CN114870848B - 一种可降低柴油发动机碳烟氧化温度的管状钙钛矿型复合氧化物催化剂 - Google Patents
一种可降低柴油发动机碳烟氧化温度的管状钙钛矿型复合氧化物催化剂 Download PDFInfo
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Abstract
本发明公开了一种用于柴油发动机尾气碳烟颗粒物净化的管状La1‑xCexCo1‑yZryO3‑δ钙钛矿型复合氧化物催化剂，该催化剂材料的晶相结构为钙钛矿晶型，具有可耐受高温的管状结构稳定性，其微纳米管状孔性结构均称，具有良好的松散接触催化碳烟颗粒氧化活性，可作为一种用于柴油车尾气碳烟颗粒净化的潜在新型材料。
Description
技术领域
本发明涉及一种用于柴油发动机尾气碳烟颗粒物净化的管状La1-xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂，具体而言，涉及一种以聚碳酸酯薄膜材料为载体制备出具有管状结构和高稳定性的La1-xCexCo1-yZryO3-δ钙钛矿复合金属氧化物催化剂材料，适用于柴油车(机)尾气中碳烟颗粒的净化。
背景技术
碳烟颗粒物(PM)具有最广泛的潜在环境影响，其中主要包括对健康的影响、气候变化和生态环境影响这几个方面。柴油机尾气中的PM被人体吸入后会严重危害身体健康。在我国，随着国六排放标准GB 17691-2018重型柴油车污染物排放限值及测量方法(中国第六阶段)的发布实施，PM排放加严50～66％，如何有效的控制碳烟颗粒物的排放成为大气污染防治的重点。机外捕集过滤DPF技术是柴油车PM净化的主流技术之，微粒捕集器在捕获碳烟后逐渐地排气背压会增加，这会影响到汽车的动力，因而微粒捕集器的碳烟再生技术是该净化器能稳定运行的关键。当前，再生技术分为主动再生和被动再生两大类。主动再生是当车辆的排气背压上升到一定阀值时，在排气管中喷射燃料和空气使之燃烧后迅速提升微粒捕集器床层的温度达到碳烟氧化燃烧温度(＞650℃)而使碳烟得到净化，微粒捕集器的纳米通道也得到再生。该方法可有效使微粒捕集器得到再生，但会增加车辆的行驶油耗成本，并且需要一套相对复杂的管理系统。被动再生是利用催化剂降低碳烟氧化燃烧反应的活化能，使碳烟氧化燃烧反应温度显著降低至柴油发动机的排气温度(＜380℃)。该方法无需额外的补入能量，仅需要在排气管中补喷入一定量的空气，控制技术相对简单。被动再生技术的核心是需要碳烟低温高效的氧化燃烧催化剂，因此开发低温型碳烟氧化燃烧催化剂一直是科学研究和技术开发努力的方向。目前的科学研究表明碳烟催化氧化燃烧催化剂主要以钙钛矿型复合氧化物表现较好。
纳米粒子型钙钛矿型复合氧化物催化剂是近二十年来被研究较多的碳烟催化氧化燃烧催化剂，但其需要在紧密接触的方式下才能表现出优良的催化性能。柴油车排放的碳烟颗粒物(PM)在宏观粒径分布大多处于0.5～1μm间的较大尺寸，粒径0.5μm以下通常占比不到40％，因而纳米颗粒钙钛矿型复合氧化物催化剂在实车使用过程中往往对碳烟的催化再生效果不理想。这主要缘于微粒捕集器上纳米粒子型催化剂与碳烟颗粒处于松散接触状态，由于碳烟颗粒物粒径较大，这种接触面微观上是有限的，因而对碳烟颗粒的催化氧化总反应效率就受到限制。近年来，具有大孔尺寸的纳米管或三维大孔钙钛矿型催化剂开始受到关注，这类催化剂可以增大催化剂活性位与碳烟颗粒的接触效率，但其几何结构稳定性是较为重要的。例如，改进制备方法制备具有特殊形貌结构的钙钛矿，特殊形貌结构主要包括三维有序大孔(doi.org/10.1021/acs.est.1c01781)和纳米管状钙钛矿型复合氧化物(doi.org/10.1016/j.apcatb.2018.05.030)等。当然，这种形貌特殊的钙钛矿催化剂也需要对金属组成进行优化，包括结构稳定性和表面缺陷的优化(如用不同金属元素部分取代钙钛矿中的A位和B位元素形成缺陷，进而提升元素价态或者增加氧空位，从而提高催化剂的催化活性)。
纳米管状钙钛矿是一种特殊的形貌结构，其管壁由纳米粒子构成，可以使碳烟颗粒进入孔内部空间，增加催化剂与碳烟颗粒的接触面积和几率，纳米管的窗孔效应和电荷效应可大大促进碳烟催化燃烧反应速度。Fang等人报道(doi.org/10.1016/j.apcatb.2018.05.030)，当纳米管钙钛矿催化剂与碳烟颗粒混合时，其碳烟颗粒转化50％的温度T50比颗粒状催化剂的下降了50℃左右。纳米管状钙钛矿催化材料的制备已有报道主要采用静电纺丝制备(doi.org/10.1016/j.apcatb.2018.05.030)，其主要原理为：将硝酸盐水溶液与N,N-二甲基甲酰胺混合均匀后加入聚乙烯吡咯烷酮，以形成溶胶凝胶，该溶胶凝胶被注入不锈钢细管，在一定的电压下通电进行静电纺丝，纺丝于700℃高温煅烧得到目标催化剂。
Sun等人(doi.org/10.1016/j.jre.2019.05.014)报道，LaCoO3催化剂中掺杂Ce制备的钙钛矿型纳米颗粒LaCeCoO3复合氧化物催化剂表现出更高的表面吸附氧浓度，从而增强了碳烟催化氧化活性，La0.9Ce0.1CoO3钙钛矿催化剂的碳烟催化氧化活性T10、T50和T90分别达到了371℃、444℃和497℃的低温(T10、T50和T90定义为碳烟转化率为10％、50％和90％时对应的温度)，但该催化剂为纳米颗粒状。Zou等人(doi.org/10.1007/s10853-008-2460-1)报道，他们采用有机模板分解法合成了LaCeCoZrOx混合金属氧化物催化剂用于催化氧化CO，但该催化剂无钙钛矿XRD特征衍射峰(如2θ＝32.8°)，因而不是钙钛矿复合氧化物。该混合型金属氧化物中的Zr/Co摩尔比为2，且观察到ZrO2的XRD特征衍射峰，表明Zr未能完全进入钙钛矿晶格。由于钙钛矿结构需要相对合理的A位和B位原子的计量比，Zr/Co比过大应该是其不能生成钙钛矿结构的主要原因之一。
有鉴于此，本发明旨在开发一种用于柴油发动机尾气碳烟颗粒物净化的管状La1- xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂，该催化剂含有Zr组分，具有较好的几何稳定性和碳烟催化氧化活性。本发明目的物的制备原理为：采用聚碳酸酯薄膜作为模板，将含硝酸盐的水溶液，加入2-羟基丙酸调节，再将该溶液填充在聚碳酸酯薄膜的毛孔中，通过煅烧除去模板，得到管状催化剂，其中2-羟基丙酸与金属离子的弱络合作用，可使金属离子在聚碳酸酯薄膜的毛孔中的扩散速率减缓以形成均匀的扩散，使生成的复合氧化物管状尺寸均匀。
发明内容
本发明的目的是针对柴油发动机尾气碳烟颗粒物特性及催化氧化反应特征，开发一种管状La1-xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂(其中，δ表示复合氧化物中存在氧空位或氧缺陷)。本发明的管状催化剂通过聚碳酸酯薄膜作为模板制备而得，具有稳定均称的几何结构和碳烟催化氧化活性。
本发明提供了一种管状La1-xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂并用于柴油发动机尾气碳烟颗粒物净化，通过以下步骤制备而得：
(1)按La1-xCexCo1-yZryO3-δ中的组成比，计算称量水合硝酸镧、水合硝酸铈、水合硝酸锆和水合醋酸钴用量并溶解于去离子水中，室温下搅拌20分钟，超声震荡30分钟，配制成金属离子总浓度为1.0mol/L的混合液，继续加入2-羟基丙酸，搅拌溶解后静止陈化6小时以上使络合反应完全。其中，x为A位离子La和Ce合计计量数中Ce所占比例分数，其值为0.05～0.2；y为B位离子Zr和Co合计计量数中Zr所占比例分数，其值为0.05～0.1；混合液中2-羟基丙酸的质量百分比浓度为2～5％；。
(2)在注射器过滤系统中，使用多孔聚碳酸酯薄膜作为模板和滤膜，用注射器吸入一定量步骤(1)所得混合溶液慢慢地压入注射器过滤系统中，以保证硝酸盐前驱体溶液能尽可能多的填充毛孔。其中，聚碳酸酯薄膜的孔径范围为200～1200nm。
(3)将步骤(2)所得均匀分散有步骤(1)所得混合溶液的聚碳酸酯薄膜在微波炉中进行脱水干化，微波炉功率设置和微波处理时间以不造成聚碳酸酯薄膜碳化(发黑)为准。例如，800W功率下微波干化3～10分钟。
(4)将步骤(3)所得干化样品置入马弗炉中，空气气氛下以2～5℃/min升温速率将炉温从室温升到650～850℃煅烧2～6小时，然后自然降温至室温，得到纳米管状钙钛矿型复合氧化物催化剂材料La1-xCexCo1-yZryO3-δ。
本发明所得La1-xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂为管状，具有钙钛矿晶型的均称管状孔性结构，孔径范围为100～1100nm。该纳米管状钙钛矿型复合氧化物催化剂材料具有可耐受650～850℃的高温结构稳定性。本发明以聚碳酸酯薄膜作为模板，以2-羟基丙酸调节使金属离子在聚碳酸酯薄膜毛孔中可形成均匀的扩散，所得管状产物管径尺寸均匀，高温煅烧后结构稳定性好，应用于柴油发动机尾气碳烟颗粒催化氧化燃烧反应具有低的转化温度。
附图说明
图1为实施例所得管状钙钛矿的XRD晶相结构图。
图2为实施例所得管状钙钛矿的高清SEM形貌图。
图3为实施例所得管状钙钛矿的催化活性图。
具体实施方式
以下通过具体实施例对本发明进行详细说明。
实施例1
(1)按La0.9Ce0.1Co0.95Zr0.05O3-δ化学式组成比，称取38.97g六水硝酸镧、4.34g六水硝酸铈、23.66g四水醋酸钴和2.15g五水硝酸锆，加入到200mL去离子水中，室温下磁力搅拌20分钟。继续以40kHz和130W功率的超声振荡清洗器超声震荡30分钟，使金属盐完全溶解，溶液呈透明状。随后加入13.5g食品级2-羟基丙酸，搅拌溶解后静止陈化12小时。
(2)在注射器过滤系统中，使用200nm多孔聚碳酸酯薄膜作为模板和滤膜，用注射器吸入足量步骤(1)所得混合溶液慢慢地压入注射器过滤系统中，使薄膜以混合溶液填充毛孔，充分浸润。
(3)将步骤(2)所得充分浸润的薄膜放入微波炉中，设置微波炉功率为800W，干化脱水3分钟。
(4)将步骤(3)所得干化样品置入马弗炉中，空气气氛下以约2℃/min升温速率将炉温从室温升到800℃，煅烧4小时，然后自然降温至室温，得到管状La0.9Ce0.1Co0.95Zr0.05O3-δ钙钛矿型复合氧化物催化剂。
(5)对照的纳米颗粒状La0.9Ce0.1Co0.95Zr0.05O3-δ钙钛矿型复合氧化物催化剂通过凝胶法制备：
按步骤(1)相同的金属盐比例，称取7.794g六水硝酸镧、0.868g六水硝酸铈、4.733g四水醋酸钴和0.429g五水硝酸锆，加入到200mL去离子水中，室温下搅拌使金属盐完全溶解，溶液呈透明状。加入12.296g食品级柠檬酸，继续搅拌使其完全溶解。将得到的混合溶液置于80℃水浴锅上水浴6小时，得到湿凝胶。把湿凝胶转移到100℃的烘箱中空气气氛下干燥12小时，得到疏松多孔的干凝胶。将干凝胶破碎研磨后转移到马弗炉中，以约10℃/min升温速率将炉温从室温升到200℃煅烧2小时，再以约10℃/min升温速率继续将炉温升到800℃煅烧4小时，得到纳米颗粒状催化剂。
(6)实施例管状La0.9Ce0.1Co0.95Zr0.05O3-δ钙钛矿型复合氧化物催化剂结构分析
结构分析所用仪器：以X'Pert3 Powder型多功能X-射线衍射仪(荷兰帕纳科公司)测试其晶相结构(XRD)；以日立高新热场式场发射扫描电镜SU5000表征材料形貌；以电感耦合等离子体发射光谱(ICP，Aglient 5110型电感耦合等离子体发射光谱)测定催化剂中金属组分的含量。
实施例合成所得管状钙钛矿材料的晶相结构(XRD)如附图1所示，样品在2θ＝23.22°、32.87°、40.65°、47.49°、58.69°、68.92°处的衍射峰，分别与晶格面(012)、(110)、(202)、(024)、(300)和(220)六方对称的钙钛矿LaCoO3(PDF#48-0123)相对应。
附图2高清SEM形貌表明，管状钙钛矿为细长管子，结构均称。使用扫描电镜的标距功能，测量出管内径平均约130nm左右、壁厚约10nm。此结构具有较大的孔性结构，可以更好的接触碳烟颗粒，从而具有更佳的催化活性。
ICP分析表明，管状钙钛矿产物中，金属组分La、Ce、Co、Zr离子的含量分析分别为质量百分比61.94％、7.64％、27.81％和2.61％，经计算，A位离子中La与Ce的摩尔计量数比为0.891：0.109，B位离子中Co与Zr的摩尔计量数比为0.943：0.057，结果与投料比相近，表明发明目的物可按设计要求合成。
(7)实施例催化剂的碳烟催化氧化性能分析
催化剂的碳烟催化氧化性能测试方法：采用程序升温氧化法(TPO)评价催化剂对碳烟催化氧化燃烧的催化活性，催化剂床层采用固定床。其中，采取管状催化剂与碳烟松散接触方式进行催化反应，而纳米颗粒状催化剂采取与碳烟紧密接触方式进行催化反应(混合时进行适当研磨)。碳烟与催化剂的质量比为1：10，其中将碳烟与催化剂按相应的接触方式预先混合均匀。称取0.15g碳烟与催化剂混合物放入鼓泡石英反应管(内径8mm)中。反应气体组成为2000ppm NO，6％O2，余气为N2，气体总流量为100mL·min-1。反应气体经催化剂同时消除NO和碳烟，尾气中的CO、CO2和O2使用FGA10型在线烟气分析仪检测(深圳市贝特分析仪器有限公司)。碳烟催化氧化燃烧特性以CO2生成浓度来间接评价，催化活性用碳烟颗粒的燃烧温度来表示，温度越低，表明催化活性越高。分别以碳烟转化率为10％、50％和90％时的温度T10、T50和T90，CO2最大生成浓度时对应的温度Tm来评价催化剂的燃烧活性。大多数据情况下Tm与T50相近，因此可以Tm值表示T50值。T10、T50和T90是通过碳烟颗粒燃烧产生的CO2和CO的浓度随温度变化积分来计算。
采用TPO法测试的所制备催化剂催化氧化碳烟颗粒的性能结果如下表及附图3所示。在没有催化剂参与反应的情况下，纯碳烟颗粒的燃烧温度很高。在催化剂的作用下，碳烟氧化燃烧的温度有了较大幅度的下降。其中，管状催化剂的T10、T50(Tm)和T90分别为298℃、370℃和442℃，均低于纳米颗粒状催化剂的，其中T50(Tm)和T90均低70℃左右。同时，对比Sun等人(doi.org/10.1016/j.jre.2019.05.014)报道的纳米颗粒La0.9Ce0.1CoO3钙钛矿催化剂的在紧密接触时碳烟催化氧化活性(T10、T50和T90分别为371℃、444℃和497℃)，本发明所得管状La0.9Ce0.1Co0.95 Zr0.05O3-δ钙钛矿型复合氧化物催化剂的碳烟催化氧化活性T50和T90均低60～70℃左右，显示了更优良的碳烟催化氧化活性。
综上，通过实施例的结果表明，本发明的管状La1-xCexCo1-yZryO3-δ钙钛矿型复合氧化物催化剂具有较好的碳烟催化燃烧反应的催化活性，相比纳米颗粒型具有更低的碳烟催化燃烧反应温度。本发明的管状结构较为稳定，具有较大的均匀孔性结构，与碳烟颗粒松散接触较为紧密，具有更好的松散接触催化活性。本发明所得的管状钙钛矿材料可作为潜在的用于柴油车尾气中碳烟颗粒净化的新型材料。
Claims (4)
1.一种可降低柴油发动机碳烟氧化温度的纳米管状钙钛矿型复合氧化物催化剂材料，其特征在于，其化学式为La1-xCexCo1-yZryO3-δ，其中，A位离子La和Ce合计计量数中Ce离子所占比例分数x值为0.05～0.2，B位离子Zr和Co合计计量数中Zr离子所占比例分数y值为0.05～0.1，δ表示该复合氧化物中存在氧空位或氧缺陷；该纳米管状钙钛矿型复合氧化物催化剂材料的具体制备步骤如下：
（1）按La1-xCexCo1-yZryO3-δ中的组成比，计算称量水合硝酸镧、水合硝酸铈、水合硝酸锆和水合醋酸钴的用量并混溶于去离子水中，室温下搅拌20分钟，超声振荡30分钟，配制成金属离子总浓度为1.0 mol/L的混合液，继续加入2-羟基丙酸，搅拌溶解后静止陈化6小时以上使络合反应完全；其中，x为A位离子La和Ce合计计量数中Ce所占比例分数，其值为0.05～0.2；y为B位离子Zr和Co合计计量数中Zr所占比例分数，其值为0.05～0.1；混合液中2-羟基丙酸的质量百分比浓度为2～5%；
（2）在注射器过滤系统中，使用多孔聚碳酸酯薄膜作为模板和滤膜，用注射器吸入一定量步骤（1）所得混合溶液慢慢地压入注射器过滤系统中，以保证硝酸盐前驱体溶液能尽可能多的填充毛孔；其中，聚碳酸酯薄膜的孔径范围为200～1200 nm；
（3）将步骤（2）所得均匀分散有步骤（1）所得混合溶液的聚碳酸酯薄膜在微波炉中进行脱水干化，微波炉功率设置和微波处理时间以不造成聚碳酸酯薄膜碳化为准；
（4）将步骤（3）所得干化样品置入马弗炉中，空气气氛下以2～5 ℃/分钟的升温速率将炉温从室温升到650～850 ℃煅烧2~6小时，然后自然降温至室温，得到纳米管状钙钛矿型复合氧化物催化剂材料La1-xCexCo1-yZryO3-δ。
2.根据权利要求1所述的催化剂材料，其特征在于：该纳米管状钙钛矿型复合氧化物催化剂材料为钙钛矿晶型的均称管状孔性结构，孔径范围为：100～1100nm。
3.根据权利要求1所述的催化剂材料，其特征在于：该纳米管状钙钛矿型复合氧化物催化剂材料具有可耐受650～850 ℃的高温结构稳定性。
4.权利要求1-3中任意一项所述的催化剂材料的应用，其特征在于：该纳米管状钙钛矿型复合氧化物催化剂材料应用于柴油发动机尾气碳烟颗粒的松散接触催化氧化净化反应。
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