CN110508275A - 一种介孔材料负载二氧化锰催化剂及其制备方法 - Google Patents
一种介孔材料负载二氧化锰催化剂及其制备方法 Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 17
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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Abstract
本发明提供了一种介孔材料负载二氧化锰催化剂的制备方法,其特征在于,包括:步骤1:以低阶酚醛树脂作为碳源、TiCl4作为钛源、F127作为模板剂,采用自组装法经碳化制备有序C‑TiO2介孔材料;步骤2:将所述的有序C‑TiO2介孔材料放入KMnO4溶液中超声后,用去离子水洗涤后烘干,即得到介孔材料负载二氧化锰催化剂。本发明的有序C‑TiO2介孔材料负载MnO2催化剂有较高的脱硝效率。
Description
技术领域
本发明适用于选择性催化还原(SCR)催化剂的研究领域,尤其涉及于一种有序C-TiO2介孔材料负载MnO2催化剂的制备方法。
背景技术
造成雾霾污染的主要因素之一是细颗粒物,它通常指环境空气中空气动力学当量直径小于等于2.5微米的颗粒物,简称PM2.5,这些细粒子在被人体吸入呼吸道后,会使人产生呼吸道疾病,严重的还能导致癌症病发率增加。而造成雾霾的主要污染物PM2.5主要由一次污染物氮氧化物(NOx),硫氧化物(SOx),挥发性有机物(VOCs)及一次排放的细粒子经大气中的复杂气相反应生成。作为三大一次污染物之一的氮氧化物(即NOx),主要由一氧化氮(NO)及二氧化氮(NO2)构成,其余氮氧化物如一氧化二氮(N2O)虽然作为温室气体之一,也对大气有负面作用,但是毒性相对较低。NOx的存在不仅可反应生成二次污染物导致雾霾,同时还可经过气相反应形成光化学烟雾污染及酸雨,提高大气氧化性,对建筑物及土壤产生严重酸化影响,除此之外,作为一次污染物的氮氧化物,在吸入后也将危害人体健康,破坏呼吸系统及神经系统。
钒钛复合型催化剂表面呈酸性容易结合碱性的还原剂NH3,在350℃高温下具有较高的脱硝效率,但其催化剂产物不能自然分解,采用填埋法会造成土壤硬化、污染环境,所以在废弃催化剂的回收、处理方面存在较多困难。近年来大多采用Mn基催化剂,由于MnOx中的锰元素具有多种价态,在催化反应的过程中能通过价态间的电子转移,提高催化剂的氧化还原能力,因此使催化剂表现出良好的脱硝活性。但单组分MnOx的脱硝反应温度区间过高,且极易在煅烧过程中发生团聚,由于活性组分的分散度直接影响催化剂的脱硝活性,所以MnOx的团聚会使催化剂的脱硝效率降低[Yao X J,Kong T T,Yu S H,et al.Influenceof different supports on the physicochemical properties and denitrationperformance of the supported Mn-based catalysts for NH3–SCR at lowtemperature.Applied Surface Science,2017,402:208-217],因此提高锰基SCR催化剂的分散度一直是脱硝催化剂的研究方向。
由于碳富含多级孔,具有较大比表面积和大容量的NO吸附能力,且绿色环保利于回收,因此作为一种非常有应用前景的新型SCR催化剂载体被广泛应用。但纯碳载体亲水性较差,直接影响盐溶液的水热或浸渍过程,具体表现在盐溶液无法进入孔结构,多级孔利用率极低,煅烧后使金属氧化物在孔外部严重堆积,因此存在缺陷。TiO2因其热稳定性好、机械强度强、高耐硫性的特征,一直被应用于催化剂载体。且TiO2含有大量表面羟基,具有很好的亲水性,且表面含有丰富的Lewis酸性位点,有利于吸附碱性还原剂NH3,促使催化剂具有良好活性和选择性。但其本身比表面积较小,且因TiO2与多数金属氧化物具有较强相互作用,易使催化剂中毒后部分催化剂组分无法再生[孟亚楠.Ag掺杂TiO2/SBA-15催化剂的合成及光催化性能的研究.哈尔滨工业大学,2014]。
发明内容
本发明目的是提供一种具有较高的SCR脱硝效率的介孔材料负载二氧化锰催化剂及其制备方法。
基于上述现有纯TiO2、纯碳基载体型SCR催化剂的缺点,本发明提出采用自组装法制备有序C-TiO2介孔材料,改善碳基载体亲水性差的缺点,并利用超声法促进MnO2颗粒的分散,从而有效提高SCR脱硝效率。
为了达到上述目的,本发明提供了一种介孔材料负载二氧化锰催化剂的制备方法,其特征在于,包括:
步骤1:以低阶酚醛树脂作为碳源、TiCl4作为钛源、F127作为模板剂,采用自组装法经碳化制备有序C-TiO2介孔材料;
步骤2:将所述的有序C-TiO2介孔材料放入KMnO4溶液中超声后,用去离子水洗涤后烘干,即得到介孔材料负载二氧化锰催化剂。
优选地,所述的低阶酚醛树脂和F127的质量比为2.5~4:1。
优选地,所述的步骤1中的低阶酚醛树脂与TiCl4的质量比为1.3~7.5:1。
优选地,所述的步骤2中的超声频率为40KHz,超声时间为0.5~6h。
优选地,所述的步骤2中的KMnO4的浓度为0.5mM~0.1M,KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为30~90mL:1g。
优选地,所述的低阶酚醛树脂的制备方法包括:将1.7~2.4重量份、20wt%的NaOH溶液滴入8.0~12.0重量份苯酚中,搅拌后加入14.2~22.4重量份37wt%甲醛溶液,在70~80℃反应1~3h,冷却至室温后,将溶液调至中性,在真空干燥箱中脱水,然后配制成浓度为20~25wt%的乙醇溶液,即为低阶酚醛树脂。
优选地,所述的自组装法的具体步骤包括:将1~2.5重量份F127溶解在5~10重量份醇水混合液中,35~50℃水浴并搅拌2~4h制成溶液A;将6~9重量份无水乙醇和0.5~1.5重量份去离子水混合,0℃水浴,逐滴加入1.0~2.5重量份TiCl4,搅拌30~60min,即制成溶液B;将溶液B滴入溶液A中,搅拌30~60min,然后加入2.5~10重量份低价酚醛树脂,搅拌1~4h。
与现有技术相比,本发明的有益效果是:
TiO2具有表面超亲水性,能提高载体整体亲水性,使KMnO4溶液能充分进入有序C-TiO2载体的介孔结构中;KMnO4溶液进入孔道中后,在超声作用下,会发生如下反应:4MnO4 -+4H2O+3C→4MnO2+CO3 2-+2HCO3 -,由此MnO2颗粒被固定在C组分表面,又因为孔壁是由C和TiO2间隔排列组成的,因此有效提高了MnO2组分的分散度;有序C-TiO2介孔载体的介孔孔道具有限域效果,在负载MnO2组分时能有效限制其颗粒的生长,为催化剂提供了优良的催化空间;进一步的,TiO2有提供丰富的Lewis酸性位点,使催化剂在SCR反应过程中能吸附更多的碱性还原剂NH3,促进SCR反应的加速进行。本发明的有序C-TiO2介孔材料负载MnO2催化剂有较高的脱硝效率。
附图说明
图1为1g有序C-TiO2介孔材料和1g介孔碳,分别在60mL KMnO4溶液(5mM)中超声反应制得的两种催化剂的SCR脱硝效率图。
图2是实施例1所得的有序C-TiO2介孔材料的小角XRD图。
图3是实施例1所得的有序C-TiO2介孔材料的广角XRD图。
图4是实施例1所得的有序C-TiO2介孔材料的热重曲线图。
图5是实施例1所得的有序C-TiO2介孔材料的N2吸脱附等温线及孔径分布曲线。
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。
本发明中所述的F127为市售产品,成分是聚氧乙烯聚氧丙烯醚嵌段共聚物,是一类高分子非离子表面活性剂。
实施例1
将1.7g NaOH溶液(20wt%)滴入8.0g苯酚中,搅拌后加入14.2g甲醛溶液(37wt%),将混合液放入水浴锅中70℃冷凝回流反应1h,冷却至室温后用2mol/L的HCl将溶液调至中性,在47℃的真空干燥箱中脱水,然后配制成20wt%的乙醇溶液,即低阶酚醛树脂。将1g模板剂F127溶解在9.0g醇水混合液(EtOH和H2O的质量比为8:1)中,40℃水浴并搅拌2h制成溶液A;将7.5g无水乙醇和0.5g去离子水混合,0℃水浴,逐滴加入1.9g钛源TiCl4,搅拌30min即制成溶液B;将溶液B滴入溶液A中搅拌30min,然后加入2.5g低价酚醛树脂(低阶酚醛树脂和F127的质量比为2.5:1,低阶酚醛树脂与TiCl4的质量比为1.3:1)搅拌2h,将得到的酒红色溶液倒入蒸发皿中,置于通风橱中使乙醇完全挥发,然后放入100℃烘箱保留24h,将得到的红色薄膜刮出并放入管式炉中进行600℃碳化1h,制成有序C-TiO2介孔材料。
图2是此样品的小角XRD图,在0.7°出现的峰表示样品属于有序介孔材料。图3是此样品的广角XRD图,2θ为25°、38°、48°、54°、56°、63°、69°、71°和75°处出现了锐钛矿相特征衍射峰,由于无定形碳特征衍射峰(26°左右)与锐钛矿的特征衍射峰重叠,因此在广角XRD图中观察不到,现象表明样品由无定形碳和锐钛矿相TiO2组成。图4是此样品的热重曲线图,测试条件为空气气氛,图象表明样品含有31.23%的碳和68.29%的TiO2。图5是此样品的N2吸脱附等温线及孔径分布曲线,显示了典型的IV型吸脱附等温线,并有毛细凝聚作用引起的H2型滞后环,证明该样品具有圆柱状孔,且样品的BET比表面积为182.5m2/g。
将有序C-TiO2介孔材料研磨并称取1g放入60mL KMnO4溶液(5mM)中(KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为60mL:1g),静置2h后放入超声波清洗机中超声3.5h,超声频率为40KHz,用去离子水洗涤后烘干,制成有序C-TiO2介孔材料负载MnO2催化剂。对该催化剂进行模拟SCR脱硝测试,在260℃达到87%的脱硝效率。
实施例2
将2.4g NaOH溶液(20wt%)滴入12.0g苯酚中,搅拌后加入22.4g甲醛溶液(37wt%),将混合液放入水浴锅中80℃冷凝回流反应3h,冷却至室温后用2mol/L的HCl将溶液调至中性,在47℃的真空干燥箱中脱水,然后配制成25wt%的乙醇溶液,即低阶酚醛树脂。将1.5g模板剂F127溶解在9.0g醇水混合液(EtOH和H2O的质量比为8:1)中,40℃水浴并搅拌2h,即制成溶液A;将7.5g无水乙醇和0.5g去离子水混合,0℃水浴,逐滴加入1.9g钛源TiCl4,搅拌30min即制成溶液B;将溶液B滴入溶液A中搅拌30min,然后加入5g低价酚醛树脂(低阶酚醛树脂和F127的质量比为3.3:1,低阶酚醛树脂与TiCl4的质量比为2.6:1)搅拌2h,将得到的酒红色溶液倒入蒸发皿中,置于通风橱中使乙醇完全挥发,然后放入100℃烘箱保留24h,将得到的红色薄膜刮出并放入管式炉中600℃碳化1h,制成有序C-TiO2介孔材料。
将有序C-TiO2介孔材料研磨并称取1g放入60mL KMnO4溶液(0.5mM)中(KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为60:1),静置2h后放入超声波清洗机中超声1.5h,超声频率为40KHz,用去离子水洗涤后烘干,制成有序C-TiO2介孔材料负载MnO2催化剂。对该催化剂进行模拟SCR脱硝测试,在260℃达到82%的脱硝效率。
实施例3
将1.7g NaOH溶液(20wt%)滴入8.0g苯酚中,搅拌后加入14.2g甲醛溶液(37wt%),将混合液放入水浴锅中70℃冷凝回流反应1h,冷却至室温后用2mol/L的HCl将溶液调至中性,在47℃的真空干燥箱中脱水,然后配制成20wt%的乙醇溶液,即低阶酚醛树脂。将2g模板剂F127溶解在5g醇水混合液(EtOH和H2O的质量比为8:1)中,35℃水浴并搅拌3h,即制成溶液A;将6g无水乙醇和1.0g去离子水混合,0℃水浴,逐滴加入1.0g钛源TiCl4,搅拌45min即制成溶液B;将溶液B滴入溶液A中搅拌45min,然后加入7.5g低价酚醛树脂(低阶酚醛树脂和F127的质量比为3.8:1,低阶酚醛树脂与TiCl4的质量比为7.5:1)搅拌1h,将得到的酒红色溶液倒入蒸发皿中,置于通风橱中使乙醇完全挥发,然后放入100℃烘箱保留24h,将得到的红色薄膜刮出并放入管式炉中进行600℃碳化1h,制成有序C-TiO2介孔材料。
将有序C-TiO2介孔材料研磨并称取1g放入30mL KMnO4溶液(0.1M)中(KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为30:1),静置2h后放入超声波清洗机中超声6h,超声频率为40KHz,用去离子水洗涤后烘干,制成有序C-TiO2介孔材料负载MnO2催化剂。对该催化剂进行模拟SCR脱硝测试,在260℃达到75%的脱硝效率。
实施例4
将1.7g NaOH溶液(20wt%)滴入8.0g苯酚中,搅拌后加入14.2g甲醛溶液(37wt%),将混合液放入水浴锅中70℃冷凝回流反应1h,冷却至室温后用2mol/L的HCl将溶液调至中性,在47℃的真空干燥箱中脱水,然后配制成20wt%的乙醇溶液,即低阶酚醛树脂。将2.5g模板剂F127溶解在15.0g醇水混合液(EtOH和H2O的质量比为8:1)中,50℃水浴并搅拌4h,即制成溶液A;将9.0g无水乙醇和1.5g去离子水混合,0℃水浴,逐滴加入2.5g钛源TiCl4,搅拌60min即制成溶液B;将溶液B滴入溶液A中搅拌60min,然后加入10.0g低价酚醛树脂(低阶酚醛树脂和F127的质量比为4:1,低阶酚醛树脂与TiCl4的质量比为4:1)搅拌4h,将得到的酒红色溶液倒入蒸发皿中,置于通风橱中使乙醇完全挥发,然后放入100℃烘箱保留24h,将得到的红色薄膜刮出并放入管式炉中进行600℃碳化1h,制成有序C-TiO2介孔材料。
将有序C-TiO2介孔材料研磨并称取1g放入90mL KMnO4溶液(0.05M)中(KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为90:1),静置2h后放入超声波清洗机中超声3.5h,超声频率为40KHz,用去离子水洗涤后烘干,制成有序C-TiO2介孔材料负载MnO2催化剂。对该催化剂进行模拟SCR脱硝测试,在260℃达到72%的脱硝效率。
对比例1
将1.0g苯酚于45℃熔融,在该温度下加入0.21g 20wt%NaOH水溶液搅拌10min,加入1.7g 37wt%甲醛水溶液,升温到70~75℃反应1h,降温至室温,用0.6M HCl溶液调节溶液至中性,47℃真空减压脱水1~2h。将得到的粘稠液体溶于乙醇配制成20wt%的乙醇溶液,即制成酚醛树脂预聚体。将1.0g F127完全溶于20.0g乙醇中,然后加入5.0g A阶酚醛树脂预聚体乙醇溶液(含有0.61g苯酚和0.39g甲醛),搅拌10min,得到均匀的溶液,将该溶液转移到培养皿中,在通风橱中挥发乙醇24h,再将培养皿置于100℃烘箱内热聚24h,得到透明的薄膜材料,将材料置于管式炉中通入N2,350℃焙烧3h(升温速率为2℃/min),即制成介孔碳。
将介孔碳研磨并称取1g放入60mL KMnO4溶液(5mM)中(KMnO4溶液的体积与介孔碳的质量数值比为60:1),静置2h后放入超声波清洗机中超声3.5h,用去离子水洗涤后烘干。对该催化剂进行模拟SCR脱硝测试,在260℃仅达到54%的脱硝效率。
Claims (7)
1.一种介孔材料负载二氧化锰催化剂的制备方法,其特征在于,包括:
步骤1:以低阶酚醛树脂作为碳源、TiCl4作为钛源、F127作为模板剂,采用自组装法经碳化制备有序C-TiO2介孔材料;
步骤2:将所述的有序C-TiO2介孔材料放入KMnO4溶液中超声后,用去离子水洗涤后烘干,即得到介孔材料负载二氧化锰催化剂。
2.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的低阶酚醛树脂和F127的质量比为2.5~4:1。
3.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的步骤1中的低阶酚醛树脂与TiCl4的质量比为1.3~7.5:1。
4.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的步骤2中的超声频率为40KHz,超声时间为0.5~6h。
5.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的步骤2中的KMnO4的浓度为0.5mM~0.1M,KMnO4溶液的体积与有序C-TiO2介孔材料的质量数值比为30~90mL:1g。
6.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的低阶酚醛树脂的制备方法包括:将1.7~2.4重量份、20wt%的NaOH溶液滴入8.0~12.0重量份苯酚中,搅拌后加入14.2~22.4重量份37wt%甲醛溶液,在70~80℃反应1~3h,冷却至室温后,将溶液调至中性,在真空干燥箱中脱水,然后配制成浓度为20~25wt%的乙醇溶液,即为低阶酚醛树脂。
7.如权利要求1所述的介孔材料负载二氧化锰催化剂的制备方法,其特征在于,所述的自组装法的具体步骤包括:将1~2.5重量份F127溶解在5~10重量份醇水混合液中,35~50℃水浴并搅拌2~4h制成溶液A;将6~9重量份无水乙醇和0.5~1.5重量份去离子水混合,0℃水浴,逐滴加入1.0~2.5重量份TiCl4,搅拌30~60min,即制成溶液B;将溶液B滴入溶液A中,搅拌30~60min,然后加入2.5~10重量份低价酚醛树脂,搅拌1~4h。
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