CN112121815A - 一种用于co2加氢的钙钛矿催化剂和应用 - Google Patents
一种用于co2加氢的钙钛矿催化剂和应用 Download PDFInfo
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Abstract
本发明涉及LaFeMnO3钙钛矿催化剂,用于CO2加氢制备乙烯、丙烯、丁烯。本发明强调了还原温度的重要性,发现在400‑650℃还原,在反应条件为H2/CO2=1~4,150~300℃、2~8MPa,1000~4000 h–1,尤其催化剂通过Mg、Na、Zn、K至少一种元素浸渍修饰后,能表现出良好的低碳烯烃选择性。具有一定的工业价值。
Description
技术领域
本发明涉及CO2加氢催化剂制备技术领域,涉及钙钛矿催化剂,及催化剂制备乙烯、丙烯、丁烯的应用。
背景技术
以二氧化碳为原料加氢制备低碳烯烃,不但能够缓解二氧化碳排放带来的环保压力,更能实现二氧化碳资源的有效利用。二氧化碳直接加氢制低碳烯烃可分为两个步骤:逆水气转换反应和连续的费托合成。目前在二氧化碳制备低碳烯烃过程中,降低烷烃特别是甲烷的生成以及提高烯烃的选择性是研究的重点。
关于反应机理的研究非常多,但结论并不完全一致,这是因为催化剂不同,对二氧化碳的吸附形式就可能不同,产生的中间体就不同,反应机理也就不同。
钙钛矿型金属氧化物因其较强的氧选择性和离子传导能力而被用作过滤膜、化学反应或高温空气分离的催化剂和吸附剂。钙钛矿型金属氧化物具有这种优势主要是由于其独特的氧传输机制,通过掺杂使钙钛矿型金属氧化物结构中产生一定的氧缺陷(即氧空位),氧离子在晶格中从一个氧空位跳到另一个氧空位上从而实现氧离子的传输。掺杂是指以一种金属离子部分占据另一种金属离子的位置,如果两种金属离子的价态不同,则会形成电荷缺陷,进而形成氧空位。氧空位的存在使钙钛矿型金属氧化物可以捕获并活化气相氧,为燃料的氧化反应提供活性的氧。
钙钛矿前躯体中B位离子的还原(或部分还原)可使金属态的B更好地高分散于A的氧化物(或钙钛矿复合氧化物)上。通过控制还原温度所制备的这种结构有利于催化剂的稳定性和积碳气化。因此,钙钛矿催化剂可以用于CO2加氢反应,并且是一种很有前景的催化剂。
发明内容
本发明催化剂具有适宜的CO2吸附解离能力,抑制烯烃的再吸附,降低烯烃的二次反应,提高烯烃选择性。为突破A-S-F产物分布,高选择性获得低碳烯烃和抑制副产物甲烷,C5 +等副产物提供有力基石。本发明催化剂能有效的抑制初级烯烃二次加氢反应,调控出附加值高的产物分布,尤其α烯烃的获得占到C2-C4低碳烯烃中90%以上。La元素相邻铁锰原子附近位点存在缺陷,富集晶格氧,巩固晶体堆叠取向,影响钙钛矿暴露特定晶面,显著增强材料吸附位点和催化活性。
技术方案中,Mg,Na、Zn、K的元素浸渍修饰,可以进一步调控材料的吸附性能及加氢性能,制备出高性能的钙钛矿功能材料。
本发明在探究时发现,催化剂的还原温度起到非常重要的作用。通过常压下,2000h–1条件下,分别考察还原温度400℃、500℃、600℃、650℃、700℃、750℃、800℃,还原后催化剂应用于CO2加氢反应。结果发现,催化剂在400-650℃区间还原下,催化剂表现出良好的加氢活性。在700℃及以上还原后,推测催化剂结构坍塌,催化剂金属颗粒发生积碳堵塞,催化剂CO2加氢反应时二次加氢反应加剧,主要生成烷烃,烯烃选择性显著降低。
为了实现本发明的上述目的,本发明采用的技术方案如下:本发明催化剂核心是LaFeMnO3,由于制备因素等原因,会留有金属氧化物,包括La2O3、Fe2O3。催化剂的制备方法是按摩尔比计:La:Fe=0.3-0.6:1,Fe:Mn=1-2:1,称取镧、铁、锰的硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶;凝胶经105-120℃干燥,在600-900℃焙烧获得目标催化剂。催化剂应用于CO2加氢制备低碳烯烃。反应条件为H2/CO2 =1~4,150~300℃、2~8MPa,1000~4000 h–1;应用前须经400-650℃还原。催化剂的优化通过Mg、Na、Zn、K至少一种元素浸渍修饰。
附图说明
图1是样品1的XRD图。
具体实施方式
下面通过实施案例对本发明作进一步详细说明。本实施案例在以本发明技术为前提下进行实施,现给出详细的实施方式和具体的操作过程来说明本发明具有创造性,但本发明的保护范围不限于以下的实施案例。
根据本申请包含的信息,对于本领域技术人员来说可以轻而易举地对本发明的精确描述进行各种改变,而不会偏离所附权利要求的精神和范围。应该理解,本发明的范围不局限于所限定的过程、性质或组分,因为这些实施方案以及其他的描述仅仅是为了示意性说明本发明的特定方面。实际上,本领域或相关领域的技术人员明显能够对本发明实施方式作出的各种改变都涵盖在所附权利要求的范围内。
为了更好地理解本发明而不是限制本发明的范围,在本申请中所用的表示用量、百分比的所有数字、以及其他数值,在所有情况下都应理解为以词语“大约”所修饰。因此,除非特别说明,否则在说明书和所附权利要求书中所列出的数字参数都是近似值,其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。
下述各实施例中,若无特殊说明,所有原料组分无特殊说明,均为本领域技术人员熟知的市售产品。
实施例1
称取6.5g硝酸镧、10.1g硝酸铁、8.9g硝酸锰,用蒸馏水溶解,再加入19.21g柠檬酸,蒸馏水溶解后,于水浴条件下机械搅拌,水浴温度80℃,搅拌速度500r/min。搅拌至凝胶状态后,于100℃干燥 12h。将粉末置于马弗炉,按10℃/min 的速率升温,在800℃保温4h,冷却后研磨得催化剂样品。记为样品1。图1是样品1的XRD谱图。图1说明形成了LaFeMnO3钙钛矿。
实施例2
称取6.5g硝酸镧、5.2g硝酸铁、8.9g硝酸锰,用蒸馏水溶解,再加入19.21g柠檬酸,蒸馏水溶解后,于水浴条件下机械搅拌,水浴温度80℃,搅拌速度500r/min。搅拌至凝胶状态后,于100℃干燥 12h。将粉末置于马弗炉,按10℃/min 的速率升温,在800℃保温4h,冷却后研磨得催化剂样品。按质量分数称取2%碳酸钾,即浸渍2% K。记为样品2。
实施例3
称取10.82g硝酸镧、10.1g硝酸铁、8.9g硝酸锰,用蒸馏水溶解,再加入25.2g柠檬酸,蒸馏水溶解后,于水浴条件下机械搅拌,水浴温度80℃,搅拌速度500r/min。搅拌至凝胶状态后,于100℃干燥 12h。将粉末置于马弗炉,按10℃/min 的速率升温,在800℃保温4h,冷却后研磨得催化剂样品。按质量分数称取10%碳酸钾,即浸渍10% K。记为样品3。
实施例4
称取6.5g硝酸镧、5.2g硝酸铁、8.9g硝酸锰,用蒸馏水溶解,再加入19.21g柠檬酸,蒸馏水溶解后,于水浴条件下机械搅拌,水浴温度80℃,搅拌速度500r/min。搅拌至凝胶状态后,于100℃干燥 12h。将粉末置于马弗炉,按10℃/min 的速率升温,在800℃保温4h,冷却后研磨得催化剂样品。按质量分数称取2%碳酸锌,即浸渍2% Zn。记为样品4。
实施例5
称取6.5g硝酸镧、5.2g硝酸铁、8.9g硝酸锰,用蒸馏水溶解,再加入19.21g柠檬酸,蒸馏水溶解后,于水浴条件下机械搅拌,水浴温度80℃,搅拌速度500r/min。搅拌至凝胶状态后,于100℃干燥 12h。将粉末置于马弗炉,按10℃/min 的速率升温,在800℃保温4h,冷却后研磨得催化剂样品。按质量分数称取5%碳酸镁,即浸渍5% Mg。记为样品5。
催化剂性能测试:
实施例1~5制备的催化剂均制成20~40目的催化剂颗粒。在微型固定床反应器中进行性能评价,具体操作步骤如下:称取1.0 mL样品催化剂装入反应管中部恒温区,原料气H2/CO2=3,温度为320°C,压力为2.0MPa、空速(GHSV)为1000 h-1,达到稳定状态后,采样分析,间隔3 h采样一次。利用气相色谱对原料气和产物经行定量和定性分析。
考察样品2分别在不同还原温度后CO2加氢活性。见表1。
表1样品2在不同还原温度后CO2加氢活性
还原温度 | CO2转化率(%) | CH<sub>4</sub>(%) | C<sub>2</sub>-C<sub>4</sub><sup>=</sup>(%) | C<sub>2</sub>-C<sub>4</sub><sup>0</sup>(%) | C<sub>5</sub><sup>+</sup>(%) | O/P |
400 | 35.12 | 34.42 | 37.12 | 15.89 | 12.57 | 2.34 |
450 | 38.45 | 37.48 | 35.45 | 13.62 | 13.45 | 2.60 |
500 | 39.47 | 36.45 | 38.12 | 9.89 | 15.54 | 3.85 |
550 | 35.41 | 37.46 | 34.45 | 15.31 | 12.78 | 2.25 |
600 | 34.42 | 35.47 | 36.12 | 13.86 | 14.55 | 2.60 |
650 | 37.45 | 34.54 | 33.28 | 15.66 | 16.52 | 2.13 |
700 | 40.45 | 38.54 | 8.41 | 40.53 | 12.52 | 0.21 |
750 | 42.68 | 39.45 | 2.1 | 45.05 | 13.4 | 0.04 |
800 | 43.72 | 40.48 | 0 | 44.12 | 15.4 | 0 |
表1说明了还原温度对催化剂性能影响非常关键,在400-650℃区间,催化剂表现出较好的活性和低碳烯烃选择性。800℃还原后的催化剂,催化效果最差。
考察不同样品在600℃还原后的CO2加氢活性。见表2。
表2实施例1~5制备的样品加氢催化反应结果对比表
催化剂 | CO<sub>2</sub>转化率(%) | CH<sub>4</sub>(%) | C<sub>2</sub>-C<sub>4</sub><sup>=</sup>(%) | C<sub>2</sub>-C<sub>4</sub><sup>0</sup>(%) | C<sub>5</sub><sup>+</sup>(%) | O/P |
样品1 | 21.21 | 32.45 | 28.15 | 26.95 | 12.45 | 1.04 |
样品2 | 34.42 | 35.47 | 36.12 | 13.86 | 14.55 | 2.61 |
样品3 | 35.51 | 36.28 | 37.28 | 13.76 | 12.68 | 2.71 |
样品4 | 36.45 | 37.46 | 32.37 | 15.05 | 15.12 | 2.15 |
样品5 | 34.26 | 38.45 | 33.45 | 15.73 | 12.37 | 2.13 |
表2为本发明上述实施例制备的样品的加氢催化工艺参数及性能测试结果对比表。由表2可以看出所制样品表现出较好的CO2加氢活性,在产物分布中,烃类产物变化明显。低碳烯烃选择性保持在30%以上,烯烷比(O/P)可达2.7。
Claims (4)
1.一种用于CO2加氢的钙钛矿催化剂和应用,其特征在于:
所述催化剂核心是LaFeMnO3;催化剂的制备方法是镧、铁、锰的硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶;凝胶经105-120℃干燥,在600-900℃焙烧获得目标催化剂;所述催化剂经400-650℃还原,应用于CO2加氢制备低碳烯烃。
2.根据权利要求1所述的一种用于CO2加氢的钙钛矿催化剂和应用,其特征在于:
应用反应条件为H2/CO2 =1~4,150~300℃、2~8MPa,1000~4000 h–1。
3.根据权利要求1所述的一种用于CO2加氢的钙钛矿催化剂,其特征在于所述催化剂中按摩尔比计:La:Fe=0.3-0.6:1,Fe:Mn=1-2:1。
4.根据权利要求1所述的一种用于CO2加氢的钙钛矿催化剂,其特征在于催化剂的优化通过Mg、Na、Zn、K至少一种元素浸渍修饰。
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