CN114904506A - 一种臭氧催化剂及其制备方法和应用 - Google Patents
一种臭氧催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
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- 238000002360 preparation method Methods 0.000 title abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
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- 239000002808 molecular sieve Substances 0.000 claims description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 25
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 21
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- 229910000420 cerium oxide Inorganic materials 0.000 description 13
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
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- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 229910021536 Zeolite Inorganic materials 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
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- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 superoxide anions Chemical class 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明公开了一种臭氧催化剂,其比表面积为80~120cm2/g,平均孔径为2~10nm。同时还公开了一种臭氧催化剂的制备方法和一种臭氧催化剂在水处理领域的应用。本发明改进了依赖载体修饰提高单位金属氧化物催化活性位点暴露量的覆载型催化剂的制备方法,制得的催化剂纯度高、结晶好、介孔结构、比表面积大,催化臭氧氧化活性高,能够高效的催化降解水中难降解的有机污染物。
Description
技术领域
本发明涉及一种催化剂,具体涉及一种臭氧催化剂及其制备方法和应用,属于臭氧催化剂技术领域。
背景技术
催化臭氧氧化技术是一种高效、清洁的高级氧化技术,能快速地杀灭病菌、降解有机污染物,在水处理领域应用前景广泛。该技术利用臭氧催化剂催化臭氧产生强氧化性的活性氧物种,如羟基自由基、超氧负离子等,消杀病菌,降解甚至矿化有机污染物。臭氧催化剂按照作用形态分为均相臭氧催化剂和异相臭氧催化剂两种,均相催化剂以离子态溶于水,催化活性高,但因不易回收且易产生二次污染,使用较少。异相催化剂以固态形式存在,易回收、无二次污染,是臭氧催化剂的市场推广的方向。如何提高异相催化剂催化活性是目前亟待解决的问题。
CN113426451A公开了一种微米型臭氧催化剂的制备方法。其所述微米型臭氧催化剂包括凹凸棒载体的预处理、Fe和Ce盐溶液的浸渍,活性组分焙烧、催化剂筛分、洗涤烘干等步骤。该发明克服了毫米型臭氧催化剂催化效率低,纳米型臭氧催化剂回收成本高的难题,解决了均相臭氧催化剂重复利用难的问题。
CN113289606A公开了一种臭氧催化剂及其制备方法。其所述臭氧催化剂至少包括活性组分和载体,活性组分包括镧系金属氧化物,载体为SiO2。臭氧催化剂比表面积≥200m2/g,有机物去除率更高;粒径更大,不易产生板结;使用寿命长,10年内不需更换。
CN113856691A公开了一种臭氧催化剂及其制备方法。其所述臭氧催化剂包括载体和覆载于所述载体的活性组分,载体为颗粒状氧化铝,活性组分包括第一金属元素的氧化物和第二金属元素的氧化物,第一金属元素为铈,第二金属元素为铁、锰、铜、镍、锌、钛中的至少一种。
CN113976118A公开了一种臭氧催化剂及其制备方法。其所述臭氧催化剂的制备方法包括:将催化剂活性组分、沸石和固化剂混合造粒,再进行养护。其中,催化剂活性组分、固化剂和沸石的质量比为1:(0.2~10):(0.2~5);催化剂活性组分选自过渡金属羟基氧化物、金属氧化物和金属氢氧化物中的至少一种;固化剂的主要成分为硅酸盐。该方法避免了采用高温烧结的工艺,最大程度上避免了对催化剂活性成分的晶相结构产生破坏,保证了催化剂颗粒能充分发挥其催化活性,提升对有机废水处理的处理效果。
上述方案均充分利用碳、硅、铝等等多孔材料的分散性好,比表面积大的特点,以载体覆载的形式提高催化组分的催化活性。然而没有催化性能的载体在催化剂中含量过高,在实际应用中这是一种资源浪费。因此,开发一种不依赖于载体的修饰,金属氧化物自身具有高比表面积、大孔体积等特点的高效催化剂是十分必要的。
发明内容
本发明要解决的技术问题是克服现有技术的上述不足,提供一种臭氧催化剂及其制备方法和应用。
为解决上述问题,本发明采用以下技术方案:一种臭氧催化剂,其比表面积为80~120cm2/g,平均孔径为2~10nm,其为有序介孔金属氧化物。
一种臭氧催化剂的制备方法,包括以下步骤:
(1)、将金属离子源加入到介孔分子筛与溶剂的悬浊液中,金属离子源与介孔分子筛与溶剂的悬浊液混合的同时进行搅拌,搅拌速度为150~600r/min,搅拌时间为2~6小时,将混匀的悬浊液静置6~12h,进行固液分离,将静置液的上清液去除后进行干燥,干燥温度为60~80℃,干燥时间为3~6h,得到前驱体;
(2)、将步骤(1)得到的前驱体煅烧,煅烧的温度为300~600℃,煅烧时间为4~6h,然后进行清洗,将洗后的样品进行干燥,干燥温度为50~60℃,干燥时间为3~6h,干燥后得到有序介孔金属氧化物,即为臭氧催化剂。
以下是本发明对上述方案的进一步优化:在上述步骤(1)中,所述金属离子源为可溶性金属盐中的至少一种。
进一步优化:在上述步骤(1)中,所述介孔分子筛为SBA-15。
进一步优化:在上述步骤(1)中,所述溶剂为去离子水和乙醇的混合液,去离子水和乙醇的混合比为(3~6):1。
进一步优化:在上述步骤(1)中,所述介孔分子筛与溶剂量比为1g:(50~200)mL。
进一步优化:在上述步骤(1)中,所述金属离子源中的金属离子与介孔分子筛的量比为1mol:(100~300)g。
进一步优化:在上述步骤(2)中,所述清洗分为碱洗、水洗、醇洗。
一种臭氧催化剂的应用,用于降解水中有机污染物。
相对于现有技术,本发明的优势在于:
(1)、本发明制得的催化剂纯度高、结晶好、介孔结构且有序,具有大的比表面积,催化臭氧氧化活性高,在水处理领域应用前景广阔;
(2)、本发明制得的催化剂可高效促进臭氧催化降解酚类、抗生素等生物难降解有机污染物;
(3)、本发明制得的催化剂充分发挥金属氧化物自身理化特点,无需覆载即可实现高效催化,节约资源。
下面结合附图和实施例对本发明进一步说明。
附图说明
图1为本发明实施例1制得催化剂的XRD图;
图2为本发明实施例1制得催化剂的SEM图;
图3为本发明实施例1制得催化剂的EDX数据;
图4为本发明实施例1制得催化剂的TEM图;
图5为本发明实施例1制得催化剂的氮气吸附脱附曲线;
图6为本发明实施例1制得催化剂的孔径分布图。
具体实施方式
实施例1,一种臭氧催化剂,其比表面积为80~120cm2/g,平均孔径为2~10nm,其为有序介孔金属氧化物。
同时本发明公开了一种臭氧催化剂的制备方法,包括以下步骤:
(1)、将金属离子源加入到介孔分子筛与溶剂的悬浊液中,金属离子源与介孔分子筛与溶剂的悬浊液混合的同时进行搅拌,搅拌速度为150r/min,搅拌时间为6小时,将混匀的悬浊液静置6h,进行固液分离,将静置液的上清液去除后进行干燥,干燥温度为60℃,干燥时间为3h,得到前驱体;
所述金属离子源为可溶性金属盐中的至少一种,优选地可溶性金属盐为硝酸盐或氯盐,例如,制备氧化铈可选用硝酸铈六水合物或氯化铈七水合物或醋酸铈水合物;制备氧化锰可选用50%硝酸锰溶液或氯化锰;
所述介孔分子筛优选为SBA-15;例如孔径为6-11nm,比表面积为550-600m2/g的SBA-15,所制备臭氧催化剂的微观直径与介孔分子筛的孔径基本相同;
所述溶剂为去离子水和乙醇的混合液,去离子水和乙醇的混合比为(3:1~6:1),例如:37.5mL水/12.5mL乙醇;40mL水/10mL乙醇;41.7mL水/8.3mL乙醇;42.9mL水/7.1mL乙醇,溶剂的用量要确保金属盐完全溶解;
所述介孔分子筛与溶剂量比为1g:(50~200)mL,例如:1gSBA-15/50mL溶剂;0.75gSBA-15/50mL溶剂;0.5gSBA-15/50mL溶剂;0.25gSBA-15/50mL溶剂;
所述金属离子源中的金属离子与介孔分子筛的量比为1mol:(100~300)g,以铈氧化物为例:0.01mol硝酸铈/1gSBA-15;0.005mol硝酸铈/1gSBA-15;0.0033mol硝酸铈/1gSBA-15。
(2)、将步骤(1)得到的前驱体煅烧,煅烧的温度为300℃,煅烧时间为4h,然后进行清洗,将洗后的样品进行干燥,干燥温度为50℃,干燥时间为3h,干燥后得到有序介孔金属氧化物,即为臭氧催化剂;
所述清洗分为碱洗、水洗、醇洗,例如:使用2mol/L的NaOH溶液润洗烧制样品3次,每次使用NaOH溶液体积至少为烧制样品的2~3倍,完全去除SBA-15;然后用去离子水洗至清洗液pH=7,完全去除清洗液;再用体积为烧制样品的2~3倍的无水乙醇清洗,充分净化烧制样品。
实施例2,一种臭氧催化剂的制备方法,包括以下步骤:
(1)、将金属离子源加入到介孔分子筛与溶剂的悬浊液中,金属离子源与介孔分子筛与溶剂的悬浊液混合的同时进行搅拌,搅拌速度为400r/min,搅拌时间为4小时,将混匀的悬浊液静置9h,进行固液分离,将静置液的上清液去除后进行干燥,干燥温度为70℃,干燥时间为4.5h,得到前驱体;
所述金属离子源为可溶性金属盐中的至少一种,优选地可溶性金属盐为硝酸盐或氯盐,例如,制备氧化铈可选用硝酸铈六水合物或氯化铈七水合物或醋酸铈水合物;制备氧化锰可选用50%硝酸锰溶液或氯化锰;
所述介孔分子筛优选为SBA-15;例如孔径为6-11nm,比表面积为550-600m2/g的SBA-15,所制备臭氧催化剂的微观直径与介孔分子筛的孔径基本相同;
所述溶剂为去离子水和乙醇的混合液,去离子水和乙醇的混合比为(3:1~6:1),例如:37.5mL水/12.5mL乙醇;40mL水/10mL乙醇;41.7mL水/8.3mL乙醇;42.9mL水/7.1mL乙醇,溶剂的用量要确保金属盐完全溶解;
所述介孔分子筛与溶剂量比为1g:(50~200)mL,例如:1gSBA-15/50mL溶剂;0.75gSBA-15/50mL溶剂;0.5gSBA-15/50mL溶剂;0.25gSBA-15/50mL溶剂;
所述金属离子源中的金属离子与介孔分子筛的量比为1mol:(100~300)g,以铈氧化物为例:0.01mol硝酸铈/1gSBA-15;0.005mol硝酸铈/1gSBA-15;0.0033mol硝酸铈/1gSBA-15。
(2)、将步骤(1)得到的前驱体煅烧,煅烧的温度为450℃,煅烧时间为5h,然后进行清洗,将洗后的样品进行干燥,干燥温度为55℃,干燥时间为4.5h,干燥后得到有序介孔金属氧化物,即为臭氧催化剂;
所述清洗分为碱洗、水洗、醇洗,例如:使用2mol/L的NaOH溶液润洗烧制样品3次,每次使用NaOH溶液体积至少为烧制样品的2~3倍,完全去除SBA-15;然后用去离子水洗至清洗液pH=7,完全去除清洗液;再用体积为烧制样品的2~3倍的无水乙醇清洗,充分净化烧制样品。
实施例3,一种臭氧催化剂的制备方法,包括以下步骤:
(1)、将金属离子源加入到介孔分子筛与溶剂的悬浊液中,金属离子源与介孔分子筛与溶剂的悬浊液混合的同时进行搅拌,搅拌速度为600r/min,搅拌时间为2小时,将混匀的悬浊液静置12h,进行固液分离,将静置液的上清液去除后进行干燥,干燥温度为80℃,干燥时间为6h,得到前驱体;
所述金属离子源为可溶性金属盐中的至少一种,优选地可溶性金属盐为硝酸盐或氯盐,例如,制备氧化铈可选用硝酸铈六水合物或氯化铈七水合物或醋酸铈水合物;制备氧化锰可选用50%硝酸锰溶液或氯化锰;
所述介孔分子筛优选为SBA-15;例如孔径为6-11nm,比表面积为550-600m2/g的SBA-15,所制备臭氧催化剂的微观直径与介孔分子筛的孔径基本相同;
所述溶剂为去离子水和乙醇的混合液,去离子水和乙醇的混合比为(3:1~6:1),例如:37.5mL水/12.5mL乙醇;40mL水/10mL乙醇;41.7mL水/8.3mL乙醇;42.9mL水/7.1mL乙醇,溶剂的用量要确保金属盐完全溶解;
所述介孔分子筛与溶剂量比为1g:(50~200)mL,例如:1gSBA-15/50mL溶剂;0.75gSBA-15/50mL溶剂;0.5gSBA-15/50mL溶剂;0.25gSBA-15/50mL溶剂;
所述金属离子源中的金属离子与介孔分子筛的量比为1mol:(100~300)g,以铈氧化物为例:0.01mol硝酸铈/1gSBA-15;0.005mol硝酸铈/1gSBA-15;0.0033mol硝酸铈/1gSBA-15。
(2)、将步骤(1)得到的前驱体煅烧,煅烧的温度为600℃,煅烧时间为6h,然后进行清洗,将洗后的样品进行干燥,干燥温度为60℃,干燥时间为6h,干燥后得到有序介孔金属氧化物,即为臭氧催化剂;
所述清洗分为碱洗、水洗、醇洗,例如:使用2mol/L的NaOH溶液润洗烧制样品3次,每次使用NaOH溶液体积至少为烧制样品的2~3倍,完全去除SBA-15;然后用去离子水洗至清洗液pH=7,完全去除清洗液;再用体积为烧制样品的2~3倍的无水乙醇清洗,充分净化烧制样品。
下面列举两个案例进行介绍:
案例1:铈氧化物的制备:配置无水乙醇和超纯水体积比1:6的混合液35mL;将1.5gSBA-15和4.34gCe(NO3)3•6H2O同时加入到乙醇水混合液中,在室温下持续搅拌5h,搅拌速度为400r/min;将搅拌后的悬浊液静置10h,去除上清液,得到白色泥状物;将白色泥状物在80℃下烘干,干燥时间为3h,得到白色粉末;将白色粉末转移至坩埚中煅烧,煅烧温度为300℃,煅烧时间为4h,自然冷却得到淡黄色粉末;将淡黄色粉末用100mL的2mol/LNaOH浸洗3次,每次浸润0.5h,得到淡黄色泥状物;将淡黄色泥状物用去离子水反复清洗至清洗液PH=7,再用20mL乙醇清洗3次,在60℃下干燥1h 制得淡黄色的铈氧化物。
所述催化剂的XRD图如图1所示,可以看出,所述催化剂结晶度高,平均晶粒尺寸为10nm。
所述催化剂的SEM图如图2所示,可以看出,所述催化剂分散性好。
所述催化剂的EDX数据如图3所示,可以看出,所述催化剂纯度高,铈氧化物质量比在99%以上。
所述催化剂的TEM图如图4所示,可以看出,所述催化剂微观孔径有序。
所述催化剂的氮气吸附脱附曲线如图5所示,可以看出,所述催化剂结构为介孔,比表面积为95m2/g。
所述催化剂的孔径分布图如图6所示,可以看出,所述催化剂的平均孔径4nm。
应用实施例:铈氧化物催化臭氧氧化氟喹诺酮类抗生素诺氟沙星;反应在体积为600mL的长颈玻璃容器中进行,配置浓度为20mg/L诺氟沙星溶液500mL,加入铈氧化物使其浓度为20mg/L,持续搅拌30min,将臭氧持续通入诺氟沙星溶液中,臭氧浓度为20mg/L,流速为0.2L/min,通气时间为30min,在上述条件下,诺氟沙星的矿化率为45%。
对比实施例:商业铈氧化物催化臭氧氧化氟喹诺酮类抗生素诺氟沙星;反应在体积为600mL的长颈玻璃容器中进行,配置浓度为20mg/L诺氟沙星溶液500mL,加入商业铈氧化物使其浓度为20mg/L,持续搅拌30min,将臭氧持续通入诺氟沙星溶液中,臭氧浓度为20mg/L,流速为0.2L/min,通气时间为30min,在上述条件下,诺氟沙星的矿化率为35%。
案例2:锰氧化物的制备:配置无水乙醇和超纯水体积比1:3的混合液50mL;将3gSBA-15和4.65mL50%硝酸锰溶液同时加入到乙醇水混合液中,在室温下持续搅拌5h,搅拌速度为400r/min;将搅拌后的悬浊液静置10h,去除上清液,得到白色泥状物;将白色泥状物在80℃下烘干,干燥时间为3h,得到白色粉末;将白色粉末转移至坩埚中煅烧,煅烧温度为400℃,煅烧时间为4h,自然冷却得到淡灰色粉末;将淡灰色粉末用100mL的2mol/LNaOH浸洗3次,每次浸润0.5h,得到淡灰色泥状物;将淡灰色泥状物用去离子水反复清洗至清洗液PH=7,再用20mL乙醇清洗3次,在60℃下干燥1h制得淡灰色的锰氧化物,制得催化剂的比表面积为100m2/g,平均孔径10nm。
应用实施例:锰氧化物催化氧化苯酚;反应在体积为600mL的长颈玻璃容器中进行,配置浓度为20mg/L苯酚溶液500mL,加入锰氧化物使其浓度为20mg/L,持续搅拌30min,将臭氧持续通入苯酚溶液中,臭氧浓度为40mg/L,流速为0.25L/min,通气时间为30min,在上述条件下,苯酚的矿化率为35%。
对比实施例:商业锰氧化物催化氧化苯酚;反应在体积为600mL的长颈玻璃容器中进行,配置浓度为20mg/L苯酚溶液500mL,加入锰氧化物使其浓度为20mg/L,持续搅拌30min,将臭氧持续通入苯酚溶液中,臭氧浓度为40mg/L,流速为0.25L/min,通气时间为30min,在上述条件下,苯酚的矿化率为27%。
综上所述,本发明实施例中所制得的催化剂和空白金属氧化物对比,可以发现本发明实施例中所制得的催化剂能有效催化臭氧氧化降解水中难降解有机污染物,矿化率显著提高;
本发明改进了依赖载体修饰提高单位金属氧化物催化活性位点暴露量的覆载型催化剂的制备方法,制得的催化剂纯度高、结晶好、介孔结构、比表面积大,催化臭氧氧化活性高,能够高效的催化降解水中难降解的有机污染物。
以上仅为本发明的实施例,并不限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种臭氧催化剂,其特征在于:其比表面积为80~120cm2/g,平均孔径为2~10nm,其为有序介孔金属氧化物。
2.一种如权利要求1所述的臭氧催化剂的制备方法,其特征在于:包括以下步骤:
(1)、将金属离子源加入到介孔分子筛与溶剂的悬浊液中,金属离子源与介孔分子筛与溶剂的悬浊液混合的同时进行搅拌,搅拌速度为150~600r/min,搅拌时间为2~6小时,将混匀的悬浊液静置6~12h,进行固液分离,将静置液的上清液去除后进行干燥,干燥温度为60~80℃,干燥时间为3~6h,得到前驱体;
(2)、将步骤(1)得到的前驱体煅烧,煅烧的温度为300~600℃,煅烧时间为4~6h,然后进行清洗,将洗后的样品进行干燥,干燥温度为50~60℃,干燥时间为3~6h,干燥后得到有序介孔金属氧化物,即为臭氧催化剂。
3.根据权利要求2所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(1)中,所述金属离子源为可溶性金属盐中的至少一种。
4.根据权利要求2所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(1)中,所述介孔分子筛为SBA-15。
5.根据权利要求2所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(1)中,所述溶剂为去离子水和乙醇的混合液,去离子水和乙醇的混合比为(3~6):1。
6.根据权利要求2所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(1)中,所述介孔分子筛与溶剂量比为1g:(50~200)mL。
7.根据权利要求6所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(1)中,所述金属离子源中的金属离子与介孔分子筛的量比为1mol:(100~300)g。
8.根据权利要求7所述的一种臭氧催化剂的制备方法,其特征在于:在上述步骤(2)中,所述清洗分为碱洗、水洗、醇洗。
9.一种如权利要求1-8任意一项所述的臭氧催化剂,其特征在于:用于降解水中有机污染物。
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