CN109954411A - 一种负载有TiO2/SiO2的PES超滤膜及其制备方法和应用 - Google Patents
一种负载有TiO2/SiO2的PES超滤膜及其制备方法和应用 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000012528 membrane Substances 0.000 title claims abstract description 127
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 90
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 90
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 90
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 90
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 90
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 89
- 229920006393 polyether sulfone Polymers 0.000 claims description 49
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical group C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 23
- 239000004021 humic acid Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- -1 acyl acetone Chemical compound 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 17
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000010148 water-pollination Effects 0.000 abstract description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明公开了一种负载有TiO2/SiO2的PES超滤膜,还公开了上述负载有TiO2/SiO2的PES超滤膜的制备方法和应用。本发明负载有TiO2/SiO2的PES超滤膜是将PES超滤膜浸没在PAM溶液中,然后通过真空抽滤将TiO2/SiO2纳米颗粒负载于PES超滤膜表面,得到膜表面负载有TiO2/SiO2的PES超滤膜。本发明负载有TiO2/SiO2的PES超滤膜由于膜表面具有亲水性,因此超滤膜的水接触角减小,有利于减缓膜污染,进而增加膜通量;另外在紫外光照射下,膜表面的TiO2/SiO2纳米颗粒能够降解PES超滤膜表面沉积的污染物,从而进一步减缓膜污染,增加膜通量。
Description
技术领域
本发明涉及一种负载有TiO2/SiO2的PES超滤膜,还涉及上述负载有TiO2/SiO2的PES超滤膜的制备方法以及该PES超滤膜在分离过滤溶液中大分子有机污染物方面的应用,属于过滤膜技术领域。
背景技术
聚醚砜(PES)具有良好的机械性能以及抗腐蚀耐酸碱性能,操作运行时,具有化学能耗低、效率高等优点,是一类优良的膜材料。但膜污染降低了膜的处理性能,限制了膜分离技术的发展应用,因此对需要聚醚砜超滤膜进行表面改性。
当前饮用水源的有机污染已经成为危害人类饮水安全的主要问题之一,其中水中的腐殖酸是水体中有机物污染的主要成分。腐殖酸除了影响水的色度外,腐殖酸在饮用水消毒过程中会生成消毒副产物,对人体具有毒害作用,如何高效地去除饮用水源中的腐殖酸已成为水环境领域的研究热点。
发明内容
发明目的:本发明所要解决的技术问题是提供一种负载有TiO2/SiO2的PES超滤膜,该超滤膜能在一定操作压差下进行大分子有机污染物的有效分离和污染物的降解,并且还具有强的抗污染能力。
本发明还要解决的技术问题是提供上述负载有TiO2/SiO2的PES超滤膜的制备方法。
本发明最后要解决的技术问题是提供上述负载有TiO2/SiO2的PES超滤膜在分离过滤溶液中大分子有机污染物方面的应用。
为解决上述技术问题,本发明所采用的技术方案为:
一种负载有TiO2/SiO2的PES超滤膜,所述PES超滤膜表面负载有一定量的TiO2/SiO2纳米颗粒。TiO2/SiO2纳米颗粒通过PAM(聚丙烯酰胺)的粘连性负载于PES超滤膜表面。PES超滤膜表面TiO2/SiO2纳米颗粒的负载量为10mg。
上述负载有TiO2/SiO2的PES超滤膜的制备方法,将PES超滤膜浸泡在PAM溶液中,通过真空抽滤将TiO2/SiO2纳米颗粒负载于PES超滤膜表面,即可得到膜表面负载有TiO2/SiO2的PES超滤膜。即通过真空抽滤法将TiO2/SiO2纳米颗粒负载于PES超滤膜表面。
上述负载有TiO2/SiO2的PES超滤膜的制备方法,具体包括如下步骤:
步骤1,制备PES超滤膜;
步骤2,制备TiO2/SiO2纳米颗粒;
步骤3,制备负载有TiO2/SiO2的PES超滤膜:将步骤1制得的PES超滤膜浸泡在PAM溶液中,将步骤2制得的TiO2/SiO2纳米颗粒配制成悬浮液,通过真空抽滤将TiO2/SiO2纳米颗粒负载在PES超滤膜表面,得到膜表面负载有TiO2/SiO2的PES超滤膜。
其中,步骤1中,PES超滤膜具体采用如下方式制备得到:将所需量的聚醚砜和聚乙烯吡咯烷酮溶于N,N-二甲基乙酰胺溶剂中,搅拌得到铸膜液;将铸膜液脱气后均匀涂覆于玻璃板表面,将涂覆有铸膜液的玻璃板平整放入水中进行相的转换,静置后得到PES超滤膜。
其中,步骤2中,TiO2/SiO2纳米颗粒具体采用如下方式制备得到:将所需体积比的钛酸四丁酯、乙醇和乙酰丙酮混合,得到混合液A;将一定量的正硅酸乙酯、去离子水、氨水和无水乙醇混合,得到混合液B;将混合液A和混合液B持续搅拌一段时间,高温下反应后再进行煅烧,得到TiO2/SiO2纳米颗粒。
其中,步骤3中,所述PAM溶液的质量分数为0.1%,PES超滤膜在PAM溶液中的浸泡时间为4~6h,真空抽滤时,TiO2/SiO2悬浮液的质量分数0.005%。
其中,相转换时间为24h。
其中,将混合液A和混合液B持续搅拌的时间为60~80min,高温下反应的反应温度为180℃,反应时间为10h,反应后煅烧的温度为550℃,煅烧时间为2h。
上述负载有TiO2/SiO2的PES超滤膜在分离过滤溶液中大分子有机污染物方面的应用。
其中,所述大分子有机污染物为腐殖酸。
相比于现有技术,本发明的技术方案所具有的有益效果为:
本发明负载有TiO2/SiO2的PES超滤膜由于膜表面具有到TiO2/SiO2纳米颗粒,因此PES超滤膜的水接触角变小,膜的亲水性增加有利于减缓膜污染,增加膜通量;在紫外光照射下,膜表面的TiO2/SiO2纳米颗粒能够降解PES超滤膜表面的污染物,从而进一步减缓膜污染,增加膜通量;本发明负载有TiO2/SiO2的PES超滤膜对水体中的腐殖酸有机污染物具有良好的分离过滤和降解效果。
附图说明
图1为本发明负载有TiO2/SiO2的PES超滤膜的工艺流程图;
图2为本发明负载有TiO2/SiO2的PES超滤膜进行腐殖酸溶液膜通量和腐殖酸溶液截留率的试验装置图;
图3为本发明TiO2/SiO2的电镜图;
图4为本发明TiO2/SiO2的FT-IR图;
图5为本发明TiO2/SiO2的XRD图;
图6为本发明负载有TiO2/SiO2的PES超滤膜表面的电镜图;
图7为本发明负载有TiO2/SiO2的PES超滤膜横截面的电镜图。
具体实施方式
以下结合附图对本发明的技术方案做进一步说明,但是本发明要求保护的范围并不局限于此。
实施例1
本发明负载有TiO2/SiO2的PES超滤膜的制备方法,具体包括如下步骤:
步骤1,制备PES超滤膜:将8g聚醚砜和1g聚乙烯吡咯烷酮加入到43.5mL N,N-二甲基乙酰胺溶剂中,室温下密封搅拌24h,得到铸膜液;将铸膜液置于室温下脱气6h,然后将大约15mL的铸膜液倒在玻璃板上,用刮膜刀在玻璃板上以0.5cm/s匀速刮膜;将涂覆有铸膜液的玻璃板平整放入去离子水中进行相的转换,经过24h后得到PES超滤膜;
步骤2:制备TiO2/SiO2纳米颗粒:将17ml钛酸四丁酯、50ml乙醇和5mL乙酰丙酮混合,搅拌1h得到混合液A;将2.25mL正硅酸乙酯、10mL去离子水、20mL氨水和20mL无水乙醇混合,搅拌1h得到混合液B;将混合液A和混合液B混合,持续搅拌1h得到混合液C,将混合液C置于反应釜中,于180度下反应10h,将得到的产物研磨,研磨后用无水乙醇和去离子水离心洗涤2次,将洗涤后的产物于550度管式炉中煅烧2h,得到TiO2/SiO2纳米颗粒;TiO2/SiO2纳米颗粒的粒径为7nm;
步骤3,将步骤1制得的PES超滤膜浸泡在质量分数为0.1%的PAM溶液中4~6h,将步骤2制得的TiO2/SiO2纳米颗粒配制成质量分数为0.005%的悬浮液;通过真空抽滤将TiO2/SiO2纳米颗粒负载于PES超滤膜表面,得到膜表面负载有TiO2/SiO2的PES超滤膜。
对实施例1制得的负载有TiO2/SiO2的PES超滤膜用图2所示的实验装置进行腐殖酸污染物膜通量以及腐殖酸污染物分离效果的测试试验:
取初始浓度为10mg/L的腐殖酸溶液1L,对实施例1制得的负载有TiO2/SiO2的PES超滤膜和PES超滤膜(步骤1制得的PES超滤膜)在图2所示实验装置中分别进行腐殖酸溶液膜通量和腐殖酸溶液截留率的测试试验,其中,PES超滤膜的直径为5cm,真空泵操作压力为0.1MPa,在有光照和无光照情况下分别测试,每次测试时间为60min。腐殖酸溶液膜通量计算公式为其中J1为腐殖酸溶液的膜通量,单位为L·m-2·h-1,Q1为腐殖酸容量过膜水体积,单位为m3;腐殖酸溶液截留率为其中Cp为渗滤液浓度,Cf为腐殖酸溶液浓度(随时间变化),腐殖酸浓度用分光光度计测量。测试实验结果见表1和表2。
表1为实施例1制得的负载有TiO2/SiO2的PES超滤膜和PES超滤膜对腐殖酸膜通量在有无光照条件下的对比:
试验60min后膜通量(L·m<sup>-2</sup>·h<sup>-1</sup>) | |
实施例1(无光照) | 191 |
实施例1(紫外光) | 291 |
PES超滤膜(无光照) | 102 |
PES超滤膜(紫外光) | 108 |
表2为实施例1制得的负载有TiO2/SiO2的PES超滤膜和PES超滤膜对腐殖酸溶液截留率在有无光照条件下的对比:
截留率R% | |
实施例1(无光照) | 98 |
实施例1(紫外光) | 95 |
PES超滤膜(无光照) | 90 |
PES超滤膜(紫外光) | 91 |
由表1可知,在紫外光下运行60min后,负载有TiO2/SiO2的PES超滤膜对腐殖酸有机污染物溶液的膜通量高于无光照下的膜通量,分别为291L·m-2·h-1和191L·m-2·h-1。这是因为在紫外光照情况下,激发膜表面的TiO2/SiO2纳米材料产生电子和空穴,从而产生强氧化自由基,导致膜表面的污染物发生了光降解,使膜污染有了一定的缓解,从而腐殖酸有机污染物溶液膜通量有所上升。本发明负载有TiO2/SiO2的PES超滤膜将膜分离与光催化材料耦合,可以从多个方面有效减缓膜污染问题(TiO2/SiO2纳米材料一方面可增大PES超滤膜的亲水性能,另一方面光催化材料的掺杂能够降解沉积在PES超滤膜表面的污染物),从而增加膜通量。
由表2可知,在紫外光照射情况下,负载有TiO2/SiO2的PES超滤膜对污染物的截留率有所降低,截留率高于无光照情况下的截留率,分别为98%,95%。这是由于污染物被光催化材料降解,导致截留率有所升高。另外,在无光照情况下,负载有TiO2/SiO2的PES超滤膜因为TiO2/SiO2的负载使PES超滤膜孔径减小,孔隙率增加,所以负载有TiO2/SiO2的PES超滤膜截留率比没有负载的PES超滤膜高。
如图2所示,该实验装置属于直流式过滤,同时属于光催化膜分离耦合反应器。腐殖酸溶液由蠕动泵吸取至膜组件中,膜组件由真空泵提供跨膜压力,紫外灯位于膜组件上方,提供紫外光照。
如图3所示,TiO2/SiO2纳米颗粒的尺寸比较窄,其粒径分布范围在5nm~15nm内,明亮的球形颗粒为SiO2,较暗的球形颗粒为TiO2。如图4所示,TiO2/SiO2纳米颗粒在波长范围3000cm-1-3500cm-1内和1640cm-1波长位置处的吸收峰分别是O-H和H-O-H的伸缩振动,分别表示是表面羟基和吸附水分子;在1060cm-1和930cm-1波长位置处的吸收峰表示Si-O-Si和Ti-O-Si伸缩振动,表明TiO2/SiO2纳米颗粒成功合成。如图5所示,TiO2/SiO2纳米颗粒的晶型全部为锐钛矿相。如图6所示,经过真空抽滤,TiO2/SiO2纳米颗粒负载于PES超滤膜上,如图7所示,负载有TiO2/SiO2的PES超滤膜具有多孔支撑层和致密分离层。
本发明负载有TiO2/SiO2的PES超滤膜由于膜表面具有亲水性,因此超滤膜的水接触角减小,有利于减缓膜污染,进而增加膜通量;另外在紫外光照射下,膜表面的TiO2/SiO2纳米颗粒能够降解PES超滤膜表面沉积的污染物,从而进一步减缓膜污染,增加膜通量。
Claims (10)
1.一种负载有TiO2/SiO2的PES超滤膜,其特征在于:所述PES超滤膜表面负载有一定量的TiO2/SiO2纳米颗粒。
2.权利要求1所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:通过真空抽滤和PAM将TiO2/SiO2纳米颗粒负载于PES超滤膜表面,得到膜表面负载有TiO2/SiO2的PES超滤膜。
3.根据权利要求2所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于,具体包括如下步骤:
步骤1,制备PES超滤膜;
步骤2,制备TiO2/SiO2纳米颗粒;
步骤3,制备负载有TiO2/SiO2的PES超滤膜:将步骤1制得的PES超滤膜浸泡在PAM溶液中,将步骤2制得的TiO2/SiO2纳米颗粒配制成悬浮液,通过真空抽滤将TiO2/SiO2纳米颗粒负载在PES超滤膜表面,得到膜表面负载有TiO2/SiO2的PES超滤膜。
4.根据权利要求3所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:步骤1中,PES超滤膜具体采用如下方式制备得到:将所需量的聚醚砜和聚乙烯吡咯烷酮溶于N,N-二甲基乙酰胺溶剂中,搅拌得到铸膜液;将铸膜液脱气后均匀涂覆于玻璃板表面,将涂覆有铸膜液的玻璃板平整放入水中进行相的转换,静置后得到PES超滤膜。
5.根据权利要求3所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:步骤2中,TiO2/SiO2纳米颗粒具体采用如下方式制备得到:将所需体积比的钛酸四丁酯、乙醇和乙酰丙酮混合,得到混合液A;将一定量的正硅酸乙酯、去离子水、氨水和无水乙醇混合,得到混合液B;将混合液A和混合液B持续搅拌一段时间,高温下反应后再进行煅烧,得到TiO2/SiO2纳米颗粒。
6.根据权利要求3所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:步骤3中,所述PAM溶液的质量分数为0.1%,PES超滤膜的浸泡时间为4~6h,真空抽滤时,TiO2/SiO2悬浮液的质量分数0.005%。
7.根据权利要求4所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:相转换时间为24h。
8.根据权利要求5所述的负载有TiO2/SiO2的PES超滤膜的制备方法,其特征在于:将混合液A和混合液B持续搅拌的时间为60~80min,高温下反应的反应温度为180℃,反应时间为10h,反应后煅烧的温度为550℃,煅烧时间为2h。
9.权利要求1所述的负载有TiO2/SiO2的PES超滤膜在分离过滤和降解溶液中大分子有机污染物方面的应用。
10.根据权利要求9所述的负载有TiO2/SiO2的PES超滤膜在分离过滤和降解溶液中大分子有机污染物方面的应用,其特征在于:所述大分子有机污染物为腐殖酸。
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