CN109999827A - 一种钼酸锰包覆的铜网及其应用于油水乳液的分离及水中有机污染物的降解 - Google Patents
一种钼酸锰包覆的铜网及其应用于油水乳液的分离及水中有机污染物的降解 Download PDFInfo
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- CN109999827A CN109999827A CN201910319974.9A CN201910319974A CN109999827A CN 109999827 A CN109999827 A CN 109999827A CN 201910319974 A CN201910319974 A CN 201910319974A CN 109999827 A CN109999827 A CN 109999827A
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- manganese
- copper mesh
- molybdate
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 86
- 239000010949 copper Substances 0.000 title claims abstract description 86
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 44
- 239000011572 manganese Substances 0.000 title claims abstract description 44
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000005253 cladding Methods 0.000 title claims abstract description 36
- 238000000926 separation method Methods 0.000 title claims abstract description 12
- 230000015556 catabolic process Effects 0.000 title claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 150000002696 manganese Chemical class 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 22
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 16
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000011565 manganese chloride Substances 0.000 claims description 16
- 235000002867 manganese chloride Nutrition 0.000 claims description 16
- 229940099607 manganese chloride Drugs 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 12
- 239000001509 sodium citrate Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000006210 lotion Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- OAGSFHDUINSAMQ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium;hydrate Chemical compound O.[Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OAGSFHDUINSAMQ-UHFFFAOYSA-N 0.000 description 1
- 241000207961 Sesamum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- -1 Sodium dialkyl sulfate Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明的目的是提供一种钼酸锰包覆的铜网及其应用于油水乳液的分离及水中有机污染物的降解,通过两步水热法在铜网表面生长大量的纳米钼酸锰,从而制备出多功能性的复合材料,能有效分离油水乳液并降解水中的有机污染物,可重复使用性好,可再重复性好,最主要的是产品可工业化生产,以达到治理水污染的目的。
Description
技术领域
本发明属于功能材料技术领域,具体涉及到一种钼酸锰包覆的铜网作为油水分离材料的制备方法与应用。
背景技术
水和油是人们赖以生存的宝贵资源,然而大量的油排入水中从而形成油水乳液,不仅造成水资源的污染同时造成宝贵的油资源浪费。因此,需要开发一种高效的水处理材料。铜网是一种机械性能好、易得、廉价且无毒的网状材料,应用于诸多领域,但因其润湿性较差,不能直接应用在油水乳液的分离中。
发明内容
本发明的目的是提供一种钼酸锰包覆的铜网的制备方法,通过两步水热法在铜网表面生长大量的纳米钼酸锰,从而制备出多功能性的复合材料,能有效分离油水乳液并降解水中的有机污染物,可重复使用性好,可再重复性好,最主要的是产品可工业化生产,以达到治理水污染的目的。
为了达到上述目的,本发明具体技术方案如下:
钼酸锰包覆的铜网,其制备方法包括以下步骤,将预处理的铜网浸没在锰盐前驱体溶液中,水热反应,得到反应铜网;然后将反应铜网浸没在钼酸钠溶液中,水热反应,得到钼酸锰包覆的铜网;所述锰盐前驱体溶液包括锰盐、碳酸钠、柠檬酸钠。
本发明还公开了钼酸锰包覆的铜网的制备方法,包括以下步骤,将预处理的铜网浸没在锰盐前驱体溶液中,水热反应,得到反应铜网;然后将反应铜网浸没在钼酸钠溶液中,水热反应,得到钼酸锰包覆的铜网;所述锰盐前驱体溶液包括锰盐、碳酸钠、柠檬酸钠。
本发明中,所述锰盐为四水合氯化锰。
本发明还公开了一种氯化锰前驱体溶液,溶液包括氯化锰、碳酸钠、柠檬酸钠。
本发明还公开了一种油水分离的方法,包括以下步骤:
(1)将预处理的铜网浸没在锰盐前驱体溶液中,水热反应,得到反应铜网;然后将反应铜网浸没在钼酸钠溶液中,水热反应,得到钼酸锰包覆的铜网;所述锰盐前驱体溶液包括锰盐、碳酸钠、柠檬酸钠;
(2)将待分离油水导入钼酸锰包覆的铜网中,完成油水分离。
本发明还公开了一种降解水中有机物的方法,包括以下步骤:
(1)将预处理的铜网浸没在锰盐前驱体溶液中,水热反应,得到反应铜网;然后将反应铜网浸没在钼酸钠溶液中,水热反应,得到钼酸锰包覆的铜网;所述锰盐前驱体溶液包括锰盐、碳酸钠、柠檬酸钠;
(2)将钼酸锰包覆的铜网加入含有有机物的水中,光照,完成水中有机物的降解。
上述技术方案中,室温下,在水中溶解锰盐,搅拌后加入柠檬酸钠粉末,搅拌至溶液呈无色透明后再加入碳酸钠粉末,得到锰盐前驱体溶液。
优选的,锰盐、碳酸钠、柠檬酸钠的质量比为2.47∶1.325∶3.68。
上述技术方案中,钼酸钠的物质的量与锰盐的物质的量之比为1∶1。
上述技术方案中,得到反应铜网的水热反应温度为160 ℃,时间为12 h,在此温度下,柠檬酸锰会发生分解,并与碳酸钠反应生成碳酸锰,生长在铜网表面;得到钼酸锰包覆的铜网的水热反应的温度为140℃,时间为12 h,在此温度下,碳酸锰与钼酸钠反应得到钼酸锰。
上述技术方案中,铜网分别用丙酮、乙醇和去离子水超声清洗,得到预处理的铜网;预处理步骤能增强铜网的反应活性,使其更易生长晶体。
本发明以氯化锰为前驱体,配置一定量的氯化锰前驱体溶液;将预处理的铜网浸没在溶液中,在反应釜中进行两步水热反应,最后得到钼酸锰包覆的铜网,用于油水分离。
本发明还公开了氯化锰前驱体溶液在制备上述钼酸锰包覆的铜网中的应用或者上述钼酸锰包覆的铜网在油水分离和/或降解水中有机物中的应用;或者钼酸锰作为半导体光催化剂在油水乳液分离领域或者降解水中有机物中的应用。
本发明中,进行油水分离时,待分离的油水为油水乳液;降解水中有机物时,有机物优选为亚甲基蓝。
本发明中,钼酸锰作为半导体光催化剂,首次在油水乳液分离领域应用,可以用于降解各种有机污染物,并具有优异的性能。
本发明通过水热法两步步合成了钼酸锰包覆的铜网,具有分离乳液和降解有机污染物的功能。这种材料制备简单,原材料易得,分离效果好,循环性好,在工业污水处理和乳液分离方面具有良好的应用前景。
附图说明
图1为修饰前和修饰后的铜网扫描电镜图;
图2为修饰后的铜网的润湿性测试图;
图3为修饰后的铜网的油水乳液分离效果图;
图4为修饰后的铜网的循环测试效果图;
图5为修饰后的铜网的光降解效果图。
具体实施方式
实施例一
氯化锰前驱体溶液的制备,具体步骤如下:
室温下,在100毫升水中溶解2.47克四水合氯化锰固体,搅拌20分钟;向上述溶液中加入3.68克二水合柠檬酸钠粉末,继续搅拌至溶液无色透明,最后加入1.325克碳酸钠,搅拌20分钟,得到氯化锰前驱体溶液。
室温下,在100毫升水中溶解2.62克钼酸钠粉末,搅拌20分钟,得钼酸钠溶液。
铜网分别用丙酮、乙醇和去离子水超声清洗,得到预处理的铜网,SEM图见图1。
水热法的具体操作步骤如下:
将预处理的铜网浸没在氯化锰前驱体溶液中,然后将氯化锰前驱体溶液和铜网转移至150 毫升的不锈钢反应釜中,在160 ℃下反应12小时,反应完后取出铜网用乙醇和去离子水清洗产物两次,得到反应铜网;之后将反应铜网浸没在钼酸钠溶液中,然后将钼酸钠溶液和铜网放入反应釜进行二次反应,在140 ℃下反应12小时,反应完后取出铜网用乙醇和去离子水清洗产物两次,得到钼酸锰包覆的铜网,SEM图见图1。
附图1为修饰前和修饰后的铜网的SEM图,(a)图为修饰前的铜网SEM图,(b)、(c)、(d)图为不同分辨率下的产物SEM图,由图可看出铜网上均匀负载了大量的钼酸锰。
实施例二
钼酸锰包覆的铜网的润湿性测试,附图2为实施例一制备的钼酸锰包覆的铜网在空气中呈现超亲水性,当水滴和油滴接触到铜网表面后,迅速铺展开,接触角为0°。而把铜网浸没在水下时,氯仿在铜网表面聚集成球状,接触角为157°;当铜网置于甲苯中时,水滴同样在表面聚集成球状,接触角为151°。结果表明修饰的铜网具备油水分离所需的润湿性要求,其中,(a)图为水在空气中的接触角,(b)图为甲苯在空气中的接触角,(c)图多种液滴的接触角。
实施例三
乳液分离测试,具体步骤如下:将10毫升甲苯加入到90毫升水中,然后再加入50毫克十二烷基硫酸钠,搅拌2小时,配制乳液;之后使用配制好的乳液进行乳液分离测试。
取实施例一制备的钼酸锰包覆的铜网装入玻璃过滤器中,然后倒入100毫升油水乳液,附图3为油水乳液分离步骤以及效果图,从图上可以看出,将乳白色的油水乳液倒入夹有修饰的铜网的玻璃过滤器后,澄清的水流入玻璃滤瓶中,说明其具有良好的乳液分离效果。
实施例四
分离效率和流量的测试,具体步骤如下:分离效率和渗透通量:使用以下等式计算油/水乳液的分离效率:
R(%)=(1-Cp / Co)×100%
其中R(%)是排油系数,Cp和Co分别是收集的水和油/水乳液的油浓度。纯化水通过紫外可见分光光度法进行分析。通过根据以下等式计算单位时间内的渗透量来确定乳剂的通量:
Flux = V / At
其中A(cm2)是膜的有效过滤表面,V(L/m2h)是渗透物的体积,t(h)是分离时间。每次试验中倒入等量的油水乳液。
图4为实施例一制备的钼酸锰包覆的铜网对水包甲苯乳液的循环分离效果和流量图,可以发现材料在经过多次的循环测试之后依旧保持良好的分离效果。将实施例一中二水合柠檬酸钠的用量调整为1.84克,其余不变,得到的钼酸锰包覆的铜网首次进行油水乳液分离的分离效率在99.3%左右。
实施例五
有机污染物降解测试,具体步骤如下:在1升去离子水中溶解5毫克亚甲基蓝,搅拌均匀,得到浓度为5 ppm的亚甲基蓝溶液,之后使用配制好的溶液进行有机污染物降解测试。
取实施例一制备的钼酸锰包覆的铜网装入烧饼中,然后倒入100毫升亚甲基蓝溶液,搅拌,在紫外光照下进行降解。附图5为亚甲基蓝溶液浓度随光照时间的变化,在120分钟后,溶液中的亚甲基蓝基本降解完全。将实施例一中二水合柠檬酸钠的用量调整为7.2克,其余不变,得到的钼酸锰包覆的铜网在90分钟后,溶液中的亚甲基蓝残留为实施例一钼酸锰包覆的铜网的1.35倍,需要160分钟左右溶液中的亚甲基蓝基本降解完全。
总结
通过以上分析,本发明通过水热法两步合成了钼酸锰包覆的铜网,具有分离乳液和降解有机污染物的功能。这种材料制备简单,原材料易得,分离效果好,循环性好,在工业污水处理和乳液分离方面具有良好的应用前景。
Claims (10)
1.钼酸锰包覆的铜网,其制备方法包括以下步骤,将预处理的铜网浸没在锰盐前驱体溶液中,水热反应,得到反应铜网;然后将反应铜网浸没在钼酸钠溶液中,水热反应,得到钼酸锰包覆的铜网;所述锰盐前驱体溶液包括锰盐、碳酸钠、柠檬酸钠。
2.根据权利要求1所述钼酸锰包覆的铜网,其特征在于,所述锰盐为四水合氯化锰;铜网分别用丙酮、乙醇和去离子水超声清洗,得到预处理的铜网。
3.根据权利要求1所述钼酸锰包覆的铜网,其特征在于,室温下,在水中溶解锰盐,搅拌后加入柠檬酸钠粉末,搅拌至溶液呈无色透明后再加入碳酸钠粉末,得到锰盐前驱体溶液。
4.根据权利要求1所述钼酸锰包覆的铜网,其特征在于,得到反应铜网的水热反应温度为160 ℃,时间为12 h;得到钼酸锰包覆的铜网的水热反应的温度为140℃,时间为12 h。
5.根据权利要求1所述钼酸锰包覆的铜网,其特征在于,锰盐、碳酸钠、柠檬酸钠的质量比为2.47∶1.325∶3.68;钼酸钠的物质的量与锰盐的物质的量之比为1∶1。
6.氯化锰前驱体溶液,包括氯化锰、碳酸钠、柠檬酸钠。
7.根据权利要求6所述氯化锰前驱体溶液,其特征在于,所述氯化锰前驱体溶液的制备方法为,室温下,在水中溶解氯化锰,搅拌后加入二水合柠檬酸钠粉末,搅拌至溶液呈无色透明后再加入碳酸钠粉末,得到氯化锰前驱体溶液。
8.权利要求6所述氯化锰前驱体溶液在制备权利要求1所述钼酸锰包覆的铜网中的应用。
9.权利要求1所述钼酸锰包覆的铜网在油水分离或者降解水中有机物中的应用。
10.钼酸锰作为半导体光催化剂在油水乳液分离或者降解水中有机物中的应用。
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