CN111450829B - 催化过硫酸盐降解有机废水的氧化铜纳米催化膜及其制备方法 - Google Patents
催化过硫酸盐降解有机废水的氧化铜纳米催化膜及其制备方法 Download PDFInfo
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 37
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 35
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000002071 nanotube Substances 0.000 claims abstract description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- 238000011068 loading method Methods 0.000 claims description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
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- 238000003980 solgel method Methods 0.000 abstract 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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Abstract
本发明公开了一种催化过硫酸盐降解有机废水的氧化铜纳米催化膜及其制备方法,属于废水处理技术领域。本发明以阳极氧化铝膜(AAO)为模板,利用溶胶‑凝胶法将氧化铜负载在AAO膜的纳米孔道内壁上,形成有序排列的氧化铜圆形纳米管,从而得到氧化铜纳米管阵列催化膜。本发明以过硫酸盐为氧化剂,当通过氧化铜膜时可活化成强氧化性物质,进而实现水体中有机污染物的降解去除。相比较于液相催化反应,纳米催化膜催化体系因纳米限域作用强化了污染物和过硫酸盐向氧化铜催化剂表面的传质扩散,提升了氧化性物质的产生,展现出更高催化效率。
Description
技术领域
本发明属于废水处理技术领域,具体涉及一种催化过硫酸盐降解有机废水的氧化铜纳米催化膜及其制备方法。
背景技术
近年来,随着我国经济的快速发展,工业废水的排放量逐渐增大。主要包括制药行业废水、炼制及化工废水、印染废水、电镀废水等。对于工业废水而言,根据生物降解的难易程度一般分为易生物降解、可生物降解和难生物降解废水。其中难生物降解废水大多含有多环芳烃、卤代烃、杂环类化合物等大分子有机物,这些有机污染物及其代谢产物不仅毒性高而且大多具有持久性和顽固性,其COD浓度较高,可生化性极差,一旦进入水体会在不断地积累和富集中对水环境造成严重的污染,最终危害人类的生命健康,而传统的物化和生化方法都难以满足此类有机废水的处理。
近年来,以硫酸根自由基为基础的高级氧化工艺因其较强的氧化能力而成为研究热点。硫酸根自由基可以通过紫外光、加热和过渡金属介导的过硫酸盐或过氧单硫酸盐(PMS)的激活产生。在这些工艺中,过渡金属因其成本低、操作简单而倍受关注,包括铜、铁、锰和钴在内的过渡金属已被证明能有效地激活过硫酸盐。据报道,虽然Co2+、Ru3+、Fe2+等金属离子具有较高的催化活性,由于均相催化剂存在pH依赖性高、金属离子浓度高、催化剂回收困难,含过渡金属的多相催化剂被广泛用于激活过硫酸盐。而采用活性炭、活性炭负载金属及金属氧化物催化氧化处理废水的方法优势明显。铜系催化剂是目前工业上常用催化剂之一,铜元素被广泛用于催化剂的制备。与其他金属氧化物相比,氧化铜成本低、可用性好、毒性低,是激活过硫酸盐的有力选择。但由于金属催化剂的天然聚集倾向,负载型金属催化剂暴露的金属位点数量较少,传质效率慢,降低了催化反应中的催化活性。
发明内容
针对现有技术中存在的不足,本发明的目的在于提供了一种催化过硫酸盐降解有机废水的氧化铜纳米催化膜及其制备方法。
为了达到上述目的,本发明采用如下技术方案:
一种氧化铜纳米催化膜,是氧化铜负载在阳极氧化铝膜的纳米孔道内壁上,形成有序排列的氧化铜圆形纳米管,所得到的一种氧化铜纳米管阵列催化膜。
在上述方案的基础上,所述阳极氧化铝膜的孔径为15~300nm。
上述氧化铜纳米催化膜的制备方法,步骤如下:
将铜的可溶性前驱体化合物与表面活性剂溶于n-甲基吡咯烷酮溶剂中,在65℃超声处理,直至溶解得到澄清均匀的溶胶;再将阳极氧化铝膜浸入到溶胶中,在100~300℃下反应1~6h,自然冷却至室温,取出反应后的阳极氧化铝膜,冲洗、烘干后于300~500℃氛围下煅烧1~3h,得到氧化铜纳米催化膜。
在上述方案的基础上,所述铜的可溶性前驱体化合物为铜的可溶性盐;优选为铜的硝酸盐、硫酸盐或醋酸盐。
在上述方案的基础上,所述溶胶中铜离子的浓度为0.1~1.0mol/L。
在上述方案的基础上,所述表面活性剂为十六烷基三甲基溴化铵、十八烷基二甲基苄基氯化铵中的一种。
在上述方案的基础上,所述表面活性剂在溶胶中的浓度为0.01~0.5mol/L。
上述方法制备的氧化铜纳米催化膜在催化过硫酸盐降解有机废水中的应用。
一种利用氧化铜纳米催化膜催化过硫酸盐降解有机废水的方法,是将废水溶液与过硫酸盐混合,泵入装有上述方法制备的氧化铜纳米催化膜的过滤器进行过滤。
在上述方案的基础上,所述混合液泵入过滤器的流速为0.1~10mL/min,废水溶液中有机污染物浓度为5~100mg/L;过硫酸盐可为钠盐,铵盐以及钾盐中的一种,过硫酸盐的浓度为1~50mmol/L。
本发明的原理:
本发明中利用氧化铜纳米催化膜的限域效应催化过硫酸盐降解污染物。在纳米限域作用下强化了污染物和过硫酸盐通过纳米孔道时向氧化铜催化剂表面的传质扩散,可迅速活化产生硫酸根自由基和羟基自由基,实现污染物的快速降解。相比较于普通的液相反应,展现出更高催化效率。此外,本发明所构建的反应体系具有绿色、高效、适用pH范围广等优点。
本发明所具有的优点在于:
(1)本发明制备的纳米催化膜孔径分布均匀,提供了规则的纳米空隙,防止了负载催化剂的聚集,提供更大的比表面积和更多的活性位点。
(2)本发明制备的双通道纳米阵列膜与其他具有盲孔或盲角的多孔结构相比较,孔道内的传质均匀且充分,极大的提高了传质效率,强化污染物向膜壁的传质与扩散,因此可以强化污染物的氧化降解。
(3)本发明所制备的材料不会产生二次污染,同时不需要提供光超声等额外能量。本发明在常温常压下即可进行,适用pH范围广,催化活性高。
具体实施方式
在本发明中所使用的术语,除非有另外说明,一般具有本领域普通技术人员通常理解的含义。
下面结合具体实施例,并参照数据进一步详细的描述本发明。以下实施例只是为了举例说明本发明,而非以任何方式限制本发明的范围。
实施例1
氧化铜纳米催化膜的制备:将1.28g醋酸铜与0.87g十六烷基三甲基溴化铵溶于20mL n-甲基吡咯烷酮溶剂中,在65℃超声处理,直至溶解得到澄清均匀的溶胶,将反应液转移到聚四氟乙烯高压釜中,再将AAO(20-30nm)膜浸入到溶胶中,在180℃下反应4小时,待反应釜自然冷却至室温,取出反应后的AAO膜,用去离子水冲洗、烘干后于400℃下煅烧2h,得到氧化铜纳米催化膜。
在罗丹明B浓度为30mg/L的废水溶液中加入过硫酸钠,使其在混合溶液中的浓度为1.0mmol/L,在终端过滤模式下,用蠕动泵将混合溶液泵入装有氧化铜纳米催化膜的过滤器,流速为0.5mL/min。一次过滤后,停留时间为1.2s,该污染物的去除率达到95%以上。
实施例2
氧化铜的纳米催化膜制备方法同实施例1。所不同的是加入1.6g醋酸铜,1.09g十六烷基三甲基溴化铵。
在甲基橙浓度为30mg/L的废水溶液中加入过硫酸氢钾,使其在混合溶液中的浓度为5.0mmol/L,在终端过滤模式下,用蠕动泵将混合溶液泵入装有氧化铜纳米催化膜的过滤器,流速为0.8mL/min,一次过滤后,停留时间为1s,该污染物的去除率达到92%以上。
实施例3
氧化铜纳米催化膜的制备方法同实施例1,所不同的是AAO膜的孔径为50-60nm。
在罗丹明B浓度为20mg/L的废水溶液中加入过硫酸钠,使其在混合溶液中的浓度为1.0mmol/L,在终端过滤模式下,用蠕动泵将混合溶液泵入装有氧化铜纳米催化膜的过滤器,流速为0.5mL/min,一次过滤后,停留时间为1.2s,该污染物的去除率达到93%以上。
对比例1
在罗丹明B浓度为30mg/L的废水溶液中加入过硫酸钠,使其在混合溶液中的浓度为1.0mmol/L,在终端过滤模式下,用蠕动泵将混合溶液泵入不含有AAO膜的过滤器,流速为1mL/min,一次过滤后,计算反应时间为0.5s,该污染物的去除率为3%。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (2)
1.一种氧化铜纳米催化膜的制备方法,其特征在于,步骤如下:
将铜的可溶性前驱体化合物与表面活性剂溶于n-甲基吡咯烷酮溶剂中,在65℃超声处理,直至溶解得到澄清均匀的溶胶;再将阳极氧化铝膜浸入到溶胶中,在100~300℃下反应1~6h,自然冷却至室温,取出反应后的阳极氧化铝膜,冲洗、烘干后于300~500℃氛围下煅烧1~3h,得到氧化铜纳米催化膜;
所述氧化铜纳米催化膜是氧化铜负载在阳极氧化铝膜的纳米孔道内壁上,形成有序排列的氧化铜圆形纳米管,所得到的一种氧化铜纳米管阵列催化膜;
所述铜的可溶性前驱体化合物为铜的硝酸盐、硫酸盐或醋酸盐;
所述溶胶中铜的浓度为0.1~ 1.0mol/L;
所述表面活性剂为十六烷基三甲基溴化铵、十八烷基二甲基苄基氯化铵中的一种;
所述表面活性剂在溶胶中的浓度为0.01~0.5 mol/L。
2.一种利用氧化铜纳米催化膜催化过硫酸盐降解有机废水的方法,其特征在于,是将废水溶液与过硫酸盐混合,泵入装有权利要求1所述方法制备的氧化铜纳米催化膜的过滤器进行过滤;
所述混合液泵入过滤器的流速为0.1~10mL/min,废水溶液中有机污染物浓度为5~100mg/L;过硫酸盐为钠盐,铵盐以及钾盐中的一种,过硫酸盐的浓度为1~50mmol/L。
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