CN108927167A - 一种纳米湿式氧化催化剂的制备方法 - Google Patents
一种纳米湿式氧化催化剂的制备方法 Download PDFInfo
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- CN108927167A CN108927167A CN201710364999.1A CN201710364999A CN108927167A CN 108927167 A CN108927167 A CN 108927167A CN 201710364999 A CN201710364999 A CN 201710364999A CN 108927167 A CN108927167 A CN 108927167A
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- oxidizing catalyst
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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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
- B01J23/889—Manganese, technetium or rhenium
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
本发明公开了一种纳米湿式氧化催化剂的制备方法,包括(1)将活性氧化铝打浆;(2)将铜源前驱体溶解形成溶液;(3)将步骤(1)、(2)的物料混合均匀;(4)将步骤(3)形成的物料调节pH值至碱性,沉淀,过滤、干燥、焙烧,形成粉状物;(5)将锰源前驱体形成的溶液与步骤(4)的粉状物混合成浆状,搅拌后,加造孔剂,二次搅拌,密封静置后挤压成三叶草状,干燥后涂敷纳米级氧化铈,焙烧后得到湿式氧化催化剂。本发明制备的湿式氧化催化剂用于废碱液,具有性能稳定、催化效率高等特点。
Description
技术领域
本发明涉及一种复合金属氧化物催化剂的制备方法,具体是一种用于湿式氧化催化剂的制备方法。
背景技术
湿式(空气)氧化(wet air oxidation,WAO)处理高浓度难降解有机废水,通常需要较高的温度和压力(200~3l5℃,2~21MPa)以及较长的停留时间,其反应条件非常苛刻。催化湿式氧化catalytic wetair oxidation,CWAO)在保持处理效果的条件下,可降低反应温度和压力,极大地推动湿式氧化的发展和应用。因此,研制具有较高活性和稳定性并适用于CWAO的催化剂,成为目前研究的重点和难点。炼油或乙烯废碱液(碱渣)中除含有不同浓度的游离碱(NaOH),还含有大量高浓的Na2S、有机酸性物质(以钠盐形式存在,如杂酚、环烷酸、硫醇、硫酚等)、硫醚以及噻吩等有机硫化物,呈恶臭、有毒,COD含量高达10000~150000mg/L,在催化湿式氧化过程中易发生催化剂中毒、金属活性成分流失以及COD去除效率低等问题,成为研究的难点。
CN1358567公开“一种用于催化湿式氧化处理工业废水的铜基催化剂及其制备方法”,一种用于催化湿式氧化处理工业废水的铜基催化剂的制备及应用。催化剂的主要成分为铜、锌、镍、镁、铝、铬、铁和一部分稀土金属的氧化物,其中以氧化物的含量来计算:CuO为20~55%;ZnO、NiO或MgO为20~55%;Cr2O3、Al2O3或Fe2O3为10~40%;稀土金属氧化物为0~10%。该催化剂由含有各种金属的盐共沉淀得到类水滑石结构的催化剂前驱体,并焙烧所得。该催化剂经过一次共沉淀、焙烧而成,能有效处理含酚、磺基水杨酸、H-酸和表面活性剂等有毒难降解的工业有机废水,铜流失量较低,但难以适应处理含有多种有毒、有害物质废水的需要,尤其是炼油或乙烯废碱液的处理中COD去除效率低。
CN1669643公开了一种稀土复合氧化物催化剂,其为固体粉末状,组分为ZrO2和CeO的复合氧化物,Zr和Ce的摩尔比为1∶1~1∶11。本发明还公开了所述催化剂的制备方法:将锆盐和铈盐溶液混合,采用一步沉淀法,一次干燥、焙烧得到催化剂。本发明所制备的催化剂仅对于含高浓度难降解的小分子有机酸废水有良好的活性和较高的稳定性,难以适应处理含有多种有毒、有害物质废水的需要,尤其是炼油或乙烯废碱液的处理。
CN104667934公开“一种催化湿式氧化催化剂的制备方法”,采用过度和稀土金属为活性金属组分,浸渍于载体上,采用一次浸渍和一次焙烧后,实现催化剂的制备。
综上所述,湿式氧化催化剂的制备均采用一次沉淀,一次焙烧而成,在催化湿式氧化过程中对废水中的COD、有机物有一定的去除作用,但是,目前的湿式氧化催化剂对废碱液处理效果过程中,催化剂易中毒、COD去除效率低、活性组分铜易于流失,影响催化剂的性能。
发明内容
本发明提供一种纳米湿式氧化催化剂的制备方法,使制备的催化剂既可以抵抗在多种污染物共存体系中的中毒、失活,有效成分流失,又提高催化剂强度,改善网状微孔,提高催化剂性能。
本发明一种纳米湿式氧化催化剂的制备方法,包括如下步骤:
(1)将活性氧化铝打浆;
(2)将铜源前驱体溶解形成溶液;
(3)将步骤(1)、(2)的物料混合均匀;
(4)将步骤(3)形成的物料调节pH值至碱性,沉淀,过滤、干燥、焙烧,形成粉状物;
(5)将锰源前驱体形成的溶液与步骤(4)的粉状物混合成浆状,搅拌后,加造孔剂,二次搅拌,密封静置后挤压成型,干燥后涂敷纳米级氧化铈,焙烧后得到湿式氧化催化剂,其中以重量百分比计,含活性氧化铝30~75%,含氧化铜10~30%,含氧化铈5%~20%,含氧化锰为10~30%。
本发明方法中,采用活性氧化铝,其内部具有丰富的纳米级微孔,更有利于活性物质的分散和吸附。活性氧化铝与离子态的铜混合后,可以促进无定型氧化铜更好地分散、吸附活性氧化铝内部,同时氧化铜与活性氧化铝更加紧密包裹,提高催化剂强度,提高了催化剂比表面积和孔隙率,增加了催化剂内部的活性位,提高催化剂的效率,同时在催化剂制备过程中不需要惰性气体保护,降低了制备成本。
本发明方法中,在催化剂成型后,又在其表面涂敷一层纳米级氧化铈,可显著提高其催化活性。所述氧化铈来源于可溶性的铈盐。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(1)所述的活性氧化铝,优选比表面积为60~200m2/g,孔容0.40~0.80cm3/g。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(1)所述,首先将活性氧化铝打浆,形成含Al2O3为50~600g/L的浆液,含量优选100~500g/L。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(2)所述铜源前驱体为可溶性的铜盐,优选为硝酸铜,对铜源前驱体的溶解,形成溶液以CuO计,含量优选为15~40g/L。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(3)和步骤(5)中混合时间均优选为0.5~3h,所述步骤(5)中搅拌时间优选为10~60min,所述步骤(5)中密封静置时间优选为8~30h。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(4)pH值的调节可采用氨水、氢氧化钠等酸碱调节剂,优选氨水,pH范围8~13,优选8~11。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(5)所述锰源前驱体为可溶性的锰盐,优选为硝酸锰,所述步骤(5)形成物料以MnO计,含量优选为15~40g/L。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(5)所述造孔剂可以是柠檬酸、尿素、三氧乙酸、活性炭、田菁粉中的一种或多种。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(4)和步骤(5)中焙烧温度为400~850℃均优选为500~650℃,焙烧时间不少于1小时,均优选为2~7h。焙烧温度过低,金属氢氧化物不能完全分解转化成有催化活性的氧化物,氧化物晶型不能充分重排,影响催化剂的催化性能;焙烧温度过高,造成氧化物晶型改变,同时出现催化剂过度烧结,也会降低催化剂的催化剂性能。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(3)、(5)中所述的混合方法包括各种机械搅拌、流体混合和超声波混合,其中优选超声波法。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(5)所述催化剂静置后可以挤压成条状、三叶草状或蜂窝状等,优选三叶草状。
本发明纳米湿式氧化催化剂的制备方法,其中步骤(5)所述催化剂挤压成型后,干燥温度为60~180℃,优选70~130℃,然后在其表面涂敷纳米级氧化铈。
本发明方法制备的纳米湿式氧化催化剂,以重量百分比计,其中含活性氧化铝30~80%,含氧化铜10~30%,含氧化铈5%~20%,含氧化锰为10~30%;比表面为60~130m2/g,孔容0.30~0.70cm3/g,优选含活性氧化铝40~75%,含氧化铜10~20%,含氧化铈5%~12%,含氧化锰为10~20%;比表面为80~120m2/g,孔容0.40~0.60cm3/g。
本发明方法制备的纳米湿式氧化催化剂以Cu的金属氧化物作为活性组份,同时添加了Ce、Mn的氧化物作助剂。其中组份CuO的作用是促进有机物的氧化反应,组份Al2O3的主要作用是调整催化剂的结构,但如果太高,则活性组份含量将不足,同样影响催化剂的性能;试验表明,CuO含量越高催化剂转化率越高而流失严重,催化剂性能不稳定;助催化剂Mn、Ce的氧化物主要起到对有机物(大量高浓的Na2S、有机酸性物质如杂酚、环烷酸、硫醇、硫酚等以及硫醚、噻吩等有机硫化物)深度氧化和抗硫中毒的作用,试验中发现:单独使用助剂氧化锰,催化剂活性明显较差,单独使用助剂铈的氧化物,催化剂活性也不理想,当铜、铈、锰、铝的氧化物同时存在时,所制得的催化剂综合性能较只含其中某几种成份的催化剂有明显提高。
本发明的纳米湿式氧化催化剂制备方法,将铝源、铜源经过一次焙烧后,又在其表面覆盖一层氧化锰,同时加入了造孔剂,进行二次焙烧,使催化剂颗粒表面具有更多氧化锰附着,同时还拥有丰富的空间网络状纳米级微孔和较高的压碎强度,既可以减少铜离子的流失,又可以保证高的催化性能。制备方法简单,无贵金属成分,成本低,应用前景广。
使用本发明方法制备的催化剂处理高炼油与乙烯生产过程中产生的废碱液,COD含量范围10000~150000之间的废水可直接进行处理,在压力为1.0~5.0MPa,反应温度190~260℃、反应时间0.5~4.0h,以过量空气或富养空气为氧化介质,经过催化湿式氧化处理后,硫化物的转化率可达99.9%以上,酚类转化率可达90%以上,对COD的去除率可达85.0%以上,废水处理后BOD/COD的比值由0.1以下提到0.40以上,有利于废水的进一步达标处理。
具体实施方式
以下实施例是对本发明的具体说明,实施例和对比例所述的“%”指质量百分含量。
实施例1
将70g活性氧化铝打浆,形成含Al2O3为300g/L浆液,加入含以CuO计15g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至8.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,620℃下焙烧2h;焙烧后粉体再与以MnO计20g的硝酸锰溶液制成含水30%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置24h、挤压成三叶草状,烘干后涂敷10g纳米级氧化铈、650℃焙烧7h后得到湿式氧化催化剂样品A。
对比例1:
其他条件不变,降低CuO用量。将70g活性氧化铝小球打浆,形成含Al2O3为300g/L浆液,加入含以CuO计5g的硝酸铜溶液,超声波振荡2h后逐步加入氨水调节pH值至8.5,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,620℃下焙烧2h;焙烧后粉体再与以MnO计20g的硝酸锰溶液制成含水30%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置24h、挤压成三叶草状,烘干后涂敷10g纳米级氧化铈、650℃焙烧7h后得到湿式氧化催化剂样品F。
实施例2
将30g活性氧化铝小球打浆,形成含Al2O3为100g/L浆液,加入含以CuO计8g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至9.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计2g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,500℃下焙烧7h;焙烧后粉体再与以MnO计10g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷3g纳米级氧化铈、550℃焙烧2h后得到湿式氧化催化剂样品B。
对比例2
其他条件不变,降低CeO用量。将30g活性氧化铝小球打浆,形成含Al2O3为100g/L浆液,加入含以CuO计8g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至9.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计1g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,500℃下焙烧7h;焙烧后粉体再与以MnO计10g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷1g纳米级氧化铈、550℃焙烧2h后得到湿式氧化催化剂样品G。
实施例3
将40g活性氧化铝小球打浆,形成含Al2O3为100g/L浆液,加入含以CuO计15g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至9.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,550℃下焙烧7h;焙烧后粉体再与以MnO计15g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷6g纳米级氧化铈、550℃焙烧2h后得到湿式氧化催化剂样品C。
对比例3
其他条件不变,降低MnO用量。即将40g活性氧化铝小球打浆,形成含Al2O3为100g/L浆液,加入含以CuO计15g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至9.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,550℃下焙烧7h;焙烧后粉体再与以MnO计5g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g田菁粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷6g纳米级氧化铈、550℃焙烧2h后得到湿式氧化催化剂样品H。
实施例4
将50g活性氧化铝小球打浆,形成含Al2O3为500g/L浆液,加入含以CuO计15g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至10.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,600℃下焙烧5h;焙烧后粉体再与以MnO计15g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g活性炭粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷6g纳米级氧化铈、550℃焙烧5h后得到湿式氧化催化剂样品D。
对比例4
其他条件不变,降低焙烧温度。即将50g活性氧化铝小球打浆,形成含Al2O3为500g/L浆液,加入含以CuO计15g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至10.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计3g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,380℃下焙烧5h;焙烧后粉体再与以MnO计15g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g活性炭粉,搅拌40min、密封静置20h、挤压成三叶草状,烘干后涂敷6g纳米级氧化铈、390℃焙烧5h后得到湿式氧化催化剂样品I。
实施例5
将50g活性氧化铝小球打浆,形成含Al2O3为400g/L浆液,加入含以CuO计12g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至10.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计2g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,600℃下焙烧5h;焙烧后粉体再与以MnO计12g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g聚氧乙烯,搅拌40min、密封静置24h、挤压成蜂窝状,烘干后涂敷6g纳米级氧化铈、650℃焙烧2h后得到湿式氧化催化剂样品E。
对比例5
其他条件不变,提高焙烧温度。即将50g活性氧化铝小球打浆,形成含Al2O3为400g/L浆液,加入含以CuO计12g的硝酸铜溶液,超声波振荡3h后逐步加入氨水调节pH值至10.0,沉淀完全后,过滤、洗涤;再将洗涤后物料用去离子水制成含水率为50%的浆料,加入以CeO计2g的硝酸铈溶液,搅拌的同时超声波振荡1.5h,直接干燥后,600℃下焙烧5h;焙烧后粉体再与以MnO计12g的硝酸锰溶液制成含水40%的浆料,搅拌后加入1g聚氧乙烯,搅拌40min、密封静置24h、挤压成蜂窝状,烘干后涂敷6g纳米级氧化铈、900℃焙烧2h后得到湿式氧化催化剂样品J。
对比例6
其他条件同实施例5,采用一次共沉淀、焙烧法制备湿式氧化催化剂。即将50g活性氧化铝小球打浆,形成含Al2O3为400g/L浆液,将以CuO计12g的硝酸铜溶液,将以CeO计2g的硝酸铈,将以MnO计12g的硝酸锰溶液,将6g纳米级CeO物料,以及将1g聚氧乙烯,转移到一个烧杯内,超声波振荡3h后,逐步加入氨水调节pH值至10.0,沉淀完全后,密封静置24h、过滤、洗涤、成型、干燥后,650℃下焙烧2h得到湿式氧化催化剂样品K。
对比例7
采用CN1358567方法,制备湿式氧化催化剂即:取550ml浓度为1.0mol/L的Na2CO3溶液,置于水浴温度为70℃的恒温水浴槽内,加热20min。取1.0mol/L的Cu(NO3)2溶液100ml,1.0mol/L的Zn(NO3)2溶液110ml,取0.5mol/L的Al(NO3)3溶液75ml,转移到一个烧杯中,混合均匀后用分液漏斗缓慢滴加到Na2CO3溶液的烧杯中,同时快速搅拌。滴定结束后保证母液的pH≥9,并且让沉淀和母液一起老化24h。老化后采用真空抽滤使母液与沉淀分离,抽滤过程中采用去离子水洗涤四次。把沉淀物挤压成Ф3条状,在空气中晾干,然后在110℃条件下干燥2h,马弗炉中焙烧8h,焙烧温度为700℃,冷却后研成70目粉末,得到催化剂样品L。
各催化剂样品的物理性质如表1所示:
表1催化剂样品物性数据
评价结果
将上述A~L催化剂取5ml,装填在微型连续流动固定床反应器中,通入含废碱液,组成COD为85000mg/L、硫化物含量7500mg/L、酚类含量为12000mg/L,加入压缩空气,控制反应压力为3.5Mpa,温度230℃,反应时间2.5h的条件下进行评价试验。
通过评价试验,各催化剂的转化率数据分别见表2、表3。
表2实施例催化剂评价结果
表3对比例催化剂评价结果
从表2、表3可以看出:应用本发明的制备方法和条件制备的催化剂,处理炼油废碱液或含酚有机废水,硫化物去除率可达99.9%,COD去除率可达85%以上,酚类去除率可达90%以上。
反应时间为2小时,其他实验条件不变,检测反应液中铜离子的浓度,结果见表4。由实验结果可以看到,本发明的催化剂处理废碱液后,催化剂D、E与以前文献报道催化剂L以及与对比例6催化剂K相比较,铜离子流失情况带到较好控制,COD去除效果更好。
表4废碱液COD去除率以及铜离子流失情况
反应时间为2小时,其他实验条件不变,催化剂重复使用6次,检测反应液中铜离子的浓度,结果见表5。由实验结果可以看到,本发明的催化剂处理废碱液后,催化剂D、E与以前文献报道催化剂L以及与对比例6催化剂K相比较,铜离子流失情况带到较好控制,COD去除效果更高,且催化剂活性保持稳定。
表5废碱液COD去除率以及铜离子流失情况
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (10)
1.一种纳米湿式氧化催化剂的制备方法,其特征在于,包括如下步骤:
(1)将活性氧化铝打浆;
(2)将铜源前驱体溶解形成溶液;
(3)将步骤(1)、(2)的物料混合均匀;
(4)将步骤(3)形成的物料调节pH值至碱性,沉淀,过滤、干燥、焙烧,形成粉状物;
(5)将锰源前驱体形成的溶液与步骤(4)的粉状物混合成浆状,搅拌后,加造孔剂,二次搅拌,密封静置后挤压成型,干燥后涂敷纳米级氧化铈,焙烧后得到纳米湿式氧化催化剂,其中以重量百分比计,含活性氧化铝30~75%,含氧化铜10~30%,含氧化铈5%~20%,含氧化锰为10~30%。
2.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述铜源前驱体为可溶性的铜盐。
3.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述氧化铈来源于可溶性的铈盐。
4.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述pH值为8~13。
5.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述锰源前驱体为可溶性的锰盐。
6.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述造孔剂是柠檬酸、尿素、三氧乙酸、活性炭、田菁粉中的一种或多种。
7.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述焙烧温度为400~850℃。
8.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述催化剂静置后挤压成条状、三叶草状或蜂窝状。
9.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于,所述催化剂挤压成型后,干燥温度为60~180℃。
10.根据权利要求1所述纳米湿式氧化催化剂的制备方法,其特征在于所述pH值为8~11。
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