CN104525115A - 一种碳纳米管复合wo3绿色深度水处理剂的制备方法 - Google Patents
一种碳纳米管复合wo3绿色深度水处理剂的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- -1 CNT compound Chemical class 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
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- 230000021523 carboxylation Effects 0.000 abstract 1
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- 239000002781 deodorant agent Substances 0.000 abstract 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 abstract 1
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Abstract
本发明涉及一种碳纳米管复合WO3绿色深度水处理剂的制备方法,包括:(1)将碳纳米管依次羧基化、氨基化改性、2,4,6-三氟-5-氯嘧啶改性制备反应型碳纳米管;(2)将纳米WO3、稳定剂、模板剂和反应型碳纳米管加入到磷酸盐缓冲液中,搅拌30~60min,形成悬浊液;(3)过滤干燥得产物即可。本发明的成本低廉,制备方法简单,对设备的要求低,可操作性好;本发明的水处理剂可以去除水中高浓度有机污染物,适用于各种废水的深度处理,环保无二次污染,且具有抗菌、除臭、可以吸附其他重金属离子等优点。
Description
技术领域
本发明属于水处理剂领域,特别涉及一种碳纳米管复合WO3绿色深度水处理剂的制备方法。
背景技术
全球仅约10%的水是直接为人类所用。最大的份额,70%用于农业,剩余的20%为工业用。中国的排污约为全球的20%,而它只得到全球的5%的新鲜水。因此,解决污染问题已列入议事日程。在纺织印染、皮革、造纸行业加工过程中,大量使用了污染环境和对人体有害的助剂,这些助剂大多以液体的形态排放而污染环境,生物降解性差,毒性大,游离甲醛含量高,重金属离子的含量超标。其中,印染湿整理更是无可争议地成为水污染大户。从上浆开始到退浆、水洗、练漂、丝光,然后染色印花、可能还需涂层,按此流程每道工序都涉及水洗,而每道工序每千克材料需20L耗水。结果是湿整理过程中每千克原棉的用水量加起来多达200L。当一件标准的男式衬衣定制后在商店橱窗展示时,超过2000L水在生产加工它时被用掉了(布料:纯棉,125g/m)。
目前使用的处理废水的方法主要有:物理分离法、生物降解法、化学分解法,但这些方法都存在一定的局限性,不利于可持续发展。因而,人们开始致力于开发高效、低能耗、适用范围广和有深度氧化能力的污染物清除技术。近年来,很多学者将WO3用于光催化降解水中有机污染物,将WO3负载到碳纳米管上,制备高效的光催化剂成为当前研究的热点。
发明内容
本发明所要解决的技术问题是提供一种碳纳米管复合WO3绿色深度水处理剂的制备方法,该方法操作简单,成本低廉,对设备的要求低;水处理剂适用于各种废水的深度处理,环保无二次污染。
本发明的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,包括:
(1)将碳纳米管在H2SO4和HNO3混合液中室温超声反应30~60min,水洗到中性,室温真空烘干,得到羧基化碳纳米管;然后将羧基化碳纳米管分散到过量二乙烯三胺中,加入2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯,40~50℃反应5~6h,乙醇洗涤,室温真空烘干,得到氨基化碳纳米管;然后将氨基化碳纳米管超声分散到水和丙酮的混合液中,调节pH值为5~6,冰水浴滴加2,4,6-三氟-5-氯嘧啶,调节pH值为6~6.5,20~30℃超声反应24~48h,乙醇洗涤,水洗,室温真空烘干,辐照(在222nm准分子紫外光源下辐照3min)得到反应型碳纳米管;
(2)将纳米WO3、稳定剂、模板剂和步骤(1)中的反应型碳纳米管加入到磷酸盐缓冲液中,搅拌30~60min,形成悬浊液;其中,纳米WO3与反应型碳纳米管的质量比为1:5~1:20;
(3)用碱性溶液调节pH值为5~6,加热至80~100℃回流6~24h并过滤,得到碳纳米管复合WO3绿色深度水处理剂。
所述步骤(1)中的碳纳米管与H2SO4和HNO3混合液的比例为10~20g:4L;其中,H2SO4和HNO3的体积比为1:1~5:1。
所述步骤(1)中的羧基化碳纳米管与2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸的质量比为5~8:0.1~0.6。
所述步骤(1)中的氨基化碳纳米管与水和丙酮的混合液的比例为4~4.5g:1L;其中,水和丙酮的体积比为3:1~5:1。
所述步骤(1)中的氨基化碳纳米管与2,4,6-三氟-5-氯嘧啶的质量比为4~4.5:4~6。
所述步骤(1)中采用碳酸钠溶液调节pH值。
所述步骤(2)中的纳米WO3浓度为0.01~0.2mol/L。
所述步骤(2)中的稳定剂为乙二胺四乙酸二钠、乙二胺四乙酸四钠、葡萄糖酸钠、丁烷四羧酸中的一种;稳定剂浓度为0.01~0.1mol/L。
所述步骤(2)中的模板剂为质量比1:3的三嵌段聚醚P123和三嵌段共聚物F127的混合物;模板剂浓度为0.01~0.1mol/L。
所述步骤(2)中的磷酸盐缓冲液由浓度0.025~0.05mol/L磷酸二氢钠和0.05~0.1mol/L磷酸氢钠组成。
所述步骤(3)中的碱性溶液为浓度0.5mol/L~1.5mol/L的氢氧化钠或氢氧化钾的水溶液。
碳纳米管作为一种多孔物质,具有特殊的层间特性,可在其表面负载纳米WO3微粒,制备成负载型催化剂。这种负载型光催化剂可以提高光催化剂的分散性,利于回收重复利用。
本发明利用碳纳米管的多孔、吸附能力强、与水易分离等特点和纳米WO3的光催化活性结合起来,将纳米WO3成功地负载到碳纳米管上,制备成可以悬浮于废水中而又可以顺利与水分离的高催化活性的可见光光催化材料,并且将其应用于废水的深度处理,可以实现对水中高浓度有机污染物氧化去除,而不是转移到其他地方,是一个环保型的工艺技术。
有益效果
(1)本发明成本低廉,制备方法简单,对设备的要求低,可操作性好;
(2)本发明的水处理剂可以去除水中高浓度有机污染物,适用于各种废水的深度处理,环保无二次污染,且具有抗菌、除臭、可以吸附其他重金属离子等优点;
(3)本发明的水处理剂可以克服现有铋基水处理剂的不足,水处理效果好,可以循环使用。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
(1)将10g碳纳米管在4L体积比为1:1的H2SO4和HNO4混合液中室温超声反应30min,水洗到中性,室温真空烘干48h,得到5g羧基化碳纳米管;然后将上述5g羧基化碳纳米管分散到过量二乙烯三胺中,加入100mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯,40℃反应5h,乙醇洗涤,室温真空烘干48h,得到4g氨基化碳纳米管;最后将4g氨基化碳纳米管超声分散在1L体积比为3:1的水和丙酮的混合液中,用碳酸钠溶液调节pH值为5,冰水浴滴加4g 2,4,6-三氟-5-氯嘧啶,用碳酸钠溶液调节pH值为6,20℃超声反应24h,乙醇洗涤,水洗,室温真空烘干48h,在222nm准分子紫外光源下辐照3min得到反应型碳纳米管;
(2)将纳米WO3、乙二胺四乙酸二钠、质量比为1:3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.025mol/L磷酸二氢钠和0.05mol/L磷酸氢钠组成的缓冲液中,搅拌30min,形成悬浊液;其中纳米WO3的浓度为0.01mol/L、稳定剂的浓度为0.01mol/L、模板剂的浓度为0.05mol/L。
(3)用浓度0.5mol/L的氢氧化钠水溶液调节上述悬浊液的pH值为5,加热80℃下,回流6h,过滤,得反应产物;其中纳米WO3与碳纳米管的质量比为1:5。
实施例2
(1)将10g碳纳米管在4L体积比为3:1的H2SO4和HNO4混合液中室温超声反应45min,水洗到中性,室温真空烘干54h,得到6.5g羧基化碳纳米管;然后将上述5g羧基化碳纳米管分散到过量二乙烯三胺中,加入300mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯,45℃反应5h,乙醇洗涤,室温真空烘干48h,得到4.2g氨基化碳纳米管;最后将4.2g氨基化碳纳米管超声分散在1L体积比为4:1的水和丙酮的混合液中,用碳酸钠溶液调节pH值为5.5,冰水浴滴加5g 2,4,6-三氟-5-氯嘧啶,用碳酸钠溶液调节pH值为6.2,25℃超声反应36h,乙醇洗涤,水洗,室温真空烘干48h,在222nm准分子紫外光源下辐照3min得到反应型碳纳米管;
(2)将纳米WO3、葡萄糖酸钠、质量比为1:3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.03mol/L磷酸二氢钠和0.05mol/L磷酸氢钠组成的缓冲液中,搅拌45min,形成悬浊液;其中纳米WO3的浓度为0.01mol/L、稳定剂的浓度为0.03mol/L、模板剂的浓度为0.07mol/L。
(3)用浓度0.5mol/L的氢氧化钠水溶液调节上述悬浊液的pH值为7,加热90℃下,回流16h,过滤,得反应产物;其中纳米WO3与碳纳米管的质量比为1:15。
实施例3
(1)将10g碳纳米管在4L体积比为5:1的H2SO4和HNO4混合液中室温超声反应60min,水洗到中性,室温真空烘干60h,得到8g羧基化碳纳米管;然后将上述8g羧基化碳纳米管分散到过量二乙烯三胺中,加入600mg 2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯,50℃反应5h,乙醇洗涤,室温真空烘干48h,得到4.5g氨基化碳纳米管;最后将4.5g氨基化碳纳米管超声分散在1L体积比为5:1的水和丙酮的混合液中,用碳酸钠溶液调节pH值为6,冰水浴滴加6g 2,4,6-三氟-5-氯嘧啶,用碳酸钠溶液调节pH值为6.5,30℃超声反应48h,乙醇洗涤,水洗,室温真空烘干48h,在222nm准分子紫外光源下辐照3min得到反应型碳纳米管;
(2)将纳米WO3、丁烷四羧酸、质量比为1:3的三嵌段聚醚P123和三嵌段共聚物F127的混合物和上述步骤(1)中反应型碳纳米管加入到浓度为0.05mol/L磷酸二氢钠和0.1mol/L磷酸氢钠组成的缓冲液中,搅拌60min,形成悬浊液;其中纳米WO3的浓度0.15mol/L、稳定剂的浓度为0.05mol/L、模板剂的浓度为0.1mol/L。
(3)用浓度1.5mol/L的氢氧化钾水溶液调节上述悬浊液的pH值为9,加热100℃下,回流24h,过滤,得反应产物;其中纳米WO3与碳纳米管的质量比为1:20。
以同一时间取样的印染厂的印染废水为处理对象,在废水中分别加入不同浓度的实施例1~3所得的水处理剂,经过6小时日光照射后,水处理剂对印染废水的脱色率如下表所示:
脱色率 | COD去除率 | |
实施例1 | 99.3% | 90.8% |
实施例2 | 99.4% | 91.2% |
实施例3 | 99.5% | 91.9% |
Claims (10)
1.一种碳纳米管复合WO3绿色深度水处理剂的制备方法,包括:
(1)将碳纳米管在H2SO4和HNO3混合液中室温超声反应30~60min,水洗到中性,室温真空烘干,得到羧基化碳纳米管;然后将羧基化碳纳米管分散到过量二乙烯三胺中,加入2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯,40~50℃反应5~6h,乙醇洗涤,室温真空烘干,得到氨基化碳纳米管;然后将氨基化碳纳米管超声分散到水和丙酮的混合液中,调节pH值为5~6,冰水浴滴加2,4,6-三氟-5-氯嘧啶,调节pH值为6~6.5,20~30℃超声反应24~48h,乙醇洗涤,水洗,室温真空烘干,辐照得到反应型碳纳米管;
(2)将纳米WO3、稳定剂、模板剂和步骤(1)中的反应型碳纳米管加入到磷酸盐缓冲液中,搅拌30~60min,形成悬浊液;其中,纳米WO3与反应型碳纳米管的质量比为1:5~1:20;
(3)用碱性溶液调节pH值为5~6,加热回流并过滤,得到碳纳米管复合WO3绿色深度水处理剂。
2.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(1)中的碳纳米管与H2SO4和HNO3混合液的比例为10~20g:4L;其中,H2SO4和HNO3的体积比为1:1~5:1。
3.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(1)中的羧基化碳纳米管与2-(7-偶氮苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸的质量比为5~8:0.1~0.6。
4.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(1)中的氨基化碳纳米管与水和丙酮的混合液的比例为4~4.5g:1L;其中,水和丙酮的体积比为3:1~5:1。
5.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(1)中的氨基化碳纳米管与2,4,6-三氟-5-氯嘧啶的质量比为4~4.5:4~6。
6.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(1)中采用碳酸钠溶液调节pH值。
7.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(2)中的稳定剂为乙二胺四乙酸二钠、乙二胺四乙酸四钠、葡萄糖酸钠、丁烷四羧酸中的一种;稳定剂浓度为0.01~0.1mol/L。
8.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(2)中的模板剂为质量比1:3的三嵌段聚醚P123和三嵌段共聚物F127的混合物;模板剂浓度为0.01~0.1mol/L。
9.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(2)中的磷酸盐缓冲液由浓度0.025~0.05mol/L磷酸二氢钠和0.05~0.1mol/L磷酸氢钠组成。
10.根据权利要求1所述的一种碳纳米管复合WO3绿色深度水处理剂的制备方法,其特征在于:所述步骤(3)中的碱性溶液为浓度0.5mol/L~1.5mol/L的氢氧化钠或氢氧化钾的水溶液。
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