CN105854892B - 多孔棒状尖晶石结构催化剂的制备方法 - Google Patents
多孔棒状尖晶石结构催化剂的制备方法 Download PDFInfo
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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
- B01J23/76—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
- 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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- 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
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Abstract
多孔棒状尖晶石结构催化剂的制备方法,涉及一种催化剂的制备方法,用去离子水分别配制A类和B类金属盐溶液;量取将二者在磁力搅拌下混合均匀,得到澄清的深蓝色溶液;向混合溶液中逐渐加入NH4 (OH)溶液,将十六烷基三甲基氯化铵加入水中,形成凝胶;配置一水合肼水溶液,将上述搅拌好的混合液持续加热、冷却至室温,得到绿色蓬松的固体产物;去离子水和无水乙醇洗涤数次,干燥后获得固体粉末;移入到石英反应器中,升温煅烧获得蓬松粉体。该催化剂解决了柴油车尾气中PM净化不理想的技术问题。
Description
技术领域
本发明属于柴油车尾气净化领域,具体涉及一种结构与性能优化的净化柴油车尾气碳烟颗粒用的棒状尖晶石催化剂及其制备方法。
技术背景
随着汽车排放法规的加严和人们对提高空气质量意识的增强,空气污染指数——PM2.5被人们所熟识。PM2.5即细颗粒物(也称为可入肺颗粒物),是指空气动力学直径≤2.5μm 的颗粒物。其表面吸附大量有毒有害的化学物质,并可通过呼吸沉积在肺泡,甚至可直接进入血液循环分布到全身,引发支气管和心脑血管,甚至肺癌等重大疾病,对人体危害极大。PM2.5由一次微粒(直接排入空气中的)和二次微粒(空气中的气态污染物通过化学转化生成的)组成。其中,柴油车尾气排放的颗粒物(PM)是一次微粒的主要贡献源,同时也是二次颗粒的主要组分。就此,环保部《轻型汽车污染物排放限值及量方法(中国第五阶段)》的征求意见稿中PM排放限值加严82%,并增加了PM粒子数量控制项目。因此,研发高效的PM排放控制技术,对于满足日益严格的排放法规,保障人民健康具有重要的环保意义和社会效益。
目前,Pt、Pd、Rh和、Au等贵金属催化剂对柴油车PM的净化展示了良好的催化活性,但成本高、易中毒等问题限制了其应用和推广,因而选用非贵金属催化剂是必然趋势。非贵金属催化剂主要包括单一金属氧化物催化剂和复合金属氧化物催化剂。单一金属氧化物催化剂(如TiO2、V2O5、CuO和CeO2)的活性取决于氧化物比表面积与原子表面移动性能,但单一金属氧化物催化剂最大的缺点就是热稳定性不高,导致催化剂活性降低。而相对于单一金属氧化物催化剂,复合金属氧化物催化剂由于活性组分间存在协同效应,使其表现出更高的活性和稳定性。近年来,钙钛矿型、尖晶石等复合型金属氧化物作为净化柴油车尾气催化剂的相关报道较多,而具有较好的热稳定性和机械强度的尖晶石催化剂净化柴油车尾气PM催化性能的研究报道较少,尤其本发明所涉及的低温合成多孔棒状尖晶石结构的催化剂。
发明内容
本发明的目的是提供一种具有高孔隙率、高比表面积、纳米棒状尖晶石结构的消除柴油车尾气中PM的催化剂及其制备方法,解决了催化剂对柴油车尾气中PM净化效果不理想的技术问题。该催化剂具有纳米级多孔棒状结构,该结构可以提供高效的内部比表面积,有效增加催化剂的表面活性位,有利于增加反应物与催化剂之间的接触点,从而提高催化剂的催化活性。
本发明的目的是通过以下技术方案实现的:
一种用于柴油车尾气净化的AB2O4尖晶石催化剂,由第二主族元素(Mg、Ca、Sr和Ba元素),或过渡金属元素(Cu、Mn、Co、Zn、Ni和Fe等元素)构成尖晶石AB2O4结构的A位,铬元素构成B位,A位元素和铬元素与氧元素的摩尔比为1:2:4。通过晶相分析,所述的催化剂中呈尖晶石结构占95%~99%
该种净化柴油车PM的ACr2O4尖晶石催化剂的制备方法如下:
1)用去离子水分别配制离子浓度为0.5~1.0mol/L的A类金属盐溶液和离子浓度为1~2.0mol/L的B类金属盐溶液;
所述的A类金属盐溶液为第二主族元素盐溶液,也可为过渡金属元素盐溶液;其中,盐可为硝酸盐、硫酸盐、氯酸盐、醋酸盐中的一种。
所述的B类金属盐为硝酸铬、硫酸铬、氯化铬、醋酸铬中的一种。所制备出的消除柴油车尾气PM催化剂为具有纳米棒状尖晶石结构的多金属氧化物。
2)分别量取5~60mlA类金属盐溶液,5~60mlB类金属盐溶液,将二者在磁力搅拌下混合均匀,将得到澄清的深蓝色溶液;
3)向上述深蓝色的混合溶液中逐渐加入质量百分比浓度为10~20%的NH4 (OH)溶液,致混合溶液逐渐变为绿色;
4)将一定质量的十六烷基三甲基氯化铵加入到30ml的水中,通过剧烈搅拌2小时后形成凝胶;
5)配置质量浓度为70~95%的一水合肼水溶液后,与上述混合盐溶液、十六烷基三甲基氯化铵水溶液混合,并将混合溶液在磁力搅拌器作用下强力搅拌0.5~2小时;
6)将上述搅拌好的混合液移入到特氟隆内衬的不锈钢高压釜中密封,然后将高压釜加热到200℃并持续加热18个小时,然后将其冷却至室温,将得到绿色蓬松的固体产物;
7)将上述蓬松的绿色固体产物通过离心机以5000rpm分别用去离子水和无水乙醇洗涤数次,然后在空气中100℃干燥6小时后获得固体粉末;
8)将上述干燥后的固体粉末移入到石英反应器中,在管式炉内以1℃/min的升温速度升至700℃煅烧1~3小时,获得蓬松粉体。
本发明的技术效果为:本发明的尖晶石催化剂具有如下优点:1)该催化剂具有纳米级多孔棒状结构,该结构可以提供高的比表面积,增加反应物与活性位之间的接触点,有效提高催化剂的催化活性,并且,该催化剂合成温度低(150℃即可合成)。2)在紧密接触的条件下,催化剂可以使柴油车PM起燃温度低于300℃,3)该催化剂中,占据尖晶石结构A位的第二主族,或过渡金属元素与铬元素之间的协同作用与铬元素之间的协同作用,有效的提高了催化剂的抗硫性和催化活性;4)该催化剂合成工艺简单,制备温度低,成本低廉,对环境无毒性作用。
附图说明:
图1:本发明实施例1制得的多孔棒状结构CuCr2O4催化剂SEM照片;
图2:本发明实施例1制得的多孔棒状结构CuCr2O4催化剂TEM照片;
图3:本发明实施例1制得的多孔棒状结构CuCr2O4催化剂XRD图谱。
具体实施方案
本发明是用具体实施方案来阐述本发明,而不是对本发明的限制,本发明可实施的情况不仅限于实例的范围:
实施例1:
化学分子式为CuCr2O4催化剂的制备
一种用于净化柴油车尾气PM的CuCr2O4尖晶石催化剂,由呈正二价的铜元素构成尖晶石AB2O4结构的A位,铬元素构成B位,其中:催化剂中铜元素、铬元素与氧元素的摩尔比为1:2:4。通过晶相分析,所述的催化剂中呈尖晶石结构占99%。
1)用去离子水分别配制离子浓度为0.5 mol/L的硝酸铜盐溶液和离子浓度为1.0mol/L的硝酸铬盐溶液;
所制备出的消除柴油车尾气PM催化剂为具有纳米棒状尖晶石结构的多金属氧化物。
2)分别量取30ml硝酸铜盐溶液,30ml硝酸铬盐溶液,将二者在磁力搅拌下混合均匀,得到澄清的深蓝色溶液;
3)向上述深蓝色的混合溶液中逐渐加入质量百分比浓度为15%的NH4 (OH)溶液,致混合溶液逐渐变为绿色;
4)将一定质量的十六烷基三甲基氯化铵加入到30ml的水中,通过剧烈搅拌2小时后形成凝胶;
5)配置质量浓度为80%的一水合肼水溶液后,与上述混合盐溶液、十六烷基三甲基氯化铵水溶液混合,并将混合溶液在磁力搅拌器作用下强力搅拌1.5小时;
6)将上述搅拌好的混合液移入到特氟隆内衬的不锈钢高压釜中密封,然后将高压釜加热到200℃并持续加热18个小时,然后将其冷却至室温,将得到绿色蓬松的固体产物;
7)将上述蓬松的绿色固体产物通过离心机以5000rpm分别用去离子水和无水乙醇洗涤10次,然后在空气中100℃干燥6小时后获得固体粉末;
8)将上述干燥后的固体粉末移入到石英反应器中,在管式炉内以1℃/min的升温速度升至700℃煅烧1.5小时,获得的蓬松粉体,既为纳米棒状CuCr2O4尖晶石催化剂。
实施例2:
化学分子式为ZnCr2O4催化剂的制备
一种用于净化柴油车尾气PM的ZnCr2O4尖晶石催化剂,由呈正二价的锌元素构成尖晶石AB2O4结构的A位,铬元素构成B位,其中:催化剂中锌元素、铬元素与氧元素的摩尔比为1:2:4。通过晶相分析,所述的催化剂中呈尖晶石结构占99%。
1)用去离子水分别配制离子浓度为0.5 mol/L的氯化锌盐溶液和离子浓度为1.0mol/L的氯化铬盐溶液;
所制备出的消除柴油车尾气PM催化剂为具有纳米棒状尖晶石结构的多金属氧化物。
2)分别量取30ml氯化锌盐溶液,30ml氯化铬盐溶液,将二者在磁力搅拌下混合均匀,得到澄清的深蓝色溶液;
3)向上述深蓝色的混合溶液中逐渐加入质量百分比浓度为15%的NH4 (OH)溶液,致混合溶液逐渐变为绿色;
4)将一定质量的十六烷基三甲基氯化铵加入到30ml的水中,通过剧烈搅拌2小时后形成凝胶;
5)配置质量浓度为80%的一水合肼水溶液后,与上述混合盐溶液、十六烷基三甲基氯化铵水溶液混合,并将混合溶液在磁力搅拌器作用下强力搅拌1.5小时;
6)将上述搅拌好的混合液移入到特氟隆内衬的不锈钢高压釜中密封,然后将高压釜加热到200℃并持续加热18个小时,然后将其冷却至室温,将得到绿色蓬松的固体产物;
7)将上述蓬松的绿色固体产物通过离心机以5000rpm分别用去离子水和无水乙醇洗涤15次,然后在空气中100℃干燥6小时后获得固体粉末;
8)将上述干燥后的固体粉末移入到石英反应器中,在管式炉内以1℃/min的升温速度升至700℃煅烧1小时,获得的蓬松粉体,既为纳米棒状ZnCr2O4尖晶石催化剂。
实施例3:
化学分子式为MnCr2O4催化剂的制备
一种用于净化柴油车尾气PM的MnCr2O4尖晶石催化剂,由呈正二价的锰元素构成尖晶石AB2O4结构的A位,铬元素构成B位,其中:催化剂中锰元素、铬元素与氧元素的摩尔比为1:2:4。通过晶相分析,所述的催化剂中呈尖晶石结构占99%。
1)用去离子水分别配制离子浓度为0.25 mol/L的硫酸锰盐溶液和离子浓度为0.5mol/L的硫酸铬盐溶液;
所制备出的消除柴油车尾气PM催化剂为具有纳米棒状尖晶石结构的多金属氧化物。
2)分别量取30ml硫酸锰盐溶液,30ml硫酸铬盐溶液,将二者在磁力搅拌下混合均匀,得到澄清的深蓝色溶液;
3)向上述深蓝色的混合溶液中逐渐加入质量百分比浓度为15%的NH4 (OH)溶液,致混合溶液逐渐变为绿色;
4)将一定质量的十六烷基三甲基氯化铵加入到30ml的水中,通过剧烈搅拌2小时后形成凝胶;
5)配置质量浓度为85%的一水合肼水溶液后,与上述混合盐溶液、十六烷基三甲基氯化铵水溶液混合,并将混合溶液在磁力搅拌器作用下强力搅拌1小时;
6)将上述搅拌好的混合液移入到特氟隆内衬的不锈钢高压釜中密封,然后将高压釜加热到200℃并持续加热18个小时,然后将其冷却至室温,将得到绿色蓬松的固体产物;
7)将上述蓬松的绿色固体产物通过离心机以5000rpm分别用去离子水和无水乙醇洗涤10次,然后在空气中100℃干燥6小时后获得固体粉末;
8)将上述干燥后的固体粉末移入到石英反应器中,在管式炉内以1℃/min的升温速度升至700℃煅烧2小时,获得的蓬松粉体,既为纳米棒状MnCr2O4尖晶石催化剂。
在程序升温装置中对上述实施例1-3得到的催化剂进行性能测试。升温速度为10℃/min,测试温度范围为150~650℃。模拟的反应物由纯O2和高纯He以及模拟PM的Degussa公司的Printex U商业炭黑组成,高纯He根据需要将混合气体稀释成不同浓度。固定床反应器为管式炉内的石英管,石英管反应器内装有碳与催化剂比例为1:9的混合物50mg, O2为10%,空速为25000h-1,气体组分由北京北分瑞丽分析仪器厂生产的sp-3420色谱(装有FID和TCD检测器)进行在线分析。测试结果见表1
表1本发明催化剂净化柴油车尾气PM与NOx的催化活性数据
催化剂编号 | T10/℃ | T50/℃ | T90/℃ |
实施例1 | 319 | 418 | 488 |
实施例2 | 289 | 410 | 475 |
实施例3 | 309 | 433 | 509 |
从表1的测试结果可以看出:本发明的上述实例中,选择不同的过渡金属元素为变化条件,在权利要求所述范围内,其PM的氧化温度为279~500℃,对PM的催化氧化能力突出。因此,该系列催化剂具备应用推广应用前景。
Claims (2)
1.多孔棒状尖晶石结构催化剂的制备方法,其特征在于,所述方法包括以下过程:
1)用去离子水分别配制离子浓度为0.5~1.0mol/L的A类金属盐溶液和离子浓度为1~2.0mol/L的B类金属盐溶液;
2)分别量取5~60mLA类金属盐溶液,5~60mLB类金属盐溶液,将二者在磁力搅拌下混合均匀,将得到澄清的深蓝色溶液;
3)向上述深蓝色溶液中逐渐加入质量百分比浓度为10~20%的NH4 (OH)溶液,致混合溶液逐渐变为绿色;
4)将十六烷基三甲基氯化铵加入到30mL的水中,通过剧烈搅拌2小时后形成凝胶;
5)配置质量浓度为70~95%的一水合肼水溶液后,与步骤3)得到绿色混合溶液、步骤4)得到的十六烷基三甲基氯化铵凝胶混合,并将混合溶液在磁力搅拌器作用下强力搅拌0.5~2小时;
6)将上述搅拌好的混合液移入到特氟隆内衬的不锈钢高压釜中密封,然后将高压釜加热到200℃并持续加热18个小时,然后将其冷却至室温,将得到绿色蓬松的固体产物;
7)将上述蓬松的绿色固体产物通过离心机以5000rpm分别用去离子水和无水乙醇洗涤数次,然后在空气中100℃干燥6小时后获得固体粉末;
8)将上述干燥后的固体粉末移入到石英反应器中,在管式炉内以1℃/min的升温速度升至700℃煅烧1~3小时,获得蓬松粉体;
所述的B类金属盐为硝酸铬、硫酸铬、氯化铬、醋酸铬中的一种;
所述的催化剂由第二主族元素Mg、Ca、Sr和Ba元素,或过渡金属元素Cu、Mn、Co、Zn、Ni和Fe元素构成尖晶石AB2O4结构的A位,铬元素构成B位,A位元素和铬元素与氧元素的摩尔比为1:2:4;通过晶相分析,催化剂中呈尖晶石结构占95%~99%。
2.根据权利要求1所述的多孔棒状尖晶石结构催化剂的制备方法,其特征在于,所述所制备出的多孔棒状尖晶石结构催化剂为具有纳米棒状尖晶石结构的多金属氧化物。
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