有机相单体，以多元胺为酸接受剂，通过界面聚合反应在上述陶瓷膜的表面形成有机功能层，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜，上述陶瓷膜的无机功能层的孔经为10-100nm，上述陶瓷膜的材质为氧化铝、氧化钛或氧化锆，上述交联剂为聚乙二醇或纤维素类交联剂。
  2. 如权利要求1所述的制备方法，其特征在于：包括如下步骤：
    (1)将所述陶瓷膜经超声处理后，浸泡于1-10mol/L的强碱溶液中进行活化处理，然后烘干，冷却后用纤维素继续冲洗，然后用乙醇和去离子水进行洗涤，再经烘干后，获得活化后的陶瓷膜；
    (2)将活化后的陶瓷膜用浓度为1-20wtwt％的交联剂溶液冲洗10-60min，然后烘干，获得接枝后的陶瓷膜；
    (3)将接枝后的陶瓷膜浸泡于浓度为0.2-2wtwt％的有机相单体溶液中，于室温下反应，除去未反应的有机相单体溶液，然后浸泡于水相溶液中，于室温下反应，除去未反应的水相溶液，该水相溶液中含有1-10wtwt％的水相单体和0.5-5wtwt％的酸接受剂，溶剂为水；
    (4)将步骤(3)所得的物料风干后，于50-80℃热处理，自然冷却后，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
  3. 一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜的制备方法，其特征在于：包括如下步骤：
    (1)将所述陶瓷膜经超声处理后，浸泡于强碱溶液中进行活化处理，烘干、冷却后用纤维素冲洗，再用乙醇和去离子水进行洗涤，再经烘干，获得活化后的陶瓷膜；
    (2)将活化后的陶瓷膜用浓度为1-20wtwt％的交联剂溶液冲洗10-60min，然后烘干，获得接枝后的陶瓷膜；
    (3)将接枝后的陶瓷膜浸泡于浓度为0.2-2wtwt％的有机相单体溶液中，于室温 下反应，除去未反应的有机相单体溶液，然后浸泡于水相溶液中，于室温下反应，除去未反应的水相溶液，该水相溶液中含有1-10wtwt％的水相单体和0.5-5wtwt％的酸接受剂，溶剂为水；
    (4)步骤4、重复步骤(2)及(3)；
    (5)经数次循环步骤(4)后所得的物料风干后，于50-80℃热处理，自然冷却后，即得所述有机无机哌嗪聚酰胺复合陶瓷纳滤膜。
  4. 一种有机无机哌嗪聚酰胺复合陶瓷纳滤膜，其特征在于：在经强碱活化陶瓷膜上负载交联剂，接枝上均苯三甲酰氯为有机相单体，再以哌嗪为水相单体，以多元胺为酸接受剂，通过界面聚合反应在上述陶瓷膜的聚酰胺致密功能层，膜层厚度为300-400nm，膜面具有的水接触角为38°，所述陶瓷膜的无机功能层的孔经为10-100nm，所述陶瓷膜的材质为氧化铝、氧化钛或氧化锆，所述交联剂为聚乙二醇或纤维素类交联剂。
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